Final-Demystifying Physical Chemistry

DEMYSTIFYING PHYSICAL CHEMISTRY (A‟LEVEL)
A simplified, well elaborated and illustrative approach to the

physical chemistry
Joseph Jobs Kayiira,

BSCED(Chemistry/mathematics)(Hons)
+256753247098
All rights reserved. No part of this book may be reproduced, stored in a
retrieval system or transmitted in any means, electronic or mechanical,
photocopied or in any other way without prior permission from the
author.
PREFACE
The author has an inexorable curiosity in streamlining the chemistry concepts that
majority of the students in Uganda consider a nut to crack.
He has taught Chemistry and Mathematics in various schools in Entebbe, Kampala,
Wakiso and Butambala. This means that he has analysed the problems students at
A‟ level face in Chemistry.
This physical chemistry collation has been substantially organised and fully
compatible with the NCDC Chemistry syllabus-2013
The author is contented that this edition contains more than enough material as
regards A‟ level physical chemistry and the subject matter has been arranged and
structured so that it can be tackled by students of different abilities and the text is
in a readable font to all kinds of eyes.
Indeed this book is vital for a student to teach him/herself even in absence of a
teacher. However, the teacher is as well vital in cases where you may not well
interprete the content. The author has tried to link physical chemistry with
inorganic and organic concepts where he feels it is necessary.
Variety of examples are given, more than one methods of solving a problem
illustrated and a diversity of typical examinable revision questions in each subtopic
but no answers such that research and consultation is enhanced.
Also feel free to contact the author using contacts or social media platforms at the
back cover of the book for clarity, recommendations, guidance or advice.
This is the only book that you will not regret to have come across.
DEDICATION
All my parents and friends for their support, discipline and a spiritual guidance
My dear students in the various schools I have worked for their encouragement and
courage
Lastly to my lovely daughters Joselyne Fortunate Kayiira and Jacqueline
Franches Kayiira
ACKNOWLEDGEMENTS
I wish to thank the following people without whom I would not be able to produce
this book.
First, my parents; Mrs. Nakavuma Harriet and Mr. Ssentume Fahad who
thought it wise that they should transmit some of the traits they are gifted with
through me to the next generations and my dear spouse, Noeline Nakasumba for
giving me ample time to make this wonderful compilation.
Senior teachers like Mr.Opia Richard, Mr.Mawejje Henry and Mr. Sseruuma
for the inspiration I got from them to write this book. Through their wonderful
lessons, I was guided and directed throughout my course of studying and applying
chemistry.
All colleagues in the profession, with whom we shared online or by a call for
solving some problems before we incorporated them in this text
I am finally grateful to Mr. Kibira Ivan, Hajj Sulait Kato Kasagga and Hajj
Mukasa Ibrahim for their guidance and encouragement in releasing this edition.
TABLE OF CONTENTS
CHAPTER ONE ........................................................................................................................... 1
MATTER ....................................................................................................................................... 1
The structure of an atom .......................................................................................................... 1
The sub atomic particles ........................................................................................................... 2
Fundamental particles of an atom ........................................................................................... 2
Isotopic notation ........................................................................................................................ 4
Ionic formation .......................................................................................................................... 4
IUPAC nomenclature for cations, anions and salts ............................................................... 6
Naming monoatomic ions; cations and anions...................................................................................... 6
Naming polyatomic ions and compounds ............................................................................................. 7
The Stock system .................................................................................................................................. 9
Systemic/Correct/unambiguous name of some compounds ............................................................... 10
The selection of correct Roman numeral ............................................................................................ 10
Writing the formula of a binary compound......................................................................................... 11
MASS SPECTROMETRY ..................................................................................................... 11
The essential parts and operation of a modern mass spectrometer ..................................................... 11
Diagram showing the essential parts of a modern mass spectrometer ................................................ 12
Operation of a modern mass spectrometer .......................................................................................... 12
Uses of a mass spectrometer ............................................................................................................... 13
Advantages of a mass spectrometer over other methods of determining atomic or molecular mass .. 14
The mass spectrum .............................................................................................................................. 14
Interpreting a mass spectrum .............................................................................................................. 14
The use of a mass spectrum ................................................................................................................ 17
Average atomic mass .......................................................................................................................... 17
Relative atomic mass(Ar).................................................................................................................... 17
Relative molecular mass(Mr) .............................................................................................................. 18
More calculations involving data from mass spectrometry ................................................................ 18
Questions............................................................................................................................................. 21
THE MOLE CONCEPT ......................................................................................................... 24
Calculating molar masses of elements and compounds ...................................................................... 25
Molar mass-mole conversions ............................................................................................................ 25
Limiting reactants and excess reactants .............................................................................................. 27
Percentage yields in a chemical reaction ............................................................................................ 28
Experiment to demonstrate concept of limiting and excess reactants, theoretical yield, actual yield
and percentage yield............................................................................................................................ 28
Avogadro‟s law ................................................................................................................................... 32
Gay-Lussac‟s law ................................................................................................................................ 34
LABORATORY APPARATUS AND CHEMICALS ....................................................................... 34
Selection of apparatus for different experiments ................................................................................ 35
Laboratory rules and regulations for handling chemicals and apparatus ............................................ 35
Concentration ...................................................................................................................................... 36
Molarity (M) ....................................................................................................................................... 36
Difference between molarity and molality.......................................................................................... 36
Percentage by mass (% w/w) .............................................................................................................. 37
Percentage by volume (% v/v) ............................................................................................................ 38
PRIMARY AND SECONDARY STANDARDS .................................................................. 40
Preparation of standard solutions by weighing and dissolving in water ............................................. 42
VOLUMETRIC ANALYSIS .................................................................................................. 43
Common terms used in volumetric analysis ....................................................................................... 43
Set up of apparatus for volumetric analysis ........................................................................................ 44
Acid-base titrations and use of data obtained ..................................................................................... 44
Exercise on dilution and standardisation............................................................................................. 48
Practical exercises on standardisation ................................................................................................. 48
Back titrations ..................................................................................................................................... 50
OXIDATION NUMBER (OXIDATION STATE) ............................................................... 54
Calculating oxidation state .................................................................................................................. 54
REDOX REACTIONS............................................................................................................ 57
(OXIDATION-REDUCTION REACTIONS) ...................................................................... 57
Deriving equations for redox reactions ............................................................................................... 61
Balancing redox reactions in alkaline media ...................................................................................... 65
Titration of redox reactions ................................................................................................................. 67
Potassium manganate(VII) titrations in acidic medium ...................................................................... 68
Sodium thiosulphate titrations ............................................................................................................ 71
PHYSICAL STATES OF MATTER ..................................................................................... 76
Inter-conversion between the states .................................................................................................... 76
Plasma ................................................................................................................................................. 77
The kinetic theory of matter ................................................................................................................ 77
Differences in the states of matter....................................................................................................... 78
Comparison of physical properties ..................................................................................................... 78
GASEOUS STATE OF MATTER ..................................................................................................... 79
The gaseous state in terms of kinetic theory of matter ........................................................................ 79
AN IDEAL GAS ................................................................................................................................. 79
Gas pressure ........................................................................................................................................ 79
Gas laws .............................................................................................................................................. 80
Examples on calculations involving gas laws ..................................................................................... 82
Ideal gas law ....................................................................................................................................... 82
Graham‟s law of gaseous diffusion ..................................................................................................... 85
Mole fraction of a gas, ................................................................................................................... 91
Dalton‟s law of partial pressure .......................................................................................................... 92
Maxwell-Boltzmann distribution ........................................................................................................ 96
Deviation from Ideal behaviour .......................................................................................................... 97
Differences between a real gas and ideal gas ...................................................................................... 97
Conditions under which real gases behave like ideal gases ................................................................ 97
Correction of real gas behaviour by using van der Waals‟ equation ................................................ 100
Liquefaction of gases ........................................................................................................................ 101
LIQUID STATE OF MATTER ........................................................................................................ 103
The liquid state in terms of kinetic theory of matter ......................................................................... 103
Properties of a liquid ......................................................................................................................... 104
SOLID STATE OF MATTER .......................................................................................................... 107
The solid state in terms of kinetic theory of matter ......................................................................... 107
Phase changes in solids ..................................................................................................................... 108
Types of solids .................................................................................................................................. 108
EMPIRICAL FORMULA, MOLECULAR FORMULA AND PERCENTAGE
COMPOSITION BY MASS ................................................................................................. 113
The percentage composition by mass of an element or a molecule in a compound ......................... 113
Empirical formulae and molecular formulae .................................................................................... 115
Calculations on empirical formulae and molecular formulae ........................................................... 116
CHAPTER TWO ...................................................................................................................... 133
ATOMIC STRUCTURE AND THE PERIODIC TABLE ................................................... 133
Fundamental particles of the atoms and radioactivity ...................................................... 133
Historical development of the atomic theory .................................................................................... 133
Modern theory of the atom................................................................................................................ 133
(a) John Dalton‟s atomic theory ..................................................................................................... 133
(b) The J.J Thomson model of an atom .......................................................................................... 134
(c) Ernest Rutherford‟s atomic model ............................................................................................ 135
Fundamental particles of the atom .................................................................................................... 135
RADIOACTIVITY ........................................................................................................................... 136
Discovery .......................................................................................................................................... 136
Types of radiations and their discovery ............................................................................................ 137
A comparison between the characteristics of the different types of radiations ................................. 138
Some other important particles involved in radioactivity ................................................................. 138
Radioisotopes .................................................................................................................................... 139
Nuclear reactions .............................................................................................................................. 139
Differences between chemical and nuclear reactions ....................................................................... 139
Balancing nuclear reaction equations................................................................................................ 140
RADIOACTIVE DECAY................................................................................................................. 146
Half life ............................................................................................................................................. 148
Graphical representation of radioactive decay .................................................................................. 152
Nuclear energy .................................................................................................................................. 155
Discovery .......................................................................................................................................... 155
Nuclear fission .................................................................................................................................. 155
Nuclear fusion ................................................................................................................................... 156
Nuclear power ................................................................................................................................... 157
Applications of radioactivity ............................................................................................................. 157
NUCLEAR STABILITY ...................................................................................................... 158
A summarized comparison between stable and unstable nuclei ....................................................... 158
Factors affecting nuclear stability ..................................................................................................... 159
ELECTRONIC STRUCTURE OF ATOMS ...................................................................... 161
Electromagnetic radiation ................................................................................................................. 161
Relationship between wavelength frequency, , and energy, . ................................................. 162
Using the equation in calculations .................................................................................................... 162
Atomic spectra .................................................................................................................................. 163
Types of spectra ................................................................................................................................ 163
A description of the hydrogen emission spectrum ............................................................................ 164
An explanation of the hydrogen spectrum ........................................................................................ 164
The application of the Rydberg equation .......................................................................................... 165
Energy level diagram for the hydrogen atom.................................................................................... 167
The significance of lines in the hydrogen spectrum.......................................................................... 168
The importance of the Convergence limit......................................................................................... 168
The Bohr‟s model of the hydrogen atom .......................................................................................... 168
Ionisation energy ............................................................................................................................... 169
Heisenberg‟s Uncertainty principle .................................................................................................. 171
The concept of quantum numbers ..................................................................................................... 171
Differentiation between an orbital and an orbital ............................................................................. 173
The Aufbau principle ........................................................................................................................ 174
Pauli Exclusion principle .................................................................................................................. 174
Hund‟s rule........................................................................................................................................ 174
Electronic configuration of atoms ..................................................................................................... 175
Electronic configuration of ions ........................................................................................................ 176
THE PERIODIC TABLE ..................................................................................................... 179
The historical development of the Periodic Table ............................................................................ 179
Unique position of Hydrogen in the Periodic Table ......................................................................... 180
The Modern Periodic Table .............................................................................................................. 181
Periodicity of atomic properties in the Periodic Table...................................................................... 185
Atomic and Ionic radius .................................................................................................................... 186
Electron affinity ................................................................................................................................ 195
Electronegativity ............................................................................................................................... 198
Electropositivity ................................................................................................................................ 200
Metallic character.............................................................................................................................. 201
CHAPTER THREE .................................................................................................................. 206
STRUCTURE AND BONDING .............................................................................................. 206
CHEMICAL BONDING ...................................................................................................... 206
Lewis Dot symbols ........................................................................................................................... 206
The octet rule and ions ...................................................................................................................... 209
Ionic bond formation......................................................................................................................... 210
Giant ionic structures ........................................................................................................................ 211
The properties of ionic compounds ................................................................................................... 212
Covalent character in ionic compounds ............................................................................................ 213
Covalent bond formation .................................................................................................................. 216
Types of covalent bonding ................................................................................................................ 218
Covalent bond strength ..................................................................................................................... 222
Giant covalent structures ................................................................................................................... 223
Properties of covalent compounds .................................................................................................... 223
Intermolecular forces ........................................................................................................................ 224
Van der Waals‟ forces ....................................................................................................................... 224
The hydrogen bond ........................................................................................................................... 228
Types of hydrogen bonding .............................................................................................................. 229
Metallic bonding ............................................................................................................................... 236
Properties of metals........................................................................................................................... 237
Strength of a metallic bond ............................................................................................................... 238
VALENCE BOND THEORY .............................................................................................. 239
Sigma and pi bonds .................................................................................................................. 239
Hybridisation of atomic orbitals ....................................................................................................... 240
Geometry for different types of hybridisation .................................................................................. 243
The formation of single, double and triple bonds ............................................................................. 243
The double bond formation in benzene............................................................................................. 245
DRAWING LEWIS STRUCTURES OF MOLECULES AND POLYTATOMIC IONS
................................................................................................................................................. 245
Lewis structures ................................................................................................................................ 245
Drawing Lewis structures of some simple molecules ....................................................................... 246
Steps for writing Lewis structures for more complex molecules/ polyatomic ions .......................... 246
Exceptions of the Octet rule .............................................................................................................. 249
Formal charges .................................................................................................................................. 250
Resonance ......................................................................................................................................... 252
VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR) THEORY ................. 252
Predicting the shapes of molecules and ions ..................................................................................... 253
(a) Steps followed to draw the structure of molecules and cations ................................................ 255
(b) Steps followed to draw the structure of oxy-anions and oxy-molecules................................... 257
The effect of lone pairs on Molecular Geometry .............................................................................. 273
The effect of electronegativity on size of bond angles...................................................................... 275
Polarity of molecules ........................................................................................................................ 277
Factors that determine the polarity of molecules .............................................................................. 277
Differences between polar and non-polar molecules ........................................................................ 278
Miscellaneous Questions................................................................................................................... 278
CHAPTER FOUR ..................................................................................................................... 281
THERMOCHEMISTRY .......................................................................................................... 281
(CHEMICAL ENERGETICS) ................................................................................................ 281
CHEMICAL ENERGY ........................................................................................................ 281
Heat content of a substance ............................................................................................................... 281
Enthalpy, ....................................................................................................................................... 282
Enthalpy change, ........................................................................................................................ 282
Standard enthalpy change, ........................................................................................................ 282
TYPES OF HEAT OF REACTIONS .................................................................................. 282
Energy level diagrams for exothermic and endothermic reactions ................................................... 283
Applications of exothermic reactions in everyday life ..................................................................... 284
Applications of endothermic reactions in everyday life ................................................................... 285
Factors affecting enthalpy of reactionEX ............................................................................. 285
CALORIMETRY .................................................................................................................. 286
Heat capacity of a calorimeter .......................................................................................................... 286
Experiment to determine heat capacity of a simple calorimeter/ plastic cup calorimeter ................. 286
TYPES OF ENTHALPY CHANGES ................................................................................. 287
Enthalpy of formation ....................................................................................................................... 287
Standard enthalpy of formation .............................................................................................. 287
Prediction of relative stability of compounds from enthalpy of formation ....................................... 287
Determination of enthalpy of formation ........................................................................................... 288
Calculating using heats of formation ............................................................................. 288
Enthalpy of combustion .................................................................................................................... 291
Standard enthalpy of combustion .......................................................................................... 291
Experiment to determine enthalpy of combustion of low molecular mass alcohols (ethanol, propanol
and butanol) ...................................................................................................................................... 291
Experiment to determine enthalpy of combustion of a solid substance for example carbon (graphite)
or coke............................................................................................................................................... 294
Calculation of enthalpy of reaction and enthalpy of formation, using enthalpies of combustion ..... 295
Calculating heats of combustion from other experimental data........................................................ 301
Application of heat of combustion in real life situation .................................................................... 303
The fuel values of various fuels ........................................................................................................ 303
Enthalpy of neutralisation ................................................................................................................. 303
Standard enthalpy of neutralisation ....................................................................................... 304
Experiment to determine enthalpy of neutralisation between a strong acid and strong alkali .......... 304
Calculations on enthalpy of neutralisation ........................................................................................ 306
Enthalpy of displacement .................................................................................................................. 308
Standard enthalpy of displacement ................................................................................................... 308
Determination of enthalpy of displacement between zinc powder and copper(II) sulphate solution 308
Calculations involving heat of displacement .................................................................................... 309
Atomisation energy ........................................................................................................................... 310
Standard enthalpy of atomisation .......................................................................................... 310
Standard enthalpy of sublimation ..................................................................................................... 311
Electron affinity ................................................................................................................................ 311
Lattice energy.................................................................................................................................... 312
Factors affecting lattice energy ......................................................................................................... 312
Standard enthalpy of hydration ......................................................................................................... 313
Factors affecting enthalpy of hydration ............................................................................................ 314
Calculations involving enthalpy of hydration ................................................................................... 314
Standard enthalpy of solution ........................................................................................................... 315
Experiments to determine enthalpy of solution ................................................................................ 316
Calculations involving enthalpy of solution ..................................................................................... 318
Application of enthalpy of solution in real life situation .................................................................. 320
Heat of precipitation ......................................................................................................................... 320
Experiment to determine heat of precipitation of silver chloride...................................................... 320
Calculations involving heat of precipitation ..................................................................................... 321
Bond energy ...................................................................................................................................... 323
Bond dissociation energy .................................................................................................................. 323
Average bond energies (enthalpies) .................................................................................................. 324
Using bond energies to calculate enthalpy of a reaction ................................................................... 324
Calculations involving bond energies ............................................................................................... 324
Hess‟s law of constant heat summation ............................................................................................ 327
Demonstration of Hess‟s law using an experiment ........................................................................... 327
Application of Hess‟s law in some more calculations ...................................................................... 328
ENTHALPY CYCLES (BORN HABER CYCLES) .......................................................... 331
Terms used in Born-Haber cycle ...................................................................................................... 331
Point to note when drawing Born Haber cycles ................................................................................ 331
(a) Enthalpy diagram or energy level diagram ............................................................................... 331
(b) Born-Haber cycle in form of a usual enthalpy cycle................................................................. 335
Born-Haber cycle involving bond energies....................................................................................... 340
Questions........................................................................................................................................... 342
CHAPTER FIVE ...................................................................................................................... 348
PHYSICAL EQUILIBRIA ...................................................................................................... 348
SYSTEMS, PHASES, COMPONENTS AND PHASE DIAGRAMS ............................... 348
System..................................................................................................................................... 348
COMPONENT SYSTEMS ................................................................................................... 349
One component systems.................................................................................................................... 349
The water system .............................................................................................................................. 349
The carbon dioxide system ............................................................................................................... 352
The sulphur system ........................................................................................................................... 354
Two component systems ................................................................................................................... 358
Completely miscible liquid mixtures ................................................................................................ 358
Partially miscible liquid mixtures ..................................................................................................... 359
Immiscible liquid mixtures ............................................................................................................... 359
IDEAL SOLUTIONS AND NON-IDEAL SOLUTIONS .................................................. 360
Ideal solutions ................................................................................................................................... 360
Raoult‟s law ...................................................................................................................................... 360
Characteristics of ideal solutions ...................................................................................................... 361
Examples of ideal solutions .............................................................................................................. 361
Vapour pressure-composition diagram for an ideal solution ............................................................ 362
Boiling point-composition diagram for an ideal solution ................................................................. 363
Calculations involving Raoult‟s law ................................................................................................. 364
Non-ideal (real) solutions.................................................................................................................. 370
Characteristics of real solutions ........................................................................................................ 370
Deviation from Raoult‟s law ............................................................................................................. 370
Negative deviation from Raoult‟s law .............................................................................................. 371
Examples of solutions that deviate negatively from Raoult‟s law .................................................... 371
Characteristic vapour pressure-composition diagram for negative deviation from Raoult‟s law ..... 372
Maximum boiling point-composition diagram ................................................................................. 372
Positive deviation from Raoult‟s law ................................................................................................ 373
Examples of solutions that deviate positively from Raoult‟s law ..................................................... 373
Characteristic vapour pressure-composition diagram for positive deviation from Raoult‟s law ...... 374
Minimum boiling point-composition diagram .................................................................................. 375
Azeotropic mixtures and azeotropes ................................................................................................. 375
Methods of separation of components of azeotropes ........................................................................ 376
Distillation of a binary liquid mixture............................................................................................... 376
The process of fractional distillation ................................................................................................. 377
Distillation of an ideal solution ......................................................................................................... 377
Distillation of non-ideal solutions ..................................................................................................... 378
Miscellaneous questions ................................................................................................................... 382
Immiscible liquid mixtures ............................................................................................................... 385
Vapour pressure of a system of two immiscible liquid ..................................................................... 385
STEAM DISTILLATION .................................................................................................... 387
The principle on which steam distillation is based ........................................................................... 387
The process of purification of a liquid mixture by steam distillation ............................................... 387
Conditions necessary for steam distillation ...................................................................................... 388
Advantages of steam distillation ....................................................................................................... 388
The composition of the distillate ....................................................................................................... 388
Application of Dalton‟s law of partial pressure in distillation .......................................................... 389
Calculations involving steam distillation .......................................................................................... 390
Questions on steam distillation ......................................................................................................... 392
Industrial application of steam distillation ........................................................................................ 395
THE DISTRIBUTION LAW (PARTITION LAW) .......................................................... 395
Limitations of the partition law/ conditions under which partition law is valid ............................... 396
Experimental determination of .................................................................................................. 396
Calculations involving ............................................................................................................... 397
Obtaining values of partition coefficients using graphical approach ................................................ 400
The applications of partition coefficients .......................................................................................... 401
(a) Solvent extraction ..................................................................................................................... 401
(b) Determining formulae of complex ions .................................................................................... 408
Experimental determination of formula of a complex ion ................................................................ 410
Ion exchange ..................................................................................................................................... 418
EUTECTICS .......................................................................................................................... 419
1. Solidification of an aqueous solution of solids ......................................................................... 419
2. Solidification of mixtures of two liquids without compound formation ................................... 421
Examples of substances that form eutectic mixtures ........................................................................ 421
Cooling curve for a pure substance or a eutectic mixtures ............................................................... 425
Cooling curve for a mixture .............................................................................................................. 426
Differences between a eutectic mixture and a compound ................................................................. 426
Tests that can show that a eutectic mixture is not a pure compound ................................................ 427
Similarities between a pure substance and a eutectic mixture .......................................................... 427
Application of eutectic mixtures ....................................................................................................... 427
Questions........................................................................................................................................... 427
COLLIGATIVE PROPERTIES.......................................................................................... 430
Limitations of colligative properties ................................................................................................. 431
Vapour pressure lowering ................................................................................................................. 431
Elevation of boiling point (Ebullioscopy) ......................................................................................... 440
Freezing point depression (Cryoscopy) ............................................................................................ 449
Osmotic pressure, .......................................................................................................................... 459
CHAPTER SIX ......................................................................................................................... 468
CHEMICAL EQUILIBRIA ..................................................................................................... 468
THE CONCEPT OF CHEMICAL EQUILIBRIUM ......................................................... 468
The characteristics of a chemical equilibrium .................................................................................. 468
Reversible and irreversible reactions ................................................................................................ 468
Dynamic equilibrium ........................................................................................................................ 469
Types of chemical equilibria ............................................................................................................. 469
THE LAW OF MASS ACTION OR EQUILIBRIUM LAW ........................................... 470
The concentration equilibrium constant, ..................................................................................... 471
The pressure equilibrium constant, ............................................................................................. 471
Using the law of mass action to write equilibrium constant expressions ( or ) and units...... 471
The relationship between and ............................................................................................. 473
EXPERIMENTS ON CHEMICAL EQUILIBRIUM ........................................................ 474
CALCULATIONS INVOLVING CONCENTRATION EQUILIBRIUM CONSTANT
AND PRESSURE EQUILIBRIUM CONSTANT .............................................................. 478
Interpretation of magnitude of or in relation to equilibrium position................................. 509
Comparing the reaction quotient (Q) and to determine direction of a chemical reaction ........ 509
L CHATELIER‟S PRINCIPLE AND THE EFFECTS OF VARIOUS FACTORS ON
THE EQUILIBRIUM OF REVERSIBLE CHEMICAL REACTIONS.......................... 511
INDUSTRIAL APPLICATION OF CHEMICAL EQUILIBRIUM ............................... 520
CHAPTER SEVEN ................................................................................................................... 524
IONIC EQUILIBRIA ............................................................................................................... 524
ACIDS, BASES AND SALTS .............................................................................................. 524
Acids and bases ................................................................................................................................. 524
The concept of acids and bases according to various theories .......................................................... 524
Conjugate acid and bases .................................................................................................................. 526
Classification of strong acids and bases, weak acids and bases ........................................................ 527
Relative strength of Bronsted-Lowry acids and bases ...................................................................... 528
Derivation of expressions for acid dissociation constant, and base dissociation constant, ... 535
Calculations involving ................................................................................................................ 535
Calculations involving ................................................................................................................ 537
The auto ionisation ( self-ionisation ) of water ................................................................................. 538
The concept of ............................................................................................................................ 539
The scale ..................................................................................................................................... 540
Calculations involving for strong acids and bases ........................................ 540
Expression of for weak acids and bases ..................................................................................... 544
calculations for weak acids and weak bases ............................................................................... 545
HYDROLYSIS OF SALTS .................................................................................................. 552
Salt hydrolysis................................................................................................................................... 552
The various types of salts .................................................................................................................. 553
Prediction and explaining of a salt solution, and hydrolysis basing on its composition ............ 555
The hydrolysis constant, ............................................................................................................. 558
Calculations involving of salt solutions ....................................................................... 559
BUFFER SOLUTIONS ........................................................................................................ 567
Types of buffers ................................................................................................................................ 567
The action of a buffer ........................................................................................................................ 568
The Henderson-Hasselbalch equation ............................................................................................... 570
Calculations involving for buffer solutions ............................................................................... 572
Preparation of buffer solutions of known .................................................................................. 578
Application of buffers ....................................................................................................................... 579
ACID-BASE TITRATIONS ................................................................................................. 582
Terms used in acid-base titration ...................................................................................................... 582
Acid-base indicators.......................................................................................................................... 582
Action of an indicator ....................................................................................................................... 583
range for indicators ..................................................................................................................... 584
Choice of indicator ............................................................................................................................ 584
-volume curves for acid-base titrations ....................................................................................... 586
SOLUBILITY EQUILIBRIA .............................................................................................. 595
Solubility ........................................................................................................................................... 595
Molar solubility ................................................................................................................................. 595
Experiment to determine solubility of a soluble salt ......................................................................... 596
Factors that affect solubility of a soluble salt.................................................................................... 597
Solubility curves ............................................................................................................................... 597
Calculation of solubility .................................................................................................................... 599
Solubility curves ............................................................................................................................... 600
The concept of dynamic equilibrium in a saturated salt solution ...................................................... 601
Sparingly soluble salts/ electrolytes .................................................................................................. 601
Solubility product.............................................................................................................................. 601
Expressions for solubility product .................................................................................................... 601
Conditions under which solubility product is valid .......................................................................... 602
Experimental determination of solubility product ............................................................................ 602
Factors affecting solubility of sparingly soluble electrolytes............................................................ 606
The relationship between ionic product, solubility product ( ) precipitation............................... 611
Application of solubility product, .............................................................................................. 613
CHAPTER EIGHT ................................................................................................................... 628
CHEMICAL KINETICS ......................................................................................................... 628
Introduction ....................................................................................................................................... 628
Rate of a chemical reaction ............................................................................................................... 628
Units of rate of reaction .................................................................................................................... 628
The rate law....................................................................................................................................... 629
The rate constant, .......................................................................................................................... 629
Order of a reaction ............................................................................................................................ 630
Molecularity ...................................................................................................................................... 630
Differences between order of reaction and molecularity .................................................................. 631
Mechanism of a reaction ................................................................................................................... 631
MATHEMATICAL DERIVATION OF ZERO, FIRST AND SECOND ORDER RATE
EQUATIONS AND HALF LIFE ......................................................................................... 633
Sketching plotting and interpreting the graphs obtained using rates of reaction data and rate
equations ........................................................................................................................................... 637
USING KINETICS DATA TO OBTAIN ORDER OF REACTION, RATE OF
REACTION, RATE CONSTANTS AND HALF-LIFE .................................................... 644
EXPERIMENTAL PROCEDURE FOR DETERMINING RATES OF REACTION AND
ORDERS OF A REACTION ............................................................................................... 662
FACTORS AFFECTING RATES OF REACTIONS ....................................................... 668
Theories of chemical reactions (collision theory and transition state theory) ................................... 668
Using the theories of reaction to explain factors affecting rates of reaction ..................................... 672
Experimental investigation of factors affecting rates of reactions .................................................... 679
CHAPTER NINE ...................................................................................................................... 684
ELECTROCHEMISTRY ........................................................................................................ 684
MODES OF CONDUCTION OF SUBSTANCES........................................................................... 684
ELECTROLYSIS .................................................................................................................. 684
The common terms used in electrolysis ............................................................................................ 684
Explaining the changes that take place during electrolysis ............................................................... 686
Principles of electrolysis (selective discharge of ions) ..................................................................... 686
Laws of electrolysis .......................................................................................................................... 688
Calculations of electrolysis ............................................................................................................... 690
The applications of electrolysis in industry ...................................................................................... 696
CONDUCTIVITY OF SOLUTIONS OF ELECTROLYTES .......................................... 697
The common terms used ................................................................................................................... 697
Measurement of conductivity of solutions ........................................................................................ 700
Calculations involving electrolytic conductance .............................................................................. 701
Factors affecting electrolytic conductivity of electrolytes ................................................................ 704
Factors affecting molar conductivity of electrolytes ......................................................................... 705
Kohlrausch‟s law of independent migration of ions and its application ........................................... 710
Application of conductance (conductivity measurements) ............................................................... 720
Conductimetric titrations................................................................................................................... 721
ELECTRODE POTENTIAL AND ELECTROCHEMICAL CELLS ............................ 728
ELECTRODE POTENTIAL ............................................................................................................ 728
Electrochemical series....................................................................................................................... 730
Absolute and relative electrode potential .......................................................................................... 732
The structure and functioning of the Standard Hydrogen Electrode (SHE)...................................... 732
Standard electrode potential, ................................................................................................. 733
Experiment to measure standard electrode potential of a metal........................................................ 733
Factors affecting magnitude of electrode potential ........................................................................... 734
Variation of electrode potential in group II and period 3 .................................................................. 735
ELECTROCHEMICAL CELLS....................................................................................................... 736
Construction of a Daniel cell ............................................................................................................ 738
The cell notation/cell convention ...................................................................................................... 739
Calculation of cell emf and prediction of spontaneity/feasibility of a reaction ................................ 743
Gibb‟s free energy, , as a measure of spontaneity........................................................................ 745
Applications of electrode potentials .................................................................................................. 746
Questions........................................................................................................................................... 746
A simplified, well elaborated and illustrative approach to Physical Chemistry
CHAPTER ONE
MATTER
Matter is anything that occupies space and has weight.
Matter is made up of very tiny particles (building blocks) known as atoms, molecules or
ions.
An atom is the smallest electrically neutral particle of an element that takes part in a
chemical reaction.
A molecule is the smallest electrically neutral particle of a compound or an element
that is formed by the combination of atoms in a whole number ratio and can exist on
its own.
In a molecule of an element, the combining atoms are the same (for example; the oxygen
molecule, )
In a molecule of a compound, different atoms combine (for example the hydrogen
DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

chloride molecule, )
A molecule retains the properties of that element or compound it contains.
An ion is an atom or a group of chemically combined atoms that has either lost one or
more electrons, making it positively charged (a cation), or gained one or more electrons,
making it negatively charged (an anion).
The structure of an atom

An atom is spherical in shape and has a small region in the center called the nucleus. The
atom contains protons and neutrons, and electrons as fundamental particles.
The protons and neutrons are concentrated in a very small nucleus in the center of the
atom while the electrons are all outside the nucleus in the energy levels and are
constantly rotating around the nucleus.
The number of electrons in the energy levels (negative charges) is equal to the number of
all protons in the nucleus (positive charges) hence an atom is neutral.
The energy level closest to the nucleus is called the first energy level or the K energy
level. The second closest energy level to the nucleus is the second energy level or the L
energy level. This is followed by the third energy level or the M energy level. So, the
energy levels are named 1st, 2nd, 3rd, 4th, and so on or K, L, M, N and so on from the
energy level closest to the nucleus outwards.
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Email: josephkayiirab@gmail.com Call:0782601038 WhatsApp: 0753247098
Diagrammatic illustration of an atom

Energy levels
Electrons
Nucleus (Protons and neutrons)
The sub atomic particles

Electrons, protons and neutrons were the first small particles to be discovered and many
of the properties of matter are explained in terms of them. For this reason, they are called
the fundamental, basic or elementary particles of matter. More recent research has
however shown that there are many other small particles that do exist.
A study of cosmic rays and the nature of nuclear changes have led to discovery of over
200 sub atomic particles which are classified according to the strength of the forces

between them, their mass and their spin.
Some of the subatomic particles are shown below
Leptons Hadrons
baryons mesons
electron proton pions
muon neutron kaons
neutrino lambda
Most of the particles have an associated anti-particle with an equal but opposite charge.
For example a positron is an anti- particle for an electron
Fundamental particles of an atom

The fundamental particles of an atom are the electron, proton and neutron.
1. Electrons
Electrons are negatively charged particles surrounding the nucleus.
The electrons are carried in circular paths known as energy levels that surround the
nucleus
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2
An electron has a mass of ⁄ of a proton, therefore its mass is said to be
negligible; it carries a charge of negative one (-1).

The chemical reactions of an element are determined by the number of electrons (which
is equal to the number of protons in the nucleus)
2. Protons
Protons are positively charged fundamental particles which are present in all atomic
nuclei.
Protons have a unit mass of one (1) and each proton carries a charge of positive one (+1).
3. Neutrons
Neutrons are uncharged fundamental particles in the nuclei of atoms, with the exception
of hydrogen.
Neutrons also have unit mass of one and carry no charge (they are neutral).

Particle Charge Mass
Electron - ⁄
Proton + 1
Neutron No charge 1
The Nucleus
The nucleus of an atom consists of protons (positively charged) and neutrons (which have
no charge)
Protons and neutrons are collectively called nucleons.
The sum of the number of protons and neutrons in the nucleus of an atom is called
nucleon number or mass number (A).
The number of protons in the nucleus of an element is called the Proton number or
atomic number (Z).
The full symbol of an atom of an element is given notation where;
is the symbol of the element
is the nucleon number or mass number
is the proton number or atomic number
The atomic number provides some information about an element which may include;
(i) The position of an element in the Periodic Table
(ii) The number of protons present in the nucleus of an atom
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(iii) The total number of electrons present in the neutral atom

3
Isotopic notation
Isotopes are atoms of the same element with the same number of protons but different
number of neutrons.
Isotopes therefore have different mass numbers.
Isotopy is the existence of atoms of the same element with the same number of protons
but different number of neutrons.
Isotopes of the same element have very similar chemical properties because they have the
same electronic configuration, but differ slightly in their physical properties. An unstable
isotope is termed a radioactive isotope or radioisotope.
Element Isotopic name Isotopic No. of No. of No. of
formula protons electrons neutrons
Hydrogen Protium 1 1 0
Deuterium 1 1 1

Tritium 1 1 2
Carbon Carbon-12 6 6 6
Carbon-14 6 6 8
Oxygen Oxygen-16 8 8 8
Oxygen-17 8 8 9
Oxygen-18 8 8 10
Chlorine Chlorine-35 17 17 18
Chlorine-37 17 17 20
Uranium Uranium-234 92 92 142
Uranium-235 92 92 143
Uranium-238 92 92 146
Ionic formation
An ion is a charged particle formed from an atom or a group of chemically combined
atoms by gaining or losing one or more electrons. Ions are either negatively charged
(anions) or positively charged (cations).
a) Positive ions (cations)
These are formed when atoms or group of chemically combined atoms lose one or more
electrons. Atoms lose electrons so as to acquire a stable electronic configuration as the
noble gases. The positive ions are formed by metal atoms, in ammonium ion and
hydroxonium ion.
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(i) Formation of sodium ion

The sodium atom has 11 electrons hence electronic configuration, .
The atom therefore has one electron more than the stable configuration of a noble gas,
.
To form the sodium ion, the sodium atom loses the one electron in the outer most energy
level to form a noble gas configuration
→
(ii) Formation of Aluminium ion
The aluminium atom has 13 electrons hence electronic configuration, .
The atom therefore has three electrons more than the stable configuration of a noble gas,
.
To form the aluminium ion, the aluminium atom loses the three electrons in the outer
most energy level to form a noble gas configuration

→
(iii) Formation of Ammonium ion
This is an ion formed by coordination of ammonia to a hydrogen ion. The formation of
this ion is possible because the nitrogen atom in the ammonia molecule has a lone pair of
electrons which it donates to the electron deficient hydrogen ion to form a dative covalent
bond. An arrow is often used to indicate which atom has donated the lone pair and also
represents the co-ordinate bond/ dative bond.
[ ]
(iv) Formation of the oxonium ion.

This is an ion formed by coordination of water to a hydrogen ion. The formation of this
ion is possible because the oxygen atom in the water molecule has lone pairs of electrons.
It donates electrons to the electron deficient hydrogen ion to form a dative covalent bond.
[ ]
b) Negative ions (anions)

These are formed when atoms or group of chemically combined atoms gain one or more
electrons. Atoms gain electrons so as to acquire a stable electronic configuration as the
noble gases. The negative ions are formed by non-metallic atoms. Examples include the
chloride ion, oxide ion, etc.
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(i) Formation of a chloride ion.

The chlorine atom has 17 electrons hence electronic configuration, .
The atom therefore lacks an electron to gain the stable configuration of a noble gas,
.
To form the chloride ion, the chlorine atom gains one electron in the outer most energy
→
(ii) Formation of an oxide ion
The oxygen atom has 8 electrons hence electronic configuration, .
The atom therefore lacks two electrons to gain the stable configuration of a noble gas,
.
To form the oxide ion, the oxygen atom gains two electrons in the outer most energy
→

IUPAC nomenclature for cations, anions and salts
The International Union of Pure and applied Chemistry (IUPAC) recommends that every
inorganic compound should have a name from which an unambiguous formula can be
determined.
Naming monoatomic ions; cations and anions
The following rules are considered when naming monoatomic(single atom) ions
1. Monoatomic anions are named with a suffix ...ide
Consider the examples below
Mono atomic anion IUPAC name
Hydride
Nitride
Boride
Carbide
Silicide
Oxide
Chloride
Iodide
Bromide
Fluoride
Sulphide
Phosphide
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2. Monoatomic cations are simply given the name of corresponding element

followed by charge on the ion in parentheses and written in correct roman
numerals. For elements that are monovalent like Al, Zn, Mg, Ca, Ba, etc., the
charge may be ignored.
Monoatomic cation Name

Hydrogen ion
Sodium ion
Silver ion
Aluminium ion
Zinc ion
Magnesium ion
Calcium ion
Barium ion

Manganese(II) ion
Tin(II) ion
Tin(IV) ion
Lead(II) ion
Lead(IV) ion
Iron(II) ion
Iron(III) ion
Chromium(III) ion
Cobalt(II) ion
Nickel(II) ion
Copper(I) ion
Copper(II) ion
Naming polyatomic ions and compounds
There exist ions that contain more than one atom. These are called polyatomic ions. Most
of the polyatomic ions contain oxygen atoms and these are called oxyanions.
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Common polyatomic ions and their names

Formula Name
Ammonium ion
̅ Hydroxide ion
̅ Ethanoate ion
Oxalate ion
Nitrate ion
Nitrite
Hydrogencarbonate ion
Hydrogensulphate ion
Peroxide ion
Carbonate
Chlorate(VII) ion

Chlorate(V) ion
Phosphate ion
Chromate(VI) ion
Dichromate(VI) ion
Manganate(VI) ion
Manganate(VII) ion
Sulphate ion
Sulphite ion
Cyanide ion
Triiodide ion
Naming polyatomic compounds

1. The name should have the name of the cation followed by name of the anion.
2. The name of the cation is written first followed by the name of the anion
3. For cations that take on multiple charges, the charge is written using parentheses
immediately following the element name.
4. When the formula contains two or more of the same polyatomic ion, that ion is written in
parentheses with a subscript of the number of the polyatomic ions.
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The Stock system

The Stock system of nomenclature was developed by the German Chemist Alfred Stock
in 1919. In this system, the oxidation state of an element is indicated in parentheses and
in Roman numerals.
It requires that there is usually no space between the end of the element name and the
opening parentheses for example
has a correct name as copper(I) chloride and not copper (I) chloride.
Consider examples below
Formula of compound Name
Tin(II) chloride
Tin(IV) chloride
Iron(II) chloride
Iron(III) chloride

Calcium oxide
Sodium oxide
Lead(II) bromide
Chromium(III) oxide
Aluminium oxide
Aluminium carbide
The stock system is widely used in modern chemistry to name compounds and
complexes. It has been used to develop systemic names for various compounds.
Below is the procedure for naming binary ionic compounds.
1. The name should have the name of the cation followed by name of the anion.
2. For cations that take on multiple charges, the charge is written using parentheses
immediately following the element name.
It is advisable that chemists use correct names of the compounds in their work. The other
names (trivial names) may however be acceptable in Applied Chemistry.
The names Quick lime and calcium oxide both indicate the same compound. Calcium
oxide is called a systemic name (unambiguous name) and translates the structure of
Quick lime clearly. It also provides an unambiguous reference to the compound.
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Systemic/Correct/unambiguous name of some compounds

Formula Systemic name Common name
Copper(I) chloride Cuprous chloride
Copper(II) chloride Cupric chloride
Iron(II) sulphate Ferrous sulphate
Iron(III) sulphate Ferric sulphate
Sodium chloride Brine
Sodium hydroxide Caustic soda
Sodium carbonate-10-water Washing soda
Calcium oxide Lime
Calcium carbonate Limestone
Potassium hexacyanoferrate(II) Potassium ferrocyanide
Potassium hexacyanoferrate(III) Potassium ferricyanide

The selection of correct Roman numeral
Roman numerals should be used correctly when writing names of compounds. For
example the compound has only tin(IV) sulphate as the correct name.
Students normally write wrong names such as;
Wrong name Reason
Tin has more than one oxidation states (+2 and
Tin sulphate +4). Therefore its exact oxidation state in the
compound should be depicted
The oxidation state of +4 corresponds to tin and
Tin (IV) sulphate not the sulphate ion. It should be written
immediately after tin and not in the middle of the
compound
There should some little space between name of
Tin(IV)sulphate the cation with its charge, and name of the anion
Tin(iv) sulphate Roman numerals do not have dots (.) above them.
Tin(IIII) sulphate Roman numeral is wrong
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Writing the formula of a binary compound

At Ordinary level, the criss-cross method was used to write the formulae of compounds.
Another method may be used as follows;
Follow the steps below for formulae of Aluminium oxide and magnesium(II) chloride;
1. Write the symbol and charge of the
cation first and the anion next
2. Use a multiplier to make the total
charge on the cations and anions equal
and opposite to each other.
3. The multipliers are then used as
subscript for each ion.
4. The correct formula can then be
written, but the charges are left out
and all subscripts that are 1

MASS SPECTROMETRY
Mass spectrometry (mass spectroscopy) is a technique used to determine relative atomic
masses and the relative abundance of isotopes, and for chemical analysis and the study of
ion reactions.
The earliest experiments of mass spectroscopy by J. J. Thomson used a stream of positive
ions from a discharge tube, which were deflected by parallel electric and magnetic fields
at right angles to the beam. Each type of ion formed a parabolic trace on a photographic
plate (a mass spectrograph). In modern instruments, the ions are produced by ionizing the
gas with electrons.
The essential parts and operation of a modern mass spectrometer

A mass spectrometer is usually used during mass spectroscopy. It is an instrument for
producing ions in a gas and analyzing them according to their charge/mass ratio.
It mainly consists of the vapourisation chamber, ionisation chamber, acceleration

chamber, deflection chamber, the detector, amplifier and recorder.
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Diagram showing the essential parts of a modern mass spectrometer
Hot tungsten filament

Operation of a modern mass spectrometer
The whole apparatus is evacuated of air particles that may produce unnecessary ions.
1. Vapourisation chamber
The sample is heated by a tungsten filament to vapourise it. The vapourised sample is
then introduced in the ionisation chamber.
2. The ionization chamber.
In this chamber, the vapourised sample is subjected to a beam of fast moving electrons
emitted by a hot filament. These electrons bombard the atoms of the vapourised sample
from which 1 or 2 electrons are removed to form positive ions.
3. The acceleration chamber.

The positive ions produced from the ionisation chamber are accelerated by a strong
electric field of varying potentials such that only positive ions with the same
velocity/kinetic energy but with different mass-charge ratio will pass through to the
magnetic field.
4. The deflection chamber.
The magnetic field then deflects the ions according to their mass-charge ratio. The
strength of the magnetic field is varied such that ions of the same mass-charge ratio are
focused onto the detector.
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5. The detector, amplifier and recorder

The ions are changed into sizeable electric currents which are sent to the amplifier for
fine tuning and then to the recorder where they are recorded into peaks that show relative
intensities of ions of a particular mass falling at the detector at that instant.
A mass spectrum is thus obtained consisting of a series of peaks of variable intensity to
which mass/charge ratio (m/e) values can be assigned.
N.B
1. If the sample introduced was that of an element, its relative atomic mass(R.A.M)
can be obtained by the formula;
∑
2. For organic molecules, the mass spectrum consists of a series of peaks, one
corresponding to the parent ion and the others to fragment ions produced by the
ionization process. Different molecules can be identified by their characteristic

pattern of lines.
Uses of a mass spectrometer

1. Mass spectrometers are used for accurate measurements of relative atomic mass.
2. Measuring relative molecular masses, particularly for carbon compounds.
3. For determining number of isotopes present in an element and analysis of isotopic
abundance.
4. It can also be used to identify structures of organic compounds.
An organic compound bombarded with electrons forms a number of fragment ions.
(Ethane ( ), for example, might form; , , etc). The relative
proportions of different types of ions are used to find the structure of new compounds.
The characteristic spectrum can also identify compounds by comparison with standard
spectra.
5. Analysis of mixtures.
6. Detection of labeled atoms for example 18O in radioactive tracing.
7. In forensic science. This is because it requires very small amount of the sample and
usually the size of the sample received by forensic scientists at the scene of crime is
very small. A sample of about can give a mass spectrum. Specimens left at
the scene of crime can be compared by mass spectrometry with drugs or fibres found
with a suspect.
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Advantages of a mass spectrometer over other methods of determining

atomic or molecular mass
1. It gives more accurate values

2. Uses a smaller quantity of the sample
The mass spectrum

A mass spectrum is a plot of percentage abundance or relative intensity against mass to
charge ratio of the ions separated in a mass spectrometer.
The mass to charge ratio is however numerically equal to the mass of the ion since most
of the ions formed in a mass spectrometer have a single charge.
Interpreting a mass spectrum

The mass spectrum is usually has vertical lines and each vertical line represents an ion
having a specific mass-to-charge ratio ⁄ and the length of the line indicates the

relative abundance of the ion.
Relative abundance refers to the relative intensity of each isotope of an element
represented as a ratio or percentage.
The tallest line is assigned an abundance of 100 and is referred to as the base peak. The
intensities of the other ions are measured relative to this line.
Consider the mass spectrum for neon below;
According to this spectrum, there are three stable isotopes of neon. These include neon-
20(20Ne), neon-21(21Ne) and neon-22 (22Ne). The peaks at 20, 21 and 22 are due to the
ions 20Ne+, 21Ne+ and 22Ne+ respectively. These ions are formed by bombardment of the
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gaseous atoms by electrons as shown below;

14
20 20
Ne(g)+e Ne+(g)
21 21
Ne(g)+e Ne+(g)
22 22
Ne(g)+e Ne+(g)
The height of each peak is related to the relative abundance of each isotope of neon.
20
Ne+has the highest peak so 20Ne is the most abundant isotope.
21
Ne+has the lowest peak so 21Ne is the least abundant isotope.
The relative atomic mass of neon can be obtained using the mass spectrum.
The percentage abundances (proportion of isotope) should be obtained first
( )
( )
( )

∑
( ⁄ ) ( ⁄ ) ( ⁄ )
Consider the mass spectrum for bromine below;
The spectrum has five peaks at mass-to-charge ratios 79, 81, 158, 160 and 162.
The first two peaks of almost equal height correspond to the ions [ 79Br]+ and [81Br]+
respectively. The two peaks are almost of equal height because bromine-79 and
bromine-81 have almost the same abundance.
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The three more peaks are due to ionisation of molecular bromine and each peak
corresponds to a specific diatomic ion as shown in the table below.
Peak at ⁄ value of; Formula of ion

158 [79Br 79Br]+
160 [79Br 81Br]+
162 [81Br 81
Br]+
To determine the relative atomic mass of bromine, the monoatomic peaks are used as
shown below.
( )
( )

∑
( )
Consider the mass spectrum below for pentane
The largest mass-to-charge ratio value is 72. The line at this ⁄ represents the original
molecular ion, . It is formed by the reaction;
This largest value always gives the relative molecular mass of the compound. This
represents the largest ion going through the mass spectrometer. The molecular mass of
the compound is therefore 72.
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The longest line represents the most abundant ion formed by pentane which is at a ⁄ of
43. By simple calculation this ion must have 3 carbon atoms and not more. This gives a
mass of 36. The remaining mass of 7 corresponds to the mass of 7 hydrogen atoms.
Therefore this ion is . It is formed by cleavage of a carbon-carbon bond in
the original molecular ion.
The use of a mass spectrum

1. It can be used to determine the number of isotopes of an element
2. To calculate the relative atomic mass of an element
3. To identify the relative abundance of particular isotopes
4. To elucidate the structure of an organic compound
Average atomic mass

This is the sum of the masses of the isotopes of an element, each multiplied by its
natural abundance.
∑

∑
For example chlorine has two isotopes chlorine-35 and chlorine-37 of percentage
abundances 75.77 and 24.23 respectively. Its average atomic mass can be obtained by the
formula;
∑
∑
( )
Relative atomic mass(Ar)

The relative atomic mass of an element is the ratio of the average mass of its naturally
occurring atoms to ⁄ th of the mass of an atom of the carbon-12 isotope.
or
The mass of an atom of an element in grams on scale on which the mass of an atom of
the carbon-12 isotope is 12 grams.
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Relative molecular mass(Mr)

Relative is the average mass of one molecule of a compound to ⁄ th of the mass of
an atom of the carbon-12 isotope.
More calculations involving data from mass spectrometry

Examples
1. The figure below shows a mass spectrum for chlorine.

Determine the relative atomic mass of chlorine
( ⁄ ) ( ⁄ )
2. The figure below shows the mass spectrum of lead. The heights of the peaks and
the mass numbers of the isotopes are shown on the figure.
(a) Calculate the relative atomic mass of lead.
(b) Explain why the peaks have different heights.
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(a)
( )

( )
( )
( )
( ⁄ ) ( ⁄ ) ( ⁄ )
( ⁄ )
(b) The peaks have different heights because the four isotopes have different
percentage abundances. The abundances are in the order;
3. The relative atomic mass of neon is 20.18. Naturally occurring neon has two
isotopes; Neon-20 and Neon-22.
(a) Calculate the percentage abundance of the isotopes.
(b) Calculate the number of neon-22 atoms in a 13.2g sample of naturally
occurring neon.
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(a)
( ⁄ ) ( ⁄ )
The percentage abundance of neon-20 is 91 and that of neon-22 is 9

(b) ⁄

4. The table below shows the information from a mass spectrum sample of lead.
Isotopic mass Detector current(mA)
204 0.16
206 2.72
207 2.50
208 5.92
Calculate the relative atomic mass of lead.
( )
( )
( )
( )
∑
( ⁄ ) ( ⁄ ) ( ⁄ )
( ⁄ )
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5. The mass spectrum of dichloromethane shows three peaks at mass-to-

charge ratios of 84, 86 and 88.Explain why the three peaks arise as stated and
are in a ratio of 9:6:1.
Chlorine has two isotopes; chlorine-35 and chlorine-37.
The peak at 84 is due to the ion [CH235Cl35Cl]+
The peak with mass to charge ratio 84 is longest because chlorine-35 is the most
abundant isotope followed by the peak with mass to charge ratio 86 whose ion still has
chlorine-35 in it. The peak with mass to charge ratio 88 is shortest because chlorine-37 is
less abundant than chlorine-35.
Questions

1. (a) Describe how in a mass spectrometer the ions are;
(i) formed
(ii) accelerated
(iii) separated
(iv) detected
(b) Bromine has two isotopes 79Br and 81Br and the mass spectrum of bromine
shows peaks at ⁄ of 158, 160 and 162. Write the formula(e) of the ion(s)
corresponding to the peak(s)
Peak at ⁄ value of Formula of ion

158
160
162
(c) By calculation, deduce which of the isotopes in (b) above is most abundant if
the relative atomic mass of bromine is 79.9.
(d) Sketch a mass spectrum for bromine.
2. (a) With the aid of a labeled diagram, describe how a mass spectrometer can be used
to determine;
(i) Molecular mass
(ii) Isotopic ratio
(c) When water was analyzed using a mass spectrometer, peaks occurred
corresponding to the relative masses of 1, 3, 4, 17, 18, 19 and 20. Give one
formula of an ion in each case responsible to the peaks shown.
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3. (a) Define the term relative atomic mass.

(b) The table below shows the mass numbers and relative intensities of an element
R.
Mass number Relative intensity

20 0.91
21 0.0026
22 0.088
Calculate the relative atomic mass of R
(c) State two advantages of using a mass spectrometer in measuring relative
atomic mass.
4. (a) Define the term relative atomic mass.
(b) The mass spectrum of a sample of strontium contains four peaks with mass to

charge ratios ( ) and relative abundances shown below
( ) 84 86 87 88
Relative abundance 0.60 9.90 7.00 82.50

(i) Explain why strontium shows three peaks in its mass spectrum
(ii) Use the information in the table to calculate the relative atomic mass of
strontium.
5. The mass spectrum of a sample of magnesium contains three peaks with mass-charge
ratios and relative intensities show below.
⁄ 24 25 26
Relative intensity 1 0.127 0.139
(i) Explain why magnesium gives three peaks in its spectrum.
(ii) Use the information in the table to calculate an accurate value for the
relative atomic mass of magnesium.
6. The relative atomic mass of magnesium is 24.3. Naturally occurring magnesium has
three isotopes Mg-24, Mg-25 and Mg-26. If the percentage abundance of magnesium-
24 is eight times that of magnesium-26. Calculate the percentage abundances of each
magnesium isotope in the sample.
7. (a) Explain what is meant by each of the following terms;
(i) Atomic number
(ii) Mass number
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(iii) Relative atomic mass

(iv) Isotope
(b) A mass spectrometer measures the relative abundance of ions with different
values of ⁄ . Explain the meaning of the symbols and .
(c) A sample of nickel was analysed in a mass spectrometer. Three peaks were
observed with the properties shown in the table below.
Relative abundance 69 27 4
⁄ 58 60 62
(i) Write the full symbol, including the mass number and atomic number
for the ion responsible for the peak at
⁄ value 58.
(ii) Calculate the relative atomic mass of this sample of nickel.
8. The figure below shows a mass spectrum for chlorine.

(a) State the ions responsible for each of the peaks.
(b) State why the peaks of height 35 and 70 are relatively longer than other peaks.
(c) Use the spectrum to calculate the relative atomic mass of chlorine.
(d) When chloromethane is analysed in the mass spectrometer, two peaks are
observed having an abundance ratio of 3:1. Explain this observation.
(e) The mass spectrum of shows peaks corresponding to 1H, 2H, 12C, 13C,
35
Cl and 37Cl. Calculate the mass number of the
(i) most abundant molecular ion
(ii) heaviest molecular ion
(f) Write the formulae of all the possible ions that contribute to the peak at a mass
number 66.
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9. The mass spectrum of neon consists of three lines corresponding to relative

mass/charge ratios of 20, 21 and 22 with relative intensities in a ratio 0.91 : 0.0026 :
0.088 respectively. Calculate the relative atomic mass of neon.
10. Chlorine has two isotopes of relative atomic masses 34.97 and 36.96 respectively and
relative abundances of 75.77% and 24.23% respectively. Calculate the relative atomic
mass of chlorine.
11. Chlorine has two isotopes; chlorine-35 and chlorine-37. If the relative atomic mass of
chlorine is 35.5. Calculate the ratio of the two isotopes in a natural sample.
12. Natural oxygen consists of 99.76% of an isotope of mass 16, 0.04% of an isotope of
mass 17 and 0.20% of an isotope of mass 18. Calculate the average mass of an atom
of natural oxygen.
13. Copper, relative atomic mass 63.55 has two isotopes of mass numbers 63 and 65.
Calculate the percentage abundance of the isotopes.
THE MOLE CONCEPT

The number of atoms in 1 mole of 12C is obtained by dividing 12g by the mass of an
individual atom of 12C . The answer has a value and is known as the
Avogadro constant (L). It is this value that is used to define an amount of a substance
known as a mole.
A mole is therefore defined as the amount of substance containing as many elementary
particles as those in 12 g of carbon-12
or
A mole is the amount of substance which contains elementary particles.
The particles may be molecules, atoms, ions, radicals, electrons or any other specified
particle.
Summary
Substance Atomic mass/ Number of particles
molecular mass
1 mole of atoms 12g atoms
1 mole of ions 24g ions
1 mole of 98g molecules
1 mole of atoms 14g atoms
1 mole of gas 28g molecules
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Calculating molar masses of elements and compounds

Molar mass is the mass of one mole of a substance.
Its unit is grams. The molar mass of carbon is 12 g. Molar mass has units but relative
molecular mass has no units.
Number of moles of a substance
Molar mass of an element relative atomic mass expressed in grams
Molar mass of a compound relative molecular mass expressed in grams
Examples
Calculate the molar masses of the following
(i) Ethanol
(ii) Carbon dioxide
(iii) Potassium iodate
(iv) Sodium thiosulphate-5-water

A similar approach as that of O level is used. But take note that molar mass has units
Consider a compound Z whose molecular formula is , with atomic
masses
The molar mass of Z is given as
Molar mass
(i) Ethanol (ii) Carbon dioxide
(iii) Potassium iodate (iv) Sodium thiosulphate-5-

water
Molar mass-mole conversions

In order to make these conversions, molar mass should be calculated from the molecular
formula of the compound. It should be ascertained that a correct formula of the
compound in terms of number of atoms is written. If the formula is wrong, then the molar
mass cannot be correct
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1 mole of a compound weighs the relative molecular mass in grams.
Number of moles of a substance
Molar mass of a substance

Mass of a substance
Although the above formulae are well known and ease calculation work, it is advisable
to use first principles in the examination work.
Examples
(a) Calculate the number of moles in;

(i) 3.16g of potassium manganate(VII)
(ii) 0.5g of potassium persulphate

(i) Molar mass of potassium (ii) Molar mass of potassium persulphate
manganate(VII)
( ) ( )
(b) Calculate the mass contained in moles of potassium chlorate

Molar mass of potassium chlorate
( )
26
Questions
1. Work out the molar masses of each of the following
(i) Chlorine gas (x) Potassium iodate

(ii) Iodine molecule (xi) Potassium persulphate( potassium
(iii) Oxalic acid crystal peroxodisulphate)
(iv) Sodium ethanedioate (xii) Potassium dichromate(VI)
(v) Sodium carbonate decahydrate (xiii) Potassium manganate(VII)
(vi) Sodium hydrogencarbonate (xiv) Hydrochloric acid
(vii) Sodium hydroxide (xv) Hydrogen peroxide
(viii) Disodium tetraborate (xvi) Sulphuric acid
decahydrate (xvii) Iron(II) sulphate-7-water
(ix) Potassium chlorate (xviii) Diammonium iron(II) sulphate
hexahydrate

2. Calculate the number of moles in;
(i) 1.0g of potassium iodate
(ii) 19.1g of disodium tetraborate decahydrate
(iii) 1.0g of sodium ethanedioate
(iv) 6.0g of Diammonium iron(II) sulphate-6-water
(v) 1.2g of potassium dichromate
(vi) 6.2g of copper(II) sulphate pentahydrate
3. Determine the mass of;
(i) 0.01288 moles of chlorine gas
(ii) moles of potassium iodate
(iii) moles of sodium hydrogencarbonate
(iv) 0.025 mole of sodium ethanedioate
(v) 0.00833 mole of copper(II) ions
Limiting reactants and excess reactants

In a perfect reaction, we would have exactly as much of each reactant that we need to
convert everything to a product. However in real practice, it is much more likely that we
have non-stoichiometric amounts of reactants.
Consider a scenario where we are making grilled cheese sandwiches.
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Stoichiometric amounts of cheese and bread required are in a ratio 1:2. If we are provided
with 28 slices of bread and 11 slices of cheese, one would prepare 11 sandwiches using
all the provided cheese and 22 slices of bread. This leaves six slices of bread not used. In
this scenario, the number of sandwiches prepared is limited by the number of cheese
slices and the bread slices have been provided in excess.
A limiting reactant is that reactant which is completely used up in a chemical reaction
and limits the quantities of the products formed.
An excess reactant is that reactant that remains after a chemical reaction due to the
limiting reactant being used up.
Percentage yields in a chemical reaction
The amount of product that may be produced by a chemical reaction under specified
conditions, as calculated per the stoichiometry of an appropriate balanced chemical
equation is called theoretical yield of the reaction. In practice, the amount of product
obtained is called the actual yield, and is often less than the theoretical yield for a

number of reasons. This is because some reactions are inherently inefficient, being
accompanied by side reactions which produce other products. Others by nature are
incomplete. Some products are difficult to collect without some loss, and so less than
perfect recovery will reduce the actual yield.
The extent to which a reaction‟s theoretical yield is expressed as percentage yield.
( )
Experiment to demonstrate concept of limiting and excess reactants,

theoretical yield, actual yield and percentage yield.
Weigh a beaker and record its mass ( ).

Then weigh accurately 1.00g of iron powder into the beaker.
Measure 30cm3 of 1.0M copper(II) sulphate solution using a measuring cylinder and
slowly add it to the beaker above.
Stir the solution until the solution has completely turned colour from blue and a brown
copper solid formed.
Decant off the resultant solution carefully and do not lose any copper formed.
The copper formed is washed several times with distilled water, and then with acetone,
and dried.
The beaker together with dried copper is weighed ( ).
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Treatment of results;
⁄
⁄
( )
( )

Examples
1. What mass of aluminium chloride can be formed from 34.0g of aluminium and
12320 cm3 of chlorine gas?
( 1 mole of a gas occupies 22.4 litres at s.t.p; )
⁄
⁄
( )
( )
( )
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2. Sodium carbonate reacts with calcium chloride to form calcium carbonate and
sodium chloride. In an experiment, 53g of sodium carbonate and 44.4 g of
calcium chloride were mixed forming 23.6g of calcium carbonate.
(i) What is the limiting reagent of the reaction?
(ii) Calculate the percentage yield of calcium carbonate.
⁄
⁄

The limiting reagent is used to calculate percentage yield.
( )
( )
3. 0.50g of a fertilizer containing ammonium sulphate was warmed with sodium

hydroxide solution to expel all ammonia gas which was trapped and absorbed in
100cm3 of 0.10M hydrochloric acid solution. The excess acid required 55.90 cm3
of 0.1M sodium hydroxide solution for neutralisation. Calculate the percentage
of ammonium sulphate in the sample.
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Theory; Warming any ammonium salt with an alkali liberates ammonia gas. All the
ammonia formed reacted with hydrochloric acid but the acid was as excess reactant and
ammonia was limiting. So the excess hydrochloric acid(that did not react with ammonia)
was neutralized with sodium hydroxide.
Moles of that reacted with excess acid
( )
Original number of moles of hydrochloric acid

( )
Number of moles of hydrochloric acid that reacted with ammonia

( )
( )
( )
Questions
1. What is the limiting reagent when 5.00g of hydrogen and 10.0g of oxygen react to
form water?
2. Toluene is oxidised by air under carefully controlled conditions to benzoic acid.
Benzoic acid is used to prepare the food preservative, sodium benzoate. What is the
percentage yield of a reaction that converts 1.000 kg of toluene to 1.21kg of benzoic
acid?
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3. In a laboratory experiment, the reaction of 3 moles of hydrogen with 2 moles of

iodine produced 1 mole of hydrogen iodide. Determine the theoretical yield in grams
and percentage yield.
4. 1.274g of copper(II) sulphate was reacted with excess zinc metal to produce 0.392g of
copper. Calculate the percentage yield.
5. 1.07g of anhydrous sodium carbonate was dissolved in 50cm3 of an acid solution. The
resultant solution required 24.6cm3 of 0.237M sodium hydroxide for complete
neutralisation. Calculate the molarity of the acid solution.
6. 27.825g of a normal carbonate of a univalent metal Y, was dissolved in 320.0cm3 of a
2.5M monobasic acid solution. The resultant solution was boiled, cooled and diluted
to one litre of solution. 25cm3 of this solution required 34.375cm3 of 0.2M potassium
hydroxide for complete neutralisation. Calculate the relative atomic mass of Y.
7. 50cm3 of a concentrated solution of hydrochloric acid was added to 200cm3 of 0.5M
sodium hydroxide solution. The excess base required 35.0cm3 of 0.2M nitric acid

solution for complete neutralisation. Calculate the molarity of the concentrated
hydrochloric acid solution.
8. 50cm3 of concentrated potassium hydroxide solution was diluted to 250cm3. 25cm3 of
this solution was reacted with 100cm3 of 0.5M hydrochloric acid. If 26.42cm3 of
0.125M sodium hydroxide solution was needed to neutralise the excess acid.
Determine the molarity of the potassium hydroxide in the original 50cm3.
Avogadro’s law
The Italian scientist Avogadro, in 1811 suggested that in gaseous elements like chlorine
and hydrogen, the atoms joined to form larger particles containing two or more atoms. He
called the larger particles molecules. A molecule is therefore defined as a group of like or
unlike atoms, chemically combined together.
Avogadro came up with a hypothesis that then became a theory to now a law which
states that;
Equal volumes of all gases measured at the same conditions of temperature and
pressure contain the same number of molecules.
If hydrogen and chlorine were to combine therefore;
can be interpreted as;

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It follows from Avogadro‟s hypothesis that if equal volumes of gases contain equal
numbers of molecules then the volume occupied by one mole of molecules of gases must
be the same for all gases. It is called molar gas volume.
The value is
It also therefore follows that the total number of moles of a gas is directly proportional to the
volume occupied by a gas at constant temperature.

However, Avogadro‟s law cannot be true at all pressures. It only holds if the gases
behave as perfect gases, that is, at very low pressures.
Examples
1. One mole of helium gas fills up an empty balloon to a volume of 1.5 litres. What
would be the volume of the balloon if an additional 2.5 moles of helium gas is
added? (Assume that the temperature and the pressure are kept constant)
2. 50g of nitrogen gas are contained in a 3000cm3 container. The gas exerts a
pressure of 3 atmospheres on the container. If the pressure and temperature are
kept constant, calculate the mass of nitrogen that can be added the container
until the volume reaches 5000cm3. ( )
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Gay-Lussac’s law
In 1808, French Chemist Gay-Lussac provided the result of a series of experiments on the

volumes of combining gases. He summarized his results in a law which states that;
When gases combine together at constant temperature and pressure, they do so in
volumes which bear a simple ratio to each other, and to the volume of any gaseous
product.
Just like Avogadro‟s law, Gay-Lussac‟s law is only approximately true. It is only valid
when gases are at very low pressures.
We shall not look at calculation probles involving this law since you Ordinary Level
teacher must have looked at them in detail.
LABORATORY APPARATUS AND CHEMICALS

Laboratory equipment can be hazardous if they are not used or handled properly. This is
to reduce accidents and prevent injury.
When using gas burners for example, they should be placed away from other equipment,
remove all papers, notebooks and other combustible materials and containers of
flammable chemicals from the area surrounding the burner. Long hair should be tied
back. Rubber tubing should be inspected for cracks, holes or any other defects and the
hose should be securely connected on the gas valve and the burner.
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Most glass ware can only be exposed to certain high and low temperatures. Usage outside
of those ranges may cause damage or breakage to the glassware. Always watch
evaporation closely. A vessel, heated after evaporation has already occurred, may crack.
Do not put hot glassware on cold or wet surfaces as it may break with temperature
change. Never heat glassware that is cracked. It‟s advisable to use wire gauze when
heating glass ware.
Selection of apparatus for different experiments
Glass ware is designed for a specific purpose. It should only be used for that purpose.
When selecting glassware, it‟s wise to determine the compatibility of the glass ware with
the chemicals. Some chemicals react with glass ware or cause damage. If the process in
which glassware is to be used involves temperature or pressure changes, ensure that the
glassware can withstand the changes. Use the right size and type of glassware for any
given experiment.
Laboratory rules and regulations for handling chemicals and apparatus

A laboratory is a well specialized room or place where scientific experiments are done
from.
Great care must be taken while in the laboratory so that danger or accidents are avoided.
There are therefore rules and regulations that must be followed while in the laboratory.
These include;
1. Students should not enter the laboratory before the teacher tells them to do so
2. Students should not remove anything from the laboratory without the teacher‟s
permission
3. Do not taste anything in the laboratory without being instructed
4. Never handle chemicals with bare hands because come chemicals are corrosive and
others flammable
5. Bottles should never be handled by the necks
6. Unnecessary movements in the laboratory are prohibited
7. Any burn or cut or material that is accidentally swallowed should be reported to the
teacher immediately.
8. Broken glass should be discarded in a separate designated container.
9. Report any damage of the laboratory equipment to the laboratory supervisor
immediately.
10. Do not return chemicals to their original packaging. An incompatible mixture may be
accidentally formed.
11. Keep chemical containers closed. Vapour may escape from an open container or
atmospheric gases may enter the containers, changing the nature of the chemical to
change.
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12. Never use the wrong or unmarked reagent. If you are unsure about the compound, do
not use it.
13. Corks or stoppers once removed from the bottle or glass, they must be placed on a
clean surface with the opening facing down. This is to avoid contamination of the
compound and unnecessary exposure.
14. Special precautions should be taken when handling concentrated acids. Dilution of
acids should be performed by pouring the acid into water.
Concentration
Concentration is the amount of substance, solid or liquid in a known quantity of solution.
The amount of substance can be mass, moles or number of particles. The quantity in
which the amount of substance exists is normally volume.
Concentration is therefore the amount of a substance in a known volume of solvent. The
volume commonly used is 1 litre (1000cm3 or 1 dm3).

Concentration is therefore expressed in terms of grams per litre and
moles per litre
Molarity (M)
Molarity is also a measure of concentration. It is the number of moles of a substance in
one litre of a solution. It is abbreviated as M and expressed in the units of moles per litre
Try to find the concentration of the following solutions in both moles per litre and
grams per litre
(i) 0.025 moles of sodium ethanedioate in 750cm3 of water
(ii) 3.5g of Diammonium iron(II) sulphate-6-water in 250cm3 of solution
(iii) 4.0g of sodium hydroxide in 500cm3 of solution
(iv) 0.0085 moles of potassium peroxodisulphate in 500cm3 of solution
(v) 19.1g of disodium tetraborate decahydrate in 1000cm3 of solution
(vi) 0.0456 moles of copper(II) sulphate-5-water in 500cm3 of water
(vii) 49.0g of sulphuric acid in 2.5dm3 of solution
Difference between molarity and molality

The molar concentration( or molarity; symbol M) is the number of moles of a substance
in one litre of a solution, commonly given in units of moles per litre
The molal concentration (or molality; symbol m) is the amount of substance per unit mass
of solvent, commonly given in units of .
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( )
( )
Percentage by mass (% w/w)

Mineral acids are always kept in the laboratory using stock bottles and certain
specifications under certain conditions are displayed on the bottles.
The specifications include;
(i) Chemical formula
(ii) Relative formula mass
(iii) Specific gravity (density)
(iv) Percentage by mass (w/w) value of the acid
The percentage by mass is got by the expression;

Sulphuric acid is commonly and hydrochloric acid is commonly
. The Specific gravity (density) of sulphuric acid is normally ranging
from
The statement means that 100cm3 of stock solution contains 98 cm3 of
sulphuric acid.
Similarly; the statement implies that
Below is a table summarizing the approximated information about some stock solutions
Reagent Sulphuric Hydrochloric Nitric Phosphoric Ammonia
acid acid acid acid
Density(specific 1.84 1.18 1.41 1.75 0.89
gravity)
Percentage by 98 37.3 70 90 29
mass
Molecular weight 98 36.5 63 97 17
The above information can be used to find the molarity of the stock solution which can
then be used to prepare solutions of any other known concentration (standard solutions)
using the steps below.
(i) Determine the mass of acid in 1 cm3 of stock solution
(ii) Calculate the mass of the same acid in 1000cm3 of solution
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37
(iii) Using the molar mass of the acid, convert the mass got in step (ii) to moles. This
gives the molarity( ) of the acid in the stock solution
(iv) Use the expression to get the volume ( ) of the stock solution
needed to prepare a volume ( ) of a solution of known concentration ( )
Examples
1. Calculate the volume of concentrated sulphuric acid needed to prepare 500cm3 of
0.25M sulphuric acid solution.(The stock specifications of the acid are 98% w/w
and specific gravity 1.84 )
( ⁄ )
( ⁄ )

( ⁄ )
Let the volume of stock solution required be V1 cm3
500cm3 of 0.25M sulphuric acid solution is therefore prepared by putting 6.8cm3 of the
concentrated acid in a measuring cylinder and adding 493.2cm3 such that the total volume in the
cylinder is 500cm3
2. A solution is made by dissolving 11g of glucose in 250cm3 of water at 30 . What

is the percentage by mass of glucose in the solution? The density of water is
0.996gcm-3.
( )
( )
Percentage by volume (% v/v)

This is a measure of concentration of a substance in solution. It is expressed as the ratio
of the volume of the solute to the total volume of the solution, and this ratio multiplied by
100.
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The percentage by volume is got by the expression;
It is used when preparing solutions of two liquids.

Wine, for example is 12% v/v ethanol. This means that there is 12cm3 of ethanol for
every 100cm3 of wine.
70% v/v ethanol solution means that there is 70cm3 of ethanol in every 100cm3 of water.
Example
How to prepare 750cm3 of 70% ethanol

525 cm3 of ethanol are added to a measuring cylinder and water added up to the 750 cm 3
mark.
Questions
1. Determine the volume of 85% concentrated phosphoric acid, density 1.70
needed to prepare 25cm3 of 0.1M phosphoric acid solution.
2. If concentrated sulphuric acid contains 98% by mass of the acid and has a density of
1.84 , calculate the volume of the concentrated sulphuric acid that is required
to prepare a litre of 2M solution of sulphuric acid.
3. Concentrated hydrochloric acid contains 37.3% by mass of the acid and has a
specific gravity of 1.18 . Calculate the volume of the concentrated acid that is
required to prepare a litre of 2M solution of sulphuric acid.
4. Concentrated ammonia has a density of . What volume of 29%
concentrated ammonia is required to prepare a litre of 2M ammonia solution?
5. A solution is prepared by dissolving 5g of urea in 95g of water. Calculate the
percentage by mass of urea in the solution.
6. A solution of naphthalene in benzene is 2% naphthalene. What is its mass by
percentage of benzene?
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PRIMARY AND SECONDARY STANDARDS

A primary standard is a substance that is analytically pure and chemically stable such
that a known mass of it when weighed is the exact mass that dissolves in water to form
a standard solution.
A standard solution is a solution whose concentration is accurately known i.e. one that
contains a known amount of solute in a known volume of solution.
A primary standard can be used directly for the preparation of standard solutions without
reference to some other concentration standard.
A primary standard has the following characteristics;
1. Readily soluble in water at room temperature such that all the weighed mass goes into
solution.
2. It should have a fairly high molar mass such that weighing errors are minimized.
3. It should be obtainable in a pure state such that the quantity weighed indicates the

actual mass present in the standard solution prepared.
4. It should not be deliquescent, efflorescent or hygroscopic such that the mass weighed
is exactly that of the pure sample
5. It must be stable at ordinary temperatures (should not decompose easily) such that its
chemical nature is not altered.
6. It should be able to undergo stoichiometric and instantaneous reactions such that
titration errors are minimized.
Examples of common primary standards include;

Name of primary standard Formula
Anhydrous sodium carbonate
Sodium hydrogencarbonate
Ethane-1,2-dioic acid(Oxalic acid)
Sodium oxalate
Butane-1,4-dioic acid
Disodium tetraborate decahydrate
(Borax)
Potassium iodate
Sodium bromate
Most of the other substances make solutions of approximately known concentrations
which must be standardized against a primary standard. These are called secondary
standards.
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A secondary standard is a substance that is not analytically pure and chemically

unstable such that a known mass of it when weighed and dissolved in water makes
solutions of approximate concentrations hence must be standardized by titration.
Examples of secondary standards include
Name of secondary standard Formula Suitable substance(s) to standardise
the secondary standard
Sodium hydroxide Oxalic acid
Sulphuric acid Anhydrous sodium carbonate
Hydrochloric acid Disodium tetraborate decahydrate
(Borax)
Anhydrous sodium carbonate
Nitric acid Anhydrous sodium carbonate
Potassium manganate(VII) Sodium oxalate
Oxalic acid

Sodium thiosulphate pentahydrate Potassium iodate
Potassium bromate
Sodium hydroxide which cannot be used to make a standard solution because;
1. During weighing, it absorbs water vapour from the air.
2. It also reacts with carbon dioxide in the air to form sodium carbonate.
Sulphuric acid and hydrochloric acid are not suitable for use as primary standards
because the concentrations of their concentrated solutions are not accurately known.
Nitric acid is not a suitable primary standard because it always contain a little nitrous
acid which has a destructive action on so many acid-base indicators.
Potassium manganate(VII) is commonly used in volumetric analysis because;
1. It forms coloured solutions so it acts as own indicator
2. It oxidises a wide range of substances
3. It is not affected by the atmosphere while being weighed
4. It is fairly soluble in water
5. Has a high molecular mass hence minimising weighing errors
However, it is not a good primary standard because;
 It is never obtained free from manganese(IV) oxide impurity
 It is easily reduced by even weak reducing agents since it is a strong oxidising
agents
Potassium manganate(VII) can be acidified by sulphuric acid but neither acidified with
hydrochloric acid nor nitric acid during titration because;
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It oxidises hydrochloric acid to chlorine as it is reduced to manganese(II) ions.
Nitric acid is itself an oxidising agent hence interferes with the oxidising ability of
manganate(VII) ions.
Sodium thiosulphate cannot be used as a primary standard because;
1. It is efflorescent
2. When its solution is left in air it forms a yellow solid deposit and bubbles of a
colourless gas.
This is because a solution of sodium thiosulphate absorbs carbon dioxide from the air
which dissolves to form a weak carbonic acid. The acidic medium promotes
disproportionation of thiosulphate ions into sulphur dioxide and sulphur, which is
insoluble.

Preparation of standard solutions by weighing and dissolving in water
Preparing a standard solution of anhydrous sodium carbonate (for example 250cm 3 of
0.2M sodium carbonate solution)
(i) Calculate the mass of anhydrous sodium carbonate needed to make the
standard solution.
250cm3 of 0.2M sodium carbonate solution
( )
( )
(ii) Weigh a clean weighing bottle, and record its mass (to 1 or 2 decimal places). Use
a clean spatula and add pure anhydrous sodium carbonate to the weighing bottle
until the mass is the total mass of the weighing bottle and that of anhydrous
sodium carbonate required.
Sample Results:
Mass of anhydrous sodium carbonate + weighing bottle 45.30 g
Mass of empty weighing bottle 40.00 g
Mass of anhydrous sodium carbonate used 5.30 g
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(iii) Transfer the weighed mass of anhydrous sodium carbonate carefully into a clean
beaker. Using a wash bottle of distilled water, add a small volume of water so that
all the washings run into the beaker. Add about 100 cm3 of and stir with a glass
rod until all the solid has dissolved.
(iv) Pour all the solution carefully through a filter funnel into a graduated flask
(volumetric flask). Wash all the solution out of the beaker and off the glass rod to
the volumetric flask.
(v) Add distilled water until the level of the solution is about 2 cm below the
graduation mark (in this case 250cm3). Add the rest of the distilled water drop by
drop from a dropping pipette until the bottom of the meniscus is level with the
graduation mark when viewed at eye level.
(vi) Label the solution as required.
Questions;
(a) Why is sodium hydrogencarbonate a suitable substance for preparing standard

solutions?
(b) Calculate the mass of sodium hydrogencarbonate required to prepare 500cm3 of a
0.01M solution.
(c) Describe how you would prepare the solution in (b) above as accurately as possible.
VOLUMETRIC ANALYSIS
Common terms used in volumetric analysis
Titrant
This is a reagent of known concentration that is added to another solution to determine
the concentration of the second chemical species.
Titrand/ Analyte
This is a reagent whose concentration is not known and has to be determined by
titration.
Equivalence point
This is the point when the number of moles titrant is equal to number of moles of
analyte. It occurs before end point, which signals the completion of the reaction.
End point
A point in a titration at which the reaction is complete, observed by the colour change
of an indicator and occurs when small amount of solution of known concentration is
added to a solution whose concentration is to be determined. It occurs after
equivalence point.
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Standard solution
A standard solution is a solution whose concentration is accurately known i.e. one that
contains a known amount of solute in a known volume of solution.
Volumetric analysis is a means of finding the concentration of a solution. In this method,
a solution of an acid is added to a solution of a base until there is just enough of the acid
to neutralize the base. This is done by titration.
The concentration of one of the two solutions should be known, and the volumes of both
the solutions must be measured.
A standard solution of a base may be used to find the concentration of the solution of an
acid. The volume of the acid solution of unknown concentration required to neutralise a
known volume, usually 25.0 cm3 of a standard solution of the base is determined. An
indicator is used to determine when the right volume of a solution has been added to
another solution for complete neutralisation.
Set up of apparatus for volumetric analysis
Acid-base titrations and use of data obtained

Acid-base titrations may involve one- indicator titrations or double indicator titrations.
Double indicator titrations will be exploited more in practical lessons by your teacher.
One indicator titrations involve standardizing an acid or base using a standard solution of
a base or acid with the aid of a suitable indicator. Calculation problems involving
standardisation involve the following steps;
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44
(i) Calculating the moles of the standard solution in the total volume of solution(
commonly the total volume is 250cm3 of the solution but can be any other value)
(ii) Calculating the moles of the standard solution used during the reaction (usually
25.0, 20.0 or can be 10.0cm3)
(iii) Calculating moles of the solution that is standardized using equation of the
reaction(mole ratio)
(iv) Determining the molarity of the solution that is standardized.
Examples
1. Standardization of hydrochloric acid using Borax
5.7g of disodium tetraborate decahydrate(Borax) were dissolved

3 3
in 100 cm distilled water in a 250cm volumetric flask, shaken to dissolve and the
mixture made up to the mark with distilled water. 25.0 cm3 of the resultant solution
is pipetted into a clean conical flask and titrated against dilute hydrochloric acid

solution which was approximately 0.1M using phenolphthalein indicator. 18.0 cm3
of the acid was required for complete neutralisation. Calculate the molarity of the
hydrochloric acid solution used.
(i) Moles of in the 250cm3 of the solution
(ii) moles of used during the reaction (moles in 25.0cm3)
( )
(iii) moles of the solution that is standardized using equation of the reaction(mole ratio)
Equation;
( ) ( )
(iv) molarity of hydrochloric acid

( )
( )
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45
Note; The concentration of the acid given in the question is approximate hence used
nowhere in the calculation. Remember standardizing means we are ascertaining the
actual concentration of the acid.
Over rounding should be avoided before getting the final answer to minimize errors in
calculation.
2. Standardisation of hydrochloric using anhydrous sodium carbonate.
You are provided with the following:

FA1 which is 60 cm3 of hydrochloric acid solution
Solid Y which is anhydrous sodium carbonate
Methyl orange indicator
You are required to determine the molarity of FA1 using a standard solution of
anhydrous sodium carbonate.
PROCEDURE:

Accurately measure 40 cm3 of FA1 and add exactly 60 cm3 of distilled water. Label the
resultant solution FA3.
Weigh accurately 1.5g of solid Y into a clean 250cm3 volumetric flask and add about 100
cm3 of distilled water. Shake well to dissolve. Add more distilled water to fill up to the
mark and label the resultant solution FA2
Pipette 25.0 cm3 (or 20.0 cm3) of FA2 into a clean conical flask. Add 2 or 3 drops of
methyl orange indicator.
Titrate the resultant mixture against FA3 from the burette until the endpoint is reached.
Repeat the titration until you obtain consistent results.
Record your results in the table below.
Sample Results:
Mass of Y and weighing bottle 41.50 g
Mass of empty weighing bottle 40.00 g
Mass of Y used 1.50 g
Volume of pipette used 20.0 cm3
Final burette reading(cm3) 27.50 37.40 32.50
Initial burette reading(cm3) 0.00 10.00 5.00
Volume of FA3 used(cm3) 27.50 27.40 27.50
Record the titre values used to calculate the average volume of FA3 used.
cm3
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46
Average volume of FA3 used cm3

Questions:
Calculate the molarity of hydrochloric acid in FA1.
We should begin the treatment of results with the standard solution which is in this case
FA2.
(i) Moles of solid Y in the 250cm3 of FA2.
Since the same mass of Y(1.5g) in 100cm3 of FA2 is also in the 250cm3 of FA2, the
moles of anhydrous sodium carbonate in both volumes is the same.
(ii) moles of used during the reaction (moles in 20.0cm3)

( )
(iii) moles of hydrochloric acid in FA3 that reacted with in FA2 Equation;
( ) ( )
(iv) molarity of FA1
Note that in the experiment, FA1 is not directly used but instead the diluted solution which is
FA3. Moles of HCl in the volume used of FA3 should be calculated first. Then moles of the acid
in the diluted solution (60+40)cm3
( )
( )
Dilution does not change number of moles in a given solution. Therefore moles of HCl in 100cm3
of FA3 are the same as those in 40cm3 of FA1
( )
( )
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47
Exercise on dilution and standardisation

1. During a titration, 20cm3 of 0.2M sodium hydrogencarbonate solution reacted
completely with 32.80cm3 of a solution of nitric acid. Calculate the molarity of nitric
acid.
2. 30 cm3 of sodium hydroxide solution reacted completely with 25.0 cm3 of 0.5M
hydrochloric acid solution. Determine the molarity of sodium hydroxide solution.
3. 25.0 cm3 of 0.2M sodium ethanedioate solution was warmed up to 65℃ and titrated
against a solution of potassium manganate(VII). Calculate the molarity of potassium
manganate(VII) if 17.20 cm3 of the oxidant was used.
4. 1.50g of anhydrous sodium carbonate were dissolved in 100 cm3 distilled water in a
250cm3 volumetric flask, shaken to dissolve and the mixture made up to the mark
with distilled water. 20.0 cm3 of the resultant solution is pipetted into a clean conical
flask and titrated against dilute hydrochloric acid solution using methyl orange
indicator. 27.50 cm3 of the acid was required for complete neutralisation. Calculate

the molarity of the hydrochloric acid solution used.
Practical exercises on standardisation

1. You are provided with:
FA1 which is approximately 0.1M hydrochloric acid solution
Solid Q which is hydrated disodium tetraborate (Borax)
Phenolphthalein indicator
You are required to standardise hydrochloric acid in FA1 using a standard solution of
Borax.
PROCEDURE:
Weigh accurately 4.7g of solid Q into a clean 250cm3 volumetric flask and add about 100
cm3 of distilled water. Shake well to dissolve. Add more distilled water to fill up to the
mark and label the resultant solution FA3
phenolphthalein indicator and shake the flask carefully.
Titrate the solution carefully against FA1 from the burette until the endpoint is reached.
Results:
Mass of Q and weighing bottle.................................................................................g
Mass of empty weighing bottle.................................................................................g
Mass of Q used.........................................................................................................g
Volume of pipette used..........................................................................................cm3
Final burette reading(cm3)
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48
Initial burette reading(cm3)

Volume of FA1 used(cm3)
...............................................................................................................................cm3
Average volume of FA1 used............................................................................... cm3
Questions:
Calculate the concentration of hydrochloric acid in FA1 per litre of solution.
................................................................................................................................................
................................................................................................................................................
................................................................................................................................................
................................................................................................................................................
................................................................................................................................................
................................................................................................................................................
................................................................................................................................................
................................................................................................................................................

................................................................................................................................................
................................................................................................................................................
2. You are provided with:
FA1 which is approximately 0.2M hydrochloric acid solution
Solid M which is anhydrous sodium carbonate
Methyl orange indicator
You are required to standardise hydrochloric acid in FA1 using a standard solution of
anhydrous sodium carbonate.
PROCEDURE:
Weigh accurately 2.7g of solid M into a clean 250cm3 volumetric flask and add about
100 cm3 of distilled water. Shake well to dissolve. Add more distilled water to fill up to
the mark. Label this solution FA2
methyl orange indicator and shake the flask carefully.
Titrate the solution against FA1 from the burette until the solution just turns orange.
Results:
Mass of M and weighing bottle.................................................................................g
Mass of empty weighing bottle.................................................................................g
Mass of M used.........................................................................................................g
Volume of pipette used..........................................................................................cm3
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49
Final burette reading(cm3)

Initial burette reading(cm3)
Volume of FA1 used(cm3)
...............................................................................................................................cm3
Average volume of FA1 used............................................................................... cm3
Questions:
Calculate the percentage error in the concentration of hydrochloric acid in FA1.
................................................................................................................................................
................................................................................................................................................
................................................................................................................................................
................................................................................................................................................
................................................................................................................................................
................................................................................................................................................

................................................................................................................................................
................................................................................................................................................
................................................................................................................................................
................................................................................................................................................
NOTE:
(i) Volume of pipette is recorded to 1 decimal place.
(ii) Titre values in the table must be recorded to 2 decimal places
(iii) Titre values chosen to obtain average volume should be within difference
(iv) All steps in your calculations should be shown and strictly use first principles.
Back titrations
Back titration is a technique in volumetric analysis in which a known volume of an
excess standard solution is added to the solution to be analysed. The amount of the
unreacted standard solution is then determined by titration with another standard solution.
For example an excess of a solution of iron(II) ions of known concentration can be added
to a solution of potassium peroxodisulphate or potassium chlorate(V). Some of the
iron(II) ions are oxidised to iron(III) ions as shown by the equations below;
The resultant solution which then contains unreacted iron(II) ions can then be titrated
against a standardised potassium manganate(VII) solution in acidic medium or any other
oxidising agent.
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50
The analysis usually flows by the steps below;

(i) Calculate the number of moles of permanganate that reacted with the excess
iron(II) ions.
(ii) Use mole ratio to determine the number of moles of excess moles of iron(II)
ions. (moles of iron(II) ions that did not react with
peroxodisulphate/chlorate(V).
(iii) Calculate the number of moles of iron(II) ions in the original solution
(iv) By subtraction, obtain the number of moles that reacted with the
peroxodisulphate/ chlorate(V)
(v) Moles ratio of the reaction, percentage purity or formula mass can then be
determined using the usual approaches.
Example
(a) A solution was made by dissolving 39.2g of ammonium ferrous sulphate,

in a litre of distilled water. 25.0cm3 of this solution
was pipetted into a conical flask. To it was added 20 cm3 of 2M sulphuric acid
and titrated against potassium manganate(VII) solution. 25.00cm3 of the
permanganate was required for complete reaction. Calculate the concentration
of manganate(VII) ions in moles per litre.
(b) 0.5g of a solid was accurately weighed and put in a beaker. 50 cm3 of
distilled water was added and the mixture stirred to dissolve. The resultant
solution was transferred into a 250cm3 volumetric flask and 150 cm3 of the same
ammonium ferrous sulphate used in (a) was added. The solution in the flask was
made up to the mark with distilled water, shaken and allowed to stand for about
5 minutes. 25.0cm3 of this solution was pipetted into a conical flask and to it was
added 10cm3 of 2M sulphuric acid and titrated with the same potassium
manganate(VII) solution used in (a). 11.30 cm3 of the permanganate was
required for complete reaction. Calculate the number of moles of:
(i) excess iron(II) ions in 250cm3 of the solution in the volumetric flask
(ii) iron(II) ions that reacted with
(iii) molar mass of
(iv) formula mass of
(a)
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51
( )
The sulphuric acid is just used to provide acidic medium for the redox reaction but its
volume and concentration is not used anywhere in the calculation.
( )

( )
(b)
(i) number of moles of excess iron(II) ions in 250cm3 of the solution in the volumetric
flask
( )
( )
Note that are the moles of excess iron(II) ions that reacted with
manganate(VII) ions but they are the excess moles in 25.0cm3 of solution.
( )
(ii) number of moles of iron(II) ions that reacted with

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52
( )
Note that of iron(II) ions were added to the persulphate solution. Some of
these reacted with the persulphate and the excess moles calculated above did not react.
(iii) molar mass of
( )

( )
(iv) formula mass of
Question
3
(a) 10.0cm of a solution of ammonium iron(II) sulphate-6-water, of unknown
concentration was pipetted into a conical flask. To it was added an equal volume of
2M sulphuric acid and then titrated against a solution made by dissolving of
3
potassium manganate(VII) in a litre of distilled water. 9.90cm of the permanganate
solution was required for complete reaction. Calculate the molar concentration of the
solution of ammonium iron(II) sulphate-6-water.
(b) 0.5g of an impure solid potassium chlorate was accurately weighed and put in a
beaker. 100 cm3 of distilled water was added and the mixture stirred to dissolve. The
resultant solution was transferred into a 250cm3 volumetric flask and the solution was
made up to the mark with distilled water. 10.0cm3 of this solution was pipetted into a
conical flask and to it was added 35.0 cm3 of the same ammonium iron(II) sulphate-6-
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53
water solution used in (a) followed by an equal volume of 2M sulphuric acid. The
mixture was heated to about 85℃ and then cooled in cold water for 3 minutes and the
cold mixture titrated with the same permanganate solution used in (a). 25.20 cm3 of
the permanganate was required for complete reaction. Calculate the number of moles
of:
(i) excess iron(II) ions that reacted with manganate(VII) ions.
(ii) iron(II) ions that reacted with the 10 cm3 of chlorate(V) ions.
(iii) Percentage purity of the potassium chlorate.
OXIDATION NUMBER (OXIDATION STATE)

Oxidation number the net charge that would remain on an atom in a given compound
when all the other atoms bonded to it are removed one by one, each in its normal
valency state.
Oxidation number can also mean the combining power of a substance with oxygen.

Calculating oxidation state
Rules to consider
 Oxidation numbers must be written with symbols (+ or -) to distinguish them from
valency. Superscripts (+3), subscripts (+3), and mere numbers (3) or words(three) are
not allowed
 Atoms in the elementary state have an oxidation number of zero.
 The molecules such as are assigned an oxidation number of
zero.
 In the case of simple atoms but in the combined state, the element has an oxidation
number with the same size and sign of the charge on its ion. For example
have oxidation numbers of +1, +2 and +3 respectively and have
oxidation number of -1.
 Atoms that are monoatomic can be assigned an oxidation number equal to their
charge
 The oxidation number of H is +1 in most of its compounds but -1 in metallic hydrides.
 When two or more atoms of the same element occur in a compound, the oxidation
number of the element is an average of the oxidation number of the group.
 The oxidation state of the atom that is required is assigned an unknown letter say, x,
and the sum of the oxidation numbers on all atoms in the species is equated to the
overall charge on the species.
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54
Examples
Calculate the oxidation state of the stated atom in the following species.
(i) Oxygen in
(ii) Oxygen in
(iii) Chorine in
(iv) Manganese in
(v) Chromium in
(vi) Sulphur in
(vii) Iron in [ ]
(viii) Cobalt in [ ]
(i) Let the oxidation state of O in be x. (v) Let the oxidation state of Cr in
be t.

The oxidation state of O is therefore -2.
The oxidation state of Cr is therefore +6.
(ii) Let the oxidation state of O in be m. (vi) Let the oxidation state of S in
be a.
The oxidation state of O is therefore -1.

The oxidation state of S is therefore +7.
(iii) Let the oxidation state of Cl in be n. (vii) Let the oxidation state of Fe in
[ ] be y.
The oxidation state of Cl is therefore +5.
The oxidation state of Fe is therefore +3.
(iv) Let the oxidation state of Mn in be (viii) Let the oxidation state of Co in
p. [ ] be q
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55
The oxidation state of Mn is therefore +6.
The oxidation state of Co is therefore +3.
Questions
Calculate the oxidation state of the stated atom in the following species.
(i) Sulphur in (ii) Sulphur in
(iii) Sulphur in (iv) Sulphur in
(v) Copper in (vi) Chromium in
(vii) Chromium in [ ] (viii) Chromium in[ ]

(ix) Manganese in [ ] (x) Manganese in [ ]
(xi) Iron in [ ] (xii) Iron in
(xiii) Iron in [ ] (xiv) Iron in [ ]
(xv) Iron in [ ] (xvi) Cobalt in [ ]
(xvii) Nickel in [ ] (xviii) Chromium in [ ]
(xix) Chromium in [ ] (xx) Iron in [ ]
(xxi) Cobalt in [ ] (xxii) Chromium in [ ]
(xxiii) Chromium in [ ] (xxiv) Nickel in
(xxv) Platinum in [ ] (xxvi) Cobalt in
(xxvii) Copper in [ ] (xxviii)Chromium in
[ ]
(xxix) Chromium in (xxx) Chromium in [ ]
[ ]
(xxxi) Silver in (xxxii) Nickel in [ ]
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56
REDOX REACTIONS
(OXIDATION-REDUCTION REACTIONS)
Oxidation numbers are very important in deciding whether a reaction is reduction,
oxidation and therefore a redox one.
Consider the half reactions below
In the first half reaction, copper(II) ions are converted to copper. The subsequent change
in oxidation number is therefore from +2 to 0. This is evident that the oxidation number
has decreased. Electrons are also gained in the reaction. This is therefore a reduction
reaction.
Reduction is therefore a reaction in which the oxidation number of an element is
decreased
or

A reaction in which electrons are gained
In the second half reaction, zinc is converted to zinc ions. The subsequent change in
oxidation number is therefore from 0 to +2. This is evident that the oxidation number
has increased. Electrons are also lost in the reaction. This is therefore an oxidation
reaction.
Oxidation is a reaction in which the oxidation number of an element is increased

or
A reaction in which electrons are lost
When the combined cell of the two reactions and is made, an overall reaction can
be generated by crossing out the electrons.
This reaction involves ; oxidation number 0 , being converted to ; oxidation

number +2. ; oxidation number +2 is converted to ; oxidation number, 0
Zinc has been oxidised and copper has been reduced. This is therefore a redox reaction.
A redox reaction is a reaction in which oxidation and reduction take place
simultaneously.
The zinc metal loses (donates) the electrons that are gained (accepted) by copper(II) ions.
Any substance that donates electrons is a reducing agent and any substance that accepts
electrons is an oxidizing agent.
An oxidizing agent is an acceptor of electrons
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57
A reducing agent is a donor of electrons

The mnemonics below can be used to remember the concepts well.
OIL RIG – Oxidation is loss of electrons, Reduction is gain of electrons
LEORA says GEROA- loss of electrons is oxidation (Reducing agent). Gain of electrons
is reduction (Oxidising agent)
Oxidizing species and their reduction products

No. Oxidizing agent Colour Reduction product Colour
1 Purple solution Colourless
2 Orange solution Green
3 Black solid Colourless
4 Yellow solution
5 Yellow solution
6 Dark brown solid Colourless
7 Colourless Brown

8 Colourless Colourless gas
9 Colourless Brown fumes
10 Colourless Colourless
11 Yellow or brown Green
solution
12 Colourless Colourless
13 Brown
14 Reddish brown
15 Greenish yellow gas
 The first ten species act as oxidizing agents in acidic medium and the species 11-15
gain electrons in the redox reactions in which they behave as oxidizing agents.
 The colours of some species in solutions have not been indicated because the colour
of solutions in which they exist depend on the colour of cations present.
 Below are half-cell reactions for some of the species showing the electron gain. In
each of the reactions, the electrons balance the total charge on the left hand side and
on the right hand side.
Try to write out half-cell reactions for the other species on your own in the provided
space below.
1.
2.
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58
3.
4.

Reducing agents and their oxidation products
No. Reducing agent Colour Oxidation Colour
product
1
2
3 Orange solution Blue solution
4 Yellow solution Blue solution
5 Pale pink solution Purple solution
6 Greenish yellow gas
7 Reddish brown solution
8 Brown solution
9 Colourless gas with a Yellow solid
rotten egg smell
10 Colourless solution Colourless gas
11 Colourless liquid Colourless gas
12 Brown solid Blue solution
13 Green solution Yellow or Brown solution
14 Colourless solution Colourless solution
15 Colourless solution Colourless solution
 The first five species act as reducing agents in solution (presence of water)
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59
 The colour of some species in solutions have not been indicated because the colour of
solutions in which they exist depend on the colour of cations present.
 Below are half-cell reactions for some of the species showing the electron loss. In
each of the reactions, the electrons balance the total charge on the left hand side and
on the right hand side.
Try to write out half-cell reactions for the other species on your own in the provided
space below.
1.
2.
3.
4.

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60
Deriving equations for redox reactions

General steps taken
1. Identify the reducing and oxidizing species in the redox reaction. The oxidizing species is
normally that one whose central atom is in the highest oxidation state such that it is
reduced to a lower oxidation state. The reducing agent is that one whose central atom
exists in the lowest oxidation state such that is oxidised to a higher oxidation state.
2. Write well balanced half-cell reactions for both the oxidation and reduction processes.
Make sure the equations are balanced both in terms of atoms and charge.
The atoms are balanced the usual way of balancing any equation and the charge is
balanced in terms of electrons.
You should note that in the reduction half equation, electrons are always on the left hand
side and in the oxidation half equation they are on the right hand side.
3. Multiply each of the half equations by suitable factors so as to make the number of
electrons in each equation equal.
4. Cross out everything that appears on the left hand side of one equation and on the right

hand side of the other. Species to always consider for this step are electrons, and .
The hydrogen ions or water species in one equation are normally more than those in the
other. Subtraction is done and the remaining hydrogen ions or water molecules written on
the side which originally had more of the species. Once electrons still appear in this
equation, then something is not correct
5. The overall equation is now written with all the species on the left hand side maintained
there as well as those on the right hand side.
6. Note that for examination purposes space is not enough to do all this hence side work is
done and only overall equation written in the space provided. Writing other equations
other than overall equation may lead to loss of marks. Half equations can only be written
if required by examiner.
If the observation is as well required, then it is written first before the general equation.
Examples
State what would be observed and explain your observation when;
1. Concentrated hydrochloric acid was added to potassium manganate(VII)
solution
Step 1; Oxidizing species is from potassium manganate(VII) and
reducing species is from hydrochloric acid.
Step 2;
Reduction half equation;
Oxidation half equation;

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61
Step 3;
The first equation is mutiplied by 2 and the second equation by 5. This is intended to
make the number of electrons in each equation the same (10). Also note that these
factors do not multipy only the electrons but also every other species in the equation.
This now gives;
Step 4;
The electrons are equal and crossed out.

Step 5;
Observation; The purple solution turns colourless and bubbles of a greenish yellow gas
evolved.
Explanation;
Potassium manganate(VII) oxidises hydrochloric acid to chlorine as it is reduced to
manganese(II) ions.
2. Hydrogen sulphide gas was bubbled through acidified potassium dichromate(VI)

solution.
Step 1; Oxidizing species is from potassium dichromate and reducing
species is
Step 2;
Step 3;
The first equation is left as it is but the second equation multiplied by 3. This is
intended to make the number of electrons in each equation the same (6). If you choose
to multiply the first equation by 2 and the second by 6. Then you will have to divide
the stoichiometric coefficients in the final equation by a given factor through out.
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62
This now gives;
Step 4;
The electrons are equal and crossed out. The are subtracted from the to
give on the left hand side.
Step 5;
Observation; The orange solution turns green and a yellow solid deposited.
Explanation;
In acidic medium, dichromate ions oxidise hydrogen sulphide to Sulphur as they are
reduced to chromium(III) ions.

3. Hydrazine was added to acidified potassium manganate(VII) solution
Step 1; Oxidizing species is from potassium manganate(VII) and
reducing species is .
Step 2;
Step 3;
The first equation is multiplied by 4 and the second equation multiplied by 5. This is
intended to make the number of electrons in each equation the same (20).
This now gives;
Step 4;
The electrons are equal and crossed out. The are subtracted from the to
give on the left hand side.
Step 5;
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63
Observation; The purple solution turns colourless and bubbles of a colourless gas
evolved.
Explanation;
Manganate(VII) ions oxidise hydrazine to nitrogen gas as they are reduced to
manganese(II) ions.
4. Chlorine was bubbled through potassium nitrite solution.

Step 1; Oxidizing species is and reducing species is .
Step 2;

Step 3;
Since the number of electrons in both equations is the same, the overall equation can be
written right away
Step 4;
Step 5;
Observation; Greenish yellow gas dissolved and a colourless solution is formed.
Explanation;
Chlorine oxidises nitrate ions to nitrite ions and itself reduced to chloride ions.
5. Manganese(IV) oxide was added to acidified solution of sodium oxalate and the
mixture heated
Step 1; Oxidizing species is and reducing species is .

Step 2;
Step 3;
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64
Since the number of electrons in both equations is the same, the overall equation can be
written right away
Step 4;
Step 5;
Observation; Black solid dissolved forming a colourless solution and bubbles of a
colourless gas
Explanation;
Manganese(IV) oxide oxidises oxalate ions to carbon dioxide and itself reduced to
manganese(II) ions.
Balancing redox reactions in alkaline media

Although manganate(VII) ions are strongly oxidizing in acidic medium, they can also
oxidise in neutral or weakly alkaline medium, in which the half reaction is;
̅
It oxidises potassium iodide to potassium iodate in the alkaline medium
Qn. State what would be observed and write an equation for the reaction when
potassium iodide was added to an alkaline solution of potassium manganate(VII)
Then;
̅
On crossing out the electrons and combining the two equations we have;
̅
The on the right hand side are as a result of complete neutralisation of the
by 6 of the ̅ leaving a remainder of ̅ . Subtraction leaves
only one water molecule on the reactant side.
Observation;
Purple solution forms a colourless solution and black solid deposited.
Equation
̅
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65
Although hydrogen peroxide is a strong oxidizing agent in acidic medium, it sometimes

shows reducing properties depending on the conditions. Thus in alkaline conditions,
hydrogen peroxide reduces iron(III) ions to iron(II) ions.
The half reaction is;
̅
Qn. State what would be observed and write an equation for the reaction when
Iron(III) chloride was added to an alkaline solution of hydrogen peroxide.
̅
Then;
̅
Observation; Brown solution turns green and bubbles of a colourless gas.

Equation;
̅

Questions
State what would be observed and write equation for the reaction when;
1. Sodium bromide solution was added to tin(IV) chloride solution
2. Potassium iodide was added tin(IV) chloride solution
3. Concentrated hydrochloric acid was added to potassium manganate(VII) solution
4. Manganese(IV) oxide was added to hot concentrated hydrochloric acid
5. An acidified solution of hydrogen peroxide was added to manganese(IV) oxide.
6. Concentrated hydrochloric acid was added to lead(IV) oxide and the mixture heated
7. Tin(II) sulphate solution was added to acidified potassium permanganate solution
8. Chlorine was bubbled through iron(II) chloride solution.
9. Hydrogen sulphide gas was bubbled through acidified potassium dichromate(VI)
solution.
10. Bromine water was added to iron(II) chloride solution.
11. Hydrazine was added to acidified potassium manganate(VII) solution
12. Tin(II) sulphate solution was added to iron(III) sulphate solution
13. Chlorine was bubbled through potassium nitrite solution.
14. Chlorine gas was bubbled through sodium sulphite.
15. Limited chlorine gas was bubbled through sodium thiosulphate solution.
16. Excess chlorine gas was bubbled through sodium thiosulphate solution.
17. Sulphur dioxide was bubbled through acidified potassium manganate(VII) solution.
18. Sodium sulphite was added to acidified potassium manganate(VII) solution.
19. Iodine solution was added to sodium thiosulphate solution.
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66
20. Chlorine was bubbled through potassium bromide solution

21. Concentrated sulphuric acid was added to solid sodium iodide
22. Hydrogen sulphide gas was bubbled through acidified potassium permanganate
solution.
23. Hydrogen peroxide was added to an acidified solution potassium dichromate(VI)
solution.
24. Potassium bromide solution was added to concentrated sulphuric acid
25. Sodium iodide was added to acidified potassium chlorate(I) solution.
26. Potassium iodide solution was added to acidified hydrogen peroxide solution.
27. Tin(II) sulphate solution was added to acidified potassium dichromate(VI) solution
28. Potassium sulphite was added to acidified potassium dichromate(VI) solution.
29. Zinc powder was added to iron(III) sulphate solution.
30. Potassium nitrite solution was added to acidified potassium dichromate(VI)
solution.

31. Iron(II) sulphate solution was added to acidified potassium dichromate(VI)
solution
32. Manganese(IV) oxide was added to acidified solution of sodium oxalate and the
mixture heated
33. Iron(II) sulphate solution was added to acidified potassium manganate(VII)
solution
34. Acidified potassium peroxodisulphate solution was added to iron(II) sulphate
solution
35. Lead(IV) oxide was added to manganese(II) sulphate solution followed by dilute
nitric acid and the mixture heated
36. Hydrogen peroxide was added to an acidified solution of iron(II) sulphate.
37. Iron(III) chloride was added to an alkaline solution of hydrogen peroxide.
38. Potassium iodide solution was added to acidified potassium dichromate solution.
39. Potassium iodide was added to an alkaline solution of potassium manganate(VII)
40. Potassium nitrite was added to acidified potassium permanganate solution.
Titration of redox reactions

Redox reactions are used in titrimetric analysis. A solution of unknown concentration of a
reducing agent is titrated against a standard solution of an oxidizing agent. From the
volumes of the two solutions used and the overall equation of the reaction, the unknown
concentration of one of the solutions can be determined. The process involves transfer of
electrons from the reducing agent to the oxidizing agent. The half-cell reactions may be
given to generate the overall reaction or the student may be required to derive it oneself
during practical assignments and examinations. It is very important to check the overall
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67
equation to make sure it is well balanced by both mass and charge. When the equation is
not balanced, many marks are lost because the mole ratio is important in the subsequent
calculation work.
Common redox titrimetric reactions include;
1. Potassium manganate(VII) titrations in acidic medium
2. Sodium thiosulphate titrations
Potassium manganate(VII) titrations in acidic medium

In these reactions, no indicator is used because the coloured potassium permanganate acts
as own indicator. The permanganate ion is reduced to manganese(II) ions in acidic
medium as shown by the half reaction below;
Examples
1. 1.50g of an impure potassium manganate(VII) was dissolved in water to make

250cm3 of solution. 20.0cm3 of this solution was acidified with dilute sulphuric
acid, warmed and titrated against sodium ethanedioate solution made by
dissolving 1.70g of anhydrous sodium ethanedioate to make 250cm3. 24.0cm3 of
the ethanedioate solution was required. Calculate the percentage of impurity in
the potassium manganate(VII).
Sodium ethanedioate is the standard solution and our treatment of results should begin with
this!
( )
( )
( )
( ) ( )
( )
( )
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68
( )
2. Bronze is an alloy of copper and tin. 9.40g of powdered bronze was warmed with
an excess dilute sulphuric acid. The mixture was filtered and the resultant
solution made up to 250 cm3 using distilled water. 25.0cm3 of the filtrate required
19.20cm3 of 0.02M potassium manganate(VII) for oxidation.(Sn=119)
(a) Explain why;
(i) the bronze was warmed with excess dilute sulphuric acid
(ii) the mixture obtained from bronze was filtered

(b) Calculate the percentage by mass of tin in the bronze.
(a) (i) Bronze was warmed with excess dilute sulphuric acid to dissolve the all tin available as
tin(II) sulphate. It is the tin(II) ions in this solution that are oxidised to tin(IV) ions by
manganate(VII) ions in acidic medium.
(ii) Copper does not react with dilute sulphuric acid hence it is filtered off as residue to
remain with a filtrate of tin(II) sulphate.
(b) The standard solution in this case is potassium manganate(VII)
( )
( ) ( )
( )
( )
( )
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69
Questions
1. Calculate the volume of 0.01M potassium manganate(VII) solution required to
oxidise 50.0cm3 of a 0.02M acidified iron(II) ethanedioate solution
2. 25.0cm3 of an acidified solution of iron(II) sulphate required 17.5cm3 of 0.025M
potassium manganate(VII) solution for complete oxidation. Calculate the molarity of
the iron(II) sulphate solution.
3. 25.0cm3 of a solution of hydrogen peroxide required 27.5 cm3 of a solution made by
dissolving 1.58g of potassium permanganate in 500cm3 of distilled water. Calculate
the;
(i) concentration of hydrogen peroxide in grams per litre
(ii) volume of oxygen at s.t.p evolved during the reaction.
4. 1.93g of a sample of an ethanedioate salt was dissolved in water and made up to
250cm3. 25.0cm3 of this solution when warmed required 30.4 cm3 of acidified 0.02M
potassium permanganate solution. Calculate the percentage by mass of ethanedioate

ions in the original salt.
5. 20.0cm3 of a 0.01M solution of manganate(VII) ions required exactly 16.65cm3 of a
solution containing 4.8gl-1 of an oxalate . Calculate the relative
atomic mass of Y.
6. A sample of potassium nitrate was decomposed by heating. The residue was dissolved
in water and the volume of the solution made up to 250cm3. 25.0cm3 of this solution
required 28.9cm3 of acidified potassium manganate(VII) solution of concentration
0.015 moldm-3. Calculate the;
(i) mass of the residue obtained after decomposition
(ii) percentage conversion of potassium nitrate to the residue
7. Air contaminated with Sulphur dioxide was bubbled through an acidified solution of
potassium manganate(VII). It was found that 500dm3 of air decolourised 100cm3 of
0.01M potassium permanganate. Calculate the mass of Sulphur dioxide in the 500
dm3 of air.
8. Steel is an alloy of mainly iron and carbon. 0.20g of steel was warmed with an excess
dilute sulphuric acid. The resultant solution required 34.00cm3 of 0.02M potassium
manganate(VII) for oxidation. Calculate the percentage by mass of iron in the steel.
9. 5.76g of crystals a mixed salt of iron; diammonium iron(II) sulphate,
were accurately weighed and dissolved in dilute sulphuric
acid. The solution was made up to the 250 cm3 mark with more dilute sulphuric acid.
20.0cm3 of this solution required 23.5cm3 of a 0.01M solution of potassium
manganate(VII) solution for complete reaction. Calculate the value of X in
.
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70
Sodium thiosulphate titrations

Sodium thiosulphate is a reducing agent. If it is standardized, it is used
in titrimetric analysis for reducing iodine to iodide ions as it is oxidised to sodium
tetrathionate. Starch indicator is used to give an intense blue colour in presence of iodine.
At the end point when all the iodine has been converted to iodide ions, the blue colour
varnishes. Sodium thiosulphate cannot be used as a primary standard because it is
efflorescent.
The reactions occur by the two half reaction equations shown below and therefore the overall
equation.
The thiosulphate can be titrated with aqueous iodine directly or the iodine can be obtained
commonly be the redox reactions involving oxidation of potassium iodide by the reducing agents
to iodine shown below:

(i) Reaction between potassium manganate(VII) in acidic medium with excess potassium
iodide.
(ii) Reaction between potassium dichromate(VI) in acidic medium with excess potassium
iodide.
(iii) Reaction between potassium iodate(V) in acidic medium with excess potassium iodide.
(iv) Reaction between sodium chlorate(I) (usually from domestic bleach or Jik) in acidic
medium with excess potassium iodide solution.
During this process, a dilute acid is added to Jik. Jik is a mixture of sodium hypochlorite and
sodium chloride. When a dilute acid is added to jik, chlorine is given off.
The chlorine can then oxidise the iodide ions in potassium iodide to iodine as it is reduced to
chloride ions.
The two equations (i) and (ii) when combined give the overall equation above.
Chlorine can also be obtained by adding a dilute acid to bleaching powder (calcium
hypochlorite)
(v) Addition of copper(II) ions to excess potassium iodide solution.

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71
Examples
1. 1.185g of potassium dichromate(VI) was dissolved in water to make 250cm3 of
solution. 25.0cm3 of this solution was acidified and added to excess potassium
iodide solution. The resultant solution was titrated against sodium thiosulphate
and 17.50cm3 of the thiosulphate was required. Find the concentration of the
thiosulphate solution in grams per litre.
( )
( )

( ) ( )
( ) ( )
( )
2. (a) A solution of potassium iodate was prepared by dissolving 1.0g of potassium

iodate in 250cm3 of distilled water. 10.0cm3 of this solution was pipetted into a
conical flask and to it was added 10.0cm3 of 1.0M sulphuric acid followed by
10.0cm3 of 0.5M potassium iodide solution. The iodine liberated required
11.10cm3 of sodium thiosulphate solution using starch indicator. Calculate the
molar concentration of sodium thiosulphate solution.
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72
( )
( )
( ) ( )

( ) ( )
( )
(b) 30.0cm3 of a liquid bleach containing sodium hypochlorite was diluted to 250cm3
of solution using distilled water. 10.0cm3 of this solution was pipetted into a
conical flask and to it was added 10.0cm3 of 1.0M sulphuric acid followed by
10.0cm3 of 0.5M potassium iodide solution. The iodine liberated required
10.20cm3 of the same sodium thiosulphate solution in (a) above using starch
indicator. Calculate the percentage by mass of aqueous chlorine in the 30.0cm3 of
liquid bleach.
Part (a) was to standardise sodium thiosulphate which is now to be used in this part and
should be the beginning point of our calculation.
( )
( )
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73
( )
Since dilution does not change number moles in the original volume, the 30cm3 of liquid
bleach also contain 0.012875 moles of
( )

Note that the values of volume and molarity of sulphuric acid and potassium iodide are not
used in the calculation. The acid is just to provide acidic medium.
3. A copper coin of mass 2.00g consists of copper alloyed with small quantities of
tin and zinc. The coin was dissolved in moderately concentrated nitric acid and
the resultant solution was made up to 250cm3. 25.0cm3 of this solution was
pipetted , neutralised and added to an excess potassium iodide solution. The
iodine liberated required 30.0cm3 of 0.1M sodium thiosulphate solution using
starch indicator in a titration. Calculate the percentage of copper in the coin.
Copper reacts with moderately concentrated nitric acid to form copper(II) nitrate
solution. the copper(II) ions then react with potassium iodide to liberate iodine by the
reaction already stated before.
( )
( )
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74
( )
( )
( )

Questions
1. 0.89g of potassium iodate were weighed accurately and transferred into a clean
250cm3 volumetric flask. About 100cm3 of distilled water was added to dissolve the
iodate and the solution was further diluted to the mark with more distilled water.
25.0cm3 of the solution formed was pipetted into a clean conical flask, 1.0g of
potassium iodide was added followed by 3.0 cm3 of 1.0M sulphuric acid solution. The
iodine liberated required 20.0cm3 of sodium thiosulphate solution. calculate the
concentration of the sodium thiosulphate in grams per litre
2. 10.0cm3 of Jik was measured and then diluted to 250cm3 of solution in a volumetric
flask. 25.0cm3 of this solution was pipetted and added to an excess of potassium
iodide acidified with ethanoic acid. The resultant solution required 20.4cm3 of 0.1M
sodium thiosulphate for complete reaction. Calculate the percentage of available
chlorine in the Jik
3. 1.2g of bleaching powder were dissolved in water to make 250cm3 of solution.
25.0cm3 of this solution were added to an excess of potassium iodide solution
acidified with ethanoic acid and the iodine liberated required 22.3cm3 of 0.05M
sodium thiosulphate solution for complete reaction. Calculate the percentage by mass
of available chlorine in the bleaching powder.
4. 8.0g of a copper ore was leached with dilute nitric acid and the resulting solution
diluted to 250cm3. 30.0cm3 of this solution was accurately measured and added to
excess 10% potassium iodide solution. The liberated iodine required 20.0cm3 of a
0.05M solution of sodium thiosuphate for complete reaction. Calculate the percentage
of copper in the ore.
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75
5. 2.4g of brass was dissolved in dilute nitric acid to make 250cm3 of solution. To
10.0cm3 of the resultant solution was added excess potassium iodide solution. The
iodine liberated required 9.60cm3 of 0.1M sodium thiosulphate for complete oxidation
using starch as indicator. Calculate the percentage of copper in the sample of brass.
6. The formula of double salt of copper; , can be determined
from the following data.
(a) When 2g of the salt was boiled with excess sodium hydroxide, the ammonia
evolved was absorbed in 40cm3 of 0.5M hydrochloric acid in a conical flask.
The resultant solution required 20cm3 of 0.5M sodium hydroxide for
neutralisation. Calculate the mass of ammonium ions in 2 g of the salt.
(b) Another 2g of the salt was dissolved in water and treated with an excess of
barium chloride solution. The mass of the dried precipitate formed was 2.33g.
Calculate the mass of sulphate ions in 2g of the double salt.
(c) 10g of the salt was dissolved to form 250cm3 of solution. 25.0cm3 of this

solution was treated with excess potassium iodide and the resultant solution
required 25cm3 of 0.1M sodium thiosulphate solution for complete
reaction.Calculate the mass of copper(II) ions in 2g of the salt.
(d) Hence determine the mass of water of crystallisation in 2g of the salt.
(e) Deduce the formula of the double salt of copper.
PHYSICAL STATES OF MATTER

There are three states of matter, i.e. solids, liquids and gases. The states can also be
referred to as phases. However, at very high temperatures, matter exists as plasma which
has its own strange characteristics.
Inter-conversion between the states

A
SOLID LIQUID
B
C D E F
GAS
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76
A. Melting
B. Freezing or solidification
C. Sublimation
D. Deposition
E. Condensation
F. Evaporation or vapourisation
Plasma
As a gas is heated to about 10,000K, the intermolecular and interatomic collisions
become more and more violent until the molecules disintegrate into electrons and
positively charged particles. A mixture of these is what is called plasma. Plasmas are
neutral overall but the strong forces between charged particles are different from those
between the neutral molecules or atoms in a gas. This makes plasmas very different from
gases. External magnetic and electric fields affect the charged particles in plasma but
have little or no effect on neutral particles in a gas. Plasmas also emit a lot of light and

other electromagnetic radiation at such high temperatures. More modern research is
taking place to fully understand the characteristics of plasmas in detail.
The kinetic theory of matter

The kinetic theory was developed between 1860 and 1890, mainly by R.J. Clausius,
J.C. Maxwell and Boltzmann. It accounts for the known properties of gases, but it also
clarifies many problems concerned with liquids and solids.
The theory can be summarized as follows;
(a) Matter is made up of particles which may be small groups of atoms (molecules) or
single atoms in monoatomic gases.
(b) The particles in a gas are in continual, rapid, random motion in straight lines in every
direction and collide with each and with the walls of the container in which they are.
The pressure exerted by the gas on the walls of the container is due to bombardment
by the moving particles. The random motion also applies to liquids but greatly
decreased and also further decreased in a solid.
(c) The particles in a gas are separated from each other by distances which are large
compared to the size of the particles. In a liquid, the particles are closer together, and
they are still closer in a solid.
(d) The particles are regarded as being perfectly elastic so that the collisions they undergo
in a gas do not result in any change in the total amount of kinetic energy of the gas.
(e) Increase in temperature causes the motion of the particles to increase, the average
kinetic energy of the particles in a gas being proportional to the absolute temperature
of the gas.
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77
Differences in the states of matter

Parameter State of matter
Gas Liquid Solid
The particles are closely
The particles are far The particles are packed and orderly
Particle apart and are not orderly closer to each other arranged, fixed in three
arrangement arranged and are not orderly dimensional structures.
arranged
Forces of Forces of attraction Intermolecular forces Attraction between the
attraction between the molecules of attraction are molecules is even more
are negligible weaker than those in dominant
solids
Movement The particles are mobile Particles randomly Movement of the particles
with different speeds in move, as in a gas, but is restricted to vibration
various directions not as fast as in gases about mean/fixed positions

Comparison of physical properties
Physical property State of matter
Gas Liquid Solid
Gases are highly
compressible.
Increasing the
pressure on a gas
decreases its volume Liquids are only Solids are
Compressibility and decreasing the slightly compressed incompressible.
pressure will increase
its volume
Gases have low Densities of liquids Solids have very high

Density densities. When a gas are higher than gases densities.
is cooled, its density but lower than those
increases. of solids
Gases have no
definite volume. They Liquids have definite Solids have definite
Volume take up volume of volumes volumes.
containers they
occupy.
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Gases have no Liquids have no Solids have definite

Shape definite shape. They shape, they take up shapes.
take up shape of the shape of the
container they containers they
occupy. occupy.
GASEOUS STATE OF MATTER

A gas is predicted as a random movement of atoms or molecules, not closely packed,
with very weak forces between them so that they can move about quite freely.
That is why gases have low densities, they expand to occupy any container and are easily
compressed.
The gaseous state in terms of kinetic theory of matter

According to the kinetic theory;
1. The gas molecules occupy only a tiny fraction of the volume of the container in which
they are contained. The intermolecular distance is many times larger than the diameter
of the molecules. A sample of a gas is nearly empty space and the molecules are
scattered throughout this space.
2. The gas molecules are constantly moving in straight lines until they collide with each
other and with the walls of the container, exerting no force upon one another. The
collisions made are perfectly elastic, meaning that the molecules bounce apart with no
loss of energy.
3. The average kinetic energy of the molecules is proportional to absolute temperature,
therefore at a certain temperature; all gases have the same average kinetic energy.
AN IDEAL GAS
An ideal gas is also called a perfect gas.
An ideal gas is a gas that obeys all gas laws accurately at all temperatures and
pressures, has no intermolecular forces of attraction and occupies a negligible volume.
However there are known examples of ideal gases and the concept is just a theoretical
one.
Gas pressure
This is the pressure exerted by a gas per unit area. The main unit of pressure is
.
is called a .
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79
Other units of pressure are and

.
Gas laws
Boyle‟s law
Boyle‟s law states that; at a constant temperature, the volume of a given mass of a gas
is inversely proportional to the pressure.
Or at a constant temperature, the pressure of a given mass of a gas is inversely
proportional to the volume.

Therefore if a gas has a volume at a pressure and the pressure is changed to , the new
volume , , at a constant temperature is given by the equation;
Real gases do not fully obey Boyle‟s law. The deviations from the law particularly occur
at high pressures and low temperatures, and for gases which are easily liquefied.
The deviations from the law occur due to interactions between the molecules in a gas. If
such interactions did not exist, then a gas would obey Boyle‟s law (would be ideal or
perfect)
Real gases approach the ideal or perfect behaviour at low pressures and high
temperatures.
Charles‟ law
Charles‟ law states that; at a constant pressure, the volume of a given mass of a gas is
directly proportional to the temperature in Kelvin.
Or at a constant pressure, the volume of a given mass of a gas is directly proportional
to the absolute temperature.
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80
Therefore if a gas has a volume at a temperature and the temperature is changed to , the
new volume , , at a constant pressure is given by the equation;
Real gases also deviate from Charles‟ law as they do for Boyle‟s law.
Combined gas laws
When Boyle‟s law and Charles‟ law are combined, one equation is obtained. This is
called the equation of state for an ideal gas. The equation relates pressure, volume and
the temperature of a gas.
From Boyle’s law;
If a given mass of a gas has a volume of at a pressure of , it will a volume at a
pressure at a constant temperature.

From Charles’ law;
If now the temperature at which the volume of the gas, is measured is changed from to
, the new volume will be given by;
Equating equations and yields;
Multiplying through by yields;
and in a more general form, this can be expressed as

and the temperature expressed in Kelvin.
The equation of state of an ideal gas helps us to calculate the effect of a change in
temperature and pressure on the volume of a gas. We cannot compare gas volumes unless
they are stated at the same temperature and pressure. Gas volumes are usually compared
at 273K and 101325Pa (standard temperature and pressure).
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81
Examples on calculations involving gas laws

In these calculations, it is very crucial to remember to change the temperature to the
Kelvin scale. The pressure may be left in its units so long as they are the same on both
sides throughout the calculation.
1. If the volume of a gas at standard temperature and pressure is 51 , calculate
the volume of the gas if it is collected at 60 and 105 kPa.

( )
2. A closed bulb contains a certain volume of a gas at 21 and 755mmHg.

Calculate the pressure of the gas if the temperature is raised to 51 .
( )
Ideal gas law

Boyle‟s law and Charles‟ law can be combined to form a single equation which
represents the relationship between pressure, volume and kelvin temperature of a given
mass of a gas under different conditions.
By combining the two gas laws;

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82
When the quantity of gas is one mole, the constant in this equation is called the molar gas
constant, represented by .
Therefore for 1 mole of a gas;
And for moles of a gas;
The above equation is known as the ideal gas equation because it only holds when gases behave
as ideal or perfect gases.
The molar gas constant is commonly used as when the units of pressure,
volume and temperature are and Kelvin respectively.
Recall that;

( )
83
Examples
1. Calculate the volume occupied by 200g of carbon dioxide gas at a temperature
30 and a pressure of 98.65 kPa.
2. 0.539g of a vapourised sample of gas X occupies 200 at a temperature of

373K and a pressure of 0.938 atm. Calculate the relative molecular mass of X.

Questions
1. A certain mass of a gas has a volume of 241 at 18 and a pressure of 100400 Pa.
determine its volume at s.t.p.
2. A gas occupies a volume of 1500 at 27 and 102,700 pressure. What
would be its volume at s.t.p?
3. A certain gas has a volume of 75 at 15 and 104 kPa. What would be its
volume at 27 and ?
4. A sealed flask contains oxygen at 17 and 99.3 . What would be the
pressure of the oxygen if the temperature was lowered to ?
5. At s.t.p, a certain mass of a gas has a volume of 1 litre. At 30 atm, the volume is 31.2
and at 60 atm, the volume is 14.9 . Explain whether the gas shows ideal
behaviour.
6. (a) 1 mole of hydrogen iodide gas at 25 was introduced into a container of volume
20 litres. Calculate the pressure of the gas assuming ideal behaviour.( 1 mole of an
ideal gas occupies 22.4 litres under standard conditions)
(b) The sample of hydrogen iodide, considered above was raised to a temperature of
300 and it decomposed into hydrogen and iodine. Calculate the pressure of the
equilibrium mixture at 300 assuming no change in volume.
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84
7. Calculate the volume occupied by 200g of chlorine gas at a temperature 15 and a

pressure of 54.71 kPa.
8. 1212.5 of a gas J has a mass of 0.88g at 50 and a pressure of 115000 .
Calculate the relative molecular mass of the gas.
9. A gas Q contains 30.43% nitrogen and the rest being oxygen. 0.23g of Q occupied
154.11cm3 at 150 and 840mmHg. Determine the;
(i) Empirical formula of Q
(ii) Molecular formula of Q.
More of the application of this concept is covered in empirical and molecular

formula.
Graham’s law of gaseous diffusion
The concept of diffusion is not a new one to us at this level since you already have an
idea from Ordinary level.

The rates at which different gases diffuse are not equal. A lighter gas diffuses more
rapidly than a heavier one. After carrying out a number of experiments on the rates at
which gases mix together, Graham(1832) came up with Graham‟s law which states that;
At constant temperature and pressure, the rate of diffusion of a gas is inversely
proportional to the square root of its density.
√
Consider two gases and which diffuse at rates and respectively. If the densities of the
gases are and respectively;
√ √
√ √
Dividing equation (i) by equation (ii) yields;
√
√
√ √
√
√
√
√
If the volume is kept constant, then density is directly
|
proportional to the relative molecular mass of the gas. We then have;

85
√ √
√ √
Dividing equation (i) by equation (ii) yields;
√
√
√
√
√
√
Graham‟s law can therefore also be stated as; at constant temperature and pressure, the
rate of diffusion of a gas is inversely proportional to the square root of its relative
molecular mass.
Rate of diffusion of a gas can also be expressed as a reciprocal of the time taken for the

gas to diffuse. Therefore;
√
√
√ Similarly;
√ √
√ √
⁄
√
Rate of diffusion of a gas can also be expressed in terms of volume of the gas and time
taken by the gas to diffuse.
Avoid the common mistake done by students during most of these calculations by
forgetting that most gases are diatomic. This should be observed when calculating molar
masses of gases.
Examples
1. A given volume of gas W diffuses through a hole in 14.1 seconds while the same
volume of carbon dioxide diffuses through the same hole in 10 seconds. Calculate the
molecular mass of gas W.
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86
√
√
( ) √
( ) √
( )
2. A given volume of a gas X diffuses in two thirds of the time taken by an equal
volume of hydrogen chloride under the same physical conditions. Calculate the
relative molecular mass of the X.
( ) √
⁄

( ) √
√
( )
√
( ) ( )
( )
√
√
3. Oxygen diffuses 0.9 times faster than a hydrocarbon Y. Calculate the relative
molecular mass of Y.
√
√
( )
√
√
4. The time taken for of oxygen to diffuse through a porous partition is

10 seconds. Another gas Z at the same conditions of temperature and pressure
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87
diffuses through the partition at the rate of in 20s. Determine the

relative molecular mass of gas Z.
( ) √
⁄
( ) √
( ) ( )
√
( )
√
5. Two pieces of cotton wool were each soaked separately in concentrated ammonia
solution and concentrated hydrochloric acid respectively and simultaneously
inserted into opposite ends of a horizontal wide glass tube. After a short time a
white ring was across the tube. If the distance between the inner surfaces of the
cotton wool plugs is 50cm.

(i) Name the white ring
(ii) Write the equation leading to formation of the white ring.
(iii) Determine how far from the ammonia plug the white ring is formed.
(i) Ammonium chloride

(ii)
(iii)
Since ammonia gas from concentrated ammonia solution diffuses faster than hydrogen chloride
gas from hydrochloric acid, the white ring is formed nearer the cotton wool soaked in
hydrochloric acid. White ring
50cm
50-x x
Cotton wool soaked Cotton wool soaked
in concentrated in concentrated
hydrochloric acid ammonia solution
( ) √
⁄
( ) √
( ) ( )
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88
√
√( )
√
6. Oxygen diffuses 2.3 times as fast as a compound Z with the formula; .

Determine the molecular formula of Z.
( )
√
√
√

√
Questions
1. Calculate the ratio of diffusion of a gas at 91 and 0 at a constant pressure.
2. A gas Q diffuses 4 times as rapidly as sulphur dioxide under the same conditions. If
the density of sulphur dioxide under the same conditions of temperature and pressure
is , calculate the density of Q.
3. 100 of oxygen diffused through a membrane in 5 minutes. 120 of an
unknown gas under the same conditions, diffused through the membrane in 10
minutes. Calculate the molecular mass of the unknown gas.
4. Oxygen diffuses 1.19 times faster than an amine, .
(i) Determine the molecular formula of the amine.
(ii) Deduce the structural formulae and names of all possible isomers of the
amine.
5. 250 of an alkene diffuse through a porous medium in 10 seconds and 716 of
oxygen diffuse through the same medium in 25 seconds under the same conditions.
Calculate the molecular mass of the alkene and deduce its structural formula.
6. Oxygen diffused through a porous partition in 1.87 minutes. Under similar conditions,
the same volume of an alkene, T diffused in 2.15 minutes.
(a) Determine the formula of T
(b) Write equation and outline mechanism for the reaction between T and benzene.
Indicate the conditions for the reaction.
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89
7. 141.4 of an inert gas diffused through a porous plug in the same time as it took
50 oxygen to diffuse through the same plug under the same conditions. Calculate
the relative atomic mass of the inert gas.
8. Two pieces of cotton wool were each soaked separately in concentrated amine Q and
concentrated hydrochloric acid respectively and placed at opposite ends of a 2m long
glass tube. After some time a white ring was formed at 0.96m from the end
containing concentrated hydrochloric acid. Determine the relative molecular mass of
amine Q.
9. Two pieces of cotton wool were each soaked separately in concentrated amine Y and
concentrated hydrochloric acid respectively and placed at opposite ends of a 1m long
glass tube. After some time a white ring was formed at 0.52m from the end
containing the concentrated ammine. Determine the relative molecular mass of amine
Y.
10. of gas L diffuses through a porous partition in 5s. of oxygen

diffuses through the same partition in the same time. Calculate the molecular mass of
L.
11. Nitrogen gas diffuses 1.25times faster than gas X. calculate the relative molecular
mass of gas X.
12. 25 of gas Q diffuse through a small aperture in 48 seconds while 25 of an
alkane diffuse through the same aperture in 40 seconds.
(i) Deduce the molecular formula of the alkane.
(ii) Write equations to show how the alkane can be synthesized from
Pent-2-yne.
13. Gas X diffuses through a membrane in 20.5 minutes and under the same conditions,
an equal volume of hydrogen diffuses through the same membrane in 3 minutes.
Calculate the molecular mass of X.
14. 141.4 of gas X diffused through a porous plug in the same time it took 50
of oxygen to diffuse through the same plug under identical conditions. Calculate
the relative molecular mass of X.
15. State Graham‟s law of gaseous diffusion.

(b) Nickel forms a gaseous carbonyl; . Deduce the value of n if carbon
monoxide diffuses 2.46 times faster than the carbonyl compound.
(c) State the ;
(i) name of the nickel carbonyl
(ii) coordination number of nickel in the compound.
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90
16. (a) State Graham‟s law of gaseous diffusion.

(b) A hydride of silicon contains 9.65% by mass of hydrogen and was found to
diffuse through a porous plug at two thirds of the rate of diffusion of nitrogen.
Determine the molecular formula of the hydride.
17. A gaseous compound X contained 46.1% carbon and 53.9% nitrogen. In 20 seconds,
50 of X diffused through a porous plug and the same volume of oxygen diffused
in 15.7 seconds.
(i) Determine the molecular formula of X.
(ii) Calculate the volume of carbon dioxide that diffuses in 20 seconds under
the same conditions.
18. A compound, B has an empirical formula of . Oxygen gas diffuses 1.345 times
faster than B.
(a) (i) Determine the molecular formula of B
(ii) Write the structural formulae of all the possible isomers of B.

(b) (i) B does not Fehling‟s solution. Using equations, show how B can be formed
from propene
(ii) Write an equation for the reaction of B with sodium hydrogen sulphite
and write the mechanism.
19. A gaseous oxide of sulphur, diffused through a porous partition in 2.68 minutes
while equal volume methane at the same temperature diffused in 1.1985 minutes.
(a) Determine the value of in the oxide
(b) The oxide in (a) above reacts with benzene via an electrophilic substitution
mechanism.
(i) State whether the oxide in (a) above acts as an electrophile or nucleophile.
Give a reason for your answer.
(ii) Write equation for the reaction with benzene and outline the mechanism.
Mole fraction of a gas,

Mole fraction of a gas is the ratio of the number of moles of the gas present to the total
number of moles of all the gases in the mixture.
Therefore for a mixture of two gases and . The mole fractions of gases and are
given respectively as
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Also from Avogadro‟s hypothesis, it follows that;
Dalton’s law of partial pressure

In a mixture of gases, each gas behaves as if it was the only gas present assuming there
are no chemical interactions between the gases. In a container in which a mixture of
gases, that not react are enclosed, the total pressure exerted is a result of the individual
pressures of each of the gases. Each of these pressures is called partial pressure.
Partial pressure of a gas is the pressure which that gas exerts if it occupies a vessel

alone which was initially occupied by a mixture of gases.
In 1801, Dalton came up with Dalton‟s law of partial pressure which states that; in a
mixture of gases which do not react chemically, the total pressure is the sum of the
partial pressures of the components.
Let us now consider a mixture of three gases and and placed in a vessel each having
partial pressures , and respectively.
According to Dalton‟s law of partial pressures; the total pressure exerted by the gases is;
and if each of the gases has the number of moles as and and respectively,
Then the mole fractions of the gases and and are given by;
The partial pressures of each of the gases respectively are given as a product of
their respective mole fractions and the total pressure,
( )
( )
( )
Dalton came with his law experimentally but it can be deduced from the ideal gas
equation. Therefore if each of the gases has the number of moles as and and
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respectively and occupy a volume V, then, the pressures of each of the gases
respectively are given as;
The total pressure can then be expressed as
Examples
1. (a) State Dalton‟s law of partial pressures.
(b) Explain why a mixture of ammonia and hydrogen chloride does not hold for
Dalton‟s law of partial pressures.
(c) A mixture of 20% ammonia, 55% hydrogen and 25% nitrogen by volume has

a pressure of . Calculate the partial pressure of each gas.
(b) Ammonia reacts with hydrogen chloride to form ammonium chloride. For Dalton’s law to
hold, there should be no chemical interactions between the gases.
(c) According to Avogadro‟s hypothesis;
2. 1.3g of carbon dioxide and 2.4g of oxygen were mixed in a 1 litre vessel. If the
total pressure of the mixture is 100 atmospheres, calculate the partial pressure of
each gas present in the container.
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( ) ( )
3. 50.0 of carbon dioxide at are mixed with 150 of

hydrogen at the same pressure. If the pressure of the mixture is
. Calculate the partial pressure of carbon dioxide.
( )
4. In a vessel of volume 10.0 are introduced 4.0 of methane at a

pressure of , 12.5 of ethane at a pressure of

and 1.50 of propane at a pressure of . Calculate
the pressure of the resulting gas mixture.
( ) ( )
( )
5. A sample of air at 27 contains 0.62 g of oxygen gas, 1.34g of carbon

dioxide gas and 0.06g of nitrogen gas. Calculate;
(i) the partial pressures of each gaseous component in the mixture
(ii) the total pressure of the mixture of gases.
(i)
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(ii)
Alternatively;
( )
( )
( )

6. At constant temperature, a vessel contains two gases, and . The partial
pressure of is and its mole fraction is 0.85. Calculate the;
(i) total pressure exerted by the mixture of gases.
(ii) partial pressure of gas .
(i) (ii)
Questions
1. A mixture of gases, at a pressure of has the volume composition of
30% carbon monoxide , 50% oxygen and 20% carbon dioxide. Calculate the partial
pressure of each gas.
2. A mixture of gases at s.t.p contains 65% nitrogen, 15% of carbon dioxide and 20% of
oxygen by volume. Calculate the partial pressure of each gas in kPa.
3. 12g of nitrogen, 0.4g of hydrogen and 9g of Oxygen are put in a 1 vessel at a
pressure of 17.02mmHg. Calculate the partial pressure of each of the gases.
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4. The partial pressures of the components of a mixture of gases are 26.64 kPa oxygen
34 kPa nitrogen and 42.66 kPa hydrogen. What is the percentage by volume of
oxygen in the mixture?
5. 400 of gas A at 2 atmospheres and 200 of gas B at 1 atmosphere are put in
a 500 container at the same time. Calculate the total pressure in the container.
Maxwell-Boltzmann distribution
According to the kinetic theory, the gas molecules are constantly moving in straight lines
until they collide with each other and with the walls of the container. As a result of these
numerous collisions within the gas, the velocities of the individual molecules vary
enormously. Most molecules within the gas have velocity close to the mean, but some
may acquire higher or lower values as a result of a series of favourable or unfavourable
collisions. The distribution of velocities amongst molecules was calculated by Maxwell
and Boltzmann, from the laws of probability and some typical results are shown below
graphically.

c'
c
u
The graph shows the distribution of molecular velocities in a gas a temperature , , and
a higher temperature, .
At both temperatures, the number of molecules with very high or very low speeds is
small, the bulk of the molecules having intermediate speeds. The peaks of the curves
represent the most probable velocities possessed by an individual molecule at the given
temperature. The most probable velocity(c') is not the same as either the mean/ average
velocity(c) or the root mean square velocity (u). At , the most probable velocity (c'),
the mean velocity (c) and the root mean square velocity(u) are all shown.
It is noted that the distribution curve for the higher temperature, has a lower peak. It
also more spread out although the total number of molecules ( represented by areas
under the curves) remain the same. The most probable velocity, the mean/ average
velocity and the root mean square velocity are all higher, but the proportions of the
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molecules with these speeds are lower. This is because at higher temperature, there a
greater range of possible velocities.
The distribution of kinetic energy amongst the molecules follows a similar pattern. It can
be expressed as
⁄
Where is the total number of molecules and is the number having an energy greater
than the value E.
Deviation from Ideal behaviour
Previously, we discussed that Boyle‟s law is not valid over a wide range of pressures.
Deviations from the law occur at low temperatures and high pressures.
Such deviations are due to the fact that real gases are not ideal.
A real gas is a gas that does not obey gas laws accurately at all temperatures and
pressures, has intermolecular forces of attraction and occupies an appreciable volume.

Differences between a real gas and ideal gas
Real gas Ideal gas
Possesses intermolecular forces Has no intermolecular forces
Occupies an appreciable volume Volume occupied is negligible
Collisions between particles are inelastic. Collisions are perfectly elastic ( particles
( particles lose kinetic energy on collision) do not lose any kinetic energy on collision)
Conditions under which real gases behave like ideal gases

1. Low pressure. At low pressures, molecules of a gas are far away from each other,
neither repulsive nor attractive forces are significant and the volume occupied by the
real gas becomes negligible, behaving as an ideal gas.
2. High temperature. At high temperatures, the kinetic energy of the molecules
increases, intermolecular collisions are high and are perfectly elastic, intermolecular
forces of attraction become insignificant, molecules become far away from each other
and the volume occupied by the real gas becomes negligible, behaving as an ideal gas.
Real gases are not ideal because the intermolecular forces of attraction have a significant
effect on their pressure and their volume is not negligible. At low temperatures and high
pressures, the molecules of a gas are close together and forces operate between them. At
sufficiently low temperature and high pressure, a gas liquefies. Some of the ideas of the
kinetic theory have to be modified to account for non-ideal behaviour of gases.
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An ideal gas would obey Boyle‟s law such that , known as compression or
compressibility factor( ).
Compressibility factor is a measure of deviation real gas from ideal gas behaviour.
For any ideal gas the compressibility factor is equal to one.
However, for real gases, only approaches a value of one at very low pressures as shown
in the figure below. At other pressures, may be greater than one (meaning the gas is
more difficult to compress than an ideal gas) or less than one.
The graph below shows a plot of against pressure for some gases at the same
temperature.
2

1
Explanations
At high pressures, the molecules of a gas are close to each other, there are strong
repulsive forces between the molecules, and these hinder compression.
At moderate pressures, the forces between the molecules are attractive and favour
compression.
At very low pressures, neither repulsive nor attractive forces are significant and that is
why real gases approach ideal behaviour at low pressures.
Deviation for hydrogen and helium
For hydrogen and helium, there is a small deviation from ideal behaviour. This is because
the gases have small molecules, with small molecular masses and held by weak van der
Waals forces of attraction. The value of the compressibility factor is greater than
1 and continuously increases with increase in pressure. This is because deviation due to
molecular volume is greater than the deviation due to molecular attraction at all
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pressures. The molecules of hydrogen repel each other strongly thus this repulsion
increases the volume of a gas.
Deviation for methane, ammonia, oxygen and carbon dioxide
For methane, ammonia, oxygen and carbon dioxide, the deviation from ideal behaviour
increases in the order . This is because the gases have larger
molecules, with larger molecular masses that increase in the same order. The strength in
the van der Waals forces of attraction between the molecules increase with the increase in
molecular weight and reducing the volume occupied by the gases. For each of the gases,
the value of the compressibility factor initially decreases to a minimum. This is
because the deviation due to molecular attraction is greater than the deviation due to
molecular volume. The value of thereafter increases with increase in pressure because
the effect of molecular volume overcomes that of molecular attraction.
Questions
1. (a) What is meant by the term compressibility factor?

(b) On the same axes, draw a graph to show the variation of pressure with the
compressibility factor for each of the gases; hydrogen, ammonia, propane and an ideal
gas.
(c) Explain the shape of the curve for;
(i) hydrogen
(ii) ammonia
(iii) propane
2. (a) State what is meant by an ideal gas
(b) Explain how liquefaction of a gas can be affected by;
(i) pressure
(ii) temperature
(c) The curves below show the deviation of some gases from ideal behaviour.
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(i) Explain why hydrogen shows a small deviation from ideal behaviour
compared to other gases.
(ii) Compare the deviation of oxygen and carbon dioxide from ideal gas
behaviour
(Hint; the idea of compressibility factor should not be incorporated in your
answer in this question)
3. A plot of the compressibility factor, , against pressure for one mole of methane at
273K is as shown below. Use the graph to answer the questions that follow.

(a) Give reasons for the behavior of methane at 273K when the pressure is:
(i) lower than 200 atmospheres
(ii) higher than 200 atmospheres
(b) On the same graph, sketch graphs for ethane and nitrogen at 273K and give reasons
for your sketches.
Correction of real gas behaviour by using van der Waals’ equation

In 1873, Van der Waals replaced the simple gas equation by the equation;
( )
Where and are numerical constants.

Van der Waals argued that the actual size of the gas molecules means that the volume in
which they are free to move is less than the total volume which a gas occupies. He
replaced by
He also argued that the attractive forces between the gas molecules lower the pressure
that they can exert by lowering the frequency of impact with the walls of the containing
vessel. This also lowers the force of impact of the gas with the walls of the vessel.
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Since both these effects are proportional to gas density and inversely proportional to
volume, Van der Waals replaced by ( )
The Van der Waals‟ equation fits the experimental data better than the simple gas
equation, and the values of and for different gases can be obtained by fitting the
equation to known values of and .
Liquefaction of gases
If a gas is cooled sufficiently at atmospheric pressure, it can be liquefied. The conditions
of temperature and pressure under which gases liquefy were first investigated by
Andrews in 1869.
Andrews subjected carbon dioxide to various pressures at different temperatures and
plotted the effect of pressure on the volume.
The isothermals for carbon dioxide which are defined as curves for variation of
pressure with volume of the gas at particular temperatures were obtained as shown

below.
D
C B
𝑽𝒐𝒍𝒖𝒎𝒆 𝒎𝟑
KEY
Permanent gas
Liquid
Vapour
Liquid and vapour
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The isothermal at shows that the volume of the gas (carbon dioxide)
decreased with increase in pressure. This isothermal is in accordance with Boyle‟s law.
At a lower temperature , the volume of the gas first decreased in accordance to
Boyle‟s law along AB until the pressure increased to about 60 atm. At this pressure, there
is a sudden break in the curve and liquid carbon dioxide forms. The pressure remains
constant along BC until all the carbon dioxide is converted into liquid form. At C,
liquefaction of the gas is complete. Any further increase in pressure causes no change in
volume of the liquid carbon dioxide along CD. ( This is in accordance with the fact the
extremely high pressures are required to compress a liquid appreciably).
Similar changes take place in the effect of change in pressure on the volume of carbon
dioxide at temperatures below , although the pressure required to liquefy the
gas becomes smaller as the temperature decreases.
Liquefaction of the gas can be brought about at all temperatures below but
above this temperature, no liquefaction occurs no matter how much pressure is increased.

This temperature is called the critical temperature of carbon dioxide. The pressure
required to liquefy the gas at the critical temperature is called the critical
pressure and the volume of 1 mole of the substance at the critical temperature and
pressure is called the critical volume. Point is called the critical point.
Definitions;
Critical temperature is the temperature above which a gas cannot be liquefied however
much pressure is exerted on it.
Critical pressure is the minimum pressure required to liquefy the gas at critical
temperature.
The conditions for liquefaction of a gas are therefore; low temperature below critical
temperature and high pressure.
Above critical temperature, a gas is regarded as a permanent gas since it cannot be
liquefied.
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Question
1. The graph below shows isotherms of a gas.

B C
(a) Explain what is meant by the terms
(i) Isothermal of a gas
(ii) Critical temperature
(b) What is the critical temperature of the gas?
(c) Which isothermal represents the behaviour of an ideal gas?
(d) What does the region ABC represent.
(e) Explain the shape of the isothermal at 285K
(f) On the sketch graph, show the regions under which the gas exists as;
(i) Vapour
(ii) Liquid
(iii) Permanent gas
(g) State the conditions for liquefaction of a gas to occur.
LIQUID STATE OF MATTER

The liquid state in terms of kinetic theory of matter
Most liquids are miscible like all gases. Liquids can be compressed although to a smaller
extent than gases.
According to the kinetic theory, molecules in a liquid are in a state of random motion, as
in a gas, but the motion is very much less than it is in a gas and the molecules in a liquid
are very much closer.
Liquids actually lie midway between the disorderly, scattered distribution found in a gas
and the orderly compact arrangement found in a crystalline solid.
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The random distribution of molecules found in a liquid is shown by a phenomenon of

Brownian motion. Brownian motion was first observed by a botanist Robert Brown in
1827, who found out that very small pollen grains immersed in water undergo an
irregular motion when observed under a microscope. Such motion is due to bombardment
of the pollen grains by molecules of the liquid in which the grains are suspended.
Properties of a liquid
1. Compressibility
Compressibility of a liquid ( )is the fractional change in its volume per unit increase in
pressure. Liquids have low compressibility because the particles are closer to each other
and the intermolecular forces of attraction are weaker than those in solids hence the
particles can randomly move although not as fast as in gases.
The property of compressibility of liquids is applied in;
(i) Hydraulic breaks. In a hydraulic break, there is a brake fluid whose compressibility is
affected by temperature and the presence of trapped air and moisture. When the brake

pedal is pressed, force is exerted on the pistons causing the brake fluid to flow into a
pressure chamber. This increases the pressure in the entire hydraulic system. This
pressure effect is also exerted on the brake pads to reduce the vehicle speed.
(ii) Hydraulic car jack. The car jack is used to lift even the heaviest cars using a small
force that is applied to a fluid from one piston of the car jack. This force builds up
pressure in the fluid that then forces another piston to rise. This generated pressure lifts
the car up.
2. Viscosity
The viscosity of a liquid is the resistance to flow of a liquid. Edible oil has a greater
viscosity than water. Viscosity may be thought of as internal friction between the
molecules. Viscosity is a major factor in determining the forces that must be overcome
when fluids are used in lubrication and transported in pipelines. It controls the liquid flow
in processes like spraying, injection moulding and surface coating. The viscosity of
liquids decreases rapidly with an increase in temperature. That is why upon heating,
liquids flow more easily. The viscosities of water at 27℃ and 77℃ are
and respectively.
3. Surface tension
Molecules in the interior of a liquid are attracted equally on all sides by the molecules
around them. Molecules on the surface are only attracted inwards and sideways. As a
result, the liquid surface is always under tension and tends to contract so as to reduce the
surface area to a minimum. The mutual attraction of the molecules in the liquid surface
produces a resistance to penetration since work has to be done to force the molecules
apart. The surface has a certain amount of “hardness” which is basically similar to the
hardness of a solid metal surface. Therefore small metal objects such as a greased steel
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needle can float on water and certain insects can move freely on a water surface without
getting wet. The values of surface tension decrease with increase in temperature.
Surface tension of a liquid, , is the force in newtons acting parallel to the surface
along a line of one metre in length in the surface and at right angles to the line.
4. Diffusion
Like gases, liquids also diffuse since their molecules are also moving. The diffusion in
liquids is however slower than in gases because the molecules are more closer together
than in gases. When two miscible liquids are added together, they diffuse throughout the
whole mixture until it is homogeneous. Solids can also diffuse in liquids to form
solutions. For example copper(II) sulphate and potassium manganate(VII) crystals can
diffuse in water.
5. Vapourisation/ Evaporation
Evaporation is the change of state from liquid to gas (or vapour) at a temperature below
the boiling point of the liquid. Evaporation can take place at any temperature, the rate
increasing with increase in temperature. Some molecules in the liquid have enough

energy to escape into the gas phase (if they are near the surface and moving in the right
direction). Because these are the molecules with higher kinetic energies, evaporation
results in a cooling of the liquid. Evaporation is an endothermic process.
The rate of evaporation of a liquid depends on a number of factors which include its
vapour pressure(which is most important), molar heat of vapourisation, molar heat
capacity and other factors. Liquids with a high vapour pressure evaporate easily than
those with a lower vapour pressure
6. Condensation
The change of a vapour or gas into a liquid. The change of phase is accompanied by the
evolution of heat i.e. it is exothermic.
The evaporation of a liquid seen above can continue until no liquid remains. However, if
the liquid is in a closed container, the molecules in the vapour state collide with the walls
of the container and some fall back into the liquid(condense). Equilibrium will be reached
when the rate at which molecules condense is equal to the rate at which molecules of
vapour condense.
7. Boiling
When a liquid is heated, its temperature increases until there are molecules with sufficient
energy to escape from the liquid surface. The temperature reaches a high enough value
and the saturated vapour pressure becomes equal to the external pressure. At this point
the liquid changes rapidly and completely into vapour. This process is called boiling and
the temperature at which it occurs is the boiling point. The boiling point of a liquid
depends on the cohesive forces in the liquid. If the cohesive forces are weak, the boiling
point is low. When the cohesive forces increase in strength, the boiling point increases.
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Boiling therefore occurs when the vapour pressure is equal to the external pressure
exerted on the liquid.
Boiling point of a liquid is the constant temperature at which its saturated vapour
pressure becomes equal to the external pressure on the liquid.
8. Vapour pressure
Vapour pressure of a pure liquid is the pressure exerted by the vapour over the liquid
surface. The vapour pressure of a liquid depends on;
(i) The temperature of the liquid
When the temperature of a liquid is raised, its molecules move more rapidly. This results
into an increase in the average kinetic energies of the molecules. At higher temperatures,
a greater number of molecules possess energy greater than the escape energy and
therefore a greater number of molecules escape as vapour. This increases the vapour
pressure of the liquid.
(ii) External pressure

The boiling point of a liquid depends on the external pressure. At a given temperature,
vapour pressure of a liquid is equal to the external pressure. Therefore the vapour
pressure of the liquid at a given temperature increases with increase in external pressure.
A liquid therefore boils at a higher temperature than its normal boiling point when the
external pressure is increased.
(iii) Intermolecular forces
The vapour pressure of a liquid depends on the strength of its intermolecular forces. A
liquid with weak intermolecular forces acting between its molecules has a higher
tendency to escape as a vapour hence a higher vapour pressure, said to be volatile. A
liquid with stronger intermolecular forces acting between its molecules has a lower
tendency to escape as a vapour hence a lower vapour pressure, said to be less volatile or
non-volatile.
Question;
The table below shows the boiling points of different pure liquids.
Compound Boiling point( )
(a) Arrange the compound in order of increasing vapour pressure.

(b) Explain your answer in (a) above.
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(a) Vapour pressure increases in the order;
(b) The vapour pressure increases from water to ethanol to ethoxyethane to nitrogen to
hydrogen, since boiling point decreases in the same order.
The vapour pressure of a liquid depends on the strength of its intermolecular forces.
Water molecules interact through strong intermolecular hydrogen bonds which
require a high amount of energy to break. This reduces escaping tendency of water
molecules into the vapour phase hence a low vapour pressure. Ethanol has a higher
vapour pressure than water because the intermolecular hydrogen bonds in it are
weaker than in water. This is because each ethanol molecule has only one hydrogen
atom that is sufficiently partial positive hence forms only two hydrogen bonds unlike
each water molecule that forms four hydrogen bonds. Ethanol molecules therefore
have a higher escaping tendency than water molecules. Ethoxyethane molecules,

liquid nitrogen molecules and liquid hydrogen molecules all interact through weak
van der Waals forces of attraction whose strength decrease with decrease in molecular
size and molecular weight and can easily be broken. Since molecular mass and
molecular size decreases from ethoxyethane to nitrogen to hydrogen, strength of van
der Waals forces decreases in the same order, amount of energy required to break the
forces decreases in the same order, escaping tendency of the molecules into vapour
phase increases in the same order, hence increasing the vapour pressure.
(also refer to the topic; bonding and structure)
SOLID STATE OF MATTER

A solid is a substance of definite shape, high density and with strong intermolecular
forces of attraction between its molecules.
The solid state in terms of kinetic theory of matter

According to the kinetic theory, the molecules, atoms or ions in a solid are closely packed
and orderly arranged. Movement of the particles is restricted to vibration or oscillation
about mean/fixed positions. This makes solids incompressible. Attraction between the
particles is even more dominant.
The slight motion observed in a solid at ordinary temperatures is shown by the fact that
two solids when placed in close contact may diffuse very slightly into each other and also
by the fact that solids can exert a vapour pressure. The vapour pressure of a solid at
normal temperature is so small to be negligible but some solids like iodine and
naphthalene exert considerable vapour pressures at temperatures below their melting
points. On heating, they sublime (change directly to gas) and on cooling, the vapour
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Majority of solids melt into liquid when heated because the cohesive forces between their
molecules are broken and can no longer hold them together.
Phase changes in solids

1. Melting point
Melting point of a solid is the constant temperature at which the solid and liquid
phases are in equilibrium at a given external pressure.
In a solid, the particles are in a constant state of vibration. When a solid is heated, energy
is absorbed and the amplitude of vibration increases. The solid melts and the heat energy
of its particles increases sufficiently to overcome the cohesive forces which hold them
together. The process is a gradual one and the temperature remains constant even though
heat is being supplied. Solids which have covalent and ionic bonds usually require a
higher amount of energy to melt than those held by hydrogen bonds or van der Waals
forces.
2. Freezing point

Freezing point is the constant temperature at which the liquid and solid phases are in
equilibrium at a given external pressure.
The freezing point of a substance in its liquid form is the same as the melting point of its
solid form and depends on factors such as purity of the substance and its external
pressure.
3. Sublimation
A solid which when heated changes directly into vapours without an intermediate liquid
stage, is said to have undergone sublimation. Every solid exerts a vapour pressure
although it is usually very small. The vapour pressure of solids increases with increase in
temperature. When the vapour pressure of a solid reaches the external pressure before it
melts, then the solid will vapourise before it melts (it sublimes). Such substances include
iodine, solid carbon dioxide (dry ice), naphthalene, camphor, etc.
4. Deposition
Under certain conditions, a gas can transform directly into a solid without passing
through the liquid phase by a process called deposition. Examples are conversion of
water vapour to ice and soot deposition on the walls of chimneys
Types of solids
Giant ionic solids
Ionic compounds are formed when metallic elements combine with non-metallic
elements. The ionic bonds formed in these compounds are strong electrostatic attractions
between the ions of opposite charges (cations and anions).
Each ion is surrounded by the greatest number of oppositely charged ions called the
coordination number. Examples of giant ionic solids include sodium chloride, caesium
chloride and zinc blende.
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In sodium chloride, each sodium ion is surrounded octahedrally by six chloride ions,
and each chloride ion is surrounded by six sodium ions.
In caesium chloride, each caesium ion is surrounded by eight chloride ions, and each
chloride ion is surrounded by eight caesium ions.

In zinc blende, each zinc atom is surrounded tetrahedrally by four Sulphur atoms, and
each Sulphur atom is surrounded by four zinc atoms. The structure is similar to that of
diamond
Giant ionic solids have the following properties;

(a) They have high melting and high boiling points due to the strong electrostatic
attractions between the ions that require a high amount of energy to break.
(b) They are strong electrolytes in molten state or when dissolved in solution because
ions become free to move.
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(c) Soluble in polar solvents like water because they consist of oppositely charged ions
but insoluble in organic solvents like ether and benzene.
(d) Very hard and brittle.
Giant covalent solids

Covalent bonds are formed between atoms of non-metallic elements. When many very
strong covalent bonds link one atom to another to form an extensive three dimensional
lattice, a giant covalent structure is formed.
Examples of giant covalent solids include diamond, graphite, silicon and fullerene.
In diamond, each carbon atom is covalently bonded to four other carbon atoms to form a
tetrahedral structure which is continuous to form a 3-dimensional giant covalent
structure. The giant covalent structure has very many strong covalent bonds between
carbon atoms which require a high amount of energy to break. This is why diamond is
very hard and strong. All the four valence electrons of each carbon atom are used for

bonding and none is delocalized. This makes diamond a non-conductor.
Carbon atoms
Strong covalent bonds
In graphite, each carbon atom is covalently bonded to three other carbon atoms to form
two dimensional layers of hexagonal rings of carbon atoms. The hexagonal layers held
together by weak Van-der-Waals‟ forces of attraction which allow the layers to slide over
each other, a reason as to why graphite is soft and slippery, hence acts as a solid
lubricant. For each carbon atom, one electron is not used for bonding. These electrons,
one per carbon atom, are delocalized and used by graphite to conduct electricity.
Strong covalent bond

Layer one
Weak van der Waals forces
Carbon atoms
Layer two
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Silicon also has a giant covalent diamond like structure. Each silicon atom is covalently
bonded to four other silicon atoms to form a tetrahedral structure which is continuous to
form a giant covalent structure.
Fullerene
Fullerene is an allotrope of carbon whose molecule contains a range of 30-70 carbon
atoms. The carbon atoms are joined by single and double covalent bonds to form a closed
mesh like structure, which is also a giant covalent structure with fused rings of five to
seven carbon atoms each. The molecule can be a hollow sphere or in form of many other
shapes and sizes. The most common fullerene is .

Giant covalent solids have high melting points and are non-volatile due to the strong
covalent bonds holding the atoms together.
Molecular covalent solids

Iodine and phosphorus are molecular covalent solids.
Iodine is a diatomic molecule ( ) in which the iodine atoms are held by strong covalent
bonds. However, the diatomic iodine molecules interact through weak van der Waals
forces of attraction. When iodine is heated, the weak van der Waals forces are broken and
the molecules are set free, making iodine to sublime.
Covalent bond between two Van der Waals forces holding iodine molecules
iodine atoms in the iodine
molecule
Both white phosphorus and red phosphorus exist a tetratomic molecule ( ). They are
molecular covalent solids. White phosphorus has the four phosphorus atoms joined by
covalent bonds but the tetratomic molecules are held by weak van der Waals forces
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which require a low amount of energy to break. This is why white phosphorus has a low
melting point. Red phosphorus has the four phosphorus atoms joined by covalent bonds
and the tetratomic molecules are also held by strong covalent bonds which require a low
amount of energy to break. This is why red phosphorus has a high melting point
White phosphorus Red phosphorus
Giant metallic solids

A metallic solid consists of a lattice of ions with the outer most electrons forming a “sea”
of delocalized electrons. The delocalized electrons freely move throughout the structure
and can conduct electricity. Electrostatic attractions exist between the delocalized

electrons and the metal ions. The giant metallic structures occur in metals such as iron,
copper, titanium, etc.
Solid copper has a giant metallic structure which consists of a lattice of copper ions
surrounded by a sea of delocalized electrons moving randomly throughout the lattice of
regularly spaced positive ions. Strong metallic bonds hold the crystal together. Copper
has a face centred cubic close packed structure. Iron has a body centred cubic structure
and titanium has a hexagonal close packed structure.
Giant metallic solids have the following properties;
1. High melting and boiling points because a high amount of energy is required to break
the strong metallic bonds. Melting point increases as the number of electrons
contributed per atom of a metal towards metallic bonding increases.
2. Good conductors of electricity and heat due to presence of free mobile electrons
throughout the lattice. They conduct heat due to exchange of kinetic energy between
free mobile electrons in the lattice.
3. Strong but malleable and ductile.
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4. Insoluble in polar and non-polar solvents. The metal-metal attractions are much
stronger than the metal-metal attractions or the metal-solvent attractions. The solvent
molecules cannot penetrate the metal lattice.
EMPIRICAL FORMULA, MOLECULAR FORMULA AND

PERCENTAGE COMPOSITION BY MASS
The percentage composition by mass of an element or a molecule in a
compound
From the formula of a compound and the relative atomic masses of the elements in it, the
percentage of each element or molecule in the compound can be determined. This is
called percentage composition by mass.

Examples
1. The Single Superphosphate(SSP) fertilizer is common phosphatic fertilizer

chemically known as calcium dihydrogenphosphate. Calculate the percentage of
phosphorus in the fertilizer.
2. State the element with the highest percentage by mass in one mole of copper(II)
sulphate-5-water.
Therefore oxygen has the highest percentage by mass in copper(II) sulphate-5-water.

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3. Calculate the percentage by mass of water of crystallization in diammonium

iron(II) sulphate-6-water, .
4. A hydrated aluminium sulphate contains 8.1% by mass of aluminium. Calculate

the percentage by mass of the water of crystallization in it.

Exercise
1. Calculate the percentage by mass of the named element in each of the following
compounds
(a) nitrogen in Sodium nitrate
(b) nitrogen in Ammonium sulphate
(c) magnesium in magnesium nitride
(d) bromine in calcium bromide
2. Calculate the percentage of water of crystallization in;
(a) sodium carbonate decahydrate
(b) Iron(II) sulphate heptahydrate
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3. A metal sulphate, contains 28% by mass of metal Y. Determine the relative

atomic mass of Y and the relative molecular mass of
4. Hydrated iron(III) sulphate, contains 19.9% by mass of iron. Find
the value of Y.
Empirical formulae and molecular formulae

The empirical formula is the simplest formula that expresses the simplest ratio of the
atoms present in a given compound. It is the formula obtained by experimental analysis
of a compound and it can be related to a molecular formula only if the molecular weight
is known.
The molecular formula simply gives the types and numbers of atoms present. The
formula of a compound showing the number and types of the atoms present in one
molecule of the compound, but not the arrangement of the atoms. For example,
represents the molecular formula both of ethanol and methoxymethane
. The molecular formula can be determined only if the molecular mass is

known. The molecular mass can be obtained from the following known formulae;
(i)
(ii)
(iii)
(iv)
(v) Data from colligative properties.
The molecular formula can be got from the empirical formula using the relationship;
Molecular formula can be the same as empirical formula if

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Name of compound Empirical formula Simplest ratio Molecular formula Value of

Ethanoic acid 1:2:1
Glucose 1:2:1
Water 2:1
Ethene 1:2
Benzene 1:1
Phosphorus(V) oxide 2:5
The table above shows the empirical formula-molecular formula relationship for some
compounds.
Note; during the process of obtaining the empirical formula, the simplest ratio is obtained
as a decimal fraction. This ratio should have whole numbers only. Therefore figures of
the type 1.1, 1.2, 2.7, 3.8 and 4.9, can be rounded off to 1,1,3,4 and 5 respectively.
However, values of the type; 1.333, 2.4, 1.5, and 3.666 should not be rounded off.
Rounding them off creates a very big error. They must be multiplied by a factor to make

them whole numbers as summarized below.
Sample calculated ratio Factor Correct ratio
1 : 1.333 3 3 : 4
1.5 : 2 2 3 : 4
2 : 2.499 2 4 : 5
1 : 3.666 : 3 3 3 : 11 : 9
3 : 2.4 2 6 : 5
Calculations on empirical formulae and molecular formulae
Examples
(a) From percentage composition
1. An organic compound Y contains 66.7% carbon, 11.1% hydrogen and the rest
being oxygen. If the vapour density of Y is 36, determine its molecular formula.
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2. A compound Q contains 54.5% carbon, 9.09% hydrogen and the rest being
oxygen.
(a) Calculate the empirical formula
(b) 0.542g of Q occupies 148cm3 at a temperature of 20 and a 740mmHg
pressure. Determine the molecular formula of Q.
(c) If Q which produces effervescence with magnesium powder, deduce its
structural formula.
(a)

(b)
( )
(c) Hint; its carboxylic acids that form hydrogen

when reacted with magnesium.
( )
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3. A compound J contains 62.1% carbon, 10.3% hydrogen and the rest being
oxygen. If J has a density of at s.t.p;
(a) Determine the empirical formula of J
(b) Molecular formula of J
(a)

(b)
( )
(b) From combustion data

4. When a hydrocarbon L was burnt in excess air, 14.4g of water and 13.44dm3 of
carbon dioxide were obtained at s.t.p.
(a) Determine the empirical formula of L.
(b) If the vapour density of L is 22. Determine the molecular formula of L.
(a)
( )
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(b)
5. When 0.236g of organic compound Q on combustion gave 0.528g of carbon

dioxide and 0.324g of water. If the same mass of Q at s.t.p gave 44.8cm3 of
nitrogen gas, determine the molecular formula of Q if its relative molecular mass
is 59.
( )
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(c) From other experimental data

One analytical method for determination of molecular formula of a hydrocarbon is
Eudiometry which uses Avogadro‟s hypothesis, “equal volumes of different gases at
the same temperature and pressure contain the same number of molecules”. i.e. doubling

the number of molecules present doubles the volume at constant pressure. In this process,
an unknown volume of a gaseous hydrocarbon is exploded with excess oxygen. The
hydrocarbon completely burns to form carbon dioxide and water as the only products.
The vapour is then cooled and contraction in volume occurs due to condensation of water
vapour. The resultant volume (residual gas) left is due to carbon dioxide formed and the
unreacted oxygen. The volume of carbon dioxide is determined by adding aqueous
sodium hydroxide or potassium hydroxide. All the carbon dioxide formed is absorbed
and the diminution (reduction) in the volume of the gases is due to carbon dioxide. The
volume of gas that remains at this point is the unreacted oxygen. The volume of water
formed is regarded as negligible.
( )
Assume J cm3 of hydrocarbon was exploded in Q cm3 of excess oxygen to form V cm3 of gas. On
addition of concentrated potassium hydroxide, the volume reduced to W cm3.
Volume of carbon dioxide formed is
Volume of oxygen that reacts is
From the above equation,
Relating the volumes;
Similarly; ( )
Relating the volumes;
( )
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6. 20 cm3 of a hydrocarbon Z was exploded with 200 cm3 of oxygen. On cooling to

room temperature, the residual gases occupied 160 cm3. When the residual gases
were passed through sodium hydroxide solution, the volume reduced to 20 cm3.
(a) Write equation for the reaction between Z and oxygen.
(b) Determine the molecular formula of Z.
(c) Compound Z burns with a sooty flame. When Z was treated with hot
alkaline potassium manganate(VII) solution followed by dilute
hydrochloric acid, compound T was formed. T reacts with magnesium
ribbon liberating hydrogen gas.
(a) Identify Z and T
(b) Write equation to show how Z can be obtained from an alkyne.
(a) ( )

(b) Volume of carbon dioxide formed is
Volume of oxygen that reacted
Similarly; ( )
( )
( )
(c) Hint; burning with a sooty flame indicates Z is aromatic. On reacting it with
alkaline potassium manganate(VII) solution followed by dilute hydrochloric
acid, the compound T formed is a carboxylic acid since it liberates hydrogen
gas when reacted with magnesium.
(i) Z is
and T is
(ii) Try this on your own (convert ethyne to methylbenzene)

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7. 15 dm3 of gaseous hydrocarbon X was exploded with 105dm3 of excess oxygen.

The residual gas occupied 75dm3. On addition of concentrated potassium
hydroxide, the volume reduced by 45dm3. Determine the molecular formula of X.
( )
Volume of carbon dioxide formed
Volume of unreacted oxygen
Volume of oxygen that reacted
Similarly; ( )
( )

( )
( )
8. When 142cm3 of a hydrocarbon Y, of formula, and molecular mass 58g

was exploded with excess oxygen and cooled to room temperature, the volume of
the residual gas was 694cm3. On treatment with concentrated potassium
hydroxide solution, the volume decreased to 126cm3.
(i) Determine the molecular formula of Y.
(ii) Write the structural formula and IUPAC name of all possible isomers
of Y.
( )
(i) Volume of carbon dioxide formed is

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(ii)
Structural formula of isomer Name of isomer
Butane
2-Methypropane
Questions
Note; some of the questions in this exercise will require you to apply knowledge
from either other topics or branches of chemistry. Feel free to consult those topics
or consult your teacher or wait for them to be covered and revisit the questions.

1. Compound G, with molecular mass 237.9g, contains 24.8% cobalt, 29.8% chlorine,
the rest being water of crystallisation.
(a) Calculate the empirical formula
(b) Determine the molecular formula of G.
2. 0.464g of an organic compound Q when burnt gave 1.32g of carbon dioxide and
0.315g of water. When 0.2325g of Q was separately burnt, 7.08 cm3 of nitrogen gas at
s.t.p was produced. Determine the molecular formula and structural formula of Q if its
relative density is 46.5.
3. 1.363g of compound Y containing carbon, hydrogen and bromine on complete
combustion gave 1.10g of carbon dioxide and 0.45g of water. When 0.35g of Y was
vapourised, it occupied 39.5cm3 at 20 and 750mmHg. Calculate;
(i) the simplest formula of Y
(ii) the molecular formula of Y
(b) Y forms a compound Z when treated with a mixture of potassium hydroxide and
an alcohol under reflux. Z reacts with ammoniacal silver nitrate to form a white
precipitate Q. Identify Y, Z and Q.
(c) Write;
(i) equation for the reaction between Z and ammoniacal silver nitrate solution.
(ii) the mechanism for the reaction leading to formation of Z.
4. (a) A gaseous hydrocarbon Q contains 90% carbon. The density of Q is
at stp. Determine;
(i) the empirical formula of Q
(ii) the molecular formula of Q.
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(b) Q forms a white precipitate with ammoniacal silver nitrate solution. Identify Q.
(c) Using equations only, show how Q can be synthesized from propanoic acid.
5. (a) When 2.3g of a compound P, containing carbon, oxygen and hydrogen was burnt
in excess oxygen, 2.2g of carbon dioxide and 0.9g of water was produced. Calculate
the empirical formula of P
(b) The density of P is 2.0536 at s.t.p. Determine the molecular formula of P.
(c) P dissolves in sodium hydrogencarbonate solution with effervescence. Write the
structural formula of P.
(d) State what would be observed and write equation for the reaction that would take
place when a solution of P is treated with:
(i) acidified potassium manganate(VII) solution
(ii) Fehling‟s solution.
6. 20cm3 of a gaseous hydrocarbon W were exploded with 120cm3 of Oxygen. After the
explosion, the volume of gases remaining was 90cm3 and this decreased to 50cm3 on

treatment with aqueous potassium hydroxide. Determine the molecular formula of the
hydrocarbon.
7. 30cm3 of a gaseous hydrocarbon Z was mixed with 140cm3 of oxygen and exploded.
After cooling to room temperature and pressure, the residual gas occupied 95cm3. On
absorption with concentrated potassium hydroxide solution there was a fall in volume
by 60cm3. Determine the molecular formula of Z.
8. 15 cm3 of a gaseous hydrocarbon were exploded with 105 cm3 of oxygen in a sealed
vessel after cooling, the residual volume occupies 75cm3. On addition of caustic
potash, there was a diminution of volume to 30cm3 Determine the molecular mass of
a hydrocarbon.
9. 30cm3 of a gaseous hydrocarbon Z was exploded with 200cm3 of oxygen, which was
in excess. The residual gas volume was found to be 155cm3 on cooling to room
temperature. The volume of the residual gas reduced to 35cm3 on treatment with
concentrated potassium hydroxide solution.
(a) (i) Write the general equation for the reaction between Z and oxygen
(ii) Calculate the molecular formula of Z.
(b) When Z was treated with ammoniacal copper(I) chloride solution, a red precipitate
was formed.
(i) Identify Z
(ii) Write equation for the formation of the red precipitate.
(c) Z was reacted with water in the presence of dilute sulphuric acid and mercury(II)
sulphate at 60℃. Write equation for the reaction and the accepted mechanism.
(d) Write equations to show how Z can be synthesized from but-1-ene.
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10. When 20cm3 of a gaseous alkyne P, , was exploded with 135cm3 of excess
oxygen and on cooling to room temperature, the residual gas occupied a volume of
105cm3. When the residual gas was passed through concentrated sodium hydroxide
solution, the volume decreased by 80cm3.
(a) (i) Write the equation for combustion of P.
(ii) Determine the molecular formula of P.
(b) Write the structural formulae and names of possible isomers of P.
(c) P reacts with sodium metal in presence of liquid ammonia to form compound Q.
Identify;
(i) P
(ii) Q.
(d) P was bubbled through ammoniacal silver nitrate solution.
(i) State what was observed
(ii) Write equation for the reaction

(e) Write equation and suggest a mechanism for the reaction between;
(i) P and bromine water
(ii) Q and 1-bromopropane
(f) With the aid of an equation, describe how P reacts with water.
11. A compound Z, whose molecular mass is 142, contains 16.9% magnesium, 33.8%
carbon, 45.1% oxygen, and the rest being hydrogen.
(a) (i) Determine the empirical formula of Z.
(ii) Work out the molecular formula of Z.
(b) On heating, Z decomposes to form a white residue, X and a gas Y that forms a
yellow precipitate with 2,4-dinitrophenylhydrazine in acidic medium.
(i) Deduce the chemical formula of Z.
(ii) Identify X and Y.
(c) Write equation for the reaction that;
(i) takes place when Z is heated.
(ii) leads to formation of the yellow precipitate.
(d) (i) State what will be observed when dilute sulphuric acid is added to X.
(ii) Write equation for the reaction between dilute sulphuric acid and X.
(e) Write;
(i) the mechanism for the reaction in (c)(i)
(ii) equation(s) for conversion of Y to ethene.
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12. A solid inorganic sulphate contains 9.76% of magnesium 13.00% of sulphur and
51.22% of water.
(a) Determine the empirical formula of the compound.
(b) Hence determine the molecular formula of the compound (the molecular mass of
compound is 245)
(c) Name the reagent(s) that can be used to confirm the ions present in the compound.
In each case state what is observed.
13. An organic compound Y consists of 48.6% carbon, 8.1% hydrogen and the rest being
oxygen.
(a) Determine the empirical formula of Y.
(b) 0.453g of a vapourised sample of Y occupied 200cm3 at 100℃ and 95.0kPa
pressure.
(i) Calculate the molecular mass of Y.
(ii) Determine the molecular formula of Y.

(c) Y reacts with magnesium metal with evolution of a gas. Write;
(i) the structural formula of Y
(ii) the equation for the reaction between Y and magnesium.
14. (a) An organic compound, Z, contains carbon 80%, hydrogen 6.7%, the rest being
oxygen. Calculate the empirical formula of Z.
(b) 0.25g of Z when vapourised at 150℃ and 760mmHg occupies .
Determine the:
(i) molecular mass of Z
(ii) molecular formula of Z
(c) Z burns with a yellow sooty flame and forms a yellow-orange solid with
Brady‟s reagent. Z also reacts with a solution of iodine in sodium hydroxide to
form a yellow solid.
(i) Identify Z
(ii) Write the mechanism for the reaction between Z and Brady‟s reagent.
15. (a) A compound Y contains 22.6% by mass of oxygen, 8.57% by mass hydrogen and
the rest being carbon.
(iii) Calculate the empirical formula of Y.
(iv) When 0.3g of Y was vapourised at ℃ and 700mmHg , it occupied a
volume of . Determine the molecular formula of Y.
(b) Y forms a yellow precipitate with 2,4-dinitrophenylhydrazine and does not react
with Tollen‟s reagent.
(c) Write equation for the formation of the yellow precipitate in (b).
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16. (a) A compound P contains carbon, hydrogen and oxygen. 0.0291g of P on

combustion gave 0.0581g of carbon dioxide and 0.0239g of water.
(i) Calculate the empirical formula of P.
(ii) When 0.14g of P was vapourised at 20℃ and 740mmHg pressure, it
occupied a volume of 39.5 . Determine the molecular formula of P.
(b) When P was treated with sodium bicarbonate, effervescence of a colourless
gas occurred. Identify P.
(c) P was treated with iron(III) chloride solution. State what was observed and
write equation for the reaction that takes place.
17. A compound Q contains 63.7% lead, 14.8% carbon, 1.8% hydrogen and the rest being
oxygen. When vapourised, 0.225g of Q occupy 15.5 cm3 at standard temperature and
pressure.
(a) (i) Calculate the empirical formula of Q.
(ii) Deduce the molecular formula of Q.

(b) Compound Q decomposed on heating to form a yellow residue on cooling and a
colourless vapour that turned limewater milky and formed a yellow precipitate
with 2,4-dinitrophenyl hydrazine in presence of sulphuric acid.
(i) Write the name and formula of Q.
(ii) Write equation leading to formation of the yellow precipitate.
18. A compound P contains 52.2% carbon, 13.0% hydrogen and the rest being oxygen.
(a) Determine the empirical formula of P
(b) When vapourised, 0.1g of P occupied 78.8 cm3 at 157℃ and a pressure of
740mmHg.
(i) Calculate the formula mass of P
(ii) Determine the molecular formula of P.
(c) Write the structural formulae of all possible isomers of P
(c) P does not react with sodium metal. Identify P.
(d) Write an equation to show how P can be prepared from methanol.
19. (a) An organic compound A contains carbon, hydrogen and oxygen only. On
combustion, 0.463g of A gave 1.1g carbon dioxide and 0.563g of water. Determine
the empirical formula of A
(b) When vapourised, 0.1g of A occupies at ℃ and . Determine
the molecular formula of A.
(c) A reacts with sodium metal with evolution of a gas. Write the structural formula
of all possible isomers of A.
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(d) A reacts with anhydrous zinc chloride and concentrated hydrochloric acid to give a
cloudy solution in about 5 minutes.
(i) Identify A
(ii) Show how A could be synthesised from but-2-ene
20. A solid inorganic nitrate contains 9.37% by mass of magnesium, 10.93% nitrogen and
42.18% of water. Determine the molecular formula of the nitrate if its molecular mass
is 256.
21. When 0.203g of hydrated magnesium chloride, , was dissolved in water
3
an titrated with 0.1M silver nitrate solution, 20.0cm of the silver nitrate solution was
required for complete reaction. A sample of the hydrated chloride lost 53.2% of its
mass when heated in a stream of hydrogen chloride gas. Calculate the value of x and
n.
22. A compound Z contained 19.1% nitrogen, 43.6% oxygen and the rest being
manganese.

(i) Calculate the empirical formula of Z
(ii) 10g of Z in 1000g of water lowered the freezing point of water by 0.127oC.
Calculate the molecular formula of Z ( for water is )
(b) When Z was strongly heated, brown fumes were given off. Z dissolved in water
to form a pink solution which decolourises acidified potassium manganate(VII)
solution. Identify Z.
(c) State what would be observed and write equation(s) for the reaction(s) that took
place when to the solution in (b) was;
(i) added concentrated nitric acid and lead(IV) oxide and the mixture boiled.
(ii) sodium carbonate solution was added
23. (a)When 0.1g of aluminium was vapourised at 350 oC and a pressure of 1 atmosphere,
19.2 cm3 of vapour was formed.
(i) Calculate the relative molecular mass of aluminium chloride.
(ii) Write the structural formula and molecular formula of aluminium chloride
in the gaseous state at 350 oC.
(b) Aluminium chloride is normally contaminated with traces of iron(III) chloride.
(i) Name one reagent that can be used to detect the presence of iron(III) ion in a
contaminated solution of aluminium chloride.
(ii) State what would be observed if the contaminated aluminium chloride solution
was treated with the reagent you have named in (b)(i)
(iii) Write equation for the reaction leading to the observation you have stated in
(b)(ii)
(c) Water was added drop wise to aluminium chloride.
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(i) State what was observed.

(ii) Write equation for the reaction that took place.
(d) State one use of aluminium chloride in organic synthesis.
24. When 0.13g of a chloride of iron was vapourised at 600K and 1 atmosphere, 20 cm3
of a vapour was formed.
(a) Calculate the relative molecular mass of the chloride of iron.
(b) Determine the;
(i) Molecular formula of the chloride of iron,
(ii) Structural formula of the chloride of iron in vapour phase.
25. An organic compound, Q contains 58.8% carbon, 9.8% hydrogen and the rest
oxygen.
(a) Calculate the empirical formula of Q.
(b) Determine the molecular formula of Q
(c) (i) Q reacts with aqueous sodium hydroxide under reflux to produce propan-1-ol

as one of the products. Identify Q.
(ii) Write an equation to show how R can be synthesized from propan-1-ol
and indicate a mechanism for the reaction.
26. A compound Q contains 60.0% carbon, 13.3 % hydrogen and the rest being oxygen.
(a) Calculate the simplest formula of Q.
(b) When 0.698g of Q was dissolved in 100g of a solvent, there was 0.19 oC
depression in freezing point of the solution. ( Kf of the solvent = 1.630C)
Calculate;
(i) The empirical formula of Q
(ii) The molecular formula of Q
(c) Write the names and structural formulae of all possible isomers of Q.
(d) When Q was reacted with iodine in aqueous sodium hydroxide, a yellow precipitate
was formed.
(i) Identify Q
(ii) Write equation for the reaction between Q and iodine in aqueous sodium
hydroxide.
(iii) State what would be observed when Q is reacted with acidified potassium
dichromate(VI) solution and name the major organic product.
(e) When Q was heated with excess concentrated sulphuric acid, a gas W which turned
the purple solution of acidified manganate(VII) to colourless was evolved. Write
equation for the reaction between:
(i) Q and sulphuric acid and suggest a mechanism for the reaction.
(ii) W and acidified manganate(VII) ions and name the product.
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(f) Suggest a plausible mechanism for the reaction between Q and hot concentrated
sulphuric acid.
27. A compound Q contains 76.32% carbon, 6.38% hydrogen and the rest being oxygen.
A solution of Q in water is acidic but does not liberate carbon dioxide from
carbonates. A solution of 1.50g of Q in 20.90g of benzene freezes at 1.3℃ while pure
benzene freezes at 5.50℃.
(a) Determine;
(i) the empirical formula of Q.
(ii) the molecular formula and write the structural formula of Q.
(
(b) Explain why a solution of Q in water is acidic.
(c) Describe the reaction between Q and bromine water.
(d) Write equation and outline mechanism for the reaction between Q and;
(i) ethanoylchloride

(ii) chloromethane in presence of sodium hydroxide.
(e) Write equations to show how Q can be;
(i) Prepared from benzene and propene.
(ii) Converted to methylbenzene.
28. (a) An organic compound Z contains by mass 51.90% carbon, 4.86% hydrogen and
the rest being bromine. Determine the empirical formula of Z.
(c) When 0.8g of Z was vapourised at 80℃ and a pressure of 700mmHg, it occupied a
volume of 136 cm3. Determine the molar mass of Z.
(d) Deduce the molecular formula of Z.
(e) When Z was heated with excess sodium hydroxide solution, it formed a
compound Y. On heating Y with acidified manganese(IV) oxide, a substance W
was formed. W formed a yellow precipitate with 2,4-dinitrophenylhydrazine in
presence of dilute sulphuric acid but gave no observable change with aqueous
ammonia in the presence of silver nitrate solution.
(i) Write the chemical equation leading to formation of substances Y and W
indicating all reagents and conditions.
(ii) Write the chemical equation for the reaction between substance W and
semicarbazine in presence of dilute sulphuric acid. Outline the mechanism for the
reaction.
(iii) Write equation(s) to show how compound Y can be synthesized from benzene.
Indicate the necessary conditions and reagents.
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29. 8.15g of a saturated bromocompound X, with a general formula of

contains 49.08% by mass of bromine.
(a) (i) Determine the molecular formula of X.
(ii) Write the name and structures of possible isomers of X.
(b) When X was heated with sodium hydroxide , a product Y was formed.
When Y was heated with concentrated orthophosphoric acid, cyclohexene was
formed.
(i) Name X and Y.
(ii) Write equation for the reaction between X and sodium hydroxide and
that for formation of cyclohexene.
(c) Discuss the reactions between X and;
(i) Sodium hydroxide
(ii) Silver ethanoate
(iii) Phenol

(Your answer should include conditions and mechanisms for the
reactions)
30. (a) A gaseous hydrocarbon X contains 11.11% by mass of hydrogen.
(i) Calculate the empirical formula of X.
(ii) If the vapour density of X is 27, determine the molecular formula of X.
(iii) Write the structural formulae and IUPAC names of all possible isomers of X.
(b) 1 mole of X reacts completely with 1 mole of hydrogen gas in the presence of
nickel catalyst at 150℃. Identify X.
(c) When X was warmed with a mixture of concentrated sulphuric acid and water,
substance Y was formed. Y was readily oxidised to compound Z when treated
with hot acidified potassium dichromate solution. Identify;
(i) Y
(ii) Z
(d) Write equation for the reaction and suggest a mechanism for the reaction when;
(i) X was warmed with a mixture of concentrated sulphuric acid and water
(ii) Z was reacted with acidified solution of semicarbazide.
31. An organic compound ,T , on complete combustion yielded 13.2g of carbon dioxide
and 2.7g of water. When 4.7g of T was vapourised at standard temperature and
pressure, it occupied a volume of .
(a) (i) Calculate the empirical formula of T
(ii) Determine the molecular formula of T.
(b) T burns with a sooty flame. Identify T
(c) Discuss the reactions of T with;
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(i) Bromine
(ii) Propene
(iii) Ethanoylchloride.
(Your answer should include conditions for the reactions and
mechanisms for the reactions where applicable)
(d) Write equation to show how T can be synthesized from benzaldehyde.
32. A compound Y contains by mass 61.02% carbon, 15.25% hydrogen and the rest
being nitrogen.
(a) Determine the empirical formula of Y
(b) Compound Y has a density of at s.t.p. Determine the molecular
formula of Y.
(c) Write the structural formula of possible isomers of Y.
(d) Compound Y forms yellow oils when reacted with cold concentrated hydrochloric
acid and sodium nitrite.

(i) Identify Y
(e) (i) Name the reagent that can be used to confirm the functional group in compound
Y.
(ii) State the observation made
(iii) Write equation for the reaction for the reaction that takes place when the
named reagent in (e)(i) is reacted with compound Y.
Questions 22, 26 and 27 will be simpler after covering colligative properties in Phase
equilibria and gaining more knowledge of organic chemistry.
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CHAPTER TWO
ATOMIC STRUCTURE AND THE PERIODIC
TABLE
Fundamental particles of the atoms and radioactivity
Historical development of the atomic theory
It was the Greek philosophers Democritus and Leucippus who first considered the idea
that matter is made up of particles in about 400BC. This was later supported by Boyle
and Newton. The idea was however not accepted because there was no experimental
evidence for it.
In 1808, a Manchester school teacher, John Dalton restated and extended the older

concepts. He gathered experimental evidence with which people were convinced. In his
Atomic Theory, Dalton said that “matter is made up of atoms”. Dalton, however never
dreamt that anyone would be able to see an atom.
Modern instruments like X-ray diffraction and advanced microscopes have provided
direct evidence for existence of atoms
Modern theory of the atom

(a) John Dalton’s atomic theory
The main points in Dalton‟s Atomic theory can be summarized as follows;
 All matter is made up of tiny particles called atoms.

 The atoms are chemically indivisible, indestructible and cannot be created.
 All the atoms of any one element are identical i.e. they have the same mass, same
volume and the same chemical properties.
 Atoms of different elements have different mass, volume and chemical properties.
 Chemical combination occurs between elements by atoms joining in small whole
numbers to form a small group of atoms chemically combined together. Dalton
called such a group “a compound atom”. It is now called a molecule.
By using Dalton‟s theory, we can clearly understand that;
When a reaction occurs in a closed vessel, all the atoms present before the reaction are
still present after the reaction. They just merely become rearranged. Since the masses of
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the atoms are constant, the total masses of the substances before and after the reaction
should be the same.
Point of thought; What can make us disagree with Dalton on the

question whether atoms can be created or destroyed or split?
(b) The J.J Thomson model of an atom

Although John Dalton had thought that the atom could not be broken down into anything
simpler, physicists further investigated whether atoms could be made of smaller particles.
In 1895, Crookes, through his experiments on the discharge of electricity through gases at
low pressure, he discovered that a beam of rays was given off by the cathode (the
negative electrode). He called them cathode rays. He also showed that cathode rays
behave like negatively charged particles.

In 1897, Sir Joseph John Thomson, as a result of experimental work still on the
conduction of electricity through gases at low pressure, measured the velocity of cathode
rays and the value of charge to mass ratio of the cathode rays. He obtained the same value
of ⁄ regardless of which gas he used.
 J.J. Thomson therefore deduced that negatively charged particles were present in
all matter.
 The negatively charged particles were named electrons and were recognized as
particles of which an electric current is composed
 He described an atom as a sphere of positive electricity in which negative electrons
are embedded
Point of thought; What is the main difference between this J.J.Thomson’s

model and Dalton’s model?
J.J. Thomson‟s atomic model is popularly known as the plum pudding model. However,
it had to be abandoned in 1911 on both theoretical and experimental grounds in favour of
Rutherford‟s atomic model.
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(c) Ernest Rutherford’s atomic model

In 1909, Rutherford and colleagues found out that when particles from a Radium
source were directed to a very thin sheet of gold or platinum foil;
 The particles penetrated the gold foil

 A great majority of the particles passed through the foil without change in
direction.
 A small fraction (about 1 in 20,000) of the particles were scattered deflected
through large angles( as high as or more)
Scattered particles
Undeflected particle
Nucleus

To explain the above facts; Rutherford deduced that;
 Since particles are positively charged, the few deflections that occurred were
because the protons of the atom are collected in a heavy, small positively charged
central nucleus which makes up just a tiny fraction of the atom.
 Since most of the particles passed through the gold foil undeflected, most of the
atom is empty space and the electrons rotate in this space around the nucleus in the
in the same way planets rotate around the sun
The analysis led Rutherford to propose a model in which an atom consists of a very small
positively charged nucleus, in which most of the mass of the atom is concentrated,
surrounded by negatively charged electrons, so that the atom is electrically neutral.
Fundamental particles of the atom

The fundamental particles of an atom include the; protons, neutrons and electrons.
The discovery of the fundamental particles of the atom

The existence of electrons in atoms was first suggested by J.J.Thomson, as a result of
experimental work on the conduction of electricity through gases at low pressures which
produces cathode rays and X-rays, and a study of radioactivity.
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An atom is electrically neutral. This means that if it contains negatively charged

electrons, it must also contain some positively charged particles. These positively
charged particles are the protons and they were discovered after Rutherford‟s
experiments after bombardment of elements with and rays given off by
radioactive elements.
The neutron was discovered by Sir James Chadwick in 1932, by bombarding beryllium
with rays. Chadwick found out that particles which had properties quite different
from those of protons and electrons were given off. They were not deflected at all by
electric and magnetic fields and therefore possessed no charge. The particles had almost
the same mass as a proton. Since they were neutral particles, they were called neutrons.
Later experiments showed that all atoms contain neutrons apart from that of hydrogen.
Properties of the fundamental particles of the atom

Property Electron Proton Neutron

Approximate relative charge
Have equal but opposite charges
Approximate relative mass ⁄
Actual mass (kg)
Have almost equal masses
Charge (C)
RADIOACTIVITY
Discovery
The discovery of radioactivity took place over several years beginning with the discovery
of X-rays in 1895 by Wilhelm Conrad Roentgen. The work continued with Henri
Becquerel who had learnt of Roentgen‟s discovery of X-rays through the fluorescence of
some materials.
In 1896, a year following the discovery of X-rays, A.H. Becquerel found out that
Uranium and Uranium compounds would also emit a penetrating radiation capable of
affecting wrapped photographic plates. He was experimenting on salts which fluoresced(
glowed in the dark). One day he developed a photographic plate which had been left
wrapped in a drawer of his working table to be used the next day. To his surprise, he
found that the plate had been exposed. Since he knew that no light could penetrate the
wrapping, he perhaps thought the plate was penetrated by some rays coming from the
Uranium salts. He though it wise to investigate this mysterious radiation and gave the
problem to a young research worker called Marie Curie.
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Marie Curie later found out that this strange effect happened with all Uranium salts and it
depended on the amount of Uranium present in the compound. She realized that the
ability to give off the radiation was a property of the atoms of uranium and that it was a
completely new type of property quite different from a chemical reaction. Marie Curie
called this property of the Uranium atom radioactivity.
In 1898, Marie Curie‟s husband left his own research work and joined her with this
exciting discovery. They discovered two new radioactive elements. They called one
Polonium, after Marie‟s native country Poland and the other as Radium.
The naturally occurring elements now known to be radioactive are polonium, radon,
radium, actinium, thorium, protactinium, francium and uranium. Elements that are not
naturally radioactive can also be induced to undergo artificial radioactivity.
In 1903, Rutherford put forward the theory that radioactivity was caused by
disintegration or decay of the large heavy atoms of Radium, Uranium etc., into simpler
atoms of other elements.

Definition;
Radioactivity is the spontaneous disintegration of heavier unstable nuclei to form

lighter stable nuclei with emission of radioactive particles such as alpha particles, beta
particles and gamma rays.
Types of radiations and their discovery

When an atom splits, the nucleus divides and the protons and neutrons in it form two new
nuclei. The electrons divide themselves between the two. Radioactive substances
therefore have unstable nuclei.
Three types of radiation are given off by radioactive substances. They include the beta
rays ( ), gamma rays ( ) and alpha rays ( ). All these radiations
cause certain substances such as zinc sulphide to luminesce. They also ionize gases
through which they pass.
Radiation Symbol Nature

Beta rays are streams of high speed electrons emitted by
unstable nuclei
Beta( ) rays N.B. These electrons do not come from the extra-nuclear
part of the atom. Beta particles are distinguished from
electrons by their source and high energy.
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Alpha rays are a stream of helium nuclei called alpha

particles and are emitted with high energies from
Alpha( ) rays radioactive nuclei.
An alpha particle is a positively charged particle
consisting of two neutrons and two protons and is
identical to the nucleus of a helium atom.
Gamma ( )rays Gamma rays are light rays(electromagnetic radiations) of
extremely high energy therefore very short wave lengths
A comparison between the characteristics of the different types of

radiations
Radiation
Property Beta rays Alpha rays Gamma rays
Make up High speed electrons Helium nuclei Electromagnetic
radiations
Mass number Negligible
Charge

Velocity that of light of that of Same as that of light
light
Effect of Deflected towards the Deflected towards the Not deflected
electric field positive pole negative pole
Effect of Deflected much more Deflected in a direction
magnetic field readily and in an opposite that shows that they
direction to that of alpha consisted of positively Not deflected
particles charged particles
Tissue 1 0.01 100
penetration
Penetrating Higher penetrating power very low penetrating Very high penetrating
power than alpha particles power power
(can pass through 0.01m (cannot penetrate more (can pass through 0.1m
of a metal) than through 0.01mm of of a metal)
a metal)
Ionizing power Lower ionizing power Have high ionizing A very low ionizing
than beta particles power power
Some other important particles involved in radioactivity

Particle Symbol
Neutron
Proton
Deuterium
Tritium
Positron
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Radioisotopes
From their name, they are isotopes which are radioactive. They can also be called
radioactive isotopes.
Radioisotopes are heavier unstable atoms of the same element with the same number of
protons but different number of neutrons that undergo spontaneous disintegration to
form lighter stable atoms with emission of radioactive particles such as alpha particles,
beta particles and gamma rays.
Very many radioactive isotopes have been artificially made and are very useful.(check
under applications of radioactivity.
Nuclear reactions
In a chemical reaction, the nature of the elements does not change. For example sodium
reacts with chlorine to form sodium chloride. When molten sodium chloride is
electrolyzed, sodium and chlorine can be got again. This means the nature of sodium and
chlorine has not changed. The sodium atom changes to sodium ion and the chlorine atom

changes to chloride ion. The number of protons and neutrons in the nuclei of the elements
does not change in a chemical reaction. It is only the number of electrons in the extra-
nuclear part that are transferred or shared. In a nuclear reaction however, both the nucleus
and electrons are involved.
Therefore in a chemical reaction, there is no change in the atomic nuclei of the
combining elements whereas in a nuclear reaction, there is a change in the number of
protons in the atomic nucleus of the element.
Differences between chemical and nuclear reactions

Chemical reaction Nuclear reaction
Only the valence (outermost)electrons are There is a change in the composition of the
involved nucleus.
Elements do not lose their identities New elements are formed
The number of protons and neutrons in The number of protons in the atomic nucleus
the atomic nucleus does not change. changes
A small amount of energy is evolved or A very large amount of energy is given out
absorbed
It‟s rate is affected by external factors Not affected by temperature, catalyst or pressure
like temperature, catalysts or pressure changes
Can be reversed by changing the reaction It cannot be reversed( irreversible)
conditions
All isotopes of an element undergo the Isotopes of an element give different products in
same reactions nuclear reactions
Mass is conserved Some of the mass is converted into energy
( )
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Balancing nuclear reaction equations

When balancing nuclear reaction equations, the sum of nucleon numbers (mass
numbers) should be the same on both sides. The sum of the proton numbers (atomic
numbers) should also be the same.
Examples
1. Reactions involving emission of the, alpha particles, beta particles ,gamma rays and
some other particles
(i) Emission of an alpha particle
Consider the reaction;
To balance the equation;

The equation becomes;
Emission of an alpha particle therefore reduces proton
number(atomic number) by 2 units and reduces the mass
number by 4 units
(ii) Emission of a beta particle


Emission of a beta particle therefore has no effect the mass
number on and increases proton number(atomic number)by 1 unit
(iii) Emission of gamma rays


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Emission of a gamma ray therefore has no effect on both

proton number(atomic number) and mass number
(iv) Emission of a neutron


Emission of a neutron therefore has no effect on the proton
number(atomic number) and reduces mass number by 1 unit
(v) Emission of a positron



Emission of a positron therefore reduces the proton
number(atomic number) by 1 unit and has no effect on mass
number.
2. Bombardment by particles
(i) Bombardment of nitrogen-14 by an alpha particle to form oxygen-17
Let the other particle emitted be

The particle with atomic number 1 and mass number 1 is a proton.

(ii) Name the particle that must bombard with Cadmium-113 to convert it to
Cadmium-114 with expulsion of a gamma ray
Let the bombarding particle be

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The particle with atomic number 0 and mass number 1 is a neutron.

(iii) Alpha bombardment of element Y produces two neutrons and astatine-211.
Identify Y.
N.B. Strictly use the atomic number and not the mass number to identify the element
from the Periodic Table
The element with atomic number 83 is .
3. A nuclear reaction can be written in the form;

This in detail means
The reactions shown in the bombardments above can therefore be represented as;
(i)
(ii)
(iii)
4. Other problems
(i) Complete the equation
........
Let the mass number and atomic number of the other product be x and y respectively.
Note that the atomic number got is 0. But there is no element in the Periodic table with
atomic number 0. Therefore this should be the particle but multiplied by 4
The equation therefore becomes;
4
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(ii) Balance the equation

2
Let the mass number and atomic number of the other product be x and y respectively.
The element with atomic number 36 is

The equation therefore becomes;
2
(iii) Determine the number of alpha particles and beta particles that must be
emitted for to transform to .
Let the number of alpha particles and beta particles emitted be x and y respectively
Note that atomic numbers of the elements can be obtained from the Periodic Table

Therefore 2 alpha particles and 3 beta particles must be emitted
(iv) A series of radioactive decays can be represented as;
→ → →
(a) Name the particles 1 and 2
(b) Identify elements X , Y and Z.
(c) State the groups to which X, Y and Z belong.
Equations;
(a) 1 is beta particle

2 is alpha particle
(b) X;
Y;
Z;
(c) X;
Y;
Z;
Questions
1. Explain with use of suitable examples; the terms;
(i) Atom
(ii) Ion
(iii) molecule
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2. (a) Explain what is meant by each of the following terms;

(i) Radioactivity
(ii) Radioactive isotopes
(iii) Nuclear reaction
(iv) nucleons
(b) State the differences between a nuclear reaction and a chemical reaction.
3. (a) Explain the difference between;
(i) a and an
(ii) a proton and a deuteron
(iii) and a helium atom
(b) Explain why when alpha particles are directed to thin metal foils, most of them
pass through and a few are scattered backwards.
(c) State the effect of emission of each of the following on the nucleus of an atom;
(i) a positron

(ii) a neutron
(iii) an alpha particle
(iv) a beta particle
(v) a gamma ray
4. Identify the unknown elements in each of the
following equations using the Periodic Table. Add mass numbers and atomic numbers
wherever they are missing.
(i)
(ii)
(iii)
(iv)
(v)
(vi)
(vii)
5. Complete each of the following equations
(i)
(ii)
(iii)
(iv)
(v) ........
(vi)
(vii)
(viii)
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(ix)
(x)
(xi)
(xii)
(xiii)
(xiv)
(xv)
6. Naming the particle involved in each case, complete each of the equations.
(i)
(ii)
(iii)
(iv)
(v)
(vi)

7. State the atomic number and mass number of the new element formed when;
(i) emits a neutron
(ii) emits a positron
(iii) emits a beta particle
(iv) emits gamma rays
(v) emits an alpha particle
(vi) emits 3 alpha particles and 4 beta particles
(vii) emits 4 alpha particles and 2 beta particles
8. Write well balanced equations for the following nuclear reactions;
(i) (v)
(ii) (vi)
(iii) (vii)
(iv)
9. Write well balanced equations for the following nuclear reactions;

(i) Decay of radioactive phosphorus-30 to form silicon-30 with emission of a
positron.
(ii) Proton bombardment of lithium-7 to form alpha particles
(iii) Fusion of deuterium and tritium to form an alpha particle and a neutron
(iv) Bombardment of nitrogen with and alpha particle to form a proton and
oxygen-12
(v) Uranium loses first one and then a second .
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(vi) Uranium loses first one and then a second .

(vii) loses five .
(viii) loses two .
10. Find the;
(i) the number beta particles and alpha particles that must be emitted for
to transform to .
(ii) the number beta particles and alpha particles that must be emitted for to
decay to .
(iii) the number beta particles and alpha particles that must be emitted for to
decay to .
(iv) the number beta particles and alpha particles that must be emitted for to
transform to .
(v) the number beta particles and alpha particles that must be emitted for to
transform to .

(vi) the number beta particles and alpha particles that must be emitted for to
transform to .
11. (a)A series of radioactive decays can be represented as;
→ → →
State the mass number and atomic number of element Z. Show your working
(b) In a radioactive emission, actinium loses an alpha particle and the product
loses another alpha particle. The product also loses one beta particle. Calculate the
mass number and atomic number of the element that is finally formed.
RADIOACTIVE DECAY
The rate at which a radioactive isotope decays cannot be speeded up or slowed down by
any physical or chemical means. The rate depends on the identity of the isotope and the
amount of isotope present. Radioactive isotopes do not decay at the same rate. Some
decay very rapidly in a few millionths of a second and others can even take billions of
years to decay.
All radioactive decay processes follow first order kinetics.
The rate of radioactive decay at time is directly proportional to the number of

radioactive atoms present. The rate of decay therefore decreases and continues to
decrease as more and more atoms break up.
Therefore if represent number of atoms, then;

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∫ ∫

[ ] [ ]
( )
Equation can also be written in the form shown below
( )
( )
Any of the equations (i) or (ii) can be used any of the unknown values it by substitution
so long as all the others are known.
Since Activity is proportional to number of We can also express the equations in terms of
radioactive atoms present, we can also have the counts per unit time
equations in the form;
( ) ( ) ( ) ( )
We can also express the equations in terms of mass
( ) ( )
Activity of a radioactive sample is the number of disintegrations per second of a

radioactive sample.
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The decay constant is the proportionality between the number of radioactive atoms and
the rate at which the radioactive atoms decay.
Half life
The time taken for a number of radioactive atoms to decay to ⁄ atoms is called the
half-life. The half-life of Radium is about 1600 years. This means that 1g of Radium
decays to 0.5g in 1600 years. 0.5g decay to 0.25g in a further 1600 years, and so on.
Half-life is the time taken for the amount of a radioactive sample to decay to half its
original value.
Derivation of expression for half life
It can be derived using any of the equations (i) or (ii) above
( ) ( )
when decays to half its original value, then at when decays to half its original value, then

⁄ and at ⁄ and
( ) ⁄ ( ) ⁄
⁄ ⁄
⁄
⁄
⁄
⁄
The equation ⁄ can be used to find half life when the decay constant is known or the
decay constant when the half life is known.
Examples
1. A radioactive isotope decays from an initial count of 160 counts per minute to 20
counts per minute in 27 days. Calculate its half-life.
( ) ⁄
( ) ⁄
( ) ⁄
⁄
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2. The nuclide of carbon-14 has a half-life of 5600 years. Calculate the age of a
wood from an ancient tomb, if this wood gave 10 counts per minute per gram of
carbon compared with the 15 counts that are given by the carbon from new
wood.
N.B. This is a process of carbon dating that will be seen later. The counts per minute tend to
reduce after the tree is cut and wood begins to decay. This helps us interpreted the values of and
. Mistaking them will yield a negative value of time. Time cannot be negative!!!
⁄ ( )
( )
⁄
⁄
( )
3. If the decay constant for radium is . Calculate the time

required for 90% of a sample of radium to disintegrate.
( )
( )
( )
4. The half-life of Radium is 1590 years. How long will it take for a sample of
Radium to decay to 25% of its original amount?
⁄
⁄ ( )
⁄
( )
( )
5. The half-life of radioisotope bromine-82 is 36 hours. Calculate the fraction of a

sample of the isotope will remain after one day.
NB. In our previous calculations, you note that units for the decay constant, counts or amount and
time were not consistent but we did not change them. This is because the ratio cancels the units
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out. In this question however, half-life and time should have consistent units.
149
⁄
⁄
( )
⁄
( )
6. The half-life of a radioactive element is 150 seconds. What percentage of the

isotope will remain after 600 seconds?
⁄
⁄
( )
⁄

( )
7. If a sample of a radioactive isotope has a half-life of 3.11 hours and an activity of

1000 at a certain time, calculate the activity one hour later.
⁄ ( )
⁄
( )
⁄
8. It takes 1620 years for 0.03 moles of Radium-226 to decay to 0.015 moles.
Calculate the number of moles of Radium-226 left when 26g decayed for 6 years?
( ) ( )
⁄
⁄
( )
⁄
( )
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Questions
1. A radioactive sample of caesium-136 decays from 480 counts per minute to 60 counts
per minute in 42 days. Calculate its half-life.
2. The half-life of strontium-90 is 29 years. Calculate its decay constant.
3. The disintegration constant of lead-199 is . Determine its half-life.
4. A sample of wood has an activity of . A freshly cut wooden tree has an
activity of . Calculate the age of the wood sample. The half-life of
carbon-14 is 5600 years.
5. A radioactive isotope decays at such a rate that after 68 minutes, only one fourth of its
original amount remains. Calculate its half-life.
6. The half-life of Bismuth is 19.7 minutes. Determine the time taken for 43% by mass
of Bismuth to decay.
7. A radioactive element to a count rate of 120 counts per minute. After 3 hours, it
dropped to 15 counts per minute. Determine the half-life of the isotope.

8. The half-life of Sulphur-31 is 2.54 seconds. How long will it take for 99% of Sulphur-
31 to get converted to phosphorus?
9. 1.0g of strontium-90 was reduced to 0.953g after 2 years. Calculate the half-life of
strontium-90.
10. Radium undergoes radioactive decay according to the following equation forming
relatively stable nuclides and .
→ → →
(a) Identify the particles and .
(b) 0.02 moles of were allowed to decay for years. The half life of
Radium-226 is 1600 years. Calculate the number of atoms of Radium-226 left at
the end of years.
(c) State any two practical applications of radioactive isotopes.

11. (a) (i) The decay law is given in the expression below . State what the
symbols represent.
(ii) Using the above expression derive the expression for relating the half-life
⁄ and the decay constant.
(b) (i) Nickel (63 ) decays to copper (63 ). Name the particle emitted and write the
equation for the reaction.
(ii) Calculate the time taken for of nickel to change to copper. (The half-life
of nickel is 120 years)
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Graphical representation of radioactive decay

The decay of a radioactive substance can be represented graphically by plotting various
kinds of graphs depending on data experimental data provided.
Note that in each of these graphs can be substituted with Activity (A), amount,
Number of moles, mass or counts
( )
( )
A graph of ( ) agaist time(t) is a ( )

straight line through the origin and its slope
is from which can be obtained and

used to find ⁄ from the expression
( )
( )
152
The graph has a slightly different look if

some or all the values of are less than 1.
A graph of agaist time(t) is a straight
line with an intercept on the axis.
This intercept = and can be used to
find the initial amount, . The graph has a
negative slope = from which can be
obtained and used to find ⁄ from the
expression ⁄

( )
A graph of ( ) agaist time(t) is a ( )

straight line through the origin and its slope
can be obtained and used to find ⁄ from
the expression ⁄
( )
153
A graph of agaist time(t) is a straight The graph has a slightly different look if
line with an intercept on the axis. This some or all the values of are less than 1.
intercept = and can be used to find the
initial amount, . The graph has a negative
slope = from which can be obtained
and used to find ⁄ from the expression
The commonest graph is that of Activity or

mass or amount or number of atoms plotted
against time. The uniqueness with this
graph is that it is a curve with a negative

slope. From this graph half-life can be got
directly from the graph and can be used to
find the decay constant using the (units)
expression ⁄ .
Half-life is got by getting the time that
corresponds to and then . The half-life
can then be got by the expression
⁄ . The values and are got
from the graph by and
It is advisable that when plotting graphs on radioactivity, the axes begin from the origin.
Questions
1. (a) State what is meant by the terms
(i) Radioactivity
(ii) Half-life
(b) The table below shows data for radioactive decay of element W.
Time (hours) 0.0 5.0 10.0 15.0 20.0 25.0 30.0

Activity (counts per minute) 25.00 23.00 21.25 19.50 18.00 16.50 15.25
(i) Plot a graph of activity against time
(ii) Determine the half-life of element W.
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(iii) Determine the decay constant and state its units.

2. A sample of bromine was irradiated in a nuclear reactor. The table below shows the
radioactivity count rates at various times
Time(hours) 0 1.0 2.0 5.0 10 25 50 75 100
Count rate 500 268 242 225 204 154 95 55 35
(a) Plot a graph of count rate against time
(b) Use your graph to determine;
(i) half life
(ii) the rate constant in
(iii) order of the reaction
3. The table below shows the results of radioactive decay of
Time(seconds) 20 40 60 80 100 120
Mass of (g) 48.2 38.5 31.5 26.0 21.0 17.2
(a) Plot a graph of against time

(b) Use your graph to determine;
(i) initial mass of
(ii) slope and hence the decay constant of
(iii) half-life of
Nuclear energy
Nuclear energy is energy released during nuclear fission or nuclear fusion. Nuclear
energy has been increasingly used to provide electricity and to drive large ships.
Discovery
In 1935, Enrico Fermi discovered that when a radioactive substance such as Uranium was
bombarded by neutrons, it produced by-products that were not Uranium and were lighter
than the original sample.
In 1938, Otto Hahn, Fritz Strassman, Lise Meitner and Otto Frisch discovered fission.
They found out that the lighter by-products of neutron bombardment on Uranium-235
also released energy. This proved Albert Einstein‟s theory put forth 33 years earlier
that . This was the first time that all the components of fission were known. This
discovery resulted into making of the atomic bomb and nuclear power plants.
Nuclear fission
A very large amount of energy is released in splitting heavy atomic nuclei. Uranium-235
nuclei can be split into smaller elements when a controlled nuclear reaction is carried out.
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Nuclear fission is the process by which a nucleus of a heavier atom is split into nuclei
of lighter atoms, by bombardment with neutrons, with release of a large amount of
energy.
When Uranium-235 is bombarded with neutrons, it undergoes fission to form lighter

elements. The lighter elements include barium ( ), lanthanum ( ), rubidium ( ),
krypton ( ), strontium ( ), and others. Three neutrons are released per Uranium-235
fission. These neutrons produced induce three more fission reactions which release 9
neutrons. The 9 neutrons will also induce nine fission reactions and so on. Therefore a
chain reaction occurs and a large amount of energy is liberated.
The fission products and are unstable too and emit radiations until stable
isotopes are formed.

The energy released in accordance with Einstein‟s law
Nuclear fusion
Nuclear fusion is a process of combining nuclei of lighter atoms to form heavier nuclei
at very high temperature, liberating a very large amount of energy.
The lighter elements include hydrogen, helium and lithium. The energy produced
comes from decrease in mass of the nuclides.
The fusion reactions only take place at extremely high temperature more
than . This is because a very large amount of energy is required for the
positively charged nuclei to overcome strong repulsion between them. The nuclear fusion
reactions are therefore also known as thermonuclear reactions.
Energy from nuclear fusion is used in the hydrogen bomb
Some examples of nuclear fusion reactions include;

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Nuclear power
Nuclear power is electricity created from a nuclear power plant. The heat produced
during fission of Uranium-235 is used to convert water into steam. This steam is used to
drive turbines that generate electricity.
Applications of radioactivity
Radioactive isotope Use/ application
or radiation
Radium-226 In radiotherapy for treatment of cancer
(from Taking radiographs in radiotherapy instead of X-rays
Radium or Radon)
Phosphorus-32 In radioactive tracing for the uptake of phosphorus by a plant from a
phosphate fertilizer
To elucidate the nature of photosynthesis
In carbon dating, to estimate the age of old objects. Living plants and
animals take in carbon which includes a small proportion of carbon-14.

When a plant or animal dies, the carbon-14 present in it starts to decay.
The amount of carbon-14 in the dead object after years is determined as
. The amount of carbon-14 in the similar live object is also determined
Carbon-14 as . Using a known half-life of carbon-14, ⁄ , the decay constant ( )
is determined using the equation ⁄ . The value of is then
substituted in the rate equation ( ) to determine the age of the
object ( ) in years.
Iron-59 To study the role of iron in blood formation
Iodine-131 Diagnosis of thyroid diseases and in research on the functioning of the
thyroid gland and the kidneys
Measure thicknesses in materials. The amount of radiation passing
through a material decreases as the material gets thicker. A source of
is placed on one side of the material and a
detector on the other side. The scale reading on the detector will give a
measure of the thickness.
Cobalt-60 It gives out which are used to kill cancerous cells
Plutonium-239 Plutonium-239 which is produced from Uranium-238 in chain reacting
units is used as a fuel in some nuclear reactors.
To determine the mechanism of esterification of monocarboxylic acids
with primary alcohols. An alcohol with oxygen atom labeled with oxygen-
18 is reacted with the carboxylic acid in presence of concentrated
Oxygen-18 sulphuric acid to form an ester and water. On analysis of the ester and
water formed using a mass spectrometer, it is found that the oxygen-18 is
present in the ester and not in water. This proves that the bond in
the alcohol and bond in the acid cleaved.
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18O 18O
The reverse of esterification is acid alkaline ester hydrolysis. An ester
containing a labeled radioactive oxygen-18 atom is heated with sodium
hydroxide solution. Analysis of the products using a mass spectrometer
shows that the oxygen-18 is not in the carboxylic acid formed. This means
that the bond cleaved.
18O ̅ 18O-
NUCLEAR STABILITY
Many atomic nuclei are stable but others decay by giving out radiations. All nuclei with
atomic numbers greater than 83 are unstable and therefore radioactive.
Nuclear stability is the ability of the nucleus of an atom to resist spontaneous decay

that would result into formation of other nuclei and emission of radiations.
A summarized comparison between stable and unstable nuclei

Stable nucleus Unstable nucleus
Number of protons is approximately equal to The number of neutrons is much greater
the number of neutrons than the number of protons or has a high
number of protons than neutrons
Does not undergo radioactive disintegration. Undergoes radioactive decay emitting
alpha and beta particles to attain stability
Those with odd numbers of both protons and Those with even numbers of both protons
neutrons are least stable and neutrons are most stable.
The stability of a nucleus is related to the ratio of the number of neutrons to the number
of protons. This ratio is represented as ( ⁄ ).
Lighter elements with mass number up to 20 have the ⁄ approximately equal to one.
After atomic number 20, addition of protons is not favoured because of the creation of
more repulsive forces in the nucleus. Addition of neutrons is favoured up to ⁄ .
Beyond this value, atomic nuclei become unstable due an increased number of protons
that lead to increased repulsive forces within the nuclei. The nuclei therefore emit
radiations to become stable and get converted to new nuclei.
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Factors affecting nuclear stability

1. .
Nuclear stability depends on the ⁄ value. Nuclei that have ⁄ value equal to one are
stable. Those with ⁄ have more neutrons than protons and those with ⁄
have more protons than neutrons hence unstable.
2. Atomic number
Stability of the nucleus decreases as the atomic number increases. Atoms with atomic
number 83 are have unstable nuclei.
3. Mass number
As mass number increases, the number of protons in the nucleus also increases, repulsive
forces increase much more rapidly than the attractive forces making the nucleus unstable.

4. Half-life
The higher half-life of a radioactive isotope, the slower the decay rate and the nucleus
becomes more stable and the lower the half-life, the higher the decay rate and the nucleus
is less stable. For example iodine-131 with half-life about 8 days is less stable than
Uranium-238 with half-life of about 4.5 billion years.
5. Binding energy
This is the energy given out when a nucleus is formed from its constituent neutrons
and protons
or The energy required to separate the nucleus into its constituent neutrons and
protons.
The greater the binding energy, the more stable the nucleus and the lower the binding
energy, the less stable the nucleus.
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Variation in number of neutrons and protons

Z
Number of neutrons Stability belt
80 X ⁄
Stability line
60
20

0 20 60 80 83 Number of protons
The dotted line is a line along which number or protons is equal to number of neutrons. It
is called the stability line and along this line ⁄
The stability belt or stability region or band of nuclear stability is the area on the
graph where all stable nuclei lie. Any nuclei out of this band are unstable and undergo
radioactivity to achieve stability.
The band of nuclear stability starts to deviate from the line of stability( ⁄ ) at
atomic number 20. This is because as atomic number or number of protons increases,
there is a strong repulsive force that develops in the nucleus. More neutrons are needed to
counterbalance the repulsive forces. This increases the neutron- proton ratio.
The stability belt stops abruptly at atomic number 83 because no stable isotope exists
beyond atomic number 83.
The nuclei in regions and outside the stability zone are unstable and therefore
undergo radioactive decay to form isotopes which lie in the stability zone. This can occur
by electron capture(or positron emission), beta emission and alpha emission.
Region X
In this region, number of neutrons is greater than number of protons. The neutron-
proton ratio is greater than one. To stabilize the nucleus, the neutron–proton ratio can be
reduced by reducing the number of neutrons and increasing the number of protons.
This happens by beta emission which reduces the number of neutrons by one and
increases the number of protons by one.
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Region Y
In this region, number of protons is greater than number of neutrons. The neutron-
proton ratio is less than one. To stabilize the nucleus, the neutron–proton ratio can be
increased by reducing the number of protons and increasing the number of neutrons.
This happens by electron capture or positron emission. Both electron capture and
positron emission reduces number of protons by one and increases number of neutrons by
one.
Region Z
In this region, the nuclides have atomic number greater than 83 and are heavy. To
stabilize the nucleus, both the number of protons and the number of neutrons must be
reduced. This happens by a series of alpha emissions. Alpha emission reduces both the
number of protons and the number of neutrons. There must be a series of alpha

emissions until a very stable nuclide is formed because stability cannot be gained by one
alpha emission.
ELECTRONIC STRUCTURE OF ATOMS

Electronic structure is the state of motion of electrons in an electrostatic field created by
stationary nuclei. The term encompasses both the wave functions of the electrons and the
energies associated with them. In Rutherford‟s “planetary” model, it was proposed that
electrons rotated around the nucleus and could not fall into the nucleus by centrifugal
force. However, it was found out that a charged particle like the electron should radiate
energy, causing a decrease in its velocity and would fall into the nucleus. For this reason,
the electron part of Rutherford‟s model was soon rejected but his concept of the nucleus
remained.
The modern ideas on electronic distribution in atoms originated from the model of the
hydrogen atom by Bohr. Bohr‟s theory was based on the spectrum of the hydrogen atom.
Electromagnetic radiation
Electromagnetic radiation is the energy resulting from the acceleration of electric charge
and the associated electric fields and magnetic fields. The energy can be regarded as
waves propagated through space involving oscillating electric and magnetic fields at right
angles to each other and to the direction of propagation.
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Alternatively, the energy can be regarded as a stream of photons (which are bundles of
light energy) travelling at the speed of light as quantized harmonic waves.
Electromagnetic radiation as quanta

Planck, in his quantum theory of absorption and emission of radiation, proposed that all
material systems can absorb or give off electromagnetic radiation only in “chunks” of
energy called quanta . Quanta are described as discrete packets of energy because it
requires a certain amount of energy to be released by an atom when an electron goes from
a higher energy level to a lower energy level.
The quanta are proportional to the frequency of the radiation, .

Relationship between wavelength frequency, , and energy, .
The energy of an electromagnetic radiation is directly proportional to its frequency but
inversely proportional to its wave length.
Using the equation in calculations

Examples
1. Find the energy of a photon with wavelength 415nm.
2. Calculate the energy of a photon with frequency .

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Atomic spectra
Atoms of different elements can be made to absorb or emit energy when they are excited.
The emission spectra from the vapours of the elements are known as atomic or line
spectra. They consist of a series of lines, each corresponding to a particular wavelength,
and indicating that the number of possible energy changes that can take place within the
atom of the element is in some way limited. Each element produces a unique set of
spectral lines and no two elements can emit the same series of spectral lines. This means
that an element can be identified by its line spectrum.
The word spectrum was first used in optics to describe the rainbow of colours in visible
light after passing through a prism. After advancement in the understanding of light, the
concept came to apply to the entire electromagnetic spectrum.
A spectrum can be defined as a range of electromagnetic energies arranged in order of
increasing or decreasing wavelength or frequency of electromagnetic radiation emitted
or absorbed by an atom or molecule.

An electromagnetic spectrum is the entire range of wave length or frequency of
electromagnetic radiation extending from gamma rays to the longest radio waves and
including visible light.
The emission of radiation may be induced by a variety of methods; for example, by high
temperature, bombardment by electrons, absorption of higher-frequency radiation, etc.
Types of spectra
Emission spectrum
If atoms are heated to sufficiently high temperatures, they emit light of certain wave
lengths. The emission of energy occurs as a result of electrons moving from higher
energy levels to lower energy levels. The observed spectrum consists of a number of
coloured lines on a black background. The spectrum is called an atomic emission
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spectrum. The emission spectra of atoms provide evidence that the electrons are
distributed around the nucleus in various energy levels.
Absorption spectrum
If atoms absorb light of a certain wave length, black lines appear in the spectrum where
light of some wave length has been absorbed. The absorbed energy by the atoms causes
energy changes from lower to higher energy levels. The observed spectrum is called an
absorption spectrum.
A description of the hydrogen emission spectrum

When electricity is passed through a discharge tube containing hydrogen at low
pressure, the hydrogen molecules break up to form single hydrogen atoms. The
hydrogen atoms emit radiations in the and ultraviolet, visible and infrared part of the
spectrum. When the radiations are analysed by a spectrograph, a line spectrum is
formed. Each line in the spectrum represents a definite wavelength of a radiation.
The wave length is given by the Rydberg equation, ( ) where is
Rydberg constant, and being simple whole numbers and is the wavelength.
A series of lines in the ultra violet region is called the Lyman series. The series of lines
in the visible region is the Balmer series and there is a series of lines in the infra-red
region. The series in the infra-red region consist of the Paschen, Brackett and Pfund
series.
In each series, the intervals between the frequencies of the lines become smaller and
smaller towards the low wave length or high frequency end of the spectrum until the
lines run together or converge to form a continuum of light.
An explanation of the hydrogen spectrum

When the hydrogen atom absorbs energy, it causes the electron to experience a
transition from a lower to a higher energy level. The observed lines in the spectrum are
due to electronic transitions from the higher energy levels to the lower energy levels in
the atom with emission of energy. When an electron from jumps from a higher energy
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energy of the two energy levels in the form of small packets of light known as photons.
For every transition of the electron, there is a line in the spectrum and there are different
types of spectral series formed.
The Lyman Series is formed when the electron jumps from any higher energy level to
first energy level .
The Balmer Series is formed when the electron jumps from any higher energy level to
the second energy level .
The Paschen Series is formed when the electron jumps from any higher energy level to
the third energy level .
The Brackett series is formed when the electron jumps from any higher energy level to
the fourth energy level .
The Pfund series is formed when the electron jumps from any higher energy level to the
fifth energy level .
The observed convergence between the lines towards the high frequency end in each

series is because the differences in energy between successive energy levels in atoms
become smaller and smaller with increasing distance of the energy levels from the
nucleus until they finally merge to form a continuum of light (continuous band of
radiation)
Red Green Violet Ultraviolet
The Balmer series of hydrogen
The application of the Rydberg equation

The Rydberg equation is the equation ;
( )
where is Rydberg constant,

and being simple whole numbers and
is the wavelength.
For the Lyman Series, the electron jumps to from
For the Balmer Series, the electron jumps from from
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For the Paschen Series, the electron jumps to from

For the Brackett series, the electron jumps to from
For the Pfund series, the electron jumps to from
Examples
1. If an electron falls from an energy level to an energy level . Calculate
the;
(i) wavelength in nanometers of the emitted radiation.
(ii) the frequency
(iii) change in energy of the radiation .
(ii)
(i) ( )

( )
(iii)
2. Use the Rydberg equation to calculate the wavelength in of the light emitted
when the electron in a hydrogen atom undergoes a transition from to
. Determine the region of light emitted.
( )
( )
Note; The units in which the Rydberg constant is given determine the way in which you
carry out the calculation. Also note that to convert from m to nm, a multiplication
factor of is used.
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Energy level diagram for the hydrogen atom

Pfund series
Bracket series
Paschen series
Balmer series
Principal quantum
number(n) Ionisation
energy

Lyman series Lowest(innermost) energy level
The principle quantum number ( ) only takes on integral values from 1 to infinity( ).
As frequency increases in each of the series of lines, each line becomes closer to the
previous line until the lines converge and the spectrum becomes continuous. The
Lyman series arises from electron transition to the ground state from higher energy
levels. The ground state occurs when the electron is at the lowest energy level ,
and the atom is most stable in this state. The electron normally occupies this energy level
unless given sufficient energy to move up to a higher energy level.
The highest frequency lines relate to the highest energy levels. The limit of the Lyman
series(the convergence of the lines) corresponds to a transition from the to the
energy level. The is the energy level where the electron has escaped from
the atom and the atom has ionised.
The atom is said to be in an excited state when the electron is found in the higher energy
levels. When an electron is excited from the ground state to a higher energy, it becomes
unstable and falls back to one of the lower energy levels by emitting
photon(s)/electromagnetic radiation
By convention, the energy level is usually assigned an energy value of .
The lower the energy level, the more negative the energy value associated with that level.
Thus, the more negative energy states correspond to more stable states. Negative value of
energy indicates that the electron is bound to the nucleus and there exists an attractive
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force between the electron and the nucleus. Also, since the potential at infinity is defined
as zero, energy levels at a distance below infinity are negative.
The energy difference between any two adjacent levels gets smaller as n increases, which
results in the higher energy levels getting very close and crowded together just below
.
The ionization energy of an atom is the energy required to remove the electron
completely from the atom (transition from ground state to infinity ). For
hydrogen, the ionization energy
The significance of lines in the hydrogen spectrum

Explain the significance of lines in the hydrogen spectrum
The spectrum consists of a series of lines, each corresponding to a particular wavelength,

and indicating that the number of possible energy changes that can take place within the
atom of the element is in some way limited. The observed lines in the spectrum are due to

electrons making transitions from the higher energy levels to the lower energy levels in
the atom with emission of energy.
The importance of the Convergence limit

State the importance of the Convergence limit
The convergence limit is reached when the electron is completely removed from the atom
and corresponds to a transition from the to the energy level. The transition
happens when an electron collides with an ion and returns to the ground state. The
convergence frequency can be used to calculate the ionisation energy.
The Bohr’s model of the hydrogen atom

Rutherford‟s model of an atom could not explain that facts as to why the atomic spectra
consisted of separate lines. The model did not explain why atoms absorb or emit light
of certain frequencies. In his model too, Rutherford could not explain why the spectral
lines converge to form a continuum.
In 1913, Niels Bohr put forward his theory that explained these facts. He based on
Planck‟s quantum theory which fundamentally proposed that matter cannot absorb or
emit energy in continuous amounts, but only in small discrete units called quanta.
According to Bohr‟s theory;
 The single hydrogen electron could travel around the nucleus in various possible
orbits but only certain orbits in which the electron possessed a whole number of
quanta of energy were permissible.
 No energy was radiated while the electron was rotating in a permissible orbit.
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 The permissible orbits were called stationary states or energy levels.

 The atom could be excited by an electric discharge or strong heat.
 The electron could absorb energy and jump to one of the higher energy levels.
 The excited state was however unstable and the electron could fall back to the
ground state.
 As the electron falls back to the lower energy level, it gives out some of its energy in
the form of radiation. The wavelength of the radiation emitted was determined by
the energy difference of the electron in the two energy levels.
Bohr deduced that if was the energy of the electron in the higher energy level and that
is that in the lower energy level, then is the energy difference for an electron
falling from the higher energy level to a lower energy level and was proportional to
wavelength, . If is the frequency, then;

Bohr assigned quantum numbers to the orbits or energy levels . He gave the orbit of
lowest energy(nearest to the nucleus) the quantum number 1. The next energy levels
quantum numbers and so on.
The weaknesses of Bohr‟s atomic model
 Bohr’s theory cannot explain the atomic spectra of atoms with more than one
electron.
 Bohr’s model could not explain the hydrogen atomic spectrum under the influence
of external magnetic field i.e. the Zeeman effect, when the spectral line is split into
several components in the presence of a magnetic field.
 It could not explain the hydrogen spectrum under the influence of an external
electric field. i.e. the Stark effect, when the spectral line gets split into fine lines in
the presence of an electric field.
Ionisation energy
Energy is required to remove an electron from a free gaseous atom against the attraction
of the nucleus. For a single atom, the energy required to remove one electron from the
atom in its ground state is called the first ionisation energy.
The first ionisation energy results into formation of a free gaseous ion from a free
gaseous atom and not formation of an ion of an element in its normal state. Successive
ionisation energies refer to the loss of a second, third,...... th electron.
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Ionisation energy is quoted in units as ionisation potentials in
The value of first ionisation energy for hydrogen can be found by the formula relating the
wavelengths of the lines in the various spectral lines; ( ).
When an electron is removed from the Lyman series( ) to ,
( )
( )
To convert this value to , multiply the
ionisation energy of one electron by Avogadro‟s
number.

Calculations involving ionisation energies
1. The limits of the spectral lines formed by transitions from ground state occur at
229.9nm for lithium and 285.6nm for potassium. Calculate the molar ionisation
energies of the two elements.
For lithium; For Sodium;
If it’s the frequency, given, then use the formula . Your answer may be left in
Joules.
2. If the ionisation energy of sodium is 496 . Calculate the wavelength of

the convergence limit for sodium.
From ,
( )
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Heisenberg’s Uncertainty principle

According to De Broglie, moving electrons had waves of definite wavelength associated
with them. Further experiments showed that a stream of electrons could be diffracted just
as X-rays can. Since it is only possible to account for diffraction in terms of waves, it was
necessary to assume that a stream of electrons behaves as a wave-like radiation.
As far as atomic structure is concerned, the idea of tiny, negatively charged particles
existing in fixed orbits around the nucleus of an atom is replaced by the idea of charge
clouds of varying charge density existing in a wave like pattern around the nucleus.
An electron can no longer be considered to occupy a specific, limited orbit but instead it
exists in a much more diffuse region known as atomic orbital.
An electron is different from a larger particle in a way that its wave-like nature is of
much greater significance than the wave-like nature of the larger particle.
The other difference is that both the position and the velocity of a large particle like a

planet can be measured with reasonable accuracy. However, there is no way of measuring
the velocity of an electron exactly and locating it exactly at any one time. This is because
any method used affects the electron being measured.
The information which can be obtained about an individual electron is therefore far from
precise. This an example of application of the Heisenberg Uncertainty Principle in
1927 which states that;
The more accurately the position of a particle is defined, the less accurately is its
velocity known, and the more accurately the velocity is defined, the less accurately is its
position known.
The concept of quantum numbers

The term quantum number is used to label the various energy levels. A set of four
quantum numbers are used to describe completely the movement and trajectories of each
electron within an atom. Each electron in an atom has a unique set of quantum numbers
and no two electrons can share the same combination of the four quantum numbers.
Quantum numbers are important in determining the electronic configuration of an atom
and the location of the electrons in the atom. They are also used to understand other
characteristics of atoms such as ionisation energy and atomic radius.
Quantum numbers are a set of four integers which are necessary to locate the energy
level or position of an electron and to specify the size, shape and orientation of orbital.
In atoms, there are a total of four quantum numbers. These include;

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1. The Principal quantum number

2. The Azimuthal quantum number or angular momentum quantum number
3. The magnetic quantum number
4. The electron spin quantum number
Principal quantum number, .
This specifies the energy level of an electron and its distance from the nucleus. The
first orbital nearest to the nucleus has principal quantum number, and is also called
the ground state. The second principal quantum number, and is called the excited
state and so on. As increases, the size of the orbit increases and the electron is far away
from the nucleus. An increase in also means that the electron has higher energy and is
therefore less bound to the nucleus. Energy levels closer to the nucleus have lower
energy. All the orbitals having the same value of are said to be in the same level. The
total number of electrons that can occupy any energy level is given by where
principal quantum number.

Principal quantum Maximum number of
number electrons
2
8
18
32
Azimuthal quantum number (angular momentum quantum number),
This determines the shape of an orbital and the angular distribution. It represents the
various sub energy levels within an energy level. Each value of indicates a specific
or subenergy level.
Azimuthal quantum Sub energy level

number
p
d
f
g
The values of are in a range of to for each value of . If an electron has a
principal quantum number and an angular momentum quantum number ,
then it is said to be a electron. The different combinations of the two quantum
numbers and are shown in the table below.
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Principal quantum Azimuthal quantum Possible combination of n

number number and l
Magnetic quantum number,

This gives the maximum number of orbitals for the different values of the azimuthal
quantum number, and their orientation in space within a sub energy level. This
quantum number accounts for the splitting of the spectral lines in the line spectrum of
elements. For each value of , there are subdivisions. These m values range
from – .
Azimuthal No. of
quantum Sub energy level subdivisions Values of m
number

1 0
p 3 -1,0,+1
d 5 -2,-1,0,+1,+2
f 7 -3,-2,-1,0,+1,+2,+3
Electron spin quantum number,
It represents the spin of an electron on its own axis, which can be clockwise or
anticlockwise relative to the orbital of the electron. The electron spin quantum number
does not depend on any other quantum number. It designates the direction of the electron
spin. An electron may have a spin of (represented as ) or (represented as ).
Because an electron spins, it creates a magnetic field which can be oriented in one of the
two directions.
Differentiation between an orbit and an orbital

Orbit Orbital
An orbit is a path traced by an electron An orbital is a region of space around the
revolving around the nucleus of an atom nucleus in which there is maximum probability
of finding an electron of a particular energy
level
The distance of the orbit from the nucleus for a It is impossible to know the exact trajectory of
given electron is fixed an electron in an atom
An orbit is a one dimensional path of an An orbital is a three dimensional space around
electron the nucleus
The movement of an electron in an orbit is It is in accordance with Heisenberg
known definitely which is against Heisenberg Uncertainty Principle
Uncertainty Principle
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The Aufbau principle

“Aufbau” is a German word meaning „building up‟. Aufbau principle is a principle that
gives the order in which orbitals are filled in successive elements in the periodic table.
It states that electrons enter orbitals of lowest energy first. The electrons are added to
atomic orbitals starting with the lowest energy orbitals and building up to higher energy
orbitals
The order is as follows:

The filling proceeds as
Pauli Exclusion principle

It states that all the electrons in any atom must be distinguishable or that no two
electrons in a single atom can have all their quantum numbers alike. It follows that if
two electrons in an atom have the same values of n, l and m, they must have different
values of s. Their spins must be opposed. One must spin up and the other spins down.
Hund’s rule
It is also called Hund‟s Multiplicity Rule. According to the rule, when electrons occupy
orbitals of equal energy, they do not pair up in an orbital until all the other orbitals in
the sub energy level have been occupied by a single electron.
The filling shown first is acceptable but not the second case
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Electronic configuration of atoms

The Hund‟s rule, Pauli Exclusion principle and the Aufbau principle are all applied in
writing of electronic configurations of atoms.
The notation is used and the subenergy levels contain a maximum number of
electrons as shown. The atomic number is used to write the configuration.
The table below shows the first 20 elements with their electronic configurations. Some
configurations are written and others are not. Complete the table
Element Symbol Atomic number Electronic configuration

Hydrogen H 1
Helium He 2
Lithium Li 3
Beryllium Be 4
Boron B 5
Carbon C 6
Nitrogen N 7
Oxygen O 8
Fluorine F 9
Neon Ne 10
Sodium Na 11
Magnesium Mg 12
Aluminium Al 13
Silicon Si 14
Phosphorus P 15
Sulphur S 16
Chlorine Cl 17
Argon Ar 18
Potassium K 19
Calcium Ca 20
Below is another table for the electronic configurations of the first transition series for
elements scandium to zinc.
An atom of an element is only stable if its outermost sub energy level is either completely
filled or half filled with electrons. In this series, this affects the electronic configuration
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of chromium and copper. An electron that would be in the 4s sub energy level is filled
in the 3d sub energy level do make it half-filled for copper and completely filled for
chromium. Complete the table too to show the electronic configurations of the other
elements.
Scandium 21
Titanium 22
Vanadium 23
Chromium 24
Manganese 25
Iron 26
Cobalt 27
Nickel 28
Copper 29
Zinc 30
More other elements with atomic numbers greater than 30 are shown below with some

electronic configurations filled. Follow the same procedure to complete the electronic
configurations for the other elements.
Germanium Ge 32
Bromine Br 35
Strontium Sr 38
Silver Ag 47
Tin Sn 50
Iodine I 53
Barium Ba 56
Lead Pb 82
Electronic configuration of ions
Ions are formed by gaining electrons (anions) or losing electrons (cations). When writing
their electronic configurations, electrons are either removed or added to the outer most
sub energy levels depending on the charge on the ion. For cations of the elements in the
first transition series (scandium to zinc), electrons in the 4s sub energy level are removed
first before those in the 3d sub energy level. Similarly, we can subtract or add electrons to
the atomic number of the neutral atom and use the remaining electrons to write the
configuration. Write configurations for the following ions.
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Ion Electronic configuration

Questions
1. What is meant by the terms?
(i) Orbital
(ii) Pauli‟s exclusion principle
(iii) Ionisation energy
2. (a) Describe and explain the atomic spectrum of hydrogen

(b) Explain how the hydrogen spectrum is related to the idea of quantized energy
levels in atoms and ionisation energy.
3. (a) (i) What is meant by stability of a nucleus?

(ii) State and explain the factors that affect stability of a nucleus.
(b) The graph below shows how the number of neutrons varies with that of
protons.
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Number of neutrons B
80 P ⁄
60
20
0 20 60 80 83 Number of protons

(i) State what line A and region B represent.
(ii) State why nuclei in the following regions P, Q and R are unstable
(iii) Briefly explain how nuclei in the regions P and R can gain stability
4. The diagram below shows the Lyman series part of a hydrogen emission spectrum.
A B C D EFG
(a) State;
(i) the information obtained from the separate lines about the electronic
structure of hydrogen
(ii) the direction in which energy increases
(iii) the direction in which frequency increases
(iv) the direction in which wavelength increases
(v) how the emission spectrum arises
(b) Briefly explain why the lines get closer together from left to right
(c) State what is meant by the term “principal quantum number”
5. (a) What is meant by the term quantum number?
(b) State the significance each of these quantum numbers on information about an
atom.
(i) the spin quantum number
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(ii) the angular momentum quantum number

(iii) the magnetic quantum number
(iv) the principal quantum number
6. (a) Write the electronic configuration of:
(i) nitrogen
(ii) phosphorus
(b) Explain why nitrogen only forms nitrogen trichloride while phosphorus forms
both phosphorus trichloride and phosphorus pentachloride.
THE PERIODIC TABLE

The historical development of the Periodic Table
Prout, an Englishman, made the earliest attempt to show a connection between atoms of
different elements. This was in 1815, seven years after the publication of the atomic
theory.

He found out that the many atomic weights determined by Dalton, Berzelius and others
were approximately whole number multiples of the atomic weight of hydrogen. Prout
therefore suggested that atoms of different elements were composed of hydrogen atoms
in various numbers. This whole number rule as however abandoned soon.
In 1858, Cannizzaro introduced a method of finding relative atomic masses. Chemists
soon observed a periodic relationship between the properties of elements and their
relative atomic masses.
In 1864, Newlands showed that if elements were arranged in order of their atomic
weights, elements with similar properties appeared in intervals. Part of his table is shown
below.
Elements that were chemically similar such as lithium, sodium and potassium usually
occurred in every eighth position. From his observation, Newland put forward the
following periodic law; the properties of elements are a periodic function of their
atomic weights.
Newlands‟ law however did not convince majority of the chemists. This is because some
elements were placed in the table but assigned incorrect relative atomic masses. In
addition, no allowance was given for the possibility of the undiscovered elements.
In 1869, the Russian chemist, Demitri Mendeleeff, used Newlands basic idea to devise a
new kind of table. He arranged all the known elements in order of their relative atomic
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masses to show the relationships between the elements more clearly. He improved
Newlands‟ table by;
1. Leaving gaps in the Periodic Table on a prediction the new elements would be
discovered to fill the gaps. He predicted the properties of the undiscovered elements.
When the elements were discovered and found to have relative atomic mass and the
physical and chemical properties Mendeleeff predicted, chemists strongly believed in
his Periodic Table.
2. Introducing long rows periods for the elements now called transition elements. This
implied that the elements were not placed under nonmetals as in
Newlands‟ system.
Below is part of Mendeleef‟s Periodic Table;
1 2 3 4 5 6 7 8
1

2
3
4 ... ... ... ... ...
5 ... ...
More elements were soon discovered including the noble gases which now make the
Modern Periodic Table.
Unique position of Hydrogen in the Periodic Table

The position of hydrogen in the Periodic Table is a great source of argument. Whereas
some authors place it above lithium in group I, others place it above fluorine in group
VII. Others place isolate it to a central position to indicate that it is unique and has no
genuine analogues.
From its electronic structure, , hydrogen resembles group I elements which have one
electron in the outermost sub energy level. Hydrogen is also similar to group I elements
in being electropositive because it is liberated at the cathode when aqueous solutions of
acids are electrolyzed.
Also just like group VII elements, the hydrogen atom is one electron short of a noble gas
configuration. Therefore hydrogen resembles elements in both groups in being
consistently monovalent when combining with other elements.
The properties of hydrogen relate it much more to the halogens than alkali metals. It has a
much higher ionisation energy and electronegativity than alkali metal. This gives it a
nonmetallic character. It also resembles halogens by existing as diatomic molecules. Just
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like salts of halogens, when fused metallic hydrides liberate hydrogen at the anode on
electrolysis.
The Modern Periodic Table

The structure of the Modern Periodic Table
In the modern Periodic Table, elements are arranged in order of increasing atomic
numbers instead of atomic mass. Atomic numbers increase from left to right and from
top to bottom in the table. The modern Periodic Table has more elements than
Mendeleef‟s table because many elements have been discovered since his time. The
elements can be classified in three classes; metals, metalloids and non-metals.
In the modern Periodic Table, each element is represented by its chemical symbol, atomic
mass and mass number. The rows in the table are called Periods and the columns are the
groups. The table has a total of 18 groups and 7 periods.
The first period has only 2 elements. The second and third periods have 8 elements each.

The fourth and fifth have 18 elements each. The sixth has 32 elements. The seventh
period has 32 elements including Nihonium-113, Moscovium-115, Tennesine-117 and
Oganeson-118. These new elements were approved in 2015 by IUPAC and added to the
table to complete the seventh period to 32 elements.
There is a separate group of elements at the bottom of the table. It consists of 14 elements
of the sixth period called the lanthanides and 14 elements of the seventh period called
the actinides.
Elements in the same group have similar chemical properties and the same outermost
configuration.
GROUPS
IA IIA IIIA IVA VA VIA VIIA VIII IB IIB IIIB IVB VB VIB VIIB O
1
2
PERIODS
3
4
5
6
7
Lanthanum series
Actinium series
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Classification of elements based on the electronic configuration as s, p, d and f

blocks.
The Periodic Table is divided into four main blocks; these blocks are s-block, p-block, d-
block and f-block
s-block elements
They are placed in the left hand block of the table. The s-block contains the elements
whose outermost electrons occupy the s sub-energy level. The s-block consists of two
groups of elements;
IA whose electronic configuration ends with ,
IIA whose electronic configuration ends with .
p-block elements
These occupy the right hand block of table. The p-block contains the elements whose
outermost electrons occupy the p sub-energy level except helium.

All elements placed in groups IIIB, IVB, VB, VIB, VIIB and O are p-block elements.
d-block elements
They occupy the middle block of the table. The d-block contains the elements with the
outermost electrons in the d sub-energy level after the s sub-energy level is filled. The d-
block elements are classified according to the outer energy sub-energy level and the
period number into three series which are:
1. The first transition series:
It includes the elements in which the 3d sub-energy level is filled successively. It
lies in the fourth period and includes the elements from scandium ( 21Sc ) to
zinc ( 30Zn ) .
2. The second transition series:
It includes the elements in which the 4d sub-energy level is filled successively. It
lies in the fifth period and includes the elements from yttrium (39Y) to
cadmium ( 48Cd ) .
3. The third transition series:
It includes the elements in which the 5d sub-energy level is filled successively. It lies
in the sixth period and includes the elements from lanthanum ( 57La ) to
mercury ( 80Hg ) , excluding the lanthanides.
f-block elements
They are separated down the Periodic table , to avoid being a very wide table , In which
the f sub-energy level is filled successively , The f-block is divided into 2 series, each
with 14 elements. These are:
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1. The lanthanides
These are in the sixth period, in which the 4f sub-energy level is filled successively.
The elements of this series are quite similar in behaviour and very difficult to be
separated as the outermost energy level for all of them is 6s² .
2. The actinides
These are placed in seventh period, in which the 5f sub-energy level is filled
successively. All the elements of this series are radioactive and their nuclei are
unstable.

The table below shows the common elements. Use their electronic configurations to
classify them into groups, periods and the s, p, d and f blocks
Element Atomic Electronic configuration Group Period Periodic

number Block
H 1
He 2
Li 3
Be 4
B 5
C 6
N 7
O 8
F 9
Ne 10
Na 11
Mg 12
Al 13
Si 14
P 15
S 16
Cl 17
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Ar 18
K 19
Ca 20
21
22
23
24
25
26
27
28
29
30
32
38

50
53
56
82
Classification into metals, metalloids and non-metals
184
Metals
Metalloids
Non-metals
The elements in the Modern Periodic table can be classified as metals, metalloids or non-
metals. Most of the elements in the table are metals. In the periodic table, there is a
change from metallic to non-metallic properties across the table, and an increase in
metallic properties down a group. Consequently there is a diagonal nearer the center of
the table ( ) in which there is a borderline between metals and non-metals, and
the metalloids are the borderline cases.
The metals are good conductors of heat and electricity have a shiny lustre, malleable and
ductile, usually have high melting points and high densities.
The non-metals are poor thermal conductors, good heat insulators, and are neither
malleable nor ductile.

Metalloids are a class of chemical elements that are intermediate in properties between
metals and non-metals. Elements such as arsenic, germanium, and tellurium are
semiconductors and their conductivity increases as their temperature increases.
Periodicity of atomic properties in the Periodic Table

The common atomic properties include
 Atomic radius
 Ionisation energy
 Electron affinity
 Electronegativity
 Electropositivity
 Metallic character
 Standard electrode potential
The factors affecting atomic properties of elements include;
1. Nuclear charge
2. Shielding effect/ screening effect
3. Electronic configuration
4. Atomic radius.
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1. Nuclear charge
This is simply the total number of positive charges in the nucleus of an atom. It is an
equivalent to the number of protons.
2. Shielding effect/ screening effect

This is the repulsion of the outermost electrons by those in the innermost sub energy
levels from nuclear attraction. Electrons in an atom shield each other from the pull of the
nucleus. Shielding effect describes the decrease in attraction between an electron and the
nucleus in any atom with more than one energy level. The greater the number of energy
levels, the greater the shielding effect.
3. Effective nuclear charge( )

This is the net positive charge experienced by an electron in an atom. Effective nuclear
charge is given by the equation;

Using the formula, it can be interpreted that if the nuclear charge is high and the
screening effect is low, then effective nuclear charge increases. When the screening effect
is high and nuclear charge is low, the effective nuclear charge reduces.
Atomic and Ionic radius

Atomic radius is half the internuclear distance between two atoms in a covalently
bonded diatomic molecule with similar atoms or in a metallic bond.
Similar atoms
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The variation in atomic radius down a group or across a period is determined by the
factors;
1. Nuclear charge
The higher the nuclear charge, the more strongly are the outermost electrons attracted
closer to the nucleus, reducing the atomic radius. The lower the nuclear charge, the
weaker the attraction of the outer most electrons to the nucleus hence the increasing the
atomic radius.
2. Screening effect.
The greater the screening effect, the stronger the repulsion of the outermost electrons
from the nuclear attraction. The electrons are thus far and weakly attracted to the nucleus,
increasing the atomic radius. The lower the screening effect, the lower the repulsion of
the outermost electrons from the nuclear attraction. The electrons are thus nearer and
strongly attracted to the nucleus, reducing the atomic radius.

Variation in atomic radius and ionic radius in Periods and groups
1. The table below shows variation in atomic and ionic radii across Period 3
Element Na Mg Al Si P S Cl
Atomic radius(nm) 0.156 0.136 0.125 0.117 0.110 0.104 0.099
Ionic radius(nm) 0.095 0.065 0.054 0.212 0.184 0.181
(a) State and explain the trend in atomic radius of the elements
Atomic radius decreases from sodium to chlorine.
This is because from sodium to chlorine, nuclear charge increases because a proton is
added to nucleus from element to element. Screening effect almost remains constant,
because electrons are added to the same energy level. Effective nuclear charge increases,
and outer most electrons get closer and more strongly attracted than repelled by the
nucleus.
(a) Explain why:

(i) the ionic radii of and are smaller than those of the
corresponding atoms.
The ions are formed by losing electrons. When the electrons are lost, the number of
protons becomes greater than the number of remaining electrons. Screening effect is
reduced. Effective nuclear charge increases. The remaining electrons become strongly
attracted by the nucleus than they are repelled.
(ii) the ionic radii of and are larger than those of the
corresponding atoms
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The ions are formed by gaining electrons. When the electrons are gained, the number of
electrons becomes greater than the number of existing protons. Screening effect
increases. Effective nuclear charge reduces. The electrons become more strongly
repelled by the nucleus than they are attracted.
(b) The ions and have the same electronic configuration, yet they
have different ionic radii. Suggest a reason for this.
The ions are formed by losing electrons, reducing the screening effect. The number of
protons however remains unchanged. The effective nuclear charge therefore increases in
the order since proton number increases in the same order. The
ionic radius therefore decreases in the order
2. The table below shows the atomic radii and ionic radii of the elements in Group II of
the Periodic Table.
Element Be Mg Ca Sr Ba

Atomic radius(nm) 0.089 0.136 0.174 0.191 0.198
Ionic radius(nm) 0.031 0.065 0.099 0.113 0.135
(a) State and explain the trend in atomic radius of the elements
Atomic radius increases from Beryllium to Barium.
This is because from Beryllium to Barium, nuclear charge increases; screening effect
also increases, because an extra energy level completely filled with electrons is added.
Increase in screening effect outweighs increase in nuclear charge. Effective nuclear
charge decreases, and outer most electrons are far and weakly attracted by the nucleus.
(b) Explain why the ionic radius is smaller than the atomic radius of corresponding
neutral atom for each element.
The cations are formed by losing electrons. When the electrons are lost, the number of
remaining electrons becomes lower than the number of existing protons. Screening effect
decreases. Effective nuclear charge increases. The electrons become more strongly
attracted by the nucleus than they are repelled reducing the ionic radius. In the neutral
atom, the screening effect is counterbalanced by nuclear charge.
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Ionisation energy
This is the minimum amount of energy required to remove an electron from a gaseous
atom to form a charged gaseous ion.
Ionisation energy can be first, second or third,… ionisation energies depending on which
electron is being removed from the atom
First ionisation energy is the minimum amount of energy required to remove an

electron from a gaseous atom to form a unipositively charged gaseous ion.
The variation in first ionisation energy down a group or across a period is determined by
the factors;
1. Nuclear charge

The higher the nuclear charge, the higher the first ionisation energy because the
outermost electron is strongly attracted by the nucleus, requiring a high amount of energy
to be removed. The lower the nuclear charge, the lower the first ionisation energy
because the outermost electron is weakly attracted by the nucleus, requiring a low amount
of energy to be removed.
2. Screening effect
The higher the screening effect, the lower the first ionisation energy because the
outermost electron is more strongly repelled than it is attracted by the nucleus, requiring a
low amount of energy to be removed. The lower the screening effect, the higher the first
ionisation energy because the outermost electron is more strongly attracted by the nucleus
than it is repelled, requiring a high amount of energy to be removed.
3. Atomic radius
The larger the atomic radius, the lower the first ionisation energy because the outermost
electron is far and weakly attracted by the nucleus, requiring a low amount of energy to
be removed. The smaller the atomic radius, the higher the first ionisation energy because
the outermost electron is nearer and strongly attracted by the nucleus requiring a higher
amount of energy to be removed.
4. Electronic configuration/ electronic structure
Atoms with outermost sub energy levels half-filled or completely filled with electrons are
thermodynamically stable and require abnormally higher amount of energy to remove an
electron. Atoms whose outermost sub energy levels are neither half-filled nor completely
filled with electrons are unstable and require a low amount of energy to remove an
electron.
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5. Penetrating power of valence electrons

If an electron is to be removed from a sub energy level which is more penetrating, the
first ionisation energy is higher. If the electron is in a less penetrating sub energy level,
the ionisation energy is lower. Penetrating power increases in the order; .
Variation in ionisation energy in Periods and groups
1. The table below shows the first ionization energies of the elements in Period 2 of the
Periodic Table.
Element Li Be B C N O F Ne
First ionization energy 520 899 800 1086 1402 1314 1681 2080
(kJmol-1)
(a) State and explain the general trend in first ionisation energy
(b) Briefly explain why;
(i) Beryllium has an abnormally higher value than boron

(ii) Oxygen has an abnormally lower value than nitrogen
(iii) the ionisation energy of neon is very high
(a) First ionization energy generally increases from lithium to neon.

This is because from lithium to neon, nuclear charge increases because a proton is
because electrons are added to the same energy level. Effective nuclear charge
increases, atomic radius reduces and outer most electron is closer and more strongly
attracted than repelled by the nucleus requiring a high amount of energy to be
removed.
(b) (i)
For Beryllium, an electron is removed from a completely filled 2s-sub energy level which
is thermodynamically stable. Higher amount of energy is required to remove the electron
For Boron, an electron is removed from a 2p-sub energy level which has only one
electron hence thermodynamically unstable. Lower amount of energy is required to
remove the electron.
(ii)
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For oxygen, the electron is removed from a 2p-sub energy level which has four electrons
hence thermodynamically unstable. Lower amount of energy is required to remove the
electron.
For nitrogen, an electron is removed from a half filled 2p-sub energy level which is
thermodynamically stable. Higher amount of energy is required to remove the electron
(iii)
For neon, an electron is removed from a completely filled 2p-sub energy level which is
thermodynamically stable. High amount of energy is required to remove the electron
2. The table below shows the first ionization energies of Group VII elements.
Element F Cl Br I
First ionisation energy (kJmol-1)

1681 1255 1142 1007
State and explain the trend in ionization energy of the elements

First ionization energy decreases from fluorine to iodine.
This is because from fluorine to iodine, nuclear charge increases, screening effect also
increases, because an extra energy level completely filled with electrons is added from
element to element. Increase in screening effect outweighs increase in nuclear charge.
Effective nuclear charge decreases, atomic radius increases and outer most electron is
far and weakly attracted by the nucleus requiring a low amount of energy to be removed.
Successive ionisation energies
The evidence for arrangement of electrons in energy levels of atoms is provided by

values of successive ionisation energies for elements. A plot of successive ionisation
energies against the order in which electrons can be made for any atom. A logarithmic
plot of the ionisation energies is used to give a condensed graph.
1. Below is a plot of Ionisation energy against number of electrons removed

for element Q
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Log of ionisation energy 6
0 2 4 6 8 10 12 14 16 18

Number of electrons removed
A lot of information can be obtained from the graph about element Q.
(i) The atomic number

From the graph, a total of 19 electrons are removed from the atom. Since number of
electrons is equal to proton number for a neutral atom, Q has atomic number 19. The
number of successive ionisation energies indicate the number of electrons removed from
an atom.
(ii) Group of an element in the Periodic Table.

From the graph, the removal of the first electron requires the lowest ionisation energy.
This electron is the easiest to remove because it is strongly shielded from nuclear
attraction and weakly attracted by the nucleus. Q therefore is in group I
(iii) Valency
Q has valence one since it has one electron in the outermost energy level, strongly
shielded from the nucleus and easily lost.
(iv) Electronic configuration and number of energy levels.

From the graph, there is an abnormally large increase from first to second ionisation
energies. This implies that the second electron is removed from an inner energy level,
completely filled with electrons, thermodynamically stable and closer to the nucleus than
the outermost energy level. The outermost energy level therefore has one electron. There
is a gradual increase from second to ninth ionisation energies. This implies that the next
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eight electrons occupy the same energy level, nearer to the nucleus than the outermost
energy level. There is an abnormally large increase from the ninth to tenth ionisation
energies. This implies that the tenth electron is removed from an inner energy level,
completely filled with electrons, thermodynamically stable and closer to the nucleus.
There is a gradual increase from tenth to seventeenth ionisation energies. This implies
that the next eight electrons occupy the same energy level and nearer to the nucleus.
There is an abnormally large increase from the seventeenth to eighteenth ionisation
energies. This implies that the eighteenth electron is removed from an inner energy level,
completely filled with electrons, thermodynamically stable and closer to the nucleus. The
last two electrons occupy the innermost energy level, closest to the nucleus and require
the highest amount of energy to be removed due to a very strong nuclear attraction.
Q therefore has four energy levels with electronic configuration as shown below.
Energy level

Number of electrons 2 8 8 1
Electronic configuration
(v) Period in the Periodic Table
Q is in Period 4 since it has four energy levels
From all the information above, it can be concluded that element Q is potassium.
Successive ionisation energies can also be used to determine whether an element is

metallic or non-metallic. Nonmetals have first ionisation energy values of magnitude
and above while metals have first ionisation energies normally below
.
Noble gases have the highest first ionisation energies because they have stable
configurations and require very high energies to remove an electron.
2. The table below shows the first four successive ionisation energies of elements A,
B, C, D and E.
Element Ionisation energy(kJmol-1)
1st 2nd 3rd 4th
A 800 2400 3700 25000
B 900 1800 14800 21000
C 500 4600 6900 9500
D 1090 2400 4600 6200
E 1310 3400 5300 7500
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(a) Explain the trend in the ;

(i) Successive ionisation energies for the elements.
(ii) Successive ionisation energies for element E.
(b) With reasons, state the group to which the elements A, B, C and D belong.
(a) (i) Successive ionisation energies increase from first to second to third to fourth
because as successive electrons are removed, the number of protons becomes greater
than the number of the remaining electrons, screening effect reduces, effective
nuclear charge increases and the remaining electrons become strongly attracted by
the nucleus thus requiring a high amount of energy to be removed.
(ii) For element E, successive ionisation energies increase from first to second to third to
fourth because as successive electrons are removed, the number of protons becomes
greater than the number of the remaining electrons, screening effect reduces, effective

nuclear charge increases and the remaining electrons become strongly attracted by the
nucleus thus requiring a high amount of energy to be removed. However, there is a
greater increase in ionisation energy from first to second compared to the second and
third, third and fourth ionisation energies because the second electron is in an inner
energy level, completely filled with electrons, thermodynamically stable and nearer the
nucleus.
(b) A belongs to group III. This is because the difference between the third and fourth
ionisation energies is very big compared to the difference between first and second,
second and third ionisation energies. This implies that the fourth electron is removed
from an inner energy level, completely filled with electrons, thermodynamically
stable and closer to the nucleus and the first three electrons are in an outermost
energy level.
B belongs to group II. This is because the difference between second and third
ionisation energies is very big compared to the difference between first and second,
third and fourth ionisation energies. This implies that the third electron is removed
stable and closer to the nucleus and the first two electrons are in an outermost energy
level.
C belongs to group I. This is because the difference between first and second
ionisation energies is very big compared to the difference between second and third ,
third and fourth ionisation energies. This implies that the second electron is removed
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stable and closer to the nucleus and the first electron is in an outermost energy level.
D belongs to group I. This is because the difference between first and second
ionisation energies is very big compared to the difference between second and third ,
third and fourth ionisation energies. This implies that the second electron is removed
stable and closer to the nucleus and the first electron is in an outermost energy level.
Electron affinity
When an electron is gained by an atom, energy is given out.
This enery is called first electron affinity.

First electron affinity is the energy given out when one mole of electrons combines with
one mole of gaseous atoms to form one mole of uninegatively charged gaseous ions
or

The energy given out when an electron is added to a gaseous atom to form a
uninegatively charged gaseous ion
First electron affinity is an exothermic process (energy is given out)
The uninegatively charged gaseous ion can gain one more electron to form a dinegatively
charged ion. This is called second electron affinity and is an endothermic process
(energy is absorbed)
1. Explain why the first electron affinity of oxygen is and the

second electron affinity of oxygen is
First electron affinity of oxygen is negative because heat is given out when an electron is
added to neutral gaseous oxygen atom to form uninegatively charged gaseous oxygen
atom. This incoming electron experiences a greater attraction by the nucleus than it is
repelled. There is however repulsion when an electron is being added to the negatively
charged gaseous ion. Energy must be absorbed to add this electron such that the
repulsion is overcome. This makes the second electron affinity positive.
The variation in first electron affinity down a group or across a period is determined by
the factors;
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1. Nuclear charge
The higher the nuclear charge, the higher the first electron affinity because the incoming
electron is strongly attracted than it is repelled by the nucleus, giving off a high amount
of energy. The lower the nuclear charge, the lower the first electron affinity because the
incoming electron is weakly attracted by the nucleus, giving off a low amount of energy.
2. Screening effect
The higher the screening effect, the lower the first electron affinity because the incoming
electron is strongly repelled than it is attracted by the nucleus, giving off a low amount of
energy. The lower the screening effect, the higher the first electron affinity because the
incoming electron is more strongly attracted by the nucleus than it is repelled, giving off
a high amount of energy.
3. Atomic radius
The larger the atomic radius, the lower the first electron affinity because the incoming
electron is far and more strongly repelled than it is attracted by the nucleus, giving off a

low amount of energy. The smaller the atomic radius, the higher the first electron affinity
because the incoming electron is nearer and more strongly attracted by the nucleus than it
is repelled giving off a higher amount of energy.
thermodynamically stable and resist addition of an incoming electron. Energy must be
absorbed to add this electron because it experiences greater repulsion than attraction. This
results into a low amount of energy of first electron affinity. Atoms whose outermost sub
energy levels are neither half-filled nor completely filled with electrons are unstable. The
incoming electron experiences more attraction than repulsion, giving off a higher amount
of energy.
2. The table below shows the variation in the first electron affinity of the elements
in Period 3 of the Periodic Table.
Element Na Mg Al Si P S Cl Ar
-1
First electron affinity (kJmol ) -21 +67 -44 -135 -72 -200 -364 0
(a) Plot a graph of first electron affinity against atomic number
(b) State and explain the general trend in first electron affinity from sodium to
argon
From sodium to argon, nuclear charge increases because a proton is added to nucleus
from element to element. Screening effect almost remains constant, because electrons are
added to the same energy level. Effective nuclear charge increases, atomic radius
reduces. The attraction for the incoming electron increases thus increasing the electron
affinity.
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(i) the first electron affinity of magnesium is lower than the rest.
For magnesium, the electron is added to a completely filled 3s-sub energy level which is
thermodynamically stable. The incoming electron experiences greater repulsion by the
existing electrons than nuclear attraction. Energy must therefore be absorbed to add the
incoming electron. The first electron affinity is therefore endothermic.
(ii) the first electron affinity of aluminium is higher than that of magnesium
For aluminium, the electron is added to the 3p-sub energy level which has one electron
and thermodynamically unstable. The incoming electron experiences more attraction by
the nucleus than repulsion, hence giving off a higher amount of energy.
For magnesium, the electron is added to a completely filled 3s-sub energy level which is

thermodynamically stable. The incoming electron experiences greater repulsion by the
existing electrons than nuclear attraction, hence giving off a lower amount of energy.
(iii) the first electron affinity of phosphorus is lower than that of Sulphur.
For phosphorus, the electron is added to a half filled 3p-sub energy level which is
thermodynamically stable. The incoming electron experiences more repulsion than
attraction by the nucleus.
For Sulphur, the incoming electron is added to a 3p-sub energy level which has four
electrons, thermodynamically unstable. The incoming electron experiences more nuclear
attraction than repulsion by the existing electrons.
3. The table below shows the first electron affinities and atomic numbers of the
elements in Group VII
Element F Cl Br I
Atomic number 9 17 35 53
First electron affinity(kJmol-1) -354 -370 -348 -320
(a) Explain what is meant by the term first electron affinity

(b) Plot a graph of first electron affinity against atomic number of the elements.
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(To be done by student. When plotting the graph, the negative sign may be eliminated
since it’s on all values and it just indicates that the process is exothermic. The graph
below is just a sketch and not on scale)
(c) (i) Explain the general trend in variation of the first electron affinities
(ii) Explain why fluorine has an abnormal value
A graph of first electron affinity

against atomic number
First electron affinity (kJmol-1)
380
370
360
350
340
330
320

310
300
290
9 17 Atomic number 35 53
(a) (i) Generally, first electron affinity decreases from fluorine to iodine.
This is because from fluorine to iodine, nuclear charge increases, screening effect
also increases, because an extra energy level completely filled with electrons is
added from element to element. Increase in screening effect outweighs increase
in nuclear charge. Effective nuclear charge decreases, atomic radius increases
and incoming electron is far and weakly attracted by the nucleus giving off a low
amount of energy.
(ii) Fluorine has the smallest atomic radius, highest electron density, strongly
repels the incoming electron and energy is consumed to add the electron to its
atom.
Electronegativity
The tendency of an atom to attract bonding electrons towards itself in a covalent bond.
Electronegativity is very important factor in determining the degree of polarity of any

covalent bond. The greater the difference between the electronegativities of two atoms,
the greater the ionic character. In hydrogen fluoride, the electron density of the bonding
electrons lies more towards the fluorine atom than the hydrogen atom because fluorine is
more electronegative than hydrogen. This makes fluorine gain a partial negative charge
and hydrogen a partial positive charge, making the hydrogen fluorine bond polar.
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Fluorine is the most electronegative element, followed by oxygen and nitrogen. The
halogens follow after the three elements. Alkali metals have lowest values of
electronegativity.
The table below shows some common elements and their electronegativity values
The variation in electronegativity down a group or across a period is determined by the

factors;
1. Nuclear charge

The higher the nuclear charge, the higher the electronegativity because the bonding
electrons are strongly attracted by the nucleus. The lower the nuclear charge, the lower
the electronegativity because the bonding electrons are weakly attracted by the nucleus.
2. Screening effect
The higher the screening effect, the lower the electronegativity because the bonding
electrons are strongly repelled. The lower the screening effect, the higher the
electronegativity because the bonding electrons are less shielded from the nuclear
attraction.
3. Atomic radius
The larger the atomic radius, the lower the electronegativity because the bonding
electrons are far and weakly attracted by the nucleus. The smaller the atomic radius, the
higher the electronegativity because the bonding electrons are nearer and strongly
attracted by the nucleus.
1. The table below shows the electronegativity values of the elements in Period 3 of
the Periodic Table.
Element Na Mg Al Si P S Cl
Electronegativity 1.0 1.2 1.5 1.8 2.1 2.5 3.0
State and explain the trend in electronegativity values of the elements
Electronegativity increases from sodium to chlorine.
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because electrons are added to the same energy level. Effective nuclear charge increases,
atomic radius reduces and the bonding electrons experience a greater nuclear attraction.
2. The table below shows the electronegativity values of the elements in Group II of
the Periodic Table.
Electronegativity 1.57 1.31 1.00 0.95 0.89
Electronegativity decreases from Beryllium to Barium.
This is because from Beryllium to Barium, nuclear charge increases, screening effect
also increases, because an extra energy level completely filled with electrons is added
from element to element. Increase in screening effect outweighs increase in nuclear
charge. Effective nuclear charge decreases, atomic radius increases, and the bonding

electrons experience a greater repulsion than nuclear attraction.
Electropositivity
The tendency of an atom of an element to lose its valence electrons to become positively
charged
The variation in electropositivity down a group or across a period is determined by the

factors;
1. Nuclear charge
The higher the nuclear charge, the lower the electropositivity because the valence
electrons are strongly attracted and cannot easily be lost. The lower the nuclear charge,
the higher the electropositivity because the valence electrons are weakly attracted by the
nucleus and can easily be lost.
2. Screening effect
The higher the screening effect, the higher the electropositivity because the valence
electrons valence electrons are weakly attracted by the nucleus and can easily be lost. The
lower the screening effect, the lower the electropositivity because the valence electrons
are strongly attracted by the nucleus and cannot easily be lost.
3. Atomic radius
The larger the atomic radius, the higher the electropositivity because the valence
electrons are far and weakly attracted by the nucleus hence are easily lost. The smaller
the atomic radius, the lower the electropositivity because the valence electrons are nearer
and strongly attracted by the nucleus hence not easily lost.
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thermodynamically stable hence do not easily lose the valence electrons, reducing
electropositivity. Atoms whose outermost sub energy levels are neither half-filled nor
completely filled with electrons are unstable. The valence electrons are weakly attracted
hence easily lost, increasing electropositivity.
Variation of electropositivity across period 3
Electropositivity decreases from sodium to chlorine.
because an electron is added to the same energy level. Effective nuclear charge
increases, atomic radius reduces and the valence electrons experience a greater nuclear
attraction hence not easily lost.

Variation of electropositivity across group II
Electropositivity increases from beryllium to Barium.
This is because from Beryllium to Barium, nuclear charge increases, screening effect
also increases, because an extra energy level completely filled with electrons is added
from element to element. Increase in screening effect outweighs increase in nuclear
charge. Effective nuclear charge decreases, atomic radius increases and the valence
electrons experience a lower nuclear attraction than repulsion hence easily lost.
Metallic character
Metallic character decreases from left to right across a period because electropositivity
decreases for reasons already explained. Metallic character also increases down a group
since electropositivity increases for reasons also already explained.
For variation in Standard electrode potential check under electrochemistry in this

same book and for variation in melting and boiling points in groups and periods,
check Demystifying Inorganic Chemistry by the same author,
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Questions
1. The table below shows the values for atomic and ionic radii of alkali metals.
Element Atomic number Ionic radius
Lithium 1.23 0.68
Sodium 1.57 0.97
Potassium 2.03 1.33
Rubidium 2.16 1.47
Caesium 2.35 1.67
(a) In every case, the ionic radius is smaller than the corresponding atomic radius.
Explain.
(b) Explain the increase in atomic radius along the series Lithium to Caesium
(c) The ions and , have the same electronic configuration yet they
have different ionic radii. Suggest a reason for this.
(d) Which one of the alkali metal ions in the gaseous state is likely to have the highest

hydration energy? Give a reason.
2. The table below shows the atomic radii and ionic radii of the elements in Group VII
of the Periodic Table.
Element F Cl Br I
Atomic radius(nm) 0.072 0.099 0.114 0.133
Ionic radius(nm) 0.136 0.181 0.195 0.216
(a) State and explain the trend in atomic radius of the elements.
(b) Explain why the ionic radius is larger than the atomic radius of corresponding
neutral atom for each element.
3. The table below shows the first ionization energies of the elements in Period 3 of the
Periodic Table.
Element Na Mg Al Si P S Cl Ar
Atomic number 11 12 13 14 15 16 17 18
-1
First ionization energy (kJmol ) 496 738 578 786 1012 1000 1251 1521
(a) Plot a graph of ionization energy against atomic number of the elements
(b) State and explain the trend in ionization energy of the elements
(c) Explain why the;
(i) first ionization energy of argon is very high
(ii) first ionization energy of Sulphur is less than that of phosphorus
(iii) first ionization energy of aluminium is less than that of magnesium
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4. The table below shows the first ionization energies of Group II elements
-1
First ionisation energy (kJmol ) 899 738 589 549 502
(a) Define the term first ionisation energy.

(b) State and explain the trend in ionization energy of the elements
5. (a)(i) What is meant by the term ionisation energy of an element?
(ii) Write an equation to show the first ionisation of magnesium
(b) The second and third ionisation energies of magnesium are and
respectively. Give a reason for the large difference between the
second and the third ionisation energies of magnesium.
6. The table below shows the results obtained for the ionisation energies of element X.
Electron number 1st 2nd 3rd 4th 5th

Ionisation energy (kJmol-1) 800 2400 3700 25000 32800
(a) Plot a graph of against number of electron removed.
(b) Explain the shape of your graph
(c) Write the formula of the chloride of X.
7. The graph below shows a plot of the logarithm of all the successive ionisation
energies against number of electrons removed for element Y.
log (Ionisation energy)
Number of electrons removed.

(a) Explain the shape of the graph
(b) State the electronic configuration of element Y.
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8. Successive ionisation energies(kJmol-1) for some elements in Period 3 of the periodic

Table are shown in the table below.
Element Ionisation energy
1st 2nd 3rd 4th 5th
Silicon 787 1577 3230 4355 16090
Phosphorus 1060 1896 2908 4954 6272
Sulphur 1000 2258 3381 4565 6995
(a) State and explain the trend in successive ionisation energies.
(b) Explain why the;
(i) First ionisation energy of sulphur is less than that of phosphorus
(ii) third ionisation energy of phosphorus is less than that of silicon.
(iii) the first ionisation energy of aluminium is less than that of magnesium.
9. The table below shows the first three successive ionisation energies of elements A, B,
C, D, E and F.
Ionisation Element

energy(kJmol-1) A B C D E F
st
1 1013 1000 1255 1519 418 590
nd
2 1904 2255 2297 2665 3067 1146
rd
3 2916 3389 3853 3933 4393 4916
With a reason in each case; state which element;
(i) is a noble gas

(ii) belongs to group I
(iii) belongs to group II
10. The table below shows the first five ionisation energies of elements W, X, Y and Z.
Ionisation energy(kJmol-1)
Element 1st 2nd 3rd 4th 5th
W 577 1816 2745 11575 13251
X 738 1450 7730 10550 12756
Y 495 4563 6912 9540 11936
Z 1255 2297 3849 5163 13989
(a) Identify the group to which each of the elements belongs and give a reason for your
answer.
(b) Give a pair of elements which;
(i) forms an ionic bond between them
(ii) forms an ionic compound.
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11. Explain what is meant by the term first electron affinity.

(b) State three factors that can affect electron affinity.
(c) The first electron affinities of some elements in Period 3 are given in the table
below.
Element Al Si P S
First electron affinity -44 -134 -71.7 -200
(i) State the trend in variation in electron affinities
(ii) Explain your answer in c(i) above.
12. The table below shows the electronegativity values of the elements in Group VII of
the Periodic Table.
Element F Cl Br I
Electronegativity 4.10 2.83 2.74 2.21
13. Explain the following observations;

(a) The potassium ion is larger than the calcium ion yet the two ions have the same
electronic configurations.
(b) The ions and have the same electronic configuration but the ionic
radius of is lower than that of
(c) The first electron affinities of the halogens generally decrease down the group.
However, the first electron affinity of fluorine is abnormally high.
(d) There are no compounds containing the or ions although the first
electron affinities of oxygen and Sulphur are and
respectively.
(e) Oxygen is more electronegative than Sulphur although more energy is released
when a Sulphur atom accepts an electron than when an oxygen atom accepts an
electron.
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CHAPTER THREE
STRUCTURE AND BONDING
CHEMICAL BONDING
Chemical bonding is one of the basic fundamentals of chemistry that explain other
concepts such as chemical reactions. An atom consists of the nucleus containing protons
and neutrons and electrons in certain energy levels rotating around the nucleus. In
chemical bonding, only the valence electrons (electrons located in the outermost energy
levels) of an atom are involved.
Chemical bonds are forces that hold atoms, ions or molecules together to make
compounds. During formation of a chemical bond, atoms combine in order to acquire a
noble gas electronic structure. This can be achieved by either transfer of electrons from

one atom to another or by sharing electrons contributed by each atom or by electrostatic
attraction between delocalized electrons and positively charged ions.
Lewis Dot symbols

The American chemist G.N. Lewis devised a system of symbols called Lewis electron
dot symbols that can be used to predict the number of bonds formed by most elements in
their compounds. Each Lewis Dot symbol consists of the chemical symbol of the element
surrounded by dots. The dots represent the valence electrons of an element.
The following steps can be followed to draw Lewis Dot symbols of different elements
1. Identify the number of valence electrons for the element. These are the total number
of electrons in the outermost energy level. They can be known by the electronic
configuration
2. Write the correct chemical symbol of the element
3. Put one dot in all directions; up, down, left and right of the element symbol
4. If some electrons are left, begin doubling the dots
From the Lewis Dot symbol of each element, we can predict the number of bonds an
element can form during bonding.
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Examples
Draw the Lewis Dot symbols for the elements Boron, Carbon, Nitrogen and Oxygen
Element Atomic Electronic Number Lewis Dot Number of bonds

number configuration of structure that can be formed
Valence
electrons
3 1 Three bonds
6 4 Four bonds
7 5 Three bonds

8 6 Two bonds
Note that the Lewis Dot symbols below cannot be correct because dots have to be placed
in all directions before pairing occurs.
The table below shows the electronic configuration of the first 20 elements of the
Periodic Table. Use the valence electrons of each element to draw its Lewis Dot
structure and predict the number of bonds the element can form
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Symbol Atomic Electronic configuration Lewis Dot Number of

number structure bonds that can
be formed
H 1
He 2
Li 3
Be 4
B 5
C 6
N 7
O 8

F 9
Ne 10
Na 11
Mg 12
Al 13
Si 14
P 15
S 16
Cl 17
Ar 18
K 19
Ca 20
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The octet rule and ions

Most elements, except noble gases, combine with other elements to form compounds.
Compounds are the result of formation of chemical bonds between two or more atoms of
different elements.
In the formation of a chemical bond, atoms lose, gain or share valence electrons to
completely fill their outermost energy levels and attain a noble gas configuration. This
tendency of atoms to have eight electrons in their outermost energy levels is known as the
octet rule.
It states that; an atom is most stable when there are eight electrons in its outermost
energy level.
Only the and electrons are involved in the octet rule. It does not apply to or
electrons.

Atoms of metallic elements have few electrons in their outer most sub energy levels. By
losing those electrons, metals can gain a noble gas configuration and satisfy the octet
rule. Similarly, atoms of nonmetals have close to eight electrons in their outermost sub
energy levels. They tend to readily accept electrons to achieve the noble gas
configuration, satisfying the octet rule.
The octet rule is important in the following ways;
1. It explains the formation of chemical bonds in various compounds depending on

the nature of the elements involved.
2. It is used to predict stability of atoms
Point of thought;
1. Outline the importance of the Octet rule in formation of ions and
stability of compounds.
2. Identify the stable ions of the first 20 elements of the Periodic Table
using the Octet rule.
Stable ions without an Octet
There are a number of elements whose atoms can exist in stable compounds by forming
bonds with less than eight valence electrons. When this occurs, the atom of the element
within the molecule is said to have an incomplete octet. The examples include; hydrogen
ion, beryllium ion, boron ion and aluminium ion. The boron ion and aluminium ion can
form stable ions in covalent compounds like boron trifluoride and aluminium chloride.
The phosphorus atom in phosphorus pentachloride has 10 electrons and Sulphur in
Sulphur hexafluoride has 12.
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Ionic bond formation

An ionic bond is also called an electrovalent bond.
It is formed by complete transfer of one or more electrons from one atom to another to
form oppositely charged ions.
The electron or electrons are transferred from a metallic element to a nonmetallic
element.
The element that loses electrons is electropositive since it forms a positive ion. The

element gaining electrons is electronegative since it forms a negative ion.
The cation and anion formed are held together by strong electrostatic forces of
attraction.
Examples;
(i) Formation of sodium chloride
𝑵𝒂 𝑪𝒍 𝑵𝒂 𝑪𝒍
The sodium atom has electronic The chlorine atom has electronic configuration,
configuration, . The 3s . The 3p subenergy level has
subenergy level has one electron and is five electrons and is unstable. The electron
unstable. This electron is transferred to the transferred from sodium occupies this sub energy
chlorine atom by sodium to form noble gas level to form noble gas
configuration, . A Sodium ion is configuration, . A chloride ion
formed. is formed.
The sodium ion and chloride ion get hold together by strong electrostatic forces of
attraction.
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(ii) Formation of magnesium oxide
2 2
𝑴𝒈 𝑶 𝑴𝒈 𝑶
The magnesium atom has electronic The oxygen atom has electronic configuration,
configuration, . The two 3s . The 2p sub energy level has four
electrons are transferred to the oxygen atom electrons and is unstable. The two electrons
by magnesium to form noble gas transferred from magnesium occupy this sub
configuration, . A magnesium energy level form noble gas
ion is formed. configuration, . An oxide ion is
formed.

The magnesium ion and oxide ion get hold together by strong electrostatic forces of
attraction.
Giant ionic structures

In giant ionic structures, metallic elements combine with non-metallic elements.
The ionic bonds formed in these compounds are strong electrostatic attractions between
the ions of opposite charges (cations and anions).
Each ion is surrounded by the greatest number of oppositely charged ions called the
coordination number.
Examples of giant ionic solids include sodium chloride, caesium chloride and zinc
blende.
Check under matter (specifically under the solid state of matter for details about
giant ionic structures)
Structures of some ionic compounds
Compound Structure
Sodium oxide
Magnesium oxide
Calcium chloride
Sodium hydride
Magnesium sulphate
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The properties of ionic compounds

Property Explanation
1. High melting and boiling There are strong electrostatic forces of attraction between
points. the oppositely charged ions that require a high amount of
energy to break.
2. They are strong electrolytes in In the ionizing solvent, the forces of attraction between the
molten state or aqueous state ions are greatly reduced and the oppositely charged ions
become free to move in molten or aqueous state under the
influence of an electric field.
3. They readily dissolve polar The ion-solvent interactions are stronger than ion-ion
solvents like water but interactions of the compound for polar solvents. Ion-ion
insoluble in non-polar solvents interaction is stronger than ion-solvent interaction and
like methylbenzene solvent-solvent interaction for non-polar solvents.
4. Exist as crystalline solids at There are strong electrostatic forces of attraction between
room temperature the oppositely charged ions that require a high amount of
energy to break at room temperature, keeping the
molecules so closely packed together.

Explain why sodium chloride is soluble in water but insoluble in benzene.
On dissolving in water, the electrostatic forces of attraction between the sodium ions and
chloride ions in the crystal lattice are greatly reduced. The ions become free to move in
solution. Since water is a polar molecule, the sodium ions get attracted to the negative
end of water molecules and the chloride ions get attracted to the positive end of the water
molecules. The formation of ion-solvent interactions releases enough energy to break the
sodium-chlorine bonds. The ion-solvent interactions are stronger than ion-ion
interactions in sodium chloride.
Benzene is non-polar. Ion-ion interaction is stronger than ion-solvent interaction and

solvent-solvent interaction in benzene.
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Covalent character in ionic compounds

The partial covalent character of an ionic bond is explained in terms of polarising power
and polarisability.
1. Polarising power
Polarising power is the power of a cation to distort the electron cloud of an anion.
The greater the polarising power of the cation, the greater the tendency of the cation to
form a covalent bond.
Polarising power of a cation depends on;

(i) Charge of the cation
Cations with high charges have high polarising power. The larger the positive charge on
the ion, the greater the attraction of the valence electrons. The ion therefore has a
higher polarising power than the due to its higher charge.
(ii) Cationic radius

The smaller the ionic radius, the higher the polarising power of the cation. The ion
therefore has a higher polarising power than the due to its smaller ionic radius.
(iii) Charge density or charge-radius ratio.

Charge density is the ratio of ionic charge to ionic radius.
Ion
Ionic radius(nm) 0.095 0.065 0.050
Charge density
The higher the charge density, the higher the polarising power of the cation. From the
table above, charge density and hence polarising power increases in the order
.The covalent character of the chlorides formed by the elements
increases from sodium chloride to magnesium chloride to aluminium chloride due to the
increase in polarising power.
In general, compounds in which a cation has a high charge and small ionic radius tend
to have a high charge density and high polarising power. This makes such compounds
tend to a covalent character and exhibit properties contrary to ionic compounds
Aluminium chloride, beryllium chloride, aluminium hydride, beryllium hydride,

beryllium oxide and beryllium hydroxide are partly covalent for reasons explained above.
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1. Polarisability
Polarisability is the ease by which the electron cloud of the anion can be distorted.
The greater the polarisability of the anion, the greater the tendency of the anion to form a
covalent bond.
Polarisability of an anion depends on the size of the anion
The smaller the anion, the lower it is polarizable and the larger the anion, the easier it is
polarized.
If we consider the halide ions, polarisability increases in the order
Examples to show effect of polarising power of cations and polarisability of anions

(i) The table below shows the melting points of the chlorides formed by the three
Period 3 elements.
Chloride
Melting point of the choride (oC) 801 712 180

State and explain the trend in melting points of the chlorides of the three metals.
Melting points of the chlorides decrease from sodium chloride to aluminium chloride.
Sodium chloride and magnesium chloride have giant ionic structures held by strong
ionic bonds which require a high amount of energy to break. The decrease in melting
point from sodium chloride to magnesium chloride is because magnesium ion has a
smaller ionic radius, higher charge density and higher polarising power than sodium
ion making magnesium chloride less ionic than sodium chloride. Aluminium chloride has
the lowest melting point because among the cations, the aluminium ion has the smallest
ionic radius, highest charge density and highest polarising power. Aluminium chloride
is therefore predominantly covalent. Covalent bonds require a low amount of energy to
break
(ii) Aluminium chloride dissolves in methylbenzene but sodium chloride does not.
The aluminium ion in aluminium chloride has a higher charge and a smaller ionic
radius than the sodium ion in sodium chloride. The aluminium ion therefore has a higher
charge density and higher polarising power than the sodium ion. The chloride ion being
greatly polarized by the aluminium ion makes aluminium chloride mainly covalent
hence soluble in non-polar methylbenzene. However, sodium chloride is purely ionic and
insoluble in non-polar solvents.
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(iii) The melting point of lead(II) chloride is 500℃ whereas that of tin(II) chloride
is 247℃. Explain this observation.
Lead(II) ion has a larger ionic radius than tin(II) ion. Therefore the tin(II) ion has a
higher charge density and polarising power than the lead(II) ion. This makes tin(II)
chloride mainly covalent whereas lead(II) chloride is mainly ionic. Covalent bonds need
a lower amount of energy to break than ionic bonds.
(iv) Lead(II) chloride is insoluble in ethanol whereas lead(IV) chloride readily
dissolves in ethanol.
The lead(II) ion in lead(II) chloride has a smaller charge and a larger ionic radius than
the lead(IV) ion in lead(IV) chloride. Therefore the lead(II) ion has a lower charge
density and lower polarising power than the lead(IV) ion. This makes lead(II) chloride
mainly ionic hence insoluble in nonpolar solvents whereas lead(IV) chloride is mainly
covalent hence soluble in non-polar solvents.

(v) the melting point of calcium oxide is higher than that of calcium chloride
The oxide ion in calcium oxide has a smaller ionic radius than the chloride ion in
calcium chloride. Therefore the oxide ion less easily polarized by the calcium ion
whereas the chloride ion is more easily polarized by the calcium ion. This makes
calcium oxide more ionic than calcium chloride. The ionic bonds in calcium oxide
require a higher amount of energy to break.
(vi) The table below shows the melting points of magnesium halides.
Formula of halide
Melting point(OC) 1263 714 711 634
Explain the general trend in melting points of the halides.
The melting points of the halides decrease from magnesium fluoride to magnesium
iodide. This is because the anionic radius increases from the fluoride ion to the iodide
ion. The degree of polarization of the anions also therefore increases from the fluoride
ion to the iodide ion, increasing the covalent character of the halides. Thus a
decreasing amount of energy is required to break the magnesium-halogen bonds that
become increasingly more covalent.
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Questions
1. Explain why
(a) calcium iodide is ionic whereas aluminium iodide is covalent
(b) Sodium chloride melts at 800 oC whereas aluminium chloride sublimes at 180 oC
(c) Beryllium chloride is more soluble in ethanol than in water whereas barium
chloride is more soluble in water than in ethanol
(d) The solubility of lithium chloride in ethanol is higher than the solubility of
potassium chloride in ethanol.
(e) aluminium fluoride sublimes at whereas aluminium chloride sublimes at
(f) aluminium chloride is soluble in methylbenzene and has a low melting point yet
aluminium fluoride is soluble in water and has a higher melting point.
(g) tin(II) chloride is a solid whereas tin(IV) chloride is a liquid at room temperature
(h) lead(II) fluoride has a higher melting point than lead(IV) fluoride

(i) iron(II) chloride is more ionic than iron(III) chloride
2. Explain why
(i) the solubility of lead(II) halides increases in the order;
(ii) melting points of the halides of aluminium decrease in the order;
3. The table below shows the melting points of the chlorides of Group II elements.
Chloride
Melting point (OC) 405 714 782 875 962
Explain why;
(i) the melting point of beryllium chloride is very low
(ii) melting point increases from magnesium chloride to Barium chloride
Covalent bond formation

A covalent bond is formed when electrons are shared in pairs between two bonded
atoms.
In a single covalent bond between two atoms, one electron is contributed by each atom
and is shared as a pair of electrons.
The shared pair of electrons is called a covalent bond.
The shared pair of electrons occupies the same orbital with opposing spins and each of
the electrons must be unpaired from the orbital in which it is got.
In double covalent bonds, two pairs of electrons are shared and in a triple covalent bond,
three pairs of electrons are shared.
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Covalent bonds may be formed between atoms of the same element or atoms of
different elements
Usually the bonding atoms contribute an equal number of electrons towards formation of
a normal covalent bond.
Examples
(i) Formation of chlorine molecule
𝑪𝒍 𝑪𝒍 or
The chlorine atom has electronic configuration, . The

chlorine molecule is formed by each of the chlorine atom sharing one of its

valence electrons with another atom. The two atoms approach each other
closely for their atomic orbitals to overlap.
(ii) Formation of hydrogen chloride molecule
or
𝑯 𝑪𝒍
The hydrogen atom has electronic configuration and the chlorine atom has
electronic configuration, . Hydrogen contributes its only electron and
chlorine contributes one of its valence electrons. The electron pair is shared to make
hydrogen have a full s sub energy level and chlorine to have a full octet.
(iii) Formation of ethene

In an ethene molecule, each carbon atom shares one pair of electrons with a hydrogen
atom and two pairs of electrons with the other carbon atom. When atoms share two pairs
of electrons, a double bond is formed between them. Each carbon atom forms single
bonds to two hydrogen atoms and a double bond to the other carbon atom.
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𝑯 𝑯
or
𝑪 𝑪
𝑯 𝑯
In a simple way, covalent bonds are usually represented by a line to indicate a pair of
shared electrons, double lines to indicate two shared pairs and triple lines to indicate a
three shared pairs.
Other covalent molecules include; .
Types of covalent bonding

There are three types of covalent bonds which include; normal covalent bond, polar
covalent bond and a dative covalent bond.

1. The normal covalent bond
In a normal covalent bond, two atoms with very similar electronegativities or almost
similar electronegativities are bonded together and the combined atoms contribute an
equal number of electrons to be shared.
One electron is contributed by each atom for a single covalent bond.
The two electrons that are shared between the atoms must be unpaired and the must also
have opposite spins from the orbitals from which they are got.
The normal covalent bond results from overlapping of the atomic orbital or charge cloud
of one electron with another.
The two atomic orbitals produce one molecular orbital on overlapping as shown below.
𝑯 𝑯 𝑯 𝑯
Overlapping of atomic orbitals of hydrogen Resulting molecular orbital of hydrogen
2. Polar covalent bond

When a covalent bond is formed between two atoms whose electronegativity values are
greatly different, the bond becomes polar. For example in hydrogen fluoride molecule,
fluorine is more electronegative than hydrogen. The fluorine atom therefore pulls the
bonding electrons more towards its self. This makes fluorine gain a partial negative
charge and hydrogen a partial positive charge, making the hydrogen fluorine bond polar.
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The bonding electron density is greater towards the fluorine atom with a small negative
charge than towards hydrogen with a small positive charge
Other polar covalent bonds as a result of difference in electronegativity of the bonding

atoms include; , , , , , etc.
For two equal but opposite separated electrical charges, there exists an electric dipole
moment. An electric dipole moment is a product of one of the charges, or and
the distance between the atomic nuclei. Any individual polar covalent bond must have a

corresponding dipole moment.
However, there are molecules in which the individual bonds in it are polar but the
molecule as a whole is non-polar. This will be seen later under polarity of molecules.
3. Dative covalent bond

A dative covalent bond is a covalent bond formed when the shared pair of electrons is
contributed by only one of the bonded atoms.
A dative covalent bond is also called a coordinate covalent bond.
The atom that contributes the pair of the electrons is the donor atom and the other atom
is called the acceptor atom. For an atom to act as a donor atom, it must have atleast one
pair of unshared electrons, called a lone pair.
For an atom to act as an acceptor atom, it must have atleast one vacant orbital. An
acceptor can be a transition metal atom or an atom in a molecule.
An arrow ( ) is always drawn from the donor atom to the acceptor atom to show a
dative bond.
Examples
(i) Formation of hydroxonium ion.
[ ]
This ion is formed by coordination of water to a hydrogen ion. The oxygen atom in the
water molecule has two lone pairs of electrons. The hydrogen ion has electronic
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configuration .The hydrogen ion therefore accepts one of the lone pairs of electrons
from oxygen to have a full 1s sub energy level. This results into formation of the
hydroxonium ion.
(ii) Formation of Ammonium ion
[ ]
This ion is formed by coordination of ammonia to a hydrogen ion. The nitrogen atom in
the ammonia molecule has a lone pair of electrons. The hydrogen ion has electronic
configuration .The hydrogen ion therefore accepts the lone pair of electrons from
nitrogen to have a full 1s subenergy level. This results into formation of the ammonium
ion.
(iii) Formation of dimerised aluminium chloride , dimerised iron(III)

chloride and dimerised beryllium chloride .
(iv) Reaction between ammonia and anhydrous aluminium chloride
or
The nitrogen atom in the ammonia molecule has a lone pair of electrons. The aluminium
atom has only three valence electrons. When aluminium covalently bonds with three
chlorine atoms in aluminium chloride, it has six electrons in its outermost energy level,
requiring two electrons to complete its octet. Since nitrogen is more electronegative than
hydrogen in ammonia, it has a partial negative charge. Also aluminium is less
electronegative than chlorine in aluminium chloride, hence has a partial positive charge.
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There is therefore an attraction between nitrogen atom and aluminium atom. The lone
pair of electrons on the nitrogen atom is donated to the aluminium atom to form a dative
bond.
Ammonia can also form coordinate bonds with boron trifluoride or boron trichloride
or
or
(v) Formation of transition metal complexes

In transition metal complexes, the donor atoms in ligands donate lone pairs of electrons
to the central metal atoms. These electrons occupy the empty d-orbitals of the transition
metal atoms. The ion formed is called a complex ion. An example is the

tetraamminecopper(II) ion.
[ ]
A distinction between the different types of covalent bond
Normal covalent bond Polar covalent bond Dative or coordinate

covalent bond
Can be formed between two The atoms involved must be A dative bond is formed
similar atoms of the same different between two different atoms
element
Can occur between atoms of The bond occurs between atoms with different
the same electronegativity or electronegativities
almost similar
electronegativities
Each atom contributes an equal number of electrons to be The bonding electrons are
shared contributed by only one of
the involved atoms
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Covalent bond strength

The strength of a bond is represented by its bond dissociation energy.
Bond dissociation energy is defined as the heat absorbed when one mole of a covalent
bond is broken down into its constituent gaseous atoms.
Bond dissociation energy is an endothermic process hence denoted by a positive value.
Strength of a covalent bond depends on the following factors;

(i) Bond length
The shorter the bond length, the stronger the covalent bond and the longer the bond
length, the weaker the covalent bond. This is because when bond length increases, the
region of space between atoms in which electrons are shared becomes proportionally
smaller as atomic radius increases.
(i) Atomic radius
The larger the atomic radii of bonding atoms, the greater the bond length and the lower

the bond dissociation energy. The lower the bond dissociation energy the lower the bond
strength. The smaller the atomic radii, the smaller the bond length and the higher the
bond dissociation energy. The higher the bond dissociation energy the higher the bond
strength.
(ii) Electronegativity difference of bonding atoms
The greater the electronegativity difference between the atoms covalently bonded
together, the greater the bond polarity and the higher the bond dissociation energy. Bond
strength increases with increase in polarity of bonds
(iii) Number of bonding electron pairs
Triple bonds involve three electron pairs and are shorter and stronger than double bonds
which involve two electron pairs which are also shorter and stronger than single bonds
that involve one electron pair between similar atoms. The energy required to break the
bonds therefore decreases as for the case of carbon-carbon bonds shown below
Bond Bond dissociation energy( )
Examples
1. The respective bond energies of the covalent bonds of group IV elements are
given below.
Bond C C Si Si Ge Ge
-1
Bond dissociation energy(kJmol ) 346 175 168
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State the trend in bond energy. Give a reason for your answer.
222
The bond energy decreases from carbon-carbon bond to silicon- silicon bond to
germanium-germanium bond. This is because the atomic radius increases from carbon
to germanium, bond length increases and bond strength decreases.
2. The table below gives bond energies of hydrogen halides.

Hydride HF HCl HBr HI
-1
Bond energy(kJmol ) 556 431 336 299
Explain the observed trend in bond energy
The bond energy decreases from hydrogen fluoride to hydrogen iodide. This is because
the atomic radius increases from fluorine to iodine, bond length increases and bond
strength decreases.
Question
The table below gives bond energies of Carbon-halogen bonds.
Bond C F C Cl C Br C I

-1
Bond energy(kJmol ) 452 351 293 234
Explain the observed trend in bond energy
Giant covalent structures

When many very strong covalent bonds link one atom to another to form an extensive
three dimensional lattice, a giant covalent structure is formed.
Examples of giant covalent solids include diamond, graphite, silicon, silicon(IV) oxide
and fullerene.
Giant covalent solids have high melting points and are non-volatile due to the strong
covalent bonds holding the atoms together.
Check under matter (specifically under the solid state of matter for details about
giant covalent structures)
Properties of covalent compounds

Property Explanation
1. Low melting and boiling There are weak forces of attraction between the molecules thus
points. a low amount of energy is required to break them.
2. They do not conduct They neither form free mobile ions nor have delocalized
electricity except graphite electrons to conduct electricity.
3. Most covalent substances are In polar solvents, the solvent-solvent interaction is much
insoluble in polar solvents like greater than interaction between the covalent molecules in the
water but soluble in non-polar solute or the interaction between the covalent molecules and
solvents like benzene, ethanol the polar molecules in the solution. Covalent compounds tend
or propanone to dissolve in non-polar solvents because van der Waals’
forces are the binding forces in both cases.
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Note that some covalent compounds containing polar bonds as

or may dissolve in water due to interaction
between the polar bond and the water.
4. Exist as gases or liquids at There are weak van der Waals’ forces of attraction between
room temperature the molecules that require a low amount of energy to break at
room temperature, keeping the molecules far apart.
Point of thought; Compare properties of ionic and covalent compounds.
Intermolecular forces
Intermolecular forces are forces that exist between molecules. There a number of types of
intermolecular forces. They include; van der Waals forces and the hydrogen bond.
They are different from forces holding individual atoms in a molecule. The forces
between atoms in a molecule are called the intramolecular forces.

Intermolecular forces Intramolecular forces
van der Waals forces Covalent bond
Hydrogen bonds Ionic bond
Metallic bond
Intermolecular attraction intramolecular attraction (polar covalent bond)

(hydrogen bond)
Van der Waals’ forces

These forces are neither ionic nor covalent. The van der Waals forces may exist between
polar molecules and these are called dipole-dipole interactions. The van der Waals
forces that exist between non-polar molecules are called London dispersion forces
(temporary dipole-dipole attractions).
(i) Dipole- dipole interactions

Polar molecules like hydrogen chloride and ammonia, interact to form an ordered
arrangement. In this arrangement, partial positive charge in one molecule is adjacent to
partial negative charge in another molecule.
The dipole-dipole attractive forces are increased by one dipole inducing a dipole in
another neighbouring molecule.
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(ii) London dispersion forces (temporary dipole-dipole)

Attractions also exist between non-polar molecules like the molecules of gases
, halogens and noble gases.
This is due to momentary polarization of the molecules.
If two nonpolar molecules are very close to each other, the arrangement of electrons is on
average symmetrical.
However at any given instant, the electron distribution in one molecule may be
unsymmetrical and a dipole may be in that molecule at that particular instant. This dipole
is called a temporary dipole.
The temporary dipole in one molecule can attract the electron cloud of the neighbouring
molecule and this makes both molecules to have dipoles.
The dipoles are in such a way that the molecules attract each other.
Since electrons move at high speed, the dipole may be in the other molecule in the next
instant. The induced dipole by one molecule into another results into an attraction.

The dipoles are temporary, but the net attraction which they produce is permanent. This
attraction is due to London dispersion forces.
The London dispersion form of van der Waals force is usually very weak and only
function when the molecules are very close to each other.
The size of the force however increases as the number of electrons in the molecules
increase.
Van der Waals forces are in general very weak compared to ionic or covalent bonds. This
is shown by the low melting and boiling points of substances held together by van der
Waals‟ forces
Examples to explain the effect of van der Waals’ forces
1. Explain why graphite is soft and slippery.
Each carbon atom in graphite is covalently bonded to three other carbon atoms to form
two dimensional layers of hexagonal rings of carbon atoms. The hexagonal layers held
together by weak Van-der-Waals’ forces of attraction which allow the layers to slide over
each other.
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Strong covalent bond

Layer one
Weak van der Waals forces
Carbon atoms
Layer two
2. The table below shows the melting points of the some elements in Period 3 of the
Periodic Table.
Element P S Cl Ar
Melting point(OC) 44.2 115.2 -101.5 -189.4

Explain the trend in the melting points the elements
Phosphorus, Sulphur, chorine and argon have simple molecular structures with weak
Van-der-Waal’s forces of attraction whose magnitude increases in strength with
increase in molecular weight. Sulphur is octatomic (S8) with a higher molecular weight
hence stronger Van der Waal’s forces of attraction than Phosphorus which is
tetratomic(P4). Chlorine is diatomic (Cl2), with a higher molecular weight and stronger
Van-der-Waal’s forces than argon which is monoatomic. The energy required to break
the Van-der-Waal’s forces therefore decreases from phosphorus to argon.
3. Silicon, phosphorus, Sulphur and chlorine are period 3 elements that form
oxides whose melting points decrease in the order .
Explain the trend in melting points of the oxides
Silicon(IV) oxide has a giant covalent structure in which each silicon atom is bonded to
four oxygen atoms making very many strong covalent bonds that require a high amount
of energy to break. Phosphorus pentoxide, sulphur trioxide and Chlorine(VII) oxide have
simple molecular structures whose molecules are held by weak van der waal’s forces of
attraction whose strength decreases with decrease in polarity of the molecules as a
result of increase in electronegativities of the atoms bonded to oxygen
4. Briefly explain why carbon dioxide is a gas whereas silicon(IV) oxide is a solid at
room temperature.
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Carbon dioxide is non-polar. It has discrete molecules with a simple molecular structure
held by weak van der Waals forces of attraction which are easily overcome at room
temperature keeping the molecules far apart from each other.
However, in silicon(IV) oxide, each silicon atom is covalently bonded to four oxygen
atoms to form a tetrahedral structure which is continuous to form a giant molecular
structure with very many strong covalent bonds that are not easily broken at room
temperature, keeping its molecules very close to each other.
5. The table below shows the boiling points of the hydrides of group IV elements.
Hydride CH4 SiH4 GeH4 SnH4 PbH4

0
Boiling point( C) -161.5 -111.9 -88 -52 -13

Explain the trend in variation of the melting points of the hydrides.
(Note that all these hydrides are gases)
Boiling point increases from methane to plumbane.
This is because molecules of the hydrides are held by weak van der Waals’ forces of
attraction whose strength increases with increase in molecular weight and molecular
size.
6. Explain why fluorine and chlorine exist as gases whereas bromine and iodine
exist as liquid and solid respectively at room temperature
From fluorine to iodine, atomic radius increases, molecular size and molecular mass
increases, hence magnitude of Van der Waals’ forces of attraction holding the molecules
increase in the order; . The Van der Waals’ forces in bromine and
iodine are strong enough to hold the molecules closer to each other existing as liquid and
solid respectively. Fluorine and chlorine have weaker Van der Waals’ forces due to their
small size and low molecular masses. Their molecules are therefore far apart.
7. The table below shows the boiling points some alkylhalides
Element
Boiling point(OC)
Explain the trend in boiling points of the chloroalkanes.
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Boiling point increases from chloromethane to chloroethane to chloropropane to

chlorobutane.
This is because molecules of the chloroalkanes are held by weak van der Waals’ forces of
attraction whose strength increases with increase in molecular weight and molecular
size.
8. The table below shows the boiling points some alkylhalides
Element
Boiling point(OC)
Explain the trend in boiling points of the alkylhalides
Boiling point increases from fluoromethane to chloromethane to bromomethane to

iodomethane.
This is because the atomic radius of the halogen atoms increases in the order;
, molecular size and molecular mass of the alkylhalides increases,

hence magnitude of Van der Waals’ forces of attraction holding the molecules increases.
9. 2, 2-dimethyl propane boils at a lower temperature than n-pentane yet both are
of the same molecular weight.
2, 2-dimethyl propane is a branched isomer giving it a spherical shape which reduces its
size and weaker Vander Waal’s forces of attraction will exist between the molecules.
n-pentane is a straight chain molecule which gives the molecule an extended structure
resulting into relatively stronger Vander Waal’s forces.
The hydrogen bond

A hydrogen bond is a dipole- dipole attraction which occurs between a hydrogen atom
attached to a strongly electronegative atom and a second strongly electronegative atom
with a lone pair of electrons.
The electronegative atoms are commonly fluorine, oxygen or nitrogen.
Fluorine has the highest electronegativity. For this reason, hydrogen fluoride forms the
strongest hydrogen bonds which persist even in vapour state.
The greatest number of hydrogen bonds known are those which unite two oxygen atoms.
The hydrogen bond is weaker than a normal covalent bond.
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Types of hydrogen bonding

(i) Intermolecular hydrogen bonding
This is the type of hydrogen bond that occurs between two or more similar or different
molecules.
Intermolecular hydrogen bonds occur in the following examples;
(a) Hydrogen fluoride , water and ammonia molecules
Hydrogen fluoride
If two polar hydrogen fluoride molecules are close enough, there is an attraction between
the positive end of one molecule and the negative end of the other molecule. Since the
attraction between the hydrogen atom in one molecule and the fluorine atom in the other
molecule is stronger than the repulsion between the two hydrogen atoms and between the
two fluorine atoms, the two molecules are bonded together by a hydrogen bond.

Intermolecular hydrogen bond
This explains why hydrogen fluoride is a liquid whereas other group VII hydrides are
gases at room temperature; hydrogen fluoride has a higher boiling point than any other
hydride of group VII.
Water molecules
Water molecules also associate through intermolecular hydrogen bonding. Each water
molecule forms four hydrogen bonds with other water molecules. This explains why
water has higher boiling point and is a liquid whereas hydrogen sulphide has a lower
melting point and is a gas although both Sulphur and oxygen are group VI elements.
Intermolecular hydrogen bonds
229
Ammonia
Both ammonia and phosphine are trigonal pyramidal but ammonia has a
higher boiling point than phosphine . This is because nitrogen has a
smaller atomic radius and is more electronegative than phosphorus. This makes the
nitrogen- hydrogen bond strongly polar whereas the phosphorus- hydrogen bond is non-
polar. Ammonia molecules are therefore held together by strong hydrogen bonds which
require a high amount of energy to break than the weak van der Waals‟ forces in
phosphine.
Comparison between hydrogen fluoride, water and ammonia
Molecule Boiling point

Although fluorine is more electronegative than oxygen, meaning the hydrogen- fluorine
bond is more polar than hydrogen-oxygen bond and hydrogen fluoride would have
stronger hydrogen bonds than water, this is not shown by the boiling points of the two
compounds. Water has a higher boiling point than hydrogen fluoride because each
water molecule forms four hydrogen bonds whereas each hydrogen fluoride molecule
forms two hydrogen bonds. The higher the number of hydrogen bonds a compound
forms, the higher the boiling point. Since nitrogen is the least electronegative element,
the nitrogen- hydrogen bond is less polar than oxygen- hydrogen bond or hydrogen-
fluorine bond. Ammonia therefore forms weaker hydrogen bonds than those in water
or hydrogen fluoride.
(b) Alcohols
Alcohols associate in their liquid form due to intermolecular hydrogen bonding. The
boiling points of alcohols are higher than boiling points of corresponding alkanes or alkyl
halides with similar molar mass because of association through hydrogen bonding.
For example the boiling point of methanol is whereas that of methane is
.
Alcohols are also more soluble in water than alkanes or alkyl halides of similar molecular
mass because of the ability to form hydrogen bonds with water.
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Alcohols with more hydroxyl groups have higher boiling points than alcohols with one
hydroxyl group. Propane-1,2,3-triol, ethane-1,2-diol and ethanol have boiling points
, and respectively.
Viscosity of alcohols also increases as number of hydroxyl groups increases due to
increased hydrogen bonding.
(c) Carboxylic acids
When methanoic acid or ethanoic acid is dissolved in benzene or
other organic solvents and the relative molecular mass of the acid determined by
cryoscopic method, the value obtained is normally twice the actual value. This is
because in liquid state form or in solution in benzene, the acids associate through
intermolecular hydrogen bonds to form dimers. The same scenario happens when

measurements in the vapour phase of the acids are done.
Association(dimerization of methanoic acid) Association(dimerization of ethanoic acid)
Intermolecular hydrogen
bond
In aqueous solution however, molecules of carboxylic acids do not dimerise but form
intermolecular hydrogen bonds with water. This explains their solubility in water.
(d) Amines
Amines also associate in their liquid form due to intermolecular hydrogen bonding. The
boiling points of amines are higher than boiling points of corresponding alkanes with
similar molar mass because of association through hydrogen bonding.
Amines are also soluble in water because of the ability to form hydrogen bonds with
water.
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Amines have lower boiling points than corresponding alcohols or carboxylic acids
because nitrogen is less electronegative than oxygen. The nitrogen-hydrogen bonds are
less polar than oxygen- hydrogen bonds so the hydrogen bonds formed in amines are
weaker than in alcohols.
Primary amines have higher boiling points than secondary amines which also have higher
boiling points than tertiary amines of the same molecular mass. This is because the
nitrogen atom in primary amines has two hydrogen atoms hence can form more
intermolecular hydrogen bonds than the nitrogen atom in secondary amines which has
one hydrogen atom hence can form one intermolecular hydrogen bond. The nitrogen
atom in tertiary amines has no hydrogen atom that can form hydrogen bonds.

(e) Phenols
Phenols associate in their liquid form due to intermolecular hydrogen bonding. The
boiling points of phenols are higher than boiling points of corresponding alkanes or alkyl
halides because of association through hydrogen bonding.
Phenols are more soluble in water than corresponding alkanes or alkyl halides because of
the ability to form hydrogen bonds with water just like alcohols.
(ii) Intramolecular hydrogen bonding

This is the type of hydrogen bonding that occurs within the same molecule.
An example is the intramolecular hydrogen bond formed in 2-nitrophenol,
2-chlorophenol, 2-hydroxybenzaldehyde and 2-hydroxybenzoic acid |
232
2-nitrophenol 2-hydroxybenzaldehyde 2-hydroxybenzoic acid
Intramolecular
hydrogen bonds
The intramolecular hydrogen bonding prevents intermolecular hydrogen bonding

between two or more molecules. Intramolecular hydrogen bonding is not possible for 3-
and 4- substituted isomer (para and meta isomers) because of the substituent groups are
far apart. However the para and meta isomers can form intermolecular hydrogen bonds.

The intramolecular hydrogen bonding in ortho- substituted compounds explains their
difference in physical properties from their para- and meta-substituents. For example 2-
nitrophenol boils at whereas 3-nitrophenol and 4-nitrophenol boil at and
respectively.
Examples to explain the effect of hydrogen bonding

1. Explain why hydrogen fluoride is a liquid whereas other hydrides are gases at
room temperature.
Fluorine atom has the smallest atomic radius and highest electronegativity among the
halogens making the hydrogen-fluorine bond highly polar. The molecules of hydrogen
fluoride are held by strong intermolecular hydrogen bonds which keep the molecules
closer to each other. Molecules of hydrogen chloride, hydrogen bromide and hydrogen
iodide are held by weak Van der Waals’ forces that keep the molecules far apart.
2. The table below shows both boiling points of group VII hydrides.
O
Boiling point( C) +19.9 -85.0 -66.7 -35.4
Explain the variation in boiling points, including any anomalies involved.
Boiling points increases from hydrogen chloride to hydrogen iodide. However, hydrogen
fluoride has an abnormally high value of boiling point.
The increase in melting point from hydrogen chloride to hydrogen iodide is because the
three hydrides have simple molecular structures held by weak Van der Waals’ forces
whose magnitude increases with the increasing molecular weight leading to an increase
in amount of energy required to break the forces.
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Hydrogen fluoride has an abnormally high melting point because the fluorine atom
has the smallest atomic radius and the highest electronegativity, making the hydrogen-
fluorine highly polar. The hydrogen fluoride molecules are therefore held by strong
intermolecular hydrogen bonds which require a high amount of energy to break.
3. Explain why;
(i) 2-chlorophenol is less soluble in water than 4-chlorophenol.
Intramolecular
hydrogen bond
Molecules of 2-chlorophenol form intramolecular hydrogen bonds because the choro

group is nearer the hydroxyl group. This suppresses the hydroxylic character of the
compound or prevents formation of intermolecular hydrogen bonds between
2-chlorophenol and water molecules reducing its solubility. However, molecules of
4-chlorophenol cannot form intramolecular hydrogen bonds because the chloro group is
far from the hydroxyl group. Molecules 4-chlorophenol therefore form intermolecular
hydrogen bonds with water. This increases its solubility.
(ii) The boiling point of 2-nitrophenol is whereas that of 3-nitrophenol is

.
Intramolecular
hydrogen bond

Molecules of 2-nitrophenol form intramolecular hydrogen bonds because the nitro
group is nearer the hydroxyl group. This suppresses the hydroxylic character of the
compound or prevents formation of intermolecular hydrogen bonds between
2-nitrophenol molecules hence only weak van der Waals’ forces hold the molecules.
However, molecules of 3-chlorophenol cannot form intramolecular hydrogen bonds
|
because the nitro group is far from the hydroxyl group. Molecules of 3-nitrophenol
234
therefore form intermolecular hydrogen bonds which are stronger hence not easily
broken.
4. Explain why ice is less dense than water
Intermolecular
hydrogen
bonds
In ice, each oxygen atom in a water molecule is surrounded tetrahedrally by four other

oxygen atoms through extensive intermolecular hydrogen bonds. This gives ice an open
structure. The water molecules in ice are spaced and further apart than they are in
liquid water. Therefore ice occupies a bigger volume than that of liquid water of the
same mass. Since density is inversely proportional to volume, ice has a lower density
than water. However when ice melts, the hydrogen bonds break down and the molecules
pack closely together so that liquid water has a lower volume hence a higher density
than ice.
Questions
1. Explain why
(a) The melting of silicon is much higher than that of phosphorus yet both silicon and
phosphorus are covalent substances.
(b) hydrogen and helium gases show a small deviation from ideal behaviour
(c) For gases methane, ammonia, oxygen and carbon dioxide, the deviation from ideal
behaviour increases in the order .
(d) The boiling point of the given arylhalides increases in the order
(e) The boiling point of chlorobenzene is higher than benzene which is also higher
than cyclohexane
(f) Both carbon and silicon are group IV elements. However, the melting point of
carbon dioxide is whereas that of silicon dioxide is .
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2. The table below shows the boiling points some alkanes
Element
Boiling point(OC)
Explain the trend in boiling points of the alkanes.
3. The table below shows the boiling points of halogens
Element F2 Cl2 Br2 I2
O
Boiling point( C) -187.9 -34.0 58.2 +184.5
Explain the trend in boiling points of the halogens
(a) hydrogen fluoride has a higher boiling point than hydrogen chloride.
(b) melting point of 4 – nitrophenol is much higher than that of 2 – nitrophenol
(c) 4-nitrophenol is more soluble in water than 2-nitrophenol

(d) 2-hydroxybenzaldehyde has a lower boiling point than 3-hydroxybenzaldehyde
although the relative molecular masses of the two compounds are the same.
(e) boiling points of the given homologous series decreases in the order;
of the same molecular
mass.
(f) methyl amine ( ) boils at -6.3oC while methanol
( ) boils at 46oC.
(g) 2-methylpropan-2-ol boils at a lower temperature than butan-1-ol yet they all have
the same molecular weight.
(h) ethane boils at lower temperature than butane.
(i) water( ) is a liquid at room temperature whereas hydrogen
sulphide ( ) is a gas at room temperature
Metallic bonding
A metallic bond is the electrostatic force of attraction between positive metal ions and
delocalized electrons.
A metallic solid consists of a lattice of metal ions with the outer most electrons forming a
“sea” of delocalized electrons. The delocalized electrons freely move throughout the
structure and can conduct electricity. Electrostatic attractions exist between the
delocalized electrons and the metal ions.
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Properties of metals
The metallic bond is the bond that is responsible for the properties of metals.
1. High melting and boiling points.

This is because of a high amount of energy is required to break the strong metallic bonds.
Melting point increases as the number of electrons contributed per atom of a metal
towards metallic bonding increases. Transition elements have higher melting points than

main group elements because their atoms contribute both 4s and 3d electrons towards
bonding.
Qn. Explain why group II elements form metals with higher melting and boiling
points than group I elements
Both group I and group II elements form metallic bonds whose strength depend on the
number of electrons contributed per atom to the formation of the metallic bonds. Group
II elements contribute two electrons per atom forming stronger metallic bonds that
require a higher amount of energy to break than Group I elements which only
contribute one electron per atom towards forming weaker metallic bonds that require a
lower amount of energy to break.
Qn. Explain why the melting point of chromium is higher than that of calcium
Calcium has a larger atomic radius and only contributes the two 4s electrons per atom
towards metallic bonding hence forming weaker metallic bonds that require a lower
amount of energy to break than chromium which has a smaller atomic radius and
contributes both the one 4s electron and the five 3d electrons forming stronger metallic
bonds that require a higher amount of energy to break.
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2. Electrical conductivity
Metals are good conductors of electricity and heat due to presence of free mobile
electrons throughout the lattice. If a potential difference is applied between the ends of a
metal, the delocalized electron cloud will towards the positive potential.
However, electrical conductivity of a metal decreases with increase in temperature
because resistance increases. This is because increase in temperature increases thermal
vibration within the metal. The regularity within the metallic lattice is upset and therefore
the electrons cannot easily move in the lattice.
3. Thermal conductivity
They conduct heat due to exchange of kinetic energy between free mobile electrons in the
lattice. When heat is supplied to one end of a piece of a metal, the kinetic energy of the
electrons is increased. This increase in kinetic energy is transmitted through the system of

delocalized electrons to other parts of the metal.
4. Malleability and ductility

Metals are malleable (can be hammered-beaten into sheets) and ductile ( can be drawn
out under tension-pulled out into wires). This is due to the ability of layers of atoms to
roll over each other into new positions without breaking the metallic bond.
5. Insoluble in polar and non-polar solvents.

The metal-metal attractions are much stronger than the solvent-solvent attractions or the
metal-solvent attractions. The solvent molecules cannot penetrate the metal lattice.
Strength of a metallic bond

The strength of a metallic bond is determined by three factors;
1. Charge of the cation

The higher the cationic charge, the stronger the metallic bond because there will be a
stronger attraction of the delocalized electrons.
2. Number of delocalised electrons per atom

The higher the number of electrons contributed per atom towards metallic bonding, the
stronger the metallic bond. This is because there will be a greater attraction between the
nucleus and the delocalised electrons.
3. Ionic radius
The smaller the ionic radius of the cation, the stronger the metallic bond because there
will be a stronger attraction of the delocalised electrons.
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VALENCE BOND THEORY

The Valence Bond Theory (VBT) is one of the theories that were developed to explain
chemical bonding, along with the molecular orbital theory.
According to the theory, a covalent bond is formed between two atoms by the overlap of
atomic orbitals of each atom containing an unpaired electron.
The atomic orbitals of two atoms overlap to form chemical bonds but they do not lose
their identity.
The shape of a molecule depends upon the shapes of the combining atomic orbitals. Only
outer atomic orbitals for a valence energy level are involved in bonding. The number of
covalent bonds formed is equal to half the number of combining atomic orbitals.
Sigma and pi bonds

The nomenclature and used for atomic orbitals is replaced by and for molecular
orbitals.

Sigma bond
A sigma bond is formed by head to head or collinear overlap of two atomic orbitals
along their internuclear axis.
Only one sigma bond can exist between any two atoms. It is a strong bond because
orbitals can overlap to a greater extent.
pi bond
A pi bond is formed by sideways or collateral overlap of two atomic orbitals.

One or two bonds can exist between any two atoms. A bond shortens the bond
length (internuclear distance). Two bonds (as in a triple bond) shorten the bond length
to a greater extent than one bond (as in a double bond). It is a weak bond because of
poor overlapping of orbitals.
It exists only when a bond is already present between two atoms.
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239
Hybridisation of atomic orbitals

and orbitals of comparable energy can combine within an atom to form hybrid
orbitals. The hybrid orbitals have different shapes from and orbitals and they form
stronger bonds due to great overlap during bonding.
Below are some important points about hybridization:
1. Usually atomic orbitals containing one electron each are considered in

hybridisation
2. In most cases, one or more electrons are promoted to the next higher energy levels
so that the number of unpaired electrons becomes equal to the oxidation state of the
central atom in the molecule.
3. Lone pairs are also involved in hybridization if the geometry of the molecule can be

explained by involving them.
4. An orbital can accommodate a maximum of two electrons with opposite spins.
5. Hybrid orbitals have greater potential for overlapping than the ground state orbitals
from which they are constructed.
6. The experimentally determined bond angles of molecules are very close to the
directions of the hybrid orbitals.
Hybrid orbitals
(a) -hybridisation
This occurs when one and one -orbital of the same atom combine to form a set of two
equivalent -hybrid orbitals which are to each other.
The beryllium atom with electronic configuration has both the and
subenergy levels completely filled with electrons.
From the configuration in the ground state of Beryllium, it may not form compounds
since it has no unpaired electrons. However beryllium is known to form compounds in
which it is divalent.
For beryllium to form compounds, one of the electrons is promoted to the
subenergy level to form an excited beryllium atom, .
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The two and electrons combine to form two collinear hybrid orbitals.
In formation of beryllium chloride for example, the two hybrid orbitals overlap with
the two orbitals of two chlorine atoms to form to form two sigma bonds.
Two collinear hybrid orbitals Formation of two -bonds in beryllium
chloride
(b) -hybridisation
This occurs when one and two -orbitals of the same atom combine to form a set of
three equivalent -hybrid orbitals which are trigonal planar with a bond angle .
The boron atom with electronic configuration has the subenergy level
having one unpaired electron.

From the configuration in the ground state of Boron, two of the three two orbitals are
unoccupied.
For boron to form compounds, one of the electrons is promoted to one of the empty
orbitals to form an excited boron atom, . The excited boron atom therefore has two p
electrons.
Hybridization occurs between the remaining orbital and the two orbitals to form three
equivalent hybrid orbitals.
The axes of these orbitals lie in the same plane and at to each other.
This resulting hybridization therefore implies that the compounds of boron are
trigonal planar.
Three hybrid orbitals in the same
plane at
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(c) -hybridisation
This occurs when one and three -orbitals of the same atom combine to form a set of
four equivalent -hybrid orbitals which point towards the corners of a regular
tetrahedron with a bond angle of to each other.
The carbon atom with electronic configuration has the subenergy level
having one unpaired electron.
From the configuration in the ground state of carbon, two of the three two orbitals have
one unpaired electron each.
For carbon to form compounds, one of the electrons is promoted to the empty
orbital to form an excited carbon atom, . The excited carbon atom therefore has three p
electrons.
Hybridization occurs between the orbital and the three orbitals to form four
equivalent hybrid orbitals.
These are directed outwards from the carbon atom at an angle of with each other.
This resulting hybridization therefore implies that the molecules of methane or
tetrachloromethane are in a shape of a regular tetrahedron with the carbon atom at the
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centre and the hydrogen or chlorine atoms at the four corners.
242
Four hybrid orbitals directed

outwards from the carbon atom at an
angle of
Geometry for different types of hybridisation

Type of Spatial Bond angle Examples
hybridization arrangement

Linear
Trigonal planar
Tetrahedral
The formation of single, double and triple bonds

The formation of single, double and triple bonds in organic compounds is due to
hybridization.
(i) the carbon-carbon single bond
The carbon-carbon single bonds are all -bonds formed by
hybridization.
(ii) the carbon-carbon double bond
The carbon-carbon double bond for example in ethene consists of one -bond and one
bond formed by hybridization.
One of the electrons is promoted to the empty orbital to form an excited carbon
atom, .
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Hybridization occurs between the and the orbitals to form three equivalent
hybrid orbitals. Two of the hybrid orbitals form -bonds with the orbitals of
hydrogen. The remaining hybrid orbital forms a -bond between the carbon atoms
The unhybridised orbital forms a bond between the carbon atoms.
The two carbon atoms and four hydrogen atoms are all in the same plane and the bond
angle is . This gives ethene a trigonal planar shape.
(iii) the carbon-carbon triple bond

The carbon-carbon triple bond for example in ethyne consists of one -bond and two
bonds formed by hybridization.
One of the electrons is promoted to the empty orbital to form an excited carbon
atom, .
Hybridization occurs between the and the orbitals to form two equivalent
hybrid orbitals. One of these two hybrid orbitals forms a -bond with the orbital of
hydrogen. The remaining hybrid orbital forms a -bond between the carbon atoms.
The two unhybridised and orbitals form two bonds between the carbon
atoms.
This gives ethyne a linear shape.
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244
The double bond formation in benzene

Benzene has the structure as shown below;
or
Between each pair of adjacent carbon atoms is a sigma bond formed by overlapping
hybrid orbitals.
Because orbitals are planar, all the six carbon atoms and six hydrogen atoms lie in
the same plane and the bond angles are .
There are unhybridised orbitals for each of the carbon atoms with an axis at right
angles to the plane of the carbon atoms.
These six orbitals overlap with each other all around the ring to form delocalised
bonds.
The electrons in these orbitals are free to move between all the carbon atoms in the
ring and they are described as delocalised electrons.

NOTE: Benzene, just like ethene is formed by hybridisation but the difference is
what happens with the unhybridised orbitals.
DRAWING LEWIS STRUCTURES OF MOLECULES AND

POLYTATOMIC IONS
Lewis structures
A Lewis structure is a simplified representation of the arrangement of the outermost
electrons of each atom in a molecule and the lone pairs of electrons that may exist in the
molecule or polyatomic ions.
The electrons are shown as dots or as lines (for bonding electrons between two atoms).
For example when two chlorine atoms combine to form a chlorine molecule, the
following Lewis structure can be drawn;
The Lewis structure of a chlorine molecule shows 3 unshared electron pairs for each atom
(lone pairs) and one shared pair of electrons (bonding pair).
A line is sometimes used to indicate a shared pair of electrons.
The single shared pair of electrons is called a single bond.
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Drawing Lewis structures of some simple molecules

Molecule Description Lewis structure
It is known from the Lewis
Dot symbol of Nitrogen that
Ammonia it has one lone pair and can
form three bonds. Hydrogen
can form one bond and has
no lone pair
Dot symbol of Oxygen that it
Water has two lone pairs and can
form two bonds. Hydrogen
can form one bond and has
no lone pair
Dot symbol of Sulphur that it
can form two bonds and has

two lone pairs Each oxygen
Sulphur dioxide atom also has two lone pairs
and can form two bonds. But
for oxygen to form the two
bonds, one lone pair of
Sulphur must be used.
Dot symbol of Carbon that it
has no lone pair and can
Carbon tetrachloride form four bonds. Each
Chlorine atom has three
lone pairs and can form one
bond.
Steps for writing Lewis structures for more complex molecules/

polyatomic ions
1. Write the skeleton structure of the molecule or ion. The central atom is usually the
least electronegative element in the compound and then place a bonding pair of
electrons between each pair of adjacent atoms or draw a line to indicate a single
bond. In the water molecule for example, there is a bonding pair of electrons between
each oxygen atom and each hydrogen atom.
2. Determine the total number of Valence electrons for the atoms in the molecule or ion.
For a neutral molecule, this is the sum of valence electrons on each atom. This can be
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246
got from the Lewis Dot symbol of the atom or its electronic configuration. For a
negatively charged ion, add one electron for each negative charge.
For a positively charged ion, subtract one electron for each positive charge.
3. Subtract two valence electrons for each bond formed in the skeleton structure.
4. Beginning with the terminal atoms, add enough electrons of the remaining electrons
as valence electrons to satisfy the octets of the atoms (two for hydrogen). These
electrons are the lone pairs.
5. The remaining electrons are then placed on the central atom (some central atoms can
accommodate more than eight electrons)
6. If the central atom has fewer electrons than an octet, use lone pairs from terminal
atoms to form multiple (double or triple) bonds to the central atom to achieve an
octet. This will not change the number of electrons on the terminal atoms
Examples
In this table, we are using each of the steps 1-7 for different molecules or polyatomic

ions to draw their Lewis structures.
[ ]
Since there is a positive

charge, the total electrons
remain
3
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247
[ ]
6 Not applicable
Nitrogen cannot get an octet for

reasons explained later.
1
[ ]

* +
Since there is a positive charge, the total electrons

remain
Since there are 2 negative charges, the total
electrons becomes
3
4
[ ]
5
* +
All the remaining 18 electrons have been used

but carbon doesn’t have a full octet yet. Rule 6
must be satisfied.
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248
6 Not applicable
* +
More resonance structures can be made for this

ion as we shall see later.
Exceptions of the Octet rule

We already have an idea about the octet rule and we have applied it in many bonding
situations in this topic. We have equally used it in drawing Lewis structures.
However, there are three exceptions of the Octet rule, which include;
(a) Incomplete octet

(b) Expanded octet
(c) Odd number electron

(a) Incomplete octet
Molecules with atoms containing an incomplete octet of electrons generally contain the
lighter s-block and p-block elements especially beryllium with just four electrons around
the central atom and boron, typically with six electrons. Examples include;
 Beryllium chloride
 Boron trichloride
(b) Expanded octet
This is the most exception of the Octet rule. In applies to a molecule or an ion with at
least one atom that possesses more than an octet of electrons.
This applies commonly to compounds in period 3 and beyond. Examples from the p-
block elements include;
 Sulphur hexafluoride
 Sulphate ion
 Phosphate ion
 Phosphorus pentafluoride
Try to come up with probable Lewis structures of the above molecules/ ions
(c) Odd number electron
There are molecules such as nitrogen monoxide that have an odd number of electrons.
This is seen in one of the examples above.
Molecules of most s-block and p-block elements contain an even number of electrons.
Their bonding can therefore easily be described using the rules stated above.
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249
However, molecules or ions containing d-block elements commonly contain an odd

number of electrons. Their bonding cannot adequately be explained using the rules seen
above.
There also a few molecules however for the p-block elements that have an odd number of
electrons. These include;
Molecule Total number of electrons
Nitrogen monoxide
Nitrogen dioxide
Chlorine dioxide
Questions
Write the Lewis structures for the following species

1. 9.
2. 10.
3. 11.
4. 12.
5. 13.
6. 14.
7. 15.
8. 16.
Formal charges
A formal charge compares the number of electrons around a neutral atom and the number
of electrons around an atom in a molecule.
A formal charge is assigned to an atom in a molecule on assumption that the electrons in
all chemical bonds are shared equally between atoms regardless of relative
electronegativity.
( ) ( )
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250
Examples
1. Calculate the formal charges of the atoms in ammonia.
( )
( )

2. Calculate the formal charges of the atoms in the carbonate ion
* +
( )
( )
( )
Note;
(a) When formal charges on each of the atoms in a molecule are added, they must give
the total charge on the molecule.
(b) The structure with the most formal charges of zero on its atoms is the most stable
Lewis structure.
(c) In the case where there must be either positive or negative formal charges on
various atoms, the most stable structures have negative formal charges on the more
electronegative atoms and positive charges on the less electronegative atoms.
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251
Resonance
This is the situation in which two or more Lewis structures can be written. Resonance is
used when a single Lewis structure cannot fully describe the bonding in a molecule or
ion. Resonance structures arise when there are more than one way to draw a Lewis
structure that satisfies the Octet rule. They are drawn by placing double bonds between
different atoms and lone pairs on different atoms. Molecules with multiple resonance
structures are more stable than those with fewer resonance structures. Some resonance
structures contribute more to the stability of a molecule than others. This can be
determined using the concept of formal charges. The most stable resonance structure is
one with the least formal charge.
An illustration of how resonance structures arise
The carbonate ion

* + * + * +
The nitrate ion
* + * + * +
VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR)

THEORY
Beryllium chloride is a linear molecule without a dipole moment whereas tin(II)
chloride is a bent molecule with a dipole moment. Boron trichloride is
trigonal planar whereas ammonia is trigonal pyramidal.
A theory was put forward to explain the differences in shapes of molecules and ions. This
theory is known as the Valence Shell Electron Pair Repulsion Theory.
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252
The theory points out that the arrangement of electron pairs around a central atom in a
molecule depends of the number of electron pairs.
Between any electron pair and any other electron pair, there is a force of electrostatic
repulsion.
The electron pairs can be bonding or shared pairs which constitute the covalent bonds or
unshared (lone pairs).
Any lone pairs of electrons on the central atom repel the bonding pairs of electrons and
this affects the geometry (bond angle and shape) of the molecule.
For the purpose of determining electron geometry, the VSEPR theory considers the
electron pairs in a double bond or a triple bond are treated as one pair
Since the lone pairs are closer the to the central atom, they cause greater repulsion than
bonding pairs and the repulsions are in the order;

.
Predicting the shapes of molecules and ions

Note; In some of the three dimensional structures, the lone pairs of electrons are not
shown. These will be shown in further examples.
Number
of Total Number Number
valence electron of of lone Shape of molecule 3-dimensional Examples
electrons pairs bonding pairs presentation
pairs
4 2 2 0 Linear
, ,
[ ]
Bent or
6 3 2 1 V-shaped
6 3 3 0 Trigonal planar
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253
8 4 4 0 Tetrahedral
8 4 3 1 Trigonal

pyramidal
Bent or
8 4 2 2 V-shaped
Trigonal
10 5 5 0 bipyramidal
10 5 4 1 Irregular
tetrahedral
10 5 3 2 T-shaped
10 5 2 3 Linear
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254
12 6 6 0 Octahedral
12 6 5 1 Square pyramidal
12 6 4 2 Square planar

(a) Steps followed to draw the structure of molecules and cations
1. Determine the number of valence electrons on the central atom from its electronic
configuration or the number of its group in the Periodic Table.
 If the structure is for a cation, subtract an electron for each positive charge on the
number of valence electrons.
 If the central atom is a transition element, calculate the oxidation state and use it as
Molecule or ion Electronic Number of valence
configuration of electrons for central
central atom atom
2. Add one electron to the valence electrons in (1) above for each atom/ligand bonded to
the central atom as shown below.
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255
Molecule or ion Number of valence Total number of

electrons on central valence electrons
atom
3. Divide the total number of valence electrons by two to get the total number of
electron pairs. This is because electrons bond in pairs
Molecule or ion Total number of Total number of
valence electrons electron pairs

4. From the total number of electron pairs, subtract the number of bonding pairs to get
the number of lone pairs. The number of bonding pairs corresponds to the number of
bonded atoms to the central atom.
Molecule or ion Total number of Number of Number of
electron pairs bonding pairs lone pairs
5. Then draw the structure of the molecule using the summary in the table above,
showing prediction of shapes of molecules. The lone pairs are shown as two dots
around the central atom for each electron pair. Put the VSEPR theory into
consideration as you draw the molecule/ion.
Molecule or ion Number of Number of Structure Shape
bonding pairs lone pairs
Trigonal
̈ pyramidal
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256
[ ] Tetrahedral
Octahedral
..
O.. Bent
NOTE;
(i) It is strictly that number of bonding pairs and lone pairs that guide us on the

geometry of the molecule.
(ii) Bond angles and bond lengths should be put into consideration when
drawing the structures
(iii) The lines that represent the bonds should strictly not leave a lot of space
between the atoms.
(b) Steps followed to draw the structure of oxy-anions and oxy-

molecules
These are molecules or anions containing oxygen atoms. They are treated in a
special way since they contain –OH bonds , =O bonds and bonds.
1. Determine the number of valence electrons on the central atom from its electronic
configuration or the number of its group in the Periodic Table.
 If the central atom is a transition element, calculate the oxidation state and use it as
 The number of valence electrons is used to deduce the expected number of bonds to be
formed by the central atom.
Molecule or ion Electronic Number of valence
configuration of electrons on central
central atom atom
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257
Oxidation state of Mn
is
6. Deduce the nature of bonds in the ion or molecule. Begin with bonds, followed
by bonds and then bonds.
(i) For every negative charge in the anion, there is one bond.
(ii) For every hydrogen atom, there is one bond.
(iii) All the remaining oxygen atoms are double bonded after (i) and (ii) or if (i)
and (ii) do not apply to the molecule.
Molecule or ion Expected number Nature of bonds
of bonds formed by
central atom
bonds

bonds
bond
bonds
bond
bond
bond
bonds
bonds
bond
bond
bond
bonds
bonds
7. Since for each single bond, one electron of the valence electrons of the central atom is
used, and two for a double bond, the unbounded electrons are the lone pairs. The lone
pairs are obtained by subtracting the number of bonds formed from the number of
valence electrons.
Number of valence Number of
Number of electrons involved in non-bonding
Molecule or valence Nature of bonds bonds electrons
ion electrons of (lone pairs)
central atom
bonds
bonds
bond (1 lone pair)
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258
bonds
bond
bond
bond (1 lone pair)
bonds
bonds
bond
bond
bond
bonds
bonds
8. Draw the structure of the molecule/ion using the nature of bonds and lone pairs.
Where there are no lone pairs in the molecule/ ion, the bonds are symmetrically
placed around the molecule.

Molecule or Nature of bonds Number of Structure Shape
ion lone pairs
bonds Trigonal
planar
̈
bonds Trigonal
bond pyramidal
bonds Tetrahedral
bond
̈
bond Bent
bond
bonds Tetrahedral
bonds
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259
bond
bond Trigonal
bond planar
bonds Tetrahedral
bonds
(a) Molecules or ions with a linear shape

Linear molecules have two bonding pairs and no lone pairs. The molecules are linear
with a bond angle of because the bonding pairs greatly repel themselves.
The molecules in gaseous beryllium chloride are linear because the two bonded pairs

around the beryllium atom repel each other as fully as possible giving the molecule a
bond angle of .
For example in ,
 It is treated as an oxy-molecule.
 The carbon (central) atom has valence electrons from its electronic
configuration.
 Carbon is therefore expected to form bonds with the oxygen atoms.
 Each oxygen atom forms a double bond to the carbon atom and no lone pair
remains.
 The two bonding pairs greatly repel themselves greatly to form a linear molecule,
bond angle .
Some ions also form a linear structure. These have two bonding pairs and three lone
pairs.
For example in ,
 The iodine (central) atom has valence electrons from its electronic configuration.
 Since the structure is for an anion with negative charge one, the total electrons
are .
 of these electrons are used for bonding with the chlorine atoms.
 This leaves 6 electrons not used for bonding and form the three lone pairs.
 The geometry of two bonding pairs and three lone pairs corresponds to a linear
molecule, bond angle .
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260
In or , there are three lone pairs and one bond pair surrounding the central
oxygen atom. They are also linear species.
Molecule Structure Shape
Linear
[ ̈ ]
(b) Molecules or ions with a bent shape

Bent molecules or ions are also called V-shaped molecules or ions. They either have;
(i) two bonding pairs and one lone pair or

(ii) two bonding pairs and two lone pairs

For example in ,
 The sulphur (central) atom has valence electrons from its electronic
configuration.
 Since it is bonded to two hydrogen atoms, the total number of valence electrons in
the molecule is .
 The total number of valence electrons divided by two gives four electron pairs.
 Of the four electron pairs, there are two bonding pairs since Sulphur is bonded to
two hydrogen atoms and two lone pairs.
 The repulsion between the two lone pairs of electrons is greater than the repulsion
between lone pairs and bonding pairs of electrons which is also greater the
repulsion between the bonding pairs of electrons.
 This reduces the bond angle to making the molecule V-shaped.
For example in ,
 The lead atom has valence electrons from its electronic configuration.
 Since it is bonded to two chlorine atoms, the total number of valence electrons in
the molecule is .
 The total number of valence electrons divided by two gives three electron pairs.
 Of the three electron pairs, there are two bonding pairs since lead is bonded to two
chlorine atoms and one lone pair.
 The two bonding pairs of electrons repel each other but the lone pair-bond pair
repulsion is greater.
 This reduces the bond angle to a value smaller than making the molecule
|
V-shaped.
261
Some ions also form a bent structure.

For example in ,
 It is an oxy-anion
 The chlorine atom has valence electrons from its electronic configuration.
 Chlorine is therefore expected to form seven bonds.
 The negative charge in the anion means there is one bond.
 The remaining oxygen atom is doubly bonded to chlorine
 This implies that 3 of the 7 electrons are used for bonding and the remaining 4
form two lone pairs.
 The repulsion between the two lone pairs of electrons is greater than the repulsion
between lone pairs and bonding pairs of electrons which is also greater the
repulsion between the bonding pairs of electrons.
 This reduces the bond angle making the molecule V-shaped.

.. ..
S
̈
V-shaped
..
Cl..
(c) Molecules or ions with a trigonal planar shape

Trigonal planar molecules have three bonding pairs of electrons and no lone pairs. The
three bonding pairs lie in the same plane and the molecules have a bond angle of
because the bonding pairs greatly repel each other equally.
For example in ,
 The boron atom has valence electrons from its electronic configuration.
 Since it is bonded to three fluorine atoms, the total number of valence electrons in
the molecule is .
 The total number of valence electrons divided by two gives three electron pairs.
 All the three electron pairs are used in bonding to form three bonding pairs since
boron is bonded to three fluorine atoms and there is no lone pair.
 The three bonding pairs of electrons repel each other equally.
 This makes the bond angle making the molecule trigonal planar.
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For example in ,
 The carbon atom has valence electrons from its electronic configuration.
 Two of these are used to bond to each hydrogen atom and two to form a double
bond with oxygen .No lone pair remains.
 This gives the molecule three bonding pairs and no lone pair.
 The three bonding pairs of electrons repel each other equally.
 This makes the bond angle making the molecule trigonal planar.
Trigonal planar

C
(d) Molecules or ions with a tetrahedral shape

Tetrahedral molecules or ions have four bonding pairs of electrons and no lone pairs.
They have a bond angle of because the bonding experience mutual repulsion.
For example in ,
 The silicon atom has valence electrons from its electronic configuration.
 Since it is bonded to four chlorine atoms, the total number of valence electrons in
the molecule is .
 All the four electron pairs are bonding pairs since silicon is bonded to four chlorine
atoms and no lone pairs.
 The four bonding pairs of electrons mutually repel each other, resulting into a bond
angle of making the molecule tetrahedral.
Some ions also form a tetrahedral structure.
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263
For example in ,
 The phosphorus atom has valence electrons from its electronic configuration.
 Phosphorus is therefore expected to form five bonds.
 The three negative charges in the anion means there are three bonds.
 The remaining oxygen atom is doubly bonded to phosphorus
 This gives a total of five bonds, and all the electrons are used for bonding. There is
no lone pair.
 The four bonding pairs of electrons mutually repel each other, resulting into a bond
angle of making the molecule tetrahedral.
Some complexes also form a tetrahedral structure.
For example in ,

Tetrahedral
[ ]
(e) Molecules or ions with a trigonal pyramidal shape

Trigonal pyramidal molecules or ions have three bonding pairs of electrons and one
lone pair. They have a bond angle smaller than , which is observed in the
tetrahedral molecules. This is due to increased repulsion caused by the lone pair.
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264
For example in ,
 Since it is bonded to three hydrogen atoms, the total number of valence electrons in
the molecule is .
 Of the four electron pairs, there are three bonding pairs since phosphorus is bonded
to three hydrogen atoms and one lone pair.
 The three bonding pairs of electrons repel each other but the lone pair-bond pair
 This reduces the bond angle to making the molecule trigonal pyramidal.
For example in ,
 It is an oxy-molecule/ oxy-acid
 The chlorine atom has valence electrons from its electronic configuration.

 Phosphorus is therefore expected to form seven bonds.
 For the hydrogen atom present, there is one bond.
 The two other oxygen atoms form two bonds.
 This gives a total of five bonds, and two electrons are not used for bonding. There is
one lone pair therefore.
 This reduces the bond angle making the molecule trigonal pyramidal.
Some ions also form a trigonal pyramidal structure.
For example in ,
 The Sulphur atom has valence electrons from its electronic configuration.
 Phosphorus is therefore expected to form six bonds.
 The two negative charges in the anion mean there are two bonds.
 The remaining oxygen atom is doubly bonded to Sulphur, .
 This gives a total of four bonds, and two electrons are not used for bonding. There
is one lone pair therefore.
 This reduces the bond angle making the molecule trigonal pyramidal.
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265
̈ Trigonal pyramidal
(f) Molecules or ions with a trigonal bipyramidal shape

Trigonal bipyramidal molecules have five bonding pairs of electrons and no lone pairs.

For example in ,
 Since it is bonded to five fluorine atoms, the total number of valence electrons in
the molecule is .
 The total number of valence electrons divided by two gives five electron pairs.
 All the five electron pairs are used in bonding as bonding pairs.
The complex also has a trigonal bipyramidal shape,
Trigonal bipyramidal |
266
(g) Molecules or ions with an irregular tetrahedral shape

Irregular or distorted tetrahedral molecules have four bonding pairs of electrons and one
lone pair.
For example in ,
 The Sulphur atom has valence electrons from its electronic configuration.
 Since it is bonded to four fluorine atoms, the total number of valence electrons in
the molecule is .
 The total number of valence electrons divided by two gives five electron pairs.
 Four of the five electron pairs are used as bonding pairs to bond with the four
fluorine atoms.
 One electron pair remains as a lone pair.
 The four bonding pairs of electrons repel each other but the lone pair-bond pair

̈ Irregular tetrahedral
(h) Molecules or ions with an octahedral shape

Octahedral molecules have six bonding pairs of electrons.
For example in ,
 The sulphur atom has valence electrons from its electronic configuration.
 Since it is bonded to six chlorine atoms, the total number of valence electrons in the
molecule is .
 The total number of valence electrons divided by two gives six electron pairs.
 All the six electron pairs are used in bonding as bonding pairs.
The complex also has an octahedral shape,
Octahedral
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267
Octahedral
[ ]
(i) Molecules with a square pyramidal shape

Square pyramidal molecules have five bonding pairs of electrons and one lone pair.
For example in ,
 The bromine atom has valence electrons from its electronic configuration.
 Since it is bonded to five fluorine atoms, the total number of valence electrons in
the molecule is .

 The total number of valence electrons divided by two gives six electron pairs.
 Five of the six electron pairs are used in bonding as bonding pairs.
 One electron pair remains as a lone pair.
 The five bonding pairs of electrons repel each other but the lone pair-bond pair
̈
Square pyramidal
(j) Molecules or ions with a square planar shape

Square planar molecules have four bonding pairs of electrons and two lone pairs.
For example in ,
 The iodine (central) atom has valence electrons from its electronic configuration.
 Since the structure is for an anion with negative charge one, the total electrons
are .
 of these electrons are used for bonding with the chlorine atoms.
 This leaves 4 electrons not used for bonding and form the two lone pairs.
 The lone pair-lone pair repulsion is greater than lone pair-bond pair repulsion
which is also greater than bond pair- bond pair repulsion.
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268
* + Square planar
Qn. Draw the structure and name the shapes of the following molecules or ions

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269

|
270

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271

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272

The effect of lone pairs on Molecular Geometry
The effect of lone pairs on molecular geometry is explained basing on the VSEPR theory.
1. Explain the structures of the following species;

(i) beryllium chloride
(ii) nitrate ion
(iii)
(iv) Chlorate(V) ion
(v) Hydrogen sulphide
Molecule / ion Structure Explanation
Beryllium chloride molecule has two bonding pairs
of electrons and no lone pair. The two bonding pairs
repel each other greatly to form a linear molecule
with a bond angle of .
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The nitrite ion possesses three bonding pairs of

electrons and no lone pair. The three bonding pairs
lie in the same plane and repel each other equally
to form a trigonal planar shape with a bond angle of
.
̈ Nitrosyl chloride molecule has two bonding pairs of
electrons and one lone pair. The two bonding pairs
of electrons repel each other but the lone pair-bond
pair repulsion is greater.
This reduces the bond angle making the molecule
V-shaped.
The chlorate(V) ion possesses three bonding pairs of
̈ electrons and one lone pair. The three bonding pairs
of electrons repel each other but the lone pair-bond
pair repulsion is greater. This reduces the bond
angle making the molecule trigonal pyramidal.
The hydrogen sulphide molecule has two bonding

pairs and two lone pairs.
The repulsion between the two lone pairs of
.. ..
S electrons is greater than the repulsion between lone
pairs and bonding pairs of electrons which is also
greater the repulsion between the bonding pairs of
electrons alone. This reduces the bond angle to
making the molecule V-shaped.
2. Explain why;
(i) Beryllium bromide has a bond angle of but tin(II) bromide has a bond
angle less than
̈
Beryllium bromide molecule has two bonding pairs of electrons and no lone pair. The
two bonding pairs repel each other greatly to form a linear molecule with a bond angle
of . Tin(II) bromide molecule has two bonding pairs of electrons and one lone
pair. The two bonding pairs of electrons repel each other but the lone pair-bond pair
repulsion is greater. This reduces the bond angle making the molecule V-shaped.
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(ii) The sulphate ion is tetrahedral but the sulphite ion is trigonal pyramidal
The sulphate ion has four bonding pairs and no lone pairs. The four bonding pairs of
electrons mutually repel each other, resulting into a bond angle of making the
molecule tetrahedral. The sulphite ion possesses three bonding pairs of electrons and
one lone pair. The three bonding pairs of electrons repel each other but the lone pair-
bond pair repulsion is greater. This reduces the bond angle making the molecule
trigonal pyramidal.
(iii) Sulphur dioxide has a bond angle of while Sulphur dichloride has bond
angle of although both are V-shaped molecules.

.. ..
S
̈
The Sulphur dioxide molecule has two bonding pairs and one lone pair. The two
bonding pairs of electrons repel each other but the lone pair-bond pair repulsion is
greater. This makes the bond angle .The Sulphur dichloride molecule also
possesses two bonding pairs of electrons but has two lone pairs. Since the Sulphur
dichloride molecule has more lone pairs than the Sulphur dioxide molecule, there exists
lone pair-lone pair repulsion, and the lone pair-bond pair repulsion is also greater than
in Sulphur dioxide. This reduces the bond angle in Sulphur dichloride.
The effect of electronegativity on size of bond angles

For two molecules or ions in which the central atoms are different but the bonded atoms
are the same, the increase in electro negativity increases the attraction for the
bonding electrons by the central atoms in their molecules. This makes the bonding
pairs of electrons closer to the more electronegative atom than to the less
electronegative element. This implies that the bonding pairs of electrons are closer to
the central atom leading to an increased repulsion between them, which increases the
bond angle.
For two molecules or ions in which the central atoms are similar but the bonded atoms
are the different, the increase in electro negativity of the bonded atoms increases the
attraction for the bonding electrons by the bonded atoms in their molecules. This
makes the bonding pairs of electrons closer to the more electronegative atom than to
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the less electronegative element. This implies that the bonding pairs of electrons far
apart leading to a decreased repulsion between them, which reduces the bond angle.
Examples
Explain why;
(i) the bond angle in ammonia is while that in phosphine is .
̈ ̈
107O 94O
Both ammonia and phosphine molecules adopt a trigonal pyramidal shape. However, the
nitrogen atom is more electronegative than the phosphorus atom. The bonding pairs of
electrons are closer to the nitrogen atom in ammonia than they are to the phosphorus
atom in phosphine. This causes an increased repulsion between the bonded pairs of
electrons in ammonia than it is in phosphine, therefore ammonia has a bigger bond
angle than phosphine.

(ii) the bond angle in hydrogen sulphide is while that in water is .
.. .. .. ..
S O
Both hydrogen sulphide and water molecules adopt a V- shaped structure. However, the
oxygen atom is more electronegative than the sulphur atom. The bonding pairs of
electrons are closer to the oxygen atom in water than they are to the sulphur atom in
hydrogen sulphide. This causes an increased repulsion between the bonded pairs of
electrons in water than it is in hydrogen sulphide, therefore the water molecule has a
bigger bond angle than hydrogen sulphide.
(iii) the bond angle in phosphorus trifluoride is while that of phosphorus

trichloride is .
̈ ̈
96O 107O
Both phosphorus trifluoride and phosphorus trichloride molecules adopt a trigonal

pyramidal shape. However, the fluorine atom is more electronegative than the chlorine
atom. The fluorine atoms therefore withdraw away the bonded pairs of electrons from
the phosphorus atom more than the chlorine atoms do. This makes the bonded pairs to
be far apart in phosphorus trifluoride than they are in phosphorus trichloride,
reducing the repulsion between them. Therefore phosphorus trifluoride has a smaller
bond angle than phosphorus trichloride.
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Polarity of molecules
Polarity is a condition of a molecule to have positive and negative charges. Polarity of
molecules is related to the electronegativity difference of the bonding atoms and bond
symmetry.
Factors that determine the polarity of molecules

(i) electronegativity difference of atoms in the molecule
(ii) bond symmetry or spatial arrangement of various bonds in the molecule
Polar covalent bonds are formed as a result of difference in electronegativity of the
bonding atoms. These include; , , , ,
, etc.
For two equal but opposite separated electrical charges, there exists an electric dipole
moment. An electric dipole moment is a product of one of the charges, or and
the distance between the atomic nuclei. Any individual polar covalent bond must have a
corresponding dipole moment.

However, there are molecules in which the individual bonds in it are polar but the
molecule as a whole is non-polar. An example is tetrachloromethane which has a zero
dipole moment, although the individual carbon-chlorine bonds in it have dipole moments.
This is due to the symetrical distribution of the chlorine atoms around the carbon atom
such that the effects of the four dipoles cancel each other. Another example is the carbon
dioxide molecule.
All molecules in which the atoms are symmetrically distributed around the central atom
are non polar. This is only possible if all the symmetrically distributed atoms around
the central atom are the same. These include;
(i) linear molecules

(ii) trigonal planar molecules
(iii) square planar molecules
(iv) tetrahedral molecules
(v) trigonal bipyramidal molecules
(vi) octahedral molecules
Explain why;
(a) Carbon tetrachloride is non-polar yet the carbon-chlorine bond is polar.
Chlorine is more electronegative than carbon. The chlorine atom therefore tends to
attract the bonding electrons towards itself hence acquires a partial negative charge
(δ −) and the carbon atom gains a partial positive charge (δ+). This makes the
carbon- chlorine bond polar.
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However, the whole molecule is non-polar because it has a tetrahedral structure in

which the chlorine atoms are symmetrically distributed about the carbon atom. This
creates equal and opposite dipole moments in all directions that cancel out making the
resultant dipole moment zero.
Note; For the same reason, a stream of tetrachloromethane is not deflected by a

charged rod while that of chloroform is deflected.
(b) The carbon- oxygen bond is polar but carbon dioxide is non-polar.
Oxygen is more electronegative than carbon. The oxygen atom therefore tends to attract

the bonding electrons towards itself hence acquires a partial negative charge
(δ −) and the carbon atom gains a partial positive charge (δ+). This makes the
carbon- oxygen bond polar.
However, the whole molecule is non-polar because it has a linear structure in which the
oxygen atoms are symmetrically distributed about the carbon atom. This creates equal
and opposite dipole moments in all directions that cancel out making the resultant
dipole moment zero.
Molecules in which the bonded atoms are not symetrically distributed around the central
atom like chloromethane, dichloromethane, trichloromethane, water and ammonia have
an overall dipole moment over the molecule. Therefore both the individual bonds and the
whole molecule are polar.
Differences between polar and non-polar molecules
Polar molecules Non-polar molecules

Asymmetrical Symmetrical
One end of the molecule is positive Does not have distribution of charges at
whereas the other has a positive charge opposite ends
Can interact through hydrogen bonds There are van der Waals forces between
non polar molecules
Have a dipole moment Have no dipole moment
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Miscellaneous Questions
1. Use dot and cross diagrams to show how the following atoms can combine
(a) Lithium and fluorine

(b) Hydrogen and fluorine
(c) Magnesium and fluorine
(d) Lithium and oxygen
(e) Sodium and fluorine
(f) Aluminium and fluorine
(g) Calcium and oxygen
2. (a) What is meant by the term hydrogen bonding?
(b) Explain how hydrogen bonding arises in;

(i) hydrogen fluoride
(ii) ice

(iii) Methylamine
(iv) Ethanoic acid
(c) Which practical evidence is there for existence of hydrogen bonds in ice and
ethanoic acid?

(i) Both graphite and copper conduct electricity
(ii) Solid copper(II) sulphate is a non-conductor but aqueous copper(II) sulphate
conducts electricity.
(iii) Nitrogen is a gas at room temperature but phosphorus can exist in several solid
forms at room temperature.
(iv) Diamond is hard and an electrical insulator whereas graphite is soft and a good
electrical conductor
(v) Both diethyl ether and butan-1-ol have the same molecular mass but diethyl
ether boils at whereas butan-1-ol boils at .
(vi) Magnesium has a higher melting point that sodium
(vii) Sodium is softer than copper
(viii) Both sodium and copper are good electrical conductors.
(ix) Chlorine is a gas whereas iodine is a solid at room temperature.
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4. Explain why;
(i) trichloromethane is deflected by a charged rod but tetrachloromethane is
not.
(ii) Boron trichloride is non-polar whereas nitrogen trichloride is polar
(iii) A stream of chloroform is deflected by a charged rod but a stream of
tetrachloromethane is not.
(iv) the bond angle in ammonium ion is whereas that in ammonia is
.
5. (a) State the type of hybridization expected in simple compounds of;
(i) Boron
(ii) Beryllium
(iii) carbon
(b) state the effect of the type of hybridization stated in (a) above on the geometry
of the following;

(i) boron trifluoride
(ii) beryllium chloride
(iii) carbon tetrafluoride
280
CHAPTER FOUR
THERMOCHEMISTRY
(CHEMICAL ENERGETICS)
Thermochemistry is the study of energy changes that accompany chemical reactions. It
is also called chemical energetics or chemical thermodynamics.
Thermochemistry investigates;
 the position of equilibrium in the reaction
 the feasibility of the reaction
 and how far the reaction can go.
CHEMICAL ENERGY

Energy is the capacity to do work. There are many forms of energy among which
chemical energy is one.
Chemical substances also have capacity to do work, thus possess chemical energy.
The chemical energy must be converted to another form of energy for chemical
substances to do work. The form of energy to which chemical energy is converted is the
heat energy.
Heat is a form of kinetic energy associated with motion of atoms and molecules. It is the
transfer of energy from regions of high temperature to regions of low temperature.
The heat evolved by a chemical substance can be used as a measure of the chemical
energy liberated. The change in chemical energy of a chemical substance is measured
only if the substance is treated in a certain way, for example when it is burnt in oxygen.
During a chemical reaction, bonds between atoms of the reactants are broken and new
bonds are formed in the products formed. Energy is absorbed to break the bonds
between atoms and energy is given out when new bonds are formed.
Heat content of a substance

Every substance has some stored chemical energy. The heat content differs from one
substance to another because the molecules of different substances differ in the number
and type of atoms and the number and type of bonds between their atoms.
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Enthalpy,
Enthalpy is the total energy content of a substance.
It is denoted by the symbol, .
Enthalpy change,
Enthalpy change is the heat content of a substance measured at standard temperature
and pressure during a chemical reaction.
Enthalpy change is called heat of reaction and is denoted as
Standard enthalpy change,

This is the heat change when molar quantities of reactants shown in the balanced
equation for the reaction in their standard states react completely at 1 atmosphere and
298K.
Standard state of the substance is the phase in which a pure substance exists at 1
atmosphere and 298K.

The units for standard enthalpy of reaction are
TYPES OF HEAT OF REACTIONS

All chemical reactions are accompanied by evolution or absorption of heat. This results
into two types of reactions namely;
(i) exothermic reaction
(ii) endothermic reaction
Exothermic reaction Endothermic reaction

 Proceed with evolution of heat to the  Proceed with absorption of heat from the
environment environment
 Denoted by a negative sign  Denoted by a positive sign
 The products are at a lower energy level  The products are at a higher energy level
than the reactants than the reactants
For example; For example;
The equation can be interpreted as; The equation can be interpreted as

1 mole of hydrogen gas reacts with 1 mole of 1 mole of carbon reacts with 1 mole of steam
gaseous iodine to form 2 moles of hydrogen to form 1mole of carbon monoxide gas and 1
iodide gas with evolution of mole of hydrogen gas with absorption of
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The sign of the enthalpy change for a reaction is an indicator of its feasibility. The more negative
(exothermic) the value of , the more is the reaction likely to be feasible.
Energy level diagrams for exothermic and endothermic reactions

An energy level diagram is a graph of potential energy of a reaction against reaction path or
reaction coordinate.
For the exothermic reaction shown above; For the endothermic reaction shown above;
Activated
complex
Activated
Potential complex
Potential
energy
energy
( )
( )

Reaction coordinate Reaction coordinate
is the activation energy for the reaction.
It can also be called activation energy for forward reaction.
is activation energy for backward reaction
is the enthalpy of reaction
Activation energy is the minimum energy which is required to be possessed by reactants in order
to react and form products.
Activated complex is the intermediate unstable compound formed immediately once the
reactants have absorbed the activation energy available.
This unstable compound undergoes bond re-organization by releasing some of the energy to form
the final stable product. The activated complex can also be called a transition state.
The enthalpy of reaction can be got from the expression ;
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Questions
1. For the reaction
(a) Draw a well labeled energy level diagram for the reaction.
(b) The activation energies for the forward and reverse reactions are known to be
respectively and . Calculate the heat of reaction.
2. (a) Define the term activation energy
(b) and react to form and according to the following equation
(i) Draw a fully labeled potential energy versus reaction coordinate diagram for
the reaction of and .
(ii) Calculate the activation energy of the backward reaction. (the activation for
forward reaction is

3. Dinitrogen tetraoxide dissociates at 40 oC and 1 atm according to the following
equation.
Draw a well labelled energy level diagram for the reaction above
Applications of exothermic reactions in everyday life

(i) In hot packs which are used to treat sports injuries and warming the body in case
of coldness. The instant hot packs have separate compartments of water and
anhydrous calcium chloride separated by a thin film placed in a plastic bag. When
the bag is squeezed, the thin film breaks and the anhydrous calcium chloride
dissolves in the water exothermically to release heat.
→
There are other salts that dissolve exothermically and can be used in a hot pack for
example anhydrous magnesium sulphate and anhydrous copper(II) sulphate
(ii) Combustion of fuels to release energy during cooking of food
(iii) In cellular respiration, where energy is obtained from carbohydrates and used by
living organisms. During the process carbohydrates react with oxygen to form
carbon dioxide, water and energy.
(iv) Condensation during formation of rain from water vapour
(v) Freezing of water into ice
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Applications of endothermic reactions in everyday life

(i) In instant cold packs which are used to treat sports injuries. The instant cold
packs have separate compartments of water and solid ammonium nitrate separated
by a thin film placed in a plastic bag. When the bag is squeezed, the thin film
breaks and the solid ammonium nitrate dissolves in water endothermically to
provide instant coldness. Heat is absorbed from the surrounding such as the
injured area of the athlete‟s body.
→
There are other salts that dissolve endothermically and can be used in a cold pack for
example ammonium chloride, potassium nitrate and sodium thiosulphate.
(ii) Photosynthesis. Energy is absorbed to convert carbon dioxide and water to sugars
in presence of chlorophyll.
(iii) Evaporation of liquid water

(iv) Melting of ice
Factors affecting enthalpy of reaction

1. Temperature at which the reaction is carried out
2. Pressure of gaseous reactants or products
3. Amount of reactants used
4. Physical state of reactants and products
Latent heat is involved in changes of state so that the state of the reagents and
products affect the enthalpy of a reaction
Combination of hydrogen and oxygen to form liquid water at 25 and atmospheric
pressure evolves
When 2g of hydrogen are burnt just above 100 , less heat is given out.
The observed difference is due to heat of vapourisation of 1 mole of water.
5. Allotropic modifications
There is an enthalpy change involved in conversion one allotrope to another. A particular
allotrope of an element used in a reaction affects the enthalpy of reaction. For example;
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CALORIMETRY
Calorimetry is a technique used to measure amounts of heat transferred to or from a
substance. A calorimeter is a container that is insulated against heat loss that is used to
measure the amount of heat involved in a chemical or physical process.
The common calorimeters used in laboratory experiments include the coffee cup
calorimeter and the bomb calorimeter.
The coffee cup calorimeter is used when measuring the heats of neutralisation, solution,
precipitation. It is constructed from a polystyrene cup with a lid. A thermometer is
usually inserted in it to measure heat changes.
The bomb calorimeter is mainly used to determine heat of combustion of a solid
substance.
Heat capacity of a calorimeter

The heat capacity of a calorimeter is the quantity of heat absorbed by the calorimeter

for each rise in temperature. Its unit is
The heat capacity of a calorimeter must be determined experimentally.
Experiment to determine heat capacity of a simple calorimeter/

plastic cup calorimeter
Using a measuring cylinder, measure of water into the calorimeter and record its
temperature, using a thermometer.
Measure another of water into a beaker and heat it to . Keep the
temperature steady to for to minutes.
Then pour the hot water quickly into the calorimeter containing cold water and stir the
mixture. Record the temperature, .
Treatment of results
[ ] [( )] ( )
[ ] ( ) [( )]
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( ) [( )]
[ ]
( )
TYPES OF ENTHALPY CHANGES

Enthalpy of formation
Enthalpy of formation of a compound is the heat evolved or absorbed when one mole
of a compound is formed from the constituent elements in their standard states.
When enthalpy of formation is determined under standard conditions, it is called
standard enthalpy of formation.
Standard enthalpy of formation

The standard enthalpy of formation of a compound, , is the heat evolved or

absorbed when one mole of the compound is formed from its elements in their normal
states at 298K and 1 atmosphere.
Enthalpy of formation can be exothermic or endothermic.
Prediction of relative stability of compounds from enthalpy of

formation
 When a compound is formed with evolution of heat (exothermically), that
compound is more stable and less reactive.
 When a compound is formed with absorption of heat (endothermically), that
compound is less stable and very reactive.
 The standard enthalpy of formation of elements in their standard states is
conventionally taken as zero. i.e. enthalpy of formation of is
The table below shows some compounds, equations and their enthalpies of formation.
Their stability can be predicted using values for enthalpy of formation. Also note that all
the equations show one mole of compound being formed.
Compound Equation for formation
Sodium chloride
Water
Hydrogen fluoride
Aluminium oxide
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Ammonia
Ethyne
Nitrogen monoxide
The first equation means that 1 mole of solid sodium chloride is formed from 1 mole of
solid sodium and 0.5 moles of chlorine gas with evolution of of heat under
standard conditions.
The last equation means that 1 mole of nitrogen monoxide gas is formed from 0.5
mole of nitrogen gas and 0.5 mole of oxygen gas with absorption of of heat
under standard conditions.
Determination of enthalpy of formation

Enthalpy of formation of compounds can be obtained directly by measuring the heat
change in the combination of known masses of the elements.
It can also be obtained indirectly by use of Hess‟ law when values of other enthalpies for

a given compound or components of the compound are known (this will be seen later).
Calculating using heats of formation

Enthalpy of reaction can be expressed as the difference between the sum of the
standard enthalpies of formation of the products and the sum of the standard
enthalpies of formation of the reactants when both reactants and products are in their
standard states at 1 atmosphere and 298K
∑ ∑
The standard enthalpy of formation of elements in their standard states is conventionally

taken as zero whenever the above equation is used.
Reactions involving ions can similarly be treated using the same equation if the values of
the standard molar enthalpies of formation of ions are known. The standard enthalpy of
formation of the hydrogen ion is 0.00 .
Examples
1. Calculate the enthalpy change for the reaction below using the information
given;
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288
∑ ∑
[ ] [ ]
[ ] [ ]
2. The enthalpies of formation of some selected compounds are shown in the

table below.
Compound
Calculate the enthalpy change for the following reaction.

→

∑ ∑
[ ] [ ]
[ ] [ ]
3. The standard enthalpies of formation of water, sodium ion and hydroxyl ion
are given in the table below.
Compound/ion Enthalpy of formation,
̅
Calculate the enthalpy of the reaction between sodium and water.
∑ ∑
[ ] [ ]
[ ̅ ] [ ]
[ ] [ ]
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Questions
1. The standard enthalpies of formation of different compounds are given in the table
below.
Compound Enthalpy of formation,
Calculate the enthalpy of the reaction;
2. Calculate the standard enthalpy change for the reaction below using the
information given the table;

below.
below.
Water
Oxygen difluoride
Hydrogen fluoride
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5. The standard enthalpies of hydrogen peroxide and water.

Compound
Calculate the enthalpy change for the following reaction.
Enthalpy of combustion
Enthalpy of combustion is the heat evolved when one mole of a substance is completely
burnt in oxygen under specified conditions, when the reactants and products are in
their standard states.
When enthalpy of combustion is determined under standard conditions
( ), it is called standard enthalpy of combustion.
Standard enthalpy of combustion

Standard enthalpy of combustion, is the heat evolved when one mole of a
substance is completely burnt in oxygen at 298K and 1 atmosphere.
Enthalpy of combustion is always a negative value indicating that heat is evolved
(reaction is exothermic)
The table below shows some compounds, equations and their standard enthalpies of
combustion.
Compound Equation for combustion

Carbon(graphite)
Methane
Ethyne
Ethane
Ethanol
Experiment to determine enthalpy of combustion of low

molecular mass alcohols (ethanol, propanol and butanol)
In this experiment we shall consider propanol but the same treatment can be done for
ethanol and butanol. The same experiment can be used for any other liquid fuel for
example liquid hexane.
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Set up
Thermometer
Stirrer
Heat shield
Thin metallic can
Water
Lamp
Propanol
A known volume of water, is put in a thin metallic can.

The can is fitted with a thermometer and a stirrer

The initial temperature of the water is read and recorded from the thermometer as
A spirit lamp is filled halfway with propanol and the mass of the lamp and its contents
is measured and recorded as
The spirit lamp is lit and the flame adjusted to just touch the bottom of the metallic can.
The water is heated while stirring until a reasonable rise in temperature is obtained.
The lamp is extinguished and the final temperature of the water recorded as
The mass of the spirit lamp and its contents is measured and recorded as
Assuming no heat was lost to the surrounding;
Heat capacity of the can is negligible
Heat produced by combustion of propanol is equal to heat absorbed by water.
( )
( )
( )
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Question;
Describe an experiment to determine the enthalpy of combustion of;
(i) Ethanol
(ii) Butanol
(iii) Liquid hexane
Use of experimental data
Example
When ethanol was burnt in a spirit lamp, the following results were obtained;
Mass of spirit lamp and ethanol before burning
Mass of spirit lamp and ethanol after burning
Volume of water heated
Initial temperature of water
Final temperature of water
(a) Calculate the heat of combustion of

ethanol.
(b) State why the value obtained in (a) above is lower than the actual value obtained in
books.
(a) Heat produced by combustion of ethanol is equal to heat absorbed by water.
( )
(b) The calculated value is less than the theoretical value because some of the heat
evolved is lost to the surroundings.
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Questions
1. A spirit burner containing ethanol was weighed and then used to heat up a copper
calorimeter containing of cold water and then reweighed. The results were
recorded as shown below;
Decrease in mass of ethanol
Rise in temperature of water
Decrease in mass of ethanol
Specific heat capacity of water
Heat capacity of calorimeter is negligible
Use the results to calculate the enthalpy of combustion of ethanol
2. When 0.95g of ethanol was burnt, the heat produced raised the temperature of
of water from to . Calculate the heat of combustion of ethanol.
Experiment to determine enthalpy of combustion of a solid

substance for example carbon (graphite) or coke
Enthalpy of combustion of a solid substance is determined using a bomb calorimeter.

Set up
Thermometer
to electric supply
Stirrer
Calorimeter
Water
Bomb calorimeter
Thin iron wire
Platinum crucible
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294
A known mass of carbon, is placed in a small platinum crucible

The crucible with its contents is placed in a bomb calorimeter
The bomb calorimeter is filled with oxygen at a pressure of about 25 atmospheres to
ensure rapid and complete combustion
The bomb calorimeter is immersed a known volume of water, placed in a
calorimeter fitted with a thermometer and stirrer
The initial temperature of the water is recorded as
The carbon is ignited by passing electric current through a small coil of iron wire
touching the carbon
The final temperature of the water is read from the thermometer as
Heat evolved by combustion of carbon and the iron wire heat absorbed by water heat gained
by calorimeter

[ ]
[ ]
[( ) ]
[( ) ]
( )
[( ) ]
( )
[( ) ]
( )
Calculation of enthalpy of reaction and enthalpy of formation,

using enthalpies of combustion
Examples
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295
1. If the heat of formation of carbon dioxide is , heat of formation of

water is and heat of combustion of butane is
Calculate the standard heat of formation of butane.
Equation for the reaction required;
Equations for reactions given;

(i)
(ii)
(iii)
According to the required equation, the 4C is obtained by multiplying equation (i) by 4. The
obtained by multiplying equation (ii) by 5. Since is on right hand side of the required
equation, the last equation is reversed. After this treatment and addition of the 3 resulting
equations the required equation is generated. The same treatment is done to the values.
Check through the working below and subsquent examples.

2. The table below shows the values of enthalpies of combustion of carbon, rhombic
sulphur and carbon disulphide.
Substance Enthalpy of combustion
Carbon
Sulphur
Carbon disulphide
Calculate the enthalpy of formation of carbon disulphide.

(i)
(ii)
(iii)
The required equation is obtained by adding all the three equations after equation (i) is
unchanged, equation (ii) multiplied by 2 and a reversed equation (iii). The same treatment
is done to the values.
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3. Given that the enthalpy of combustion of ethyne is and the

enthalpy of combustion of ethanal is Calculate the heat change
of the reaction;

(i)
(ii)
The required equation is obtained by simply adding equation (i) to a reversed equation (ii).
The same treatment is done to the values.

4. Given that the ;
Enthalpy of combustion of ethanol is
Enthalpy of formation of carbon dioxide gas is
Enthalpy of formation of water is .
Use the above information to calculate the heat of formation of ethanol

(i)
(ii)
(iii)
The required equation is obtained by adding all the three equations after equation (i)
is reversed, equation (ii) multiplied by 2 and equation (iii) multiplied by 3. The same treatment
is done to the values..
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5. The standard enthalpies of combustion of some substances are given below.

Substance
Hydrogen -286
Benzene -3268
Cyclohexene -3752
Cyclohexane -3920
(a) Calculate the enthalpy of hydrogenation of;
(i) Cyclohexene
(ii) Benzene
(b) Using the two values in a(i) and (ii) above , explain the relative stability
of benzene.
(a) (i) Equation for the reaction required;

Equations for reactions required;
The required equation is obtained by simply adding equation (i), equation (ii) and a reversed equation
(iii). The same treatment is done to the values.
(ii) Equation for the reaction required;
The required equation is obtained by adding equation (i) multiplied by 3 to equation (ii) and a
reversed equation (iii). The same treatment is done to the values.
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(b) Cyclohexene has one localized and its hydrogenation to form cyclohexane
evolves . If the three double bonds in benzene where localized, the
enthalpy of hydrogenation of benzene would be . The
enthalpy of hydrogenation of benzene is however . The difference of
is due to the delocalization energy/ resonance energy of benzene since
it has three delocalised .
Questions
1. Calculate the enthalpy of formation of methane given that its enthalpy of combustion
is and the enthalpy of formation of carbon dioxide and water are
and respectively.
2. Calculate the enthalpy of formation of carbon monoxide given that the enthalpy of
combustion of carbon is , and the enthalpy of combustion of carbon
monoxide is .

3. Calculate the standard enthalpy of formation of propane if its standard enthalpy of
combustion is and the standard enthalpies of combustion of carbon
and hydrogen are and respectively.
4. Use the data given below to find the standard enthalpy change for the reaction below
at 298K;
5. Given the following enthalpy values under standard conditions ;

Heat of combustion of hydrogen gas
Heat of combustion of carbon (graphite)
Heat of combustion of methane
Heat of combustion of ethane
Heat of formation of propane
Determine the enthalpy of the reaction;
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6. Calculate the standard enthalpy of formation of ethene using the following

information.
7. (a) The enthalpies of some reactions are given below;
Calculate the standard enthalpy of formation of phenol from its elements.

(b)From your answer in (a) above, state whether phenol is a stable compound or not.
Give a reason for your answer.
(c) Write equation(s) to show how phenol can be synthesised from chlorobenzene
8. If the enthalpies of combustion of ethane, ethene and hydrogen

are . Calculate the enthalpy of hydrogenation of
ethene.
9. (a) Define heat of reaction
(b) Calculate the standard enthalpy of hydrogenation of ethene using the following
information.
10. Calculate the standard enthalpy of hydrogenation of ethyne using the following
thermochemical data.
11. Calculate the standard enthalpy of formation of ethene using the following
information using the following information;
Enthalpy of combustion of ethane is
Enthalpy of combustion of hydrogen is
Enthalpy of combustion of carbon is
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Calculating heats of combustion from other experimental data

Examples
1. When 2 g of ethane is burnt in excess oxygen, of heat is liberated.
Calculate the enthalpy of combustion of ethane.
( )
2. The table below shows the values for standard enthalpies of formation of benzoic
acid, carbon dioxide and water in . Use the data to calculate the
enthalpy of combustion of benzoic acid.

Compound
∑ ∑
[( ) ] [ ]
[ ] [ ]
3. Calculate the enthalpy of combustion of benzene if the enthalpy of combustion

of carbon is , enthalpy of formation of benzene is
, and enthalpy of formation of water is .

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The required equation is obtained by adding equation (i) multiplied by 6 to a reversed equation (ii) and
equation (iii) multiplied 3. The same treatment is done to the values.
Questions
1. When 1 g of graphite is burnt in excess oxygen, of heat is liberated. Calculate
the enthalpy of combustion of graphite.
2. Calculate the standard enthalpy of combustion of propene using the following
information.
(i)

(ii)
(iii)
3. Calculate the standard enthalpy of combustion of ethene if the enthalpy of combustion

of carbon is , standard enthalpy of formation of ethene is
, and standard enthalpy of combustion of hydrogen is
.
4. The table below shows the values for standard enthalpies of formation of water,
carbon dioxide and benzene in . Use the data to calculate the enthalpy of
combustion of benzene.
Compound
5. (a) State what is meant by the terms;

(i) Standard enthalpy of formation of a substance
(ii) Standard enthalpy of combustion of a substance
(b) Use the data below to calculate the standard enthalpy of combustion of ethanol.
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Application of heat of combustion in real life situation

 Burning of wood or charcoal to release energy during cooking
 Petrol and diesel cars rely on combustion to release the engine driving energy
 Gas cookers use alkane gases for combustion
The fuel values of various fuels

The fuel value of a fuel is the amount of heat released during its combustion. It is also
referred to as heat or energy or calorific value. The table below fuel values of various
fuels in kilo Joules per kilogram.
Fuel Fuel value
Hydrogen 141,700
Methane 55,500
Natural gas 50,840
Propane 50,000

Butane 49,300
Petrol/ gasoline 46,940
Kerosene 46,200
Diesel 45,600
Crude oil 45,300
Butanol 37,300
Ethanol 29,700
Charcoal 29,600
Coke 28,400
Coal 27.05
Methanol 22,700
Wood 19,800
The higher the fuel value, the more valuable the fuel.
Enthalpy of neutralisation
Enthalpy of neutralisation is the heat evolved in the reaction between that mass of an
acid which provides one mole of hydrogen ions and that mass of an alkali which
provides one mole of hydroxyl ions.
When enthalpy of neutralisation is determined under standard conditions
( ), it is called standard enthalpy of neutralisation.
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Standard enthalpy of neutralisation

Standard enthalpy of neutralisation is the heat evolved when one mole of an acid
reacts with one mole of a base to form one mole of water at 298K and 1 atmosphere.
Neutralisation is the formation of water from hydrogen ions and water.
̅
The enthalpy of neutralisation is exothermic.
The enthalpies of nuetralisation of strong acids and strong alkalis are approximately
constant about a value of .
Experiment to determine enthalpy of neutralisation between a

strong acid and strong alkali
(for example nitric acid and potassium hydroxide)
Describe an experiment to determine enthalpy of neutralisation of nitric acid by
potassium hydroxide.

A known volume, of nitric acid of known concentration, M is measured and
placed in a plastic beaker.
The initial temperature of the acid solution, is noted from the thermometer.
An equal volume, of potassium hydroxide solution of the same concentration, M
is also measured into another plastic beaker.
The initial temperature of potassium hydroxide solution, is also noted from the
clean and dried thermometer.
The two solutions are added together carefully, as fast as possible while stirring and the
maximum temperature, attained is noted.
Assumptions
The solution has the same specific heat capacity as water
Heat loss to the surroundings is negligible
Heat capacity of the beaker is negligible
Density of solution is
( )
[ ( )]
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( )
( )
( )
( )
( )
Describe an experiment to determine enthalpy of neutralisation of sulphuric acid by
sodium hydroxide.
A known volume, of sulphuric acid of known concentration, M is measured and
placed in a plastic beaker.
The initial temperature of the solution, is noted from the thermometer.
of sodium hydroxide solution of the same concentration, M is also measured

into another plastic beaker.
The initial temperature of sodium hydroxide solution, is also noted from the clean
and dried thermometer.
The two solutions are added together carefully, as fast as possible while stirring and the
Assumptions
( )
[ ( )]
( )
( )
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( )
( )
( )
Calculations on enthalpy of neutralisation

Example
1. of potassium hydroxide at ℃ were mixed in a plastic beaker
of negligible heat capacity with an equal volume of hydrochloric acid at
the same temperature. If the final temperature was ℃ . Calculate the
enthalpy of neutralization of potassium hydroxide and hydrochloric acid from
the following data.

( )
( )
( )
Questions
1. of hydrochloric acid at were placed in a plastic cup.
of sodium hydroxide at were added, the mixture stirred and the
temperature rose to . Calculate the enthalpy of neutralisation.
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2. of sodium hydroxide solution and of

nitric acid, both at were mixed and stirred in a calorimeter
with negligible heat capacity. The temperature of the mixture rose to .
Calculate the enthalpy of neutralisation.
3. (a) of potassium hydroxide solution required of

sulphuric acid for neutralisation in a calorimeter with negligible heat capacity.. If the
temperature rise was . Calculate the standard enthalpy of neutralisation of
potassium hydroxide by sulphuric acid.
The difference between heat of neutralisation between strong acid and strong alkali

and weak acid and strong alkali
Strong acid and strong alkali Weak acid and strong alkali
The enthalpy of neutralisation of any strong The enthalpy of neutralisation of any weak
acid and any strong alkali is approximately acid and strong alkali is lower
constant at about . This is than . This is because for a
because strong acids and strong alkalis and the weak acid and weak alkali, some of the heat
salts they form, are completely ionised in produced due to neutralisation is used for
dilute solution. The only reaction that takes further ionisation of the weak acid. This
place is that between hydrogen ions and further ionisation is endothermic.
hydroxyl ions to form water.
̅
The table below shows enthalpies of neutralisation between different acids and
alkalis
Acid Alkali
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The enthalpy of neutralisation of sodium hydroxide by nitric acid is

whereas the enthalpy of neutralisation of sodium hydroxide by
hydrocyanic acid is .
Sodium hydroxide is a strong base and nitric acid is a strong acid hence completely
ionise in dilute solution. The sodium chloride formed is also completely ionised in dilute
solution. The only reaction involved is between hydrogen ions and hydroxyl ions to
form water.
̅
Hydrocyanic acid is a weak acid. Some of the heat is used for further ionisation of the
weak acid which is endothermic.

̅
Enthalpy of displacement
This is the heat evolved when one mole of ions of a less electropositive element is
displaced from its solution by a more electropositive element.
When enthalpy of displacement is determined under standard conditions
( ), it is called standard enthalpy of displacement.
Standard enthalpy of displacement

Standard enthalpy of displacement is the heat evolved when one mole of ions of a less
electropositive element is displaced from its solution by a more electropositive element
at 298K and 1 atmosphere.
A displacement reaction is a redox reaction.
The enthalpy of displacement is exothermic.
Determination of enthalpy of displacement between zinc powder

and copper(II) sulphate solution
A known volume of copper(II) sulphate solution of a known
concentration is put in a plastic beaker
The initial temperature, of the solution is measured and recorded from the
thermometer
An excess of zinc powder is added quickly and carefully to the solution while stirring
The final steady temperature, is read and recorded from the thermometer.
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Assumptions:
Density of solution is equal to density of water
Specific heat capacity of solution is equal to specific heat capacity of water
No heat is lost to the surroundings

Heat capacity of beaker is negligible
( )
( )
( )

( )
( )
( )
Calculations involving heat of displacement

Example
1. of copper(II) chloride solution is poured in a polystyrene cup and
the initial temperature of the solution is recorded as . 4g of zinc powder is
added to the solution and the mixture stirred. The highest temperature of the
mixture was recorded as .Calculate the heat of displacement of copper by
zinc.
( )
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( )
Note; The zinc added is excess so that all the copper is displaced. So its mass is not involved in
the calculation
Questions
1. Excess iron powder is added to copper(II) chloride solution of concentration
at an initial temperature of . If the temperature of the mixture
rose to a maximum temperature of .
(ii) Calculate the heat of displacement of copper by iron.

2. In an experiment to determine heat of displacement of iron by magnesium, excess
magnesium powder is added to of iron(II) sulphate solution at an initial
temperature of . If the temperature of the mixture rose to a maximum
temperature of . Calculate the heat of displacement of iron by magnesium.
Atomisation energy
This is the heat absorbed when an element in its normal physical state is converted into
one mole of free gaseous atoms.
Standard enthalpy of atomisation

This is the heat absorbed when an element in its normal physical state is converted into
one mole free gaseous atoms at 1 atmosphere and 298K.
Or This is the heat absorbed when a compound in its normal physical state is
converted into free gaseous atoms at 1 atmosphere and 298K.
The table below shows values of standard enthalpies of atomization for some elements.
Element
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The values shown above show the enthalpy of formation of one mole of the gaseous
monoatomic element in its standard state.
For a compound, for example butanol, atomization can be shown as below;
Standard enthalpy of sublimation

The standard enthalpy of sublimation is the heat absorbed when one mole of an
element in its solid state is converted to one mole free gaseous atoms at 1 atmosphere
and 298K.
Enthalpy of sublimation is equal to enthalpy of atomization but only for solid elements.
Ionisation energy
This is the minimum amount of energy required to remove an electron from a gaseous
atom to form a charged gaseous ion.

Ionisation energy can be first, second or third,… ionisation energies depending on which
electron is being removed from the atom.
First ionisation energy is the minimum amount of energy required to remove an

electron from a gaseous atom to form a unipositively charged gaseous ion.
For example formation of a free gaseous sodium ion from a free gaseous sodium atom
involves removal of one electron against the nuclear attraction.
Electron affinity
When an electron is gained by an atom, energy is given out.
This enery is called first electron affinity.

First electron affinity is the energy given out when one mole of electrons combines with
one mole of gaseous atoms to form one mole of uninegatively charged gaseous ions
or
The energy given out when an electron is added to a gaseous atom to form a
uninegatively charged gaseous ion
First electron affinity is an exothermic process (energy is given out)
For chlorine, it can be represented as;
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The uninegatively charged gaseous ion can gain one more electron to form a dinegatively
charged ion. This is called second electron affinity and is an endothermic process
(energy is absorbed)
For the case of Sulphur the values of first and second electron affinities are given below
The reasons for second electron affinity being endothermic are explained in the topic:
Atomic structure and the Periodic Table (Page 195)
Lattice energy
This is the heat given out when one mole of an ionic solid is formed from its
component gaseous ions under standard conditions.
For example solid sodium is formed from gaseous sodium ions and gaseous chloride ion

Lattice energy can also be defined as the heat absorbed when one mole of an ionic
solid is broken down into its component gaseous ions.
Factors affecting lattice energy

(i) Ionic charges.
The higher the product of ionic charges, the higher the lattice energy because of the
strong electrostatic forces of attraction between the oppositely charged ions. This
explains why magnesium oxide has a higher (more exothermic) lattice enthalpy
than sodium chloride yet both compounds have the same molecular structure.
(ii) Ionic radius.

The smaller the cationic radius, the higher the lattice energy because the cations will
strongly attract the anions because of the increased effective nuclear charge .
The smaller the anionic radius, the higher the lattice energy because the cations will
strongly attract the anions.
In summary, lattice enthalpy is directly proportional to the product of ionic charges but
inversely proportional to the sum of ionic radii.
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Examples
1. The values of lattice energies of potassium halides are given below.
Formula of halide
Lattice energy(kJmol-1)
Explain the trend in these values for the potassium halides.
The lattice energies of the halides decrease (become less exothermic) from potassium
fluoride to potassium iodide. This is because the anionic radius increases from the
fluoride ion to the iodide ion. The halide anions therefore become less attracted by the
potassium ion. Thus a decreasing amount of energy is evolved when the potassium
halides are formed from the free gaseous ions.
2. The values of lattice energies of sodium chloride and magnesium chloride are
given below.
Formula of chloride
Lattice energy(kJmol-1)

Explain the difference in the two values.
Magnesium chloride has a higher (more exothermic) lattice energy than sodium
chloride.
This is because the magnesium ion has a higher ionic charge and smaller ionic radius,
than the sodium ion. The magnesium ion therefore strongly attracts the chloride ion
more than the sodium ion does. Therefore greater amount energy is evolved when solid
magnesium chloride is formed into gaseous ions than sodium chloride.
Standard enthalpy of hydration

When an ionic solid is dissolved in water, the ions are first separated from the ionic
lattice. The energy involved in this process is called the lattice dissociation enthalpy.
The separate ions then interact with water molecules. The positive ions are attracted to
the negative end of the water molecules and the negative ions are attracted to the positive
end of the water molecules. Energy is released during this process and is called the
enthalpy of hydration or solvation.
→ →
Enthalpy of hydration is the heat given out when one mole of gaseous ions is
completely surrounded by water molecules to form an infinitely dilute solution with no
change in pH.
Enthalpy of hydration is exothermic hence always a negative value.
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Factors affecting enthalpy of hydration

(i) Ionic radius
The smaller the ionic radius, the higher the hydration energy because the forces of
attraction between ions for water molecules are strong.
(ii) Ionic charge
The higher the ionic charge , the higher the hydration energy because the forces of
attraction for water molecules is strong.
Which of the metal ions and is likely to have the highest hydration
energy? Give a reason.
The aluminium ion has the highest hydration energy because it has the highest ionic
charge, smallest ionic radius, highest charge density and highest polarizing power. The
ion is easily hydrated and therefore strongly attracts very many water molecules hence
giving off the highest amount of energy.
Calculations involving enthalpy of hydration

The table below shows the enthalpies of hydration of some ions
Ion Enthalpy of hydration
(a) State whether the values of enthalpies of hydration given in the table should
be positive or negative. Give reasons for your answer.
The values should be negative

Reason
Hydration of the ions involves attraction of water molecules releasing a lot of heat
(b) Explain the differences in the enthalpies of hydration of;
(i) Potassium ion and calcium ion
The potassium ion has a larger ionic radius and smaller ionic charge than the calcium
ion. The potassium ion therefore has a lower charge density thus a lower attraction for
water molecules than the calcium ion, giving off a lower amount of heat than the
calcium ion.
(ii) Fluoride ion and chloride ion
The fluoride ion has a smaller ionic radius than the chloride ion. The fluoride ion
therefore has a higher attraction for water molecules than the chloride ion, giving off a
higher amount of heat than the chloride ion.
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(c) Calculate the enthalpy of hydration of;

(i) Calcium fluoride
( )
(ii) Potassium chloride

Standard enthalpy of solution
The standard enthalpy of solution is the heat evolved or absorbed when one mole of a
substance is dissolved in a specified number of moles of water under standard
conditions.
Enthalpy of solution can be either positive (endothermic) or negative (exothermic).

The enthalpy of solution of an ionic solid involves two energy terms:
(i) Lattice enthalpy
(ii) Enthalpy of hydration
In this case the lattice enthalpy required is lattice dissociation enthalpy and is
endothermic.
The enthalpy of solution of an ionic compound is therefore the sum of lattice

dissociation enthalpy and enthalpy of hydration.
A high (more positive)lattice enthalpy and a low(less negative) makes the enthalpy of
solution more positive.
Ionic salts that dissolve endothermically include ammonium nitrate, ammonium
chloride, potassium nitrate, potassium chloride, sodium chloride, sodium thiosulphate
and sodium hydrogencarbonate.
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A low (less positive)lattice enthalpy and a high(more negative) makes the enthalpy of
solution more negative.
Ionic salts that dissolve exothermically include sodium hydroxide, calcium chloride,
sodium carbonate
The more negative the enthalpy of solution, the more soluble a compound is. The less
negative the enthalpy of solution, the less soluble the compound is.
Experiments to determine enthalpy of solution

Experiment to determine enthalpy of solution for an ionic salt that dissolves
exothermically
For example sodium hydroxide
Set up
Thermometer

Calorimeter
Stirrers Empty copper cylinder
Double thin-walled copper vessel
containing water
Water
Corks
A known volume of water is put in a calorimeter fitted with a thermometer and

stirrer.
The initial temperature, of the water is recorded from the thermometer
A known mass of solid sodium hydroxide is added to the water and the solution is
stirred until there is no further change in temperature.
The final steady temperature is read and recorded from the thermometer.
Assumptions:

Heat capacity of the calorimeter is negligible
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( )
( )
( )
( )
( )
Experiment to determine enthalpy of solution for an ionic salt that dissolves

endothermically
For example ammonium chloride

A known volume of water is put in a calorimeter fitted with a thermometer and
stirrer.
The initial temperature, of the water is recorded from the thermometer
A known mass of solid ammonium chloride is added to the water and the solution
is stirred until there is no further change in temperature.
The final steady temperature is read and recorded from the thermometer.
Assumptions:

Heat capacity of the calorimeter is negligible
( )
( )
( )
( )
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( )
Note the difference in the two experiments is the temperature rise and the sign on
the enthalpy value.
Calculations involving enthalpy of solution

1. The table below shows enthalpies of hydration and lattice energies of potassium
chloride and lithium chloride.
Salt Lattice energy Hydration energy
Potassium chloride
Lithium chloride
(a) Calculate the enthalpy of solution of potassium chloride and lithium
chloride.
(b) State which of the two salts is more soluble in water at a given temperature

and give a reason for your answer.
(a) Note that the given values of lattice energy are negative but for the compounds to
dissolve in water, the lattice enthalpy involved is lattice dissociation enthalpy which
is endothermic.
For potassium chloride For Lithium chloride
(b) Potassium chloride is more soluble in water because its enthalpy of solution is
exothermic.
3. The enthalpies of hydration of sodium ions and hydroxyl ions are

and . Calculate the lattice enthalpy of sodium hydroxide if its
enthalpy of solution is .
Note that although the values given for enthalpy of hydration have no negative
sign, it should be known that hydration enthalpies are always exothermic.
( )
̅
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4. In an experiment, of potassium nitrate is added to of water in a

polystyrene foam cup at and the mixture stirred. If the solution
achieved a minimum final temperature of . Determine the enthalpy of
solution of potassium nitrate

( )
Questions
1. In an experiment, of sodium hydroxide was added to of water in a well-
insulated polystyrene foam cup the mixture stirred. The temperature of the solution
rose by . Determine the enthalpy of solution of sodium
hydroxide.
2. When 3.21g of solid ammonium nitrate dissolves in 50.0g of water at in a
calorimeter, the temperature decreased to . Calculate the enthalpy of solution
of ammonium nitrate. State any assumptions made.
3. The table below shows hydration enthalpies of magnesium and chloride ions.
Ion Enthalpy of hydration
If the lattice dissociation enthalpy of magnesium chloride is

. Calculate the enthalpy of solution of magnesium chloride.
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319
4. The enthalpies of hydration for calcium ion and fluoride ion are and
respectively. If the lattice enthalpy of calcium fluoride is
. Calculate the enthalpy of solution of calcium fluoride.
5. (a) Define the terms;
(i) enthalpy of hydration
(ii) enthalpy of solution
(b) The enthalpies of solution and lattice energies of salts and are given in the
table below.
Salt Enthalpy of solution Lattice enthalpy
(i) Calculate the enthalpy of hydration of each salt

(ii) State the salt which has a larger value of hydration energy

Application of enthalpy of solution in real life situation
In instant cold and hot packs already explained in the beginning subtopics of the
topic.(Pages 284-285)
Heat of precipitation
When two aqueous solutions are added together and a precipitate is formed, the reaction
is called a precipitation reaction or double decomposition reaction. This reaction is
used to prepare insoluble salts for example silver chloride, barium sulphate, lead sulphate
and others.
The heat given out or absorbed is called heat of precipitation.
The heat of precipitation is the heat change that occurs when one mole of a precipitate
is formed from its ions in aqueous solution.
Heat of precipitation can be exothermic or endothermic.
Experiment to determine heat of precipitation of silver chloride

A known volume, of silver nitrate of known concentration, is
measured and placed in a plastic beaker.
The initial temperature of the silver nitrate solution, is noted from the
thermometer.
An equal volume, of sodium chloride solution of the same concentration is also
measured and poured into a separate beaker and its initial temperature, is noted
from the thermometer.
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The two solutions are added together quickly and carefully while stirring and the
Assumptions
( )
[ ( )]

( )
( ) ( )
( )
( )
( )
( )
Calculations involving heat of precipitation
Example
of silver nitrate solution was added to of sodium
chloride solution in a plastic cup. The temperature of the resulting mixture rose by .
Assuming the container has a negligible heat capacity and the specific heat capacity of
the resulting mixture is . Calculate the heat of precipitation of silver
chloride.
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( )
( )

Questions
1. In an experiment carried out to determine heat of precipitation of silver chloride,
of of silver nitrate solution is poured in a polystyrene cup
and its initial temperature recorded as . of of sodium
chloride solution was added and the resulting mixture stirred. The highest
temperature attained by the solution was . Calculate the heat of precipitation of
silver chloride.
2. When of of sodium chloride solution and of of
silver nitrate solution, both at were mixed in a coffee cup calorimeter, the
temperature increases to . Calculate the heat of precipitation of silver
chloride. State any assumptions made.
3. of silver nitrate solution at is added to of
potassium chloride solution which is at a temperature of . The
mixture is stirred and the highest temperature reached is . Calculate the heat
of precipitation of silver chloride.
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Bond energy
Bond energy is heat given out when one mole of a single covalent bond of a diatomic
molecule is formed from free gaseous atoms.
This enthalpy change resulting into formation of a covalent bond is exothermic. It is

more correctly known as bond energy of formation.
Bond energies are very important because all chemical reactions involve forming and
breaking bonds. The strength of a covalent bond is represented by its bond dissociation
energy.
Bond dissociation energy

Bond dissociation energy is energy required to break one mole of a single covalent

bond of a diatomic molecule to form free gaseous atoms.
Bond dissociation enthalpy is endothermic because energy must be absorbed to break a
covalent bond.
Bond dissociation energy is related to atomization energy.
Since
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Average bond energies (enthalpies)

For a polyatomic molecule such as , the average bond enthalpy is of the enthalpy
change of the process;
In methane, for example, the average bond enthalpy is given as
Since
This is because methane has four bonds

Average bond enthalpies are obtained from standard molar enthalpies of formation and
molar enthalpies of atomization

If the average bond enthalpy of one covalent bond in a molecule is known, then the
average bond enthalpy if the other bond can be determined.
Using bond energies to calculate enthalpy of a reaction

Enthalpy of any given reaction can be obtained if the average bond enthalpies of the
bonds involved are known. The relationship used is;
( )
∑ ∑
Calculations involving bond energies

Examples
1. (a) Define the term “standard enthalpy of atomization”
(b) Bond energies for some bonds are given below.
Calculate the standard enthalpy of atomization of methanol
Bond Bond energy
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324
(b) Equation;
∑ ∑
[ ]
2. (a) Write equation for formation of steam.

(b) The enthalpy of formation of steam is . The bond energies
of some bonds are also given below.
Bond Bond energy

Calculate the oxygen-oxygen bond energy in .
(a)
∑ ∑
[ ] [ ]
[ ]
3. Hydrazine reacts exothermically with hydrogen peroxide when used as a rocket

fuel. The table below shows some bond energies.
Bond
Bond energy 463 388 163 146 944
Calculate the enthalpy change for the reaction;
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325
∑ ∑
[ ] [ ]
[ ] [ ]
Questions
1. Bond energies for some bonds are given below.

Calculate the standard enthalpy of atomization of
Bond Bond energy
2. Bond energies for some bonds are given below.

Bond Bond energy
(a) Calculate enthalpy of hydrogenation of ethyne

(b) State whether hydrogenation of ethyne is feasible or not. Give a reason for your
answer.
3. Propan-2-ol can be prepared from propanone by the reaction;
Given the data below;

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Bond Bond energy

715
345
414
351
464
436
Calculate the enthalpy change for the reaction above.
4. The table below shows some bond energies.
Bond
Bond energy 435 415 284 256 193
(a) What is meant by the term bond energy?
(b) Calculate the enthalpy of formation of;

(i) 1,2-dibromopropane
(ii) Propane
(c) Calculate the enthalpy change for the reaction;
Note; Factors that affect strength of a covalent bond also affect bond energy. Refer
to one of the previous topics (STRUCTURE AND BONDING) and also for trends in
bond energy.
Hess’s law of constant heat summation

Hess’s law states that the enthalpy change in a chemical reaction at constant
temperature and pressure is the same whether the reaction is brought about in one
stage or through intermediate stages but depends on the initial and final states of the
reactants and products.
Demonstration of Hess’s law using an experiment

The validity of Hess‟s law can be demonstrated experimentally by measuring enthalpy
changes when a reaction is brought about in two or more different ways.
For example ammonium chloride solution can be made using 17g of ammonia , 36.5g of
hydrogen chloride and water in two ways;
(i) Reacting ammonia gas and hydrogen chloride gas to form ammonium chloride
which is then dissolved in water
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(ii) Dissolving ammonia gas and hydrogen chloride gas separately in water and the
solutions added to each other
According to Hess‟ law, the heat change in both cases is the same and then;
The Hess‟s law is very important in determining heats of reaction if direct determination
is not possible. It has already been applied in calculations involving heats of combustion.
Application of Hess’s law in some more calculations

Examples
1. (a) Calculate the enthalpy of formation of sodium chloride using the following

data
(b) Comment on the stability of sodium chloride. Give a reason for your answer.
(a) Equation for the reaction required;
328
2. (a) Define the term standard heat of reaction

(b) Given the following data:
Enthalpy of formation of magnesium chloride
Lattice energy of Magnesium chloride
Hydration energy of chloride ions
Enthalpy of solution of hydrogen chloride gas
Heat of formation of hydrogen chloride gas
Hydration energy of magnesium ions
N.B The lattice energy given is positive(endothermic). This means its lattice
dissociation energy.
(b) Equations given;

Rearrangement
The equation generated above and the equation given in the question are the same.
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Questions
1. The enthalpies of some reactions are given below.
(a) Calculate the lattice energy of sodium hydride

(b)(i) From your answer in (a); state whether sodium hydride is a stable compound or
not.
(ii)Give a reason for you answer in b(i)
2. (a) State what is meant by the term enthalpy of atomization
(b) Given the thermochemical data below
Lattice energy of rubidium chloride

Enthalpy of bond dissociation of chlorine
Enthalpy of atomisation of rubidium
Ionisation energy of rubidium atom
Standard enthalpy of formation of solid rubidium chloride
Calculate the electron affinity of chlorine
(c) Sodium chloride and potassium chloride have lattice enthalpies and
respectively. Explain the difference.
3. The thermochemical data for some processes are given below
Calculate the electron affinity of the fluorine atom.

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ENTHALPY CYCLES (BORN HABER CYCLES)

A Born-Haber cycle is a technique for applying Hess‟s law to the standard enthalpy
changes. Born Haber cycles are used to calculate enthalpy changes which are difficult, or
impossible to evaluate directly. These include theoretical values for lattice energies,
electron affinities and enthalpies of formation. The only energy term in the cycle that
cannot be measured experimentally is the lattice enthalpy and the cycle enables its value
to be determined.
The cycle can be an energy level diagram or enthalpy cycle.
Terms used in Born-Haber cycle

The common energy terms below which have been previously defined the subtopics
above, are used in the Born Haber cycle;
 Standard enthalpy of sublimation
 Standard enthalpy of ionisation
 Standard bond dissociation enthalpy

The standard bond dissociation energy is twice atomization energy
 Electron affinity
 Standard lattice enthalpy
 Standard enthalpy of formation
Point to note when drawing Born Haber cycles

 The cycles should have well balanced equations
 Ions should have correct charges
 The chemical symbols of the elements must be correct
 State symbols must be shown and should be correct
 The enthalpy values should be shown along with the reactions they represent in
the cycle.
 For the energy level diagram it’s important to consider the ranges between any
two energy terms
(a) Enthalpy diagram or energy level diagram

An energy level diagram shows the energy changes in the order they happen.
Endothermic (positive) enthalpy changes are shown upwards and the exothermic
(negative) enthalpy changes are shown down wards. The diagram also must have well
balanced equations for the reactions that take place, with state symbols inclusive and the
energy changes must be labelled.
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Examples
1. Given the following data;
Standard enthalpy of formation of aluminium fluoride
Enthalpy of atomization of aluminium
Bond dissociation energy of fluorine
First ionisation energy of aluminium
Second ionisation energy of aluminium
Third ionisation energy of aluminium
First electron affinity of fluorine
(i) Draw an energy level diagram for the formation of aluminium fluoride
(ii) Calculate the lattice energy of aluminium fluoride
(iii) If the hydration energies of aluminium ions and fluoride ions are 4690 and
364 respectively, calculate the enthalpy of solution of

aluminium fluoride.
(i) Energy level diagram for formation of aluminium fluoride;
Potential
energy
0
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(ii) By Hess‟ law;
(iii)

Note that lattice energy substituted in the equation for above is the lattice
dissociation enthalpy hence it must be positive. Hydration enthalpies are also known to
be negative although given as positive values in the question.
2. (a) Use the data below to calculate the lattice enthalpy of calcium oxide
Enthalpy of formation of calcium oxide
Bond dissociation energy of oxygen
First electron affinity of oxygen
Second electron affinity of oxygen
Atomization energy of calcium
First ionisation energy of calcium
Second ionisation energy of calcium
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Using an energy level diagram;

Potential
energy
Similarly, since oxygen shows both positive and negative values of first and second
electron affinities, they can be summed up. The value got is positive and the sum got
is represented by one arrow facing upwards. The arrow can then be labelled as
( )
By Hess‟ law;
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(b) Born-Haber cycle in form of a usual enthalpy cycle

Examples
1. Below is thermochemical data about sodium chloride.

(a) Draw a Born Haber cycle of sodium chloride and use it to calculate the
electron affinity of chlorine using the following data above
(b) If the hydration enthalpies of sodium and chloride ions are
and respectively, calculate the enthalpy of
solution of sodium chloride.
(c) Comment on your answer in (b) above and give a reason for your answer.
(a)
By Hess‟ law;
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(b)
( )
Note that lattice energy substituted in the equation in (b) above is the lattice
dissociation enthalpy hence it must be positive. Hydration enthalpies are also known to
be negative although given as positive values in the question.
(c) The enthalpy of solution of sodium chloride is endothermic because the
magnitude of its lattice energy is higher than the magnitude of its hydration

energy.
1. The information below shows thermochemical data of aluminium oxide.
(a) Construct a Born Haber cycle relating the enthalpy changes and use it to
calculate the enthalpy of formation of aluminium oxide
(b) Comment on the stability of aluminium oxide. Give a reason for your
answer.
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(a)

→
By Hess‟ law;
(b) Aluminium oxide is stable because its enthalpy of formation is exothermic.
Born-Haber cycle involving enthalpies of combustion and formation
The standard heats of formation of ethanol, carbon dioxide and water ,

and respectively.
(a) Draw a Born-Haber cycle to relate the energy changes stated above
(b) Calculate the standard heat of combustion of ethanol using the drawn cycle.
(c) From your answer in (b) above and the energy changes in (a) , state one ideal
use of ethanol in chemistry. Give a reason for your answer.
(a)
→
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(b) By Hess‟ law
(c) Ethanol is used as a fuel because its enthalpy of combustion is highly exothermic.
Determination of heat of hydration of hydrated and anhydrous compounds by use

of the Born Haber cycle and applying Hess‟ law
Example
In an experiment to determine hydration energy of anhydrous copper(II)
sulphate of the anhydrous salt was added to of water and the

temperature rose by . When of the hydrated copper(II) sulphate was
added to of water and the temperature dropped from to .
(a) Calculate the enthalpy of solution of;

(i) anhydrous copper(II) sulphate
(ii) hydrated copper(II) sulphate
(b) State which of the two salts is more soluble in water and explain your
answer.
(c) Construct a Born Haber cycle and use it to determine the heat of hydration of
anhydrous copper(II) sulphate.
Solution
(a) (i)
( )
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N.B The enthalpy of solution for this reaction is negative (exothermic) because there
is an increase in temperature.
(ii)
( )
N.B The enthalpy of solution for this reaction is positive (endothermic) because
there is a decrease in temperature.

(b) Anhydrous copper(II) sulphate is more soluble than hydrated copper(II) sulphate
since its enthalpy of solution is exothermic whereas that of the hydrated salt is
endothermic.
This is because the copper(II) ion and sulphate ion in hydrated copper(II) sulphate
are already partly hydrated. When the hydrated salt is dissolved in water, its
lattice energy outweighs the enthalpy of hydration associated with any further
hydration. This makes the enthalpy of solution positive. For the anhydrous salt,
the hydration energy outweighs the lattice energy making the enthalpy of
solution negative.
(c) →
By Hess‟ law
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Born-Haber cycle involving bond energies

1. (a) Distinguish between atomization energy and bond energy
(b) Draw a labelled Born Haber cycle and identify the energy changes involved
at each step when carbon reacts with hydrogen to form methane
(c) Given the enthalpy of formation of methane and atomisation energy of
carbon and hydrogen are , and
respectively, calculate the average bond energy for – bond.
(b) →
By Hess‟ law

2. (a) Draw a Born Haber cycle for formation of chloroethane
(b) Calculate the enthalpy of formation of chloroethane using following
thermochemical data.
Bond energy of bond

Bond energy of bond
Bond energy of bond
Atomization energy of hydrogen
Bond dissociation energy of chlorine
Enthalpy of atomization of graphite
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Solution
𝑯𝑩𝑬 [𝟓 𝑪 𝑯 𝑪 𝑪 𝑪 𝑪𝒍 ]
𝟓 𝟒𝟏𝟑 𝟑𝟏𝟖 𝟑𝟑𝟔
In this calculation you should clearly note that bond energy of formation is exothermic
(negative)
By Hess‟ law
[ ]

3. Calculate the bond energy of given that the bond energy is
, bond energy is and the enthalpy of
formation of hydrogen chloride is
By Hess‟ law
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4. The standard heat of formation of phosphorus trichloride is . The

bond dissociation energy and enthalpy of atomisation of chlorine and
phosphorus are 242 and 314 respectively.
(i) Draw a Born-Haber cycle for the formation of phosphorus trichloride.
(ii) Use the Born-Haber cycle to calculate the bond energy.
→

( )
Questions
Questions involving enthalpy cycles
1. The thermochemical data of lithium and oxygen are given below.
(a) (i) Draw an energy level diagram for the formation of lithium oxide
(ii) Use your diagram to find the second electron affinity of oxygen
(b) Comment on the electron affinities of oxygen
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2. (a)Draw an energy level diagram for formation of lithium fluoride.

(b) Using the diagram in (a) above and the data below calculate the standard enthalpy
of formation of lithium fluoride
Atomization energy of fluorine
Electron affinity of fluorine
Atomization energy of lithium
Ionisation energy of lithium
Lattice energy of lithium fluoride
3. Carefully study the information given below. Enthalpy changes are given in
.
First ionisation energy of calcium
Atomization energy of calcium
Second ionisation energy of calcium
Heat of atomization of oxygen

First electron affinity of oxygen
Second electron affinity of oxygen
Heat of formation of calcium oxide
From the information above, draw a labelled Born Haber cycle for calcium oxide.
Calculate the lattice energy for calcium oxide.
4. Using the information below, draw a Born-Haber cycle and use it to calculate the
lattice energy of potassium bromide.
Enthalpy of formation of potassium bromide
Atomization energy of potassium
Dissociation energy of bromine
Electron affinity of bromine
Ionisation energy of potassium
5. Construct a Born-Haber cycle for the formation of solid potassium chloride from its
elements in their standard states. Use the data below to calculate the standard enthalpy
of formation of potassium chloride. |
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6. (a) State Hess‟ law of heat summation.

(b) Some thermochemical data for silver, fluorine and silver fluoride are given below;
(i) Draw an energy level for the formation of solid silver fluoride.
(ii) Use the energy level diagram above to calculate the first electron affinity of
fluorine.
(c) (i) Define the term enthalpy of solution.
(ii) Describe an experiment to determine enthalpy of solution of silver
fluoride.

(iii) Explain the energy terms that determine the magnitude of the enthalpy of
solution of any ionic salt.
(iv) Sketch a labelled energy diagram for the dissolution of silver fluoride.
7. (a) Draw a Born Haber for the formation of solid Rubidium chloride
(b) Calculate the electron affinity of chlorine atom using the following data;
Enthalpy of formation of rubidium chloride
Lattice enthalpy of rubidium chloride
Enthalpy of sublimation of rubidium
Ionisation energy of rubidium
8. The enthalpies of formation of water and carbon dioxide are
and respectively. The enthalpy of combustion of methane is
. Construct a Born-Haber cycle and use it to calculate the enthalpy of
formation of methane.
9. The heat of formation of carbon dioxide is , heat of formation of water
is and heat of combustion of butane is
(a) Draw a Born Haber cycle to relate the energy changes above.
(b) Calculate the standard heat of formation of butane using the Born Haber cycle
in(a) above.
10. Draw a Born-Haber cycle that can be used to calculate the heat of oxidation of ethanol
to ethanal if the enthalpies of combustion of ethanol and ethanal are -1367 kJmol-1
and -1167kJmol-1 respectively.
Use your cycle to calculate the enthalpy change for oxidation of ethanol to ethanal.
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11. The bond dissociation energies of hydrogen, chlorine and hydrogen chloride are ,
and respectively. Using a Born-Haber cycle, calculate the
enthalpy of formation of hydrogen chloride.
12. Calculate the standard enthalpy of formation of ethene from the following data using
a Born-Haber cycle.
Bond energy of bond
Bond energy of bond
Bond energy of bond
Bond dissociation energy of hydrogen
Enthalpy of sublimation of carbon
13. The average bond enthalpy and some atomization enthalpies are given below.
Bond Bond Atomization energy
energy

(a) Draw a Born Haber cycle for formation of ethane
(b) Use the information above and your cycle to calculate the enthalpy of formation of
ethane.
14. (a) Define the term bond energy.
(b) Draw the structure and name the shape of phosphorus trichloride molecule
(c) The heats of atomization of phosphorus and chlorine are given below
Calculate the average bond energy for – bond.
15. The standard enthalpy change of formation of silicon(IV) chloride is .

The standard enthalpy change of atomization of silicon and chlorine are
and respectively.
(a) Use these values to construct a Born-Haber cycle for formation of silicon(IV)
chloride from its elements and indicate the energy changes involved.
(b) Calculate the average bond energy of the bond.
16. The standard enthalpy change of formation of tin(IV) chloride is . The
standard enthalpy change of atomization of tin and chlorine are and
respectively.
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(a) Use the above to construct a Born-Haber cycle for formation of tin(IV) chloride.
(b) Calculate the average bond energy of the bond.
17. The molar enthalpy of solution of anhydrous copper(II) sulphate and copper(II)
sulphate pentahydrate are and respectively.
(a)Explain the difference in the values above.
(b) Calculate the enthalpy of hydration of anhydrous copper(II) sulphate.
18. Chemical reactions are accompanied by enthalpy changes.
(a) Explain what is meant by the term standard enthalpy change of a reaction
(b) The enthalpy change for hydration of anhydrous magnesium sulphate can be
calculated by carrying out two separate experiments.
(i) In the first experiment, of water was put in a polystyrene cup and of
anhydrous magnesium sulphate was added and stirred until it completely dissolved. The
temperature of the water rose from to . Calculate the enthalpy of
solution of magnesium sulphate.
(ii) In the second experiment, of water was put in a polystyrene cup and of

hydrated magnesium sulphate was added and stirred until it completely
dissolved. The temperature of the water decreased from to . Calculate
the enthalpy of solution of hydrated magnesium sulphate.
(iii) Draw a well labelled Born-Haber cycle and use it to calculate the enthalpy change
for the reaction;
Miscellaneous questions
1. (a) State Hess‟ law
(b) State four factors that affect the enthalpy change of any system.
(c) The enthalpy of combustion of ethene is while that of ethyne is
and that of hydrogen is .Calculate the enthalpy
change of hydrogenation of ethyne to ethene.
2. (a) What is meant by the term bond energy?
(b) The bond energies of and bonds
respectively are and . Calculate the
enthalpy change for the reaction below.
(c) For each of the following compounds state the type of bonding and structure
adopted.
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Compound Bonding type Structure

Iodine
Calcium fluoride
Silicon(IV) oxide
3. (a) Copper like other transition elements forms compounds in oxidation states and
. Write the electronic configuration of:
(i) copper(I) ions
(ii) copper(II) ions
(b) The enthalpies of reduction of copper(I) and copper(II) ions are given below:
(i) Calculate the enthalpy of disproportionation of copper(I) ions to copper(II)

ions and copper

(ii) Using your answer in b(i), comment on the stability of copper(I) ions with
respect to copper(II) ions. Give a reason for your answer.
(c) State any two other properties that make copper a typical transition metal.
4. (a) Describe an experiment to determine enthalpy of combustion of butanol
(b) The standard enthalpies of combustion of the first five straight chain alkanes and
alcohols are shown in the table below
Number of carbon atoms
Enthalpy of combustion of
alkanes
Enthalpy of combustion of
alcohols
(i) On the same axes, plot a graph of enthalpies of combustion of both alkanes
and alcohols against number of carbon atoms
(ii) Use the graph to determine the enthalpy of combustion of hexane.
(iii) Explain the shape of the graph
(c) The standard enthalpies of combustion of carbon and hydrogen are
and respectively. The standard enthalpies of
atomization of carbon and hydrogen are and
respectively. Calculate;
(i) Standard enthalpy of formation of hexane
(ii) Standard enthalpy of atomization of hexane
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CHAPTER FIVE
PHYSICAL EQUILIBRIA
Equilibrium represents the state of a process in which the properties like temperature,
pressure, concentration of the system do not show any change with passage of time.
A physical equilibrium is an equilibrium that exists between different phases or physical

properties. It represents the existence of the same substance in different physical states.
This equilibrium does not involve any chemical change. It involves only physical
changes like phase changes or solubility.
SYSTEMS, PHASES, COMPONENTS AND PHASE

DIAGRAMS
System

A system is that part of the universe, the set of substances and energy associated with
them, that is being studied.
For example if reactions are occurring in a conical flask, everything inside the flask is a
system.
Phase
A phase is a homogeneous part of a system which is physically distinct from other parts
of the system by a definite boundary.
Each of the three homogeneous states (solid, liquid and gas) in which a substance can
exist is called a phase.
 For example a mixture of gases is one phase
 A solution is one phase
 A saturated solution in the presence of an excess of the solute is a two-phase
system
Except under special conditions, only two phases can exist in equilibrium.
Component
A pure substance in a system that defines part of the composition of that system
A mixture of water and ethanol has two components but one phase
A mixture of ice and water has two phases but one component
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Phase diagram
When a substance can exist in different phases, for example water which can exist as a
liquid, gas (water vapour) or solid (ice), the conditions under which each phase exists,
and the various equilibria that can exist between the three phases can be represented by a
phase diagram.
A phase diagram is a graph on which pressure is plotted against temperature showing
equilibria between different phases of a substance and the temperatures and pressures
at which each phase exists.
 An area/ region of a phase diagram represents one phase
 A line or curve represents the temperatures and pressures under which two phases
can exist in equilibrium
 A triple point represents the temperature and pressure under which three phases
can coexist in equilibrium.

COMPONENT SYSTEMS
There are two types of components systems namely;
(i) One-component system
Only one pure chemical substance is involved in the equilibrium
(ii) Two-component system
Two chemically independent components are involved in the equilibrium
One component systems

Examples of one component systems include;
 The water system
 The sulphur system
 The carbon dioxide system
The water system
Water can exist as liquid, as a solid(ice) or as a vapour. It is called steam when its
temperature is above .
Below is a phase diagram for the water system.
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Phase diagram for water

B
Pressure C
Liquid
Solid Vapour
O
A
Temperature
At low temperature and low pressure, water exists as ice. At low temperature and high

pressure, it exists as vapour. At high temperatures and high pressures, it exists as a
liquid.
Curves/lines
shows the variation of vapour pressure of ice with temperature
OA The line summarises the conditions under which solid ice and water
vapour can be in equilibrium.
This curve is called the sublimation curve of ice.
shows the variation of vapour pressure of liquid water with
temperature
OC The line summarises the conditions of temperature and pressure under
which liquid water and water vapour are in equilibrium.
This curve is called the vapourisation curve of liquid water.
shows the effect of pressure on the melting point of ice or freezing
OB point of water.
The line shows equilibrium between ice and liquid water.
It is called the freezing curve/ fusion curve.
Note: Line OB slopes upwards to the left because the melting point of ice decreases as
the pressure increases.
This decrease in melting point with increase in pressure is related to Le Chatelier‟s
principle. (Check next Chapter)
Points
O Triple point of water
C Critical point of water
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The triple point refers to the particular temperature and the particular pressure at
which ice, water vapour and liquid water co-exist at equilibrium.
The critical point represents the particular temperature and particular pressure above
which water vapour cannot condense to liquid water no matter how much pressure is
applied.
The critical temperature is the temperature above which vapour cannot be
converted into liquid water no matter how much pressure is exerted.
Beyond the critical temperature, liquid water and water vapour are undistinguishable
Effect of temperature and pressure on the phases
Y
Pressure J Z
F H P G

B
A C
M Q
X K
Temperature
1. The diagram above is a phase diagram for the water system
(a) Name the ;
(i) regions A, B and C
(ii) points Q and Z
(iii) curves QY, QX and QW
(b) State why line QY slants to the left
2. Explain the changes that take place when ;
(i) temperature of the system is increased from F to G at a constant
pressure
(ii) pressure of the system is reduced from J to K at constant temperature.
(i) At F, water exists in the solid phase (ice).

Increase in the temperature of ice moves the system from F to H without change
in phase.
At H, ice begins to melt and the temperature remains constant until all the ice has
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After all the ice has melted, further increase in temperature will move the system
from H to P in the liquid phase.
At point P, liquid water begins to vapourise and the temperature remains constant
until all the water has vapourised.
Further increase in temperature moves the system from P to G in the vapour
phase.
(ii) At J, water exists in the liquid phase.
Reducing the pressure of liquid water moves the system from J to H without
change in phase.
At H, liquid water begins to freeze and the pressure remains constant until all the
water has frozen.
After all the liquid water has frozen, a further decrease in pressure will move the
system from H to M in the solid phase.
At point M, ice begins to sublime and the pressure remains constant until all the

ice has sublimed.
Further decrease in pressure moves the system from M to K in the vapour phase.
The carbon dioxide system

Like water, carbon dioxide can also exist as liquid, as solid or as a gas.
Below is a phase diagram for the carbon dioxide system.
Phase diagram for carbon dioxide
R
Solid Liquid S
Pressure carbon dioxide carbon dioxide
P
Gaseous carbon dioxide
Q
Temperature
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Curves/lines
This curve is called the sublimation curve of solid carbon dioxide.
It shows the variation of vapour pressure of solid carbon dioxide with
PQ temperature
The line summarises the conditions under which solid carbon dioxide and
carbon dioxide gas can be in equilibrium.
This curve is called the vapourisation curve of liquid carbon dioxide.
It shows the variation of vapour pressure of liquid carbon dioxide
PS with temperature
The line summarises the conditions of temperature and pressure under
which liquid carbon dioxide and gaseous carbon dioxide are in
equilibrium.
It is called the freezing curve/ fusion curve.
PR It shows the effect of pressure on the melting point solid carbon
dioxide or freezing point of liquid carbon dioxide.

The line shows equilibrium between solid carbon dioxide and liquid
carbon dioxide.
Note: Line PR slopes to the right because the melting point of solid carbon dioxide
increases as the pressure increases.
Points
P Triple point of carbon dioxide
S Critical point of carbon dioxide
The triple point of carbon dioxide is and . This means that
liquid carbon dioxide cannot exist at ordinary atmospheric pressure and solid carbon
dioxide sublimes when exposed to a warm temperature.
The figure below shows the phase diagram for carbon dioxide.
X
D B Y
Pressure F K H L G
A
O J
C
R E
Temperature
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(a) State what the following represent.

(i) Regions; A, B and C
(ii) Points; O and Y
(iii) Curves OX, OR and OY
(b) State why line OX slopes to the right.
(c) Explain the changes that take place when ;
(i) pressure of the system is decreased from D to E at a constant
temperature
(ii) temperature of the system is increased from F to G at constant pressure.
(i) At D, carbon dioxide is a solid.

Decrease in the pressure of solid carbon dioxide moves the system from D to H
without change in phase.
At H, solid carbon dioxide begins to melt and the pressure remains constant until
all the solid carbon dioxide has melted.

After all the solid carbon dioxide has melted, further decrease in pressure will
move the system from H to J in the liquid phase.
At point J, liquid carbon dioxide begins to vapourise and the pressure remains
constant until all the liquid carbon dioxide has vapourised.
Further decrease in pressure moves the system from J to E in the vapour phase.
(ii) At F, carbon dioxide is a solid.
Increasing the temperature of solid carbon dioxide moves the system from F to K
At K, solid carbon dioxide begins to melt and the temperature remains constant
until all the solid carbon dioxide has melted.
After all the solid carbon dioxide has melted, a further increase in temperature will
move the system from K to L in the liquid phase.
At point L, liquid carbon dioxide begins to vapourise and the temperature remains
constant until all the liquid carbon dioxide has vapourised.
Further increase in temperature moves the system from L to G in the gaseous
phase.
The sulphur system

Sulphur exhibits enantiotropic allotropy.
Enantiotropic allotropy occurs when one form of an element after being heated is
converted into another form at a definite transition temperature.
Sulphur exists in two crystalline forms; rhombic sulphur (or sulphur) and
monoclinic sulphur( sulphur)
These changes can be represented in the phase diagram for sulphur below.
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F
C
Solid monoclinic sulphur

Liquid sulphur
Pressure Solid rhombic E
sulphur
D A
O
Sulphur vapour
B

Temperature
Curves
This is the sublimation curve of solid rhombic sulphur.
It shows the variation of vapour pressure of solid rhombic sulphur with
OB temperature
Along this curve, solid rhombic sulphur is in equilibrium with sulphur vapour.
This is the sublimation curve of solid monoclinic sulphur.
It shows the variation of vapour pressure of solid monoclinic sulphur with
OA temperature
Along this curve, solid monoclinic sulphur is in equilibrium with sulphur
vapour.
This is the vapourisation curve of liquid sulphur.
AE It shows the variation of vapour pressure of liquid sulphur with
temperature
Along this curve, liquid sulphur is in equilibrium with its vapour.
It is called the transition curve.
OC shows the effect of pressure on the transition point between rhombic and
monoclinic sulphur.
The line shows equilibrium between ice and liquid water.
AC This is the fusion curve of monoclinic sulphur.
It shows the effect of pressure on the melting point of monoclinic sulphur.
CF This is the fusion curve of rhombic sulphur.
It shows the effect of pressure on the melting point of rhombic sulphur.
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Points
O Triple point for rhombic sulphur, monoclinic sulphur and sulphur vapour
C Triple point for rhombic sulphur, monoclinic sulphur and liquid sulphur
A Triple point for monoclinic sulphur, liquid sulphur and sulphur vapour
D Melting point of rhombic sulphur
At ordinary temperatures and under one atmosphere, sulphur exists as in the stable
allotropic form of rhombic sulphur.
If its heated slowly to a temperature just above (the transition temperature) , it
changes completely into monoclinic sulphur which is stable until a temperature of
is reached, which is the melting point of monoclinic sulphur.
This transition is marked by a change in direction of the vapour pressure-temperature
curve at O in the phase diagram.
On cooling monoclinic sulphur up to , it changes to rhombic sulphur.

 When rhombic sulphur is heated rapidly, its temperature is raised rapidly to point D
without conversion into monoclinic sulphur. Melting occurs at , above the
transition temperature.
 Rhombic sulphur is only stable below the transition temperature but unstable the
transition temperature.
 Liquid sulphur when cooled forms needle shaped crystals of monoclinic sulphur.
These can exist below the transition temperature but change in a few hours to rhombic
sulphur.
 The more stable rhombic sulphur has a lower vapour pressure that the unstable
monoclinic sulphur at the same temperature.
Curves OC, AC and CF all slope upwards to the right because the transition
temperature, melting point of monoclinic sulphur and melting point of rhombic
sulphur all increase with increase in pressure respectively.
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Pressure P G Q D
S
T Y O Z V
C
B H

A X
R
Temperature
(a) State what the following represent.
(i) phases; P, Q, R and S
(ii) Points; B, C and E
(iii) Curves AB, BC, CD, BE and CE
(b) State why curves BE and CE slope to the right.
(c) Explain the changes that take place when ;
(i) P is heated T to V at constant pressure.
(ii) pressure of the system is decreased from W to X at a constant
temperature
(i) At T, sulphur is in the solid rhombic form.

Heating increases the temperature of solid rhombic sulphur from T to Y without
change in phase.
At Y, solid rhombic sulphur begins to change to solid monoclinic sulphur and the
temperature remains constant until all the solid rhombic sulphur has changed to
monoclinic sulphur.
Further heating increases the temperature of solid monoclinic sulphur, moving the
system from Y to O.
At point O, monoclinic sulphur begins to melt into liquid sulphur and the
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Further heating increases the temperature of liquid sulphur, moving the system
from O to Z in the liquid phase.
At Z, liquid sulphur begins to turn into sulphur vapour and the temperature
remains constant until all the liquid sulphur has vapourised.
Further heating moves the system from Z to V in the vapour phase.
(ii) At W, sulphur is in the solid rhombic form.
Decrease in the pressure of solid rhombic sulphur moves the system from W to G
At G, solid rhombic sulphur begins to change to solid monoclinic sulphur and the
pressure remains constant until all the solid rhombic sulphur has changed to
monoclinic sulphur.
Further decreases in vapour pressure of monoclinic sulphur moves the system
from G to H.
At point H, solid monoclinic sulphur begins to sublime and the pressure remains

constant until all the solid monoclinic sulphur has sublimed.
Further decrease in pressure moves the system from H to X in the vapour phase.
Two component systems

Types of two component systems
There are three types of two component systems (liquid mixtures) which include;
 Completely miscible liquid mixtures
 partially miscible liquid mixtures
 immiscible liquid mixtures
Completely miscible liquid mixtures

These are liquids which when shaken mix completely, in any proportions to form a
solution at a given temperature.
Depending on the forces of attraction between the molecules in the solution there are two
types of miscible solutions which are;
(i) Ideal solution
(ii) Non-ideal solutions
These will be explained later
Examples of miscible liquid mixture include;
 Ethanol and water
 Methanol and water
 Ethoxyethane and benzene
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 Benzene and methylbenzene

 Propan-1-ol and propan-2-ol
For completely miscible liquids, the vapour pressure of the mixture is not constant at a
given temperature but varies with the proportions of the two liquids and also depends on
the nature of the two liquids
Completely miscible liquid mixtures can be separated by fractional distillation.
Partially miscible liquid mixtures

Partially miscible liquids are liquids which in given proportions dissolve in each other
to some extent to form conjugate solutions.
Examples of partly miscible liquid mixtures include;
 Ethoxyethane and water
 Triethylamine and water

 Phenol and water(partially miscible below )
When a few drops of ethoxyethane are shaken with a lot of water, a solution of
ethoxyethane in water is formed. If a few drops of water are shaken with a lot of
ethoxyethane, a solution of water in ethoxyethane is formed. If about equal volumes of
the two liquids are shaken, two layers are formed. The upper layer consists of a saturated
solution of water in ethoxyethane and the lower layer consists of a saturated solution of
ethoxyethane in water.
Phenol and water are only completely miscible, forming one solution above , but
two immiscible solutions are formed below the same temperature depending on the
composition of the mixture. One of the solutions is a solution of phenol in water and the
other is a solution of water in phenol.
The two solutions are called conjugate solutions.
The complete miscibility of phenol and water with increasing temperature is because
their mutual solubilities increase with increase in temperature.
Steam distillation method may be used to separate partially miscible liquid mixtures.
Immiscible liquid mixtures

Immiscible liquids are liquids which when shaken and allowed to settle, they do not
mix but form separate layers.
In most cases, immiscible liquids involve organic substances and water.
Examples of immiscible liquid mixtures include;
 Oil and water
 Chloroform(trichloromethane) and water
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 Tetrachloromethane and water

 Paraffin and water
 Benzene and water
 Carbon disulphide and water
 Mercury and water
Immiscible liquids can be separated by using steam distillation method.
IDEAL SOLUTIONS AND NON-IDEAL SOLUTIONS

Ideal solutions
Ideal solutions can also be called perfect solutions.
An ideal solution is a solution in which the cohesive forces are equal to adhesive
forces, made with no heat or volume change and obeys Raoult’s law over all
concentration ranges at a given temperature.

If a solution is made from two components A and B, the solution is ideal if forces
between A and B are equal to the forces between A and A and those between B and B.
Raoult’s law
Raoult’s law states that the partial vapour pressure of a pure component in a solution
at a given temperature is equal to the vapour pressure of the pure component at the
same temperature, multiplied by its mole fraction in the solution.
where
Vapour pressure of a pure substance is the pressure exerted the vapour over the
surface at a given temperature.
Substances with lower vapour pressure have strong intermolecular forces, while those
with higher vapour pressure have weak intermolecular forces. The higher the vapour
pressure, the faster the evaporation rate.
Mole fraction of a component in a solution is the ratio of the number of moles of
that component present to the total number of moles of all the components in the
mixture.
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Therefore for a mixture of two liquids and . The mole fractions of liquids and are given
respectively as
Where is number of moles of A and is number of moles of B
According to Raoult‟s law;

Similarly ;

The vapour composition of each component can be obtained from the expressions;
The percentage vapour composition of each component can be obtained from the expressions;
Characteristics of ideal solutions

Two substances when mixed form an ideal solution only when;
(i) they obey Raoult‟s law.
(ii) no heat change occurs on mixing
(iii) the total volume of the solution is equal to the sum of the volumes of the pure
components mixed to make the solution.
Examples of ideal solutions

 Benzene and methylbenzene
 Hexane and heptane
 Chlorobenzene and bromobenzene
 Bromoethane and iodoethane
 Propan-2-ol and propan-1-ol
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Vapour pressure-composition diagram for an ideal solution
Total vapour pressure

Liquid
𝒁
Vapour
Vapour
pressure
𝑷𝑩

𝑾 𝑿
Instead of mole fraction, percentage composition by mass may be used

is the vapour pressure of pure A
is the vapour pressure of pure B
Line shows variation in partial vapour pressure of A with its composition/ mole
fraction
Line shows variation in partial vapour pressure of B with its composition/ mole
fraction
Line shows variation in total vapour pressure of the mixture with composition/
mole fraction
 The more volatile component has a higher saturated vapour pressure at a given
temperature if the composition is the same.
 From the above diagram, A is more volatile than B
 The steeper the line , the higher the difference in the vapour formation tendency of
the two components. In the case the two components have equal vapour formation
tendencies; the line would have been horizontal.
 Ideal solutions do not form an azeotropic mixture
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Boiling point-composition diagram for an ideal solution

Boiling point composition diagram is a plot of boiling point of the mixture against
composition.
Using the saturated vapour pressures, a boiling point of a substance can be predicted.
The component with a higher saturated vapour pressure has a lower boiling point and
the component with a lower saturated vapour pressure has a higher boiling point.
From the vapour pressure-composition diagram above; . Therefore liquid A is
more volatile (has a lower boiling point) than liquid B
Increasing temperature increases the vapour pressure of both liquids in the mixture but
the vapour pressure of a more volatile component increases more rapidly, such that the
vapour above the liquid mixture boiling is richer in the more volatile component.
Vapour phase
Boiling point of pure B Vapour composition curve
Temperature

Boiling point of
pure A
Liquid phase
Instead of mole fraction, percentage composition by mass may be used

Questions
1. A mixture of benzene and methylbenzene at 330K is an ideal solution. The partial
vapour pressure of benzene above the solution varies according to Raoult‟s law as
shown in the table below.
Partial vapour pressure of benzene in solution (kPa) 10.0 15.0 25.0 30.0 40.0
Mole fraction of benzene in solution 0.20 0.30 0.50 0.60 0.80
State the effect of adding methyl benzene to the temperature and volume of a fixed
mass of benzene.
(a) On the same axes, plot a graph of ;
(i) Vapour pressure of benzene.
(ii) Total vapour pressure above the solution against mole fraction of benzene.
(the composition of benzene in the vapour is 50% when its mole
fraction in solution is 0.27).
(b) Sketch a well labeled boiling point-composition diagram for the above mixture.
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2. A mixture of methanol and water at is an ideal solution. The partial vapour

pressure of methanol in the vapour above the solution varies according to Raoult‟s
law as shown in the table below.
Partial vapour pressure of methanol (mmHg) 40.0 100.0 200.0 260.0 320.0
Mole fraction of methanol in solution 0.10 0.25 0.50 0.65 0.80
(a) (i) Define the term ideal solution.

(ii) State Raoult‟s law
(b) On the same axes, plot a graph of;
(i) Vapour pressure of methanol
(ii) Total vapour pressure above the solution against mole fraction of
methanol.
(the composition of methanol in the vapour is 50% when its mole
fraction in solution is 0.19)

(c) Use your graphs in (b) above to determine the;
(i) Saturated vapour pressure of methanol at .
(ii) Saturated vapour pressure of water at
(d) Compare the volatility of methanol and water at . Give a reason for your
answer.
(e) Draw a well labeled boiling point composition diagram for methanol-water
mixture.
3. (a) The table below shows the composition of X in the vapour and the liquid mixture
of X and Y at different temperatures.
Temperature 110 107 100 95 90 85 80
Mole fraction of X in the liquid 0 0.06 0.19 0.32 0.5 0.73 1.0
Mole fraction of X in the vapour 0 0.19 0.48 0.65 0.79 0.91 1.0
(i) Plot a boiling point-composition diagram for the system

(ii) Explain how this mixture deviates from Raoult‟s law
(b) Sketch a well labeled vapour-pressure composition diagram for the system.
Calculations involving Raoult’s law

Examples
1. The vapour pressure of a pure liquid A is at . The vapour
pressure of this liquid in a solution with liquid B is . Calculate the
mole fraction of A in the solution if it obeys Raoult‟s law.
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According to Raoult‟s law
2. Benzene and methylbenzene are two hydrocarbons that form an ideal solution.
At 313K, the vapour pressures of the pure benzene and methylbenzene are 160
mmHg and 60 mmHg respectively. Calculate the total pressure over the
following solutions;
(i) One made by combining 4 moles of methylbenzene and 1mole of benzene.
(ii) One made by combining an equal number of moles of benzene and
methylbenzene.

(iii) One made by combining equal masses of methylbenzene and benzene.
(i) One made by combining 4 moles of methylbenzene and 1mole of benzene

(ii)
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(iii)
( )
( )
Molar mass of
Molar mass of
mass of
mass of
( )
3. A solution contains 20% heptane in pure methylbenzene. The vapour pressures

of pure heptane and pure methylbenzene 92.1 mmHg and 59.1 mmHg
respectively. Calculate the total pressure of the solution.
heptane means the solution has of
( )
heptane and of methylbenzene
Molar mass of
Molar mass of
4. The vapour pressures of methanol and ethanol at 20 are 94mmHg and

44mmHg. If 20g of methanol and 100g of ethanol gave ideal solution after
being mixed together, calculate ;
(i) Partial pressure exerted by each component in a mixture
(ii) Total vapour above the mixture
(iii) Composition of vapour above the liquid mixture.
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(i)
( )
Molar mass of
Molar mass of
(ii)

(iii) Vapour composition of Vapour composition of
5. Two liquids Y and Z on mixing form an ideal solution. At 30 , the vapour

pressure of the solution containing 3 moles of Y and 1 mole of Z is 550 mmHg.
When 4 moles of Y and 1 mole of Z are mixed, the vapour pressure of the
solution formed is 560mmHg. Calculate the vapour pressure of pure Y and pure
Z.
For case one;
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For case two;
Solving equations and simultaneously yields;
6. The saturated vapour pressures of liquids A and B form an ideal solution at

20 are and respectively. If the total vapour pressure
above the solution is , calculate the;
(i) mole fraction of A in the liquid mixture.

(ii) composition of the vapour above the liquid mixture of A and B.
(i)
(ii) Vapour composition of A =
Vapour composition of B =
Questions
1. Calculate the partial vapour pressure of 1,1-dibromoethane at 85 for an ideal
solution with a mole fraction of 0.25. The vapour pressure of pure 1,1-dibromoethane
is 170mmHg at 85 .
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2. (a) Explain what is meant by the term ideal solution.

(b) The vapour pressures of liquids and are and
respectively at . Calculate the composition of the vapour above
an ideal solution containing 3 moles of and 4 moles of at .
3. Benzene when mixed with toluene form an essentially ideal solution. 24g of Benzene
were mixed with 61.3 g of toluene. At 80 . At this temperature, vapour pressure of
pure benzene and toluene are 740 mmHg and 290 mmHg respectively. Calculate the;
(i) partial pressure of each component above the solution
(ii) total vapour pressure and vapour composition.
4. The vapour pressures of benzene and methyl benzene at are and
respectively.
(i) Calculate the vapour pressure of a solution containing of benzene and
of methylbenzene assuming the mixture is ideal.
(ii) Calculate the composition of the vapour above the liquid mixture.
5. An ideal solution contains an equal number of moles of benzene and methylbenzene
at 60 . At this temperature vapour pressure of pure benzene and pure methylbenzene

are 94 mmHg and 28.4 mmHg respectively. Calculate partial vapour pressure, total
vapour pressure and vapour composition above the liquid mixture.
6. An ideal solution containing 3 moles of benzene and 2 moles of methylbenzene has a
total vapour pressure of 280 mmHg at 60 . When one mole of methylbenzene was
added at the same temperature, the new total pressure was found to be 300 mmHg.
Calculate the vapour pressure of pure benzene and pure toluene at 60 .
7. (a) State Raoult‟s law
(b) A liquid mixture of A and B obeys Raoult‟s law. The vapour pressures of A and B
are and respectively at 20ºC.
(i) Calculate the composition of the vapour of a mixture containing 0.7 mole fraction
of liquid A at 20ºC
(ii) Which of the liquids is more volatile? Give a reason for your answer.
8. The vapour pressures of pure propyl alcohol and pure isopropyl alcohol are
20.9mmHg and 45.2mmHg at 25ºC. If the two form an ideal solution, and the mole
fraction of propyl alcohol in the solution is 0.25. Calculate;
(i) the partial pressure of each component in equilibrium with the solution
(ii) the total pressure over the solution
9. An ideal solution containing benzene and methylbenzene has composition of 0.62
benzene in the vapour. Calculate mole fraction of benzene and toluene in the liquid
given that, vapour pressure of pure benzene and toluene are 94 mmHg and 28.4
mmHg respectively.
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10. Assuming that urea, ,forms an ideal solution in water. Calculate the
vapour pressure of an aqueous solution containing by mass of urea at 40.
(Vapour pressure of water at 40 is 55.3mmHg)
11. (a) State what is meant by the term ideal solution.
(b) The vapour pressure of water and methanol are 3.173kPa and 16.785kPa
respectively at 293K. Assuming that the mixture of the two liquids behaves as an
ideal solution and that it contains 0.88 mole fraction of water. Calculate the:
(i) vapour pressure of the mixture
(ii) percentage of methanol in the vapour.
12. (a) Heptane and octane form an ideal solution.
(i) Explain what is meant by the term „ideal solution‟
(ii) State Raoult‟s law
(iii) Calculate the vapour pressure of a solution containing 49.8g of heptane and
33.2g of octane. The vapour pressures of heptane and octane are and

respectively
(b) Compound X (boiling point 370ºC) and compound Y (boiling point 400ºC) form
an ideal solution.
(i) Sketch a labelled boiling point-composition diagram for the mixture
(ii) Using the diagram, describe and explain how pure Y can be obtained from a
mixture containing 50% compound Y.
Non-ideal (real) solutions

An ideal solution is a solution which the cohesive forces are either stronger or weaker
than adhesive forces, made with change in volume or heat does not obey Raoult’s law
over all concentration ranges at a given temperature.
Characteristics of real solutions

(i) The components do not obey Raoult‟s law.
(ii) Heat is either absorbed or given off when they are formed
(iii) The solutions are formed with a change in volume.
Deviation from Raoult’s law

For non-ideal solutions, the intramolecular forces of attraction are not equal to the
intermolecular forces of attraction hence such solutions deviate from both Raoult‟s law.
There are two deviations from Raoult‟s law that can occur for non- ideal solutions.
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Negative deviation from Raoult’s law

For a solution that deviates negatively from Raoult‟s law, the total vapour pressure
above the liquids is less than what it would be if the liquids were ideal(lower than what
is predicted by Raoult’s law or calculated value) as a result of a lower tendency for the
molecules to escape from the solution than from the pure liquids. This is due to stronger
forces of attraction between the molecules in solution than between those in pure
liquids.
The stronger forces between the components of the solution are commonly due to
association through intermolecular hydrogen bonding.
Solutions that deviate negatively from Raoult‟s law are commonly made with a
contraction in volume and an evolution of heat.
Examples of solutions that deviate negatively from Raoult’s law

They include;
 Water and nitric acid  Trichloromethane(chloroform) and

 Water and hydrofluoric acid ethoxyethane
 Water and hydrochloric acid  Trichloromethane and benzene
 Water and hydrobromic acid  Trichloromethane and propanone
 Water and hydroiodic acid  Propanone(acetone)and
 Water and chloric(VI) acid aminobenzene(aniline or
 Water and sulphuric acid phenylamine)
 Methanol and ethanoic acid  Propanone and ethanol
 Water and methanoic acid  Phenol and phenylamine
N.B. Please refer to bonding and structure to identify forces of attraction between
the individual molecules and when each of the two liquids above are mixed.
In general, for solutions that deviate negatively from Raoult‟s law;
 Forces of attraction between different molecules(A and B) are stronger than
forces of attraction between similar molecules (A and A) or (B and B)
 Heat is evolved on mixing the components of the solution
 Volume of the solution is less than the sum of the volumes of the two liquids
mixed
 The solution has a lower vapour formation tendency compared to the ideal
solution.
 The solution can’t be separated to its pure components by fractional distillation
because at a certain point during distillation the solution form an azeotropic
mixture whose liquid and vapour composition are at equilibrium and boils at
constant temperature.
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Characteristic vapour pressure-composition diagram for negative

deviation from Raoult’s law
Liquid phase
Vapour
pressure Vapour phase
Azeotrope

Instead of percentage composition, mole fraction may be used
Component A is more volatile than B (A has a higher saturated vapour than B)
Maximum boiling point-composition diagram

(Negative deviation from Raoult’s law)
When two liquids in solution associate through intermolecular bonding, their escaping
tendencies into vapour reduce, hence a reduction in vapour pressure than what is
expected basing on Raoult‟s law. For such solutions, a minimum is seen in the vapour
pressure-composition diagram. The minimum vapour pressure implies that the boiling
point at that composition will be maximum.
Considering the mixture of A and B above, the boiling-point composition diagram can
be drawn a shown below.
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Azeotropic mixture Vapour phase
Boiling point of Azeotropic

mixture
Boiling point of pure B
Temperature 𝐶 Boiling point of pure A

Liquid phase
Positive deviation from Raoult’s law

For a solution that deviates positively from Raoult‟s law, the total vapour pressure above
the liquids is greater than what it would be if the liquids were ideal(higher than what is
predicted by Raoult’s law or calculated value) as a result of a greater tendency for the
molecules to escape from the solution than from the pure liquids. This is due to weaker
forces of attraction between the molecules in solution than between those in pure
liquids. Stronger forces between the molecules of the independent pure liquids that must
be broken to form such a solution are commonly hydrogen bonds.
Solutions that deviate negatively from Raoult‟s law are commonly made with an
increase in volume and an absorption of heat.
Examples of solutions that deviate positively from Raoult’s law

They include;
 Water and ethanol  Propanone and benzene
 Water and propan-1-ol  Ethanol and trichloromethane
 Water and butanol  Ethanol and methylbenzene
 Water and pyridine  Carbon tetrachloride(tetrachloromethane)
 Hexane and ethanol and benzene
 Propanone(Acetone) and ethanol  Tetrachloromethane and chloroform
 Propanone and carbon disulphide  Tetrachloromethane and methylbenzene
N.B. Please refer to bonding and structure to identify forces of attraction between
the individual molecules and when each of the two liquids above are mixed.
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In general, for solutions that deviate positively from Raoult‟s law;
 Forces of attraction between different molecules(A and B) are weaker than

forces of attraction between similar molecules (A and A) or (B and B)
 Heat is absorbed on mixing the components of the solution
 Volume of the solution is bigger than the sum of the volumes of the two liquids
mixed
 The solution has a higher vapour formation tendency compared to the ideal
solution.
 The solution can’t be separated to its pure components by fractional distillation
because at a certain point during distillation the solution form an azeotropic
mixture whose liquid and vapour composition are similar at equilibrium and
boils at constant temperature.
 The azeotropic mixture formed in this case has a maximum vapour pressure and

a minimum boiling point.
Characteristic vapour pressure-composition diagram for positive

deviation from Raoult’s law
Azeotropic mixture
Liquid phase
Vapour
pressure
Vapour phase
Instead of percentage composition, mole fraction may be used

Component A is more volatile than B (A has a higher saturated vapour than B)
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Minimum boiling point-composition diagram

(Positive deviation from Raoult’s law)
When two liquids in solution have weaker adhesive forces than cohesive forces, their
escaping tendencies into vapour increase, hence an increase in vapour pressure than what
is expected basing on Raoult‟s law. For such solutions, a maximum is seen in the vapour
pressure-composition diagram. The maximum vapour pressure implies that the boiling
point at that composition will be minimum.
Considering the mixture of A and B above, the boiling-point composition diagram can
be drawn a shown below.
Vapour phase
Temperature 𝐶

Boiling point of pure A
Boiling point of Azeotropic
mixture Liquid phase
Azeotropic mixtures and azeotropes

An azeotrope is also called a constant-boiling mixture.
An azeotropic is the mixture of two or more compounds that boils at a constant
temperature to form a vapour of the same composition as that of mixture at a constant
pressure.
An azeotropic mixture may have either a maximum or a minimum boiling point
depending on the type of variation from Raoult‟s law, but any one pressure, its
composition is fixed.
Each non-ideal solution has its own azeotropic point as well as azeotropic composition
Azeotropes are not classified as compounds because;
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 their compositions vary with pressure.

 the azeotropic mixture can also be separated into its components fairly easily by
physical means
 azeotropes cannot be represented by simple chemical formulae
An azeotropic mixture cannot be separation by fractional distillation because the mixture
boils at a fixed constant temperature with no change in composition.
Methods of separation of components of azeotropes
(i) Addition of quick lime to remove the water for example to separate an azeotropic
mixture of water and ethanol.
When the mixture is shaken with calcium oxide, the calcium oxide reacts with
water to form non-volatile insoluble calcium hydroxide which is then filtered off
leaving behind ethanol.
(ii) Addition of concentrated sulphuric acid to remove aromatic or unsaturated

hydrocarbons from their azeotropic mixture with saturated hydrocarbons.
(iii) Distillation with a third component.
The azeotropic mixture of ethanol and water can be separated by adding benzene
and then distilled. At first an azeotropic mixture containing three components;
water, ethanol and benzene is obtained. Then a binary azeotropic mixture of
ethanol and benzene is formed and finally absolute ethanol on further distillation.
(iv) Adsorption
Addition of charcoal or silica gel can adsorb one of the components.
(v) Solvent extraction
Organic compounds are more soluble in organic solvents like ether or benzene
than in water. The organic solvents (benzene or ether) are immiscible with water.
Azeotropic mixtures containing water and some organic compounds can be
separated by adding small volumes of ether or benzene and shaking. The organic
compounds dissolve in the organic solvents. The benzene or ether can then be
distilled off from the mixture with the organic compound.
Distillation of a binary liquid mixture

When a liquid is heated, its saturated vapour pressure increases until it becomes equal to
the atmospheric pressure, normally 1 atm. At this point, boiling of the liquid takes place
and the temperature remains constant. Further heating causes the liquid to vapourise. The
vapourisation of a liquid and condensation of the resulting vapour is called distillation.
Distillation under reduced pressure is used is used in purification of substances that
decompose at their boiling points.
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The process of fractional distillation

Fractional distillation is used to separate the components of a mixture of liquids,
depending on the difference in their boiling points and also on the fact that the vapour
above the liquids is richer in the more volatile component (component with a lower
boiling point).
The apparatus used for fractional distillation has a fractionating column with a large
surface area on which the ascending vapour and the descending liquid come into
contact. A mixture richer in the more volatile component distills over at the top of the
column and the thermometer registers its boiling temperature.
As distillation continues, the temperature rises and towards the boiling temperature of the
next most volatile component.
The receiver is changed to collect the second component.
In the process, the components are distilled over at their boiling temperatures.
Distillation of an ideal solution

Vapour phase
Temperature Boiling point of

pure A
𝒗𝟏
𝒕𝟐 𝒗𝟐
Liquid phase
𝒍𝟐 𝒍𝟏
When a liquid of containing or is heated, it boils at a temperature to

form a vapour of composition , , containing a higher proportion of the more volatile
component, .
When the vapour is condensed, it forms a liquid, of the same composition as the
vapour
When this liquid is heated, it boils at a temperature to form a vapour of composition
still containing a higher proportion of the more volatile component , B.
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When the vapour is condensed, it forms a liquid , of the same composition as the
vapour. Repeated vapourisation and condensation, will yield pure B as distillate and
pure A as residue.
Trial question
Methanol and water form an ideal solution. If the boiling point of pure methanol is
and that of pure water is .
(a) Explain why the two liquids form an ideal solution
(b) Sketch a well labeled vapour pressure-composition diagram for the solution
(c) Draw a well labeled boiling point-composition diagram for the solution
(d) Using your diagram in (c) above, explain the changes that take place when;
(i) a solution containing 50% methanol is distilled.
(ii) a solution containing 85% water is distilled.
Distillation of non-ideal solutions

1. A non-ideal solution that deviates negatively from Raoult‟s law e.g. hydrochloric

acid- water solution.
A mixture of water and hydrochloric acid forms a constant boiling mixture
containing 20.2% hydrochloric acid with a boiling point of 108.5 . The
boiling points of pure water and hydrochloric acid are 100 and 85
respectively.
Azeotropic mixture
108.5
𝒗𝟏
𝒕𝟏 Vapour phase
100
𝑽𝟏 𝑻𝟏
Temperature 𝑪
𝑽𝟐
𝑻𝟐
Liquid phase 85
𝒍𝟏 𝟏𝟖 20.2% 𝟒𝟓 𝑳𝟏 𝑳𝟐
Percentage of hydrochloric acid
(a) Explain why the solution shows such a deviation from Raoult‟s law
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The acid ionises in water to form hydrogen ions and chloride ions. When the ions are
hydrated, there exist ion-dipole attractions (forces of attraction between hydrochloric
acid molecules and water molecules). The ion-dipole attractions are on average stronger
than the hydrogen bonds (forces of attraction) between individual water molecules and
the van der Waal’s forces (forces of attraction) between individual hydrochloric acid
molecules. This reduces the tendency for the molecules to escape from the solution
than from the pure liquids. Therefore the total vapour pressure above the liquids is less
than what is predicted by Raoult’s law. The solution therefore has a maximum boiling
point and a minimum vapour pressure at 20.2% hydrochloric acid, deviating
negatively from Raoult‟s law.
(b) Using your diagram in (c) above, explain the changes that take place when;
(i) a solution containing 82% water is distilled.
When a solution containing water (or hydrochloric acid) is heated, it boils

at a temperature to form a vapour of composition , , containing a higher
percentage of water than the solution .
vapour , still richer in water.
Repeated vapourisation and condensation, will yield pure water as distillate and the
azeotropic mixture as residue.
(ii) a solution containing 45% hydrochloric acid is distilled.
When a solution containing hydrochloric acid (or water) is heated, it boils

at a temperature to form a vapour of composition , , containing a higher
percentage of hydrochloric acid than the solution .
vapour , still richer in hydrochloric acid.
When the liquid is heated again, it boils at a temperature to form a vapour of
composition , , still containing a higher percentage of hydrochloric.
vapour , still richer in hydrochloric acid.
Repeated vapourisation and condensation, will yield pure hydrochloric acid as distillate
and the azeotropic mixture as residue.
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Trial question
The boiling point of pure methanoic acid is 101 . Methanoic acid and water are
miscible in all proportions and form a maximum boiling azeotrope containing
77.5% methanoic acid with a boiling point of 108 .
(i) Sketch a labeled diagram of the mixture of methanoic acid and water
showing the variation of the boiling points with composition
(ii) Explain the shape of the diagram above.
(iii) Describe briefly what happens when a mixture containing 40% methanoic
acid is distilled
(iv) Explain what will happen when a mixture containing 22.5% water is heated.
(v) Suggest one method by which methanoic acid may be obtained from the
mixture.

2. A non-ideal solution that deviates positively from Raoult‟s law e.g.
trichloromethane-ethanol solution.
A mixture of chloroform and ethanol forms a constant boiling mixture containing

67% ethanol with a boiling point of 59.3 . The boiling points of pure chloroform
and pure ethanol are 61.3 and 78.3 respectively.
Temperature 𝑪 78.3
Vapour phase
𝑽𝟏
𝑻𝟏
61.3
𝑽𝟐 𝑻𝟐
𝒕𝟏 𝒗𝟏
Liquid phase 𝟓𝟗 𝟑
Azeotropic mixture
𝟑𝟎 𝒍𝟏 𝟔𝟕 𝑳𝟐 𝑳𝟏 𝟗𝟎
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(a) Explain the shape of the graph
The solution has a minimum boiling point at 67% of ethanol which implies it deviates
positively from Raoult’s law. This is because forces of attraction between ethanol
molecules and trichloromethane molecules are on average weaker than the forces of
attraction between individual ethanol molecules and the forces of attraction between
individual trichloromethane molecules. This increases the tendency for the molecules
to escape from the solution than from the pure liquids. Therefore the total vapour
pressure above the liquids greater than what is predicted by Raoult’s law.
(b) Using your diagram in (c) above, explain the changes that take place when;
(i) a solution containing 90% ethanol is distilled.
When a solution containing ethanol is heated, it boils at a temperature to

form a vapour of composition, , containing a lower percentage of ethanol than the
original solution .

vapour, still containing a lower percentage of ethanol.
When the liquid is heated again, it boils at a temperature to form a vapour of
composition, , still containing a lower percentage of ethanol.
vapour, still a lower percentage of ethanol.
Repeated vapourisation and condensation will yield the azeotropic mixture as distillate
and pure ethanol as residue.
(ii) a solution containing 30% ethanol is distilled.
When a solution containing ethanol is heated, it boils at a temperature to
form a vapour of composition, , containing a higher percentage of ethanol than the
solution .
vapour, still richer in ethanol.
Repeated vapourisation and condensation will yield the azeotropic mixture as distillate
and pure ethanol as residue.
Trial question
The boiling point of pure propan-1-ol is 97 . Propan-1-ol and water are miscible in
all proportions and form a constant boiling mixture containing 72% propan-1-ol
with a boiling point of 88 .
(i) Sketch a labeled diagram of the mixture of propan-1-ol and water showing
the variation of the boiling points with composition
(ii) Explain why the mixture has such a deviation from Raoult‟s law.
(iii) Describe briefly what happens when a mixture containing 50% propan-1-ol
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NOTE;
(a) Fractional distillation of a liquid mixture that deviates negatively from
Raoult‟s law must yield a pure component as distillate the azeotropic mixture
as residue
(b) Fractional distillation of a liquid mixture that deviates positively from
Raoult‟s law must yield the azeotropic mixture as distillate a pure component
as residue
(c) Further distillation of the azeotropic mixture cannot separate its components
any further but methods of separation of azeotropes discussed before can be
used depending on which azeotrope to separate.
Some of the questions require you to plot graphs which you can use to identify the type
of deviation that is shown and use the graphs to answer questions. By attempting them,

you will improve your graph plotting skills.
1. (a)(i) What is a constant boiling mixture?
(ii) Explain how it is known that a constant boiling mixture is a mixture but not a
compound
(iii) Give two types of constant boiling mixtures
(b) A mixture of equal parts by weight of ethanol and water is fractionally distilled.
(i) What will be the composition of the distillate first collected?
(ii) How will the distillate change during the distillation?
(c) State one advantage of using a fractionating column as a better method of
separating liquid mixtures than its absence.
2. (a) State Raoult‟s law.
(b) A solution containing 1 mole of trichloromethane and 4 moles of propanone has a
vapour pressure of 0.4 atmospheres at . At this temperature, the vapour pressure
of pure trichloromethane and propanone are 0.359 and 0.453 atmospheres
respectively.
(i) Calculate the vapour pressure of the solution. State your assumption(s)
(ii) State whether trichloromethane and propanone form a minimum or maximum
boiling azeotrope. Give a reason.
3. Ethanol and acetone are completely miscible in all proportions. A solution was
prepared by mixing of ethanol and of acetone at . At this temperature
total vapour pressure above the liquid surface was measured to be . If the
saturated vapour pressure of a pure ethanol and pure acetone of was found to be
and respectively.
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(a) (i) State the deviation from Raoult‟s law shown by the solution.
(All your working must be shown)
(ii) Explain your answer in (a)(i) above.
(b) Sketch the vapour pressure- composition diagram for this solution.
(c) Explain why ethanol and acetone cannot completely be separated by fractional
distillation.
4. (a) Define a „constant boiling point mixture‟
(b) At atmospheric pressure, hydrochloric acid and water forms a constant boiling
point mixture (Azeotropic mixture) with a boiling point of and
composition of by mass hydrochloric acid.
(i) State the type of deviation of the mixture from Raoult‟s law.
(ii) Explain why the mixture shows this type of deviation.
(c) Sketch a labeled
(i) Vapour pressure -composition diagram,

(ii) Boiling point-composition diagram of the mixture.
(iii) Give two reasons why the boiling point mixture is a mixture and not a
compound.
(iv) Using the diagram describe what will happen if a mixture containing
of hydrochloric acid is fractionally distilled.
(d) A constant boiling point mixture in (b) above has a density of .
(i) Calculate the molarity of the solution.
(ii) Calculate the volume of the solution required to prepare of a
hydrochloric acid solution.
5. (a) What is meant by the term “azeotropic mixture” ?
(b) Nitric acid solution forms an azeotropic mixture containing water at ℃.
Its density is .The boiling points of water and nitric acid are ℃ and
℃ respectively.
(i) Draw boiling point-composition diagram for an aqueous solution of nitric acid.
(ii) State the type of deviation from Raoult‟s law shown by the mixture and explain
your answer.
(c) Explain what will happen when a nitric acid solution containing;
(i) less than 68% of the acid is distilled.
(ii) more than 68% of the acid is distilled.
(d) Calculate the:
(i) molar concentration of nitric acid in the solution in(b) above
(ii) calculate the volume of the acid required to prepare 250 of a 0.05M
solution the acid.
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(e) Describe any three methods of separating components of an azeotropic mixture.

6. An aqueous solution of ethanol forms an azeotropic mixture which boils at and
contains 90% ethanol. Pure ethanol and pure water boil at and
respectively.
(a) (i) Draw the temperature-mole fraction phase diagram for an aqueous solution of
ethanol.
(ii) Explain what will happen if dilute solution containing less than 40%
ethanol and concentrated solution containing more than 96% ethanol are
separately boiled in a beaker.
(b) (i) Give a reason(s) why it is not possible to obtain pure ethanol from its aqueous
solution by fractional distillation method.
(ii) After obtaining a 90% ethanol aqueous solution, state how a higher
percentage of ethanol be obtained.
7. The table below shows the variation in the vapour pressure of the mixture of X and Y

at 298K with composition of Y.
Mole fraction of Y 0.8 0.6 0.4 0.2 0
Vapour pressure of mixture 362.5 355 372.5 395 427
The vapour pressure of pure Y at 298K is
(a) (i) Plot a vapour pressure – composition diagram for the above system
(ii) Name the type of deviation from Raoult‟s law and give a reason for your
answer.
(iii) Explain the shape of the curve in relation to Raoult‟s law.
(b) (i) Draw a well labelled boiling point -composition diagram for the system
(ii) Describe the changes that occur when a mixture of 25% of Y is fractionally
distilled.
8. (a) Explain what is meant by the term azeotropic mixture.
(b) The boiling points and percentage composition by mass of methanol in the liquid
mixture and in the vapour above the mixture of methanol and cyclohexane are
given in the table below.
Boiling point of mixture( ) 70 60 55 57 61
Percentage composition of in the liquid mixture 12 13 50 82 94
Percentage composition of in the vapour above 27 47 56 69 83
the mixture
(i) Use the data to plot a boiling-point composition diagram for solutions of
cyclohexane in methanol. (Boiling points of pure cyclohexane and pure
methanol are 81 and 65 respectively)
(ii) Use your graph to determine the composition of the azeotropic mixture and
azeotropic temperature.
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(c) (i) State the type of deviation from Raoult‟s law shown by the mixture of
methanol and cyclohexane.
(iii) Explain your answer in (i)
9. The table below shows the partial vapour pressures for a two component mixture of
propanone and trichloromethane at 35ºC for a range of mole fractions of
trichloromethane.
Mole fraction of trichloromethane 0.0 0.2 0.4 0.6 0.8 1.0
Partial pressure of trichloromethane 0 35 82 142 219 293
Partial pressure of propanone 347 270 185 102 37 0
(i) Plot a graph to show how this system deviates from Raoult‟s law
(ii) Name the type of deviation shown by the system
(iii) State the cause of such a deviation and the characteristics of such a system
showing this deviation.
(a) When propanone is mixed with tetrachloromethane, a warm miscible mixture was

formed whose volume was lower than the sum of the volumes of the individual
components.
(b) Methanol and ethanol form an ideal mixture while a mixture of cyclohexane and
ethanol shows a positive deviation.
Immiscible liquid mixtures

Immiscible liquids are liquids which when shaken and allowed to settle, they do not
mix but form separate layers.
Examples of immiscible liquid mixtures include;
 Oil and water
 Chloroform(trichloromethane) and water
 Tetrachloromethane and water
 Paraffin and water
 Benzene and water
 Carbon disulphide and water
 Mercury and water
 Phenylamine and water
Vapour pressure of a system of two immiscible liquid

Each liquid behaves independently of the other and the vapour above an agitated/ heated
mixture of two immiscible liquids at any temperature is the sum of the vapour pressures
of the individual liquids at the same temperature.
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Agitation of the mixture is necessary to enable each liquid to establish its own vapour
phase.
Immiscible liquids have the following characteristics;
 The total vapour pressure above the immiscible liquid is equal to the sum of vapour
pressure exerted by each liquid in pure state.
 Total vapour pressure above the immiscible liquid is greater than that of any of the
individual components.
 Both the vapour pressure of each liquid and the total vapour pressure increase with
increase in temperature. When the total vapour pressure above the mixture is equal to
atmospheric pressure, the mixture will boil and the boiling point will be lower than
the boiling point of either of the two liquids.
 The immiscible liquid mixture always boil at lower temperature than boiling point

pure components
 Each component in the immiscible liquid retains its vapour formation tendency
 The forces of attraction between the components in the immiscible liquid mixture are
negligibly small because there is no interaction of the components.
Question one : Phenylamine and water have boiling points of and

respectively but a mixture of phenylamine and water boils at
Phenylamine and water are immiscible. When a mixture of the two liquids is heated, each
component exerts its own vapour pressure independently. The vapour pressure of the
above mixture is the sum of the vapour pressure of phenylamine and the vapour
pressure of water. When heating continues, both the vapour pressure of the
independent components and the total vapour pressure above the mixture increases.
The mixture will boil when the total vapour pressure is equal to the atmospheric
pressure at a temperature lower than the boiling point of either phenylamine or water
in the mixture.
Question two: Benzene (boiling point ) and water (boiling point ) form a
mixture that boils at at a pressure of one atmosphere.
The principle explained above is applied in separation of components of an immiscible
liquid mixture by steam distillation.
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STEAM DISTILLATION
Steam distillation is the technique of separating a volatile substance, immiscible with
water, at a temperature below its boiling point from another substance by bubbling
steam through the hot mixture.
The volatile substance to be separated vapourises off with steam leaving behind the non-
volatile substance.
Steam distillation depends on properties of immiscible liquids.
The process in commonly used to extract organic substances with high boiling points,
decompose on heating and cannot be distilled at atmospheric pressure.
The principle on which steam distillation is based

 When a mixture of two immiscible liquids is agitated (heated), each of the liquids
exerts its own vapour pressure independently.
 The vapour pressure above the liquid mixture is the sum of the vapour pressures of

the two components
 When heating continues, both the vapour pressure of each liquid and the total vapour
pressure above the mixture increases.
 The mixture boils when the total vapour pressure is equal to the atmospheric pressure
at a temperature below the boiling points of the two components in the mixture.
The process of purification of a liquid mixture by steam distillation
Example; The boiling point of phenylamine is and a mixture of phenylamine

and water boils at . Describe how an impure mixture of phenylamine can be
purified by steam distillation
 The impure mixture containing phenylamine is heated
 Steam is passed into the heated mixture
 At a temperature and one atmosphere, a mixture of water and phenylamine
distills off
 The distillate, which is two separate layers containing phenylamine and water is
collected in the receiver.
 Phenylamine is then separated from the water in the distillate by using a separating
funnel and then dried using a drying agent.
Similarly, the distillate containing phenylamine and water can be shaken with
ether (ethoxyethane) in a separating funnel and the two layers are separated
The extract is the purified by distillation to remove ether.
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Set up of apparatus
Steam from
generator
Clamp
Mixture of Distillate of
aminobenzene water and
and impurities aminobenzene
Heat
A mixture of 2-nitrophenol and 4-nitrophenol can also be separated by steam

distillation as described for aniline above. 2-nitrophenol boils at and 4-nitrophenol
boils respectively. In this case, the distillate contains 2-nitrophenol (which has a

lower boiling point that the meta-substituted isomer, for reasons explained in bonding
and structure) and water.
The distillate is then shaken with ether which dissolves the 2-nitrophenol. The 2-
nitrophenol is then separated from ether by distillation.
Conditions necessary for steam distillation
The substance to be separated/purified by steam distillation;
(i) must be immiscible or insoluble in water
(ii) must have a high relative molecular mass
(iii) must exert a high vapour pressure at about
(iv) Any impurities present must be non-volatile under the conditions used.
Advantages of steam distillation

(i) It purifies substances that decompose at temperatures near their boiling points
(ii) Distillation takes place at a lower temperature than during fractional distillation
The composition of the distillate

Assume that the vapour collected above the mixture, behave ideal, and so obeys ideal gas
equation.
Considering the vapour to contain water vapour and the immiscible liquid, ,
Dividing equation (i) by equation(ii) yields;

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The above equation gives the relative amounts of water and the liquid in the distillate where;
is the vapour pressure of water at the distillation temperature
is the vapour pressure of the liquid at the distillation temperature
is the number of moles of water
is the number of moles of the liquid
If instead of number of moles, it is the masses of water and the liquid given respectively; then the
expression becomes;
⁄
Where; and are the molar masses of water and the liquid respectively.
The vapour pressure of liquid is normally got from the expression for the total vapour pressure
Application of Dalton’s law of partial pressure in distillation

In 1801, Dalton came up with Dalton‟s law of partial pressure which states that; in a
mixture of gases which do not react chemically, the total pressure is the sum of the
partial pressures of the components.
Considering the vapour mixture of the two components; water and liquid, each having partial
vapour pressures and respectively
According to Dalton‟s law of partial pressures; the total vapour pressure exerted is;
and if the number of moles of water and liquid, are and respectively,
Then the mole fractions of water and liquid, are given by;
The partial pressures of water and the liquid respectively are given as a product of their
respective mole fractions and the total pressure,
( )
( )
Dividing equation (i) and equation (ii) yields;
( ) ⁄( )
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Using graphical approach to determine composition of distillate

It is known that during steam distillation, the vapour pressure above the liquid mixture is
the sum of the vapour pressures of the two components and that both the vapour pressure
of each liquid and the total vapour pressure above the mixture increase with increase in
temperature.
A plot of vapour pressure of each of the components and the total vapour pressure
against temperature yields a graph as shown below.
𝟏𝟎𝟏𝟑𝟐𝟓𝑷𝒂
Vapour 𝑷𝒀
pressure 𝑷𝒂

𝑷𝑿
𝑩𝒑𝒕𝑴 𝑩𝒑𝒕𝒀 𝑩𝒑𝒕𝑿

Temperature 𝑪
 The boiling points of the mixture, component X and component Y are the
temperatures that correspond to the standard atmospheric pressure
 The vapour pressures of the components and can be obtained from the
graph at the boiling point of the mixture and used to find the composition of the
distillate using the expression below and substituting otherwise;
Use the information to try out questions 9-11 in the exercise on steam
distillation.
Calculations involving steam distillation
Examples
1. An organic compound X is steam distilled at normal atmospheric pressure and
the distillate was found to contain 75% by composition of X at a given
temperature. If at the same temperature, the vapour pressure of water is
640mmHg. Calculate the relative molecular mass of X.
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2. A mixture of nitrobenzene and distilled water boiled at at one atmosphere.

Calculate the percentage composition of the distillate. The saturated vapor
pressure of water at is .

⁄
The distillate contains water

and nitrobenzene.
3. The vapour pressure of water at is . A liquid Y is insoluble in
water and has a relative molecular mass of 160. A mixture of Y and water steam
distills at under standard atmospheric pressure. Calculate the mass of
water collected in the distillate if the mass of Y in the distillate is 40g.
⁄
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4. Chlorobenzene forms an immiscible mixture with water. It‟s mixture with steam
distills at an atmospheric pressure of . A sample of distillate
contains chlorobenzene for every of water. Calculate the vapour
pressure of water and chlorobenzene at .
But

Questions on steam distillation
1. (a) Explain what is meant by the term steam distillation.
(b) Naphthalene distils in steam at under a pressure of .
The vapor pressure of water at this temperature is . Calculate the
percentage by mass of Naphthalene in the distillate.
2. When an organic compound was distilled in steam at at a temperature of
. The vapour pressure of water at was . If the distillate was
found to contain by mass of water. Calculate the relative molecular mass of
organic compound.
3. An organic liquid distills in steam with partial vapour pressure and
water. The distillate contains the liquid in the ration of organic liquid and of
water. Calculate the relative molecular mass of organic compound.
4. (a) Bromobenzene can be separated from it impurities by steam distillation. State the
conditions that enable purification of bromobenzene by steam distillation.
(b) of impure bromobenzene were steam distilled at and to
form a distillate containing of water. The saturated vapour pressure of water
at is . Calculate the percentage purity of bromobenzene.
5. (a) Explain what is meant by the term steam distillation
(b) (i) Draw a diagram of the set-up of apparatus that can be used to purify
aminobenzene by steam distillation
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(ii) Name one other substance apart from aminobenzene that can be isolated by
steam distillation.
(c) (i) State the requirements of a substance to be isolated by steam distillation
(ii) Explain how the properties you have named in c(i) enable the substance to be
purified by steam distillation.
6. (a) The melting point of 4-nitrophenol is much higher than that of 2-nitrophenol. The
two compounds can be separated by steam distillation.
(i) Explain why the melting point of 4-nitrophenol is higher than that of
2nitrophenol
(ii) Explain the principles of steam distillation
(iii) Describe how a mixture of 2-nitrophenol and 4-nitrolphenol can be separated
by steam distillation
(b) When substance W was steam distilled at 93ºC and 750mmHg, the distillate
contained 55% by mass of W. calculate the relative molecular mass of Y. (The

vapour pressure of water at 93ºC is 654mmHg)
7. Compound Q contains 62.1% carbon, 10.3% hydrogen, the rest being oxygen.
(a) Calculate the empirical formula of Q.
(b) Q distills in steam at 98 and . If the vapour pressure of water
at 98 is .
(i) Calculate the molecular mass of Q if the distillate contained 16.67% by
mass of Q
(ii) Q formed a grey precipitate when treated with ammoniacal silver nitrate.
Write an equation and outline a mechanism for the reaction between Q and
sodium hydrogensulphite solution.
8. A gaseous hydrocarbon Q after complete combustion produced 2.025g of water and
6.72 of carbon dioxide at standard temperature and pressure.
(a) Determine the empirical formula of Q.
(b) Q steam distills at a given temperature under a pressure of 750mmHg.The vapour
pressure of water at the same temperature is 726mmHg and the percentage of
water in the distillate was found to be 84.22%. Determine the molecular formula
of Q.
(c) Q burns with a sooty flame and reacts with 2 moles of hydrogen gas in presence
poisoned palladium catalyst supported on barium sulphate to form phenylethene.
Write the structural formula of Q.
(d) Write an equation to shown how Q can be converted to phenylethanone.
(e) Write equation(s) and indicate conditions and mechanism(s) for the reaction
between;
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(i) Q and excess dry hydrogen bromide

(ii) Phenylethanone and semicarbazide
9. 4.7g of compound Z contains carbon, hydrogen and oxygen only. Z on combustion
gave 13.2g of carbon dioxide and 2.7g of water.
(a) Calculate the empirical formula of Z.
(b) When a mixture containing compound Z was steam distilled at 760mmHg and
98℃, the distillate contained 12.75g of water and 3.7g of Z. If the vapour pressure
of water is 720mmHg at 98℃, determine the molecular formula of Z.
(c) Z burns with a sooty flame and the pH of its aqueous solution is less than 7.
Write the molecular structure of Z.
(d) Z was reacted with benzene diazonium chloride in presence of sodium hydroxide.
(i) State what was observed.

(i) Saturated vapour pressure
(ii) Partial pressure
(b) Explain the principle of steam distillation, using a suitable example.
(c) The saturated vapour pressures of phenylamine and water at various temperatures
are shown in the table below.
Temperature 70 80 90 100 110

Vapour pressure of phenylamine 1,400 2,400 3,900 6,100 9,200
Vapour pressure of water 31,200 47,300 70,100 101,300 143,300
(i) On the same axes plot a graph of vapour pressures of each of the
components and the total vapour pressure.
(ii) Calculate the proportion of phenylamine and water in the distillate
under standard atmospheric pressure.
11. The vapour pressure of water and that of an immiscible liquid X at different
temperatures are given in the table below.
Temperature 92 94 96 98 100
Vapour pressure of X 6000 8000 1200 15000 17000
Vapour pressure of water 74000 80000 88000 94000 101000
(a) On the same axes, plot graphs of vapour pressure against temperature
(b) (i) Determine the vapour pressure of the mixture of X and water at the
temperatures given in the table above.
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(ii) On the same axes in (a), plot a graph of the vapour pressure of the mixture
versus the temperature.
(c) The distillate obtained from the mixture at 101kPa contained 1.6g of water and
1.1g of X. Calculate the relative molecular mass of X using the graphs you have
drawn.
(d) State:
(i) properties a substance to be separated from its mixture by steam distillation
should have
(ii) advantages of steam distillation
12. (a) State what is meant by the term steam distillation
(b) Aminobenzene and water are immiscible liquids. The saturated vapour pressures
of pure water and pure aminobenzene at various temperatures are given in the
table below.
Temperature 85 90 95 100 105

Vapour pressure of aminobenzene 3.0 4.0 5.0 6.0 7.0
Vapour pressure of pure water 58 70 84.6 101.3 120.7
(i) Plot on the same axes, graphs of vapour pressure of aminobenzene, water and
the mixture against temperature.
(ii) Using the graphs, determine the boiling point of the mixture of
aminobenzene and water at atmospheric pressure.
(iii) Calculate the percentage by mass of aminobenzene in the distillate if the
mixture was steam distilled.
Industrial application of steam distillation

Extraction of natural products from plant materials such as essential oils used in
fragrances, perfumes and personal hygiene products
THE DISTRIBUTION LAW (PARTITION LAW)

When a non-volatile solute is shaken with two immiscible solvents in contact, both in
which it is soluble, it distributes itself such that the ratio of concentration of the solute
in one solvent to the other is a constant, at a given temperature when equilibrium is
established and when the solute remains in the same molecular state.
This is called the distribution law or partition law. The constant is called the distribution
coefficient or partition coefficient.
The distribution coefficient or partition coefficient is therefore defined as;
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This is the constant ratio of the molar concentrations of a non-volatile solute in a

mixture of two immiscible solvents in contact when equilibrium is established at a
given temperature provided the solute remains in the same molecular state.
Consider a solute, X, in a mixture of two immiscible solvents, A and B;
The partition coefficient, KD is given by;
[ ]
⁄[ ]
Limitations of the partition law/ conditions under which partition law is

valid
(i) Solvents should be immiscible
(ii) Solution should be dilute
(iii) Temperature must be constant
(iv) No association or dissociation of solute occurs in the solvents

Experimental determination of
(a) To determine partition coefficient of iodine between water and trichloromethane
A known mass of iodine is added to a known volume of trichloromethane in a
separating funnel.
A known volume of water is added to the separating funnel
The mixture is shaken for some time and left to stand for equilibrium to be established at
a given temperature.
After settling, a known volume of the aqueous layer is pipetted and titrated against a
standard solution of sodium thiosulphate using starch indicator.
The concentration of iodine in the aqueous layer is calculated using the equation;
A known volume of the organic layer is also pipetted and titrated against a standard
solution of sodium thiosulphate using starch indicator.
The concentration of iodine in the organic layer is also calculated.
The partition coefficient is then calculated using the expression;
[ ]
[ ]
(b) To determine partition coefficient of butane-1,4-dioic acid (succinic acid)

between ethoxyethane(ether) and water.
A known mass of butane-1,4-dioic acid is added to a known volume of ether in a
separating funnel.
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396
a fixed temperature.
After settling, a known volume of the ether layer is pipetted and titrated against a
standard solution of sodium hydroxide using methyl orange indicator.
The concentration of butane-1,4-dioic acid in the ether layer is calculated using the
equation;
A known volume of the aqueous layer is also pipetted and titrated against a standard
solution of sodium hydroxide using methyl orange indicator.
The concentration of butane-1,4-dioic acid in the aqueous layer is also calculated.
[ ]
[ ]
(c) To determine partition coefficient of ammonia between water and
trichloromethane.

A known mass of volume of ammonia is added to a known volume of trichloromethane
in a separating funnel.
a fixed temperature.
After settling, a known volume of the aqueous layer is pipetted and titrated against a
standard solution of hydrochloric acid using methyl orange indicator.
The concentration of ammonia in the aqueous layer is calculated using the equation;
A known volume of the trichloromethane layer is also pipetted and titrated against a
The concentration of ammonia in the trichloromethane layer is also calculated.
[ ]
[ ]
Question; Describe how partition coefficient of ethanoic acid between water and
butan-1-ol can be determined.
Calculations involving
Examples
1. To determine the partition coefficient of ammonia between water and
trichloromethane, 10 of aqueous layer required 13.2 of 0.25M
hydrochloric for complete neutralization. 25 of organic layer required
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397
6.6 of 0.05M hydrochloric for complete neutralization. Calculate the

partition coefficient.
( )
( )
[ ]
( )

( )
[ ]
[ ]
[ ]
2. 50 of 1.5M ammonia solution was shaken with 50 of trichloromethane
in a separating funnel. After the layers had settled, 20 of trichloromethane
layer was pipetted and titrated with 0.05M hydrochloric acid. 22.9 of the
acid were required for complete neutralization.
(a) Write the expression for the partition coefficient for ammonia between
water and trichloromethane.
(b) Calculate the partition coefficient (State any assumptions made)
[ ]
(a) [ ]
(b)
( )
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398
( )
[ ] [ ]
[ ] [ ]
Assumptions made
 Water and tetrachloromethane are immiscible
 Temperature is constant
 Ammonia neither associates nor dissociates in water or
trichloromethane
3. 25 portion of a 0.2M solution of iodine in carbontetrachloride was shaken
with 50 of water at . After equilibrium had been attained 25 of the
aqueous layer required 2.74 of 0.2M sodium thiosulphate solution to react

completely with iodine. Calculate the partition coefficient of iodine between
carbontetrachloride and water.
( )
( )
[ ] [ ]
[ ] [ ]
4. (a) When 100 of an aqueous solution containing 30g of ethanoic acid were
shaken with 50 of butan-1-ol, 12g of ethanoic acid remained in the aqueous
layer. Calculate the distribution coefficient of ethanoic acid between water and
butan-1-ol at .
(b) If 100 of butan-1-ol were used instead, what would be the distribution
coefficient at ?
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399
(a) ⁄
⁄
[ ]
[ ]
(b) The distribution coefficient would be the same because the ethanoic acid redistributes itself in
the two solvents to maintain the same value of distribution coefficient.
Obtaining values of partition coefficients using graphical approach

Consider a solute , soluble in two immiscible solvents and .
A graph of concentration of the solute in one solvent against the concentration of the
solute in another solvent can be plotted.
A graph of [ ] against

[ ] is usually a straight line.
[𝑿]𝑺𝒐𝒍𝒖𝒕𝒆 𝑨
The slope of the graph gives the
𝟑 partition coefficient of X between
𝒎𝒐𝒍𝒅𝒎
solute A and solute B
[ ]
[ ]
[𝑿]𝑺𝒐𝒍𝒖𝒕𝒆 𝑩
𝒎𝒐𝒍𝒅𝒎 𝟑
Questions
1. 50 of ammonia solution was shaken to equilibrium with 50 of
trichloromethane in a stoppered bottle at . 25.0 of the aqueous layer reacted
completely with 24 of 0.1M hydrochloric acid. Calculate the partition coefficient
of ammonia between water and trichloromethane.
2. A weak tribasic acid, X is soluble in benzene and water. 2.800g of the acid was
shaken with 100 of benzene and 50 of water. 25 of the aqueous layer
required 14.50 of 1M sodium hydroxide solution for neutralisation. Calculate
the distribution coefficient of X in water and benzene.
3. (a) Explain is meant by partition coefficient.
(b) The table below shows the concentrations of iodine in the two layers shaken with
a mixture of carbon tetrachloride and water at .
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400
Concentration of in 6.12 12.24 15.20 22.38

Concentration of in 0.072 0.143 0.178 0.260
Plot a graph of concentration of iodine in carbon tetrachloride against concentration of
iodine in water.
(c) From the graph determine the partition coefficient for iodine distributed between
carbon tetrachloride and water.
(d) State two applications of partition coefficient.
The applications of partition coefficients

Partition coefficients are applied in the following processes;
 Solvent extraction
 Determining formulae of complex ions
 Paper chromatography and column chromatography
 Ion exchange

 Determining equilibrium constants
(a) Solvent extraction

During preparation of organic compounds, the product is obtained as an aqueous solution
and the organic compound must be separated from the water. This is done by solvent
extraction.
Organic compounds are more soluble in organic solvents like ether or benzene than in
water and the organic solvents (ether or benzene) are immiscible with water.
An organic compound like phenylamine is more soluble in ethoxyethane (ether) than in
water. When a mixture of phenylamine and water with ether is shaken, in a separating
funnel, most of the phenylamine dissolves in dissolves in ether. Two separate layers are
formed and they can be separated by opening the tap on the separating funnel.
The phenylamine can then be removed from the ether layer by distillation.
Solvent extraction can therefore be defined as the removal of a solute from one solvent
in which it is less soluble by shaking the solution with another solvent in which it is
more soluble and both solvents being immiscible with each other, the solute remaining
in the same molecular state in both solvents.
Conditions for isolation of a solute by solvent extraction
 Solvents must be immiscible with each other
 The two solvents should not react with each other
 The solute should not associate or dissociate in any of the solvents
 Solute must be more soluble in the extracting organic solvent
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401
Ethoxyethane is most commonly used in solvent extraction of organic compounds

from their aqueous solution because;
 It is a good solvent for many organic compounds
 Ether is immiscible with water
 It does not react with most organic compounds
 It has a very volatile hence can be distilled off or removed after use
Solvent extraction is always more effective when the extracting liquid is divided into
several portions and each portion used separately rather than using the whole of the liquid
in one extraction. This is because smaller portions used successively extract more of the
solute than one big portion used once.
Applications of solvent extraction
 Separation of azeotropic mixtures
 Extraction of oil from simsim

 Purification of zinc ores
 Separation of inorganic solids for example iron(III) chloride from manganese(II)
chloride
Calculations involving solvent extraction

Examples
1. (a) Explain the principle of solvent extraction.
(b) of aqueous solution contains 5.00g of butanoic acid. Calculate the
mass of butanoic acid extracted when the solution was shaken:
(The distribution coefficient, of butanoic acid between Q and water is 40)
(i) with 50 of a solvent Q.
(ii) twice with 25 of solvent Q
(b) (i) [ ]
[ ]
⁄
⁄
The mass of butanoic acid

extracted by of is 3.3333g
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402
(ii)
⁄
⁄

extracted by first portion
of is 2.5 g
⁄
⁄

extracted by second
portion of is 1.25 g
The total mass extracted by two successive portions of is
2. 100 of 0.1M ammonia solution was shaken with 50 of chloroform. The

partition coefficient of ammonia between chloroform and aqueous solution is
25.2. Calculate percentage of ammonia extracted.
[ ]
[ ]
( )
⁄
⁄
Percentage of ammonia extracted

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403
3. (a) 0.9656g of iodine was shaken with a mixture of 50 of trichloromethane

and 50 of water in separating funnel for some time until equilibrium was
attained at 25 . After the layers had settled, 25 of the aqueous layer
required 4.4 of sodium thiosulphate solution using starch indicator.
(i) Determine the distribution coefficient of iodine between
trichloromethane and water at 25 .
(ii) If 50 of trichloromethane layer in (a) above was again shaken
with 100 of water at 25 , determine the mass of iodine that
remained in the trichloromethane layer.
(b) Explain why trichloromethane is a better solvent in the extraction of iodine
than water.
(a) (i)

( )
( )
[ ]
[ ]
⁄
⁄
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404
(ii)
⁄
⁄
The mass of Iodine extracted by

trichloromethane is 0.932331 g
(b) Both iodine and trichloromethane are non-polar hence iodine is very soluble in
non-polar trichloromethane but insoluble in water which is a polar solvent.
4. A solute Q is three times as soluble in ethoxyethane as in water. An aqueous

solution containing 4.5g of Q per litre of solution was shaken by ethoxyethane in
a separating funnel. Calculate the mass of Q that is extracted by two successive

50.0 portions of ethoxyethane.
[ ]
[ ]
[ ] ⁄
[ ] ⁄
The mass of Q extracted by

first portion of
ether is 0.587g
⁄
⁄
The mass of Q extracted by

second portion of
ether is 0.510g
The total mass extracted by two successive portions of ether is
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405
5. (a) An aqueous solution contains 10g of Y in a litre of solution.100 of this

solution was shaken with 20 of ether and the ether extracted 0.8g of Y .
Calculate the volume of ether that is required to extract 80% of Y from 500
of the aqueous solution.
(b) Give a reason why using small aliquots improves the yield.
(a)
( )
( )
[ ]
[ ]

⁄ ⁄
⁄ ⁄
( )
(b) This is because after every extraction, the solute redistributes itself uniformly in the
two solvents making it available for subsequent extractions
6. A crude sample of lead contained 2% of silver by mass. Calculate the percentage

of silver left in 150 kg of lead if it was thoroughly agitated with 10kg of zinc at
800 . The solubility of silver in a given mass of zinc is 300 times its solubility in
an equal mass of lead at 800 .
( ) ⁄
Percentage of Ag left in 150kg of

Pb
[ ] [ ]
[ ] [ ]
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406
Questions
1. The partition coefficient of J between ethoxyethane and water is 5.0. A solution
containing 10.0g of J in 5000 of water is extracted with 100 of
ethoxyethane. Calculate the mass of J extracted from the water.
2. (a) (i) What is meant by the term solvent extraction
(ii) State three limitations of solvent extraction
(iii) Explain why small portions of solvent are preferred to large portions in
solvent extraction of solute.
(b) An aqueous solution contains 5.0g of X in 100 of solution. The partition
coefficient of X between water and an organic solvent is 0.200. Calculate the mass
of X extracted by shaking 100 of the aqueous solution with;
(i) 50 of the solvent
(ii) Two successive 25 portions of the solvent.
3. (a) Define the term partition coefficient.

(b) A compound Z has a partition coefficient of 4.00 between ether and water.
Calculate the mass of Z extracted from 100 of an aqueous solution of 4.00g of Z
by two successive extractions with 50 of ether.
4. (a) Explain the partition law
(b) 18g of a compound X distributes itself between an immiscible solvent Y and an
equal volume of water such that 2g of X are left in water. Calculate the percentage of
X left in water if 1000 of water containing 1g of X are extracted by:
(i) One litre of Y
(ii) Half a litre of Y two times successively.
5. An aqueous solution contains 10g of butane-1,4-dioic acid per litre. When 100 of
this solution was shaken with 20 of ethoxyethane, the ethoxyethane layer
extracted 0.8g of butane-1,4-dioic acid .Calculate the mass of butane-1,4-dioic acid
extracted when 500 the aqueous layer was shaken with:
(a) with 50 of ethoxyethane.
(b) two successive 25 portions of ethoxyethane.
(c) Comment on your results in (a) and (b) above.
6. 100 of a solution containing 0.171g of ammonia in trichloromethane was
shaken with 100 of water until equilibrium was attained at room temperature.
Calculate the number of moles of ammonia in the trichloromethane layer. (The
distribution coefficient of ammonia between water and trichloromethane is 27.5)
7. 100 of an aqueous solution containing 10g of compound Q was shaken with
100 of benzene. Q is more soluble in benzene than and the partition coefficient
|
of Q is 12.2. Calculate the mass of Q left in the aqueous layer.
407
8. Industrially, silver is extracted from molten lead using molten zinc which is insoluble
in lead. The solubility of silver is 300 times greater in zinc than it is in an equal
volume of lead. Calculate the mass of silver extracted using of molten zinc
and of molten lead containing 5g of silver.
9. (a) (i) State the distribution law.
(ii) Under what conditions is the law you have stated in (i) valid?
(b) The table below shows the concentrations of succinic acid in ether and water at
equilibrium in .
Experiment number 1 2 3 4 5 6
[ ] 0.023 0.028 0.036 0.044 0.052 0.055
[ ] 0.15 0.18 0.24 0.3 0.36 0.38
(i) Plot a graph of concentration of succinic acid in water against concentration
of succinic acid in water.

(ii) From the graph determine the distribution constant for succinic acid
between ether and water.
(c) 100 of ether was shaken with an aqueous solution containing 18g of succinic
acid per of solution. Calculate the mass of succinic acid that remained in the
aqueous layer.
(d) State one application of the distribution constant
(b) Determining formulae of complex ions

The partition coefficient of solute between water and another solvent is used to
investigate the composition of a complex ion in aqueous solution.
This is normally applied to cations that are soluble in excess ammonia, excess
aminoethane or any other excess ammine solution i.e. copper(II) ions, zinc ions,
chromium(III) ions, nickel(II) ions, silver ions and cobalt(II) ions
Theory:
When excess aqueous ammonia is added to a solution of each of the above ions, complex
ions are formed.
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
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408
Each of the above complex ions has a characteristic colour in solution from which we can
tell that it is formed. For example [ ] is a deep blue solution and
[ ] is a colourless solution.
The general equation for all the above reactions is;
[ ]
If aminoethane is used then;
[ ]
On addition of excess aqueous ammonia to any of the ions forms a solution containing
both free and fixed (complexed) ammonia.
This solution when shaken with chloroform (trichloromethane) and left to settle, two
layers are formed.
The upper aqueous layer contains the complex ion and free ammonia in equilibrium with
free ammonia in the lower trichloromethane layer.
[ ] Aqueous layer

Trichloromethane layer
The partition coefficient of ammonia between the water and trichloromethane is 25. If the
concentration of ammonia in the trichloromethane layer is obtained by titrating a portion
of it with standard hydrochloric acid, then concentration of free ammonia in the aqueous
layer can be calculated from;
[ ]
[ ]
[ ] [ ]
The total concentration of ammonia (free and complexed) in the aqueous layer is also
obtained by titrating a portion of it with standard hydrochloric acid. During this titration,
the equilibrium is displaced to the left. The concentration of complexed ammonia is then
got by subtraction as shown below.
[ ] [ ] [ ]
[ ] [ ] [ ]
Assuming that all the cation is complexed and that the concentration of the solution of the
complexed cation [ ] is known, then the value of n in the complex, [ ]
can be obtained by;
[ ]
[ ]
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409
Experimental determination of formula of a complex ion

Experiment to determine formula of complex formed between excess ammonia and
zinc ions.
A known volume of excess ammonia solution is shaken with an equal volume of a
standard solution of zinc ions.
The resultant solution formed, that contains the complex, [ ] and excess
ammonia is shaken with a known volume of trichloromethane for about 15 minutes.
The mixture is left to stand for equilibrium to be established at a constant temperature.
A known volume of the trichloromethane layer is pipetted and titrated against a
The concentration of ammonia in the trichloromethane layer is calculated using the
equation;
A known volume of the aqueous layer is also pipetted and titrated against a standard
solution of hydrochloric acid using methyl orange indicator.

The total concentration of ammonia in the aqueous layer determined
[ ]
[ ]
[ ]
For a known value of partition coefficient, of ammonia between water and trichloromethane,
the concentration of free ammonia in the aqueous layer is calculated;
[ ]
[ ]
[ ] [ ]
[ ] [ ] [ ]
[ ] [ ] [ ]
[ ]
[ ]
The same procedure can be used for an experiment to determine the formulae of
;[ ] ,[ ] ,[ ] ,[ ] and [ ]
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410
Determining formula of a complex, [ ] using graphical approach

A graph of concentration of ammonia in a standard solution of complexed cation i.e.
[ ] against the concentration of ammonia in trichloromethane [ ] is
plotted.
A graph of [ ] against
[ ] is usually a straight line with an intercept on
[𝑵𝑯𝟑 ]𝟎 𝟏𝑀 𝑴𝒙 the [ ] axis (obtained by extrapolation).
Then;
𝟑
( )
The value of in [ ] is therefore ( )

[𝑵𝑯𝟑 ]𝑪𝑯𝑪𝒍𝟑

𝟑
Examples
1. (a) Define the term partition coefficient

(b) 50 of a ammonia solution was added to 50 of
trichloromethane in a flask. To the resultant mixture was added
cobalt(II) chloride solution. The mixture was shaken and allowed to stand
at constant temperature. When the layers had separated, 25 of the
trichloromethane layer required 20 of hydrochloric acid for
complete reaction. ( of ammonia between water and trichloromethane
is 25.0).
Calculate the molar concentration of ;
(i) ammonia in the trichloromethane layer.
(ii) free ammonia in the aqueous layer
(iii) ammonia fixed in the complex [ ]
(c) Determine the value of n in the complex in b(ii)
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411
(b) (i) ( )
( )
[ ]
[ ] [ ]
(ii) [ ]
[ ]
[ ]
(iii) [ ] [ ] [ ]
[ ] [ ] [ ]

[ ]
[ ]
(c) [ ]
2. To a solution of 25 of a copper(II) ions was added 25 of ammonia

solution at and the resulting solution was shaken with trichloromethane and
allowed to stand to form two layers. 20 of the organic layer required
10.2 of hydrochloric acid for complete neutralization. 10 of the
aqueous layer was titrated with 16.5 of hydrochloric acid. The
partition coefficient of ammonia between water and trichloromethane is 25.0.
Calculate the value of n in the complex below.
[ ]
( )
( )
[ ]
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412
[ ] [ ]
[ ]
[ ] [ ]
( )
( )
[ ]
[ ] [ ] [ ]

[ ] [ ] [ ]
[ ]
Note that when an equal volume of ammonia solution is added to a solution of copper(II) ions,
the concentration of copper(II) ions is halved. This is shown by the calculation below;
( )
Total volume of solution
( )
[ ]
[ ]
3. of a zinc ore was dissolved in excess concentrated ammonia and the

solution made up to with water. The resultant solution was shaken with
chloroform and left to stand. 25 of the organic layer required 12.50 of
0.025M hydrochloric acid for complete neutralisation. 12.50 of the aqueous
layer was neutralised by 20.0 of 0.25M hydrochloric acid. Calculate the
percentage of zinc in the ore. ( and the partition coefficient of
ammonia between chloroform and water is 0.04.)
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413
( )
( )
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]

( )
( )
[ ]
[ ] [ ] [ ]
[ ] [ ] [ ]
[ ]
( )
[ ]
( )
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414
Questions
1. (a) Explain the term partition coefficient.
(b) State two conditions under which partition coefficient is valid.
(c) Excess ammonia was shaken with equal volume of trichloromethane and a
0.05M aqueous solution of zinc sulphate and allowed to stand. Some ammonia
reacted with zinc to form a complex, [ ] . At equilibrium, the
concentrations of ammonia in the trichloromethane layer and the aqueous layer
were and respectively. (The partition coefficient of
ammonia between water and trichloromethane is 25). Calculate;

(i) the concentration of free ammonia in the aqueous layer
(ii) the concentration of ammonia that formed the complex with zinc ions
(iii) the formula of the complex ion.
2. 25 of a zinc ions was mixed with 25 of ammonia solution and the
resulting solution was shaken with trichloromethane and allowed to stand to form two
layers. 20 of the organic layer required 10.2 of hydrochloric acid for
complete neutralisation. 10 of the aqueous layer was titrated with 16.5 of
hydrochloric acid. If the partition coefficient of ammonia between water and
trichloromethane is 25. Calculate the value of n in the zinc complex, [ ] .
3. 50 of a solution of chromium(III) ions was mixed with 50 of
ammonia solution at and the resulting solution was shaken with 50
trichloromethane and the mixture left to settle. At equilibrium, the aqueous layer
required 70 of hydrochloric acid for complete reaction while the organic
layer required 20 of hydrochloric acid for complete reaction. The
partition coefficient of ammonia between water and chloroform is 25.0 and chromium
forms a complex, [ ] with ammonia. Find the value of n in the complex.
4. (a) The partition coefficient of ammonia between water and trichloromethane at
is 25.0.
(i) Define the term partition coefficient.
(ii) State two conditions under which the partition coefficient is
valid other than constant temperature.
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415
(b) 25 of nickel(II) sulphate solution were added to an equal volume

of ammonia solution at . The mixture was shaken with 50 of
trichloromethane and allowed to stand until equilibrium was established. The
trichloromethane layer required 32 of hydrochloric acid for
complete neutralization. 7.06 of the aqueous layer required 20 of
hydrochloric acid.
Nickel (II) ions react with ammonia according to the equation;
[ ]
Calculate;
(i) Molar concentration of the free ammonia in the aqueous layer.
(ii) Molar concentration of ammonia that reacted with nickel (II) ions
(iii) Use your answer b(ii) above to determine the value of n in [ ]
5. (a) In an experiment to determine the partition coefficient of ammonia between water
and trichloromethane, equal volumes of 0.1M copper(II) sulphate solution and 2M

ammonia were mixed and the mixture shaken with trichloromethane in a closed
vessel. At equilibrium, the concentration of ammonia in trichloromethane was
0.0308M.
(i) Calculate the concentration of ammonia that reacted with copper(II) ions.
[ ]
(ii) Determine the partition coefficient of ammonia between water and
trichloromethane.
(b) State any two:
(i) assumptions made in (a)(ii) above
(ii) practical application of the partition law other than determining the
formulae of complexes.
6. Excess ammonia and trichloromethane was shaken with 0.025 of an
aqueous solution of copper(II) sulphate and allowed to reach an equilibrium. At
equilibrium, the concentrations of ammonia in the aqueous layer and the
trichloromethane layer were found to be and
respectively. If the partition coefficient of ammonia between water and
trichloromethane is 25.
(a) Calculate the concentration of complexed ammonia in the aqueous layer
(b) Hence determine the value of n in the formula of the complex ion, [ ] .
7. (a) Describe briefly how the formula of the silver complex, [ ] can be
determined in the laboratory.
(b) 25.0 of excess ammonia was mixed with 25.0 of silver nitrate
solution. The resultant mixture containing the complex, [ ] was
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416
shaken with 50 of trichloromethane and allowed to stand until equilibrium

was established at room temperature. The aqueous layer required 27.5 of
hydrochloric acid while the organic layer required 18.0 of
hydrochloric acid for complete neutralization. Determine the value of n. ( of
ammonia between water and trichloromethane is 25.0 at 25 )
8. 25 of amminomethane were added to 25 of a 0.1M zinc sulphate
solution. The resultant solution was shaken with trichloromethane and left to settle.
10 of the aqueous layer required 16.5 of nitric acid. If the partition
coefficient of aminomethane between water and trichloromethane is 25 at .
(a)Calculate;
(i) the concentration of aminomethane in the organic layer
(ii) the concentration of aminomethane that formed a complex with zinc ions
(iii) the formula of the complex ion.
(b) Use your answer in (a)(ii) to write an equation for the reaction between

aminomethane and zinc ions
9. The table below shows the results for partition of aminoethane between
trichloromethane and 0.1M copper(II) sulphate solution
[ ] 0.88 1.10 1.34 1.58 1.80
[ ] 0.02 0.03 0.04 0.05 0.06
(a) Plot a graph of [ ] against [ ] .

(b) Determine the number of moles of aminomethane that form a complex with
copper(II) ion.
(c) Write equation for the reaction between copper(II) ions and aminomethane .
10. Copper(II) ions form a complex, [ ] with ammonia. The table below
shows the results for partition of ammonia between 0.1M copper(II) ions solution and
trichloromethane.
[ ] 0.88 1.08 1.34 1.56 1.80

[ ] 0.02 0.03 0.04 0.05 0.06

(b) Determine the value of n in the complex.
(c) Determine the partition coefficient of ammonia between aqueous copper(II) ions
and trichloromethane
(d) State what the value of partition coefficient obtained in (c) above indicates about
the distribution of ammonia.
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417
11. Cobalt(II) ions form a complex, [ ] with ammonia. The table below
shows the results for partition of ammonia between 0.1M cobalt(II) sulphate solution
and trichloromethane.
[ ] 0.72 0.94 1.19 1.43 1.70 1.92

[ ] 0.01 0.03 0.05 0.07 0.09 0.11

(b) Determine the value of n in [ ] .
12. The table below shows the results for partition of ammonia between 0.1M Nickel(II)
sulphate solution and trichloromethane.
[ ] 0.87 1.10 1.33 1.57 1.80

[ ] 0.02 0.03 0.04 0.05 0.06

(b) Determine the number of moles of ammonia that formed a complex with nickel(II)
ions.
(c) Write equation for the reaction between nickel(II) ions and aminomethane.
Ion exchange
Ion exchange is a type of partition of ionic compounds
An ion exchanger can be a solid which releases one ion and adsorbs another.
When the ions exchanged are cations, the material is known as a cation exchanger and
when anions are exchanged, then it‟s an anion exchanger.
A cation exchanger is usually a polymer containing an acidic group such as ,
, or .
Anion exchangers contain basic groups such as secondary, tertiary or quaternary amine
groups.
Ion exchangers are used in softening of water by removing calcium ions and magnesium
ions by using an insoluble sodium salt of a cation exchanger
Water can also be purified further so that all dissolved salts are
removed(deionisation/demineralisation) by using both a cation and an anion exchanger.
When the water is passed through a cation exchanger, all the cations in it are replaced by
hydrogen ions.
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418
The partially purified water is then passed through an anion exchanger and all the anions
are replaced by hydroxyl ions.
̅
The hydrogen ions and hydroxyl ions then combine to form water.
Determining equilibrium constants using partition coefficients
(refer to next Chapter; Chemical equilibria)
EUTECTICS
1. Solidification of an aqueous solution of solids
The diagram below is a temperature-composition diagram (phase diagram) for sodium
nitrate solutions.
Y
G

H
Solution of
Sodium nitrate in
water Saturated
Temperature 𝑪 solution + Solid
X sodium nitrate
D
Ice +
𝟏𝟕 𝟓 Solution
A E B
Solid Sodium nitrate + ice
F
Percentage composition of Sodium nitrate

When a dilute solution of sodium nitrate in water is cooled from room temperature, there
is no phase change but the temperature reduces up to .
On cooling the solution below , pure ice forms when the freezing point of the solution
is reached.
The freezing point of the solution is less than the freezing point of pure water
because the solute added lowers the freezing point of water.
When the solution is cooled further, more ice is formed and the solution becomes richer
in sodium nitrate.
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419
At , the remaining solution becomes saturated and any further cooling will
deposit a mixture of ice and solid sodium nitrate and the temperature remains constant
until the whole system solidifies.
Curves/lines
YE The solubility curve of sodium nitrate in water
XE The decrease in freezing point of water as increasing quantities of
sodium nitrate are added
AB The solid curve. Below it only the solid phase exists.
XEY The liquid curve. Above it only liquid phase exists.
Point E is the Eutectic point
At this only point; ice, solid sodium nitrate and a saturated solution of sodium nitrate
in water are in equilibrium.
At the eutectic point, the solid formed from the solution has the same composition as
the solution.

From the phase diagram above, this composition is by mass of sodium nitrate
and the point occurs at an eutectic temperature of .
The mixture formed at this composition and temperature is called an eutectic mixture.
Important definitions
A eutectic mixture is a liquid mixture which at constant pressure will solidify at
constant temperature to form a solid mixture without change in composition.
Or a eutectic mixture is a solid mixture which melts at constant temperature to form a
liquid mixture without change in composition.
A eutectic temperature is the constant temperature at which a liquid mixture solidifies
at a given pressure without change in composition.
Effect of change in temperature on the mixture
Question; Using the phase diagram for sodium nitrate- water system above, describe
what happens when;
(i) a solution containing potassium nitrate is cooled from to .
(ii) a solution containing water is cooled from to .
(i) From , at point C, the solution cools to point D without change in phase
At point D, ice begins to solidify as the composition of sodium nitrate in the
solution increases.
As the solution is further cooled, more ice solidifies, the solution becoming richer
in sodium nitrate and the freezing point decreases along DE up to the eutectic
|
point, E( ).
420
At the eutectic point, E ( ), sodium nitrate also begins to solidify and the
temperature and composition remain constant until the whole system solidifies.
The solid mixture then cools with no change in phase up to .
(ii) From , at point G, the solution cools to point H without change in phase
At point H, sodium nitrate begins to solidify as the composition of water in the
solution increases.
As the solution is further cooled, more sodium nitrate solidifies, the solution
becoming richer in water and the freezing point decreases along HE up to the
eutectic point, E( ).
At the eutectic point, E ( ), ice also begins to solidify and the

2. Solidification of mixtures of two liquids without compound formation
Eutectic mixtures can also be formed between two metals or two organic solids.
The two must be completely miscible when melted into liquids. A mixture of the two
liquids forms a eutectic mixture on freezing in the same way as an aqueous solution of a
solid.
Examples of substances that form eutectic mixtures
These include;
 Zinc and cadmium  Gold and thallium
 Tin and lead  Bromoethane and benzene
 Antimony and lead  Camphor and naphthalene
 Bismuth and cadmium
 Naphthalene and biphenyl
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The diagram below is a temperature-composition diagram (phase diagram) for a Zinc-

cadmium mixture.
H
G
ol 𝟒𝟏𝟗
C
J
Temperature 𝑪
𝟑𝟐𝟏 F
B
L
A E
𝟐𝟕𝟎
D

Mole fraction of zinc
Percentage composition may be used instead of mole fraction.

Note that the word solution should not be used for these kinds of mixtures. Only the
liquid and solid phases are emphasized.
(a) Describe how the phase diagram of a mixture of zinc and cadmium can be
obtained in the laboratory.
Mixtures of various compositions of solid zinc and solid cadmium are prepared
Each mixture is heated separately until it melts
Each mixture is allowed to cool while stirring and the constant temperature at which it
freezes is recorded.
The melting points of pure zinc and pure cadmium are determined in the same way
Then a graph of melting points against composition is plotted and a phase diagram is
drawn.
(b) State what the following represent;
(i) Regions: A, B, C and D
A-Solid cadmium and liquid C-Liquid mixture

B-Solid Zinc and liquid D-Solid cadmium and solid zinc
(ii) Points E, F and G
E-Eutectic point G-Melting point of pure zinc
F-Melting point of pure cadmium
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Note: From the phase diagram, the eutectic mixture has a mole fraction of zinc.
This is the same as zinc. In terms of cadmium, it is mole fraction of
cadmium ( cadmium). The eutectic temperature is .
The melting point of pure cadmium is and that of pure zinc is .
(iii) Curves FE and GE
FE- Decrease in freezing point of Cadmium as zinc is added

GE- Decrease in freezing point of zinc as cadmium is added
(c) Using the phase diagram for the zinc-cadmium system above, describe what
would happen when;
(i) a mixture containing zinc is cooled from to .
(ii) a mixture containing cadmium is cooled from to .
(iii) a mixture containing cadmium is cooled from to
(iv) a mixture containing zinc is heated.

(i) From , at point H, the liquid mixture cools to point J without change in
phase
At point J, zinc begins to solidify as the composition of cadmium in the liquid
mixture increases.
As the liquid mixture is further cooled, more zinc solidifies, the liquid becoming
richer in cadmium and the freezing point decreases along JE up to the eutectic
point, E( ).
At the eutectic point, E ( ), cadmium also begins to solidify and the
(ii) From , at point K, the liquid mixture cools to point L without change in
phase
At point L, cadmium begins to solidify as the composition of zinc in the liquid
mixture increases.
As the liquid mixture is further cooled, more cadmium solidifies, the liquid
becoming richer in zinc and the freezing point decreases along LE up to the
eutectic point, E( ).
At the eutectic point, E ( ), zinc also begins to solidify and the temperature
and composition remain constant until the whole system solidifies.
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423
(iii) From , the liquid mixture cools to without change in phase

At the eutectic point, E ( ), both zinc and cadmium begin to solidify and
the temperature and composition remain constant until the whole system
solidifies.
(iv) The solid mixture melts at a constant temperature of to form a liquid

mixture of the same composition.
(d) Explain what will happen when;

(i) increasing quantities of zinc are added to molten cadmium
(ii) increasing quantities of cadmium are added to molten zinc
(i) The freezing point of cadmium decreases, more and more cadmium solidifies up

to the eutectic point ( at and when the mixture contains zinc). At
the eutectic point, the freezing point is constant, zinc also solidifies. Further
addition of zinc increases freezing point towards that of pure zinc. More and
more zinc solidifies out of the mixture.
(ii) The freezing point of zinc decreases, more and more zinc solidifies up to the
eutectic point ( at and when the mixture contains cadmium). At the
eutectic point, the freezing point is constant, solid cadmium also solidifies.
Further addition of cadmium increases freezing point towards that of pure
cadmium. More and more cadmium solidifies out of the mixture.
(e) Calculate the mass of cadmium that remained in the liquid mixture when
of the liquid mixture containing zinc was cooled from 400 to 350 .
424
Cooling curve for a pure substance or a eutectic mixtures

The cooling curve of a pure substance is similar to that of a eutectic mixture. Both a pure
substance and a eutectic mixture have a sharp freezing and melting point.
Considering pure hot molten zinc that is allowed to cool until it solidifies and also a
eutectic mixture of zinc and cadmium from the information already shown above. The
cooling curves for the changes are shown below.
Cooling curve for pure zinc Cooling curve for an eutectic mixture of
zinc and cadmium
A J
Temperature 𝑪
Temperature 𝑪
B D E
419

C
K M N
270
L
F O
Time (min) Time (min)
AB- Decrease in temperature of Liquid JK- Decrease in temperature of Liquid
zinc eutectic mixture of zinc and cadmium
BE-Freezing of Liquid zinc KN-Freezing of Liquid zinc and liquid
EF-Decrease in temperature of Solid zinc cadmium
Curve BCD- Supercooling of liquid zinc NO-Decrease in temperature of Solid
Along AB, the temperature of liquid zinc eutectic mixture of zinc and cadmium
decreases. At B, liquid zinc begins to Curve KLM- Supercooling of liquid
freeze and the temperature remains eutectic mixture of zinc and cadmium
constant until all the zinc freezes along Along JK, the temperature of the liquid
BE. At E, all the zinc has frozen. Along eutectic mixture decreases. At K, the liquid
EF, the temperature of solid zinc euctectic mixture begins to freeze and the
decreases. eutectic temperature remains constant until
all the liquid mixture freezes along KN. At
N, all the liquid eutectic mixture has frozen.
Along NO, the temperature of solid eutectic
mixture of zinc and cadmium decreases.
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425
The cooling curve of pure zinc is similar to and can be used for any other pure
substance and that of the eutectic mixture can be used for any other eutectic mixture
Cooling curve for a mixture
For a mixture other than a eutectic mixture, the cooling curve similar to the one below is
obtained. The one sketched below is a cooling curve for a liquid mixture of zinc and
cadmium.
V Liquid mixture cooling
i
419
Temperature 𝑪 Solid zinc and liquid mixture cooling
𝑇 W Eutectic mixture forming
X Y Solid mixture cooling

270

𝑇
Z
Time (min)
The liquid mixture of zinc and cadmium cools from point V( temperature , ) to point
W(temperature, ) below the freezing point of pure zinc.
At W, solid zinc begins to freeze and the liquid mixture becomes richer in cadmium.
The zinc begins to freeze at a temperature, below the freezing point of pure zinc
because adding cadmium to it lowers its freezing point.
The temperature of the solid zinc and liquid mixture then decreases from W to X(at the
eutectic temperature, 270 ).
At X, cadmium also begins to freeze and the temperature remains constant until all the
mixture freezes along XY. A eutectic mixture is formed.
At Y, the whole mixture has frozen.
Further cooling of the solid mixture decreases the temperature to
Differences between a eutectic mixture and a compound
Eutectic mixture Compound
Its composition changes with change in Its composition is fixed and does not
pressure change with pressure
Its melting point changes with pressure It has a fixed melting point
Can be separated into its components by Cannot be separated into its components
physical means by physical means
Microscopic examination shows that it is a It is homogenous
heterogenous in composition
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Tests that can show that a eutectic mixture is not a pure compound
 Microscopic examination shows that it is a heterogeneous mixture of individual
crystals of the components that make it up
 X-ray diffraction pattern of an eutectic mixture does not conform to that of a pure
compound
 Determining its composition shows that it does not correspond to a chemical
formula of any known compound.
 Changing pressure changes the composition of an eutectic mixture
Similarities between a pure substance and a eutectic mixture
 Both have sharp melting points
 Have similar cooling curves
Application of eutectic mixtures

Formation of solder, an alloy of lead and tin which is used for joining other metals at

temperatures which are not so high to melt the pure metal
Questions
1. Sodium chloride and water form a eutectic mixture which melts at and
contains 23.6% by mass of sodium chloride. Draw a well labelled temperature-
composition diagram for sodium chloride-water mixture.
2. (a) Explain what is meant by;
(i) Saturated solution
(ii) Mole fraction
(iii) Eutectic mixture
(iv) Azeotropic mixture
(b) The diagram below shows a temperature-composition diagram for a dilute sodium
chloride system
F
X
Area G
Temperature 𝑪
D
Y Area B
Area A
E
Area C
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Percentage composition of Sodium chloride

427
(i) State what lines DE and EF represent

(ii) Name the substances present at each of the areas A, B, C and G.
(iii) Describe what happens when a solution at X is cooled slowly to a
temperature below the eutectic temperature.
(iv) State two reasons why eutectic mixtures are not compounds
3. (a) The graph below shows the variation in melting point of a mixture of zinc and
cadmium with composition.
Melting Y
point 𝑪
X
Z

Percentage of cadmium
Use the graph to:
(i) Determine the eutectic point of the system
(ii) Name the phases in the regions X, Y and Z.
(b) Estimate the melting points of zinc and cadmium
(c) Describe the changes that take place when a mixture containing 88% zinc is
cooled from 450 to 280 .
(d) Calculate the mass of zinc that remained in the liquid when 120g of the liquid
mixture containing 12% cadmium was cooled from 450 to 280 .
(e) State one difference and one similarity between a eutectic mixture and a pure
compound.
(i) Eutectic point
(ii) Eutectic mixture
(b) Two metals A and B form a eutectic mixture with an eutectic point 80 and
72%B. Draw a well labelled phase diagram for the two metals. (Melting points of A
and B are 242 and 185
(c) State two similarities between a eutectic mixture and a metal.
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5. (a) Define the term “Phase”

(b) The melting points of various composition of Naphthalene-biphenyl system are
given below:
Mole fraction of naphthalene 0.800 0.625 0.275 0.125

Melting points 72.6 58.0 56.0 64.5
Naphthalene-biphenyl system forms an eutectic mixture of composition of 0.47 mole

fraction of naphthalene at temperature of
(i) Plot a phase diagram for naphthalene-biphenyl system and label all regions.
(ii) Describe what happens when a mixture containing 0.70 mole fraction of biphenyl
is cooled.

(c) Draw a well labeled cooling curve for a mixture naphthalene and biphenyl and
explain the shape of your curve.
(d) State one application of eutectic mixture
6. (a) Define the terms:
(i) Eutectic mixture
(ii) Eutectic point
(b) Briefly describe how a phase diagram of a mixture of cadmium and bismuth can
be determined in the laboratory.
(c) The table below shows the melting points of various mixtures of cadmium and
bismuth.
Percentage of bismuth 5 20 35 50 65 80 100
Melting point 300 242 184 156 190 226 271
(i) Draw a labeled phase diagram for the bismuth-cadmium system. (The
melting point of pure cadmium are is 321 respectively)
(ii) State the composition and melting point of the eutectic mixture.
(iii) Using the diagram, describe what happens when a liquid mixture
containing 90% bismuth at 350 is gradually cooled.
(iv) Explain what is observed when increasing quantities cadmium are added to
bismuth.
(v) Draw a well labeled cooling curve for the eutectic mixture formed and
explain the shape of your curve.
(c) State two similarities and two differences between an eutectic mixture and a
compound.
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7. (a) The melting points of mixtures of zinc and cadmium of different compositions are
shown below.
Percentage of zinc 0 10 17 30 60 100
Melting point 321 295 270 305 360 491
(i) Draw a fully labelled phase diagram for the zinc-cadmium system.
(ii) Determine the temperature and composition of the eutectic mixture.
(iii) Using the diagram in a(i) , describe the changes that will take place when a
liquid mixture containing 5% zinc at 300 was gradually cooled.
(b) State any three tests that can be carried out on the eutectic mixture to show that it
is not a pure compound.
8. (a) Define the following terms:
(i) Eutectic temperature
(ii) Eutectic mixture
(b) The table below shows the melting points and compositions of various mixtures of

cadmium and bismuth.
Percentage of cadmium 20 35 50 65 80 95
Melting point 226 190 156 184 242 300
Draw a labelled phase diagram for the cadmium-bismuth system.
Use your graph to;
(i) determine the melting points of pure cadmium and pure bismuth
(ii) determine the composition and melting point of the eutectic mixture
(iii) describe what happens when a liquid mixture containing 90% bismuth at
350 is gradually cooled.
(iv) determine the mass of bismuth that crystallized when 200g of the mixture
containing 25% cadmium was cooled from 300 to 168 .
COLLIGATIVE PROPERTIES
All solutions containing non-volatile solutes have certain properties in common. All these
properties vary with the compositions of the solutions in a similar way.
Each of these properties can be measures over a range of concentrations of the solutions
and the results obtained depend on the total number of solute particles present in a fixed
amount of solvent and hold for dilute solutions.
The properties are called colligative properties.
Colligative properties are therefore defined as physical properties of a dilute solution
which depend on the number of non-volatile dissolved particles in the solution but do
not depend on the chemical nature of the solute particles.
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The greater the number of particles in solution, the greater the extent to which the
colligative property is affected.
The colligative properties include:
1. Lowering of the vapour pressure of a solvent
2. Elevation of boiling point
3. Freezing point depression
4. Osmotic pressure of solution
Colligative properties are important and useful for the determination of molecular
masses for non-volatile solutes
Limitations of colligative properties
A correct value of relative molecular mass obtained by use of any colligative property is
only obtained if;
(i) Solute does not associate or dissociate in solution.

When solute particles associate in solution, the number of particles in solution decreases,
lowering the colligative property and increasing the relative molecular mass.
Molecular mass obtained by a colligative property for a solute that associates in solution
is always twice the actual value
When solute particles dissociate in solution, the number of particles in solution increases,
and the colligative property also increases, reducing the relative molecular mass.
Molecular mass obtained by a colligative property for a solute that dissociates in solution
is lower than the actual value.
(ii) The solution is dilute

(iii) There is no chemical reaction between the solute and the solvent.
(iv) The solute is non-volatile
Vapour pressure lowering

Vapour pressure of a liquid is the pressure exerted by the vapour when it is in
equilibrium with the liquid at a given temperature.
The vapour pressure of a solvent in solution is less than the vapour pressure of the pure
solvent at the same temperature.
This is because the non-volatile solute particles occupy some of the surface of the
solution. This reduces the escaping tendency of the solvent particles into the vapour
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431
phase. The solution there has a lower vapour pressure than that that would be exerted
by a pure solvent.
Question; Explain why an aqueous solution of glucose has a lower vapour pressure
than water at a given temperature
Glucose is non-volatile solute . When dissolved in water, glucose particles occupy some
of the surface of the solution. This reduces the escaping tendency of the solvent
particles into the vapour phase. The solution there has a lower vapour pressure than
that that would be exerted by a pure water.
For a solvent in solution, the vapour pressure lowering ( ) is given by;

,
Derivation of expression for relative vapour pressure lowering

For a solution made up of a volatile solvent and a non-volatile solute, the total vapour

pressure of the solution is equal to the partial vapour pressure of the solvent
because the solute does not contribute to the vapour pressure.
But , where
Where represents number of moles.
From the above expression, is called relative lowering of vapour

pressure and the whole expression represents the Raoult‟s law of vapour pressure
lowering.
Raoult’s law of vapour pressure lowering therefore states that the relative lowering of
vapour pressure of a solution containing a non-volatile solute is equal to the mole
fraction of the solute in the solution at a given temperature.
For dilute solutions, is small compared to this implies that;
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Where; and are masses of the solute and solvent respectively

and are the molar masses of water and the liquid respectively.
Note: The lowering of vapour pressure of a solvent by a non-volatile solute at a given
temperature is directly proportional to the concentration of the solute and inversely
proportional to the relative molecular mass of the solute.

Assumptions/ limitations of vapour pressure lowering
Calculations involving lowering of vapour pressure
Examples
1. The vapour pressure of pure ethoxyethane at a certain temperature is
. Calculate the vapour pressure of a solution of camphor,
in ethoxyethane at the same temperature.
⁄
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433
2. (a) Define the term relative lowering of vapour pressure of a solvent.

(b) (i) At , an aqueous solution of carbamide of
concentration has a vapor pressure of . Determine
the vapour pressure of water at this temperature.
(ii) State the assumptions you have made in b(i).
(a) Relative lowering of vapour pressure is the difference of vapour pressure of a pure
solvent and the vapour pressure of the solvent above its solution with a non-volatile
solvent divided by the vapour pressure of the pure solvent.
(b) (i)
⁄

(ii) Carbamide does not associate or dissociate in solution.
The solution is dilute
There is no chemical reaction between the carbamide and water.
Carbamide is non-volatile
3. The vapour pressure of pure benzene at a certain temperature is 640mmHg. A

non-volatile, nonelectrolyte solid weighing 2.175g is added to 39g of benzene, the
vapor pressure of a solution of the solid in benzene is 600mmHg. Calculate the
molar mass of solid substance.
⁄
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434
3. The vapour pressure of carbon disulphide at a certain temperature is

. At the same temperature, a solution of 5g of sulphur in of
carbon disulphide has a vapour pressure of . If the density of
carbon disulphide at this temperature is .
(a) Calculate the relative molecular mass of sulphur
(b) Deduce the molecular formula of sulphur in carbon disulphide.
(a)
⁄

The relative molecular mass of sulphur is
⁄ 256
(b) Molecular formula of sulphur in carbon
disulphide is
4. The vapour pressure of water is at a certain temperature. Calculate
the lowering in vapour pressure that occurs when 12g of urea, are
dissolved in one litre of water at the same temperature.
⁄
5. A solution contains 4.45g of solute X in 1kg of carbon disulphide. Another

solution contains 6.42g of sulphur in the same mass of carbon disulphide. If the
two solutions have the same vapour pressure at the same temperature, calculate:
(a) the relative lowering of vapour pressure
(b) Structural formula of the dissolved sulphur
(Relative molecular mass of X=178)
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435
(a) For a solution of X in ; For a solution of Sulphur in ;
⁄ ⁄
(b) Since the two solutions have the same

vapour pressure, and the same solvent(same
vapour pressure of pure solvent) is used, then
both the lowering of vapour pressure

and the relative lowering of vapour pressure is
Molecular formula is
the same.
Structural formula is;
Questions
1. (a) State Raoult‟s law of relative lowering of vapour pressure.
(b) (i) Calculate the vapour pressure of a solution containing 18g of glucose
in 50g of water at . (Vapour pressure of water at is
150mmHg.)
(ii) State any assumptions made in (b)(i).
2. A solvent Y of molecular mass 62 has a vapor pressure of at .
23.3g of a non volatile solute of molecular mass 270 was added to 100g of Y at
.
(i) Calculate the vapor pressure of solution
(ii) State and explain the effect of increasing the concentration of the solute on
the boiling point of Y.
3. The vapor pressure of water at is . At this temperature, a solution of
of carbamide in of water has a vapour pressure of . Find the
relative molecular formula of the carbamide.
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436
4. The vapour pressure of a 3% solution of a non-volatile solute X in ethoxyethane is

at a certain temperature. The vapour pressure of pure ethoxyethane at the
same temperature is .
(i) Calculate the relative molecular mass of X
(ii) State any other assumptions made in (i) apart from X being non-volatile
5. of a certain solute were dissolved in in ethoxethane at and vapour
pressure of the solution was measured to be . At this temperature vapour
pressure of ethoxyethane was found to be . Calculate relative molecular
mass of the solute.
6. When of sucrose were dissolved in of water at , the vapour pressure
decreased by . Calculate the molar mass of sucrose ( Vapour pressure of water
at is )
7. The vapour pressure of pure water at is . The vapour pressure of a
solution of 4g of a sugar in 100g of water at the same temperature is .

Calculate the relative molecular mass of the sugar.
8. 19 g of solute K, were dissolved in 90g of water and vapour pressure of the solution
was lowered by 42 mmHg. Calculate molar mass of solute K if vapour pressure of
pure water is 92 mmHg.
9. The vapour pressure of a solution containing of a substance in 1000g of
water was reduced by of water at (The vapor pressure of water at
is .
(a) Calculate the relative molecular mass of substance .
(b) State four assumptions made in (a)
(c) Explain why the vapor pressure of the solution containing a nonvolatile solute is
less than the vapor pressure of a pure solvent.
Graphical representation of vapour pressure lowering
From the expression;

⁄
( )
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437
Comparing with the equation a graph of the lowering of vapour pressure( )

plotted against mass of solute for a given mass of water can be plotted.
A graph of lowering of vapour
pressure( )
against mass of solute is a straight
line through the origin.
𝑝 The slope of the graph gives the
𝑷𝒂 value ( )
( )
𝒎𝒂𝒔𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆
𝒈

The data you are usually given requires you to calculate first before graph plotting.
is the vapour pressure at . Each value is subtracted from the
value to get values at the different values.
Also from the expression;
⁄ ( )
( )
Since
Comparing with the equation a graph of the lowering of vapour pressure( )

plotted against mass of solute of a solute in a given solvent
can be plotted.
The density if given in must be multiplied by 1000 to convert it to
since units of concentration are usually expressed per litre
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438
A graph of lowering of vapour

pressure( )
against
of solute in a solvent is a straight
line through the origin.
𝑝 The slope of the graph gives the
𝑷𝒂 value
( )
𝟑
𝑪𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 𝒎𝒐𝒍𝒅𝒎
The data you are usually given may require you to calculate first before graph
plotting. is the vapour pressure at . Each value is

subtracted from the value to get values at the different
values.
Questions
1. (a) (i) Define the term vapour pressure
(ii) State Raoult‟s law of vapour pressure lowering
(b) The vapour pressure of aqueous solutions of glucose containing 9.0g of water at
27 varies with the mass of glucose dissolved as shown in the table below.
Mass of glucose in 9.0g of water 0.00 0.45 0.90 1.80 3.60 4.50 7.20
Vapour pressure of 31.82 31.66 31.50 31.32 30.55 30.23 29.27
solution(mmHg)
(i) Plot a graph of lowering in vapour pressure(ΔP) against mass of glucose
dissolved in 9.0g of water.
(ii) Use your graph in b(i) above to determine the molar mass of glucose.
(c) State the effect of water on the molecular state of glucose. Give a reason for your
answer using the molar mass calculated in b(i) above.
2. The lowering in vapour pressure of a volatile solvent is a colligative property.
(a) (i) Define the term colligative property
(ii) State two other examples of colligative properties
(b) The vapour pressure of different solutions of solute Y dissolved in solvent X at
40 are shown in the table below.
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439
Concentration of Y 0.00 0.10 0.20 0.30 0.40 0.50

Vapour pressure of 16.000 15.971 15.942 15.914 15.880 15.860
solution
(i) Plot a graph of lowering in vapour pressure(ΔP) against concentration of Y.
(ii) Use your graph in b(i) above to determine the relative molecular mass of
solvent X if its density is .
(iii) State two assumptions made in b(ii) above.
Elevation of boiling point (Ebullioscopy)
Boiling point of a liquid is the constant temperature at which its saturated vapour
pressure becomes equal to the external pressure on the liquid.
A pure liquid will only boil when its saturated vapour pressure is equal to the external
pressure. The external pressure is usually the atmospheric

pressure
The vapour pressure of a liquid decreases when a non-volatile solute is dissolved in it
The decreased vapour pressure implies that the solution will have to be heated to a higher
temperature than the boiling point of the pure liquid so that its equilibrium vapour
pressure becomes equal to the atmospheric pressure for boiling to take place.
Pure water boils at an aqueous solution of sodium chloride boils at at
. Explain
Sodium chloride is non-volatile solute. When dissolved in water, sodium chloride
particles occupy some of the surface of the solution. This reduces the escaping
tendency of the solvent particles into the vapour phase. The solution there has a lower
vapour pressure than that that would be exerted by pure water. The solution should
therefore be heated at a higher temperature than the boiling point of pure water so that
its equilibrium vapour pressure becomes equal to the atmospheric pressure for boiling
to take place.
In simple terms, the boiling point of a solution containing a non-volatile solute

is always higher than the boiling point of pure solvent( ). This
increase in boiling point is called the elevation in boiling point .
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Vapour pressure-temperature diagrams and boiling points

C
760 B
F
Vapour pressure A
(mmHg)
D E
𝑻𝟎𝒃 𝑻𝒃
Temperature ( 𝑪)
Curve ABC represents the variation of vapour pressure of pure solvent with
temperature
Curve DEF represents the variation of vapour pressure of solution with temperature

Curve DEF is below curve ABC at all temperatures because the vapour pressure of the
solution is always lower than that of pure solvent
is the boiling point of pure solvent
is the boiling point of the solution.
The elevation in boiling point, . The greater the concentration of the
solute particles in solution, the greater the boiling point elevation.
Therefore a curve of a more concentrated solution will still be below curve DEF at all
temperatures.
The boiling point constant of the solvent or molal boiling point constant
(Ebullioscopic constant, )
This is the elevation in boiling point caused when one mole of a non-ionizing and non-
volatile solute is dissolved in 1000g of a solvent.
The units of the ebullioscopic constant are or
Boiling point elevation is directly proportional to magnitude of vapour pressure lowering
The vapour pressure lowering is proportional to the molality, m (not molarity) of the
solute particles.
Therefore boiling point elevation is directly proportional to molality of the solute.
where is molality of the solute in solution and is the boiling point constant of the
solvent or molal boiling point constant or ebullioscopic constant.
The molal concentration (or molality; symbol m) is the amount of substance per unit mass
of solvent, commonly given in units of .
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( )
Experimental determination of molecular mass using boiling point elevation method

Using Cottrell‟s apparatus to find relative molecular mass of benzoic acid in
propanone
Beckmann thermometer
To condenser
Inner tube Side arm

Cottrell pump Wide tube
Solvent/Solution
Platinum wire
A known mass of pure propanone, is placed in a wide tube fitted with a side arm
leading to a reflux condenser.
The boiling tube is closed by a stopper through which is passed a second inner tube, open
at the lower end and fitted with a Beckmann thermometer.
In the liquid is immersed a Cottrell pump, C to prevent super heating
The propanone is then heated until the Beckmann thermometer shows a constant
temperature and the boiling point is measured.
A known mass of benzoic acid, in pellet form is then added through the side arm to
the solvent
The resulting solution is also heated until the Beckmann thermometer shows a constant
temperature and the boiling point of the solution is also measured.
Let the boiling point elevation constant of propanone be
( )
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( )
( )
The relative molecular mass of the benzoic acid is ( )

Assumptions/ limitations of the boiling point elevation method for determining
relative molecular mass
Explain why the molecular mass of ethanoic acid obtained by ebullioscopic method
is 120g using benzene as a solvent.
Molecular mass of

The molecular mass of ethanoic acid obtained by boiling point elevation method is twice
the actual value. This is because ethanoic acid associates through intermolecular
hydrogen bonds to form dimers in benzene. The number of ethanoic acid molecules in
benzene solution is half the original number in the pure solute. This lowers the boiling
point elevation but increasing the relative molecular mass to twice the actual value.
The relative molecular mass of sodium chloride obtained by boiling point elevation
method is 29.25. Explain.
Actual relative molecular mass of sodium chloride
The obtained relative molecular mass is half the actual value.
Sodium chloride being a strong electrolyte, completely ionises in water to form sodium
ions and chloride ions
Therefore 1 mole of sodium chloride will form a total of 2 moles of ions in solution.
Since boiling point elevation is a colligative property, directly proportional to the
number of solute particles in solution, the ionisation of sodium chloride increases the
boiling point elevation but reduces the relative molecular mass to half the actual value.
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Calculations involving boiling point elevation

Examples
1. (a) A solution containing 60g of and 50g of water was boiled. Calculate
the boiling point of the solution.
(b) State any assumption(s) you have made in your calculation.

(a)
( )
( )

(b) does not associate or dissociate in solution.
The solution is dilute
There is no chemical reaction between and water.
is non-volatile
2. A aqueous solution of urea ( ) has a boiling point of .

Calculate the boiling point of pure water.
( )
( )
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3. 2.00g of phosphorus raise the boiling point of 37.4g carbon disulphide by
(a) Calculate the molar mass of phosphorus in carbon disulphide
(b) (i) Hence determine the molecular formula of phosphorus in carbon

disulphide.
(ii) State any two assumptions made in the calculation in (a) above
(iii) Comment on the result in b(i) above.
(a)
( )
( )

(b) (i) Molecular formula of Phosphorus in carbon
disulphide is
There is no chemical reaction between phosphorus and carbon disulphide.
Phosphorus is non-volatile
(iii) Phosphorus exists as a tetratomic molecules in carbon disulphide
4. 0.900g of a solute was dissolved in of benzene at 25 . The solution

formed boiled at 0.25 higher than the boiling point of benzene. Calculate
relative molecular mass of the solute.
( )
( )
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3. (a) The boiling point of pure water is 100 but when 1.97g of potassium chloride
is dissolved in 125g of water, the solution boiled at 100.11 at a pressure of
760mmHg. Explain this observation.
(b) From the information given in (a) above, calculate the boiling point constant
of water.
(a) Potassium chloride is non-volatile solute. When dissolved in water, potassium chloride
particles occupy part of the surface of the solution. This reduces the escaping tendency of the
water molecules into the vapour phase. The solution there has a lower vapour pressure than
that that would be exerted by pure water. The solution should therefore be heated at a higher
temperature than the boiling point of pure water so that its equilibrium vapour pressure
becomes equal to the atmospheric pressure for boiling to take place.
(b)
( )

( )
4. (a) Define the term boiling point elevation constant of a substance.

(b) The boiling point of benzene under certain pressure condition is .
Calculate the boiling point elevation constant of benzene, if a solution
containing 5g of 2,4,6-trinitrophenol, in 100g of benzene,
boils at .
(b)
( )
( )
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5. Calculate the mass of sucrose, , that would have to be dissolved in

1000g of water to raise its boiling point to 101.7 .
( )
Questions
1. Calculate the boiling point of a solution formed by mixing 8g of glucose, ,
and 120g of water.

2. Calculate the boiling point of a solution containing 0.360g of glucose dissolved in
100g of water. The boiling point of pure water is
.
3. The boiling point of ethanol is 78 . Calculate the boiling point of a solution
containing 2.7g of ethanamide in 75g of ethanol (Boiling point
elevation for 1000g of ethanol is )
4. The boiling point of ethanol is 78 and its molal boiling point constant is
. A solution containing 0.56g of camphor in 16g of ethanol has a
boiling point of 78.278 . Calculate the relative molecular mass of camphor.
5. 0.900g of a solute was dissolved in of benzene at 25 . The solution formed
boiled at 0.25 higher than the boiling point of benzene. Calculate relative molecular
mass of the solute.
6. The boiling point of an aqueous solution containing 3g of a non-volatile solute in

200g of water is 100.45 . Calculate the molar mass of the
solute.
7. A solution containing 1.00g of a non-volatile solute in 10.0g of benzene boils at
1.22 higher than pure benzene. Calculate the molecular mass of the
solute.
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8. (a) State what is meant by the term ebullioscopic constant.

(b) 0.40g of camphor when dissolved in 33.5g of trichloromethane produces a
solution boiling at 0.30 above the boiling point of pure solvent. Calculate the
ebullioscopic constant of trichloromethane. ( ).
9. (a) Define the term boiling point elevation constant of a substance.
(b) An aqueous solution of glucose containing 12g of the solute dissolved in 100g of
water was found to boil at while pure water boils at . Calculate
the boiling point elevation constant of water.
10. Calculate the mass of sucrose, , that would have to be dissolved in 1000g
of water to raise the boiling point by 1.0 .
11. (a)Explain the terms;
(i) Boiling point of a liquid
(ii) Boiling point elevation constant of a liquid
(iii) Relative molecular mass

(iv) Colligative property
(b) Describe an experiment to determine the relative molecular mass of naphthalene in
chloroform by the elevation of boiling point method.
(c) State, with reasons why the method in (b)(i) above is not suitable for determining
relative molecular mass of;
(i) polyvinylchloride
(ii) ethanoic acid
(d) (i) A solution of 2.8g of cadmium(II) iodide in 20g of water boiled at at
standard pressure. Calculate the relative molecular mass of the solute and
comment on your answer.
(ii) A solution contains 1 mole of sugar per kg of water. Another solution contains
1 mole of urea per kg of water. State and explain which of the two solutions
will have a higher elevation in boiling point.
Graphical representation of Boiling point elevation

The elevation in boiling point is proportional to the lowering in vapour pressure
Since the lowering in vapour pressure is directly proportional to the concentration of

solute and inversely proportional to relative molecular mass of the solute;
, where is concentration in grams of solute per litre of solvent
This implies that
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where the constant is the boiling point constant

A graph of boiling point elevation against concentration can be plotted
A graph of elevation of boiling
point ( ) against
𝑇 of solute
in a solvent is a straight line
𝑪
through the origin.
value
𝟑
𝑪𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 𝒈𝒅𝒎
If of the solvent is known, the relative molecular mass of the solute can be calculated.

plotting.
Freezing point depression (Cryoscopy)
Freezing point of a liquid is the constant temperature at which the liquid coexists with
its solid form at the same saturated vapour pressure.
The vapour pressure of a solvent decreases when a solute is dissolved in it and therefore
the solid-liquid equilibrium will only exist at a temperature lower than that of the pure
solvent.
Explain why freezing point of a solution containing a non-volatile solute is always

lower than freezing point of the pure solvent
When a non-volatile solute is dissolved in a solvent, the solute particles occupy part of
the surface of the solution. This reduces the escaping tendency of the solvent molecules
into the vapour phase. The solution there has a lower vapour pressure than that that
would be exerted by pure solvent. Therefore the temperature at which the solution is at
equilibrium with the solid solvent is lower than that for the pure solvent.
In simple terms, the freezing point of a solution containing a non-volatile

solute is always lower than the freezing point of pure solvent( ). This decrease
in boiling point is called the freezing point depression( ).
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Vapour pressure-temperature diagrams and freezing point
B D
760
Vapour pressure A
(mmHg) C
E
F
𝑻𝒇 𝑻𝟎𝒇
Temperature ( 𝑪)
Curve AB represents the variation of vapour pressure of pure solvent with temperature

Curve CD represents the variation of vapour pressure of solution with temperature
Curve FCA represents the variation of vapour pressure of pure solid solvent with
temperature. It is called the sublimation curve of the solid solvent.
The point A, at which curves FCA and AB meet is the freezing point of pure solvent.
Point C is the freezing point of the solution.
Curve CD is below curve AB at all temperatures because the vapour pressure of the
solution is always lower than that of pure solvent
is the freezing point of pure solvent
is the free point of the solution.
The depression in freezing point, . The greater the concentration of the
solute particles in solution, the greater the depression in freezing point
Therefore a curve of a more concentrated solution will still be below curve CD at all
temperatures.
The freezing point constant of the solvent or molal freezing point depression
constant (Cryoscopic constant, )
This is the amount by which the freezing point of 1000g of a solvent is lowered when
one mole of a non-ionizing and non-volatile solute is dissolved in it.
The units of the cryoscopic constant are or
Freezing point depression is directly proportional to magnitude of vapour pressure
lowering
The vapour pressure lowering is proportional to the molality, m (not molarity) of the
solute particles.
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Therefore freezing point depression is directly proportional to molality of the solute.
where is molality of the solute in solution and is the freezing point constant of
the solvent or molal freezing point constant or cryoscopic constant.
Experimental determination of molecular mass using freezing point depression

method using Beckmann‟s freezing point apparatus
Beckmann thermometer
Stirrers
Side arm
Air jacket
Glass tube Ice-salt freezing mixture

Wider tube Freezing tube
Solvent/ Solution
A known mass of pure solvent, g is placed into a glass tube that is fitted with a
Beckmann thermometer, stirrer and has a side arm.
The freezing tube is placed in a wider tube that acts as an air jacket to ensure uniform
cooling.
The whole apparatus is put in a vessel containing an ice-salt freezing mixture that is kept
stirred
The solvent is allowed to cool while stirring until a constant temperature, is
obtained when it begins to freeze and recorded from the Beckmann thermometer.
The solvent is warmed until it melts.
A known mass of solute, g, in pellet form is added to the solvent through a side arm.
The solution is cooled while stirring and the steady temperature, at which it freezes,
is recorded.
Let the freezing point depression constant of the solvent be

( )
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( )
( )
( )
The relative molecular mass of the solute is ( )

Assumptions/ limitations of the freezing point depression method for determining
relative molecular mass
Explain why 0.1 mole of sodium chloride depresses the freezing point of 1 of

water twice as much as 0.1 mole of glucose does.
Sodium chloride completely ionises in water to form sodium ions and chloride ions
Glucose is non-ionising solute

Therefore 0.1 moles of sodium chloride will form a total of 0.2 moles of ions in
solution. Glucose remains in its molecular state in solution and will still exist as 0.1
moles in solution. Since freezing point depression is a colligative property, directly
proportional to the number of solute particles in solution, the amount by which freezing
point of water is depressed by sodium chloride doubles that of glucose.
Calculations involving freezing point depression

Examples
1. Liquid camphor freezes at 175 . A solution of 1.54g of naphthalene, , in
18g of camphor freezes at 148.3 . Calculate the freezing point constant of
camphor.
( )
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( )
2. (a) Explain what is meant by the term cryoscopic constant

(b) Calculate the melting point of a solution made by dissolving 0.36g of
naphthalene, , in 6.0g of camphor. The melting point of camphor is
177 and for camphor is 40 for 1 mole in 1000g.
(b)
( )
( )

3. Calculate the mass of water in which 10g of glucose, should be
dissolved to obtain a solution that freezes at .
( )
( )
4. A solution containing 1.2g of ethanoic acid in 80g of water freezes at .

Calculate the relative molecular mass of ethanoic acid.
( )
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( )
( )
5. (a) Explain what is meant by the term colligative property.

(b) 0.72g of a compound X was dissolved in 80g of water and the resultant
solution had a freezing point of . When 2.9g of the same compound
was dissolved in 111g of benzene the freezing point was depressed by .
Calculate the apparent molecular mass of X in ;

(i) water
(ii) benzene
(c) Explain why the molecular mass of X differs in the solvents.
(b)(i)
( )
( )
(ii)
( )
( )
(c) The apparent molecular mass is X in benzene is twice that of benzene in water because two
molecules of X associate in benzene to give a dimer.
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6. (a) An aqueous solution containing 7.2g of a non-cyclic substance Z in 250g of

water freezes at . Calculate the molecular mass of Z.
(b) If Z contains carbon, hydrogen, and the rest being oxygen

(i) Calculate the simplest formula of Z
(ii) Determine the molecular formula of Z
(iii) Write the structures of all possible isomers of Z
(c) Z forms a yellow precipitate with phenyl hydrazine and iodine solution in
presence of sodium hydroxide. Name Z.
(a)
( )

( )
(b) (i)
(iii) (iv)
(c) Z is Butanone
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Questions
1. A solution containing 0.368g of methanoic acid in 50g of benzene freezes at 5.093 .
(a) Calculate the relative molecular mass of methanoic acid.
( )
(b) Comment on the value in (a)
2. The melting point of camphor is 177.5 while that of a solution containing 1g of
naphthalene in 10g of camphor is 147 . Calculate the cryoscopic constant of
camphor. (Molar mass of naphthalene is 128)
3. The freezing point of a solution of 22.0g of carbon tetrachloride dissolved in 800g of
benzene is 4.59 . If the freezing point of benzene is 5.50 Calculate the molal
freezing point depression constant of benzene.
4. Calculate the freezing point of a solution containing 3.33g of ethane-1,2-diol in 14g of
water.
5. Calculate the freezing point of a solution containing 60g of glucose, in 200g

of water.
6. A solution containing 25.6g of sulphur dissolved in 1000g of naphthalene gave a
freezing point lowering of . Determine the molecular formula of sulphur in
naphthalene.
7. An organic compound W contains 22.8% nitrogen, 28% oxygen , 8.5% hydrogen and
the rest being carbon.
(a) Calculate the empirical formula of W
(b) 0.5g of W dissolved in 80g of water forming a solution that freezes at .
Calculate the molecular formula of W.
(c) When W was refluxed with potassium hydroxide, ethanoic acid and ammonia was
produced.
(i) Identify W
(ii) Write equations to show how W is obtained from a carbonyl compound.
8. (a) A compound Y contains 80% carbon, 6.7% hydrogen, and the rest being oxygen.
Calculate the empirical formula of Y.
(b) 0.48g of Y was dissolved in 50.0g of benzene and caused a freezing point
depression of 0.44 . Determine the molecular formula of Y.
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(c) Compound Y forms a yellow precipitate with 2,4-dinitrophenylhydrazine and

reacts with a mixture of iodine and sodium hydroxide to form a yellow precipitate.
Write;
(i) the structural formula of Y
(ii) equation and outline mechanism for the reaction between Y and 2,4-
dinitrophenylhydrazine.
9. of an organic compound Y on complete combustion gave 0.88g of carbon
dioxide gas and 0.18g of water. 0.53g of Y in 22g of ethanoic acid lowered the
freezing point of ethanoic acid by 0.78K.
(a) (i) Calculate the empirical formula of Y.
(ii) Determine the molecular mass of Y and write the possible structural
formula of Y.
(b) Y burns with a yellow sooty flame, gives a yellow precipitate with 2,4-
dinitrophenylhydrazine but does not form silvery deposits with ammoniacal silver

nitrate solution.
(i) Identify Y
(ii) Write an equation and suggest a possible mechanism between Y and 2,4-
dinitrophenylhydrazine in acidic media.
(c) Write equations indicating conditions to show how you would obtain
phenylethyne from Y.
10. (a) Define the term freezing point depression constant of a solvent.
(b) In an experiment, a 5 per cent solution of glucose, in water found give
the same freezing point depression as a 3.3 percent aqueous solution of .
(i) Determine the molecular formula of .
(ii) The compound in b (i) above forms a crystalline white precipitate with
saturated sodium hydrogen sulphite solution but no observable change with
ammoniacal silver nitrate solution. It also reacts with ethanoic acid in the
presence of concentrated sulphuric acid to give a product with a sweet
fruity smell. Write the structural formula and name of .
11. (a) Describe an experiment to determine the relative molecular mass of naphthalene in
benzene. (Include a well labelled diagram to illustrate your answer)
(b) The freezing point of pure benzene is . A solution containing 0.321g of
naphthalene, in 25g of benzene freezes at . A solution containing
0.305g of benzoic acid in 25g of the same solvent freezes at
(i) Calculate the molar freezing point depression constant for benzene.
(ii) Hence calculate the relative molecular mass of benzoic acid in benzene.
Also revisit questions 15, 18 and 19 under empirical and molecular formulae in matter
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Graphical representation of freezing point depression

The depression in freezing point is proportional to the lowering in vapour pressure
Since the lowering in vapour pressure is directly proportional to the concentration of

solute and inversely proportional to relative molecular mass of the solute;
, where is concentration in grams of solute per litre of solvent
This implies that
where the constant is the freezing point constant

A graph of boiling point elevation against concentration can be plotted
A graph of depression in freezing
point ( ) against

𝑇 of solute
in a solvent is a straight line
𝑪
through the origin.
value
𝟑
If of the solvent is known, the relative molecular mass of the solute can be calculated.
plotting.
From the expression;
A graph of freezing point of solution, when plotted against concentration will

be a straight line with a negative slope. The from which molar mass of the
solute can be obtained if is known. The graph has an intercept on the axis.
The intercept gives the freezing point of pure solvent, .
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Questions
1. The table below shows the freezing points of various concentrations of a non-volatile
solute Q in water at 760mmHg.
Concentration of Q 0 30 60 90 120 150
Freezing point 0 -0.16 -0.32 -0.49 -0.65 -0.81
(a) Plot a graph of freezing point depression against concentration of Q
(b) Determine the :
(i) slope of the graph you have drawn in (a).
(ii) relative molecular mass of Q.
2. (a) State what is meant by the following terms
(i) Colligative property
(ii) Freezing point constant of a substance
(b) (i) Describe an experiment to determine the molecular mass of naphthalene using

camphor as a solvent. (Diagram not required)
(ii) State three limitations of the method in (b)(i) above.
(c) The freezing points of solutions of various concentrations of a solute X in solvent
Y at 1.0 atm are given below.
Concentration 20 40 60 80 100 120 140
Freezing point -0.11 -0.22 -0.32 -0.43 -0.54 -0.65 -0.76
(i) Plot a graph of freezing point against concentration
(ii) Use your graph to determine the freezing point of Y
(iii) Determine the relative molecular mass of X.
(d) Ethanoic acid has a freezing point of 16.63 . On addition of 2.5g of an organic
solute to 40g of the acid, the freezing point was lowered by 15.48 . Calculate the
molecular mass of the solute. ( )
Osmotic pressure,
Osmosis is the movement of solvent molecules from a dilute solution to a more
concentrated solution through a semi-permeable membrane.
If two solutions of different concentrations are separated by a semi-permeable membrane,
the solvent molecules from the dilute solution will pass through the semi-permeable
membrane to the concentrated solution so that the two solutions have equal
concentrations. The osmosis can be stopped by applying pressure on the concentrated
solution. This pressure is called osmotic pressure, .
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Osmotic pressure is the minimum pressure required to prevent the movement of solvent
molecules from a dilute solution to a more concentrated solution when the solution is
separated from pure solvent by a semi-permeable membrane.
Experiment to determine osmotic pressure of a solution
(Using the Berkeley and Hartley‟s method)
Pressure applied
Piston Water reservoir
Pressure gauge
Capillary tube Solvent Tap
Gun metal casing

Solution Semi permeable membrane

A solution whose osmotic pressure is to be determined is put in a gun metal casing
The solution is separated from the solvent in a cylindrical porous tube by a semi-
permeable membrane.
External pressure is applied by pushing down the piston until the level of the solvent in
the capillary tube is just stationary.
This applied pressure is the osmotic pressure of the solution and is read off directly from
the pressure gauge.
Suitability of osmotic pressure in determining molecular mass of non-volatile large

molecules e.g. proteins or polymers or plastics
Osmotic pressure is a better method to determine relative molecular mass of large
molecules than ebullioscopic and cryoscopic methods because;
Polymers have high relative molecular masses and in dilute solutions, the give few
dissolved particles. Relative molecular mass is inversely proportional to either freezing
point depression or boiling point elevation. The freezing point depression or boiling point
depressions caused by the few dissolved polymer particles in dilute solutions are very
small and cannot be measured by ordinary thermometers. However, dilute solutions of
polymers have reasonable and accurately measurable osmotic pressures at room
temperature.
In addition, the ebullioscopic method is not suitable because polymers tend to fragment
and decompose at high temperatures.
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In general, the advantages of the osmotic pressure are;

1. Osmotic pressure of a solution containing few particles is appreciable and can be
measured accurately than its elevation in boiling point or depression in freezing point
2. Osmotic pressure can be measured at room temperature hence more suitable for
substances that are not stable at higher temperatures.
Determination of relative molecular mass by osmotic pressure measurement

If the osmotic pressure of a solution containing of a solute in of solution is
measured at a temperature, , the number of moles of solute, can be determined from
the expression;
Since where is the molar mass of the solute.

Then;

The molar gas constant, , is commonly used as when the units of
pressure, volume and temperature are and Kelvin respectively.
Recall that;
( )
Calculations involving osmotic pressures and molar masses
Examples
1. Calculate the osmotic pressure of a solution containing 4.0g of a non-volatile
solute per litre of solution at . The relative molecular mass of the solute is
40.
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2. A solution containing of a polymer was found to have an osmotic pressure

of atmospheres at . Calculate the molecular mass of the
polymer.
For osmotic pressure ONLY; 1.5% means

1.5g in a volume of 100

The molecular mass of the polymer is
1,018,332.1g
3. The osmotic pressure of an aqueous solution of a non-electrolyte containing
of solution is at . Calculate the freezing
point of solution.
( )
The molar mass of the polymer is 189.58g
Assuming density of solution is . The volume of water used is 1000 and its mass
is 1000g.
( )
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4. The osmotic pressure of a solution containing 1.4g of a polymer per 100 of

a solution is at .
(a) Calculate the relative molecular mass of
(b) Determine the number of monomers in
(a)

The relative molecular mass of the
polymer is 28,891.1g
(b)
Note that number of monomers should never be a decimal but a whole number.
Questions
1. (a) Define the term osmotic pressure.
(b) At ,a solution of a polymer has an osmotic pressure of
atmospheres. Calculate the formula mass of the polymer.
(c) Explain why in the determination of molecular mass of polymers, osmotic
pressure is used instead of ebullioscopic and cryoscopic methods.
2. A solution containing of polyphenylethene in of benzene is found to
have an osmotic pressure of at . Calculate the average relative molecular
mass of polyphenylethene.
3. The osmotic pressure of an aqueous solution of a non-electrolyte containing
per of solution is at . Calculate the freezing point of
solution.
( )
4. (a) Define the term Osmotic pressure.
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(b) A polysaccharide has the formula . A solution containing

of the sugar has an osmotic pressure of at .
Find the value of n.
(c) State any two assumptions made in (b) above.
5. A solution containing 20g of a polymer X in one litre of solvent exerts an osmotic
pressure at .
(i) Calculate the molecular formula of X
(ii) The molecular formula of the monomer of X is . Determine the
number of monomer units in X
(iii) Explain why the freezing point depression method is not suitable for
determining the molecular formula of X.
6. A solution of 42.0g of mannitol in 1 of water has an osmotic pressure of
at . Calculate the relative molecular mass of mannitol.
7. A aqueous solution of compound A has an osmotic pressure of at

. Calculate the relative molecular mass of A.
8. A 3.42% solution of substance X has the same osmotic pressure as a 5.96% solution
of substance Y. Calculate the relative molecular mass of Y. (Relative molecular mass
of X is 342)
(i) osmosis
(ii) Osmotic pressure
(b) State conditions under which osmotic pressure laws are valid.
(c) (i) Describe a method that can be used to determine the osmotic pressure of a
sucrose solution.
(ii) The osmotic pressure of a solution containing 1.4% of a polymer is
at . Determine the relative formula mass of the
polymer.
(iii) Briefly explain why osmotic pressure method is the preferred method to
determine the relative formula mass of polymers. |
464
Determining relative molecular mass from osmotic-pressure- concentration graphs

From
but
( )
but ( )
A graph of osmotic pressure, against concentration can be plotted.
A graph of osmotic pressure,

against of
𝑶𝒔𝒎𝒐𝒕𝒊𝒄 solute in a solvent is a straight line

𝒑𝒓𝒆𝒔𝒔𝒖𝒓𝒆 𝝅 through the origin.
𝟐
𝑵𝒎 The slope of the graph gives the
value
𝟑
The expression is used to calculate the relative molecular mass of the solute
where and T given in the question.
Note that if the values of osmotic pressure given are in atm or mmHg, they should be
converted as discussed earlier to while computing the slope and then use as
stated with T converted to Kelvin.
Questions
1. The osmotic pressures of various concentrations of solute X in methylbenzene at
are given in the table below.
Concentration of the solution( ) 1.0 2.0 3.0 4.0 5.0 6.0
Osmotic pressure( ) 23 37 53 75 92 109
(a) Plot a graph of osmotic pressure against concentration
(b) Use your graph to determine the relative molecular mass of X.
|
465
2. (a) Define the terms

(ii) Osmotic pressure
(b) (i) Describe an experiment to determine the molecular mass of mannitol by
osmotic pressure method.
(ii) State three limitations on this method
(c) The table below shows the osmotic pressure of a solution of mannitol of various
concentrations at .
Concentration of the solution( ) 1.5 3.0 4.5 6.0 7.5 9.0 10.5
Osmotic pressure of the solution(atm) 0.20 0.40 0.60 0.81 1.05 1.20 1.40
(i) Plot a graph of osmotic pressure against concentration of the solution

(ii) Explain the shape of the graph
(iii) Use the graph to determine the relative molecular mass of mannitol.

1. (a) Define the term colligative property.
(b) State four colligative properties of a solution.
(c) (i) Define the term mole fraction.
(ii) Calculate the mole fraction of potassium chloride in an aqueous solution
containing 10 of potassium chloride per 100 of water. ( )
(ii) Boiling point constant
(b) Describe an experiment that you would carry out to determine the relative
molecular mass of a compound using the boiling point elevation method. Use a
diagram to illustrate your answer.
(c) Explain the effect of association of the solute on the value of the relative
molecular mass determined by boiling point method.
(d) (i) State the laws of osmotic pressure.
(ii) State the conditions under which these laws are valid.
(e) The osmotic pressure of a 1.24% solution of polyvinylchloride is
at 25 . Calculate the;
(i) relative molecular mass of polyvinylchloride
(ii) number of monomer units in polyvinylchloride.
|
466

(a) When propanone is mixed with tetrachloromethane, a warm miscible mixture was
formed whose volume was lower than the sum of the volumes of the individual
components.
(b) The boiling points of water and bromobenzene are and respectively.
However a mixture of water and bromobenzene boils below at atmospheric
pressure.
(c) A 0.01M solution of sodium chloride has the same freezing point depression as a
0.02M aqueous solution of glucose
(d) An aqueous solution of ethanol boils at whereas an aqueous solution of
sodium chloride boils at at .
(e) When steam at is blown into an aqueous solution of a solid at , it raises
the temperature of the solution above .
(f) Boiling point elevation method is not suitable for measuring relative molecular mass

of a plastic.
(g) The osmotic pressure method cannot be used to measure the relative molecular mass
of sulphuric acid in solution
467
CHAPTER SIX
CHEMICAL EQUILIBRIA
THE CONCEPT OF CHEMICAL EQUILIBRIUM
Chemical reactions, just like physical changes can reach a state of equilibrium. Although
some reactions take place in one direction, like the when magnesium burns in air to form
magnesium oxide, other reactions take place in both forward and backward directions at
comparable rates for example the thermal dissociation of calcium carbonate.
The products of thermal dissociation of calcium carbonate are calcium oxide, a base and
carbon dioxide, an acidic gas which can react to form calcium carbonate again.
Apart from thermal dissociation of calcium carbonate, many other reactions do not go to

completion and then stop, since the products of the reaction themselves react to form
original reactants. Such reactions are called reversible reactions. Therefore, for
equilibrium to be established there is both a forward and backward reaction.
The characteristics of a chemical equilibrium

(i) The reaction in which it occurs should be reversible
(ii) The reaction should occur in a closed system
(iii) Temperature should be constant
(iv) Rate of forward reaction should be equal to the rate of backward reaction
Reversible and irreversible reactions

A reversible reaction is a reaction takes place in both forward and backward directions
such that both the reactants and products are present in the equilibrium hence does not
go to completion.
For example;
(i) the reaction between hydrogen gas and gaseous iodine to form hydrogen iodide
(ii) the esterification reaction for formation of ethylethanoate from ethanoic acid
and ethanol
(iii) reaction between heated iron and steam to form iron(II) diiron(III) oxide and
hydrogen
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468
An irreversible reaction is a reaction takes place only in the forward direction, such
that only the products are formed during the reaction hence the reaction can never be
at equilibrium.
(i) For example, the combustion of ethene to form carbon dioxide and water
+
(ii) Burning magnesium in air to form magnesium oxide
(iii) Alkaline hydrolysis of an ethylethanoate to form ethanoate ions and ethanol

̅ ̅
Dynamic equilibrium
A dynamic equilibrium is the equilibrium established when the rate of forward reaction
is equal to the rate of backward reaction, such that the concentration of reactants and

products remains constant.
For the reaction between known amounts of hydrogen and iodine in a sealed glass tube
heated to a higher constant temperature and then allowed to cool, the equilibrium mixture
formed contains hydrogen, iodine and hydrogen iodide.
This implies that both forward and backward reactions are still taking place and the rate
of formation of hydrogen iodide is equal to rate of dissociation of hydrogen iodide and
the concentrations of each species remains constant and the system is said to be in
dynamic equilibrium.
This can be proven by injecting iodine containing a small quantity of radioactive iodine-
131 into the equilibrium mixture. Radioactive iodine appears in the hydrogen iodide. This
confirms that both forward reaction and backward reaction are still occuring.
Types of chemical equilibria

There are two types equilibrium systems namely;
(i) Homogeneous equilibrium systems

(i) Heterogeneous equilibrium systems
A homogeneous equilibrium system is one in which all the reactants and products of a
reaction are in the same phase.
They can all gases, all liquids or all in solution.
For example;
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469
(i) the reaction between ethanol and ethanoic acid to form ethyl ethanoate
/diethyl ether (esterification)
(ii) the reaction between hydrogen gas and gaseous iodine to form hydrogen
iodide
(iii) Dissociation of dinitrogen tetroxide to form nitrogen dioxide.
A heterogeneous equilibrium system is one in which two or more phases are involved.
For example;
(i) Dissociation of calcium carbonate to form calcium oxide and carbon
dioxide.
(ii) Reaction between iron and steam to form triiron tetraoxide and hydrogen

(iii) Reaction between bismuth chloride and water to form bismuth oxychloride
and hydrochloric acid
Note; if only ions are involved in an equilibrium, an ionic equilibrium (check next
chapter) is established.
THE LAW OF MASS ACTION OR EQUILIBRIUM LAW

For a homogeneous equilibrium, represented as;
[ ] [ ]
[ ] [ ]
Where [ ] represents molar concentration at equilibrium and
is the concentration equilibrium constant
The equilibrium law/ law of mass action therefore states that if a reversible reaction is
allowed to reach equilibrium at a particular temperature, the product of the molar
concentrations of the products raised to appropriate powers divided by the product of
the molar concentrations of the reactants raised to appropriate powers is a constant
or
|
470
The law of mass action states that the in a reversible reaction, there is a fixed
relationship at a given temperature between the molar concentrations of the products
and those of the reactants in the equilibrium mixture.
The concentration equilibrium constant,

Equilibrium constant is the ratio of the product of molar concentration of products
raised to their appropriate powers to the product of molar concentration or reactants
raised to their appropriate powers in a stoichiometric equation of a reversible reaction
at constant temperature.
The pressure equilibrium constant,

For reactions involving gases, it is often more convenient to measure and express the gas
concentrations in partial pressures in atmospheres. If this is done, the equilibrium
constant is known as
For example;

Using the law of mass action to write equilibrium constant
expressions ( or ) and units
When writing expressions for equilibrium constants, the following should be noted;
1. Check whether only the concentrations /moles in a given volume are given or total
pressure at equilibrium
2. If only concentration/ moles are given, then an expression for should be written.
3. If total pressure at equilibrium is given, then expression for should be written.
4. Solids do not appear in the equilibrium constant expression since their concentration
is assumed to be constant.
5. For a expression, only gaseous reactants and products appear.
6. If water is one of the reactants, and its concentration is not given, or remains
unchanged, it is assumed to be present in a large excess hence does not appear in the
equilibrium constant expression. If water is in gaseous state, then include it in the
expression.
7. When only the expression is required, do not write the equation also as part of the
answer
8. In the case of , strictly square brackets must be used.
9. Sometimes the question may specify for you whether to write a or expression.
|
471
In each of the cases below, write the equation for the equilibrium, the equilibrium
constant expression in terms of either and or both , depending on what is
indicated in brackets and state the units.
1. Reaction between ethanol and ethanoic acid in presence of an acid catalyst ( )

2. The reaction between hydrogen gas and gaseous iodine.(both and )
3. Dissociation of dinitrogen tetroxide to form nitrogen dioxide.(both and )
4. Reaction between iodine solution and potassium iodide.( )
5. Thermal dissociation of calcium carbonate.(both and )
6. Reaction between iron and steam to form triiron tetraoxide and hydrogen .
(both and )
7. Hydrolysis of bismuth(III) chloride.( )
8. Reaction between hydrogen and nitrogen.(both and )
9. Hydrolysis of ethylethanoate using dilute hydrochloric acid.( )

10. Reaction of phosphorus trichloride and chlorine.(both and )
11. Reaction between nitrogen and oxygen.(both and )
12. Conversion of Sulphur dioxide to Sulphur trioxide.(both and )
13. Reaction between carbon monoxide and hydrogen to form gaseous methanol.(both
and )
14. Dissociation of hydrogen iodide.(both and )
15. Dissociation of phosphorus(V) chloride to phosphorus(III) chloride and
chlorine.(both and )
16. Dissociation of Sulphur trioxide.(both and )
17. Reaction between carbon disulphide and hydrogen to form methane and hydrogen
sulphide. .(both and )
18. Reaction between ammonia and oxygen to form nitrogen monoxide and water. (both
and )
19. Redox reaction between iron metal and chromium(III) ions. ( )
20. Hydrogenation of nitrogen dioxide to form ammonia and water.(both and )
|
472
The relationship between and

is related to by the expression;
where is the pressure equilibrium constant

is the concentration equilibrium constant
is the molar gas constant
is the absolute temperature(K)
is the difference between total moles of gaseous products and total
moles of gaseous reactants
Derivation;
Consider a reversible reaction;
[ ] [ ]

[ ] [ ]
If the reactants and products are gaseous,
If the gases are ideal, then according to the ideal gas equation
is therefore proportional to
From equation , [ ]
[ ]
[ ]
[ ]
Substituting for , and in equation (ii) gives;
[ ] [ ]
[ ] [ ]
[ ] [ ]
( )
[ ] [ ]
[ ] [ ]
Since [ ] [ ]
|
473
Where is the total number of moles of gaseous products total number of moles of gaseous
reactants in a balanced equation.
EXPERIMENTS ON CHEMICAL EQUILIBRIUM

(a) Experiment to determine the equilibrium constant for the hydrolysis of
ethylethanoate using hydrochloric acid.
A known amount of ethylethanoate (a moles) is mixed with a known amount of water (b
moles)
A known volume of concentrated hydrochloric acid is added to catalyze the reaction.
The mixture is kept in a sealed glass tube at a constant temperature for a week.
The tube is broken in cold water and the solution titrated with a standard solution of
sodium hydroxide using phenolphthalein indicator

The amount of ethanoic acid present at equilibrium is obtained (x moles)
Let V be the volume of the solution in dm3
If there are x moles of ethanoic acid at equilibrium, there are also x moles of ethanol at
equilibrium since mole ratio of
Moles of ester hydrolysed and moles of water used are both equal to x, since mole ratio
is also 1:1
Initial moles 0 0
Moles reacted/formed
Moles at equilibrium
concentration
[ ][ ]
[ ][ ]
⁄ ⁄
(( )( ))
|
474
(b) Experiment to determine the equilibrium constant for the esterification reaction
between ethanoic acid and ethanol
A known amount of ethanoic acid (a moles) is mixed with a known amount of ethanol
(b moles) and put in a sealed glass tube.
The sealed tube and its contents is left in a water bath at to for 7 hours
The tube is broken in cold water and the solution titrated with a standard solution of
sodium hydroxide using phenolphthalein indicator
The amount of ethanoic acid present at equilibrium is obtained (x moles)

Let V be the volume of the solution in dm3

moles of ethanoic acid at equilibrium=x
moles of ethanoic acid converted to ester and water =(a-x)
since mole ratio of

(a-x) moles of form (a-x) moles of and (a-x) moles
of at equilibrium.
Since mole ratio of
Moles of ethanol that react=(a-x)
Moles of ethanol at equilibrium=b-(a-x) =(b-a+x)
Initial moles 0 0
Moles reacted/ formed
Concentration
[ ][ ]
[ ][ ]
( )( )
(( ) ( ))
|
475
(c) Experiment to determine the equilibrium constant for the dissociation of

hydrogen iodide to hydrogen and iodine.
A known amount of hydrogen iodide (n moles) is put in a sealed glass bulb of a fixed
volume (v dm3) and kept in a thermostat at a temperature of ℃ until equilibrium is
established.
At equilibrium, the bulb is removed and rapidly cooled to stop the reaction and fix the
equilibrium such that the equilibrium does not adjust itself to the equilibrium value at a
lower temperature.
The tube is then broken under an aqueous solution of potassium iodide to dissolve the
iodine present at equilibrium.
The resultant mixture is titrated with a standard solution of sodium thiosulphate using
starch indicator
The amount of iodine present at equilibrium is obtained.

Total volume of the bulb= v dm3

Number of moles of hydrogen iodide heated= c moles
Degree of dissociation of hydrogen iodide= α
Initial moles 0 0
Moles dissociated/formed
Concentration at equilibrium
[ ][ ]
[ ]
( )
( )
|
476
(d) Experiment to determine the equilibrium constant for the reaction between
hydrogen and iodine to form hydrogen iodide.
A known amount of hydrogen (a moles) and a known amount of iodine (b moles) are
put in a sealed glass bulb of a fixed volume (v dm3), kept in a thermostat at a
temperature of ℃ until equilibrium is established.
At equilibrium, the bulb is removed and rapidly cooled to stop the reaction and fix the
equilibrium such that the equilibrium does not adjust itself to the equilibrium value at a
lower temperature.
The tube is then broken under an aqueous solution of potassium iodide to dissolve the
iodine present at equilibrium.
The resultant mixture is titrated with a standard solution of sodium thiosulphate using
starch indicator
The amount of iodine present at equilibrium is obtained.

Total volume of the bulb= v dm3

Let number of moles of iodine converted to hydrogen iodide= x moles
Moles of hydrogen iodide formed = 2x moles
Initial moles 0
[ ]
[ ][ ]
( )
( )( )
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477
CALCULATIONS INVOLVING CONCENTRATION

EQUILIBRIUM CONSTANT AND PRESSURE EQUILIBRIUM
CONSTANT
(a) Equilibria for esterification.
Examples
1. When 60g of ethanoic acid were heated with 46g of ethanol until equilibrium was
established, 12g of water and 58.7g of ethylethanoate were formed. Calculate;
(a) the equilibrium constant for the reaction
(b) the mass of ethylethanoate that would be formed under the same conditions if
90g of ethanoic acid and 92g of ethanol were heated.
(a)

Initial moles 0 0
[ ][ ]
[ ][ ]
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478
(b)
Initial moles 0 0
Moles reacted/
formed
[ ][ ]
[ ][ ]

2. A 10.0 mixture initially contained 0.0515 moles of ethanol, 0.0525 moles of
ethanoic acid, 0.0314 moles of ester, 0.0167 moles of water and 0.001 moles of
hydrochloric acid. If at equilibrium 0.0255 moles of ethanoic acid were found.
Calculate the equilibrium constant for the reaction.
Hydrochloric acid is simply added to catalyse the reaction
Initial moles
Moles reacted/
formed
Moles at
equilibrium
[ ][ ]
[ ][ ]
3. 1 mole of ethanoic acid was mixed with 5 moles of ethanol in a sealed glass tube
left in a water bath at for some hours. The tube was then broken in cold
water and the resultant solution required 289 of 0.2 M sodium hydroxide for
complete neutralisation. Calculate the equilibrium constant, for the reaction.
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479
( )
Initial moles 0 0
[ ][ ]

[ ][ ]
(b) Equilibria involving hydrogen, iodine and hydrogen iodide.

NOTE: All dissociations will be treated in terms involving degree of dissociation for
calculations.
The degree of dissociation is the fraction or percentage of the original
undissociated molecules which have dissociated.
Examples
1. (a) 3 moles of hydrogen and 1 mole of iodine were heated together in a sealed
tube at 500oC until equilibrium was established. Calculate the number of moles
of hydrogen iodide present in the equilibrium mixture at 500oC. (The equilibrium
constant , for the reaction between hydrogen and iodine is 50)
(b) Describe briefly how the concentration of iodine at equilibrium can be
obtained.
Initial moles 0
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480
[ ]
[ ][ ]
√ Moles of hydrogen iodide at equilibrium
(b) The tube is broken under an aqueous solution of potassium iodide to dissolve the iodine present
at equilibrium.
The resultant mixture is titrated with a standard solution of sodium thiosulphate using starch
indicator. The amount of iodine present at equilibrium is calculated using the equation below.

2. (a) State three characteristics of a chemical equilibrium.
(b) 25 moles of hydrogen and 18 moles of iodine vapour were heated in a 1 litre
sealed tube at 465 oC. When equilibrium was attained, the tube was rapidly
cooled and found to contain 30.8 moles of hydrogen iodide.
(i) Give a reason why the tube was rapidly cooled.
(ii) Calculate the value of the equilibrium constant for the reaction taking
place in the flask and the degree of dissociation of hydrogen iodide.
(b) (i) Tube is rapidly cooled to stop the reaction and fix the equilibrium such that the
equilibrium does not adjust itself to the equilibrium value at a lower temperature.
Initial moles 0
[ ]
[ ][ ]
[ ]
[ ]
[ ]
Note that for the dissociation of HI is the reciprocal of for reaction between
hydrogen and iodine to form HI
For dissociation of hydrogen iodide,
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481
Initial moles 0 0
[ ][ ]
[ ]
( )
( )
√

3. When stoichiometric amounts of hydrogen and iodine were allowed to reach
equilibrium in a 1 litre vessel at 450 oC and , 1.56 moles of
hydrogen iodide were formed at equilibrium. Calculate the equilibrium constant
, .
Note that stoichiometric amounts mean amounts of moles as shown by the balanced equation
Initial moles 0
( )
( )
( )
|
482
4. The equilibrium constant for the dissociation of hydrogen iodide is 0.02. 1 mole
of hydrogen and moles of iodine are heated together at 450 oC. Calculate the
mass of hydrogen iodide present in the equilibrium mixture at that temperature.
Initial moles 0
[ ]
[ ][ ] ( )

( )
5. 1g of hydrogen and 127g of iodine are allowed to attain equilibrium in an

evacuated container of volume 10 at a temperature of 450 oC. If the
equilibrium constant at the same temperature, is 50. Calculate the;
(i) the value of
(ii) the total pressure in the container
(iii) the partial pressure of hydrogen in the container
(i)
Initial moles 0
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483
(ii)
[ ]
(iii)
[ ][ ]
( )
( )
√
6. 3.20g of hydrogen iodide were heated at 450 oC in a glass bulb of volume 800cm3.

When equilibrium was attained, the bulb was rapidly cooled to room
temperature and then broken under a solution of potassium iodide. The iodine
formed required 36.0 cm3 of a 0.2M sodium thiosulphate solution in the presence
of starch indicator for complete reaction.
(i) Explain why the bulb broken under potassium iodide solution
(ii) Calculate the equilibrium constant for the reaction at 450 oC
(i) The bulb is broken under an aqueous solution of potassium iodide to dissolve
the iodine present at equilibrium.
(ii)
( )
( )
Initial moles 0 0
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484
[ ] ( )
[ ] ( )
[ ][ ]
[ ] [ ]
( )
Note: The volume was given in .
Multiplying moles in 800 by 1000
converts the concentration to moles per litre
7. The degree of dissociation of 0.5 moles of hydrogen iodide was found to be 25%
at a certain temperature in a 1.5 vessel. Calculate the equilibrium
constant,
Initial moles 0 0

( )
( )
( )
(( ) )
(( ) )
(c) Equilibria involving hydrogen, nitrogen and ammonia.

Examples
1. Nitrogen reacts with hydrogen according to the following equation
(a) Write expression for equilibrium constant,

(b) Stoichiometric amounts of nitrogen and hydrogen were reacted in a 2 litre
vessel. At equilibrium, 0.8moles of ammonia was formed. Calculate:
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485
(i) the amount of hydrogen at equilibrium.

(ii) the value of equilibrium constant, .
[ ]
(a) ]
[ ][
Initial moles
[ ] ( )
[ ] ( )
[ ]
[ ][ ]

[ ] ( )
2. 0.8 moles of nitrogen and 0.9 moles of hydrogen were heated in a 1500 closed
vessel. At equilibrium, the mixture contained 20% hydrogen. Find the value of
equilibrium constant, .
Initial moles
[ ] ( )
( ) [ ] ( )
[ ] ( )
[ ]
[ ][ ]
|
486
3. When 3 moles of hydrogen and 1 mole of nitrogen were mixed and allowed to
attain equilibrium at 100 atm and 400oC, the equilibrium mixture contained
25% of ammonia by volume. Calculate;
(i) Number of moles of nitrogen and hydrogen at equilibrium.
(ii) Value of at 400oC
Initial moles
( ) ( )
( )

( )
(ii) ( )
( )
4. Ammonia dissociates according to the following equation
Calculate the equilibrium constant, for the reaction given 3.0 moles of ammonia
were found to be 15% dissociated.
Initial moles
( )
[ ]
[ ]
[ ]
[ ][ ]
[ ]
|
487
5. 1.75 moles of ammonia were heated in a 1 litre vessel and the equilibrium
mixture was found to contain 42.9% hydrogen. Calculate the equilibrium
constant, .
Initial moles
( )

[ ] [ ]
[ ]
[ ][ ]
[ ]
(d) Equilibria involving phosphorus, chlorine and phosphorus(V) chloride

Examples
1. Phosphorus(V) chloride dissociates at high temperatures according to the
equation
83.4 g of phosphorus(V) chloride were placed in a vessel of 9.23 .At equilibrium

at a certain temperature, 11.1g of chlorine were formed at a total pressure of
.
(a) Calculate the number of moles of phosphorus(V) chloride and chlorine in the
vessel at equilibrium.
(b) Determine the equilibrium constant, , for the reaction and state its units.
(c) Calculate the value of the equilibrium constant, , for the reaction and state
its units.
|
488
(a)
Initial moles
[ ] ( )

[ ] ( )
[ ]
[ ][ ]
(b) [ ]
(c)
( )
( )
( )
2. 1.0 mole of phosphorus(V) chloride was strongly heated in a one litre closed
bulb until equilibrium was obtained. The glass bulb was then rapidly broken
under potassium iodide solution. The bulb was found to contain 40.70% of
chlorine.
(a) Write equations for the reactions that took place when:
(i) the glass bulb was strongly heated
(ii) the glass bulb was broken under potassium iodide solution.
(b) State the reasons why the bulb;
|
489
(i) was rapidly broken

(ii) was broken under potassium iodide solution
(c) Determine the;
(i) degree of dissociation of phosphorus(V) chloride
(ii) equilibrium constant for the reaction.
(a) (i)
(ii)
(b) (i) Bulb was rapidly broken to stop the reaction and fix the equilibrium such that
the equilibrium does not adjust itself to the equilibrium value at a lower
temperature.
(ii) Bulb is broken under potassium iodide to dissolve and oxidise chlorine
present at equilibrium to chloride ions as the potassium iodide is reduced to
iodine.
(c) (i)

Initial moles
[ ]
[ ]
[ ][ ]
[ ]
[ ]
3. 2.085g of phosphorus(V) chloride was heated in a 1 litre vessel until equilibrium

was attained. The vessel was then broken under excess potassium iodide
solution. The iodine liberated required 40 of 0.1M sodium thiosulphate
solution. Calculate the equilibrium constant, , for the reaction.
|
490
( )
( )
Initial moles

[ ]
[ ]
[ ][ ]
[ ]
[ ]
4. 2.00 g of phosphorus(V) chloride were allowed to reach equilibrium at 200 oC in

a capacity vessel. If the equilibrium constant of the above reaction is
at this temperature and in the conditions stated. Calculate the
percentage dissociation of phosphorus pentachloride at equilibrium.
Initial moles
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491
[ ]
[ ] √
[ ]
[ ][ ]
[ ]
5. 3.6 moles of phosphorus(V) chloride in a vessel of volume 2 litres was found to

be 38% dissociated. Calculate the equilibrium constant, , for the reaction.
Initial moles

[ ] ( )
[ ] ( )
[ ]
[ ][ ]
[ ]
6. Calculate the percentage of chlorine is the equilibrium mixture formed when 0.4
moles of phosphorus(V) chloride were heated in a one litre
vessel .
Initial moles
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492
[ ]
[ ] √
[ ]
[ ][ ]
[ ]
( )
(e) Equilibria involving sulphur trioxide, sulphur dioxide and oxygen

Examples
1. At 700ºC, and total pressure of 1.0 atm, the partial pressure at equilibrium for

sulphur dioxide and oxygen are 0.27 and 0.41 atm respectively. Calculate the
equilibrium constant, for the reaction.
( )
( )
2. 0.425 moles of sulphur dioxide and 0.294 moles of oxygen were heated in a 1.6
litre vessel and at equilibrium, it was found that 52% of oxygen had reacted.
Calculate the value of equilibrium constant, .
Initial moles
[ ] ( )
[ ] ( )
[ ] ( )
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493
[ ]
[ ] [ ]
3. 1 mole of sulphur trioxide was introduced into a vessel. The vessel was
heated to 1000K until equilibrium was attained. At equilibrium, 0.35 moles of
sulphur trioxide was present.
(i) Write equation for the dissociation of sulphur trioxide.
(ii) Write an expression for the equilibrium constant, .
(iii) Calculate the value of .
(i)
[ ] [ ]
(ii)

[ ]
Initial moles
[ ] [ ]
[ ]
[ ] [ ]
[ ]
(f) Examples involving other equilibria systems

1. Dinitrogen tetroxide and nitrogen dioxide exist in the following equilibrium.
When 11.04g of dinitrogen tetroxide were placed in a vessel of volume at a

fixed temperature, 5.52g of nitrogen dioxide were produced at equilibrium under a
pressure of 100kPa. Calculate the:
(a) equilibrium number of moles of each gas
(b) equilibrium constant, .
(c) equilibrium constant,
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494
(a)
Initial moles
(b) [ ]
[ ]
[ ]
[ ]

(c) ( )
2. For the following gas equilibrium, at 333K, the

equilibrium constant, is 1.33 atmospheres. Calculate the degree of
dissociation of one mole of dinitrogen tetraoxide at 333K if the total pressure of
the system is 2 atmospheres.
Initial moles
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495
( ) ( )
( )
( )
3. When heated, carbon dioxide dissociates according to the equation:
If at a certain temperature and a pressure of one atmosphere, 60% of the original

carbon dioxide remained undissociated. Calculate the equilibrium constant for
the reaction.
Initial moles
( )
( )
4. Nitrogen monoxide reacts with oxygen according to the reaction:
At equilibrium, the equilibrium constant is at a given temperature in

a container of volume, . The equilibrium mixture was found to contain
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496
0.0148 moles of oxygen. Calculate the ratio of [ ] to [ ] in the equilibrium

mixture.
Moles at equilibrium ?
[ ]
[ ] ( )
[ ]
[ ] [ ] [ ]
√
[ ]
[ ] [ ]
[ ] [ ] [ ]
[ ] [ ]
[ ]
[ ] [ ]

5. For the equilibrium system below:
(a) Write the expression for the equilibrium constant, .

(b) When 1 mole of steam and 1 mole of carbon monoxide are allowed to reach
equilibrium, 33.3% of the equilibrium mixture is hydrogen. Calculate the
value of and state its units.
Initial moles
Let the total pressure be P |
497
6. Methane reacts with steam according to the equation
When 0.18 moles of methane and 0.22 moles of steam were heated in a 5 litre vessel,
0.1 mole of carbon dioxide was found to be present at equilibrium. Calculate the
value of .
Initial moles
[ ] ( )
[ ] ( )
[ ] ( )

[ ] ( )
[ ][ ]
[ ][ ]
7. Sulphoryl dichloride dissociates when heated according to the following

equation:
When 67.5g of Sulphoryl dichloride was heated in a 1 litre vessel at 120ºC and 3.6
atmospheres, it was found that at equilibrium, 45% of it had dissociated.
(i) Write the expression for the equilibrium constant, .
(ii) Calculate the number of moles of each substance present at equilibrium.
(iii) Calculate the equilibrium constant, .
(i)
(ii)
Initial moles
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498
(iii)
[ ]
[ ]
[ ]
[ ][ ]
[ ]
8. The equilibrium constant, for the reaction below at ℃ is

:
Calculate the:
(i) total pressure of the system at equilibrium.

(ii) degree of dissociation of ammonium hydrogen sulphide

Initial moles
( )
√
Let the total pressure at equilibrium be P
From
Since
( )
499
General questions involving calculations on chemical equilibria

1. When 3.12g of ethanoic acid and 2.07g of ethanol were reacted in a 1 litre closed
vessel at 50ºC. 0.36g of water was found at equilibrium. Calculate the value of
equilibrium constant for the reaction, .
2. When 8.28g of ethanol were heated with 60g of ethanoic acid, 49.74g of the acid
remained at equilibrium. Calculate the;
(i) value of the equilibrium constant, .
(ii) mass of ester present in the equilibrium mixture formed from 13.8g of ethanol
and 12g of ethanoic acid.
3. When equimolar quantities of ethanoic acid and ethanol were heated, one third of
each reactant remained at equilibrium. Calculate the equilibrium constant for the
reaction
4. 1 mole of ethanol was reacted with 2 moles of ethanoic acid at ℃. If the
equilibrium constant for the reaction at the same temperature is 4. Calculate the mass
of ethylethanoate in the equilibrium mixture.

5. 5moles of ethanol, 6 moles of ethanoic acid, 6 moles of ethylethanoate and 4moles of
water were mixed together in a stoppered bottle at 15℃. At equilibrium, the bottle
was found to contain 4 moles of ethanoic acid.
(a) (i) Write an equation for the reaction between ethanol and ethanoic acid to form
ethylethanoate and water.
(ii) Suggest a mechanism for the reaction
(b) Write an expression for the equilibrium constant, for this reaction
(c) Determine the number of moles of ethanol, ethylethanoate and water present in
the equilibrium mixture hence the value of for this reaction
(d) If 1moleof ethanol, 1mole of ethanoic acid, 3 moles of ethylethanoate and 3 moles
of water are mixed together in a stoppered flask at 15℃. Determine the number of
moles of each compound present in the equilibrium mixture.
6. 3.0g of ethanoic acid and 2.3g of ethanol were equilibrated at 100℃ for an hour and
then quickly cooled in an ice bath. 50 of 1.0 M sodium hydroxide solution were
added. When the mixture was titrated with 1.0M hydrochloric acid, 33.3 of the
acid were required for complete reaction.
(a) Explain why the mixture was cooled in an ice bath.
(b) Calculate the equilibrium constant, for the reaction.
7. 4.6g of ethanol and 12.0g of ethanoic acid were mixed in a stoppered flask with
20 of 1M hydrochloric acid as catalyst at 20℃. The mixture was left for a week to
attain equilibrium, and then titrated with 137 of 1.0M sodium hydroxide. (Of the
total volume of base used, only 20 were used to react with hydrochloric acid)
(a)Work out the concentrations of the equilibrium mixture
(b) Calculate the value of equilibrium constant, .
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500
8. When 60g of ethanoic acid and 46g of ethanol were made to react to equilibrium at
100ºC, the percentage of esterification was
(i) Write equation for the esterification reaction.
(ii) Calculate the value of the concentration equilibrium constant, .
(iii) Outline the mechanism for the reaction between ethanoic acid and ethanol.
9. When 6.22 of hydrogen were heated with 5.71 of iodine in a sealed tube at
o
356 C, it was found out that 9.60 of hydrogen iodide were present at
equilibrium. Calculate the:
(i) equilibrium constant
(ii) volume of hydrogen iodide in the equilibrium mixture formed by reacting
together 6.41 of hydrogen and 10.40 of iodine at 356 oC.
( Hint: Number of moles of a gas is directly proportional to volume)
10. A mixture of 0.8 mole of hydrogen and 0.6 mole of iodine was allowed to react in a
sealed tube at 450ºC. At equilibrium, 0.2 mole of iodine had reacted.
(i) Write an expression for the equilibrium constant, , for the reaction

(ii) Calculate the value of , at 450ºC.
11. Hydrogen reacts with iodine according to the equation
(a) Calculate the equilibrium concentration of each of the following when:

(i) 0.2 mole of iodine and 0.3 moles of hydrogen are reacted in a one litre
vessel.
(ii) 0.5 mole of iodine and 0.8 mole of hydrogen are reacted in a 4 litre vessel
(b) Equimolar quantities of hydrogen and iodine were heated in a 1 litre vessel until
equilibrium was attained. The equilibrium mixture was found to contain 20.5%
hydrogen iodide Determine the equilibrium constant, .
12. (a) State the law of mass action
(b) Explain what is meant by the following terms:
(i) equilibrium constant
(ii) dynamic equilibrium
(c) Describe an experiment to determine the equilibrium constant for the reaction
between hydrogen and iodine
(d) 1.54g of hydrogen iodide were heated in a 600cm3 bulb at 530 oC. When equilibrium
was attained, the bulb was rapidly cooled to room temperature and broken under
potassium iodide solution. The iodine formed required 67 cm3 of 0.1M sodium
thiosulphate solution for complete reaction. Calculate ;
(i) Number of moles of hydrogen iodide in 1.54g
(ii) Number of moles of iodine formed
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501
(iii) Value of at 530 oC

13. 1.0g of hydrogen iodide was heated to a certain temperature in a sealed vessel and the
products rapidly cooled. The iodine which had been liberated required 15.0 of
0.1M sodium thiosulphate for complete reaction. Calculate the percentage by mass of
hydrogen iodide which remained undissociated at that temperature.
14. (a) 3.4 moles of hydrogen iodide at 460ºC are found to be 20% dissociated. Calculate
the:
(i) number of moles of hydrogen iodide, hydrogen and iodine formed at
equilibrium
(ii) equilibrium constant for the dissociation reaction.
(b) A mixture containing 28 moles of hydrogen and 22 moles of iodine was heated in
a sealed tube at 460 ºC until equilibrium was attained and 36 moles of hydrogen
iodide was obtained. Calculate the degree of dissociation of hydrogen iodide at
460ºC
15. (a)The equilibrium constant for the dissociation of hydrogen iodide into hydrogen and

iodine is 0.02. Calculate the equilibrium composition of the following if they are
heated.
(i) 0.05 mole of hydrogen iodide.
(ii) 0.2 mole of hydrogen iodide.
(b) When 0.4 mole of hydrogen iodide was heated to equilibrium, it dissociated.
Determine the degree of dissociation of hydrogen iodide, given that the
equilibrium constant is 0.025
16. (a) 1 mole of hydrogen iodide gas at 25 was introduced into a container of volume
20 litres. Calculate the pressure of the gas assuming ideal behaviour.( 1 mole of an
ideal gas occupies 22.4 litres under standard conditions)
(b) The sample of hydrogen iodide, considered above was raised to a temperature of
300 and it partially dissociated into hydrogen and iodine. At equilibrium, 1 mole of
iodine was found to be present.
(i) Write an equation for the dissociation
(ii) Calculate the pressure of the equilibrium mixture at 300 assuming no change in
volume.
(iii) Calculate the equilibrium constant at 300
17. Derive an expression for the equilibrium constant for the reaction;
in terms of and , where and are the original number of moles of hydrogen
and nitrogen respectively, and is the number of moles of nitrogen which react at a total
pressure of Pa.
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18. When 0.2 moles and 0.47 moles of nitrogen and hydrogen respectively were heated to
equilibrium in a 1 litre vessel, 0.18 moles of ammonia were formed. Calculate the
19. When 1.65 moles of hydrogen and 0.6 moles of nitrogen were heated to 150ºC in a
1.5 litre closed vessel, equilibrium was attained when 0.9 moles of ammonia were
formed. Calculate the value of equilibrium constant, for the reaction.
20. Nitrogen and hydrogen are mixed in a ratio 1:3. At equilibrium at 600OC and 10
atmospheres, the percentage of ammonia in the mixture of gases is 15%
(a) Write equation for the reaction
(b) Write an expression for the equilibrium constant.
(c) Calculate the equilibrium constant at that temperature and state its units.
21. Stoichiometric amounts of hydrogen and nitrogen were reacted at 50 atm. At
equilibrium, 0.8 moles of ammonia were formed. Calculate:
(i) Amount of hydrogen and nitrogen present at equilibrium

(ii) Value of the equilibrium constant
22. (a) For the reaction,
Calculate the molar percentage of ammonia in the equilibrium mixture formed at

o 7
400 C and at a pressure of 3 × 10 Pa, when gaseous hydrogen and nitrogen are mixed in
a 3:1 ratio and there is 61% conversion of nitrogen to ammonia.
(b) (i) Determine the equilibrium constant, of the reaction.
(ii) Given that the value of at a given temperature is ,
calculate the pressure at which ammonia is 95% dissociated into its elements
at that temperature.
23. (a) Write equation for the reaction leading to formation of ammonia
(b) The value of the pressure equilibrium constant, for the reaction in (a) above is
at 500℃ . Calculate the percentage of a 1:3 mixture of
nitrogen and hydrogen that would be converted to ammonia at 500 atmospheres.
24. (a) Write an equation for the reaction between hydrogen and nitrogen.
(b) At 500 oC, the equilibrium concentration of hydrogen is 0.250 moll-1 and that of
nitrogen is 2.7 moll-1 Calculate the equilibrium concentration of ammonia at the same
temperature given that at 500 oC.
25. When nitrogen was reacted with hydrogen at 690K, the total pressure of the system at
equilibrium was 32 atmospheres and the partial pressures of hydrogen and nitrogen
were 8 and 3 atmospheres respectively. Calculate the:
(i) partial pressure of ammonia in equilibrium mixture.
(ii) equilibrium constant for the reaction
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26. At a certain temperature, the equilibrium constant for the reaction between nitrogen
and hydrogen, , is and the partial pressures of nitrogen and
hydrogen are 30 and 120 atm respectively.
(ii) Calculate the partial pressure of ammonia at equilibrium.
27. When 80.4 g of phosphorus(V) chloride were placed in a 9.0 litre vessel and heated
at a certain pressure, 8.4 g of chlorine were formed at equilibrium. Calculate the:
(i) amount of phosphorus(V) chloride and phosphorus(III) chloride at
equilibrium in moles per litre.
(ii) equilibrium constant, , for the reaction and state its units.
28. (a) When 2.6 mole of phosphorus(V) chloride was heated in a 1.5 vessel,
equilibrium was established when 1.04 mole of phosphorus(III) chloride was formed.
(b) 3.0 mole of phosphorus pentachloride was heated in a 1 litre vessel and when
equilibrium was attained, it was found to contain 1.14 mole of chlorine gas.

Determine the value of equilibrium constant, .
29. 75.06g of phosphorus(V) chloride were heated to 200ºC in a vessel of volume
1000 at a pressure of 170kPa. Calculate the;
(a) degree of dissociation of phosphorus(V) chloride
(b) value of equilibrium constant, , at 200ºC
30. 0.2 moles of phosphorus pentachloride were heated at 500K in 5 litre flask. At
equilibrium, 60% of phosphorus pentachloride was found to have dissociated and the
total pressure was found to be 300mmHg.
(a) Calculate the equilibrium constant, .
(b) What will be the total pressure if phosphorus pentachloride dissociated only by
35%
31. When 2.4 moles of phosphorus pentachloride were heated in a 1.5 vessel and at
equilibrium, it was found to contain 23.53% phosphorus trichloride.
(a) Write equation for the dissociation of phosphorus pentachloride
(b) Write the expression for the equilibrium constants, , and , for the reaction.
(c) Determine the value of equilibrium constant, .
32. (a) 2.6 mole of phosphorus pentachloride was heated in a 500 closed vessel. At
equilibrium, it was found to contain 1.04 mole of phosphorus trichloride. Determine
the value of equilibrium constant, .
(b) 3.0 mole of phosphorus pentachloride was heated in a 750 vessel until
equilibrium was established. The vessel contained 1.14 moles of chlorine.
Determine the value of equilibrium constant, .
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33. Determine the mass of each of the components of the equilibrium mixture formed
when 0.52 moles of phosphorus(V) chloride is heated at equilibrium.
34. 0.04 moles of sulphur trioxide were allowed to dissociate at 900K in a flask of volume
3.04 litres. At equilibrium, 0.0289 moles of sulphur trioxide were found to be present.
(i) Derive the relationship between and for this reaction. Show clearly how
you arrive at your answer.
(ii) Calculate equilibrium constants and .
35. At 700℃ and total pressure of one atmosphere, the partial pressures at equilibrium for
sulphur dioxide and oxygen are 0.27 and 0.41 atmospheres respectively. Sulphur
dioxide is oxidized to sulphur trioxide according to the following equation:
Calculate the equilibrium constant, , for the reaction

36. When 0.6 and 0.425 moles of sulphur dioxide and oxygen respectively were reacted
in a 1litre vessel to equilibrium, the equilibrium mixture contained 18.75% sulphur

dioxide. Calculate the equilibrium constant value, .
37. Dinitrogen tetraoxide dissociates at 40 oC and 1 atm according to the following
equation.
(i) Write an equation for the equilibrium constant , .

(ii) Draw a well labelled energy level diagram for the reaction in (i) above
(iii) The reaction mixture of the reaction was found to contain 60% by volume of
nitrogen dioxide at equilibrium. Calculate the equilibrium constant at 40
o
C for the reaction.
38. (a) At 40℃ and under a pressure of 1 atmosphere, dinitrogen tetraoxide contains 60%
by volume of nitrogen dioxide molecules. Calculate the percentage dissociation of
dinitrogen tetraoxide and equilibrium constant in terms of the partial pressures of the
two gases.
(b) Deduce the:
(ii) percentage dissociation of dinitrogen tetraoxide at the same temperature
when the gases are under a pressure of 6 atm.
(iii) the pressure at which dinitrogen tetraoxide would be dissociated to an
extent of 80% at the same temperature.
39. 1 mole of dinitrogen tetra oxide was allowed to dissociate to nitrogen dioxide in a 5
litre flask at 50℃. At equilibrium one mole of nitrogen dioxide was found to be
present. Calculate equilibrium constant for the reaction.
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505
40. Propene reacts with steam according to the following equation.
At a certain temperature and total pressure of 197.38 atmospheres, the equilibrium partial
pressures of propene and steam are 74.02 and 93.76 atmospheres respectively. Calculate
the value of at this temperature and state its units.
41. Nitrogen monoxide combines with oxygen according to the equation
A closed vessel of 500 containing 0.33 moles of nitrogen monoxide and 0.355 moles
of oxygen was heated. Equilibrium was established when 0.105 moles of oxygen had
reacted. Calculate the value of .
42. Carbon monoxide reacts with steam according to the reaction;
When of carbon monoxide were heated with of steam at ℃ until

equilibrium, of carbon dioxide was formed. Calculate the;
(a) volume of carbon monoxide and steam left at equilibrium.
(b) equilibrium constant, .
43. At ℃, the equilibrium constant for the reaction
is 1.4. Calculate the percentage by
volume of the gases in the equilibrium mixture at the same temperature when one
volume of carbon monoxide and two volumes of steam are mixed.
44. Sulphur dioxide dichloride dissociates when heated according to the equation:
When 1.33 moles of sulphur dioxide dichloride were heated in a 2 litre vessel,
equilibrium mixture contained 5.98% sulphur dioxide dichloride. Calculate the value of
45. Ammonium hydrogen sulphide was allowed to dissociated into ammonia and
hydrogen sulphide gases at 500 . At equilibrium the total pressure was measured and
found to be 0.6 atm. Calculate the:
(i) partial pressure of each gas at equilibrium.
(ii) pressure equilibrium constant
Determining equilibrium constants using partition coefficients

Iodine reacts with potassium iodide to form potassium triiodide according to the
equation;
The equilibrium constant for the above reaction is given by the expression below and is
measured by partition method.
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[ ]
[ ][ ]
A known mass of iodine is dissolved in a standard solution of potassium iodide and the
resultant mixture shaken with trichloromethane or trichloromethane or benzene or carbon
disulphide. Some iodine forms a complex with potassium iodide according to the above
equation and some iodine remains free in the solution. The free iodine then distributes
itself between the aqueous layer and the organic solvent used.
Aqueous layer
Trichloromethane layer
The concentration of iodine in the organic layer is obtained by titrating a portion of a
known volume of it with standard sodium thiosulphate solution.
The concentration of free iodine in the aqueous layer is then got from the expression
below, if the partition coefficient value is known;

[ ]
[ ]
[ ] [ ] [ ]
The total concentration of iodine in the aqueous layer, [ ] is obtained by titrating a
portion of a known volume of it with standard sodium thiosulphate solution.
[ ] [ ] [ ]
Since [ ] is known, then [ ] can be obtained.
The total iodide ion concentration in the aqueous layer is obtained from the concentration
of potassium iodide used.
[ ] [ ] [ ]
Since [ ] is known, then[ ] can be obtained and the value of then
determined.
Example
4g of potassium iodide was dissolved in 500 of water and about 1g of iodine was
dissolved in 100 of benzene. The two solutions were then mixed and allowed to
stand. 10 of the benzene layer required 5.1 of 0.1M sodium thiosulphate
solution while 50 of the aqueous layer required 2.9 of 0.1M sodium
thiosulphate solution for complete reaction. The distribution coefficient of iodine
between benzene and water is 130. Calculate the value of the equilibrium constant
for the reaction:
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507
( )
( )
[ ]
[ ]
[ ]
[ ]
( )

( )
[ ]
[ ] [ ] [ ]
[ ] [ ]
[ ]
( )
[ ] [ ] [ ]
[ ]
[ ]
[ ][ ]
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Questions
1. A solution containing 12.7g of iodine and 166.1g of potassium iodide in 1 litre of
water was shaken with 1 litre of benzene. If the partition coefficient of iodine between
benzene and water is 400 and the equilibrium constant for the reaction:
is 730. Calculate the concentration of:
(i) iodine in benzene
(ii) triiodide ions in water
Compare concentration equilibrium constant, and pressure equilibrium
constant,
Concentration equilibrium constant, Pressure equilibrium constant,

It can be measured for any reversible reaction Measured for only reversible reactions involving
gases
Expressed in terms of molar concentrations Expressed in terms of partial pressures
N.B The two equilibrium constants are always the same value at a given temperature for equilibria
where

(
)
Interpretation of magnitude of or in relation to equilibrium

position
Consider the reversible reaction,
The proportion of products to reactants in the equilibrium mixture is described as the
position of the equilibrium.
The magnitude of the equilibrium constant, or indicates the extent to which a
reaction will proceed and the position of the equilibrium.
When or is small (k<1), it implies that the conversion of A and B into C and D is
small and the position of the equilibrium lies to the left.
When or is large(k>1), it implies that the equilibrium mixture is largely
composed of C and D is small and the position of the equilibrium lies to the right.
If K is about 1, the equilibrium is reached at some intermediate mixture.
Comparing the reaction quotient (Q) and to determine direction

of a chemical reaction
The reaction quotient( ) is defined as the ratio of the molar concentrations of the
product species over those of the reactant species involved in the chemical reaction,
taking stoichiometric coefficients of the reaction into account as powers of the
concentrations.
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509
The reaction quotient, Q, has the same mathematical form as the equilibrium-constant
expression, but Q is a ratio of the actual concentrations (not a ratio of equilibrium
concentrations).
For a given reaction,

The reaction quotient is given as;
[ ] [ ]
[ ] [ ]
 At equilibrium, Q , and this is defined as the equilibrium condition.
 If Q, the backward reaction is favoured, the reaction moves from right to left,
until equilibrium is established.
 If Q, the forward reaction is favoured, the reaction moves from left to right,
until equilibrium is established.
Examples
1. In the water–gas shift reaction, carbon monoxide produced by steam-reforming

reaction of methane reacts with steam at elevated temperatures to produce more
hydrogen:
If at 900 K and 0.010 moles of carbon monoxide and 0.010 moles of

water, 0.0080 moles of carbon dioxide, and 0.012 moles of hydrogen are injected into
a 4.0 litre reactor and heated to 900 K, will the reaction proceed to the left or to the
right ?
[ ] [ ]
[ ]
[ ] [ ]
[ ]
[ ]
, the reaction proceeds
[ ] from right to left, until equilibrium is
established.
2. Consider the following reversible reaction; .

At a certain temperature, the partial pressure were measured and found to be
for sulphur trioxide, for sulphur dioxide and for
oxygen. Predict the direction in which the reaction should proceed in order to
attain equilibrium.
( )
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510
( ) , the reaction proceeds

from right to left, until equilibrium is
( ) established.
Questions
1. For the reaction: , the equilibrium constant, , is
at 1500 K. Predict the direction the reaction will move in if the reactants
and products have the following concentrations: [ ] [ ]
, and [ ] .
2. For the reaction: , the equilibrium constant, , is
at 100°C. Predict the direction the reaction will move in if the
concentration of is and the concentration of is
3
3. 1 mole of Sulphur trioxide was introduced into a 1 dm vessel. The vessel was heated

to 1000K until equilibrium was attained. At equilibrium, 0.35 mole of Sulphur
trioxide was present.
(a) Write:
(i) equation for the decomposition of Sulphur trioxide
(ii) an expression for the equilibrium constant,
(b) Calculate the value of .
(c) 0.2 mole of Sulphur dioxide, 0.1 mole of oxygen and 0.7 mole of Sulphur
trioxide, were introduced into the vessel in (a) at 1000K. Calculate the new
value for the reaction.
(d) Using your answers in (b) and (c) above, state how the position of the equilibrium
was affected.
L ́ CHATELIER’S PRINCIPLE AND THE EFFECTS OF

VARIOUS FACTORS ON THE EQUILIBRIUM OF
REVERSIBLE CHEMICAL REACTIONS
L ́ Chatelier's Principle
The principle states that if a system in equilibrium is subjected to any change, the
equilibrium will shift if possible, to a direction which causes an opposite change.
or
If a system in equilibrium is subjected to a constraint, that change takes place which
tends to remove the constraint
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511
The system cannot completely cancel the change in the external factor, but it will move in
a direction that will minimize the change.
The external factor may be pressure, temperature, concentration, adding a noble gas
or a catalyst.
(a) Effect of pressure
Since pressure has a negligible effect on the volumes of solids and liquids, it only affects
reactions in which gases are involved.
Any reaction that occurs with an increase in volume is favoured by a decrease in
pressure.
A reaction that occurs with a decrease in volume is favoured by an increase in pressure.
Any change in pressure of the system changes the position of the equilibrium and the
rate of attainment of the equilibrium but has no effect on the equilibrium constant.
Sample questions
1. Nitrogen and hydrogen react according to the equation

Explain how the position of the equilibrium, value of the equilibrium constant and
the rate of attainment of equilibrium would be affected if ;
(i) the pressure was decreased
Note that
There forward reaction occurs by a reduction in volume, hence favoured by an increase

in pressure.
A decrease in pressure shifts equilibrium from right to left since backward reaction
occurs by an increase in volume. Ammonia dissociates to form nitrogen and hydrogen,
keeping the equilibrium constant value unchanged. Rate of attainment of equilibrium
decreases because there are fewer gas molecules in a given volume, molecules are far
apart hence there are fewer chances of successful collisions between particles.
(ii) the pressure was increased

Increase in pressure shifts equilibrium from left to right since forward reaction occurs
by a decrease in volume. Nitrogen will react with hydrogen to form ammonia so as to
keep the equilibrium constant value unchanged. Rate of attainment of equilibrium
increases because there are more gas molecules in a given volume, molecules are closer
together hence there are more chances of successful collisions between particles.
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512
2. When hydrogen iodide is heated it decomposes according to the equation
the rate of attainment of equilibrium would be affected if the pressure of the
reaction was increased
Note that
Increase in pressure has no effect on position of equilibrium since both forward and
backward reactions proceed with no change in volume. Equilibrium constant remains
unchanged but the rate of attainment of equilibrium increases because there are more
gas molecules in a given volume, molecules are closer together hence there are more
chances of successful collisions between particles.
(b) Effect of concentration

Increasing concentration of any reagent in an equilibrium mixture shifts the equilibrium
in the direction that converts some of the reagent into other products.
Addition of a reagent that reacts with one of the reactants/products, reduces the
concentration of the reactant/product in an equilibrium mixture and shifts the equilibrium
in the direction to which the reactant/ product is removed so that it is replaced.
Any change in concentration of one of the species in an equilibrium mixture changes the
position of the equilibrium and the rate of attainment of the equilibrium but has no
effect on the equilibrium constant.
Sample question
1. Sulphur dioxide reacts with oxygen according to the equation;
the rate of attainment of equilibrium would be affected if;
(i) more Sulphur dioxide was added
The concentration of sulphur dioxide increases and the excess sulphur dioxide reacts
with oxygen to produce sulphur trioxide, so as to keep the equilibrium constant value
the same. Equilibrium therefore shifts from left to right and equilibrium constant value
remains unchanged. The rate of attainment of equilibrium increases since there is an
increase in the number of particles in the reaction vessel.
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513
(ii) Sulphur trioxide was added.

The concentration of sulphur trioxide increases and the excess sulphur trioxide
dissociates to produce sulphur dioxide and oxygen, so as to keep the equilibrium
constant value the same. Equilibrium therefore shifts from right to left and equilibrium
constant value remains unchanged. The rate of attainment of equilibrium increases
since there is an increase in the number of particles in the reaction vessel.
(iii) Removing the Sulphur trioxide formed

Removing sulphur trioxide makes the sulphur dioxide to react with oxygen so as to
replace sulphur trioxide removed, keeping the equilibrium constant value unchanged.
Equilibrium therefore shifts from left to right. The rate of attainment of equilibrium
reduces since there is a reduction in the number of particles in the reaction vessel.
(c) Effect of temperature.

The effect of temperature on an equilibrium depends on whether the reaction is

endothermic ( or exothermic ( .
If the reaction is endothermic, increase in temperature favours it
If the reaction is exothermic, then it is favoured by lowering temperature.
Any change in temperature changes the position of the equilibrium, rate of attainment
of the equilibrium and also the value of the equilibrium constant.
Among all the factors, it is only temperature that affects the value of the equilibrium
constant.
For an exothermic reaction, increase in temperature favours backward reaction,
reducing the equilibrium constant value.
For an endothermic reaction, increase in temperature favours forward reaction,
increasing the equilibrium constant value.
Sample question
1. Ammonia is formed from nitrogen and hydrogen at 25°C and 10 atm.
the rate of attainment of equilibrium would be affected if the reaction is carried out
at a temperature of 250°C, while the pressure remains at 10 atm.
Since forward reaction is exothermic, increase in temperature from 25°C to 250°C will
make equilibrium shift from right to left, favouring the backward reaction which is
endothermic. The ammonia dissociates to form nitrogen and hydrogen according to L ́
Chatelier's Principle. This reduces the concentration of ammonia but increases the
concentrations of nitrogen and hydrogen, reducing the equilibrium constant.
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514
The rate of attainment of equilibrium increases because increase in temperature will

increase both the forward reaction rate and the reverse reaction rate and the collision
frequency between colliding particles.
2. Nitrogen reacts with oxygen according to the following equation
the rate of attainment of equilibrium would be affected if;
(i) the temperature was increased.
Increase in temperature will make equilibrium shift from left to right, favouring the
forward reaction which is endothermic. The nitrogen reacts with oxygen to form
nitrogen monoxide according to L ́ Chatelier's Principle. This reduces the
concentration of nitrogen and oxygen but increases the concentration of nitrogen
monoxide, increasing the equilibrium constant.

The rate of attainment of equilibrium increases because increase in temperature will
increase both the forward reaction rate and the reverse reaction rate the collision
frequency between colliding particles.
(ii) the temperature was decreased.

Decrease in temperature will make equilibrium shift from right to left, favouring the
backward reaction which is exothermic. The nitrogen monoxide dissociates to form
oxygen and nitrogen according to L ́ Chatelier's Principle. This increases the
concentration of nitrogen and oxygen but decreases the concentration of nitrogen
monoxide, reducing the equilibrium constant.
The rate of attainment of equilibrium decreases because decrease in temperature will
reduce the collision frequency between colliding particles.
(d) Effect of adding a noble gas

Addition of an inert gas for example argon to an equilibrium system does not affect the
equilibrium constant.
The noble gas effect can be investigated under two conditions i.e. constant volume
(where total pressure of the system increases) and at constant pressure( where the total
volume of the system increases).
When heated, carbon dioxide decomposes according to the equation:
Explain the effect on the equilibrium position and equilibrium constant and the rate
of attainment of equilibrium when;
(i) argon is added to the equilibrium at constant volume
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Argon being a noble gas, when added, the total pressure of the system increases, but
there is no change in partial pressure/ concentrations of the reactants and products.
The position of the equilibrium is not affected.
Since the concentration of argon does not apply in the or expression, the
equilibrium constant also remains unchanged.
The rate of attainment of equilibrium reduces since some of the particles on collision
do not react.
N.B Hence, when an inert gas is added to the system in equilibrium at constant
volume there will be no effect on the equilibrium position or equilibrium constant
but reduces the rate of attainment of equilibrium.
(ii) neon is added to the equilibrium at constant pressure
Neon being a noble gas, when added to the system at constant pressure, leads to an
increase in the total volume. As a result, partial pressures/ concentrations of the
reactants and products decrease. According to Le Chatelier's Principle, the equilibrium

will be shifted from left to right (in that direction where there is an increase in number
of moles). The equilibrium constant remains unchanged since the partial
pressure/concentration of neon does not apply in the equilibrium constant expression.
The rate of attainment of equilibrium reduces as some of the particles on collision do
not react.
N.B Hence, when an inert gas is added to the system in equilibrium at constant
pressure, there will be a shift of the equilibrium position to a direction where the
number of moles increases, no effect on equilibrium constant but reduces the rate of
attainment of equilibrium.
(e) Effect of adding a catalyst
A catalyst is a substance which alters the rate of a chemical reaction but remains
unchanged in quantity at the end of the reaction or at equilibrium.
A catalyst has no effect on position of equilibrium and no effect on the value of

equilibrium constant but only alters the rate of backward and forward reaction
equally. A catalyst therefore increases the rate of attainment of equilibrium by
decreasing the activation energy.
The explanations given above are general. A question may require you just to state
the effect of a constraint. This may not require you to go into details of explaining.
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Questions
1. Sulphur dioxide reacts with oxygen according to the following equation.
(a) State what would be happen to the concentration of sulphur(VI) oxide in the
equilibrium mixture and give a reason for your answer if;
(i) the temperature was increased
(ii) nitrogen gas was added to the mixture at a constant pressure.
(iii) pressure was increased
(iv) more oxygen was added to system at equilibrium
(v) volume of the vessel in increased
2. The reaction between nitrogen and hydrogen at 25℃ and 10 atm takes place according
to the following equation.
What would happen to the concentration of ammonia and the value of the equilibrium

constant if;
(i) Helium was added to the equilibrium mixture at constant pressure?
(ii) the temperature was increased to 250℃ but the pressure remains at 10 atm?
(iii) Argon is added to the equilibrium mixture at constant volume?
(iv) some iron is added to the equilibrium mixture
3. Iodine is sparingly soluble in water but readily dissolves in potassium iodide
according to the following equilibrium
(a) Explain why iodine is sparingly soluble in water but very soluble in potassium
iodide
(b) (i) Write an expression for the concentration equilibrium constant, .
(ii) State any three characteristics of the above equilibrium.
(c) State and explain the effect of adding sodium thiosulphate solution to the
position of equilibrium.
4. Phosphorus pentachloride decomposes at high temperatures according to the
following equation.
State how the position of the equilibrium and the value of the equilibrium constant
would be affected and in each case give a reason for your answer if ;
(i) the pressure was increased
(ii) some chlorine was added to the equilibrium
(iii) some phosphorus(III) chloride was removed from the equilibrium mixture
(iv) the temperature was increased
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(v) volume of the container was decreased

(vi) adding a catalyst
5. (a) State three characteristics of a chemical equilibrium.
(b) Phosphorus(V) chloride when heated decomposes according to the following
equation.

(ii) When 1 mole of phosphorus(V) chloride was heated in a closed vessel at 350℃,
the equilibrium mixture was found to contain 38.4% of chlorine. Calculate the
equilibrium constant at 350℃.
(iii) The equilibrium constant at 250℃ was found to b 1.54. State whether the
reaction is exothermic or endothermic. Give a reason for your answer.
(c) State what would happen to the concentration of chlorine if the pressure in the
vessel was decreased while the temperature maintained at 350℃. Give a reason for
your answer.

6. When heated at 1atm, carbon dioxide decomposes according to the equation:
State and explain the effect of ;

(i) heating the carbon dioxide at 2 atmospheres on the equilibrium concentration
of oxygen
(ii) carrying out the decomposition at a lower temperature on the value of the
7. Hydrogen and iodine were heated in a 1 litre vessel. Explain what would happen to
the equilibrium position of the reaction, equilibrium constant, and rate of attainment
of equilibrium if;
(i) sodium thiosulphate solution was added to the vessel.
(ii) the pressure was increased
(iii) concentration of iodine was increased
(iv) helium gas was added at constant volume.
8. The esterification reaction for formation of ethylethanoate from ethanoic acid and
ethanol is shown by the equation below.
State how the amount of ethylethanoate and position of the equilibrium would be
affected if:
(i) some ethanol is added to the system
(ii) some water is removed from the system
(iii) concentrated sulphuric acid is added
(iv) some sodium hydroxide solution is added
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(v) the temperature was increased

9. Nitrogen and oxygen react endothermically at high temperatures according to the
equation;
The equilibrium constant for the reaction at 2680K and 1 atm total pressure is
. Equal volumes of nitrogen and oxygen were mixed at 2680K and 1 atm total
pressure and allowed to react until equilibrium is reached.
(a) Calculate the:
(i) fraction of the original nitrogen used in the reaction
(ii) fraction of nitrogen(II) oxide in the reaction mixture
(b) State what will happen to the value in (a)(ii) above and give a reason(s) if:
(i) the pressure is increased to 10 atm
(ii) the temperature is raised to 2780K
(iii) a catalyst is added
10. Sulphur dioxide dichloride dissociates when heated according to the equation:

(a) At a temperature of 375℃ and an overall pressure of 101325 , a sample of
sulphur dioxide dichloride in the gas phase was found to be 84% dissociated.
(b) State, at constant temperature, the effect on the position of equilibrium and the
value in (a) above of:
(i) adding a catalyst
(ii) compressing the system
11. Ammonium carbamate decomposes according to the following
equation:
(a) Write the expression for the equilibrium constant

(b) At equilibrium, the total pressure of the system is 0.36 atm. at 40℃. Calculate
the value of for the reaction at 40℃ and indicate its units.
(c) State what happens to the calculated in (a) if :
(i) more solid ammonium carbamate is added to the equilibrium mixture.
(ii) the temperature is increased to 80℃.
12. Discuss the effect of each of the following factors on the position of equilibrium of a
reversible reaction, the rate of attainment of equilibrium and the value of equilibrium
constant.
(i) Temperature
(ii) Pressure
(iii) Catalyst
(iv) Concentration.
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INDUSTRIAL APPLICATION OF CHEMICAL EQUILIBRIUM

The knowledge of chemical equilibrium is applied industrially in the following processes;
 Haber process
 Contact process
 Ostwald process
1. Manufacture of ammonia (the Haber process)

The reaction between dry hydrogen (obtained from natural gas) and dry nitrogen (from
fractional distillation of liquid air) to form ammonia is exothermic and occurs with a
decrease in volume
According to L ́ Chatelier's Principle , the yield of ammonia will be greatest at low

At a low temperature however, rate of attainment of equilibrium is low and at high

temperature, the position of the equilibrium is over to the left.
At high pressure, the cost of the equipment and running costs are high.
Therefore, in practice, a compromise has to be struck. The conditions used in this process
are therefore;
 Pressures between 200-1000 atmospheres
 Temperature of about 450-550oC
 Finely divided iron catalyst
2. Manufacture of sulphuric acid (the Contact process)
The conversion of Sulphur dioxide (obtained by burning Sulphur in air, roasting
iron pyrites, copper pyrites or oxidation of zinc blende or burning hydrogen
sulphide from crude oil in air) and oxygen (obtained from fractional distillation of
liquid air) to Sulphur trioxide is an exothermic reaction and occurs with a decrease in
volume.
According to L ́ Chatelier's Principle , the yield of ammonia will be greatest at low

At a low temperature however, the rate of attainment of equilibrium is very slow.
Increase in pressure gives an increased yield of Sulphur trioxide but the effect is small
and the yield is good even at pressures just above atmospheric pressure but not as high as
those used in the Haber Process.
Still, at high pressures, sulphur dioxide liquefies.
Therefore, in practice, a compromise has to be struck. The conditions used in this
process are therefore;
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 Pressures between 1-3 atmospheres

 Temperature of about 450-500 oC
 Vanadium(V) oxide catalyst
Question
Sulphur dioxide is a raw material used in manufacture of sulphuric acid by the
contact process.
(a) With relevant equations, describe the various ways how sulphur dioxide used
in this process may be obtained on a large scale.
(b) Describe how sulphuric acid can be manufactured using one of the sources
above.
(c) Briefly describe how the sulphuric acid can be converted to superphosphate
fertilizer.
(a) Sulphur dioxide can be obtained by burning sulphur in air

or by roasting iron pyrites in air
or roasting zinc blende in air
or roasting copper pyrites
(b) Iron pyrites are roasted in air to form iron(III) oxide and sulphur dioxide.
The sulphur dioxide obtained above and oxygen obtained by fractional distillation of
liquid air are purified to clear them off any dust that may poison the catalyst and dried.
The purified gases are passed over Vanadium(V) oxide catalyst at temperatures about
450-500 oC and pressures between 1-3 atmospheres to form sulphur trioxide.
The sulphur trioxide is dissolved in concentrated sulphuric acid to form a fuming liquid
called oleum.
The oleum is carefully diluted with a correct amount of water to form 98% concentrated
sulphuric acid.
N.B. 1. Vanadium pentoxide is preferred over Platinum as catalyst because it is cheaper

and not commonly poisoned by impurities
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2. The sulphur trioxide is not dissolved in water because its reaction with water is highly
exothermic and it leads to formation of sulphuric acid sprays that damage plants and
animals
(c) Calcium phosphate is dissolved and stirred in about 65% sulphuric acid to form a
mixture calcium sulphate and calcium dihydrogen phosphate. The product is dried
and forms the superphosphate fertilizer.
N.B; The Single Superphosphate(SSP) fertilizer made above is less efficient because it is
contaminated with Calcium sulphate. A more efficient fertilizer called Triple
Superphosphate fertilizer is formed by using concentrated sulphuric acid instead.
Details of these process for conversion of ammonia formed by Haber process to nitric
acid are discussed in DEMISTYFYING INORGANIC CHEMISTRY under chemistry

of period 3 elements by the same author)
Questions
1. Ammonia is manufactured from hydrogen and nitrogen by the Haber process.

(a) Write the equation for the reaction.
(b) State one source of hydrogen and one source of nitrogen used in the above process
(c) Write an expression for the equilibrium constant, for the reaction.
(d) State Le Chatelier‟s principle.
(e) The reaction in (a) above is exothermic. State and explain the effect on the above
equilibrium of:
(i) increasing pressure
(ii) removing ammonia from the mixture of gases
(f) Explain why the synthesis of ammonia is operated at a temperature of 400℃.
(g) (i) Name the catalyst used in the Haber process
(ii) Describe how the catalyst works
(iii) Explain the effect of the catalyst on the position of the equilibrium.
(h) Write equations to show how ammonia is converted to nitric acid.
2. Sulphur dioxide is a raw material used in manufacture of sulphuric acid by the contact
process. It is initially converted exothermically to sulphur trioxide during the process.
On industrial scale, this conversion carried out at 450℃ and 2 atmospheres in
presence of a catalyst.
(a) Write equation for formation of sulphur trioxide in the contact process
(b) Name the catalyst used
(c) State the reasons for the choice of the temperature and pressure used to convert
sulphur dioxide to sulphur trioxide.
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(d) Sulphur trioxide reacts with water to form sulphuric acid.

(i) Write equation for the reaction.
(ii) State the hazard of the reaction in d(i) above and describe how it is avoided in the
contact process.
(e) Concentrated sulphuric acid contains 98% of the acid. Calculate the mass of
concentrated sulphuric acid required to make 500 of 1.5M solution of
sulphuric acid.
(f) Name one reagent that can be used to identify the anion in sulphuric acid. State
what would be observed and write the equation for the reaction that takes place
when the reagent you have named is used.
(g) State two large scale uses of sulphuric acid.

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CHAPTER SEVEN
IONIC EQUILIBRIA
ACIDS, BASES AND SALTS
Acids and bases
Acids are characterized by a sour taste and their effect on litmus and changing colour of
indicators. They react with bases and also some other compounds to form salts. They
liberate carbon dioxide from carbonates and hydrogen when reacted with metals.
Bases are characterized by a soapy feel and detergent power. They react with acids to
form a salt and water.
There have been many attempts to define acids and bases. Early definitions considered
acids as substances that provide hydrogen ions when dissolved in water and bases as

substances that react with hydrogen ions to form a salt and water.
The concept of acids and bases according to various theories

Acids and bases have been defined according three theories which include the Arrhenius
theory, Bronsted-Lowry theory and the Lewis theory.
1. Acids and bases according to the Arrhenius theory.

According to this theory;
 An acid is a substance that on dissolving in water dissociates to produce
hydrogen ions
 A base is a substance which on dissolving in water dissociates to produce

hydroxyl ions.
̅
̅
Considering the reactions above when a base is reacted with an acid, a neutralisation
reaction occurs.
̅
Arrhenius theory however didn‟t explain bases which do not contain hydroxyl ions for
example basic oxides, carbonates, and ammonia. Ammonia neutralises acids by accepting
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hydrogen ions rather than providing hydroxide ions because undissociated ammonium
hydroxide is hypothesized.
The Arrhenius theory definitions of acids and bases only applied to aqueous solution. It
could not explain acid-base reactions other solvents unlike water.
2. Acids and bases according to Bronsted-Lowry theory

The Bronsted-Lowry theory catered for some of the setbacks of the Arrhenius theory
According to this theory;
 An acid is a substance that donates protons to a base
(i)
(ii)
is a hydrated proton and is called the oxonium ion, hydroxonium ion or
hydronium ion, and is also referred to as the hydrogen ion.

 A base is a substance that accepts protons from an acid
(iii) ̅
(iv) ̅
(v) ̅
Note: In reaction(i), water accepts a proton from hydrochloric acid to form the
oxonium ion. Water behaves as a proton- acceptor(base)
In reaction(iv), water donates a proton to ethylamine to form the ethylammonium ion.
Water behaves as a proton- donor(acid)
Also note that strong acids and bases completely ionise in solution whereas weak acids
and bases partly ionise in solution.
3. Acids and bases according to Lewis theory

The Bronsted-Lowry theory of acids is based on protolysis. The Bronsted-Lowry acids
must therefore contain hydrogen according to the theory. However, there are substances
also react as acids and change the color of indicators even in dry state but they do not
contain hydrogen. The Lewis theory catered for this shortcoming.
According to the Lewis theory;
 An acid is any substance that can accept a lone pair of electrons.
 A base is any substance that can donate a lone pair of electrons.
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Examples of Lewis acids and bases include

Lewis acids Lewis bases
Aluminium chloride, Iron(III) chloride, Water, ammonia, triethylamine,
Boron trifluoride, Boron trichloride and trimethylamine and alcohols
Beryllium chloride
Hydrogen ion, aluminium ion, Hydroxyl ion, chloride ion and
iron(III) ion and copper(II) ion cyanide ion
Silicon(IV) chloride and Ethene and ethyne
phosphorus(V) chloride
[ ]
[ ]

or
or
or
or
Conjugate acid and bases

Benzoic acid ionises in its aqueous solution according to the equation;
In the equilibrium above, the benzoate ion is a conjugate base of benzoic

acid. Benzoic acid is a conjugate acid of the benzoate ion and the two form a conjugate
acid-base pair.
The conjugate base is formed when an acid loses a proton and when the conjugate base
gains a proton, it forms its conjugate acid.
Acids and bases can therefore be neutral molecules, positive ions or negative ions.
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Examples of conjugate acid-base pairs include;

Conjugate acid Conjugate base
Try to write equations showing how the conjugate base is formed from the
conjugate acid for each of the above conjugate acid-base pairs.
Classification of strong acids and bases, weak acids and bases

A strong acid is an acid which ionises completely in its aqueous solution and easily

releases protons
A weak acid an acid which partly ionises in its aqueous solution and does not easily
release protons
Examples include;
Strong acid Weak acid
Hydrochloric acid Ethanoic acid
Hydrobromic acid Methanoic acid
Hydroiodic acid Hydrocyanic acid
Nitric acid Hydrofluoric acid
Sulphuric acid Butanoic acid
Chloric(VII) acid Carbonic acid
A strong base is a base which ionises completely in its aqueous solution and easily
accepts protons
A weak base is a base which partly ionises in its aqueous solution and does not easily
accept protons
Examples include;
Strong bases Weak bases
Potassium hydroxide Aqueous ammonia
Sodium hydroxide Aqueous methylamine
Barium hydroxide Aqueous phenylamine
Lithium hydroxide Aqueous triethylamine
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Relative strength of Bronsted-Lowry acids and bases

The strength of different acids in an aqueous solution under similar conditions can be
compared using their degrees of dissociation( ) and acid dissociation constants( ),
(for weak acids) at the same dilution and temperature.
(a) Using degrees of dissociation
 The higher the degree of dissociation at a given temperature and dilution, the stronger
the acid
 The degree of dissociation of an acid increases with dilution and all acids become
equally stronger and infinite dilution because they become completely dissociated.
 The degree of dissociation for an acid that ionises endothermically increases with
increase in temperature hence the acid releases more hydrogen ions as the temperature
increases, becoming stronger with increase in temperature.
 The degree of dissociation for an acid that ionises exothermically decreases with
increase in temperature hence the acid releases fewer hydrogen ions as the

temperature increases, becoming weaker with increase in temperature.
Acid Degree of dissociation
for a solution for a solution
0.82 0.96
0.79 0.92
0.51 0.65
0.004 0.013
(b) Using acid dissociation constants
The strengths of weak acids are compared using more conveniently by use of their
dissociation constants.
The higher the acid dissociation constant, the stronger the acid. The strength can then be
explained by use of other terms like electronegativity of bonded atoms, inductive
effect and number of oxygen atom (for oxo-acids of chlorine) in relation to polarity
of the oxygen-hydrogen bond hence the bond strength.
N.B. Inductive effect is the ability of an atom or group of atoms to donate electrons
towards a neighbouring atom or ability to withdraw electrons from the neighbouring
atom.
An atom or group of atoms that donate electrons to a neighbouring atom have positive
inductive effect. These include all alkyl groups.
An atom or group of atoms that withdraws electrons from a neighbouring atom have
negative inductive effect. These include all halogen atoms,
.
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The nature of the groups attached to the carboxyl group has a great effect on the acid
strength therefore due to inductive effect.
Electron withdrawing groups make carboxylic acid stronger by making the
oxygen-hydrogen bond becomes more polar and weak hence release of hydrogen ions in
aqueous solution.
Electron donating groups makes carboxylic acid weaker by making the oxygen-hydrogen
bond less polar and strong hence release of few hydrogen ions in aqueous solution.
Examples
1. The table below shows acid dissociation constants, , of group VII hydrides.
O
( )at 25 C
Explain the trend in values of the hydrides.
The values increase in the order indicating that acid

strength increases in the same order. The strength of an acid depends on how easily it

releases protons. This is because atomic radius of the halogen atoms increases from
fluorine to iodine. This makes the hydrogen-halogen bond length longer, reducing the
bond strength from the hydrogen-fluorine bond to hydrogen-iodine bond, releasing
many hydrogen ions in solution.
Hydrofluoric acid is the weakest acid because the fluorine atom has the highest
electronegativity due to a very small atomic radius. Therefore the hydrogen- fluorine
bond is highly polar and very strong making the acid to dissociate to a considerably
smaller extent.
2. The acid strength of the oxo-acids of chlorine increases in the order
. Explain this observation.
The strength of an acid depends on how easily it releases protons. The acid strength
increases depending on the number of oxygen atoms that exert a negative inductive
effect in each molecule of the acid, increasing the polarity of the oxygen-hydrogen
bond. This is because oxygen is more electronegative than chlorine. In chloric(VII)
acid, 3 oxygen atoms exert a negative inductive effect on the O-H bond making it very
weak and breaks to release very many hydrogen ions making it stronger than chloric(V)
acid in which two oxygen atoms exert a negative inductive effect making the O-H bond
weaker than in chloric(III) acid in which only one oxygen atom has a negative inductive
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effect. Chloric(I) acid has the strongest oxygen-hydrogen bond because no oxygen atom
has a negative inductive effect in it.
3. The table below shows acid dissociation constants, for some acids at a
particular temperature.
Acid
( )
State and explain the trend in acid strength of the acids.
Acid strength decreases in the order
The strength of an acid depends on how easily it releases a proton. Methanoic acid has
a hydrogen atom instead of an alkyl group attached to the carboxyl group, which has no
inductive effect hence the oxygen-hydrogen bond in it is the weakest, easily breaks to
release many hydrogen ions. The alkyl groups in ethanoic acid and propanoic acid have
a positive inductive effect which decreases the polarity of the oxygen-hydrogen bond,

making it not easy break. The strength of the oxygen-hydrogen bond increases as the
positive inductive effect increases with the increase in number of carbon atoms in the
alkyl groups attached to the carboxyl group.
Acid
( )
State and explain the trend in acid strength of the acids.
Acid strength increases in the order
The strength of an acid depends on how easily it releases a proton. Ethanoic acid has a
methyl group attached to the carboxyl group, which has a positive inductive effect hence
the oxygen-hydrogen bond in it has lowest polarity, making it the strongest hence does
not easily break to release hydrogen ions. The chlorine atoms in chloroethanoic acid,
dichloroethanoic acid and trichloroethanoic acid are more electronegative than carbon
and have a negative inductive effect which increases the polarity of the oxygen-
hydrogen bond, making it weak and easy to break. The strength of the oxygen-hydrogen
bond decreases as the negative inductive effect increases with the increase in number
of chlorine atoms in the chain attached to the carboxyl group.
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Acid ( )
State and explain the acid strengths of the acids.

Ethanoic acid is the weakest acid among all the acids. For the other acids, acid strength
decreases in the order
The strength of an acid depends on how easily it releases a proton. Ethanoic acid has a
methyl group attached to the carboxyl group, which has a positive inductive effect hence

the oxygen-hydrogen bond in it has lowest polarity, making it the strongest hence does
not easily break to release hydrogen ions. For the halogen substituted acids, the halogen
atoms are more electronegative than carbon and have a negative inductive effect.
However, the negative inductive effect decreases with the decrease in electronegativity
from fluorine to iodine, decreasing the polarity of the oxygen-hydrogen bond, making it
stronger and not easily broken from fluoroethanoic acid to iodoethanoic acid.
The strength of different bases in an aqueous solution under similar conditions can also
be compared using their degrees of dissociation( ) and base dissociation constants( ),
(for weak bases) at the same dilution and temperature.
(a) Using degrees of dissociation

The higher the degree of dissociation at a given temperature and dilution, the stronger the
base
Base Degree of dissociation

0.95
0.93
0.90
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(b) Using acid dissociation constants

The strengths of weak bases are compared using more conveniently by use of their base
dissociation constants.
The higher the base dissociation constant, the stronger the base.
Electron withdrawing groups make bases weaker by making the lone pair of electrons
less available to accept protons.
Electron donating groups makes bases stronger by making the lone pair of electrons
readily available to accept protons.
Example
1. The table below shows the base dissociation constants of different bases in
aqueous solutions.
Base Base dissociation constant,

(a) Compare and explain the basic strength of ammonia, methylamine and
ethylamine
Basic strength increases in the order;
The basic strength of amines depends on the availability of lone pair of electrons on the
nitrogen atom. Ammonia is the weakest base because the hydrogen atoms attached to
the nitrogen atom, have no inductive effect. The alkyl groups attached to the nitrogen
atom in methylamine and ethylamine have a positive inductive effect which increases the
electron density on the nitrogen atom, making the lone pairs of electrons readily
available for protonation. The positive inductive effect increases with the increase in
number of carbon atoms in the alkyl groups attached to the nitrogen atom hence
ethylamine is a stronger base than methylamine.
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(b) Compare and explain the basic strength of methylamine, dimethylamine and
trimethylamine
nitrogen atom. The three methyl groups attached to the nitrogen atom in
trimethylamine, have the greatest positive inductive effect but due to steric hindrance to
the approach of a proton towards the nitrogen atom and poorest solvation due to lack
of nitrogen-hydrogen bonds, trimethylamine is the weakest base. The methyl groups
attached to the nitrogen atom in methylamine and dimethylamine have a positive
inductive effect which increases the electron density on the nitrogen atom, making the
lone pairs of electrons readily available for protonation. Methylamine and
dimethylamine also have nitrogen-hydrogen bonds which increase their solvation. The
positive inductive effect and solvation increase with the increase in number of alkyl
groups attached to the nitrogen atom and number of nitrogen-hydrogen bonds

respectively hence dimethylamine is a stronger base than methylamine.
(c) Compare and explain the basic strength of ammonia, ethylamine and aniline
nitrogen atom. Aminobenzene is the weakest base because the lone pairs of electrons on
the nitrogen atom interact with the delocalised pi- electrons in the benzene ring. This
reduces the electron density on nitrogen atom, making the lone pair of electrons less
available for protonation. Ammonia is a stronger base than aminobenzene because the
hydrogen atoms attached to the nitrogen atom, have no inductive effect. Ammonia also
has more nitrogen-hydrogen bonds hence more solvated than aminobenzene. The ethyl
group attached to the nitrogen atom in ethylamine has a positive inductive effect which
increases the electron density on the nitrogen atom, making the lone pair of electrons
readily available for protonation.
Note; Amides ( ) are negligibly basic or neutral in aqueous solution compared

to aliphatic amines( ) because the lone pair of electrons on the nitrogen atom in
amides is partially involved in bonding to the carbon of the carbonyl group and
therefore less available for protonation
2. Explain why ethylamine is a stronger base than ethanamide,

although both compounds have an amino group
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The ethyl group attached to the nitrogen atom in ethylamine has a positive inductive
effect which increases the electron density on the nitrogen atom, making the lone pair
of electrons readily available for protonation. In ethanamide, the lone pair of electrons
on the nitrogen atom interacts with the pi-electrons of the carbonyl group therefore less
available for protonation.
Questions
1. The oxy-acids of chlorine include; .

(a) Write the name of each oxo-acid.
(b) Draw the structure and name the shape of each of the acids
(c) Arrange the acids in order of decreasing acid strength and explain your answer.
2. (a) What do you understand by the term inductive effect?
(b) The carboxylic acids below have the following values for the acid dissociation
constant,

Acid
℃
Explain the observations in the acid dissociation constants

(c) (i) Amines are basic in nature. Explain the role of inductive effect of the alkyl
groups on the strength of bases.
(ii) How do you account for the fact that amides though having a group are not
basic in nature.
3. Ethylamine, dimethylamine and ammonia are weak bases in aqueous solution.
(a) (i) Arrange the compounds in order of increasing basic strength
(ii) Suggest why the basic strength is in that order.
(b) (i) Name a reagent that can be used to identify the functional group of the bases.
(ii) State what is observed when each of the bases is separately treated with the named
reagent.
4. The basic strength of aminobenzene, ammonia and dimethylamine are in the order. |
534
Derivation of expressions for acid dissociation constant, and base

dissociation constant,
Consider an aqueous solution of a weak binary acid, of original concentration
and with a degree of dissociation, .
Initial concentration
Concentration
dissociated/formed
[ ][ ]
[ ]
Also considering an aqueous solution of a weak binary base, of original concentration

and with a degree of dissociation, .

The equation for ionisation of the base in water would be;
̅
[ ][ ̅ ]
[ ]
The same treatment as the acid will give the expression below. The concentration of
water remains constant hence is not included in the equation.
The expression for acid dissociation constant, of a weak acid, relating
concentration, in , and the degree of dissociation, is given by;
However, if is small compared to 1, then is approximately equal to one, so
that; and √
Also from the procedure of derivation above, at equilibrium; [ ]
All the derived equations above can be used in calculations involving ionic equilibria
of weak acids.
Also note that, in calculations, for the accurate expression
or the approximated one is used depending on the value of
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535
This can be known by testing using the approximated expression first.

For example:
Using a 0.001M ethanoic acid;
Using a 0.1M ethanoic acid;
√ √
√ √
The value of is not very small as

The value of is small as compared to one compared to one so cannot be
so can be used in calculations used in calculations but rather is
used.
Examples
1. A solution was made by dissolving 1.22g of benzoic acid in 500 of water.

(a) Write the equation for ionisation of benzoic acid in aqueous solution hence the
expression for the ionisation constant,
(b) Calculate the:
(i) hydrogen ion concentration
(ii) degree of dissociation
(a)
[ ][ ]
[ ]
(b) (i)
( )
At equilibrium; [ ] [ ]
[ ]
[ ]
[ ] √ [ ] b(ii) √ , √
[ ] √
|
536
2. (a) Write the expression for the acid dissociation constant of methanoic acid in
aqueous solution.
(b) A 0.01M solution of methanoic acid is 14% dissociated at 25℃. Calculate the
dissociation constant of methanoic acid at 25℃.
(a)
[ ][ ]
[ ]
Questions

1. (a) (i) Write equation for ionisation of ethanoic acid in water
(ii) write the expression for the ionisation constant of ethanoic acid
(b) Calculate the degree of ionisation of a 0.05M solution of ethanoic acid.
( )
2. A solution containing 0.001M of methanoic acid is 1% ionised. Calculate the :
(i) Hydrogen ion concentration
(ii) Acid dissociation constant, , for methanoic acid
3. A solution is prepared by adding 0.0005 moles of ethanoic acid to half a litre of water.
Calculate the degree of ionisation of ethanoic acid.
( )
The expression for base dissociation constant, of a weak base, relating
concentration, in , and the degree of dissociation, is given by;
that; and √
Also from the procedure of derivation above, at equilibrium; [ ̅ ]
All the derived equations above can be used in calculations involving ionic equilibria
of weak bases.
|
537
Whether to use the accurate or approximated expression of ,in calculations, the

same procedure done for weak acids is considered.
Examples
1. A 0.01M solution of ammonia is 4.0% ionised.
(a) Calculate the hydroxide ion concentration
(b) Determine the base dissociation constant, , for ammonia
(a) ̅
[̅ ]
(b)
2. (a) Write the:

(i) equation for the ionisation of methylamine in water
(ii) expression for the base dissociation constant, , for methylamine
(b) The hydroxyl ion concentration of a 1M methylamine solution is
0.04 . Calculate the:
(i) degree of dissociation
(ii) base dissociation constant, , for methylamine.
(a) (i) ̅
[ ][ ̅ ]
(ii) [ ]
(b) (i) [ ]
(ii)
[̅ ]
[̅ ]
The auto ionisation ( self-ionisation ) of water

Pure water is a weak electrolyte due to the slight dissociation into oxonium and hydroxyl
ions.
̅
From the law of mass action;
[ ][ ̅ ]
[ ]
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538
Since the degree of dissociation of pure water is very small

(approximately ) or the [ ] is so very large compared to [ ]
and [ ̅ ] . Therefore [ ] can be taken to be constant such that;
[ ][ ̅ ]
The constant, is called the ionic product of water. At ℃, of water contains
approximately of both hydrogen ions and hydroxyl ions.
Hence
Since the dissociation of water is endothermic, the ionic product of water, , increases
with increase in temperature. However the value at ℃ is commonly used since most
experiments are carried out at that temperature.
Temperature Ionic product of water,

℃
℃
℃
The concept of
The is the negative logarithm to the base ten of the hydrogen ion concentration in
moles per litre of a solution.
[ ]
Since at ℃, of water contains approximately of hydrogen
ions. The of water at ℃ is given by:
The higher the concentration of hydrogen ions, the lower the hence the stronger the
acid.
The of an aqueous solution of an acid or base depends on the concentration and the
degree of ionisation.
Just like , is related to the hydroxyl ion concentration by the expression;
[̅ ]
The is also related to the ionic product of water by:
Therefore from the ionic product of water;

[ ][ ̅ ]
[ ][ ̅ ]
[ ] [̅ ]
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539
At ℃
The above equation can be used for aqueous solutions including water at ℃.
The scale
The scale ranges from 1 to 14 depending on the hydrogen ion concentration in the
solution. It is summarised below:
[ ]
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Neutral
Strong acids Weak acids Weak bases Strong bases
Calculations involving for strong acids and bases

(a) For strong acids

Strong acids are completely ionized in aqueous solution.
Therefore their [ ]
Examples
1. A solution is formed by dissolving 1120 hydrogen chloride gas in 500 of
water at standard temperature and pressure. Calculate the pH of the solution.
Hydrogen chloride gas dissolves in water to form hydrochloric acid
( )
( )
[ ] [ ]
[ ]
2. of a 0.05M sulphuric acid was added to of water.

Calculate the pH of the resultant solution.
( )
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540
( )
[ ] [ ]
[ ]
3. Calculate the mass of hydrogen chloride required per litre to form a solution
with .
[ ]
[ ]
[ ] [ ] [ ]
[ ]

4. Calculate the pH of a solution formed by mixing of 0.1M sulphuric acid
with of 0.1M potassium hydroxide.
( )
( )
( )
( )
[ ]
[ ]
[ ] [ ]
Question
1. Calculate the pH of a 0.005M sulphuric acid.
2. A solution has a pH of 5.5. Calculate its hydrogen ion concentration
3. (a) Chloric(VII) acid is a strong acid. State what is meant by the term strong acid.
(b) Calculate the pH of a 0.025 solution of chloric(VII) acid.
|
541
4. What is the pH of a solution of nitric acid

5. of 0.02M sodium hydroxide was added to of 0.025M sulphuric
acid. Calculate the:
(i) molar concentration of the hydrogen ions in the initial sulphuric acid
(ii) concentration of hydrogen ions in the resultant solution
(iii) the pH of the resultant solution
6. Calculate the of a solution obtained by adding of 0.1M sodium hydroxide
to of 0.1M hydrochloric acid.
7. Calculate the of a solution formed when of 0.3M sodium hydroxide are
added to of 0.2M hydrochloric acid at ℃.
(b) For strong bases

Strong bases are completely ionized in solution to produce hydroxyl ions in the
solution but not hydrogen ions. Therefore the hydrogen ion concentration is

obtained first using the ionic product expression for water, if [ ̅ ] is known.
[ ][ ̅ ] Or from
[̅ ]
[ ]
[̅ ]
[ ]
Examples
1. Calculate the pH of a solution made by dissolving 1.5g of potassium hydroxide in
250 of water at ℃.
( )
̅
[ ] [̅ ]
[ ][ ̅ ]
[ ]
[̅ ]
[ ]
|
542
2. At ℃, . Calculate the:
(i) at ℃.
(ii) the pH at ℃ of a 0.01M solution of sodium hydroxide.
(i)
(ii) ̅
[ ] [̅ ]
[̅ ]
3. of a 0.3M sodium hydroxide was added to of water at ℃.

Calculate the pH of the solution formed.
( )

( )
̅
̅
[ ] [̅ ]
[ ][ ̅ ]
[ ]
[̅ ]
[ ]
4. Calculate the pH of solution formed by mixing of 0.1M hydrochloric

acid with of 0.1M potassium hydroxide.
( )
( )
|
543
( )
[ ]
̅
[ ] [̅ ]
[̅ ]
Questions
1. Calculate the pH of a solution made by dissolving 4g of sodium hydroxide in one litre
of water at ℃.
2. Calculate the pH of a 0.01M potassium hydroxide solution at ℃. (The ionic
product of water is
The relationship between and for an acid-base conjugate
Considering an acid-base conjugate pair of and , in aqueous solution, the

equilibria involved for the acid, and its base, are:
̅
For the first equilibrium;
[ ][ ]
[ ]
For the second equilibrium;
[ ][ ̅ ]
[ ]
[ ][ ] [ ][ ̅ ]
[ ] [ ]
[ ] [̅ ]
[ ] [̅ ]
Expression of for weak acids and bases

Weak acids are not completely dissociated even in very dilute solutions. The expression
[ ] can be used to get the hydrogen ion concentration or the hydrogen ion
concentration can be got from the concentration and dissociation constant of the acid.
[ ]
|
544
Weak bases are also not completely dissociated solution. The expressions [ ̅ ] can
be used to get the hydroxyl ion concentration and then the hydrogen ion concentration
can be got from the expression for ionic product of water.
[ ][ ̅ ] Or from
[̅ ]
[ ]
[̅ ]
[ ]
calculations for weak acids and weak bases

(a) For weak acids
Examples
1. Calculate the of a solution of ethanoic acid.

[ ][ ]
[ ] [ ] [ ]
At equilibrium; [ ] [ ] [ ] √
[ ]
[ ] [ ]
[ ]
2. Calculate the of a solution made by dissolving of benzoic acid in one

litre of solution. ℃
[ ]
[ ][ ]
[ ] [ ] [ ]
At equilibrium; [ ] [ ] [ ] √
[ ]
[ ] [ ]
[ ]
|
545
3. The of a 0.01M solution of benzoic acid is 3.59. Calculate the:

(a) acid dissociation constant
(b) degree of dissociation
(a) [ ]
[ ] [ ]
[ ] [ ]
[ ][ ]
[ ] (b) From [ ]
At equilibrium; [ ] [ ] [ ]
[ ]
4. Propanoic acid undergoes dissociation according to the following equation.
(a) Write the expression for the acid dissociation constant, .

(b) Given that the concentration of propanoic acid is 0.1 and its degree of

dissociation is . Calculate the;
(i) of propanoic acid,
(ii) acid dissociation constant, .
(a)
[ ][ ] At equilibrium; [ ] [ ]
[ ] [ ]
(b) (i) From [ ] [ ]
[ ]
[ ]
[ ]
5. Calculate the pH of a solution containing 1 mole of methanoic acid in 10 litres of

water.
( )
[ ]
[ ]
[ ]
[ ] [ ]
[ ][ ]
[ ] √
[ ]
At equilibrium; [ ] [ ] [ ]
[ ]
|
546
6. Calculate the mass of dichloroethanoic acid that should be dissolved in

of water to make a solution of .
[ ]
[ ] [ ]
[ ] [ ]
[ ][ ]
[ ]
[ ]
[ ]
( )
[ ]
Questions

1. Calculate the of a solution of butanoic
acid.
2. Calculate the pH of a 0.01M solution of propanoic
acid.
3. (a) (i) Write the equation for the ionisation of ethanoic acid in aqueous solution.
(ii) Write the expression for the acid dissociation constant, of ethanoic
acid.
(b) The pH of a 0.1M aqueous ethanoic acid is 2.9. Calculate the dissociation constant
of ethanoic acid.
4. The pH of a solution of ethanoic acid of concentration of is 2.88.
Calculate the acid ionisation constant,
5. Calculate the dissociation constant of a 2M solution of hydrocyanic acid if the pH is
4.55.
6. A 1M solution of iodic(I) acid has a pH of 5.26. Calculate the acid dissociation
constant of the acid.
7. The dissociation constant of a 0.5M propanoic acid solution is .
Calculate the:
(a) degree of dissociation
(b) hydrogen ion concentration
(c) pH of the solution
8. (a) (i) Write the equation for the ionisation of an acid in water.
(ii) Write the expression for the ionisation constant.
(b) The ionisation constant, for is . Calculate the:
|
547
(i) value of the acid

(ii) the percentage ionisation of the acid in a 1M aqueous solution
9. Calculate the pH of 0.5M solution of methanoic acid.
10. The dissociation constant of a 0.05M solution of a very weak monobasic acid is
at ℃. Calculate the:
(a) degree of dissociation
(b) hydrogen ion concentration
(c) of the solution
11. Calculate the mass of benzoic acid that should be dissolved in one litre of water to
make a solution of . ℃
(a) For weak bases

Examples
1. Calculate the of a 0.001M ammonia solution.

̅
][ ̅ ]
[ [̅ ] [ ]
[ ] [̅ ] √
At equilibrium; [ ̅ ] [ ]
[ ] [̅ ]
[̅ ]
[ ]
2. (a) Write:
(i) equation for the ionisation of ethylamine in water
(ii) the expression for the ionisation constant, of ethylamine.
(b) The pH of a 0.01M solution of ethylamine is 11.37.
(i) Calculate the ionisation constant, of ethylamine at 25℃.
( ℃
(ii) State the assumptions you have made in b(i) above.
(a) (i) ̅
[ ][ ̅ ]
(ii) [ ]
(b) (i) [ ] [̅ ]
[ ] [ ]
[ ]
From [ ][ ̅ ]
(ii) At equilibrium;
[̅ ]
[ ] [̅ ] [ ]
[ ]
|
548
3. The pH of a solution of dimethylamine of concentration is 7.64

at ℃. Calculate the basic dissociation constant, for dimethylamine.
̅
[ ][ ̅ ]
[ ] [ ]
[ ] ̅
[ ] [ ]
From [ ][ ̅ ] [̅ ]
[ ]
[̅ ] ̅
[ ] [ ]
[ ]

4. Calculate the concentration in moles per litre of an aqueous solution of ammonia
whose pH is 10.3
̅
[ ] At equilibrium; [ ̅ ] [ ]
[ ] ̅
[ ]
[ ] [ ]
From [ ][ ̅ ]
[̅ ] [ ]
[ ]
[ ][ ̅ ] [ ]
[ ]
5. 0.02M methylamine solution is 4% ionized at ℃.
(a) Write ;
(i) an equation for the ionization of methylamine in water.
(ii) an expression for the base ionization constant for methylamine.
(b) Calculate the:
(i) pH of the methylamine
solution. ℃
(ii) base ionization constant for methylamine.
(a) (i) ̅
[ ][ ̅ ]
(ii) [ ]
|
549
(b) (i) [ ̅ ]
At equilibrium;
[̅ ] [ ]
From [ ][ ̅ ]
[ ]
[̅ ]
[ ] (ii)
[̅ ] [ ]
[ ]
6. Calculate the pH of a solution made by dissolving 7.2g of aminobenzene in

.

( )
[ ]
[ ̅
][ ] [̅ ] [ ]
[ ] [̅ ] √
[ ] [̅ ]
[̅ ]
[ ]
7. Determine the mass of aminobenzene that should be dissolved in 1 litre of water

to form a solution whose pH is 8.3.
̅
[ ] [̅ ]
[ ] [ ]
[ ]
From [ ][ ̅ ] [ ]
[̅ ] [ ]
[ ]
[ ][ ̅ ]
[ ]
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550
Questions
1. Determine the of 0.01M solution of methylamine.
℃
2. (a) Write the:
(i) equation for the ionisation of ethylamine in water
(ii) expression for the ionisation constant, of ethylamine.
(b) A solution contains 0.1 mole of ethylamine per litre of solution at 25 ℃.
(i) Calculate the pH of the solution. (The ionisation constant of ethylamine is
at 25 ℃ , )
(ii) State the assumptions made in b(i) above.
3. The pH of 0.01M solution of ammonia is 10.6. Calculate the ionisation constant for
ammonia.
4. The pH of 0.1M solution of ethylamine is 11.85. Calculate the basic dissociation
constant, for ethylamine.

5. A solution containing of ammonia is ionised.
(a) Write equation for ionisation of ammonia in water.
(b) Calculate the:
(i) pH of ammonia solution ℃
(ii) base association constant,
6. Calculate the pH of a of ammonia.
( ℃
)
7. (a) Dimethylamine partially ionises in water to form an alkaline solution.
Write an equation for the ionisation of dimethylamine in water
(b) The pH of a 0.02M dimethylamine solution at 20℃ was found to be 11.51.
(i) Calculate the molar concentration of hydroxide ions in the solution. The
ionic product of water at 20℃ is
(ii) Deduce the basic ionisation constant, of dimethylamine from your
answer in b(i) above.
(c) Explain why for ammonia at 20℃ is lower than the value calculate in b(ii)
above.
8. (a) Explain the order of increasing basicity of the following compounds.
(b) When one mole of methylamine is dissolved in water, the hydrogen ion
concentration is found to be
(i) Write an equation for the reaction between water and ethylamine
(ii) Calculate the base dissociation constant, for methylamine.
|
551
9. (a) Ethanoic acid is a weak acid and has a value of 4.74

(i) State what is meant by the term weak acid.
(ii) Write an equation for the ionisation of ethanoic acid
(iii) Derive an expression relating and the degree of dissociation of ethanoic
acid.
(iv) Calculate the of a 0.75M ethanoic acid solution.
(b) Ammonia undergoes the following reaction in water.
̅
(i) Write the expression for the ionisation constant, for the reaction.
(ii) If the ionisation constant, for ammonia is .
Calculate the pH of a 0.1M solution of aqueous ammonia.
10. (a) State Graham‟s law of gaseous diffusion.
(b) Equimolar amounts of an amine, W and oxygen were allowed to diffuse through a
porous medium under the same conditions of pressure and temperature. The amine

W diffuses 1.19 times as fast as the time taken by oxygen.
(i) Determine the molecular mass of W.
(ii) Determine the molecular formula of W.
(c) (i) Write the equation for the reaction that occurs when W was dissolved in water.
(ii) Determine the pH of 0.1M aqueous solution of compound W.
(The base dissociation constant of W is and for water at 25 ℃
is )
HYDROLYSIS OF SALTS
Salt
A salt is a substance formed when the replaceable hydrogen of an acid is either wholly
or partially replaced by a metal or an equivalent radical such as the ammonium
radical.
A salt always consists of oppositely charged ions.
An acid and base react to form a salt and water. The salt formed can may also react with
water to form an acid and a base.
Salt hydrolysis
Some salts react with water to form neutral solutions. Other salts react with water to
form acidic or alkaline solutions.
Salt hydrolysis is the reaction between a salt and water to form either a basic or acidic
solution.
|
552
The extent of the hydrolysis of the salt depends on the strengths of the acid and base from
which the hydrolysed salt can be formed.
The various types of salts

(a) Salt of a strong acid and strong base.
Salts formed from strong acids and strong bases include: sodium chloride, sodium
sulphate, potassium nitrate, potassium iodide and sodium bromide.
Such salts are not hydrolysed and their aqueous solutions are neutral, with a of 7
Salt Strong Strong Equation in aqueous solution
base acid

Considering sodium chloride in water;
The sodium chloride dissociates to form sodium ions and chloride ions.
In the solution therefore, there are sodium ions and chloride ions from sodium chloride,
then hydroxyl ions and hydrogen ions from water. However, since sodium hydroxide and
hydrochloric acid are fully ionised in solution, there is no tendency for reaction between
sodium ions and hydroxyl ions to form sodium hydroxide or hydrogen ions and chloride
ions to form hydrochloric acid. The concentrations of hydrogen ions and hydroxyl ions
remain as they are in pure water mantaining the pH of the solution neutral.
(b) Salt of a strong acid and weak base.

Examples include ammonium chloride, ammonium nitrate, ammonium sulphate.
Phenylammonium chloride, methylammonium chloride, ethylammonium sulphate,
methylammonium nitrate.
They undergo cation hydrolysis to form acidic solutions.
Salt Weak Strong Equation for hydrolysis in aqueous solution
base acid
|
553
Aluminium salts, Chromium(III) salts and iron(III) salts, copper(II) salts and zinc salts of
strong acids also undergo cation hydrolysis.
The cations in each of the salts above have small ionic radii and high charges hence a
high charge density and high polarising power. They therefore undergo cation
hydrolysis to produce hydrogen ions, making their solutions acidic and exist as
, , , and respectively.
The dissociation of the takes place in stages but the first stage being as shown below for
each of the solutions:

The final dissociation results into formation of insoluble hydrated hydroxides of each of
the metal and the hydrogen ions can react with basic anions.
To a solution of any of the above salts, including those shown in the table above, if added
a basic substance, a reaction occurs. For example: The solutions evolve:
 Carbon dioxide from carbonates and hydrogen carbonates
 Sulphur dioxide from sulphites and sulphites
 Hydrogen sulphide from sulphides
 Hydrogen gas with magnesium.
Details about these reactions and a variety of ways in which they can be written can
be seen in Demystifying Inorganic Chemistry by the same author.
(c) Salt of a weak acid and strong base.

Examples include sodium methanoate, sodium ethanoate, sodium sulphide, potassium
cyanide, potassium sulphite, sodium carbonate, sodium hydrogencarbonate, potassium
nitrite
They undergo anion hydrolysis to form alkaline solutions.

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554
Salt Weak acid Strong base Equation for hydrolysis in aqueous solution
̅
̅
̅
̅
̅
̅
̅
̅
̅
To a solution of any of the above salts, if added a solution of a cation that forms an
insoluble hydroxide, the hydroxide is precipitated. Similarly if the solutions of the salts
are warmed with an ammonium salt, ammonia gas is evolved.

Prediction and explaining of a salt solution, and hydrolysis basing
on its composition
Examples
(a) An aqueous solution of potassium nitrate is neutral to litmus whereas an aqueous

solution of potassium nitrite turns red litmus paper blue.
Potassium nitrate is a salt of a strong acid and a strong base. It does not therefore
undergo hydrolysis.
Potassium nitrite is a salt of a weak acid and a strong base. It therefore undergoes
anion hydrolysis to form hydroxyl ions that make the solution alkaline.
̅
(b) An aqueous solution of sodium sulphite is alkaline whereas that of sodium hydrogen
sulphite is acidic.
Sodium sulphite is a salt of a weak acid and a strong base. It therefore undergoes
hydrolysis to form hydroxyl ions that make the solution alkaline.
̅
Sodium hydrogensulphite is also a salt of a weak acid and a strong base. It therefore
also undergoes anion hydrolysis to form hydroxyl ions.
̅
However, the hydrogensulphite ion is a strong acid which dissociates to form
hydrogen ions more than it is hydrolysed, forming an acidic solution.
|
555
(c) Ammonium nitrate solution gives effervescence with magnesium ribbon whereas
sodium benzoate solution gives a green precipitate that dissolves in excess with
aqueous chromium(III) sulphate solution.
Ammonium nitrate is a salt of a weak base and a strong acid. It therefore undergoes
cation hydrolysis to form hydrogen ions that make the solution acidic.
The hydrogen ions react with magnesium to form hydrogen gas.
Sodium benzoate is also a salt of a weak acid and a strong base. It therefore also
undergoes anion hydrolysis to form hydroxyl ions.
̅
The hydroxyl ions react with chromium(III) ions to form insoluble chromium(III)
hydroxide.
̅

Chromium(III) hydroxide is amphoteric, hence reacts with excess hydroxyl ions to
form a soluble complex of tetrahydroxochromate(III) ions.
̅
Note; You may be required to write one equation for the reactions leading to formation
of hydrogen or precipitation of the hydroxide. This can be done by adding up two
equations to get the general equations as shown below:
The equation above is got by eliminating hydrogen ions. This done by multiplying the
first equation by 2.
The above equation is obtained by multiplying the first equation by 3 to eliminate

hyroxyl ions.
(d) When a concentrated solution of sodium carbonate is added to an aqueous

solution of chromium(III) sulphate, a green precipitate is formed with
effervescence.
The chromium(III) ion in chromium(III) sulphate has a small ionic radii and a high
charge hence a high charge density and high polarising power. It therefore exists as
hexaaquachromium(III) ion in solution and undergoes cation hydrolysis to produce
hydrogen ions, making the solution acidic. The hydrogen ions react with sodium
carbonate to form carbon dioxide gas and insoluble hydrated chromium(III)
hydroxide.
|
556
(e) When magnesium ribbon is added to aluminium chloride solution, bubbles of a

colourless gas and a brown solid is formed.
The aluminium(III) ion in aluminium chloride has a small ionic radii and a high charge
hence a high charge density and high polarising power. It therefore exists as
hexaaquaaluminium(III) ion in solution and undergoes cation hydrolysis to produce
hydrogen ions, making the solution acidic. The hydrogen ions react with magnesium
to form hydrogen gas and insoluble hydrated aluminium hydroxide.

(f) When ammonium sulphide is added to a solution of iron(III) sulphate,
effervescence occurs and a brown precipitate formed.
The iron(III) ion in iron(III) sulphate has a small ionic radii and a high charge hence a
high charge density and high polarising power. It therefore exists as
hexaaquairon(III) ion in solution and undergoes cation hydrolysis to produce
hydrogen ions, making the solution acidic. The hydrogen ions react with sulphide
ions to form hydrogen sulphide gas and insoluble hydrated iron(III) hydroxide.
(g) When sodium sulphite is added to phenylammonium chloride solution, bubbles of

a colourless gas are observed whereas phenylamine solution forms a green
precipitate soluble in excess with nickel(II) sulphate solution.
Phenylammonium chloride is a salt of a weak base and a strong acid. It therefore
undergoes cation hydrolysis to form hydrogen ions that make the solution acidic.
The hydrogen ions react with sodium sulphite to form to form sulphur dioxide gas.
or general equation:
Phenylamine is a weak base hence ionises partially to form hydroxide ions.
̅
|
557
The hydroxide ions react with nickel(II) ions to form insoluble nickel(II) hydroxide.
̅
Nickel(II) hydroxide reacts with excess phenylamine solution to form a soluble
complex of hexaphenylaminenickel(II) ions.
̅
Questions
Explain the following observations
(a) An aqueous solution of sodium sulphate is neutral to litmus whereas an aqueous
solution of sodium sulphite turns red litmus paper blue.
(b) When potassium methanoate was added to copper(II) sulphate, a blue precipitate was
formed.
(c) When ammonium sulphate solution was mixed with some sodium sulphite solution and
the mixture warmed, there was effervescence of a colourless gas that turns moist red
litmus paper blue.

(d) An aqueous solution of aluminium chloride is acidic
(e) When sodium carbonate solution is added to aqueous aluminium sulphate, bubbles of a
colourless gas and a white precipitate are observed.
(f) When sodium sulphite is added to a solution of iron(III) chloride, a brown precipitate
and bubbles of a colourless gas are observed.
The hydrolysis constant,

Derivation for an expression for
Consider a solution of a salt of a strong acid and weak base for example
methylammonium chloride. If the concentration of the solution is and the
degree of hydrolysis of the salt is .
Concentration
dissociated/formed
The hydrolysis constant, is given by:
[ ][ ]
[ ] if is small compared with 1
Also from the ionisation of methylamine,
̅
[ ][ ̅ ]
[ ]
|
558
[ ][ ̅ ] [ ][ ]
[̅ ] [ ]
[ ] [ ]
Also considering a solution of a salt of a weak acid and strong base for example
potassium ethanoate. If the concentration of the solution is and the degree of
hydrolysis of the salt is .
̅
Concentration
dissociated/formed
The hydrolysis constant, is given by:

[ ][ ̅ ]
[ ] if is small compared with 1
Also from the ionisation of ethanoic acid,
[ ][ ]
[ ]
[ ][ ] [ ][ ̅ ]
[ ] [̅ ]
[ ] [ ]
Calculations involving of salt solutions

Examples
1. Ammonium chloride undergoes hydrolysis when dissolved in water

(a) Write the equation for the hydrolysis of ammonium chloride in water
(b) Calculate the:
(i) of a 0.1M solution of ammonium chloride,
.
(ii) percentage hydrolysis of a 0.1M ammonium chloride solution.
|
559
(a)
[ ][ ] (ii) From [ ]
(b) (i) [ ] [ ]
[ ] [ ]
[ ]
[ ]
[ ] √ [ ]
[ ] √
[ ]
2. Dimethylammonium chloride undergoes hydrolysis in water.

(a) Write

(i) equation for the reaction
(ii) an expression for the hydrolysis constant, for
dimethylammonium chloride.
(b) of 0.4M solution of dimethylammonium chloride required of
a 0.01M sodium hydroxide solution for complete neutralisation. Calculate
the:
(i) of the solution
(ii) the hydrolysis constant and state any assumptions made.
(a) (i)
[ ][ ]
(ii) [ ]
(b) (i) ( )
̅
̅
̅
( )
[ ]
[ ]
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560
(ii) At equilibrium;
[ ] [ ]
[ ] [ ]
[ ]
[ ]
3. (a)Write :
(i) an equation for the hydrolysis of phenylamine hydrochloride ,

when dissolved in water.
(ii) the expression for the hydrolysis constant, , for phenylamine
hydrochloride.
(b) A solution containing 0.4 moles of phenylamine hydrochloride per litre has a

pH of 3.8. Calculate:
(i) the molar concentration of hydrogen ions in solution
(ii) the hydrolysis constant, , for phenylamine hydrochloride.
(iii) State the assumptions you have made in (b)(ii) above.
(a) (i)
[ ][ ]
(ii) [ ]
(b) (i) [ ]
[ ]
[ ]
(ii) [ ] (iii) At equilibrium;
[ ] [ ]
[ ] [ ]
4. of 0.1M aqueous ammonia solution was added to of 0.1M

hydrochloric acid and the resultant solution had a pH less than 7.
(a) Explain why the pH of the resultant solution was less than 7
(b) Calculate the pH of the solution.
( )
|
561
(a) Ammonia solution reacts hydrochloric acid to form a salt, ammonium chloride
which undergoes hydrolysis to form hydrogen ions that make the solution acidic.
(b)
( )
( )
( )

[ ]
[ ][ ]
[ ] [ ] √ [ ]
√
[ ] [ ]
[ ] [ ]
[ ]
5. Calculate the of a 0.01M solution of sodium ethanoate if the dissociation

constant of ethanoic acid is .
[ ][ ̅ ] [̅ ]
[ ]
At equilibrium; [̅ ] √
[̅ ] [ ]
[ ] [ ]
[̅ ]
̅
[ ] ̅
[ ]
[ ]
|
562
6. Determine the pH of an aqueous solution of sodium benzoate made by dissolving

7.2g of sodium benzoate in of water.
( )
[ ]
̅
[̅ ] √ [ ]
[ ][ ̅ ]
√
[ ] [ ][ ̅ ]

[ ] [ ] [ ]
[̅ ]
[̅ ]
[ ] [ ]
7. The percentage of hydrolysis of a 0.1M aqueous solution of sodium propanoate is

.
(i) Write equation for the dissolution of sodium propanoate in water
(ii) Calculate the pH of the resultant solution. ( )
(i) ̅
[ ]
[̅ ] [̅ ]
[ ][ ̅ ] [ ]
8. of 0.5M methanoic acid solution was reacted with of 0.625M

sodium hydroxide solution.
(i) Write the equation for the reaction that took place
(ii) Calculate the pH of the resultant solution.
( )
(iii) Explain why the pH of the resultant solution is not equal to seven.
|
563
(i)
(ii) ( )
( )
( )
[ ]
̅
[ ][ ̅ ]
[ ]

[̅ ] √
[ ] [ ]
̅
[ ] [̅ ]
[ ]
[̅ ] √ [ ]
(iii) The sodium methanoate salt formed is a salt of sodium hydroxide, a strong
base and methanoic acid, a weak acid. Sodium methanoate therefore undergoes
hydrolysis to form hydroxide ions that make the solution alkaline.
9. Determine the mass of sodium ethanoate that must be added to of
water to give a solution of of 8.52.
( )
̅
[ ] [̅ ]
[ ] [ ]
[ ][ ̅ ]
[̅ ] [ ]
[ ]
[ ][ ̅ ]
[ ]
At equilibrium; [ ]
[̅ ] [ ]
[ ] [ ]
|
564
( )
10. (a) Explain what is meant by the term “salt hydrolysis”

(b) Sodium sulphide undergoes hydrolysis. Write the
(i) equation for hydrolysis of sodium sulphide
(ii) expression for hydrolysis constant ( ), for sodium sulphide.
(c) Calculate the pH of solution containing of sodium sulphide
(Hydrolysis constant of sodium sulphide at ℃
(b) (i) ̅

[̅ ]
[ ][ ̅ ]
(ii) [ ]
(c) [̅ ]
[̅ ]
[ ] [̅ ]
[ ] [ ]
Questions
1. Calculate the percentage degree of hydrolysis in a 0.1M solution of ammonium

chloride. (The ionisation constant of ammonia is )
2. Determine the of a solution containing of ammonium chloride if the
hydrolysis constant of ammonium chloride is .
3. Dimethylammonium chloride undergoes hydrolysis when dissolved
in water.
(a) Write:
(i) the equation of hydrolysis
(ii) the expression for the hydrolysis constant, for dimethylammonium
chloride
(b) If the pH of a 4.0M aqueous solution of dimethylammonium chloride is 2.5.
|
565
(i) Calculate the hydrolysis constant, .

( ℃)
(ii) State the assumptions you have made in (b)(i) above.
4. (a) Phenylamine hydrochloride undergoes hydrolysis when dissolved in water.
Write equation for the reaction.
(b) A 0.2M solution of phenylamine hydrochloride has a pH of 3.5. Calculate:
(i) the molar concentration of hydrogen ions in solution
(ii) the hydrolysis constant, , for phenylamine hydrochloride.
5. Calculate the of a solution made by dissolving 6g of sodium ethanoate in water to
form one litre of solution.
6. Sodium benzoate is hydrolysed.
(i) Write the equation for the hydrolysis of sodium benzoate.
(ii) Write the expression for the hydrolysis constant, of sodium benzoate.
(iii) Calculate the of a 0.1M sodium benzoate solution

(iv) Determine the of a 0.1M sodium benzoate solution
7. Sodium benzoate undergoes hydrolysis when dissolved in water.
(a) Write an equation for the hydrolysis of sodium benzoate in water.
(b) Write an expression for the hydrolysis constant, , for sodium benzoate
(c) The hydrolysis constant of sodium benzoate is .
(i) Calculate the concentration of hydroxide ions in a 0.1M solution of sodium
benzoate
(ii) State the assumptions made in the calculation in (c) (i) above.
(iii) Using your result in c (i), calculate the of the solution.
8. Benzoic acid is a weak acid.
(a) Write equation for the ionisation of benzoic acid in water
(b) The pH of an aqueous solution of 0.2M benzoic acid is 5.25. Determine the acid
dissociation constant, for benzoic acid.
(c) Using your results from (b) above, calculate the hydrolysis constant, for
sodium benzoate. ( )
9. (a) Write an equation for the hydrolysis of sodium ethanoate in water.
(b) Write an expression for the hydrolysis constant of sodium ethanoate.
(c) Calculate:
(i) the value of for sodium ethanoate and indicate its units
(ii) pH of a 0.1M sodium ethanoate solution

(d) State what would be the effect on pH of the solution in (c) (ii) if 1.0cm3 of 0.1M
ethanoic acid was added to it.
|
566
10. Methanoic acid is a stronger acid than ethanoic acid.

(a) (i) Explain why methanoic acid is stronger than ethanoic acid
(ii) Write an equation for ionisation of methanoic acid
(iii) Write an expression for the ionisation constant, for methanoic acid
(b) of 0.1M methanoic acid solution was reacted with of 0.05M
(i) Write the equation for the reaction that took place
(ii) Calculate the pH of the resultant solution.
( )
(iii) Explain why the pH of the resultant solution is not equal to seven.
(c) Name a reagent that can be used to distinguish between methanoic acid and
ethanoic acid and state what is observed in each case when each of the acids is
treated with the named reagent.
11. Calculate the pH at the end point of a titration of a nitrous acid and

sodium hydroxide solution. The of nitrous acid is 10.66.
12. Write an equation for dissolution of each of the following salt in water. State whether
the resulting solution would be neutral, basic or acidic
(a) chromium(III) chloride
(b) Magnesium chloride
(c) ammonium methanoate
(d) phosphorus(V) chloride
(e) ethylammonium chloride
BUFFER SOLUTIONS
Water and other simple aqueous solutions do not retain a constant hydrogen ion
concentration, hence their pH values since they dissolve such as carbon dioxide from the
air or silicates from the walls of glass containers.
To obtain solutions that maintain their pH fairly constant, buffer solutions are used.
A buffer solution is a solution which resists changes in pH when a small amount of

acid or alkali is added to it.
Types of buffers
There are broadly two types of buffer solutions namely;
 Acidic buffer solution

 Basic buffer solution
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567
1. Acidic buffer solution

An acidic buffer solution is a solution made by mixing a weak acid and a salt of the
weak acid with a strong base.
Some examples include:
Methanoic acid and sodium methanoate and

Ethanoic acid and sodium ethanoate and
Propanoic acid and sodium propanoate and
Phosphoric(V) acid and sodium phosphate and
Carbonic acid and sodium hydrogencarbonate and
Hydrocyanic acid and sodium cyanide and
2. Basic buffer solution

A basic buffer solution is a solution made by mixing a weak base and a salt of the weak

base with a strong acid.
Some examples include:
Ammonia solution and ammonium chloride and

Ammonia solution and ammonium nitrate and
Phenylamine and phenylammonium chloride and
Methylamine and methylammonium chloride and
The action of a buffer

Action of an acidic buffer
Describe how a solution of ethanoic acid and sodium ethanoate acts as a buffer.
Sodium ethanonate is a strong electrolyte hence fully ionises to form ethanoate ions and
sodium ions.
Ethanoic acid is a weak base hence only slightly ionises and its ionisation is suppressed
by the high concentration of ethanoate ions from the salt.
The solution therefore contains a high concentration of ethanoate ions and a high
concentration of unionised ethanoic acid molecules.
When a small amount of acid is added, the hydrogen ions react with ethanoate ions to
form ethanoic acid resisting a decrease in .
|
568
When a small amount of base is added, the hydroxide ions react with ethanoic acid to
form ethanoate ions and water, resisting an increase in
̅
or
The hydroxide ions react with hydrogen ions to form water and the ethanoic acid ionises
to restore the hydrogen ions removed.
̅
Qn. Describe how a solution of propanoic acid and sodium propanoate acts as a
buffer.
Action of a basic buffer
Describe how a solution of ammonia and ammonium chloride acts as a buffer.

Ammonium chloride is a strong electrolyte hence fully ionises to form ammonium ions
and chloride ions.

Ammonia is a weak base hence only slightly ionises and its ionisation is suppressed by
the high concentration of ammonium ions from the salt.
̅
The solution therefore contains a high concentration of ammonium ions and a high
concentration of unionised ammonia molecules.
When a small amount of acid is added, the hydrogen ions react with ammonia
molecules to form ammonium ions, resisting a decrease in .
or
The hydrogen ions react with hydroxide ions to form water and ammonia ionises to
restore the hydroxide ions removed.
̅
When a small amount of base is added, the hydroxide ions react with ammonium ions
to form ammonia molecules and water, resisting an increase in
̅
Qn. Describe how a solution of phenylamine and phenylammonium chloride acts as
a buffer.
|
569
The Henderson-Hasselbalch equation

This equation is used to calculate pH of a buffer solution.
Derivation of the Henderson-Hasselbalch equation for an acidic buffer solution
Consider an acidic buffer solution of methanoic acid and sodium methanoate.

Sodium methanoate completely ionises whereas methanoic acid partially ionises.
The acid dissociation constant, is given by the expression;

[ ][ ]
[ ]
Assumptions;
(i) All methanoate ions come from fully ionised sodium methanoate.

Therefore; [ ] [ ]
(ii) [ ] remains constant since it is a weak acid
Therefore;
[ ][ ]
[ ]
[ ]
[ ]
[ ]
Introducing both sides yields;
[ ]
[ ] ( )
[ ]
[ ]
[ ] ( )
[ ]
[ ]
[ ] ( )
[ ]
[ ]
[ ]
Derivation of the Henderson-Hasselbalch equation for an acidic buffer solution
Consider a basic buffer solution of methylamine and methylammonium chloride.

Methylammonium chloride completely ionises whereas methylamine partially ionises.
̅
The base dissociation constant, is given by the expression;
|
570
[ ][ ̅ ]
[ ]
Assumptions;
(i) All methylammonium ions come from fully ionised methylammonium chloride.
Therefore; [ ] [ ]
(ii) [ ] remains constant since it is a weak base
Therefore;
[ ][ ̅ ]
[ ]
[ ]
[̅ ]
[ ]
Introducing both sides yields;
[ ]
[̅ ] ( )

[ ]
[ ]
[̅ ] ( )
[ ]
[ ]
[̅ ] ( )
[ ]
[ ]
[ ]
is the got from the expression;
[ ]
N.B pH of a buffer solution is not affected by adding water (on dilution) since the [ ]
[ ]
or [ ]
ratio remains constant on adding water
571
Calculations involving for buffer solutions
Examples
(a) Acidic buffers

1. of sodium ethanoate were dissolved in 1 litre of 0.01M ethanoic acid
solution. Calculate the of the resulting solution.
[ ]
[ ]
[ ]

[ ]
( )
2. Calculate the of a solution formed by adding of of 0.1M sodium
hydroxide to of 0.1M propanoic acid. State any assumptions made.
( )
( )
The excess(unreacted) and the formed constitute a buffer

solution.
( )
[ ]
|
572
( )
[ ]
[ ]
[ ]
( )
3. A 0.1M solution of sodium hydroxide was added to 50cm3 of 0.1M ethanoic acid
until when the acid is half way neutralized. Determine the pH of the resultant
solution formed. ( )
( )
( )

The excess(unreacted) and the formed constitute a buffer solution.
( )
[ ]
( )
[ ]
[ ]
[ ]
( )
4. Calculate the mass of sodium ethanoate that must be dissolved in one litre of
ethanoic acid of concentration to form a solution with a of
.
|
573
[ ]
[ ] [ ]
[ ] [ ]
( ) [ ]
[ ]
( )
[ ]
( )
[ ]
5. To of 0.035M ethanoic acid was added to 4.1g of sodium ethanoate to
make a solution. ( )
(a) Calculate the pH of the resultant solution

(b) Calculate the change in pH of the resultant solution if:
(i) of 1M hydrochloric acid was added to the resultant solution in

(a) above.
(ii) of 1M sodium hydroxide solution was added to the
resultant solution in (a) above.
(a) [ ]
[ ]
[ ]
[ ]
( )
(b) (i) ( )
( )
The hydrogen ions from the acid added react with ethanoate ions from the salt to form
ethanoic acid.
[ ] [ ]
[ ] [ ]
[ ]
[ ]
[ ]
[ ]
|
574
( )
(ii) ( )
̅ ( )
The hydroxide ions from the base added react with ethanoic acid to form ethanoate ions and
water.
̅
̅
[ ] [ ]
[ ] [ ]
[ ]

[ ]
[ ]
[ ]
( )
(b) Basic buffers

1. Determine the of a solution made by adding 25cm3 of 0.2M nitric acid to
80cm3 of 0.2M ammonia solution. ( )
( )
( )
The excess(unreacted) and the formed constitute a basic buffer solution.

|
575
( )
[ ]
( )
[ ]
[ ]
[ ]
( )
2. 0.02 moles of ammonium chloride were dissolved in of 0.1M ammonia
solution. Calculate the:
(a) before addition of the salt
(b) change after addition of the salt.

[ ]
[ ]
(a) ̅ (b)
[ ]
[ ]
[ ][ ̅ ]
[ ] ( )
[ ]
[̅ ]
[ ]
[̅ ] [ ]
[̅ ] √
3. (a) Write the expression for the ionisation constant, of methylamine in water.
(b) 0.25 moles of methylammonium chloride was added to one litre of 0.4M
methylamine
(i) Calculate the pH of the resultant solution
(
)
(ii) State the assumption(s) you have made in b(i)
[ ]
[ ]
|
576
(b) (i) (ii) Assumptions

[ ] [ ] [ ]
[ ] [ ]
Volume of solution does not change when
( ) methylammonium chloride is added to
methylamine solution
4. (a) Determine the mass of ammonium chloride that should be added to of

a 0.1M ammonia solution at ℃ to give a solution whose pH is 8.5.
( , )
(b) A few drops of sodium hydroxide were added to the solution in (b).
(i) State what happened to the pH of the solution
(ii) Give a reason for your answer in c(i)
[ ]

(a) [ ]
[ ]
[ ]
[ ]
( )
(b) (i)
[ ]
( ) The pH remained almost constant.
(ii) The sodium hydroxide added
[ ] reacted with ammonium ions
( )
to form ammonia molecules
[ ] and water.
̅
[ ]
[ ]
577
Preparation of buffer solutions of known

The Henderson-Hasselbalch equation can be used to obtain the salt : acid ratio or
salt : base ratio that can guide us to prepare buffer solutions of known pH by calculation
Examples
1. Describe how you would prepare a buffer solution of 5 using ethanoic acid.
[ ] [ ]
[ ] [ ]
[ ] [ ]
[ ] [ ]
[ ] [ ]
[ ] [ ]
The buffer solution is prepared by adding 179.9 of sodium ethanoate solution to 100 an ethanoic
acid solution of the same concentration.

or
1.799 moles of sodium ethanoate and 1 mole of ethanoic acid are dissolved in water to make a litre of
solution
or
147.518g of sodium ethanoate and 60g of ethanoic acid are dissolved in water to make a litre of solution
2. Describe how a basic buffer solution of can be prepared using

dimethylamine of value 3.29.
[ ]
[ ]
[ ] [ ]
[ ] [ ]
[ ] [ ]
[ ] [ ]
The buffer solution is prepared by adding 1622 of dimethylammonium chloride solution
to 100 an dimethylamine solution of the same concentration.
or
16.22 moles of dimethylammonium chloride and 1 mole of dimethylamine are dissolved in
water to make a litre of solution
or
1321.93g of dimethylammonium chloride and 45g of dimethylamine are dissolved in water
to make a litre of solution
|
578
Application of buffers
 Maintaining the pH of blood in the body
 Maintaining the pH of culture solutions
 Maintaining the pH during manufacture of medicines
 Manufacture of cosmetics
 Maintaining the pH during fermentation
Questions
1. Calculate the of a solution containing 0.01 moles of ethanoic acid and 0.82g of
sodium ethanoate in a litre of solution. ( )
2. of sodium methanoate are dissolved in of 0.01M methanoic acid solution.
Calculate the pH of the resulting solution.
3. (i) Calculate the of a solution made by dissolving 0.005 moles of methanoic acid

and 0.007 moles of sodium methanoate in of aqueous solution.
(i) State whether the pH value you have calculate in (a) above would increase or
decrease on dilution with water and give the reason for your answer.
4. Calculate the of a mixture of of 1M ethanoic acid with of 1M
sodium hydroxide. ( )
5. Calculate the of a solution prepared by addition of of 0.2M sodium
hydroxide to of 0.4M ethanoic acid.
6. (a) Calculate the of a 0.5M propanoic acid solution.
(b) of a 0.5M potassium hydroxide was mixed with of the

solution in (a). Calculate the change in of the solution.
7. (a) Define the term buffer solution.
(b) A 0.1M ethanoic acid solution was titrated with 0.1M sodium hydroxide solution
until the acid was exactly half neutralised. Calculate the pH of the resultant
solution. ( )
(c) State one application of a buffer.
8. Calculate the mass of sodium ethanoate that must be dissolved in one litre of
ethanoic acid to form a solution with a of .
9. (a) (i) Write the equation for the ionisation of phenol in water.
(ii) If the of a solution of phenol is 5.95. Calculate
the dissociation constant of, of phenol.
|
579
(b) 10 litres of an aqueous solution of trichloroethanoic acid was completely

neutralised by of 0.01M sodium hydroxide. Calculate the of the
solution of trichloroethanoic acid.
( ℃)
(c) The solution of trichloroethanoic acid in (b) was added to a 0.1M sodium
trichloroethanoate. Calculate the of the resultant solution.
10. (a) Calculate the pH of a 0.05M ethanoic acid solution.
( )
(b) Explain what is meant by the term acidic buffer.
(c) (i) A solution was made by dissolving 7.1g of ethanoic acid and 11.3g of sodium
ethanoate in water to make 1 litre. To the solution was added 0.8 of 1M
hydrochloric acid. Calculate the pH of the solution. State any assumptions made.
(ii) Addition of of 0.1M hydrochloric acid solution to a solution of
sodium ethanoate and ethanoic acid showed no change in pH of the

solution. Explain.
11. (a) What is meant by the term buffer solution?
(b) Calculate the mass of sodium propanoate that should be added to of a 0.1M
propanoic acid in order to give a solution whose pH is 4.5. State any assumptions
made.
( )
(c) Few drops of dilute hydrochloric acid were added to the solution in (b).
(i) State what happened to the pH of the solution
(ii) Give a reason for your answer in c(i)
12. (a) Define the term “buffer solution”
(b) Calculate the mass of sodium ethanoate that should be added to 1 litre of a 0.2M
ethanoic acid solution in order to produce a solution of
( )
(c) State what would happen to the pH of the solution in (b), if a small amount of
the following were added.
(i) sodium hydroxide solution
(ii) hydrochloric acid
(d) State one biological application of a buffer solution.
13. Explain why a mixture of ammonia and ammonium chloride in solution mantains a
fairly constant when to it a small amount of:
(i) hydrochloric acid is added
(ii) potassium hydroxide is added
|
580
14. (a) State what is meant by the term basic buffer solution.
(b) Determine the of the solution made by mixing 25cm3 of 0.1M hydrochloric
acid with 45cm3 of 0.1M ammonia solution.
( )
15. (a) State what is meant by the term buffer solution
(b) Explain how a mixture of ethylamine and ethylammonium chloride acts as a
buffer.
(c) 6.8g of ammonium chloride were added to 0.7M ammonia solution. Calculate
concentration of hydroxide ions:
(i) before addition of salt
(ii) after addition of salt.
16. One litre of buffer solution was made containing 0.2 moles of ammonia and 0.3 moles
of ammonium chloride.

(a) Write the equation to show the reaction if a little hydroxide ions were added to the
solution.
(b) Calculate the pH of the buffer solution above.
( )
17. (a) of 0.1M sodium hydroxide solution was mixed with of 0.1M
ethanoic acid.
(i) Calculate the pH of the solution.
( )
(ii) State what would happen to the pH of the solution in c(i) when of
0.1M hydrochloric acid is added. Give a reason for your answer.
(b) State one application of buffer solutions.
18. (a) At ℃ , a 0.1M solution of ethylamine is 7.3% ionised.
(i) Write an equation for the ionisation of ethylamine in water
(ii) Calculate the concentration of hydroxide ions at equilibrium
(b) 0.01 moles of ethylamine hydrochloride was added to 1 litre of ethylamine
solution in (a). Calculate the hydroxide ion concentration of the resultant solution.
State any assumptions made.
19. Describe how an acidic buffer solution of 4.2 can be prepared using methanoic
acid of value 3.74.
20. Explain how a buffer solution of pH 8 can be prepared starting from ammonia
solution.
|
581
ACID-BASE TITRATIONS
Acid-base titration is the addition of a solution of a base to an acid solution until there is
just enough of the acid to neutralize the base.
Terms used in acid-base titration

Titrant
This is a reagent of known concentration that is added to another solution to determine
the concentration of the second chemical species.
Titrand (analyte)
This is a reagent whose concentration is not known and has to be determined by
titration.
Equivalence point
This is the point when the number of moles titrant is equal to number of moles of

analyte.
It occurs before end point.
End point
A point in a titration at which the reaction is complete, observed by the colour change
of an indicator and occurs when small amount of solution of known concentration is
added to a solution whose concentration is to be determined.
It occurs after equivalence point.
Acid-base indicators
An Acid-base indicator is a substance which changes colour according to the hydrogen
ion concentration of the solution or liquid to which it is added.
Indicators are either weak acids or weak bases and slightly dissociated when dissolved in
water.
They are used to measure hydrogen ion concentration of solutions or to detect changes in
of solutions
The indicators change colour over different ranges of . Colour of an indicator depends on
the colour of the undissociated molecules and the colour of the ions produced.
Examples of indicators
 Phenolphthalein  Congo red
 Methyl orange  Bromothymol blue
 Methyl red  Universal indicator
 Thymol blue  Phenol red
 Litmus  Cresol red
|
582
Action of an indicator
The most commonly used indicators are weak acids of the form , .
Considering phenolphthalein indicator;
Phenolphthalein indicator is a weak acid hence partly ionises
The unionised molecules are colourless whereas the anions, , are pink.
When an acid is added to the indicator solution, the hydrogen ion concentration
increases and the excess hydrogen ions react ions to form unionised
molecules , shifting the equilibrium to the left, mantaining the value of the ionisation
constant. The solution becomes colourless.
When a base is added to the indicator solution, the hydroxide ions react with hydrogen
ions to form water .

̅
More of the indicator ionises, shifting the equilibrium to the right and a relatively
large concentration of ions is produced to maintain the value of the ionisation
constant. The solution becomes pink.
Considering methyl orange indicator;

Methyl orange indicator is a weak acid hence partly ionises
The unionised molecules are red whereas the anions, , are yellow.
When an acid is added to the indicator solution, the hydrogen ion concentration
increases and the excess hydrogen ions react ions to form unionised
molecules , shifting the equilibrium to the left, mantaining the value of the ionisation
constant. The solution becomes red.
When a base is added to the indicator solution, the hydroxide ions react with hydrogen
ions to form water .
̅
More of the indicator ionises, shifting the equilibrium to the right and a relatively
large concentration of ions is produced to maintain the value of the ionisation
constant. The solution becomes yellow.
|
583
range for indicators

Every indicator has a definite range of hydrogen ion concentration or over which it
changes colour. Methyl orange is red at a of 3.1, orange at a of 3.7 and yellow at
at a of 4.6.
Indicator range Colour

Acid-Alkali
Thymol blue Red-Yellow
Methyl orange Red-Yellow
Congo red Blue-Red
Methyl red Red-Yellow
Litmus Red-Blue
Phenolphthalein Colourless-Red
Choice of indicator

In an acid-base titration, it is important to use an indicator which changes colour over a
range in which there is a marked pH change during the titration.
When a strong acid is titrated with a strong base, the pH at end point is about 7.
When a strong acid is titrated with a weak base, pH at end point is below 7 because the
salt usually formed undergoes hydrolysis to form an acidic solution.
When a weak acid is titrated with a strong base, pH at end point is above 7 because the
salt usually formed undergoes hydrolysis to form an acidic solution.
Therefore the indicator to be selected for any of the above three titrations is one which
has its half-way colour nearest to the pH of the neutralised solution.
Titration Marked Examples Suitable indicator range of

change indicator
Litmus
Strong acid-strong and But almost any
base indicator can be used
Strong acid-weak and Methyl red
base
Weak acid-strong and Phenolphthalein
base
Weak acid-weak No marked and End point cannot be
base change detected accurately by
any indicator
|
584
Examples
1. The pH ranges for different indicators are shown in the table below.
Phenolphthalein Bromothymol blue Methyl orange
8.30-10.0 6.00-7.60 3.10-4.40
(i) Identify the most suitable indicator for the titration dimethylamine
with hydrochloric acid
(ii) Briefly explain your answer above.
(i) Methyl orange indicator

(ii) Dimethylamine reacts with hydrochloric acid to form a salt,
dimethylammonium chloride which undergoes hydrolysis to form an acidic
solution and the pH at end point is below 7 and within the working range of
methyl orange indicator.

2. The pH ranges of some indicators are given in the table below.
Indicator Methyl orange Phenolphthalein Cresol red
range
Which of the indicators is most suitable for the titration between methanoic acid
and sodium hydroxide? Give a reason for your answer
Phenolphthalein indicator
Methanoic acid reacts with sodium hydroxide to form a salt, sodium methanoate which
undergoes hydrolysis to form an alkaline solution and the pH at end point is above 7
and within the working range of phenolphthalein indicator.
̅
Questions
1. (a) A solution made by dissolving sodium ethanoate in a standard solution of ethanoic
acid has pH of 4.7. Explain what would happen when a small amount of sodium
hydroxide is added to the solution.
(b) of 1M sodium hydroxide was added to of 0.01M ethanoic acid.
Calculate the pH of the resultant solution.
( ℃)
(c) The pH ranges over which some indicators change colour are given below.
Indicator pH range
Phenolphthalein 8.0-10.0
Litmus 5.0-8.0
Methyl orange 3.0-5.0
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(i) Which of the indicators above would be the most suitable for the reaction
below?
(ii) Give a reason for your answer in (c)(i)

2. (a) (i) What do you understand by the term Bronsted base?
(ii) Classify the following species as Bronsted acids and /or bases
(b) The dissociation of phenolphthalein can be written as follows:
(i) What colours, if any are associated with the three species in the equation?
(ii) What should be the pH of a solution at the end point using this indicator,
assuming a strong base is added to a weak acid.
3. Explain the following observations
(a) Phenolphthalein indicator, which has a pH range 8-10 is a suitable indicator in

the titration of ethanoic acid with sodium hydroxide solution but not suitable
for ammonia with hydrochloric acid
(b) The pH of pure water is 7.0 at ℃ and 6.5 at ℃.
(c) Methylamine is a stronger base than ammonia
-volume curves for acid-base titrations

1. Titration of a strong acid and a strong base
(a) Titration of sodium hydroxide solution against hydrochloric acid
14 D
B
A
Volume of sodium hydroxide solution added

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Explanation of the shape of the graph

Initially, is low at A due to a high concentration of hydrogen ions from complete
ionisation of strong hydrochloric acid.
gradually increases along AB as sodium hydroxide solution is added due to excess
hydrogen ions still present as some of the hydrogen ions are being neutralised.
̅
sharply increases along BC even with a little sodium hydroxide solution added
because all the acid has been completely neutralised. The end point is reached.
at end point is 7 because sodium chloride salt formed does not undergo hydrolysis.
Along CD, gradually increases due to excess sodium hydroxide solution added.
(b) Titration of hydrochloric acid against sodium hydroxide solution
14

A
B
C
D
Volume of hydrochloric acid added

Initially, is high at A because sodium hydroxide completely ionises to form very
many hydroxide ions.
gradually decreases along AB as sodium hydroxide solution is added due to excess
hydroxide ions still present as some of the hydroxide ions are being neutralised.
̅
sharply decreases along BC even with a little hydrochloric acid added because all
the base has been completely neutralised. The end point is reached.
at end point is 7 because sodium chloride salt formed does not undergo hydrolysis.
Along CD, gradually decreases due to excess hydrochloric acid added.
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2. Titration of a weak acid and a strong base

(a) Titration of sodium hydroxide against ethanoic acid
14
D
7
B

Volume of sodium hydroxide solution added
Initially, is relatively low at A due to a relatively high concentration of weak
ethanoic acid.
gradually increases along AB as sodium hydroxide solution is added because very
few hydrogen ions are neutralised by hydroxide ions. Also, the un neutralised ethanoic
acid and the sodium ethanoate salt formed constitute a buffer which resists increase in
pH.
sharply increases along BC even with a little sodium hydroxide solution added
because all the acid has been completely neutralised. The end point is reached.
at end point is above 7 because the sodium ethanoate salt formed undergoes
hydrolysis to form an alkaline solution.
̅
Along CD, gradually increases due to excess sodium hydroxide solution added.
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(b) Titration of ethanoic acid against sodium hydroxide

14
A
7
C

Volume of ethanoic acid added
Initially, is very high at A because sodium hydroxide is a strong base hence
completely ionises to form very many hydroxide ions.
gradually decreases along AB as ethanoic acid is added due to excess hydroxide
ions still present as some of the hydroxide ions are being neutralised.
sharply decreases along BC even with a little ethanoic acid added because all the
base has been completely neutralised. The end point is reached.
at end point is slightly above 7 because the sodium ethanoate salt formed undergoes
hydrolysis to form an alkaline solution.
̅
Along CD, gradually decreases due to excess ethanoic acid added which together
with the sodium ethanoate salt formed form a buffer solution.
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3. Titration of a strong acid and weak base

(a) Titration of ammonia solution against hydrochloric acid
14
10
D
C
B
A

Volume of ammonia solution added

Initially, is low at A due to a high concentration of hydrogen ions from complete
ionisation of strong hydrochloric acid.
gradually increases along AB as ammonia solution is added because hydrochloric
acid is being neutralised.
sharply increases along BC even with a little ammonia solution added because all
the acid has been completely neutralised. The end point is reached.
at end point is below 7 because the ammonium chloride salt formed under goes
hydrolysis to form an acidic solution.
Along CD, gradually increases due to the excess ammonia solution added which
together the ammonium chloride salt formed form a buffer solution which resists
increase in pH.
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(b) Titration of hydrochloric acid against ammonia solution
14
10
A
B
C
D

Volume of hydrochloric acid added

Initially, is slightly above seven at A because ammonia is a weak base that partially
ionises to form few hydroxide ions.
gradually decreases along AB as hydrochloric acid is added due to excess ammonia
solution still present which together with the ammonium chloride salt formed form a
buffer solution that resists a decrease in .
Also some of the ammonia solution is being neutralised by hydrochloric acid.
sharply decreases along BC even with a little hydrochloric acid added because the
end point is reached.
at end point is below 7 because the ammonium chloride salt formed undergoes
hydrolysis to form an acidic solution.
Along CD, gradually decreases due to excess hydrochloric acid added.

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Questions
1. (a) Sketch a graph to show how pH of potassium hydroxide changes when the
following are added until in excess
(i) Hydrochloric acid
(ii) Ethanoic acid
(b) Explain the shapes of the curves
(c) of 0.01M benzoic acid was added to an equal volume of 0.01M sodium
hydroxide. Calculate the pH of the resultant solution.
2. (a) Sketch pH-volume curves to show the change in pH that happens when:
(i) 0.1M sodium hydroxide solution is added in portions to of 0.1M
ethanoic acid.
(ii) 0.1M hydrochloric acid is added in portions to of 0.1M ammonia
solution.

(b) Explain the shapes of the graphs in both cases.
3. (a) Define the term indicator as used in acid-base titration
(b) The curve below was obtained when 0.1M sodium hydroxide solution was titrated
against of 0.1M methanoic acid.
14 Z
Y
7
X
2.5 W
0 Volume of sodium hydroxide solution
(i) Explain the shape of the curve WXYZ

(ii) Name a suitable indicator for the above titration
(c) Calculate the:
(i) dissociation constant of methanoic acid in (b) above
(ii) pH of the solution formed when of sodium hydroxide has just been
added to the methanoic acid in (b) above.
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4. sodium hydroxide solution was added to of 0.1M ethanoic acid in

portions.
(i) Sketch a graph to show the change in pH
(iii) Calculate the pH of the solution formed when of 0.1M sodium
hydroxide had been added to the ethanoic acid.
5. (a) (i) What is meant by a weak acid?
(ii) Calculate the of a 0.4 ethanoic acid solution. State any assumptions
made .
(b) (i) What is meant by a buffer solution.
(ii) Calculate the of a buffer solution made by mixing 15 of 0.01 ethanoic acid
with 25 of 0.1 sodium ethanoate solution.
(c) Draw a graph to show the changes when a strong acid is titrated with a weak
base and explain its shape

6. (a) (i) Explain what is meant by an acid-base indicator.
(ii) Explain in titration experiments one or two drops of indicators are used
(b) The table below gives data obtained when 100 of propanoic acid was titrated
with 1.0M sodium hydroxide solution.
Volume of sodium hydroxide 0.0 1.0 5.0 9.0 9.5 10.5 11.0 15.0
solution added
pH of solution 2.94 3.92 4.87 5.82 6.15 11.70 12.00 12.70
(i) Draw a graph of pH against the volume of sodium hydroxide
(ii) Explain the shape of the graph you have drawn in b(i).
(iii) Determine the pH of the solutions at equivalent point.
(iv) Which of the following indicators would be suitable for titration above? Give a
reason for you answer.
Indicator Methyl red Bromothymol blue Phenol red
pH range
7. The table below shows the pH changes when 10 of ethanoic acid was titrated
with 0.1M sodium hydroxide solution.
Volume of sodium hydroxide solution 0.0 2.0 4.0 6.0 8.0 10.0 14.0
added
pH of solution 2.9 4.3 4.7 5.2 6.4 12.2 12.4
(a) Plot a graph of pH against the volume of sodium hydroxide
(b) Explain the shape of the graph you have drawn.
(c) Use your graph to determine the :
(i) pH at equivalence point
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(ii) volume of sodium hydroxide used to neutralize the acid

(d) Calculate the molarity of the ethanoic acid used
(e) The pH ranges of some indicators are given in the table below.
Indicator Methyl orange Phenolphthalein Cresol red
pH range
Which of the indicators is suitable for the titration above? Give a reason for your answer
8. (a) The table below shows the pH of the solution when measured volumes of
hydrochloric acid is added to of 0.1M ammonia solution.
Volume of hydrochloric acid 0 10.0 15.0 16.5 17.0 20.0 25.0
pH of solution 10.25 9.08 8.30 6.70 2.97 1.96 1.60
(i) Plot a graph of pH against volume of hydrochloric acid
(b) Using the graph in (a) above, calculate the:
(i) molarity of hydrochloric acid

(ii) ionisation constant, of ammonia.
(iii) Concentration of ammonium chloride formed
(iv) hydrolysis constant of ammonium chloride
(c) Calculate the pH of the solution formed when of 0.1M hydrochloric acid is
added to of 0.1M ammonia solution.
℃
9. (a) Ethanoic acid is a weak acid.
(i) What is meant by the term weak acid?
(ii) Calculate the pH of 0.25M ethanoic acid. ( of ethanoic acid is 4.76 at
℃)
(iii) State and explain how temperature affects the of ethanoic acid.
(b) Calculate the pH of the resultant solution when of 0.1M sodium ethanoate
was added to of 0.25M ethanoic acid.
(c) The table below shows pH values for the titration of sodium hydroxide solution
against of 0.1M ethanoic acid.
Volume of sodium 0 4.0 6.0 8.0 10.0 12.0 14.0 14.6 14.8 15.0 15.2 15.4 16.0
hydroxide
added( )
pH 2.8 3.8 4.2 4.6 5.1 5.5 6.2 6.8 7.6 9.0 9.8 10.5 11.4
(i) Plot a graph of pH against volume of sodium hydroxide added
(ii) From the graph, determine the volume of sodium hydroxide needed to
neutralise the acid.
(iii) Calculate the molar concentration of sodium hydroxide solution
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(iv) Determine the ratio of [ ] [ ] when of sodium

hydroxide solution has been added to of ethanoic acid.
10. (a) What is a buffer solution?
(b) Describe how a basic buffer solution works. Illustrate your answer with a
solution in which phenylammonium chloride is a constituent.
(c) A solution was made by reacting 30 cm3 of 0.1M hydrochloric acid and 50 cm3 of
0.1M ammonia. Calculate the pH of the resulting solution.
(d) The table below shows the pH of the solution formed when 25 cm3 of 0.1M ethanoic
was titrated with sodium hydroxide solution.
Volume of sodium hydroxide 0 4 8 12 16 20 22 22.5 24 28
solution( )
pH 2.8 3.5 4.0 4.5 5.1 5.8 7.0 10.5 11.4 12.3
(i) Plot a graph of pH against volume of sodium hydroxide solution

(ii) Explain the shape of your graph
(iii) Calculate the molarity of sodium hydroxide.
(iv) Calculate the ionisation constant of ethanoic acid
(e) 50 cm3 of 0.1M sodium hydroxide was added to 50 cm3 of 0.1M ethanoic acid.
Calculate the pH of the resulting solution.
( )
SOLUBILITY EQUILIBRIA
Solubility
Solubility is the maximum mass of solute in grams that can saturate 100g of a solvent
at a particular temperature in presence of excess, undissolved solute.
The units for solubility are .
Molar solubility
Molar solubility is the number of moles of a solute that can dissolve in one litre of a
solution before the solution becomes saturated.
The units for molar solubility are .
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Experiment to determine solubility of a soluble salt

Considering potassium nitrate;
Add potassium nitrate, a little at a time, while stirring to a known volume of water in a
container immersed in a thermostat at a particular temperature until no more
potassium nitrate dissolves.
The mixture is allowed to settle until the excess undissolved crystals separate from the
solution.
The excess undissolved crystals are filtered off using a dry filter paper and funnel into a
dry container to obtain a saturated solution of potassium nitrate.
The temperature of the saturated solution is measured and recorded, ℃.
A clean dry dish is weighed and its mass recorded
A known volume of the saturated solution is added to the dish. The dish and the
saturated solution are also weighed again and the mass recorded
The dish and the saturated solution is placed on a steam bath until the dry potassium

nitrate crystals are left.
Allow the dish and its contents to cool and weigh the mass of the dish and the dry salt
again
( )
( ) ℃
( ) ℃
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Factors that affect solubility of a soluble salt

1. Nature of solvent and solute.
Polar solutes easily dissolve in polar solvents and non-polar solvents easily dissolve in
non-polar solvents.
2. Temperature
The solubility of most salts increases with increase in temperature. The effect of
temperature is in accordance with Le Chatelier‟s principle.
If a solute is in equilibrium with its saturated solution, increasing temperature will favour
the change which is accompanied with absorption of heat. Therefore more or less of the
substance will dissolve according to which change is accompanied by absorption of heat.
3. Pressure
The effect of pressure on the solubility of a solid is small because high pressures are
required to affect the volumes of liquids and extremely high pressures to affect the
volumes of solids.

However, if pressure is sufficiently increased, an appreciable change in solubility may
happen. The effect of pressure on solubility of a salt is also in accordance with Le
Chatelier‟s principle.
Increase in pressure to 500 atm increases solubility of sodium chloride in water because
the salt dissolves in water with a decrease in total volume.
Increase in pressure to 500 atm decreases solubility of ammonium chloride in water
because the salt dissolves in water with an increase in total volume.
Solubility curves
The variation of solubility with temperature can be summarised by solubility curves.
Solubility
𝒈 𝒑𝒆𝒓 𝟏𝟎𝟎𝒈
𝒐𝒇 𝒘𝒂𝒕𝒆𝒓
𝑵𝒂𝟐 𝑺𝑶𝟒
𝑵𝒂𝑪𝒍
Temperature ℃
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597
For salts that form solutions endothermically, the solubility generally increases with
increase in temperature.
For salts whose solubility decreases with increase in temperature, such as anhydrous
sodium sulphate, heat is evolved on dissolving. Other examples of such salts include
calcium sulphate and calcium hydroxide.
The transition point in solubility for sodium sulphate is due to a change in hydration.
The application of solubility curves (fractional crystallisation)
Fractional crystallisation can be used to purify substances with different solubilities.

Consider a mixture of potassium chloride and potassium chlorate(V).

Solubility
𝒈 𝒑𝒆𝒓 𝟏𝟎𝟎𝒈
𝒐𝒇 𝒘𝒂𝒕𝒆𝒓
Temperature ℃
Potassium chloride and potassium chlorate(V) have different solubilities in water at

different temperatures.
When a concentrated solution of the two salts in water is heated and then cooled,
potassium chlorate(V) which is less soluble at lower temperatures crystallises first.
The first yield therefore contains potassium chlorate(V) crystals and a small amount of
potassium chloride.
When the first yield of crystals is dissolved in hot water and the process of crystallisation
repeated, pure crystals of potassium chlorate(V) are finally obtained from free from
potassium chloride.
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Calculation of solubility
Examples
(a) (a) 350 of water was saturated by 157.5g of potassium nitrate at 30℃.
Calculate the solubility of potassium nitrate at 30℃. (Density of water is
)
(b) The solution in (a) was cooled to 15℃. Calculate the mass of potassium nitrate
crystallised if the solubility of potassium nitrate at 15℃ is 25.0g per 100g.
(a)
℃
( ) ℃
℃
(b) ℃

( ) ℃
℃
℃ ℃
(b) 60g of a saturated solution of a soluble salt Q gave 17.75g of Q at 50℃. Calculate
the solubility of Q at 50℃.
℃
( ) ℃
℃
(c) The solubility of potassium chlorate(V) is 60g per 100g of water at 100℃.
Calculate the number of moles the salt that can saturate 150g of water at the
same temperature.
℃
( ) ℃
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Question
21.38g of a saturated solution of a soluble salt, X, was evaporated to dryness and 4.28g of
X were obtained at a certain temperature. Calculate the solubility of X at that
temperature.
Solubility curves
Plotting and interpreting solubility curves for soluble salts
Questions
1. (a) Describe an experiment to determine the solubility of potassium chlorate(V) in

water at room temperature.
(b) The results below were obtained for the solubility of potassium chloride and
potassium chlorate(V) in water at different temperatures.
Temperature ℃

0 28 3
20 34 7
50 42 19
100 56 59
(i) Plot the solubility curves of the two salts on the same axes
(ii) Determine the temperature at which the two salts have equal solubilities.
(iii) State which of the two salts dissolves more rapidly with increase in
temperature.
(iv) State one application of solubility curves.
2. The table below shows the solubility of potassium nitrate in water at different
temperatures.
Temperature ℃ 10 15 30 40 50 57
Solubility 20 25 45 63 85 106
(a) Plot a graph of solubility against temperature

(b) Use your graph to determine solubility at:
(ii) 36℃
(iii) 62℃
(c) Calculate the mass of potassium nitrate that crystallises on lowering the temperature
from 50℃ to 15℃
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The concept of dynamic equilibrium in a saturated salt solution

The presence of excess undissolved solute in contact with a solution ensures the solution
is saturated. There exists a dynamic equilibrium between the undissolved and the
dissolved solid. The dynamic equilibrium exists in the saturated solution when solute
particles return to the surface of the solid at the same rate as they are dissolving. The
amount of the solid dissolving balances the amount of substance that is crystallizing.
Sparingly soluble salts/ electrolytes

Many salts such as lead(II) sulphate, calcium carbonate, silver chloride and others are
described as insoluble in water. There is however, in practice, no substance completely
insoluble but some substances dissolve to a very small extent that their solubility cannot
be determined by the ordinary method already described.
Electrolytes that dissolve only slightly in water are called sparingly soluble electrolytes.
Solubility product

Consider a sparingly soluble electrolyte, . The ions of the electrolyte in its
saturated solution will be in equilibrium with the undissolved solid at a given
temperature.
From the law of mass action:

[ ] [ ]
Since the concentration of a solid remains constant, then;

[ ] [ ]
The constant, is called the solubility product of the sparingly soluble electrolyte,
.
Solubility product is therefore defined as the product of the molar concentrations of the
ions of a sparingly soluble electrolyte in its saturated solution raised to appropriate
powers at a given temperature.
Expressions for solubility product

Consider each of the sparingly soluble electrolytes below. For each the equation for
solubility in water and the solubility product expression is written.
(i) Silver bromide
(ii) Silver ethanedioate
(iii) Calcium phosphate
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(i) Silver bromide

Equation :
[ ][ ]
(ii) Silver ethanedioate

Equation :
[ ] [ ]
(iii) Calcium phosphate

Equation :
[ ] [ ]
Question
For each of the following sparingly soluble electrolytes, write the;

(i) equation for solubility of the electrolyte in water
(ii) expression for the solubility product
1. Silver chloride 22. Calcium iodate
2. Silver iodide 23. Calcium ethanedioate
3. Silver carbonate 24. Chromium(III) hydroxide
4. Silver sulphate 25. Mercury sulphide
5. Silver chromate 26. Mercury(I) iodide
6. Silver sulphide 27. Lead(II) fluoride
7. Silver oxalate 28. Lead(II) chloride
8. Silver ethanoate 29. Lead(II) iodide
9. Silver bromate(V) 30. Lead(II) sulphate
10. Silver iodate(V) 31. Lead(II) sulphide
11. Silver phosphate 32. Magnesium hydroxide
12. Aluminium hydroxide 33. Manganese(II) sulphide
13. Barium hydroxide 34. Strontium hydroxide
14. Barium sulphate 35. Tin(II) sulphide
15. Barium carbonate 36. Zinc hydroxide
16. Calcium hydroxide 37. Zinc sulphide
17. Calcium carbonate
18. Calcium sulphate
19. Copper(II) sulphide
20. Copper(II) iodate
|
21. Iron(III) hydroxide

602
Conditions under which solubility product is valid

1. Temperature is kept constant
2. Solution must be saturated
3. Electrolyte should be sparingly soluble
Experimental determination of solubility product

Solubility product of different sparingly soluble electrolytes can be determined by any of
the following methods;
 Direct titration
 Using conductivity measurements
 Using electrode potentials
The first two methods will be used in this topic but more about conductivity
measurements and electrode potentials will be seen in the topic: Electrochemistry.
However, for examination purposes, any method can be used.

Experiment to determine solubility product of calcium hydroxide
(a) By titration
Excess solid calcium hydroxide is added to a given volume of distilled water in a
container.
The mixture is shaken for some time and left to settle at a given temperature to attain
equilibrium.
The mixture is filtered to obtain a saturated solution of calcium hydroxide as filtrate.
A known volume of the filtrate is pipetted into a conical flask and titrated with a
The molar concentration of calcium hydroxide solution is calculated using the equation
above.
Taking the molar concentration of calcium hydroxide as .
̅
[ ] [ ]
̅
[̅ ] [ ]
[ ][ ̅ ]
This method can be used for any sparingly soluble metal hydroxide.
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(b) Using conductivity measurements

Excess solid calcium hydroxide is added to a given volume of distilled water in a
container.
equilibrium.
The mixture is filtered to obtain a saturated solution of calcium hydroxide as filtrate.
The electrolytic conductivity of the saturated solution, is
measured using a conductivity meter.
The electrolytic conductivity of water, at the same temperature is
obtained from books
Also the molar conductivities at infinite dilution of calcium ions and hydroxide ions
are read from the tables.
The electrolytic conductivity of calcium hydroxide is then obtained by;

The molar conductivity of calcium hydroxide at infinite dilution is obtained by the
equation;
̅
, where is molar conductivity of calcium hydroxide
̅
[ ]
[ ] [ ]
̅
[̅ ] [ ]
[ ̅
][ ]
This method can be used for any electrolyte whose solution cannot be titrated with any
suitable reagent.
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Experiment to determine solubility product of silver ethanedioate
(a) By titration
Excess solid silver ethanedioate is added to a given volume of distilled water in a
container.
The mixture is shaken for some time and left to settle at given temperature to attain
equilibrium.
The mixture is filtered to obtain a saturated solution of silver ethanedioate as filtrate.
A known volume of the filtrate is pipetted into a conical flask , acidified and warmed.
The warm solution is then titrated with a standard solution of potassium
manganate(VII) solution.
The molar concentration of the oxalate(ethanedioate) ions in the solution is
calculated using the equation below.
Taking the molar concentration of ethanedioate ions as .

[ ]
[ ] [ ]
[ ] [ ]
This method can be used for any sparingly soluble metal oxalate (ethanedioate).No
indicator is required because potassium permanganate acts as own indicator.
Excess solid silver ethanedioate is added to a given volume of distilled water in a
container.
equilibrium.
The mixture is filtered to obtain a saturated solution of silver ethanedioate as filtrate.
obtained from books
Also the molar conductivities at infinite dilution of silver ions and ethanedioate ions
The electrolytic conductivity of silver ethanedioate is then obtained by;
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The molar conductivity of silver ethanedioate at infinite dilution is obtained by the

equation;
, where is molar conductivity of silver ethanedioate
[ ]
[ ] [ ]
[ ] [ ]
[ ] [ ]
Experiment to determine solubility product of copper(II) iodate

(a) By titration
Excess solid copper(II) iodate is added to a given volume of distilled water in a
container.
The mixture is shaken for some time and left to settle at given temperature to attain
equilibrium.
The mixture is filtered to obtain a saturated solution of copper(II) iodate as filtrate.
A known volume of the filtrate is pipetted into a conical flask and a known volume
potassium iodide solution added and acidified with a known volume of sulphuric
acid.
The resultant solution containing iodine liberated is then titrated with a standard
solution of sodium thiosulphate solution using starch indicator.
The molar concentration of the iodate(V) ions in the solution is calculated using
the two equations above.
Taking the molar concentration of iodate(V) ions as .
[ ]
[ ] [ ]
[ ][ ]
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This method can be used for any sparingly soluble metal iodate.
Excess solid copper(II) iodate is added to a given volume of distilled water in a
container.
equilibrium.
The mixture is filtered to obtain a saturated solution of copper(II) iodate as filtrate.
obtained from books
Also the molar conductivities at infinite dilution of copper(II) ions and iodate ions

The electrolytic conductivity of copper(II) iodate is then obtained by;
The molar conductivity of copper(II) iodate at infinite dilution is obtained by the

equation;
, where is molar conductivity of copper(II) iodate
[ ]
[ ] [ ]
[ ] [ ]
[ ][ ]
Factors affecting solubility of sparingly soluble electrolytes

(a) Common ion effect
Common ion effect is the precipitation of a sparingly soluble electrolyte from its
saturated solution by addition of a solution of a more soluble electrolyte containing one
of the ions of the sparingly soluble electrolyte.
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When a solution contains a similar ion is added to a saturated solution of a sparingly

soluble electrolyte, the solubility of the electrolyte decreases.
Examples
1. Silver chromate is sparingly in water. Explain what will happen to the solubility
of silver chromate when each of the following is separately added.
(i) Silver nitrate
(ii) Potassium chromate
(i) Addition of silver nitrate decreases the solubility of silver chromate because silver
nitrate contains silver ions that are common to silver ions in silver chromate. The
excess silver ions added combine with chromate ions in solution to precipitate silver
chromate in order to restore the equilibrium, maintaining the value of the
equilibrium constant.

(ii) Addition of potassium chromate decreases the solubility of silver chromate because
potassium chromate contains chromate ions that are common to chromate ions in
silver chromate. The excess chromate ions added combine with silver ions in
solution to precipitate silver chromate in order to restore the equilibrium,
maintaining the value of the equilibrium constant.
2. Explain what would happen to the solubility of calcium phosphate in water
when:
(i) Sodium phosphate is added
(ii) Calcium nitrate is added
(i) Addition of sodium phosphate decreases the solubility of calcium phosphate because
sodium phosphate contains phosphate ions that are common to phosphate ions in
calcium phosphate. The excess phosphate ions added combine with calcium ions in
solution to precipitate calcium phosphate in order to restore the equilibrium,
(ii) Addition of calcium nitrate decreases the solubility of calcium phosphate because
calcium nitrate contains calcium ions that are common to calcium ions in calcium
|
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nitrate. The excess calcium ions added combine with phosphate ions in solution to
precipitate calcium phosphate in order to restore the equilibrium, maintaining the
value of the equilibrium constant.
3. State what happens to the solubility of lead(II) iodide in water when:
(i) Potassium iodide is added- solubility decreases
(ii) Lead(II) nitrate is added- solubility decreases
The applications of common ion effect
(i) Purification of sodium chloride (common salt)

Sodium chloride commonly contains small quantities of calcium chloride and magnesium
chloride that cause it to be deliquescent.
The sodium chloride is purified by adding concentrated hydrochloric acid into its
saturated solution which increases the concentration of chloride ions. The equilibrium is

displaced to the left, decreasing the degree of dissociation of sodium chloride, hence
precipitating sodium chloride since the solution is already saturated by the sodium
chloride.
(ii) Salting out soap
During saponification, hot concentrated sodium chloride is added to the mixture to
precipitate soap.
Soap is a sodium salt of a long chain carboxylic acid. In a saturated solution of soap
exists the equilibrium;
Adding concentrated sodium chloride to a saturated soap solution increases the

concentration of sodium ions. The excess sodium ions react with the carboxylate ions
hence precipitating soap.
(a) Complex ion formation

When to a saturated solution of a sparingly soluble electrolyte is added a solution of a
soluble salt that forms a complex with the electrolyte, its solubility increases.
Examples
1. Silver carbonate is sparingly soluble in water. Explain what happens to the
solubility of silver carbonate if ammonia solution is added to its saturated
solution.
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608
Addition of ammonia solution increases the solubility of silver carbonate because

ammonia solution reacts with silver ions to form a soluble complex of
diammine silver(I) ion.
This lowers the concentration of silver ions and more silver carbonate dissolves, to
restore the equilibrium, maintaining the value of the equilibrium constant.
Note: Ammonia solution has the same effect on the solubility of sparingly soluble
copper(I) chloride.
2. Copper(II) iodate is more soluble in ammonia solution than in water.
Addition of ammonia solution increases the solubility of copper(II) iodate because

ammonia solution reacts with copper(II) ions to form a soluble complex of

tetraammine copper(II) ion.
This lowers the concentration of copper(II) ions and more copper(II) iodate dissolves,
to restore the equilibrium, maintaining the value of the equilibrium constant.
3. The solubility of lead(II) chloride in cold water decreases on addition of dilute

hydrochloric acid but increases on addition concentrated hydrochloric acid.
Lead(II) chloride is sparingly soluble in cold water.
Addition of dilute hydrochloric acid to a solution of lead(II) chloride decreases its

solubility because dilute hydrochloric acid contains chloride ions that are common to
chloride ions in lead(II) chloride. The excess chloride ions added combine with chloride
ions in solution to precipitate lead(II) chloride in order to restore the equilibrium,
Addition of concentrated hydrochloric acid increases the solubility of lead(II) chloride
because the chloride ions present in high concentration react with lead(II) chloride to
form a soluble complex of tetrachloroplumbate(II) ion.
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609
Questions
1. Silver ions , iron(III) ions and calcium ions form complexes with sodium thiosulphate
solution, potassium hexacyanoferrate(II) solution and triphosphate ions respectively.
State what will happen to the solubility of:
(i) Silver chloride if sodium thiosulphate solution is added
(ii) Iron(III) hydroxide if potassium hexacyanoferrate(II) solution is added
(iii) Calcium sulphate if sodium triphosphate is added
2. Both aluminium hydroxide and zinc hydroxide are do not easily dissolve in water but
their solubility increases on addition of sodium hydroxide solution.
3. When hydrochloric acid is added to lead(II) nitrate solution drop wise until in excess,
at varying concentrations of the acid, the curve below is obtained. Explain the shape
of the graph.
Solubility(gdm-3)

Concentration of hydrochloric acid added(moldm-3)
(c) Addition of a soluble compound containing no similar ion as those of the

sparingly soluble electrolyte
When a soluble compound with no common ions to a saturated solution of a sparingly
soluble electrolyte is added, the solubility of the electrolyte increases
Example
Explain why calcium ethanedioate is less soluble in calcium nitrate but more soluble
in dilute hydrochloric acid
Calcium oxalate is sparingly soluble in water
Addition of calcium nitrate decreases the solubility of calcium oxalate because calcium
nitrate contains calcium ions that are common to calcium ions in calcium oxalate. The
excess calcium ions added combine with oxalate ions in solution to precipitate calcium
oxalate in order to restore the equilibrium, maintaining the value of the equilibrium
constant.
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610
In the presence of dilute hydrochloric acid, the hydrogen ions react with oxalate ions to
form oxalic acid.
This reduces the concentration of oxalate ions in solution hence more calcium oxalate
dissolves to restore the equilibrium, maintaining the value of the equilibrium constant.
The relationship between ionic product, solubility product ( ) and

precipitation
For any sparingly soluble electrolyte, .
[ ] [ ]
[ ] [ ]
Both the solubility product have the same expressions but the difference is that ionic
product is applicable to all types of solutions at any concentration and keeps increasing
with the increase in the concentration of ions

On the other hand, solubility product is applicable to only saturated solutions and is
constant at a constant temperature for a given electrolyte.
 When the ionic product is less than the solubility product, more of the sparingly
soluble salt dissolves since the solution is unsaturated
 When the ionic product is equal the solubility product, no more of the sparingly
soluble salt dissolves since the solution is saturated
 When the ionic product exceeds the solubility product, precipitation of a sparingly
soluble electrolyte occurs.
In general:
[ ] [ ] Solution is not saturated, more electrolyte can
dissolve
[ ] [ ] Solution is saturated, cannot dissolve any
more electrolyte can dissolve
[ ] [ ] Precipitation occurs
Examples
1. When ammonia solution is added to magnesium chloride solution, a white

precipitate insoluble in excess is formed but when the same solution is added to
calcium chloride solution, there is no observable change.
Magnesium ions react with hydroxide ions to form insoluble magnesium hydroxide.
Magnesium hydroxide is basic hence cannot react with excess sodium hydroxide
Ammonia is a weak base which partially ionises to form few hydroxyl ions
̅
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611
The concentration of the hydroxyl ions formed from the weak ammonia base is low for
the ionic product of calcium hydroxide to exceed its solubility product. Therefore, no
precipitation occurs.
2. When ammonia solution is added to a solution of magnesium sulphate, a white
precipitate is formed. However, when ammonia solution is added in presence of
ammonium chloride solution, no precipitate is formed. Explain
Ammonia is a weak base that partially ionises in water to form ammonium ions and
hydroxyl ions.
̅
The concentration of the hydroxyl ions formed from the ammonia solution is enough to
react with magnesium ions for the ionic product of magnesium hydroxide to exceed its
solubility product. Therefore, magnesium hydroxide is precipitated.
̅
Ammonium chloride is a strong electrolyte that completely ionises to form ammonium

ions.
The ammonium ions from the salt suppress the ionisation of ammonia solution due to
common ion effect. This reduces the concentration of hydroxide ions in solution hence
the ionic product of magnesium hydroxide does not exceed its solubility product.
3. When hydrogen sulphide gas is bubbled through a solution of manganese(II)
nitrate, no observation occurs in the presence of dilute hydrochloric acid but in
presence of ammonia solution, a pink precipitate is formed. Explain.
Hydrogen sulphide is a weak electrolyte that partially ionises in solution to form sulphide
ions and hydrogen ions.
In the presence of dilute hydrochloric acid which is a strong electrolyte, the hydrogen
ions from the completely ionised acid suppress the ionisation of hydrogen sulphide due
to common ion effect. This reduces the concentration of sulphide ions in solution
hence the ionic product of manganese(II) sulphide does not exceed its solubility
product. No precipitation occurs.
In the presence of ammonia solution which is a weak base, the hydroxide ions from
ammonia acid react with the hydrogen ions from hydrogen sulphide to form water.
̅
̅
This reduces the concentration of hydrogen ions in solution hence more hydrogen
sulphide ionises, forming a concentration of sulphide ions high enough for the ionic
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612
product of manganese(II) sulphide to exceed its solubility product. The insoluble

manganese(II) sulphide is formed hence precipitation then occurs.
Application of solubility product,

 Salting out soap
 Purification of common salt
 precipitation of hydroxides
 Precipitation of sulphides
 Precipitation of chlorides
Questions
Explain the following observations:
(a) Calcium phosphate is sparingly soluble in water but soluble in dilute hydrochloric
acid.

(b) Zinc sulphide is more soluble in dilute hydrochloric acid than in water.
(c) Barium chromate is more soluble in dilute nitric acid than in water
(d) A concentrated solution of calcium chloride forms a white precipitate with sodium
hydroxide solution but no observable change with ammonia solution.
(e) When hydrogen sulphide gas is bubbled through a solution containing lead(II) nitrate
and zinc nitrate, only lead(II) sulphide is precipitated.
(f) The solubility of silver(I) ethanedioate in pure water decreases on addition of silver
nitrate solution.
(g) When ammonia solution is added to a solution of manganese(II) sulphate, a dirty
white precipitate is formed. However when it is added to the same solution in
presence of ammonium chloride solution, no precipitate is formed.
Calculations involving solubility and solubility products
Examples
1. The solubility of calcium phosphate is 0.0011g per 100g of water at ℃.

Calculate the solubility product of calcium phosphate at ℃.
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613
[ ] [ ]
( )
[ ]
Then:
[ ] [ ] ( )
. Then:
[ ] [ ] ( )
[ ] [ ]

2. (a) The solubility product, , of zinc hydroxide is at
℃. Write an expression for solubility product of zinc hydroxide.
(b) Determine the concentration in moles per litre of zinc ions and hydroxide
ions in a saturated solution of zinc hydroxide at ℃
(c) State how solubility of zinc hydroxide would change if its saturated solution is
treated separately with:
(i) aqueous zinc sulphate
(ii) ammonia solution
(d) Briefly explain your answer in (c).
(a) [ ][ ̅ ]
(b)
[ ] √
[ ]
̅ . Then:
[̅ ] [ ] [ ]
[ ][ ̅ ]
[̅ ] [ ]
(c) (i) Solubility would decrease.

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614
(ii) Solubility would increase.

(d) Addition of zinc sulphate solution decreases the solubility of zinc hydroxide because zinc
sulphate contains zinc ions that are common to zinc ions in zinc hydroxide. The excess zinc
ions added combine with hydroxide ions in solution to precipitate zinc hydroxide in order to
restore the equilibrium, maintaining the value of the equilibrium constant.
Addition of ammonia solution increases the solubility of zinc hydroxide because ammonia solution
reacts with zinc ions to form a soluble complex of tetrammine zinc(II) ions.
This lowers the concentration of zinc ions and more zinc hydroxide dissolves, to restore the
equilibrium, maintaining the value of the equilibrium constant.
3. (a) Magnesium hydroxide is sparingly soluble in water.

Write:
(i) the equation for the solubility of magnesium hydroxide in water
(ii) the expression for the solubility product, of magnesium hydroxide

(b) If the solubility product of magnesium hydroxide at ℃ is
. Calculate the solubility in moles per litre at ℃ of
magnesium hydroxide in:
(i) water
(ii) a 0.01M sodium hydroxide
(c) Comment on your answers in (b) above
(a) (i) ̅
(ii) [ ][ ̅ ]
(b) (i) (ii)
̅
[ ]
̅
[ ]
̅ . Then: [ ]
[̅ ] [ ] ̅
[ ]
[ ][ ̅ ]
[̅ ]
[ ][ ̅ ]
√
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615
(c) Magnesium hydroxide is more soluble in water than sodium hydroxide. The decrease in its
solubility in sodium hydroxide is due to common ion effect.
4. The solubility of lead(II) sulphate in water is at ℃. Calculate

the solubility of lead(II) sulphate in 0.02M lead(II) nitrate solution at the same
temperature in grams per litre.
[ ][ ]
[ ]
[ ]
[ ]

[ ]
[ ][ ]
Then: [ ]
Also: [ ]
[ ][ ]
5. (a) Write:
(i) equation for the solubility of silver chromate in water.
(ii) expression for solubility product, , of silver chromate.
(b) The solubility of silver chromate at ℃ is .Calculate the
solubility product of silver chromate at ℃.
(c) A solution containing silver ions was separately added to a solution
containing chromate ions and chloride ions.
State which of the salts silver chloride or silver chromate would precipitate
first. Give a reason for your
answer
(a) (i)
(ii) [ ] [ ]
(b) Then: [ ] ( )
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616
.
Then: [ ]
[ ] [ ]
[ ]
(c) [ ] [ ] [ ][ ]
[ ] [ ]
[ ] √ [ ]
[ ]
[ ]
Silver chloride would precipitate first because it
requires a lower concentration of silver ions to
be formed.
6. Calcium hydroxide is sparingly soluble in water.
(a) Write the expression for the solubility product of calcium hydroxide

(b) If the solubility of calcium hydroxide in water at ℃ is .Calculate
the molar concentration of:
(i) calcium ions
(ii) hydroxide ions
(c) (i) Calculate the solubility product of calcium hydroxide at ℃ and give its
units.
(ii) Calculate the volume of 0.5M potassium iodate that must be added to 1
litre of a saturated solution of calcium hydroxide above to precipitate
calcium iodate at the same temperature.
(a) [ ][ ̅ ]
(b) (i)
[ ]
̅
Then:
[ ]
(ii) ̅ . Then:
[̅ ] [ ]
[̅ ]
(c) (i) [ ][ ̅ ]
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617
(ii)
[ ][ ]
[ ]
[ ]
[ ] √
. Then:
[ ] [ ]
( )
7. (a) The solubility product of silver chromate at ℃ is .

When a saturated solution of silver chromate was shaken with an aqueous
solution of silver nitrate, the solubility of silver chromate reduced by 94.5% of
the solubility in pure water. Calculate the concentration of silver nitrate solution
in grams per litre.
(b) When silver nitrate is titrated with a solution containing both potassium
chromate and potassium chloride, a white precipitate is formed rather than a
red precipitate.
(a)
[ ] [ ]
[ ]
. [ ]
Then: [ ] [ ] [ ]
[ ] [ ] [ ] [ ]
√
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618
( )
(b) Silver chloride has a lower solubility than that of silver chromate. In the solution, the ionic
product of silver chloride exceeds its solubility product before the ionic product of silver
chromate exceeds the solubility product of silver chromate. Therefore silver chromate can only be
precipitated when sufficient silver nitrate has been added to the solution to precipitate all the
silver chloride.
8. Mercury(I) iodide was dissolved in 0.3M sodium iodide solution. Calculate the
concentration of the mercury(I) iodide in the solution in . The solubility
of mercury(I) iodide in water is at ℃ and mercury(I)
iodide dissolves in water according to the following equation:

[ ]
[ ]
[ ]
Then: [ ] [ ]
[ ][ ]
. Then:
[ ] [ ]
[ ][ ]
|
619
9. (a) The solubility of lead(II) iodide in 0.2M potassium iodide at ℃ is

.Write an equation for the solubility equilibrium reaction
of lead(II) iodide.
(b) Calculate the:
(i) solubility product, of lead(II) iodide
(ii) solubility of lead(II) iodide in water
(c) Explain the difference between your answer in b(ii) above and the solubility
of lead(II) iodide in 0.2M potassium iodide.
(a)
(b) (i) (ii)
Then: [ ]

Then: [ ]
[ ][ ]
[ ]
[ ] √
[ ]
[ ]
[ ][ ]
(c) The solubility of lead(II) iodide in 0.2M potassium iodide is lower than its solubility in water.
Addition of potassium iodide decreases the solubility of lead(II) iodide because potassium iodide
contains iodide ions that are common to iodide ions in lead(II) iodide. The excess iodide ions added
combine with lead(II) ions in solution to precipitate lead(II) iodide in order to restore the equilibrium,
10. (a) The solubility product of copper(II) iodate at ℃ is
.Calculate the concentration of iodate ions in a saturated
solution of copper(II) iodate at ℃:
(b) (i) 0.25 moles of copper(II) chloride was added to 500 of a saturated
solution of copper(II) iodate and the mixture stirred. Calculate the mass of
copper(II) iodate that was precipitated.
(ii) State any assumptions made in b(i) above.
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620
(b) (i)
(a)
( )
[ ] [ ]
[ ]
[ ][ ]
[ ]
√
[ ] [ ]
[ ]

[ ][ ]
b(ii) Assumptions in b(i)
 No change in temperature occurs
 [ ] from copper(II) iodate is negligible in √
comparison to that from copper(II) chloride.
([ ] ) [ ]
 There is no change in total volume of the
solution
11. Barium sulphate is sparingly soluble in water. If the solubility product of barium
sulphate is at ℃. Calculate the mass of barium
nitrate that should be added to the saturated solution of barium sulphate in
order to reduce the concentration of sulphate ions to one third of its original
value.
[ ]
[ ] [ ] [ ]
[ ][ ] [ ]
[ ][ ]
|
621
√
[ ]
[ ] ( )
( )
12. (a) Silver sulphate is sparingly soluble in water. Write the;

(i) equation for solubility of silver sulphate in water.
(ii) expression for solubility constant.
(b) 50 cm3 of 0.13M silver nitrate was mixed with 150cm3 of 0.02M sodium sulphate
at 25 . Calculate the concentrations in the resultant soltion of;

(i)silver ions
(ii) sulphate ions
(c) (i) Calculate the ionic product of silver sulphate at 25 .
(ii) State whether silver sulphate will be precipitated or not in the solution in (b).
Give a reason for your answer. (The solubility product of silver sulphate at ℃
is )
(a)(i) (ii)
(ii) [ ] [ ] ( )
(b)(i)
( )
( )
( ) (c)(i)
[ ] [ ]
(ii) Silver sulphate will not be precipitated.

This is because the ionic product of silver
sulphate does not exceed its solubility
product.
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622
Questions
1. (a) The solubility product of a sparingly soluble base is

.
Define the term solubility product.
(b) Calculate its solubility in:
(i) Water
(ii) 0.1M sodium hydroxide solution.
(iii) 0.5M ammonia solution
(c) Explain the differences in your answers in c(i) and (ii) above
2. (a) State the two methods by which the solubility of a sparingly soluble salt may be
determined.
(b) Copper(II) iodate is sparingly soluble in water.
Write:
(i) an equation for the solubility of copper(II) iodate

(ii) an expression for the solubility product, of copper(II) iodate.
(c) The solubility product of copper(II) iodate at ℃ is .
Calculate the solubility in grams per litre at ℃ of copper(II) iodate in:
(i) water
(ii) a 0.1M potassium iodate
(d) Comment on your answer in (c) above.
3. (a) Define :
(i) Solubility
(ii) Solubility product
(b) Describe an experiment that can be carried out to determine the solubility product
of silver chromate in the laboratory.
(c) The solubility of silver chromate at ℃ is .Calculate the;
(i) solubility product at this temperature.
(ii) Solubility of silver chromate in 0.2M potassium chromate solution.
(iii) Solubility of silver chromate in 0.05M silver nitrate solution
(d) Explain the effect of adding the following solutions on the solubility of silver
chromate.
(i) Ammonia solution
(ii) Silver nitrate solution
(e) A solution of silver nitrate wad added to a solution containing 0.05M potassium
chloride and 0.05M potassium chromate. Calculate the concentration of silver ions
required to precipitate :
|
(i) Silver chloride

623
(ii) Silver chromate

(f) State which of the compounds in (d) will be precipitate first. Give a reason for
your answer.(Solubility product of silver chloride at
℃)
(g) State two applications of solubility product.

4. The solubility of silver chloride in water is .Calculate the
solubility of silver chloride in 0.1M potassium chloride solution.
5. (a) Silver carbonate is sparingly soluble in water. Write:
(i) the equation for solubility of silver carbonate in water.
(ii) the expression for for silver carbonate
(b) The solubility of silver carbonate at ℃ is Calculate the solubility
product of silver carbonate at ℃.
(c) State what would happen to the solubility of silver carbonate when a 0.1M

solution of silver nitrate is added to the saturated solution. Explain your answer.
6. (a) (i) Write an equation for the solubility of silver sulphate in water
(ii) Determine the molar concentrations of silver ions and sulphate ions in a
saturated solution of silver sulphate at ℃. (The , of silver sulphate
is at ℃)
(b) State how the solubility of silver sulphate would be affected if the following
substances were added.
(i) Sodium sulphate solution
(ii) Ammonia solution
(c) Explain your answer in (b)
7. Powdered magnesium hydroxide was shaken with water at 25 to form a saturated

solution. The mixture was filtered and 100 of the filtrate required 6.4 of a 1M
hydrochloric acid for complete reaction.
(a) Write an expression for the solubility product of magnesium hydroxide and give
its units.
(b) Calculate the solubility product of magnesium hydroxide at 25 .
(c) Explain the effect, if any, on the solubility of magnesium hydroxide if the
following substances were added separately ;
(i) sodium hydroxide solution
(ii) a compound which forms a stable complex with magenesium ions
(iii) aluminium nitrate solution℃. (The , of is
at ℃)
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624
8. (a) Explain what is meant by the terms:

(i) common ion effect.
(ii) solubility of a salt.
(b) Silver chromate is sparingly soluble in water .Write:
(i) equation for the solubility of silver chromate in water
(ii) the expression for the solubility product, , for silver chromate.
(c) A saturated solution of silver chromate contains per litre at ℃.
Calculate the value for the solubility product, , for silver chromate at ℃.
(d) Chloride ions in solution can be detected by titration with silver nitrate solution in the
presence of chromate ions. The end point is indicated by a red precipitate of silver
chromate.
(i) Explain why silver chromate does not precipitate until the end point is reached
(ii) 25cm3 of a solution containing 0.1moles of potassium chloride and 0.001
moles of chromate ion is required on titration with 50cm3 of 0.1M silver nitrate

solution to reach the end point. Calculate the concentration of chloride ions at
the end point. [Solubility product for silver chloride is ]
9. (a)Explain what is meant by the terms:
(i) salt hydrolysis
(ii) common ion effect
(iii) solubility product constant
(b) When sodium hydroxide solution is added to aqueous calcium hydroxide solution,
a white precipitate is formed but when ammonia solution is used instead of sodium
hydroxide solution, no precipitate is formed. Explain the observation.
(c) Describe an experiment to determine the solubility product of silver phosphate in
the laboratory.
(d) Write:
(i) the equation for the solubility of silver phosphate in water
(ii) an expression for the solubility product, of silver phosphate
(e) If the solubility of silver phosphate at ℃ is . Calculate the
value of the at ℃.
(f) State how solubility of silver phosphate would be affected if the following
substances were added.
(i) ammonia solution
(ii) silver nitrate solution
(g) Explain your answer in (c) above.
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625
10. (a) Silver chromate is sparingly soluble in water. Write:

(i) an equation for the solubility of silver chromate in water
(ii) an expression for the solubility product constant, for silver chromate.
(b) The solubility of silver chromate is per 100g of water at a certain
temperature. Calculate the solubility product of silver chromate.
(c) Calculate the solubility of silver chromate in of 0.1M silver nitrate
solution.
11. Lead(II) chloride is sparingly soluble in cold water.
(a)(i) Write the equation for the solubility of lead(II) chloride in water.
(ii)Write the expression for the solubility product, of lead(II) chloride
(b) At ℃ , a saturated solution contains 1.1g of lead(II) chloride per litre. Calculate
the solubility product at this temperature.
(c) Solid lead(II) chloride can be prepared in the laboratory by heating lead(II) oxide
with dilute hydrochloric acid and the mixture cooled. However, solid lead(II)

chloride cannot be formed when lead(II) oxide is reacted with concentrated
hydrochloric acid. Give reasons for this observation and illustrate your answer
with an equation.
12. (a) The solubility of lead(II) iodide is 0.122g in 100 of water at ℃.
(i) Write equation for the solubility of lead(II) iodide in water
(ii) Calculate the solubility constant, for lead(II) iodide at ℃.
(b) Sodium chromate solution was added to a saturated solution of lead(II) iodide until
in excess.
(i) State what is observed and give a reason for your answer.
(ii) Write equation for the reaction that took place
(c) 50 of 0.001M lead(II) nitrate solution was mixed with 50 of 0.001M
potassium iodide. Deduce whether lead(II) iodide will be precipitate or not. Show
your working clearly and give a reason for your answer.
(d) The saturated solution of lead (II) iodide of concentration 0.122g per 100 of
solution was heated to ℃ in a closed system.
(i) State whether the solution remains saturated at ℃
(ii) Give a reason for your answer.
13. (a) of solid silver(I) chromate solution dissolve in 1 litre of 0.1M
potassium chromate to form a saturated solution at ℃.
(i) Define the term saturated solution
(ii) Calculate the solubility of silver(I) chromate in pure water at ℃.
(b) Ammonia solution is added to a saturated solution of silver(I) chromate in water at
℃.
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626
(i) State the effects of adding ammonia on the solubility of silver(I) chromate.
(ii) Explain your answer in b(i) above
(c) State any two practical applications of solubility product.
14. Aluminium hydroxide is sparingly soluble in water.
(a) Write equation for solubility of aluminium hydroxide in water.
(b) The solubility of aluminium hydroxide is per at ℃.
Calculate the solubility product of aluminium hydroxide at ℃.
15. Calculate the solubility product, , of aluminium sulphide if its solubility in water
at ℃ is .
16. Lead(II) sulphide is sparingly soluble in water.
(a) Write an expression for the solubility product of lead(II) sulphide.
(b) 3.80g of lead(II) sulphide was shaken with one litre of water at ℃. Calculate the
percentage of lead(II) sulphide that dissolved in water.
℃

(c) If 0.05 molar solution of lead(II) nitrate was used instead of water in (b), Calculate
the percentage of lead(II) sulphide that dissolved and state any assumption made.
17. The solubility product of iron(III) hydroxide at ℃ is .
Calculate the mass of iron(III) hydroxide that can be dissolved in one litre of 0.01M
sodium hydroxide solution at ℃.
627
CHAPTER EIGHT
CHEMICAL KINETICS
Introduction
Chemical kinetics is the study of rates of chemical reactions and how the reactions
depend on the factors affecting them.
It deals with experimental determination of rates of reaction and interpretation of kinetic
data. Reaction rates cannot be predicted theoretically and so they are determined
experimentally. It as well investigates the mechanism by which a reaction occurs.
Some reactions occur very slowly and may take months for completion like rusting of
iron. Others are very fast and may take seconds like precipitation of silver chloride using
sodium chloride and silver nitrate
Rate of a chemical reaction
Rate of a chemical reaction is the decrease in concentration of reactants or the

increase in concentration of products formed per unit time.
Consider the reaction:
In terms of reactants;
[ ] [ ]
The negative sign inserted indicates that the concentrations of reactants decrease with time.
In terms of products;
[ ] [ ]
The rate of the reaction is not the same when expressed in terms of or as it is in
terms of or . It is usually necessary to specify which species is used when
expressing rate of a chemical reaction.
Units of rate of reaction

Different units can be used but if concentration is given in and time in
seconds, then ;
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628
Rate of reaction can be represented graphically in terms of concentration of reactant or

product plotted against time.
The slope of any of the

Concentration graphs gives the rate
𝒎𝒐𝒍𝒅𝒎 𝟑 of the reaction in
𝒎𝒐𝒍𝒅𝒎 𝟑 𝒔 𝟏at a
given time.
Time 𝒔
The rate law

The rate law is an experimentally determined expression that gives the relationship
between rate of reaction and concentration of reactants.
The rate law states that the rate of a reaction is directly proportional to the molar
concentrations of reactants raised to their appropriate powers which are
experimentally determined at a given temperature.
Consider the reaction:
[ ][ ] [ ]
[ ][ ] [ ]
is the rate constant. , and are experimentally determined values
The equation above is known as the rate law or rate equation.
The rate equation is an expression that relates the rate of reaction and the product
of the molar concentrations of reactants raised to their appropriate powers.
Note that the rate law for any reaction cannot be from the balanced chemical equation
using the stoichiometric coefficients but it is determined experimentally.
The rate constant,

Rate constant of a reaction is the proportionality constant in an experimentally
determined rate equation.
or
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629
Rate constant of a reaction is the ratio of rate of reaction to the product of the molar
concentrations of reactants raised to appropriate powers which are experimentally
determined at a given temperature.
The rate constant for a particular reaction has a constant value hence does not change
with changes in concentration of the reactant.
Order of a reaction
For the reaction discussed above with the rate equation;
[ ][ ] [ ]
is the order of reaction with respect to
The overall order is
Order of a reaction is the sum of the powers to which the molar concentrations of the

reactants are raised in the experimental rate equation.
Order of a reaction helps us classify reactions zero order, first order or third order
reactions.
Order of a reaction can be a whole number (positive or negative) or a fraction.
Note that the order of a reaction with respect to a given reactant cannot be deduced
using stoichiometric coefficients in the equation. For example using the equation
below:
The experimentally determined rate equation is:

[ ][ ][ ]
The order of reaction with respect to is 1
The overall order is
Molecularity
Molecularity of a reaction is the total number of molecules, atoms or ions involved in
the rate determining step of a reaction.
For a reaction that takes place in more than one step, the rate determining step is the
slowest step in the reaction mechanism.
Molecularity is always a whole number and never greater than three.
Therefor Molecularity can be one, two or three. Molecularity is a theoretical postulate
and not experimentally measured. It must be a whole number.
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Differences between order of reaction and molecularity

Order of reaction Molecularity
Sum of the powers to which the molar The number of molecules, atoms or ions
concentrations of the reactants are raised in the involved in the rate determining step of a
experimental rate equation reaction
Order is experimentally determined Molecularity is a theoretical concept
Order can be a zero or any whole number Molecularity is never more than three and
never zero
Order can be a fraction Molecularity is always a whole number
Order does not tell anything about mechanism Molecularity explains mechanism of a reaction
of a reaction
Mechanism of a reaction
Many reactions proceed through a number of stages or steps. These steps or stages are
called a mechanism. Such reactions involve formation of intermediates before the final
product(s) is/ are formed. The rates of such reactions are determined by the slowest step

which is called the rate determining step.
A rate determining step is the slowest step in the reaction mechanism of a chemical
reaction that proceeds through more than one step.
A reaction can be unimolecular, bimolecular and rarely termolecular depending on the

number of molecules, atoms or ions involved in the rate determining step.
1. Unimolecular reaction
A unimolecular reaction involves only one reactant molecule in the rate determining step.
For example
(a) the decomposition of hydrogen peroxide;
The reaction occurs in the following steps:

→
→
The first step is the rate determining step and involves only one molecule of hydrogen
peroxide forming water and an oxygen atom. The rate of reaction depends on this step
hence the rate equation if given as [ ]
Therefore the reaction is first order and has molecularity one.
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631
(b) the reaction of 2-bromo-2-methyl propane (tertiary alkylhalides) with potassium

hydroxide;
The reaction occurs by the following mechanism;
→
→
̅
The first step is the rate determining step and involves only one molecule of
2-bromo-2-methyl propane forming a carbocation and a bromide ion. The rate of
reaction depends on this step hence the rate equation if given as [ ]
Therefore the reaction between tertiary alkylhalides and potassium hydroxide to form
alcohols is first order and has molecularity 1. From the rate equation, the rate of
reaction only depends on the concentration of the alkylhalide but independent on the
concentration of hydroxyl ions.

The type of reaction is nucleophilic substitution unimolecular.
2. Bimolecular reaction
A bimolecular reaction involves two reactant molecules in the rate determining step. For
example
(a) the reaction of bromoethane (primary alkylhalides) with potassium hydroxide;
The reaction occurs by the following mechanism;
→ [ ] →
̅
The first step is the rate determining step and involves only one molecule of
2-bromo-2-methyl propane forming a carbocation and a bromide ion. The rate of
reaction depends on this step hence the rate equation if given as
[ ][ ̅ ]
Therefore the reaction between primary alkylhalides and potassium hydroxide to form
alcohols is second order and has molecularity 2. From the rate equation, the rate of
reaction depends on both the concentration of the alkylhalide and the concentration of
hydroxyl ions.
The type of reaction is nucleophilic substitution bimolecular.
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MATHEMATICAL DERIVATION OF ZERO, FIRST AND

SECOND ORDER RATE EQUATIONS AND HALF LIFE
Half-life of a reaction is the time taken for the concentration of a reactant to reduce to
half its original value.
1. Zero order reactions
A zero order reaction is a reaction in which the rate of reaction is independent of the
concentration of the reactant.
Consider a reaction:
[ ]
For a zero order reaction, the units for rate constant are
Integrated form of rate equation for a zero order reaction
[ ] [ ]

[ ] [ ]
[ ] [ ]
[ ] ∫ [ ] ∫
[ ]
[ ] [ ]
[ ] [ ][ ] [ ]
[ ] [ ] [ ]
[ ] [ ]
[ ] [ ] [ ]
Expression for half-life of a zero order reaction
[ ] [ ] ⁄
[ ] ∫ [ ] ∫
[ ]
[ ] [ ] ⁄
[ ] [ ][ ]
[ ]
[ ]
[ ] ( [ ] [ ] ) ( ⁄ )
[ ]
[ ] [ ] ⁄
[ ] [ ]
[ ] ⁄
[ ]
⁄ [ ]
⁄
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633
Examples of zero order reactions include:

(i) Iodination of propanone
This reaction is zero order with respect to iodine. The rate of reaction does not change if
the concentration of iodine is changed.
(ii) The decomposition of hydrogen iodide on a gold surface.
(iii) Decomposition of ammonia to nitrogen and hydrogen by a hot tungsten wire

catalyst.
2. First order reactions
A first order reaction is a reaction in which the rate of reaction is proportional to the
concentration of the reactant raised to power one.
[ ]
For a first order reaction, the units for rate constant can be derived.

[ ]
[ ]
Integrated form of rate equation for a first order reaction
[ ] [ ]
[ ]
[ ] ∫ ∫
[ ] [ ]
[ ] [ ]
[ [ ]][ ]
[ ]
[ ] [ ] [ ]
[ ]
[ ] [ ]
[ ] [ ]
[ ] ( )
[ ]
[ ]
[ ] [ ]
( )
[ ]
Expression for half-life of a first order reaction
[ ]
[ ]
[ ] ( )
[ ] ⁄
[ ]
[ ] ⁄
⁄
[ ]
[ ]
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634
[ ]
[ ]
[ ]
[ ]
[ ] ( )
[ ]
∫ ∫
[ ] [ ] [ ]
[ ] ⁄
[ ]
[ [ ]][ ]
[ ]
[ ] [ ] [ ]
( ) ⁄
[ ] [ ] [ ]
[ ]
( ) ⁄
[ ]
[ ]
⁄
[ ] ⁄
Examples of first order reactions include:

(i) All radioactive decays
(ii) Decomposition of hydrogen peroxide to form water and oxygen
(iii) Reaction of 2-chloro-2-methylpropane with sodium hydroxide
(iv) Decomposition of dinitrogen pentoxide to nitrogen dioxide and oxygen
3. Second order reactions

A second order reaction is a reaction in which the rate of reaction is proportional to the
concentration of the reactant raised to the second power.
Or a reaction in which the rate of reaction is proportional to the product of the
concentration of two reactants each raised to power one.
[ ]
or
[ ][ ]
For a second order reaction, the units for rate constant can be derived:
[ ]
[ ]
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635
Integrated form of rate equation for a second order reaction

[ ] [ ]
[ ]
[ ] * + [ ]
[ ]
[ ]
[ ] [ [ ] ][ ] [ ]
[ ] [ ]
[ ] [ ]
[ ] [ ] [ ]
[ ]
[ ]
[ ] [ ]
[ ] [ ] [ ]
[ ]
( )
[ ]
[ ] [ ]
[ ]
∫ ∫
[ ] [ ] [ ] [ ]
[ ]
∫ [ ] [ ] ∫ [ ] [ ]
[ ]

Expression for half-life for a second order reaction
[ ]
[ ] ( )
[ ] [ ]
[ ] [ ] [ ]
[ ]
[ ] [ ]
[ ] [ ]
[ ] ⁄
[ ]
[ ]
[ ] [ ] [ ] ⁄
[ ]
[ ]
∫ ∫ [ ] [ ] ⁄
[ ] [ ]
[ ]
[ ] [ ] ⁄
∫ [ ] [ ] ∫
[ ]
[ ] ⁄
[ ] [ ]
* + [ ]
[ ] ⁄
[ ] [ ]
[ [ ] ][ ] [ ]
[ ] ⁄ [ ]
[ ] [ ]
[ ] [ ]
[ ]
[ ] [ ]
[ ] [ ]
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636
Examples of second order reactions include:

(i) Reaction between hydrogen and iodine to form hydrogen iodide
(ii) Oxidation of iodide ions to iodine by peroxodisulphate ions
(iii) Reaction of bromoethane with sodium hydroxide
In summary:
Order of Differential rate Integrated rate equation Units for rate Expression for
reaction equation constant half-life
[ ]
Zero [ ] [ ] [ ] ⁄
[ ]
( )

[ ]
First [ ]
[ ] ⁄
[ ]
( )
[ ]
Second [ ]
[ ] ⁄
[ ] [ ] [ ]
Sketching plotting and interpreting the graphs obtained using rates of

reaction data and rate equations
1. Graphs for zero order reactions
From the rate equation: [ ]
A graph of rate of reaction against concentration of reactant is a straight line with

zero gradient.
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637
Also the integrated form of the rate equation for a zero order reaction is given as:
[ ] [ ]
The equation when expressed in the form is:
[ ] [ ]
A graph of molar concentration of reactant, [ ] against time can be plotted;

The graph of concentration of reactant
[ ]
against time is a straight line with a
[ ]
negative gradient with an intercept on
the concentration axis. The intercept
on the concentration axis gives the
initial concentration, [𝑨 ]𝟎 . The slope
of the graph , 𝑺𝒍𝒐𝒑𝒆 𝒌 from which
the rate constant can be obtained with
units 𝒎𝒐𝒍𝒅𝒎 𝟑 𝒔 𝟏

Half-life is then obtained from
[𝑨 ]𝟎
𝒕𝟏⁄
𝟐 𝟐𝒌
2. Graphs for first order reactions
A number of six graphs can be drawn to represent first order reactions.
From the rate equation [ ]
Comparing with:
A graph of rate of reaction against concentration of reactant, [ ] can be plotted
The graph of rate of

reaction against
concentration of reactant
is a straight line through
the origin. The slope of the
graph , 𝑺𝒍𝒐𝒑𝒆 𝒌 from
which the rate constant can
be obtained with units 𝒔 𝟏
Half-life is then obtained
𝟎 𝟔𝟗𝟑
from 𝒕𝟏⁄
𝟐 𝒌
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638
A graph of concentration of reactant against time

[𝑨𝟎 ]
[𝑨𝟎 ]
𝟐
𝒕𝟏
[𝑨𝟎 ]
𝟒
𝒕𝟐
The graph of concentration against time is a curve with a negative gradient. The slope of the
graph at a given point is the rate of reaction at that time.

From this graph half-life can be got directly from the graph and can be used to find the rate
𝟎 𝟔𝟗𝟑
constant 𝒌 using the expression 𝒕𝟏⁄ .
𝟐 𝒌
[𝑨𝟎 ] [𝑨𝟎 ]
Half-life is got by getting the time that corresponds to and then . The half-life can
𝟐 𝟒
𝒕𝟏 𝒕𝟐
then be got by the expression 𝒕𝟏⁄ . The values 𝒕𝟏 and 𝒕𝟐 are got from the graph by
𝟐 𝟐
𝒕𝟏 equation
The integrated form of the rate 𝑻 𝟎 andfor𝒕a𝟐 first
𝑻 order
𝑻 reaction can be given as:
[ ]
( ) [ ] [ ]
[ ]
[ ] [ ] [ ]
( )
[ ]
[ ] [ ]
The graph of 𝒍𝒐𝒈[𝑨 ]𝒕 against time is a
straight line with a negative gradient
A graph of [ ] against time(t) can be plotted;
with an intercept on the 𝒍𝒐𝒈[𝑨 ]𝒕 axis.
The intercept on the concentration axis
[ ]
gives the value of 𝒍𝒐𝒈[𝑨 ]𝟎
𝒊𝒇 𝒍𝒐𝒈[𝑨 ]𝟎 𝒙
[ ]
𝒕𝒉𝒆𝒏 [𝑨 ]𝟎 𝟏𝟎𝒙 .
𝒌
The slope of the graph , 𝑺𝒍𝒐𝒑𝒆
𝟐 𝟑𝟎𝟑
from which the rate constant can be
obtained with units 𝒔 𝟏
|
𝟎 𝟔𝟗𝟑
𝒕𝟏⁄
639
𝟐 𝒌

N.B; The graph above has a slightly different look when some or all the values of
[ ] are less than one.
[ ]
[ ]

Also:
[ ]
( )
[ ]
[ ]
( )
[ ]
[ ]
A graph of ([ ]
) against time (t) can be plotted;
[𝑨 ]
The graph of 𝒍𝒐𝒈 ( [𝑨 ]𝟎 ) against time is
𝒕
[ ] a straight line with a positive gradient
([ ]
)
through the origin.
𝒌
𝟐 𝟑𝟎𝟑
𝟎 𝟔𝟗𝟑
𝒕𝟏⁄
𝟐 𝒌
The integrated form of the rate equation for a first order reaction can also be given
as:
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640
[ ] [ ] [ ]
( ) [ ] [ ]
[ ]
[ ] [ ]
A graph of [ ] against time(t) can be plotted; The graph of 𝒍𝒏[𝑨 ]𝒕 against time is a
[ ] with an intercept on the 𝒍𝒏[𝑨 ]𝒕 axis.
The intercept on the concentration
[ ] axis gives the value of 𝒍𝒏[𝑨 ]𝟎
𝒊𝒇 𝒍𝒏[𝑨 ]𝟎 𝒙
𝒕𝒉𝒆𝒏 [𝑨 ]𝟎 𝟏𝟎𝒙 .
The slope of the graph , 𝑺𝒍𝒐𝒑𝒆 𝒌
N.B; The graph above has a slightly different look whenHalf-life
some oris all
then obtained
the values from
of
𝟎 𝟔𝟗𝟑

[ ] are less than one. 𝒕𝟏⁄
𝟐 𝒌
[ ]
[ ]
Also:
[ ]
( )
[ ]
[ ]
( )
[ ]
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641
[ ]
A graph of ([ ]
) against time (t) can be plotted;
[𝑨 ]
The graph of 𝒍𝒏 ( [𝑨 ]𝟎 ) against time is a
𝒕
[ ]
([ ) straight line with a positive gradient
]
through the origin.
The slope of the graph , 𝑺𝒍𝒐𝒑𝒆 𝒌
𝟎 𝟔𝟗𝟑
𝒕𝟏⁄
𝟐 𝒌
3. Graphs for second order reactions

From the rate equation [ ]
Comparing with:

A graph of rate of reaction against square of concentration of reactant, [ ] can be
plotted
The graph of rate of
reaction against square of
concentration of reactant
is a straight line through
the origin. The slope of the
graph , 𝑺𝒍𝒐𝒑𝒆 𝒌 from
which the rate constant can
be obtained with units 𝒔 𝟏
Half-life is then obtained
from
[ ] 𝟏
𝒕𝟏⁄
𝟐 𝒌[𝑨 ]𝟎
A graph of rate of reaction against concentration of reactant, [ ]can be plotted
The graph of rate of reaction

against concentration of
reactant is a curve through the
origin with a positive gradient.
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642
A graph of concentration of reactant against time

[𝑨𝟎 ]
[𝑨𝟎 ]
𝟐
𝒕𝟏
[𝑨𝟎 ]
𝟒
𝒕𝟐
The graph of concentration against time is a curve with a negative gradient. The slope of the
graph at a given point is the rate of reaction at that time.

From this graph half-life is inversely proportional to concentration. Therefore the half-life
gets greater as the reaction proceeds. Therefore 𝒕𝟐 𝟐𝒕𝟏
The integrated form of the rate equation for a second order reaction is given as:
[ ] [ ]
[ ] [ ]
A graph of [ ]
against time(t) can be plotted; 𝟏
The graph of [𝑨 ] against time is a straight
𝒕
line with a positive gradient and an
𝟏
intercept on the [𝑨 ] axis. The intercept is
𝒕
𝟏
[ ] equal to [𝑨 ] from which the initial
𝟎
concentration [𝑨 ]𝟎 can be obtained.
The slope of the graph , 𝑺𝒍𝒐𝒑𝒆 𝒌 from
[ ]
which the rate constant can be obtained
with units 𝒎𝒐𝒍 𝟏 𝒅𝒎𝟑 𝒔 𝟏
𝟏
𝒕𝟏⁄
𝟐 𝒌[𝑨 ]𝟎
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643
N.B: For the graphs where concentration of reactant is used, volume of reactant can
as well be used.
USING KINETICS DATA TO OBTAIN ORDER OF

REACTION, RATE OF REACTION, RATE CONSTANTS AND
HALF-LIFE
Order of reaction can be determined by the following methods:
(a) Half-life method

(b) Graphical method
(c) Initial rate method
(a) Using the half-life method.

The half-life can be used to deduce order of reaction by relating it to the initial

concentration of the reactant. This can be interpreted using a graph of concentration
against time.
For a zero order reaction, half-life is directly proportional to the initial concentration
of the reactant.
A graph of concentration of reactant against time for a zero order reaction
[𝑨 ]𝟎
[ ] 𝒕𝟏⁄
𝟐 𝟐𝒌
[ ] If it is found that
t t , then the reaction is
[𝑨𝟎 ] zero order with respect to the
𝟐 reactant. The half life decreases
as the initial concentration is
𝒕𝟏
[𝑨𝟎 ] reduced
𝟒
𝒕𝟐
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644
For a first order reaction, half-life is independent of the initial concentration of the
reactant
A graph of concentration of reactant against time for a first order reaction

[𝑨𝟎 ]
𝟎 𝟔𝟗𝟑
𝒕𝟏⁄
𝟐 𝒌
If it is found that
[𝑨𝟎 ] t t , then the
reaction is first order.
𝟐
𝒕𝟏 The half life remains
[𝑨𝟎 ] constant as the initial
𝟒 concentration is
𝒕𝟐
reduced

For a second order reaction, half-life is inversely proportional to the initial
concentration of the reactant
A graph of concentration of reactant against time for a second order reaction

[𝑨𝟎 ] 𝟏
𝒕𝟏⁄
𝟐 𝒌[𝑨 ]𝟎
If it is found that
[𝑨𝟎 ] t t , then the
𝟐 reaction is second
𝒕𝟏 order. The half life
[𝑨𝟎 ] increases as the
𝟒 initial concentration
𝒕𝟐 is reduced
Questions
1. The kinetics data for the reaction between P and sodium hydroxide is shown in the
table below.
Concentration of P 1.05 0.88 0.74 0.51 0.37 0.26 0.16 0.10
Time (minutes) 0.0 3.5 7.0 14.5 20.0 27.0 35.5 45.0
(b) Plot a graph of concentration of P against time
(c) From the graph determine:
(i) the half-life of P
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645
(ii) order of the reaction

(iii) the rate constant for the reaction.
2. Hydrogen peroxide decomposes in presence of iron(III) chloride catalyst. The order
of the reaction can be found by withdrawing aliquots of the solution, adding dilute
sulphuric acid and titrating with potassium manganate(VII) solution. The volume of
manganate(VII) solution is a measure of concentration of hydrogen peroxide
remaining after a certain time. The table below shows the volume of potassium
manganate(VII) required at various time intervals.
Time (minutes) 0 5 10 15 20 25 30
Volume of potassium manganate(VII) 30 23.4 18.3 14.7 14.2 8.7 6.8
(a) Plot a graph of volume of potassium manganate(VII) solution against time.
(b) From the graph determine the:
(i) half-life of the reaction
(ii) order of the reaction. Give a reason for your answer.
(c) Write down the rate equation for the decomposition of hydrogen peroxide

(d) Calculate the rate constant for the reaction.
3. (a) State what is meant by the term:
(i) Order of reaction
(ii) Half-life of reaction
(b) The table below shows the kinetic data obtained for hydrolysis of methylethanoate
in acidic media.
[ ] 0.241 0.161 0.109 0.073 0.046 0.034
Time (minutes) 0 60 120 180 240 320
Plot a graph of concentration of methyl ethanoate against time
(c) Using the graph in (b), determine the:
(i) half-life of the reaction
(ii) order of the reaction with respect to . Give a reason for your
answer
(d) Calculate the rate constant and indicate its units.
4. (a) Dinitrogen pentoxide decomposes according to the equation;
The mechanism for the reaction is as shown below:
(i) Define the term molecularity

(ii) Given that the above reaction is unimolecular. Identify the rate determining
step of the reaction. Give a reason for your answer.
(b) 0.2M benzene diazonium chloride decomposes in the presence of water according to
the equation:
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646
The volume of nitrogen gas evolved was recorded at different time intervals shown
below.
Time (seconds) 0 10 20 30 40 50 60 70 80
Volume of 0.0 0.42 0.70 0.90 1.08 1.22 1.28 1.30 1.30
(i) Plot a graph of volume of nitrogen gas against time. Use your graph to
determine the initial rate
(ii) The experiment was repeated with 0.05M benzene diazonium chloride at ℃
and the initial rate was found to be . Calculate the order of
reaction with respect to benzene diazonium chloride.
(c) Write the rate equation if the concentration of water remains constant during the
reaction
(d) State the effect of increasing temperature on the value of the rate constant.
5. The data below was obtained for the reaction between benzoyl chloride with
phenylamine, starting with equal concentrations of the reactants.

Time (minutes) 0 5 10 20 30
Concentration of phenylamine 0.0200 0.0133 0.0100 0.0069 0.0051
(i) Plot a graph of concentration of phenylamine against time
(ii) Use your graph to determine the deduce the order of reaction. Explain your
answer.
(b) Using the graphical method

The order of a given reaction can be obtained by finding out a suitable graph that forms a
straight line against. The graph should have a given variable of experimental data plotted
against time as summarised below. The same graphs can be used to find the rate
constants hence the half-life.
Order of reaction Zero order First order Second order

[ ] [ ]
Integrated rate [ ] [ ] [ ] [ ]
equation
[ ] [ ]
Suitable straight A graph of A graph of [ ] against time A graph of [ ]
line graph to concentration of is a straight line graph with a
verify the order reactant against negative gradient against time is a
of reaction time is a straight or straight line graph
line graph with a A graph of [ ] against with a positive
negative gradient time is a straight line graph gradient
with a negative gradient
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647
Expression to
obtain the rate
constant
Expression for [ ]
half-life ⁄ ⁄ ⁄ [ ]
Questions
1. The data in the table below was obtained for the reaction
Time (minutes) 0 1.3 2.0 4.0 5.3

[ ] 0.851 0.575 0.468 0.269 0.182
(a) Plot a graph of [ ] against time.
(b) From the graph, determine the order of the reaction. Give a reason for your
answer.

(c) Calculate:
(i) the rate constant for the reaction
(ii) the half-life of the reaction
2. The table below shows the kinetics data for oxidation of methanoic acid using
bromine water.
Time 10 20 30 40 50 60
[ ] 0.22 0.04 -0.16 -0.33 -0.51 -0.71
(i) Plot a graph of [ ] against time
(ii) Use the graph to find the order of reaction. Give a reason for your answer.
(iii) Find the original concentration of bromine solution
(iv) Calculate the rate constant.
3. The table below shows the kinetics data for the reaction:
→
Time 0 10 20 30 40 50 60
[ ] 0.398 0.199 0.041 -0.200 -0.377 -0.602 -0.796
(a) Plot a graph of [ ] against time
(b) From the graph to deduce the order of reaction. State a reason for your
answer.
(c) Calculate the ;
(i) rate constant for the reaction
(ii) half life for the reaction
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648
4. Buta-1,3-diene reacts to form products above room temperature. The table

below shows the concentration of buta-1,3-diene at ℃ after different intervals of
time.
Time, t 900 1800 3600 6000
[ ] 0.0143 0.0123 0.00952 0.00730
(a) Plot a graph of ⁄ against concentration of buta-1,3-diene.
(b) Plot a graph of [ ]

against time.
(c) Using your graph to:
(i) state the order of the reaction and give a reason for your answer.
(ii) Calculate the initial concentration of buta-1,3-diene.
(iii) Calculate the rate constant for the reaction and state its units.
(iv) Determine the half life of the reaction.
(v) Write the rate equation for the reaction

5. The decomposition of nitrogen dioxide was investigated at 300℃.
The following data was obtained.

Time, t 0 100 200 300
[ ] 0.01 0.0065 0.0045 0.0038
(a) Plot a graph of [ ]
against time.
(b) Using your graph to state the order of the reaction and give a reason for your
answer.
(c) Calculate the :
(i) rate constant for the reaction and state its units.
(ii) Determine the half life of the reaction.
(iii) Write the rate equation for the reaction
(c) Using the initial rate method

The initial rate method can be used to find the order of reaction with respect to each
reactant hence the overall order. The rate equation / rate law can therefore be deduced
hence the rate constant calculated.
A number of experiments are done by varying the concentration of one of the reactants
and the concentrations of all the other reactants are kept constant. The initial rates of the
reaction at each concentration are got as the slope form concentration-time graph.
The experiments are repeated by varying the concentration of the second reactant and
keeping the concentrations of all the other reactants constant.
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649
The orders with respect to all the reactants are then determined either by deduction or
calculation.
Order of reaction with Effect on concentration of Effect on initial rate of reaction
respect to a given reactant reactant
Halved
multiplied by a quarter
Zero order Doubled Rate remains constant
Trebled
quadrupled
Halved also halved
multiplied by a quarter also multiplied by a quarter
First order Doubled also doubled
Trebled also trebled(multiplied by 3)
Quadrupled also quadrupled
Halved divided by four (multiplied by )

multiplied by a quarter multiplied by
Second order
Doubled Quadrupled(multiplied by 4)
Trebled multiplied by six
Quadrupled multiplied by eight
Both methods will be used in the examples below but choose the simpler alternative of
your choice.
Examples
1. For the reaction
The following data was obtained.
Experiment Concentration of Concentration of Initial rate
A B
1
2
3
(a) Determine the order of reaction with respect to:
(i) A
(ii) B
(b) Write the rate equation
(c) Calculate the rate constant and state its units.
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(a)
(i) In experiments 1 and 3, when the concentration of B is kept constant and that of A doubled,
the rate of reaction quadruples. Therefore the order of reaction with respect to A is 2.
or
Let the order of reaction with respect to A be and order of reaction with respect to B be .
Considering experiments 1 and 3 where [ ] is constant;
[ ] [ ]
(i) In experiments 1 and 2, when the concentration of A is kept constant and that of B doubled,

the rate of reaction also doubles. Therefore the order of reaction with respect to B is 1.
or
[ ] [ ]
(b) [ ] [ ]
(c) Considering experiment one;
[ ] [ ]
[ ] [ ]
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2. (a) Explain what is meant by the term order of a reaction

(b) The following kinetics data was obtained for the reaction between an
alkylhalide, Q and sodium hydroxide solution
Experiment [ ] [̅ ] Initial rate
1 0.100 0.500
2 0.050 0.250
3 0.100 0.250
4 0.075 0.250
Determine the order of the reaction with respect to Q and sodium hydroxide and
give a reason for your answer.
(i) order with respect to Q and reason
(ii) order with respect to sodium hydroxide and reason
(c) (i) Write the rate equation for the reaction

(ii) Calculate the rate constant and give its units
(iii) Write the general structure of Q and give a reason for your answer.
(b)
(i) The order of reaction with respect to Q is 1.
Reason: When the concentration of ̅ is kept constant and that of Q doubled, the rate of
reaction doubles.
or
The order of reaction with respect to Q is 1.
Reason: Considering experiments 2 and 3 where [ ̅ ] is constant;
[ ] [̅ ]
(ii) The order of reaction with respect to sodium hydroxide is zero.

Reason: When the concentration of Q is kept constant and that of ̅ halved, the rate of
reaction remains constant.
or
The order of reaction with respect to sodium hydroxide is 0.
Reason: Considering experiments 1 and 3 where [ ] is constant;
[ ] [̅ ]
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(c) (i) [ ]
(ii) Considering experiment one;
[ ]
[ ]
(iii)
Reason: Q is a tertiary alkylhalide because the rate of reaction depends on the concentration of
alkylhalide but independent of the hydroxyl ion.

3. (a) What is meant by the term rate constant
(b) The following results were obtained for two compounds A and B reacting to
give product C.
Experiment Initial Initial Initial rate

[ ] [ ]
1
2
3
(i) Deduce the rate equation
(ii) Calculate the rate constant and give its units
(b)
(i) Let order of reaction with respect to A be m and order of reaction with respect to B be n.
[ ] [ ]
Also considering experiments 2 and 3;

[ ] [ ]
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[ ] [ ]
(ii) Considering experiment one;
[ ] [ ]
[ ] [ ]
4. (a)(i) Explain what is meant by the order of chemical reaction.

(ii) Name two methods used to determine orders of reactions.
(b) The results obtained for the kinetics of the decomposition of nitrogen(V)
oxide are given in the table below.
[ ] Initial rate
Calculate the:
(i) order of reaction
(ii) value of
(b) (i) When the concentration of nitrogen(V) oxide is (ii) Consider experiments 2 and 3
multiplied by 1.5, the rate of reaction also increases by
1.5 times. Therefore the order of reaction is one.
or
Let the order of reaction be f.
Considering experiments 1 and 2;
[ ]
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5. (a) Differentiate between order of reaction and molecularity

(b) The rate equation for the reaction between substances A, B and C is given by;
[ ] [ ] [ ] , where .
The kinetics of the reaction is given below.
Experiment [ ] [ ] [ ] Initial rate
1
2
3
4
(i) Deduce the order of reaction with respect to A, B and C respectively.

(ii) Determine the value of n
(iii) Calculate the value of the rate constant, and state its units.

(iv) Find the initial rate of reaction when[ ] ,
[ ] and [ ] .
(b)(i) In experiments 1 and 2, when both the concentrations of B and C are kept constant and the
concentration of A reduced four times, the rate of reaction also reduces four times. Therefore the
order of reaction with respect to A is 1.
or
Considering experiments 1 and 2 where [ ] and [ ] are constant;
From [ ] [ ] [ ] .
In experiments 1 and 3, when the concentration of C is kept constant and both the concentrations
of A and B halved, the rate of reaction is multiplied by a quarter (reduces four times). Therefore
the reaction is first order with respect to A and also first order with respect to B
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Or
From [ ] [ ] [ ]
Therefore the order of reaction with respect

to C is 2.
(ii) Consider experiments 1 and 4

[ ][ ][ ]

(iii) Considering experiment one;
[ ][ ][ ]
[ ][ ][ ]
(iv) [ ][ ][ ]
6. The kinetics data for the reaction between nitrogen monoxide and oxygen are
shown in the table below.
Experiment [ ] [ ] Initial rate
1
2
3
(a) Determine the order of reaction with respect to:
(i) nitrogen monoxide
(ii) oxygen
(b) Write the rate equation for the reaction
(c) Calculate the rate constant for the reaction and indicate its units.
(d) The rate of the reaction under certain conditions and a given temperature is
. Express the rate of reaction in terms of when the following changes are
made.
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(i) The concentration of oxygen is halved while the concentration of

nitrogen monoxide remains unchanged.
(ii) The rate constant is doubled, by increasing temperature, but keeping
the concentrations of oxygen and nitrogen monoxide unchanged.
(iii) If 90% of oxygen is removed, without affecting the concentration of
nitrogen monoxide.
(a)
(i) In experiments 1 and 3, when the concentration of oxygen is kept constant and that of nitrogen
monoxide is doubled, the rate of reaction quadruples. Therefore the order of reaction with respect to
nitrogen monoxide is 2.
or
Let the order of reaction with respect to nitrogen monoxide be and order of reaction with respect to
oxygen be . Considering experiments 1 and 3 where [ ] is constant;
[ ] [ ]

(ii) In experiments 1 and 2, when the concentration of nitrogen monoxide is kept constant and that
of oxygen doubled, the rate of reaction also doubles. Therefore the order of reaction with respect
to oxygen is 1.
or
[ ] [ ]
(b) [ ] [ ]
(c) Considering experiment one;
[ ] [ ]
[ ] [ ]
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(d) (i)
(ii)
(iii)
Questions
1. The results below were obtained in an experiment to investigate the rate of hydrolysis
of methylmethanoate at 298K.
Initial rate
Experiment [ ] [ ]
1
2
3

(a) Deduce the order of reaction with respect to:
(i) methlymethanoate
(ii) hydrogen ions
(b) (i) Calculate the overall order of reaction
(ii) Write the rate equation
(iii) Calculate the rate constant, ate 298K . State its units
2. The initial rate of the reaction between the gases and was measured in a series
of experiments at a constant temperature and the following rate equation was
determined.
Initial rate
Experiment Initial [ ] Initial [ ]
1
2
3
Using the data from experiment one, calculate the value for the rate constant, and state
its units.
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3. Various concentrations of X and Y were reacted at a constant temperature. The table

below shows the initial concentrations of X and Y and their initial rates for the
reaction.
1 0.2 0.2
2 0.4 0.4
3 0.8 0.4
(a) State the order of reaction with respect to:
(i) X
(ii) Y
(b) Give reasons for your answers in (a)
(c) Determine the overall order of the reaction
(d) Calculate the value for the rate constant for the reaction.
4. (a) Complete the following reaction and write the accepted mechanism.

̅ →
(b) The results obtained for the kinetics of the reaction in (a) above are shown in the table
below.
1
2
3
Deduce the order of reaction with respect to:
(i) ̅
(ii)
(b) Write the rate equation for the reaction
(c) Calculate the rate constant, , for the reaction and state its units.
5. The following results were obtained for the reaction between two substances A and B
at different conditions.
Experiment Initial [ ] Initial [ ] Initial rate
1
2
3
(a) Determine the :
(i) orders of reaction with respect to A and B respectively.
(ii) overall order of reaction
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(b) Write an expression for the rate of reaction.

(c) Calculate the rate constant and state its units
(d) Determine the initial rate of reaction when [ ] and [ ]
.
6. The results of the experiments on the reaction of persulphate(peroxodisulphate) ions
and iodide ions are shown below:
Concentration Initial rate

Experiment
1 0.040 0.040
2 0.080 0.040
3 0.080 0.020
(i) Write the rate equation for the reaction
(ii) Calculate the rate constant.

(iii) Find the initial rate of reaction when
[ ] and [ ] .
7. The data below was obtained for the reaction
Initial concentrations Initial rate

Experiment
1 2.0 2.0
2 2.0 4.0
3 4.0 2.0
4 4.0 4.0
(a) Write the rate equation
(b) Calculate ;
(i) the value of
(ii) the rate constant for the reaction and state its units
8. (a) An acidified solution of potassium bromide was added to aqueous potassium

bromate(V) solution.
(ii) Write equation for the reaction that took place
(d) The results of kinetics of the reaction in (a)(ii) are given in the table below.
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Initial rate
Experiment [ ] [ ] [ ]
1
2
3
4
(i) Deduce the order(s) with respect to each of the reactants
(ii) State the overall order for the reaction
(iii) Write the rate equation
9. Bromine is formed by the reaction between bromide ions and bromate(V) ions and
an acid.
The results of some experiments on the reaction in are given in the table below.
Concentration

Experiment [ ] [ ] [ ] Initial rate
1
2
3
4
(i) Deduce the rate law for the reaction.
(ii) State the overall order for the reaction
(iii) Find the value of the rate constant
10. The following data was obtained for the reaction between hydrogen peroxide and
iodine ions and hydrogen ions
Experiment Concentration Initial rate
[ ] [ ] [ ]
1
2
3
4
(i) State the order of reaction with respect to:
(ii) Write the rate equation for the reaction.

(iii) Calculate the rate constant, for the reaction and indicate its units.
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EXPERIMENTAL PROCEDURE FOR DETERMINING RATES

OF REACTION AND ORDERS OF A REACTION
(a) Experiment to show that iodination of propanone is a zero order reaction with
respect to iodine
A solution of propanone, a solution of iodine in potassium iodide and a solution of
sulphuric acid, all of known concentration are prepared and put into a thermostat bath
at the required temperature.
A known volume of the propanone solution is pipetted and put into a conical flask
followed by a known volume of the sulphuric acid to catalyse the reaction.
A known volume of iodine in potassium iodide solution is added to the mixture and a
stop watch is started simultaneously.
The mixture is shaken and allowed to settle at a constant temperature
After a few minutes, a fixed volume of the reacting mixture is pipetted and put into a
container containing sodium hydrogencarbonate solution to stop the reaction by

neutralizing the acid.
The time at which the reaction stops is recorded.
The resultant solution is titrated against a standard solution of sodium thiosulphate
using starch indicator to determine the amount of iodine remaining.
The analysis of the reacting mixture is repeated several times by changing the time
taken for the reaction to take place before adding the reacting mixture to sodium
hydrogen carbonate.
The original iodine in potassium iodide solution is also pipetted with a standard
solution of sodium thiosulphate to obtain volume of sodium thiosulphate that reacts
with it.
The volume of sodium thiosulphate required is plotted against the time elapsed since
the start of the reaction.
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The graph obtained is a straight line with a negative gradient. This shows that the
reaction is zero order with respect to iodine.
(b) Experiment to find the rate of reaction for the iodination of propanone
The procedure is the same as above but to find the rate of reaction, the gradient/slope
of the graph at a given time is calculated. The value of the slope gives the rate of
reaction.
(a) Experiment to show that the reaction between sodium thiosulphate and
hydrochloric acid is first order reaction with respect to sodium thiosulphate
A known volume of sodium thiosulphate solution of known concentration is measured

into a clean conical flask using a measuring cylinder.
The conical flask is placed on a white piece of paper marked with a cross.
A known volume of hydrochloric acid of a slightly higher concentration than sodium

thiosulphate solution is added using and a stop clock started simultaneously.
Through the mixture, the cross on the white piece of paper is viewed and the stop clock
stopped when the cross just becomes invisible.
The time taken for the cross to become invisible is recorded.
The procedure is repeated several times using different volumes of sodium thiosulphate
solution and making up with distilled water such that the total volume of solution used
in each experiment is equal but maintaining the volume and concentration of
hydrochloric acid .
Values of (reciprocals of time) for each experiment are computed.
A graph of against volume of sodium thiosulphate is plotted.
663
The graph obtained is a straight line with through the origin. This shows that the
reaction is first order with respect to sodium thiosulphate.
(b) Experiment to show find the rate of reaction for the reaction between sodium
thiosulphate and hydrochloric acid
The procedure is the same as above but instead a graph of volume of sodium
thiosulphate against time is plotted. The rate of reaction at a specific time is
determined by drawing a tangent to the curve at given time and calculating the
gradient at that point.

(a) Experiment to show that the catalytic decomposition of hydrogen peroxide is
first order reaction.
A known volume of standard hydrogen peroxide is transferred into a clean conical

flask.
A small amount of iron(III) chloride solution as a catalyst followed by a small amount
of sodium hydroxide solution are added and a stop clock is started simultaneously.
The mixture is shaken and allowed to stand at a constant temperature.
After a specific time interval, dilute sulphuric acid is added to stop the reaction.
The reaction mixture is titrated against a standard solution of potassium
manganate(VII) and the volume of potassium manganate(VII) required is noted.
The experiment is repeated several times by changing the time taken for the reaction
to take place before adding dilute sulphuric acid.
A graph of against time is plotted.
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( )
The graph obtained is a straight line with a negative gradient. This shows that the
reaction is first order.

(b) Experiment to find the rate of reaction for catalytic decomposition of hydrogen
peroxide.
The procedure is the same as above but instead a graph of volume of potassium
manganate(VII) against time is plotted. The rate of reaction at a specific time is
determined by drawing a tangent to the curve at given time and calculating the
gradient at that point.
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MORE CALCULATIONS INVOLVING RATES OF REACTION DATA
All the questions below involve first order kinetics. Try them out using the first
order rate expression.
1. (a) Derive the expression for the half-life for the first order reaction whose integrated
rate equation is , where is the initial concentration of the
reactant and is the concentration after time .
(b) The half-life for a first order reaction is 200 seconds.
(i) Calculate the rate constant
(ii) Determine the time taken for the reaction to be two-thirds complete.
2. (a) State the rate law
(b) Explain why reactions of high molecularity are rare.
(c) A solution of hydrogen peroxide when titrated against acidified potassium
manganate(VII) solution at different time intervals gave the following results.
Time (minutes) 5 10 20 30

Volume of acidified potassium manganate(VII) used 37.1 29.8 19.6 12.3
(i) Show that the decomposition of hydrogen peroxide is first order.
(ii) Calculate the half-life of the decomposition of hydrogen peroxide.
3. A certain amount of methylethanoate was hydrolysed in the presence of excess of
0.05M hydrochloric acid solution at 25℃. When portions of the reaction
mixture were removed and titrated with sodium hydroxide solution after some time
intervals, the volumes of the alkali required for neutralisation were as follows:
Time (minutes) 0 20 79
Volume of sodium hydroxide solution used 24.2 25.8 29.3
Show mathematically, that the reaction is a first order reaction.
4. In a first order reaction, the initial concentration of the reactant was
and the rate constant is . Calculate the initial rate of the
reaction.
5. The rate constant of a reaction with respect to a reactant A is . If the original
concentration of A is . Calculate the time when the concentration of A
reaches .
6. The rate of inversion of cane sugar is of first order. If of a sample of cane sugar
is hydrolysed in 60 seconds. How long will it take for to be hydrolysed?
7. (a) Explain the following terms:
(ii) Rate equation
(iii) Molecularity of a reaction
(b) In the presence of iron(III) chloride catalyst, hydrogen peroxide decomposes
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according to the equation:
666
→
The rate equation is given by: [ ]
Describe an experiment to determine the order of reaction with respect to hydrogen
peroxide.
(c) The following data was obtained for the decay of a radioactive isotope.
Time (minutes) 10 20 30 40 50
-14 2.0 19 36 52
(i) Plot a graph of against time.
(ii) Use the graph to determine the initial activity of the radioactive isotope
(d) Determine the decay constant.
(e) Calculate the half-life of the radioactive isotope.
8. Hydrogen gas reacts with nitrogen(II) oxide according to the equation below at 500K.
The rate law is given by: [ ] [ ] and the mechanism as shown below:

(i)
(ii) →
(iii)
(a) Define the term;
(ii) molecularity
(b) State the order and molecularity of the reaction. Give a reason for your answer.
(c) State the effect on the rate of reaction and in each case explain your answer.
(i) doubling the molar concentration of nitrogen(II) oxide while the partial
pressure of hydrogen is reduced to a quarter its original value
(ii) increasing temperature above 500K while the concentration of both
reactants remain constant
(d) Sketch a graph to show the variation in reciprocal of time( ) with concentration of
hydrogen gas in an experiment where nitrogen(II) oxide is used.
9. (a) Hydrogen peroxide oxidises bromide ions in an acidic solution.
(i) State what is observed
(ii) Write an equation for the reaction that takes place.
(b) The rate expression for the reaction that takes place in (a) above is;
[ ][ ][ ]
(i) Determine the overall order of the reaction
(ii) State the units for the rate constant
(c) (i) If the concentration of bromide ions was doubled, what would be the effect on
the rate of reaction.
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(ii) Explain how raising the of the reaction mixture affects the rate of
reaction.
FACTORS AFFECTING RATES OF REACTIONS

The way factors affect rates of chemical reactions is explained basing on the theories of
chemical reactions.
Theories of chemical reactions (collision theory and transition state

theory)
1. The collision theory
Also known as the Arrhenius theory and proposed by Swedish scientist,
Svante Arrhenius.
In a reaction between two gaseous substances, a molecule of one gas must collide with
a molecule of the other gas for a reaction to occur.
The basic idea of the collision theory is that if every collision results into reaction, then

rates of reaction are equal to the frequency of collision between activated molecules.
The total number of collisions between molecules in a gas per unit volume per unit
time can be calculated.
⁄
( ) ( )
On this basis, reaction rates would be expected to depend on:
–total number of collisions
-Activation energy
-Temperature
The collision frequency is therefore proportional to the product of the molar
concentrations of gaseous reactants.
However, the rate of reaction for most reactions is lower than rate of collision because
only a small fraction of collisions results into reaction.
The collision theory was developed for bimolecular reactions in the gas phase, it also
applies to reactions in solution.
The theory therefore states that in order for molecules to react, they must collide in a
favourable orientation and with enough energy to react.
2. The transition state theory

The transition state theory considers the nature of molecular collisions in a more detailed
way than the collision theory. It is also known as the activated complex theory.
For example in a reaction:
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When and are far away from each other, they have some energy. When
approaches with sufficient energy, its electrons begin to overlap with those of so
that some bonding between and begins to form. At the same time the bond
becomes longer and weaker. As the bond becomes stronger and the bond
becomes weaker, an activated complex or transition state; [ ] is formed. The
activated complex then decomposes into and .
In general; [ ]
The changes in energy can be represented on an energy profile/ enthalpy profile/
reaction profile or potential energy diagram.
This is usually a sketch of potential energy against reaction coordinate/ reaction
pathway.
(a) Reaction profile for a nucleophilic substitution bimolecular reaction
Consider a reaction between 1-chloropropane and aqueous sodium hydroxide.
The reaction is exothermic.
Activated complex

Potential energy
𝒌𝑱𝒎𝒐𝒍 𝟏 𝐶𝐻 𝐶𝐻 𝐶𝐻 𝐶𝑙 𝑂̅ 𝐻
𝐶𝐻 𝐶𝐻 𝐶𝐻 𝑂𝐻 𝐶𝑙
Reaction coordinate
is the activation energy for the reaction(can also be called the energy barrier).
is activation energy for backward reaction
(b) Reaction profile for a nucleophilic substitution unimolecular reaction

Consider a reaction between 2-chloro-2-methylpropane and aqueous sodium
hydroxide.
This reaction takes place via a reactive intermediate. The reactive intermediate is
preceded and also followed by a transition state.
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The reaction is exothermic.

Activated complex 1
Activated complex 2
Potential energy Reactive

𝒌𝑱𝒎𝒐𝒍 𝟏 intermediate
𝐶𝐻 𝐶𝐶𝑙 𝑂̅ 𝐻 𝑪𝑯𝟑 𝟑𝑪
𝐶𝐻 𝐶𝑂𝐻 𝐶𝑙
Reaction coordinate
is the activation energy for the first step.

is activation energy for second step

Activation energy is the minimum energy which is required to be possessed by
reactants in order to react and form products.
Activated complex is the intermediate unstable compound formed immediately once the
reactants have absorbed the activation energy available.
This unstable compound undergoes bond re-organization by releasing some of the energy
to form the final stable product. The activated complex can also be called a transition
state.
Questions
1. Ethylbromide reacts with aqueous sodium hydroxide as in the equation;
(a) Name the reaction

(b) (i) Write the rate equation for the reaction between the hydroxide and
ethylbromide
(ii) Outline a mechanism for the reaction involved
(iii) Sketch a labelled diagram to show the energy profile for the reaction.
(c) Write equation to show how can be converted to .
2. 2-Bromo-2-methyl propane reacts with aqueous sodium hydroxide.
(a) (i) Write an equation for the reaction.
(i) Write the rate equation for the reaction.
(ii) State the molecularity of the reaction
(b) Draw the energy diagram for the reaction
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(ii) Molecularity of a reaction
(iii) Rate constant
(iv) Rate equation
(b) Propanone reacts with iodine according to the equation:
The reaction is first order with respect to propanone and zero order with respect to iodine.
Describe an experiment to determine the rate of the reaction.
(c) The table below shows the concentration of bromine at various intervals of time for
the reaction;
Time 0 30 60 90 120 180 240 360 480 600

[ ] 10 9 8.1 7.3 6.6 5.3 4.4 2.8 2.0 1.3
(i) Plot a graph of concentration of bromine against time

(ii) Use the graph to find the order of reaction. Explain your answer.
(iii) Calculate the rate constant.
(d) The table below shows the results for the hydrolysis of a bromoalkane, with
sodium hydroxide solution. The enthalpy for the reaction is .
1
2
3
(i) Determine the order of the reaction with reasons to explain your answer.
(ii) Write the structural formula and name of the alkylhalide
(iii) Draw a well labelled energy diagram for the reaction.
4. (a) What is meant by the terms:
(ii) half-life of a reaction
(b) The equation for the reaction between sodium thiosulphate and hydrochloric acid
is:
The rate equation for the reaction is [ ][ ]

(i) State how the rate will affected if the concentrations of the reactants are both
doubled.
(ii) Describe an experiment to determine the order of reaction with respect to
sodium thiosulphate in the laboratory.
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(c) The table below shows the kinetics data for the reaction between an
alkylbromide, and aquoeus potassium hydroxide. The reaction is
exothermic.
1
2
3
(i) Determine the overall order of the reaction.
(ii) Determine the rate constant for the reaction and state its units.
(iii) Identify the alkylbromide
(d) Write the mechanism for the reaction in (c) above
(e) Draw a well labelled energy level diagram for the reaction mechanism illustrated
in (d) above.
Using the theories of reaction to explain factors affecting rates of
reaction

The following factors affect the rate of a chemical reaction:
(i) Concentration of the reactants in solution

(ii) Temperature
(iii) Pressure for gaseous reactants
(iv) Particle size/ surface area for solid reactants
(v) Catalyst
(i) The effect of concentration of the reactants in solution on rate of reaction

Increase in concentration of the reactants increases the rate of reaction. This is
because as concentration increases, the reacting molecules/ ions become closer to each
other thus colliding more frequently. The greater the number of collisions, the greater
the rate of reaction
Question
The rate equation for the reaction between substances X, Y and Z is given by
[ ] [ ][ ]
State how the rate of reaction would change if:
(i) concentration of X is doubled while concentrations of Y and Z are kept

constant
(ii) concentrations of all the reactants are halved
(iii) concentration of X is kept constant while both concentrations of Y and Z
are trebled
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(iv) concentration of X is halved, that of Y doubled and that of Z kept constant

(v) the temperature is increased to double the rate constant.
(i) [ ] [ ][ ] The rate of reaction quadruples (rate of reaction

[ ] [ ][ ] [ ] [ ][ ] increases four times)
(ii) [ ] [ ][ ]
( [ ]) ( [ ]) ( [ ])
The rate of reaction decreases by 16 times
[ ] [ ][ ]
[ ] [ ][ ]
(iii) [ ] [ ][ ]
[ ] [ ] [ ] [ ] [ ][ ] The rate of reaction increases by nine times

(iv) [ ] [ ][ ]
( [ ]) [ ] [ ] The rate of reaction is halved(decreases by 2

times)
[ ] [ ][ ]
[ ] [ ][ ]
(v) [ ] [ ][ ] The rate of reaction doubles
(ii) The effect of temperature on rate of reaction

The higher the temperature, the higher the kinetic energy of the ions or molecules of
reactants. The ions or molecules hence move at a higher speed and collide more
frequently and with more energy. The higher the collision frequency, the higher the
rate of reaction.
The rate constant is also only constant at a fixed temperature. Therefore increase in
temperature increases the value of the rate constant.
The rate of reaction doubles for every ℃ increase in temperature.
The Arrhenius theory suggests that a molecule would only react if it had higher than the
average energy (if it is activated, has gained the activation energy)
Arrhenius found the experimental relationship between the rate constant and temperature.
The Arrhenius equation is therefore given as;
⁄
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From the Arrhenius equation above, more equations can be formed as follows:
Introducing both sides The equation can also be written in terms
⁄ of :
( )
⁄
( )
From equation (i), a graph of against can be plotted.

𝟏
The graph of 𝒍𝒏 𝒌 against is a
𝑻
with an intercept on the 𝒍𝒏 𝒌 axis. The
intercept gives the value of 𝒍𝒏 𝑨

𝒊𝒇 𝒍𝒏 𝑨 𝒙
𝑻𝒉𝒆𝒏 𝑨 𝒆𝒙 .
𝑬𝒂
𝑹
from which the activation energy can
be obtained with units 𝑱𝒎𝒐𝒍 𝟏
𝑹 𝟖 𝟑𝟏𝟒𝑱𝒎𝒐𝒍 𝟏 𝑲 𝟏
From equation (ii), a graph of against can be plotted.

𝟏
The graph of 𝒍𝒐𝒈 𝒌 against is a
𝑻
with an intercept on the 𝒍𝒐𝒈 𝒌 axis.
The intercept gives the value of 𝒍𝒐𝒈 𝑨
𝒊𝒇 𝒍𝒐𝒈 𝑨 𝒙
𝑻𝒉𝒆𝒏 𝑨 𝟏𝟎𝒙 .
𝑬𝒂
𝟐 𝟑𝟎𝟑𝑹
from which the activation energy can
be obtained with units 𝑱𝒎𝒐𝒍 𝟏
𝑹 𝟖 𝟑𝟏𝟒𝑱𝒎𝒐𝒍 𝟏 𝑲 𝟏
The following conclusions can be made from the Arrhenius equation:

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1. The rate constant of a reaction increases with increase in the temperature of the
reaction.
2. The rate of reaction increases with increase in temperature
3. At the same temperature, the higher the activation energy, the slower the reaction
4. The higher the activation energy, the lower the rate constant hence the lower the
rate of reaction.
Questions
1. (a) (i) Distinguish between activation energy and rate constant.
(ii) Briefly explain how activation energy and rate constant affect the rate of
reaction
(b) Hydrogen reacts with iodine according to the following equations;
The table below shows the rate constant for the reaction varying with temperature.
Temperature, 556 629 700 781
Rate constant,

(i) Plot a graph of against
(ii) Use the graph to determine the activation energy of the reaction from the
⁄
Arrhenius equation,
(iii) Draw an energy level diagram for the reaction in (b) above and use it to
determine the activation energy for the backward reaction.
(iv) Briefly explain how temperature affects the activation energy of a reaction.
2. (a) Explain the following terms:
(i) Rate of reaction
(ii) Rate law
(iii) Activation energy
(b) Describe an experiment to show that iodination of propanone is zero order with
respect to iodine.
(c) The reaction between manganate(VII) ions and ethanedioate ions in acidic
medium is described by the equation:
The reaction was carried out at different temperatures and the following values for the
rate constant, were obtained.
Temperature, 293 308 318 338
Rate constant,
(i) Plot a graph of against
(ii) Use your graph to determine the activation energy for the reaction
(iii) Determine the value of the pre-exponential constant, .
(iv) Explain the effect of temperature on the rate of chemical reaction.
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3. The table below shows the rate constants for the decomposition of hydrogen iodide at
various temperatures.
Temperature, Rate constant,
500
600
700
800
(a) Plot a graph of against
(b) Use the graph to determine the activation energy of the reaction from the
⁄
Arrhenius equation,
(c) Determine the value of .
4. The decomposition of dinitrogen pentoxide is a first order reaction. The rate constant
depends on the rate constant as shown in the table below.
Temperature, ℃ 0 20 40 60 80

Rate constant,
(a) Complete the table above.

(b) Plot a graph of against
(c) Use the graph to determine the activation energy of the reaction from the
⁄
Arrhenius equation,
(iii) The effect of pressure for gaseous reactants on rate of reaction

Increase in pressure of gaseous reactants increases the rate of chemical reaction
because the gas molecules are pushed closer together, hence collide more frequently
and react more rapidly.
(iv) The effect of particle size/ surface area of solid reactants

The larger the surface area(the smaller the particle size), the higher the rate of reaction
because smaller reactant particles have a higher chance of colliding with each other.
(v) The effect of a catalyst

A catalyst is a substance which alters the rate of a chemical reaction but remains
unchanged in quantity at the end of the reaction or at equilibrium.
The presence of a catalyst increases the rate of a chemical reaction. This is because a
|
catalyst provides an alternative pathway/ mechanism with lower activation energy.

676
Below is an energy profile for both a catalysed and an uncatalysed exothermic reaction
Activated complex for uncatalysed reaction
Activated complex for a catalysed reaction

Potential energy
𝒌𝑱𝒎𝒐𝒍 𝟏 Reactants
𝑯𝜽
Products
Reaction coordinate

Below is an energy profile for both a catalysed and an uncatalysed endothermic
reaction Activated complex for uncatalysed reaction
Activated complex for a catalysed reaction
Potential energy 𝐸𝑎𝑐 Products

𝒌𝑱𝒎𝒐𝒍 𝟏
Reactants
Reaction coordinate
In both cases above;
is the activation energy for the uncatalysed reaction

is activation energy for the catalysed reaction
The activation energy for the catalysed reaction is lower than activation energy for the
uncatalysed reaction
Types of catalysts
A catalyst can be homogeneous or heterogeneous.

A homogeneous catalyst is one which is in the same phase as the reactants.
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A heterogeneous catalyst is one whose phase is different from that of the reactants.
How catalysts work
A homogeneous catalyst works by lowering the activation energy of the rate

determining step by forming an intermediate. It is generally used for reactions in
aqueous solution.
The catalyst reacts with one of the reactants to form an intermediate which the reacts with
the other product to form the final product, regenerating the catalyst.
Consider a reaction between A and B in presence of catalyst C to form product X.
The reaction takes place in via quicker steps as shown below:
For example:
1. Dilute sulphuric acid as a catalyst in iodination of propanone or in the reaction

between hydrogen peroxide and iodide ions.
2. Oxidation of vanadium(III) ions to vanadium(IV) ions by iron(III) ions using
copper(II) ions as catalyst.
3. Esterification of ethanol by ethanoic acid in the presence of sulphuric acid
The heterogeneous catalysts used are commonly transition metals in processes like
hydrogenation (nickel), cracking and polymerisation. It‟s the surface of the catalysts that
helps in catalysis.
They work by using their empty d-orbitals to form weak temporary bonds with the
reactant molecules. This weakens the internal bonding of the reactant molecules and
also increases the concentration of the reactant molecules at the surface of the catalyst
thereby reducing the activation energy hence increasing the rate of reaction.
For example:
1. Finely divided iron in the Haber process.
2. Nickel in hydrogenation of alkenes.
3. Combination of hydrogen and iodine vapour using platinum catalyst
Light as factor that speeds up a chemical reaction
Some reactions take place slowly or not at all in the absence of light. Reactions
accelerated by light include:
 Photosynthesis
 Decomposition of hydrogen peroxide
 Combination of hydrogen and chlorine
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 The substitution of hydrogen in methane by chlorine

 Formation of silver from silver salts
Experimental investigation of factors affecting rates of reactions

1. Experiment to show the effect of concentration on the rate of reaction between
sodium thiosulphate and hydrochloric acid

The procedure is repeated several times using different volumes of sodium thiosulphate
solution and making up with distilled water such that the total volume of solution used
in each experiment is equal but maintaining the volume and concentration of
hydrochloric acid.
The concentration of sodium thiosulphate in each of the solutions is computed.
A graph of against volume of sodium thiosulphate is plotted.
The graph obtained is a straight line with through the origin with a positive gradient.
This shows that the rate of reaction( ) increases with increase in concentration of sodium
thiosulphate.
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Note: The same experiment can be done by maintaining the concentration of sodium
thiosulphate but varying the concentration of hydrochloric acid.
2. Experiment to show the effect of temperature on the rate of reaction between

sodium thiosulphate and hydrochloric acid
The initial temperature of the solution ℃ is measured and recorded from a
thermometer.
The mixture is shaken and allowed to settle.

The mixture is poured away, the flask is rinsed and procedure is repeated several times
using the same volume of sodium thiosulphate solution and the same volume and of
hydrochloric acid of the same concentrations but in each experiment warming the
sodium thiosulphate solution to a higher recorded temperature than the previous one
before adding hydrochloric acid.
A graph of against temperature is plotted.
℃
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The graph obtained is a straight line with a positive gradient and an intercept on the
axis. This shows that the rate of reaction( ) increases with increase in temperature.
3. Experiment to show the effect of particle size(surface area) on the rate of

reaction between calcium carbonate and hydrochloric acid
A known volume of excess dilute hydrochloric acid of known concentration is

measured into a test tube tied with a thread.
The test tube and its contents is stoppered in a clean reaction flask containing a known
mass of calcium carbonate lumps and connected to a gas syringe.
The stopper is gently opened to relax the thread so that the acid pours onto the calcium
carbonate lumps and a stop clock started simultaneously.
The mixture is shaken and allowed to settle at a constant temperature.
The volume of carbon dioxide evolved is recorded at fixed specific intervals of time

until no more bubbles are formed.
The procedure is repeated using the same mass of powdered calcium carbonate and the
same volume of hydrochloric acid of the same concentration.
On the same axes, graphs of volume of carbon dioxide against time are plotted.
Powdered calcium carbonate
Calcium carbonate lumps
The rates of reaction at a specific time are determined by drawing tangents on each
curve at that point and calculating the gradient.
The values obtained are compared and those obtained from the graph when powdered
calcium carbonate is used are higher.
This shows that the rate of reaction increases when that particle size is reduced
(surface area is increased)
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More questions
1. (a) State and explain how the following factors affect the rate of a chemical reaction.
(i) Temperature
(ii) Catalyst
(b) The graph below shows the kinetics data obtained for the decomposition of
nitrogen(V) oxide dissolved in carbon tetrachloride at ℃.
Time (seconds) 250 750 1500 2000 2500
Concentration of 1.95 1.42 0.95 0.70 0.50
Plot a graph of t t against time.
(c) Use the graph in (b) to:
(i) determine the original concentration of
(ii) deduce the order of the reaction. Give a reason for your answer.
(d) Calculate the:
(iii) rate constant for the reaction and indicate its units

(ii) half-life of the reaction
2. (a) Define the term catalyst
(b) Differentiate between a positive catalyst and a negative catalyst
(c) State four general properties of a positive catalyst
(d) Give one example of a catalyst used in industry and in nature. Name the process
involved.
(e) State the difference between a homogeneous and a heterogeneous catalyst.
3. (a) Explain why transition metals commonly act as catalysts
(b) In each case, write equation for the reaction catalyzed by the following
substances.
(i) Finely divided iron
(ii) vanadium(V) oxide
(iii) manganese(II) ions
(c) Explain the action of a positive catalyst.
4. (a) Apart from temperature and concentration, state any two other factors that affect
the rate of a chemical reaction.
(b) Describe an experiment to determine the rate for the reaction between sodium
thiosulphate and hydrochloric acid.
(c) The table below shows variation in the concentration of sodium thiosulphate with
time when a fixed volume of hydrochloric acid was added to sodium thiosulphate
at various concentrations.
Time, 24 29 39 60 138
Concentration of sodium thiosulphate 0.2 0.16 0.12 0.08 0.04
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(i) Plot a graph of ⁄ against concentration of sodium thiosulphate
(ii) State the order of the reaction. Give a reason for your answer.
(iii) Calculate the rate constant for the reaction and indicate its units
(iv) Determine the time taken for the concentration of sodium thiosulphate to
decrease from to .
5. The figure below shows the variation of energy with reaction coordinate for a
catalysed and an uncatalysed reaction
Potential energy
𝒌𝑱𝒎𝒐𝒍 𝟏 𝐴 𝑔 𝐵 𝑔

𝑃
𝐶 𝑔
Reaction coordinate
(a) Identify
(i) the curve for catalyzed reaction
(ii) the curve for uncatalysed reaction
(iii) P
(iv) Q
(v) R
(b) From the figure, state how a catalyst increases the rate of reaction.
(c) The kinetic data for the reaction above are shown below.
1
2
3
4
(i) Deduce the rate equation.

(ii) Calculate the rate constant for the reaction and state its units.
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CHAPTER NINE
ELECTROCHEMISTRY
Electrochemistry is the branch of chemistry that deals with chemical changes that are
produced by passing electric current into a chemical system or the generation of
electricity by spontaneous chemical reactions.
MODES OF CONDUCTION OF SUBSTANCES
The substances that allow electric current to flow through them are called conductors.
Those that do not allow electric current to flow through them are called non-conductors
or insulators. The conductors are classified into two type i.e. metallic conductors and
electrolytic conductors.
1. Metallic conductors
Metals or alloys allow electric current to flow through them without undergoing any
chemical change. The metals conduct electric current by use of free mobile electrons

(delocalised electrons). These include copper, silver, aluminium and others. This mode
of conduction is called electronic conduction.
2. Electrolytic conductors
These include aqueous solutions of electrolytes or molten electrolytes. They are
compounds and chemical changes occur when they conduct electricity. The electrolytes
conduct electric current by use of free mobile ions. Examples include dilute hydrochloric
acid, aqueous sodium chloride, molten lead(II) bromide and others. This mode of
conduction is called electrolytic conduction.
ELECTROLYSIS
Electrolysis is the decomposition of a compound in its molten state or in solution by
passage of an electric current through it.
or
The overall chemical change that occurs at the electrodes when an electric current
passes through a fused electrolyte or its aqueous solution
The electrolyte, solvent or electrode may all be involved in the electrolytic reaction
The common terms used in electrolysis
1. Electrolytes
These are compounds which conduct electric current in solution or in molten state and are
decomposed by it.
A non-electrolyte is a substance which does not conduct electric current in molten state or
aqueous solution and cannot be decomposed by electric current. For example sucrose
Electrolytes can be salts, acids or bases.
Electrolytes can be classified as strong or weak.
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(i) Strong electrolytes

These are electrolytes which almost completely ionise in solution. Their solutions do not
contain unionized molecules.
They include most salts, strong acids and strong alkalis.
(ii) Weak electrolytes
These are electrolytes which partly ionise in solution. Their solutions contain ions in
equilibrium with unionized molecules.
They include most organic acids and bases and ammonia.
Examples of strong and weak electrolytes
Strong electrolytes Weak electrolytes
Sodium chloride Ethanoic acid
Calcium chloride Ammonia solution
Sodium hydroxide Ethylamine
Hydrochloric acid Carbonic acid

Electrolytes can as well be ionic or covalent.
(i) Ionic electrolytes
These electrolytes are made up of ions in the solid state but the ions are not free to move.
For example sodium chloride, .
When ionic electrolytes are heated, sufficient energy is absorbed to break the crystal
lattice so that the ions are free to move within the molten electrolyte.
When ionic electrolytes are dissolved in water (or any other ionizing solvent), the crystal
lattice is broken, the ions become free to move. The ions are hydrated (solvated,
completely surrounded by water molecules)
(ii) Covalent electrolytes
These electrolytes do not contain ions so they conduct electricity in the liquid state as
ionic electrolytes do. The covalent electrolytes usually contain polar bonds such as
or bonds. They react with water or any other ionizing solvent to
form hydrated ions. These include all mineral acids.
2. Electrodes
These are conductors which carry electricity into and out of the cell. The electrodes
include the anode and the cathode.
(i) Anode
This is the electrode at which oxidation takes place
(ii) Cathode
This is the electrode at which reduction takes place
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Explaining the changes that take place during electrolysis

Electrolysis is generally carried out in an electrolytic cell as shown below.
Battery
Flow of current Flow of electrons
Anode Cathode
Electrodes
Electrolyte
The electrolytic cell is set up as shown above. The electrolyte contains both cations and
anions. During electrolysis, the anions migrate to the anode and lose electrons
(are oxidised) to form neutral elements or new molecules.

The cations migrate to the cathode and combine with the electrons there (are reduced) to
form neutral elements or new molecules.
Principles of electrolysis (selective discharge of ions)
Under similar conditions, when two or more ions with a similar charge are present in a
solution, i.e. and or and ̅ , one ion is preferentially selected for
discharge at each electrode and the selection of the ion depends on the following factors:
(i) Position of the ion in the electrochemical series
(ii) Concentration of the ions in solution
(iii) Nature of the electrode.
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(i) Position of the ion in the electrochemical series
Cations (move to cathode) Anions (move to anode)
Increasing ease of discharge at
Increasing ease
of discharge at
anode
cathode
̅

If all the other factors (stated above) are constant, any ion is discharged from solution in
preference to the ions above it in the electrochemical series.
For example in electrolysis of sodium hydroxide solution, the solution contains the
cations; from water and . The hydrogen ion discharges in preference to the
sodium ion at the cathode. Hydrogen gas is formed at the cathode.
During electrolysis of silver nitrate solution, the solution contains the anions; ̅ from
water and . The hydroxide ion is discharged in preference to the nitrate ion at the
anode. Oxygen gas is formed at the anode.
̅
Note: The order of preferential discharge given in the table above only applies for
discharge from aqueous solutions containing ions at comparable concentrations
approximately 1M. Sometimes exceptions arise as a result of large differences in
concentration.
(ii) Concentration of the ions in solution
An ion present at a lower concentration is more difficult to discharge than an ion present
at a higher concentration.
The electrolysis of sodium chloride solution liberates chlorine at the anode during
manufacture of chlorine. This is because although the solution contains the anions; ̅
and . The chloride ion is discharged because it is present in a higher concentration
than the hydroxide ion.
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The electrolysis of concentrated hydrochloric acid liberates chlorine at the anode for the
same reason as in the case above.
(iii) Nature of the electrode.
Inert electrodes like platinum may not affect the products of electrolysis. Some
electrodes may affect the products of electrolysis. For example:
(a) Electrolysis of concentrated sodium chloride solution (saturated brine) using
platinum cathode and mercury cathode.
When a platinum cathode is used, hydrogen ions are discharged in preference to sodium
ions because hydrogen is lower than sodium in the electrochemical series. Hydrogen gas
is therefore formed at the platinum cathode.
When a mercury cathode is used, sodium ions are discharged in preference to hydrogen
ions because the discharge of sodium ion requires less energy than the discharge of

hydrogen ions. Sodium amalgam is therefore formed at the mercury cathode by the
reaction between sodium and the mercury cathode.
(b) Electrolysis of copper(II) sulphate solution using platinum anode and copper
anode.
When a platinum anode is used, hydroxide ions are discharged in preference to sulphate
ions because the hydroxide ion is lower than the sulphate ion in the electrochemical
series. Oxygen gas is therefore formed at the platinum anode. The solution at the anode
also becomes acidic due to the reaction between hydrogen ions and sulphate ions to form
sulphuric acid.
̅
When a copper anode is used, neither the hydroxide ions nor the sulphate ions are
discharged but instead the copper anode dissolves in the solution to form copper(II) ions.
The electrolysis is merely a transfer of copper from the anode to the cathode.
Laws of electrolysis
Micheal Faraday studied the quantitative relationships between the electricity passed
through an electrolyte and the amount of material liberated or deposited at the electrodes.
1. Faraday‟s first law of electrolysis states that the mass of the substance liberated at an
electrode during electrolysis is directly proportional to the quantity of electricity
passed through the electrolyte.
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Where; is the mass of substance consumed or produced at an electrode

is the quantity of charge passed in Coulombs
is the current in amperes
is the time in seconds for which the current was passed.
is a proportionality constant called the electro-chemical equivalent.
2. Faraday‟s second law of electrolysis states that the quantity of electricity required to
liberate one mole of any element is proportional to the charge number of its ion.
The charge number of an ion, represented by is the number of positive or negative
charges which the ion possesses. It can be positive or negative. For example for
, for , for and for .
The magnitude of the charge number is usually equal to the number of moles

electrons required for the ion to be discharged.
Note that
Experiment to determine the Faraday constant by electrolysis of copper(II) sulphate

using copper electrodes.
d.c power supply
Arrange the apparatus as shown
Variable The variable resistor is used to keep the current
Ammeter
resistor constant
Weigh the mass of the pure copper anode 𝑥 𝑔
and pure copper cathode 𝑦 𝑔 separately
Copper anode Copper cathode Pass a constant electric current 𝐼 𝐴𝑚𝑝𝑒𝑟𝑒𝑠 for a
measured time interval 𝑡 𝑠𝑒𝑐𝑜𝑛𝑑𝑠
Remove the cathode and anode and wash them
with distilled water and then propanone and dry
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Copper(II) sulphate solution them.

689
The washed and dried cathode and anode are weighed again and their new masses
and recorded respectively.
Mass of copper removed from the anode
Quantity of charge passed,
( )
( )
( )

( )
Trial question;
A student passed a constant electric current of 0.15A through a solution of silver nitrate
using pure silver electrodes for exactly 45 minutes. The mass of the anode decreased by
0.45g. Use this data to calculate the charge on a mole of electrons.
Calculations of electrolysis
Examples
1. Calculate the quantity of charge required to deposit 40.5g of aluminium during
electrolysis of a solution of aluminium ions.
( )
2. When current was passed through a solution of silver nitrate for 10 minutes,
0.54g of silver was deposited at the cathode. Calculate the current.
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( )
3. Determine the time taken to deposit 1.0g of chromium when a current of 0.120A
flows through a solution of chromium(III) sulphate.
( )

4. Calculate the mass of lead deposited at the cathode during electrolysis when a
current of 1.50A flows through molten lead(II) bromide for 20 minutes.
( )
5. An electric current was passed through a solution of copper(II) sulphate

electrolyzed using platinum electrodes for 1 hour.
(a) Calculate the strength of the current used to deposit 0.106g of copper.
(b) If the electrolytic cell above was in series with a silver nitrate cell. Calculate
the mass of silver deposited on the cathode of the second cell.
(a)
( )
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691
(b)
( )
6. A current of 89.6mA was passed through an electrolytic cell containing dilute

sulphuric acid electrolyzed between platinum electrodes for 1 hour. Calculate the
total volume of gas measured at 15℃ and 100kPa liberated.
̅
( )

( )
7. Calculate the volume of oxygen liberated at anode at s.t.p in the electrolysis of

copper(II) sulphate solution when a current of 1500 milliamperes is passed for 10
minutes.
( )
8. (a) A current of 32.2A was passed through molten lead(II) bromide for 5 hours
and the bromine liberated reacted with 94g of hydroxybenzene. Calculate the
number of moles of ;
(i) bromine liberated
(ii) hydroxybenzene that reacted
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(b) State what is observed and write equation for the reaction that took place
between bromine and hydroxybenzene in (a) above.
(a) (i)
( )
(ii)
(b) Observation: White precipitate
Equation: 𝐵𝑟 𝐵𝑟

𝐵𝑟
9. 20 of 0.05M aqueous phenylamine was mixed with 50 of 1M sodium

bromide and electrolyzed at current of 0.2A. The first permanent bromine
colour was observed after 48.25 minutes and then electrolysis was stopped.
.
(i) Calculate the moles of bromine that reacted with 1 mole of phenylamine
(ii) Hence write equation of the reaction between bromine and phenylamine.
Name the product
(i)
Hint: Electrolysis of sodium

bromide yields bromine at the
anode. The sodium bromide was
such an excess such that
( ) enough bromine is liberated to
react with all the phenylamine.
The first bromine colour only
( ) appears if just enough bromine
has been formed to react with
all the phenylamine present.
( )
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(ii) Observation: White precipitate
Equation: 𝐵𝑟 𝐵𝑟
𝐵𝑟
Name of product: 2,4,6-Tribromoaminobenzene
10. A direct current of 0.45A was passed through a dilute solution of copper(II)
sulphate using graphite electrodes for 5.96 hours.
(a) Write equation for the reaction at the:
(i) cathode
(ii) anode
(b) If 3.1767g of copper was deposited and 560 of oxygen at stp were evolved,
calculate the quantity of electricity required to produce 1 mole of each
substance at their respective electrodes.

(a) (i) At cathode:
(iii) At anode: ̅
(b)
( )
( )
Questions
1. 3 Faraday are needed to electroplate a given amount of metal using a current of 5.0A.
How long will it take to electroplate the metal?
2. Calculate the mass of copper deposited at the cathode when a current of 1.0A was
passed through copper(II) sulphate solution for 10 minutes.
3. Calculate the mass of silver deposited at the cathode during electrolysis when a
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current of 1.80A flows through an aqueous solution of silver nitrate for 45.0 minutes.
694
4. The same current was passed through molten sodium chloride and through molten
cryolite containing aluminium oxide. If 4.60g of sodium were liberated in one cell.
Calculate the mass of aluminium liberated in the other cell.
5. During the extraction of aluminium, a current of 0.2 ampere was passed for one hour
through aluminium sulphate solution.
(a) Write an equation for the reaction that took place at each electrode
(b) Calculate the mass of aluminium produced
6. Calculate the mass of chlorine that can be produced by the electrolysis of molten
sodium chloride with a current of 5.5 amperes for 25 minutes.
7. Calculate the mass of lead deposited when 0.2 moles of electrons are passed through
lead(II) nitrate solution during electrolysis.
8. Calculate the volume of oxygen liberated at anode at s.t.p in the electrolysis of
copper(II) sulphate solution when a current of 1500 milliamperes is passed for 10
minutes.

9. Calculate the volume of chlorine liberated at standard temperature and pressure by
passing 0.2 moles of electrons during electrolysis sodium chloride solution.
10. Determine the mass of hydrogen liberated by passing 0.5 moles of electrons during
electrolysis sodium chloride solution.
11. If a current is passed through a cell for 2 hours deposits 0.4818g of silver. Calculate
the volume of oxygen that would be liberated in the same circuit where dilute
sulphuric acid is electrolysed.
12. Calculate the volume of oxygen produced at room temperature when a concentrated
aqueous solution of sulphuric acid is electrolyzed for 30 minutes using a current of
0.50A.
13. During the electrolysis of a 1M copper(II) sulphate solution at ℃, a current of 0.1A
was passed for one hour through the electrolyte. The mass of the copper cathode
increased by 0.118g. State how the change in mass would be affected if the
experiment was repeated:
(a) at a current of 0.2A
(b) at ℃
(c) with a 2M copper(II) sulphate solution
(d) for a time of 2 hours
14. (a) An aqueous solution of copper(II) sulphate was electrolyzed between copper
electrodes.
Write equation for the reaction at the;
(i) Cathode
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695
(ii) Anode
(b) (i)Identify the species which carry the current through the solution and state their
direction of flow.
(ii) Explain the changes in the mass of each electrode and in the concentration
of copper(II) sulphate near the anode.
(iii) Calculate the change in mass of the anode if a current of 1.0A is maintained
for one hour.
(c) During the electrolysis of aqueous hydrogen chloride between silver electrodes,
the anode mass increases and a white coating form on it. Explain this observation.
The applications of electrolysis in industry

The elements potassium, calcium, sodium, magnesium and aluminium being very
reactive, are never found as free elements. They are extracted by electrolysis.
Potassium is extracted from fused potassium hydroxide. Sodium from molten sodium
chloride, calcium from fused calcium chloride and aluminium from Bauxite.

1. Extraction of sodium by electrolysis of molten sodium chloride in the Down‟s
process. (The same process is used for manufacture of chlorine)
Sodium is extracted by electrolysis of molten sodium chloride in the Down’s cell.
A carbon anode is used and an iron cathode and are separated from each other by an
iron gauze diaphragm.
Calcium chloride is added to the electrolyte to lower its melting point of sodium
chloride from about 800℃ to about 600℃.
Sodium chloride is decomposed by electric current to form sodium ions and chloride
ions.
Sodium ions are preferentially discharged at the cathode at the temperature used
forming sodium.
Chloride ions migrate to the anode and form chlorine gas which escapes from the cell.
2. Anodisation of aluminium
Aluminium is normally covered by a thin coating of aluminium oxide to protect it from

corrosion and to make it resistant from chemical attack. The thickness of the oxide layer
is increased by electrolyzing dilute sulphuric acid or chromic(VI) acid with the
aluminium made the anode. The oxygen liberated at the anode reacts with the aluminium
to form the protective layer of aluminium oxide.
̅
|
696
3. Electroplating
This is the electrical coating of one metal with another metal to make it resistant to
corrosion and improve its appearance. The metal to be electroplated is made the cathode
and the electroplating metal made the anode. The electrolyte must contain a solution of
ions of the electroplating metal.
4. Manufacture of sodium chlorate(I) and sodium chlorate(V) by electrolysis of

concentrated sodium chloride solution.
A cold concentrated solution of sodium chloride is electrolyzed using platinum
electrodes placed close together. The chlorine liberated at the anode combines with the
hydroxyl ions left at the cathode to form sodium chlorate(I).
̅
If the electrolysis is done using a hot concentrated solution of sodium chloride at ℃
The chlorine liberated at the anode combines with the hydroxyl ions left at the cathode to
form sodium chlorate(V).

̅
5. Extraction of aluminium by electrolysis of molten aluminium oxide
6. Manufacture of sodium hydroxide by electrolysis of concentrated sodium
chloride solution (saturated brine) using a mercury cell (Castner-Kellner cell) or
a diaphragm cell.
(The same process can as well be used for manufacture of chlorine)
7. Refining of copper
(Check for the details of 5, 6 and 7 in Demystifying Inorganic Chemistry by the
same author)
CONDUCTIVITY OF SOLUTIONS OF ELECTROLYTES

When electric current flows through an electrolyte, there is resistance to the flow of
current. The current that flows through a given solution under given conditions is
inversely proportional to the reciprocal of resistance.
The common terms used

1. Conductance
Conductance is the reciprocal of resistance of an electrolytic solution.
The SI unit of conductance is the siemens although it used to be measured in

reciprocal ohms . Therefore .
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697
High resistance means low conductance and low resistance means high conductance.
2. Resistivity
To compare resistances of different electrolytic solutions, the idea of resistivity is used.
Resistivity is the resistance of a solution placed between two parallel electrodes of
cross-sectional area and separated by a distance of apart.
Resistance of an electrolytic solution is directly proportional to the length between
the electrodes;
The resistance of an electrolytic solution is also inversely proportional to the cross sectional
area of the electrodes;
Combining (i) and (ii);

Where is resistance
is resistivity
is length between the electrodes
is the cross sectional area of the electrodes
From (iii) , then Resistivity,
Since R is measured in ohms , is Area is measured in and length in metres ,

then the SI unit of resistivity is ohm metre . But can also be used.
3. Electrolytic conductivity
It is also called specific conductivity or specific conductance.
To compare conductance of different electrolytes, electrolytic conductivity is used.
Electrolytic conductivity is defined as the conductivity of a solution of an electrolyte
placed between two parallel electrodes of cross-sectional area and separated by a
distance of apart.
or
It is the reciprocal of resistivity.
⁄
The SI unit of electrolytic conductivity is siemen per metre . But can
also be used.
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698
4. Cell constant
From , the cell constant is the value of . Its units are or can be .
and for any cell are constant.
Cell constant is therefore the distance between two parallel electrodes of a cell divided
by the cross sectional area of one electrode.
Therefore,
Also
or ⁄
5. Molar conductivity
It is also called molar conductance.
Molar conductivity is the conductivity of a solution of containing 1 mole of an
electrolyte placed between two parallel electrodes of cross-sectional area and
separated by a distance of apart.

or
It is the electrolytic conductivity divided by concentration.
since , then
The two above formulae show the relationship between electrolytic conductivity and
molar conductivity.
The SI unit of molar conductivity is . But can also be used.
The formula of molar conductivity used in calculations depends on the units of and
given.The formula used is intended to make units consistent.
If unit of is If unit of is
The expression is
and that of is then; and that of is only and only used if the
then; units are consistent.
Note: When the definitions are stated in terms of formulae, each term in the formula
should be well defined.
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699
Measurement of conductivity of solutions
Variable condenser
Conductivity cell Variable resistance
Head phones
A B (detector)
X
a.c source
A solution of the electrolyte of known concentration is prepared using conductivity water
(demineralized water or water purified by ion exchange)
A known volume of the standard solution of the electrolyte is then pipetted and placed in
a conductivity cell.

The conductivity cell and its solution is connected in a Wheatstone bridge circuit where
it‟s made the unknown resistance.
A rapidly alternating current is applied from a small induction coil or a vacuum tube
oscillator.
The variable resistance and the position X along wire AB are changed until no current
passes through the head phones
At this balance point the buzzing sound in the head phones (used as detector) is a
minimum.
The distances and at balance point are measured.
The area of the electrodes in the conductivity cell and their distance of separation
is also measured.
At the balance point ;
The resistance of the solution is then calculated and used to find conductance from; |
700
Calculations involving electrolytic conductance

Examples
1. (a) State what is meant by the term cell constant.
(b) The resistivity of 0.02M potassium chloride solution is 361 and a
conductivity cell having such a solution was found to have a resistance of
550 .
(i) Calculate the cell constant
(ii) if the same cell was filled with 0.1M zinc sulphate solution had a resistance of
72 . Calculate the conductivity of 0.1M zinc sulphate solution.
(b) (i) (ii)

2. (a) A conductivity cell with electrodes in area and apart has a
resistance of 7.25 when filled with 5 percent potassium chloride solution.
Calculate the:
(i) cell constant
(ii) the conductivity of the potassium chloride solution.
(b) If the same cell was filled with 0.02M potassium chloride with a resistivity of
361 . Calculate the resistance.
(a) (i) (b)
(ii)
3. The resistance of a 0.01M sodium chloride solution in a conductivity cell was

found to be 210 . The specific conductance of the solution is .
Determine the cell constant.
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701
4. A conductivity cell has electrodes of cross sectional area and apart.

The cell is filled with pure water of conductivity and a potential
difference of 10V applied. Calculate the current that would flow through the cell.
5. A 0.1M solution of ethanoic acid when placed between two electrodes , each
in area and separated by has a resistance of 6956 ohms.

Calculate the:
(i) specific conductivity,
(ii) molar conductivity of the solution.
(ii)
(i)
6. The molar conductivity of 0.1M ethanoic acid solution is .

Calculate the:
(i) electrolytic conductivity
(ii) resistivity.
(i) (ii)
7. The resistance of a conductivity cell of a conductivity cell when filled with 0.05M
solution of an electrolyte is 100 at 40℃. The same conductivity cell when
filled with 0.01M solution has a resistance of 50 . If the electrolytic
conductivity of 0.05M is . Calculate the:
(i) electrolytic conductivity of 0.01M solution
(ii) molar conductivity of 0.01M solution
|
702
(i)
(ii)
8. Calculate the mass of ethanoic acid that must be dissolved in a litre of water to
make a solution of molar conductivity and electrolytic
conductivity .

Questions
1. A conductivity cell with electrodes in area and apart has a resistance of
35.6 when filled with 2.085 percent barium chloride solution. Calculate the:
(i) cell constant
(ii) the electrolytic conductivity of the barium chloride solution.
2. A conductivity cell has electrodes of cross-sectional area of in area and
apart. Calculate the cell constant of the conductivity cell.
3. A conductivity cell has electrodes of cross-sectional area of in area and
apart. Calculate the cell constant of the conductivity cell.
4. The electrolytic conductivity of 2M potassium chloride solution of .
The resistance of 2M potassium chloride solution in a conductivity cell is 1.5 .
Calculate the cell constant of the conductivity cell.
5. The conductivity of an aqueous solution of sodium chloride in a cell is
92 .The resistance offered by the cell is 247.8 ohm. Calculate the cell
constant.
6. The molar conductance of 2M potassium chloride solution is .
Calculate the specific conductance of the solution.
|
703
7. A 0.05M sodium hydroxide solution offered a resistance of 31.6 in a conductivity

cell at 298K. If the cell constant of the cell is 0.367 .Calculate the molar
conductivity of the sodium hydroxide solution.
(i) conductivity
(ii) conductance
(b) Using the same conductivity cell, the resistance of potassium chloride solution
and 0.1M chloroethanoic acid solution were found to be 24.9 and 66.5 ohms
respectively at 25℃. The conductivity of potassium chloride at 25℃ is
.
(i) Calculate the cell constant
(ii) Calculate the conductivity of 0.1M chloroethanoic acid.
Factors affecting electrolytic conductivity of electrolytes

The factors affecting electrolytic conductivity include:
(i) Concentration
(ii) Temperature
(i) Concentration
For a strong electrolyte, as concentration increases, conductivity increases up to a
maximum and then decreases.
Explanation;
As concentration increases, the total number of conducting ions per unit volume
solution increases. This increases the conductivity. As concentration increases further,
the total number ions in solution increases further since the electrolyte is completely
ionized at all concentrations, inter-ionic distance decreases, ionic interference increases
and ionic mobility decreases. This decreases the electrolytic conductivity.
For a weak electrolyte, as concentration increases, conductivity increases up to a

maximum and then decreases.
Explanation;
As concentration increases, the total number of conducting ions per unit volume
solution increases. This increases the conductivity. As concentration increases further,
the total number unionized molecules of the electrolyte increases, degree of dissociation
decreases and the number of conducting ions per unit volume of solution decreases.
This decreases the electrolytic conductivity.
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704
(ii) Temperature
For a strong electrolyte, conductivity increases with increase in temperature.
Explanation;
As temperature increases, the average kinetic energy of the conducting ions increases.
The viscosity of the water decreases and the ionic mobility increases.
For weak electrolytes, the effect of temperature depends on the enthalpy change which
accompanies ionization.
For a weak electrolyte that ionizes exothermically, increase in temperature decreases
the degree of dissociation according to Le Chatelier‟s principle. Hence the number of
conducting ions per unit volume of solution decreases. This decreases the electrolytic
conductivity.
For a weak electrolyte that ionizes endothermically, increase in temperature increases
conducting ions per unit volume of solution increases. This increases the electrolytic
conductivity.

Factors affecting molar conductivity of electrolytes
The factors affecting molar conductivity include:
(i) Temperature of the solution
(ii) Magnitude of the charge on the ions
(iii) Ionic radius
(iv) Viscosity of the solvent
(v) Concentration of the solution
(i) Temperature of the solution

For a strong electrolyte, molar conductivity increases with increase in temperature.
Explanation;
As temperature increases, the average kinetic energy of the conducting ions increases.
The viscosity of the water decreases and the ionic mobility increases.
For weak electrolytes, the effect of temperature depends on the enthalpy change which
accompanies ionization.
For a weak electrolyte that ionizes exothermically, increase in temperature decreases
conducting ions per unit volume of solution decreases. This decreases the molar
conductivity.
For a weak electrolyte that ionizes endothermically, increase in temperature increases
conducting ions per unit volume of solution increases. This increases the molar
conductivity.
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705
Question
(a) Distinguish between electrolytic conductivity and molar conductivity
(b) The molar conductivity of ethanoic acid containing is 8.50
units at 18℃ and 14.7 units at 100℃. Explain the difference in molar
conductivities at the two temperatures.
(ii) Magnitude of the charge on the ions

Molar conductivity increases with increase in the magnitude of ionic charge. Ions with
high charges are more strongly attracted by the oppositely charged electrode and move
faster.
(iii) Ionic radius

Molar conductivity increases with increase in ionic radius. The higher the ionic radius,
the lower the charge density and the less hydrated the ion. The less hydrated ions move
faster than heavily hydrated ions hence ions with smaller ionic radius are more

conducting than ions with higher ionic radius.
Question; Explain why the:

(a) magnesium ion has a higher molar conductivity than the sodium ion
(b) sulphate ion has a higher molar conductivity than the chloride ion.
(c) the molar conductivity of the lithium ion is smaller than that of the sodium
ion
(iv) Viscosity of the solvent

The higher the viscosity of the solvent, the lower the ionic mobility hence the lower the
molar conductivity.
706
(v) Concentration of the solution

The sketches below show the variation of molar conductivity with the square root of
concentration for both a strong electrolyte and a weak electrolyte.
𝑴𝒐𝒍𝒂𝒓 𝒄𝒐𝒏𝒅𝒖𝒄𝒕𝒊𝒗𝒊𝒕𝒚
𝑺𝒄𝒎𝟐 𝒎𝒐𝒍 𝟏
Ethanoic acid

𝟏
𝟑 𝟐
√𝑪𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 𝒎𝒐𝒍𝒅𝒎
Explanation of the shapes of the graphs
For potassium chloride, as concentration increases, molar conductivity decreases.
Potassium chloride is a strong electrolyte. As concentration increases, the total number
of conducting ions per unit volume increases, inter ionic distance decreases, ionic
interference increases and ionic mobility decreases.
At zero concentration (infinite dilution), molar conductivity reaches a maximum value
called molar conductivity at infinite dilution because ionic interference is negligible.
N.B Molar conductivity at infinite dilution is obtained from the graph by extrapolation.
For Ethanoic acid, as concentration increases, molar conductivity decreases.

Ethanoic acid is a weak electrolyte. As concentration increases, the degree of
dissociation decreases and the number of conducting ions per unit volume of solution
decreases.
Instead of concentration, reciprocal of concentration( ), also called dilution can be used.
|
707
The sketches below show the variation of molar conductivity with the dilution for
both a strong electrolyte and a weak electrolyte.
Potassium
Potassium chloride
chloride Note that neither the
graphs against
concentration nor those
𝑴𝒐𝒍𝒂𝒓 𝒄𝒐𝒏𝒅𝒖𝒄𝒕𝒊𝒗𝒊𝒕𝒚
against dilution begin from
𝑺𝒄𝒎𝟐 𝒎𝒐𝒍 𝟏 Ethanoic acid
Ethanoic acid the origin.
The graphs do not coincide
anywhere too

𝒐𝒓 𝒅𝒊𝒍𝒖𝒕𝒊𝒐𝒏 𝒎𝒐𝒍𝒅𝒎 𝟑 𝟏
𝒄
Explanation of the shapes of the graphs
For potassium chloride, as dilution increases, molar conductivity increases to a
maximum value at which it remains constant at infinite dilution.
Potassium chloride is a strong electrolyte. As dilution increases, inter-ionic distance
increases, ionic interference decreases and ionic mobility increases.
At zero concentration (infinite dilution), the ionic interference is negligible.
N.B Molar conductivity at infinite dilution is obtained from the graph by extrapolation.
For Ethanoic acid, as dilution increases, molar conductivity increases.
Ethanoic acid is a weak electrolyte. As dilution increases, degree of dissociation
increases and the number of conducting ions per unit volume of solution increases.
Questions
1. The table below shows values of molar conductivity of ethanoic and potassium
chloride at different concentrations.
Concentration 0.0001 0.001 0.01 0.1 1 2 3
107.0 41.0 14.3 4.6 1.32 0.80 0.54
129.1 127.3 122.4 112.0 98.3 92.6 88.3

(b) On the same axes, plot graphs for molar conductivity against the square root of
concentration.
(c) State and explain the shapes of the graphs in (b) above.
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708
2. The table below shows values of molar conductivity of hydrochloric acid and
ammonia solution at different concentrations at ℃.
Concentration 0.001 0.01 0.1 1 3
377 370 351 301 215
28 9.6 3.3 0.89 0.36

(b) On the same axes, plot graphs for molar conductivity against dilution.
(c) State and explain the shapes of the graphs in (b) above.
3. The table below shows values of molar conductivity of sodium chloride solution at
different concentrations at ℃.
Concentration 0.2 0. 1 0.05 0.02 0.01 0.005 0.001
Molar conductivity of 0.01015 0.0107 0.0111 0.0116 0.0118 0.0122 0.0124
sodium chloride

√
(b) On different axes, plot a graph for:
(i) molar conductivity against dilution.
(ii) molar conductivity against √
(c) From each of the graphs determine the molar conductivity at infinite dilution of
sodium chloride.
(d) Explain the shape of each of the graphs in (b) above.
4. The table below shows values of molar conductivity of ethanoic acid solution at
different concentrations at ℃.
Concentration 0.001 0.01 0.1 1.0 3.0
41.00 14.30 4.60 1.32 0.54
( )

(b) On different axes, plot a graph for:
(i) molar conductivity against the square root of concentration.
(ii) molar conductivity against dilution
(c) Explain the shape of each of the graphs in (b) above.
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709
5. (a)Define the term molar conductivity

(b) On the same sketch, draw a graph to show variation of molar conductivity of
aluminium sulphate and ethanoic acid.
(c) Compare and explain the shape of your graph for:
(i) ethanoic acid
(ii) aluminium sulphate
Kohlrausch’s law of independent migration of ions and its application

Kohlrausch Friedrich investigated the molar conductivity at infinite dilution of a large
number of electrolytes and found that it was a sum of two quantities.
Kohlrausch’s law states that the molar conductivity at infinite dilution of an electrolyte
is equal to the sum of the molar conductivities at infinite dilution of the ions produced
by the electrolyte.

Applications of Kohlrausch‟s law
(i) Indirect determination of molar conductivity at infinite dilution for weak
electrolytes.
(ii) To determine solubility of sparingly soluble electrolytes
(iii) To determine solubility product of sparingly soluble electrolytes
(iv) To determine degree of dissociation and equilibrium constant of a weak
electrolyte
(i) Indirect determination of molar conductivity at infinite dilution for weak

electrolytes.
The molar conductivity at infinite dilution of a weak electrolyte can be obtained if the
molar conductivities of selected strong electrolytes are known.
For ethanoic acid, the molar conductivity at infinite dilution can be obtained from the
molar conductivities at infinite dilution of hydrochloric acid, potassium ethanoate and
potassium chloride.
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710
Since equation (iv) can be obtained by adding (i) and (ii) and subtracting equation (iii);
Therefore;
[ ] [ ] [ ]
Examples
1. Given that the molar conductivities at infinite dilution of some electrolytes are as
shown below;
Compound
Sodium chloride 113
Ammonium chloride 134.1
Sodium hydroxide 225.2
Sodium methanoate 101.2
Hydrochloric acid 397.8
(a) Calculate the molar conductivity at infinite dilution of:

(i) methanoic acid
(ii) ammonia solution
(iii) ammonium methanoate
(b) Explain the differences in your answers in a(i) and (iii) above
(i)
(ii)
(iii)
(b) The molar conductivity at infinite dilution of methanoic acid is higher than that of
ammonium methanoate because the hydrogen ion in methanoic acid has a higher
molar conductivity than the ammonium ion in ammonium methanoate.
2. The molar conductivity at infinite dilution of the sulphate ion is 160

. If the molar conductivity at infinite dilution of aluminium
sulphate is 858 , calculate the molar conductivity at infinite
dilution of the aluminium ion.
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711
(i) Determining solubility and solubility product of sparingly soluble

electrolytes
The solubility of a sparingly soluble salt can be determined from the molar conductivity
of its saturated solution using the steps below:
The electrolytic conductivity of the saturated solution is measured using a
conductivity meter.
Using a known value of , the electrolytic conductivity of the electrolyte is then
obtained from the expression;
The molar conductivity at infinite dilution of the electrolyte is obtained from the
known values molar conductivity at infinite dilution of its constituent ions or from the
known values molar conductivity at infinite dilution of selected electrolytes using
Kohlrausch‟s law. Since the solution is very dilute then; .
The expression; is then used to calculate the

solubility, depending on the units of .
The stoichiometry of reaction is then used to determine the solubility product, .
Experiment to determine solubility and solubility product of silver chloride

Excess solid silver chloride is added to a given volume of distilled water in a container.
equilibrium.
The mixture is filtered to obtain a saturated solution of silver chloride as filtrate.
obtained from books
Also the molar conductivities at infinite dilution of silver ions and chloride ions are
read from the tables.
The electrolytic conductivity of silver chloride is then obtained by;
The molar conductivity of silver chloride at infinite dilution is obtained by the equation;
, where is molar conductivity of silver chloride
[ ]
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712
[ ] [ ] [ ]
[ ][ ]
(Revisit the experiments on solubility product in the topic IONIC EQUILIBRIA for
more experiments on solubility product)
Examples
1. The electrolytic conductivity of a saturated solution of silver chloride at ℃ is
.The molar conductivities at infinite dilution of silver and
chloride ions are and
respectively.
The electrolytic conductivity of pure water at ℃ is
Calculate the:
(a) solubility of silver chloride at ℃ in grams per litre
(b) solubility product of silver chloride

(a)
Solubility in
(b)
[ ][ ]
2. The electrolytic conductivity of a saturated solution of silver bromide at ℃ is

. The electrolytic conductivity of pure water at ℃ is
. Calculate the solubility product of silver bromide.
(The molar conductivities at infinite dilution of potassium bromide, silver nitrate
and potassium nitrate at infinite dilution are 137.4, 133 and 131
respectively at ℃)
[ ][ ]
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713
3. (a) Calcium phosphate is sparingly soluble in water.

Write:
(i) equation for the solubility of calcium phosphate in water
(ii) the expression for the solubility product of calcium phosphate
(b) The molar conductivities of calcium chloride, sodium phosphate and sodium
chloride at infinite dilution at ℃ are 271.8, 390.3 and 126.5
respectively. Calculate the:
(i) molar conductivity of calcium phosphate at infinite dilution at ℃.
(ii) solubility product of calcium phosphate at ℃.
(Electrolytic conductivity of calcium phosphate is )
(a) (i)
(iii) [ ] [ ]
(b) (i)

[ ]
(ii)
[ ] [ ]
[ ] [ ]
[ ] [ ]
(ii) Determining degree of dissociation and equilibrium constant of a weak

electrolyte
The degree of dissociation of a weak electrolyte can be obtained if the molar

conductivity at a given concentration and the molar conductivity at infinite
dilution are known.
|
714
The acid dissociation constant, of a weak acid can then be obtained from the
expression;

that;
The concentration of hydrogen ions is obtained from the expression [ ] and the
can be calculated.
The base dissociation constant and hydrolysis constant for salts.
Examples
1. The electrolytic conductivity of a 0.16M ethanoic acid solution at ℃ is
. The molar conductivity at infinite dilution of hydrogen ion and
ethanoate ion are and

(i) degree of dissociation , of ethanoic acid.
(ii) acid dissociation constant, , at ℃.
(i) (ii) Since is very small

compared to one, (0.3486%)
2. (a) (i) Define the term “molar conductivity at infinite dilution, ”.

(ii) State how you would expect the molar conductivity of sodium chloride
solution to vary as the dilution of the solution is increased. Give a
reason for your answer.
(b) The values of at ℃ for some electrolytes are as follows;
Electrolyte
104.7
126.5
426.2
(i) Calculate at ℃ for methanoic acid.
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715
(ii) If the value of molar conductivity, , for 0.01M methanoic acid is

50.5 at ℃. Calculate the acid dissociation constant, ,
for methanoic acid.
(b) (i) (ii) The value of is not very small
as compared to one(12.49%) so
cannot be used in the
calculation.
3. The molar conductivity of a 0.093M solution of ethanoic acid at ℃ is

. The molar conductivity at infinite dilution of hydrogen
ion and ethanoate ion are and

(i) molar conductivity of ethanoic acid at infinite dilution.
(ii) degree of dissociation , of ethanoic acid.
(iii) acid dissociation constant, , at ℃.
(iv) of the acid.
(i) (ii)
(iii) The value of very small as compared to (iv) [ ]

one(1.5%) so can be used in the
calculation. [ ]
4. The conductivity of a 0.063M solution of 2-hydroxypropanoic acid was found to

be . The molar conductivity of the acid at infinite dilution at
℃ is . Calculate the of the solution and the acid
dissociation constant.
( ) [ ]
[ ]
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716
5. The molar conductivities at infinite dilution of the ammonium ion and the
chloride ion are and respectively. The
electrolytic conductivity of a 0.1M ammonium chloride is .
Calculate the hydrolysis constant of ammonium chloride.
The value of is not very small as compared to

one(86%) so cannot be used in the
calculation.
Questions

1. Calculate the molar conductivity of water at infinite dilution at ℃ if at the same
temperature, ,
and .
2. Calculate the molar conductivity at infinite dilution of ethanoic acid from the
following data.
Compound
Hydrochloric acid 426
Sodium chloride 126
Sodium ethanoate 91
3. The molar conductivity at infinite dilution of sodium ion and the carbonate ion
respectively are 50.11 and 144 respectively. Calculate the molar
conductance at infinite dilution of sodium carbonate.
4. (a) State Kohlrausch‟s law of independent conductivity of ions.
(b) Some ionic conductivity at infinite dilution at ℃ are shown below:
Ion Ionic conductivity
̅ 198.6
76.4
73.6
50.1
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717
Calculate the molar conductivity at infinite dilution of:

(i) Sodium hydroxide
(ii) Ammonium chloride
5. The electrolytic conductivity of a saturated solution of silver chloride at ℃ after
deducting the electrolytic conductivity of water is .The molar
conductivities at infinite dilution of silver and chloride ions are and
respectively at ℃. Calculate the:
(a) solubility of silver chloride at ℃
(b) solubility product of silver chloride ℃.
6. (a) Explain what is meant by solubility product
(b) The electrolytic conductivity of a saturated solution of silver chloride in pure
water at ℃ is and the electrolytic conductivity of pure
water is . The molar conductivities at infinite dilution of
the following salts are given as:

Salt
Molar conductivity 133.4 145.0 149.9
Calculate the solubility product of a saturated solution of silver chloride at ℃.
7. (a) Define the following terms in relation to an aqueous solution of an electrolyte;
(i) specific conductance
(ii) molar conductance
(b) The electrolytic conductivity of an aqueous saturated solution of at ℃ is
. The molar conductivities at infinite dilution of
, sodium hydroxide and sodium chloride are 273, 248 and 126
(i) molar conductivity at infinite dilution of
(ii) the solubility of in water at ℃ in
8. The conductivity of dichloroethanoic acid at a dilution of is .
The molar conductivity at infinite dilution for the acid is . Calculate
the degree of ionization of the acid at a concentration of .
9. The conductivity of a 0.01M ethanoic acid at is . The molar
conductivities of hydrogen ion and ethanoate ion at infinite dilution are
and respectively. Calculate the acid dissociation
constant, , of ethanoic acid.
10. The electrolytic conductivity of a solution containing 6.66g of ethanoic acid per litre
is at ℃. The molar conductivity of the acid at infinite dilution at
this temperature is . Calculate the degree of dissociation of
ethanoic acid.
|
718
11. (a) Write an equation for the:

(i) acid dissociation constant, , for ethanoic acid
(ii) relationship between acid dissociation constant, , and degree of ionisation
of an acid.
(b) The electrolytic conductivity of a at ℃ is
and its molar conductivity at infinite dilution is
. Calculate:
(i) the molar conductivity of the ethanoic acid at ℃
(ii) the degree of ionisation of the acid at ℃
(iii) the of the acid
(c) Besides concentration, state one other factor that can affect the of the acid.
12. (a) State factors that can affect molar conductivity of an electrolyte.
(b) The molar conductivities at infinite dilution at ℃ for some electrolytes are
given in the table below.

Electrolyte ℃
Sodium nitrate 122
Nitric acid 421
Sodium ethanoate 91
Calculate the molar conductivity at infinite dilution for ethanoic acid.

(c) The molar conductivity of a aqueous solution at ℃ is
. Calculate the acid dissociation constant ( for ethanoic acid).
13. (a) Explain why hydrogen fluoride is a weaker acid than hydrogen chloride.
(b) Molar conductivities at infinite dilution at ℃ for some compounds are shown
in the table below.
Compound ℃
Nitric acid 0.0421
Potassium nitrate 0.0145
Potassium fluoride 0.0129
The conductivity of a aqueous solution of hydrogen fluoride is
. Calculate the:
(i) molar conductivity of solution
(ii) degree of ionization of hydrogen fluoride.
14. (a) Explain the molar conductivity of an electrolyte.
(b) Sketch a graph to show the variation of conductivity of a strong electrolyte with
dilution.
(c) Briefly explain the shape of the graph in (b) above.
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719
(d) The molar conductivities of nitric acid, potassium nitrate and potassium fluoride
are 421, 145 and 129 respectively at infinite dilution. Calculate
the:
(i) molar conductivity of hydrofluoric acid at infinite dilution
(ii) dissociation constant of , of 0.1M hydrofluoric acid solution.
(Electrolytic conductivity of hydrofluoric acid is )
(i) conductivity
(ii) molar conductivity
(iii) conductance
(b) The table below shows the molar conductivities of aqueous potassium hydroxide
at given dilutions.
Dilution 100 25 11.11 6.25 4.0 2.8

Molar conductivity 239 228 224 215 210 201

(i) Plot a graph of molar conductivity against dilution
(ii) Use the graph to determine molar conductivity of potassium hydroxide at
infinite dilution.
(iii) Explain the shape of the graph
(c) (i) Draw a sketch graph to show change in conductivity with volume of aqueous
sodium hydroxide when of a 0.1M propanoic acid is titrated with 0.1M
(ii) Explain the shape of the graph.
(d) The conductivity of a saturated solution of silver phosphate at 25℃ is
and that of pure water is . If the molar
ionic conductivities of phosphate ions and silver ions are 240 and 62
at infinite dilution at 25℃ respectively, calculate the:
(i) solubility of silver phosphate at 25℃
(ii) solubility product of silver phosphate at 25℃ and give its units.
Application of conductance (conductivity measurements)

The applications of conductivity measurements include:
(i) To determine solubility of sparingly soluble salts
(ii) To determine solubility product of sparingly soluble salts
(iii) To determine degree of dissociation of weak electrolytes
(iv) To determine the ionisation constant of a weak electrolyte
(v) To determine ionic product of water
(vi) To determine formulae of complexes
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(vii) Conductimetric titrations
Conductimetric titrations
The conductivity of a solution changes during an acid-base titration. The change in
conductivity of the solution can be measured. There is a sharp change in conductivity at
the end point. Such a titration is called a conductimetric titration.
The different velocities of the ions are used to ascertain the end point of a titration.
1. Titration of a strong base against a strong acid (sodium hydroxide solution against
hydrochloric acid)
A
Conductivity
𝟏
𝒄𝒎 𝟏 C

Volume used at
B end point
Volume of sodium hydroxide solution added 𝒄𝒎𝟑

Explanation of shape of the graph
Initially, conductivity is high at A due to very many fast moving and highly conducting
hydrogen ions from the strong completely ionized hydrochloric acid.
Conductivity decreases along AB as sodium hydroxide solution is added because the
fast moving highly conducting hydrogen ions are being neutralized to form water and
being replaced by the slow moving less conducting sodium ions.
At B, the end point is reached. Conductivity is low and is due to the sodium ions and
chloride ions from the sodium chloride salt formed.
Along BC, conductivity increases because the concentration of sodium ions is being
increased and also the fast moving hydroxyl ions are being added.
Note: The volume at end point is usually obtained by extrapolation since the minimum
point from plotted graphs is not usually as shown on the sketch above. The point where
two extrapolated lines meet gives the end point.
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721
2. Titration of a weak base against a strong acid (ammonia solution against sulphuric
acid or hydrochloric acid)
A
Conductivity
𝟏
𝒄𝒎 𝟏
B C
Volume of ammonia solution added 𝒄𝒎𝟑

Initially, conductivity is high at A due to very many fast moving and highly conducting

hydrogen ions from the strong completely ionized sulphuric acid.
Conductivity decreases along AB as ammonia solution is added because the fast moving
highly conducting hydrogen ions are being replaced by the slow moving less
conducting ammonium ions.
At B, the end point is reached. Conductivity is low and is due to the ammonium ions
and sulphate ions from the ammonium sulphate salt formed.
Along BC, conductivity remains almost constant because the ionization of the excess
weak ammonia solution added is suppressed by the ammonium ions from the
completely ionized ammonium sulphate salt formed. This makes the conductivity of
hydroxyl ions negligible.
Note: Using data obtained practically, when a graph is plotted, the conductivity may
slightly increase along BC but the explanation still holds.
3. Titration of a strong base against a weak acid (sodium hydroxide solution against
ethanoic acid)
D
Conductivity C
𝟏
𝒄𝒎 𝟏
A
|
B
Volume of sodium hydroxideWhatsApp:
solution added 𝒄𝒎𝟑
722
Email: josephkayiirab@gmail.com Call:0782601038 0753247098

Initially, conductivity is low at A due to very few fast moving, conducting hydrogen ions
from the weak partially ionized ethanoic acid.
Conductivity slightly decreases along AB as sodium hydroxide solution is added
because the few fast moving highly conducting hydrogen ions are being neutralized to
form water and being replaced by the slow moving less conducting sodium ions.
Also the ethanoate ions from completely ionised sodium ethanoate salt formed suppress
the ionisation of the weak ethanoic acid.
Conductivity gradually increases along BC due to increase in number of conducting

ethanoate ions and sodium ions from completely ionized sodium ethanoate formed.
At C, the end point is reached. Conductivity is only due to the sodium ethanoate salt
formed.
Along CD, conductivity rapidly increases because excess fast moving hydroxyl ions are

being added.
4. Titration of a weak base against a weak acid (ammonia solution against ethanoic
acid)
Conductivity
𝟏 C D
𝒄𝒎 𝟏
A
B
Volume of ammonia solution added 𝒄𝒎𝟑
Initially, conductivity is low at A due to very few highly conducting hydrogen ions from
the weak partially ionized ethanoic acid.
Conductivity slightly decreases along AB as ammonia solution is added because the
ethanoate ions from ammonium ethanoate formed suppress the ionisation of the weak
ethanoic acid.
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Conductivity gradually increases along BC due to increase in number of conducting

ethanoate ions and ammonium ions from completely ionized ammonium ethanoate
formed.
At C, the end point is reached. Conductivity is only due to the ammonium ethanoate
salt formed.
Along CD, conductivity remains almost constant because the ionization of the excess
weak ammonia solution added is suppressed by the ammonium ions from the
completely ionized ammonium ethanoate salt formed.
However, conductimetric titration is not only confined to acids and bases. Copper(II)
sulphate can be titrated with sodium hydroxide, sodium ethanoate with hydrochloric acid,
etc.
Explain why in the conductimetric titration of aluminium nitrate solution against
sodium hydroxide solution, the conductivity of the mixture decreases to a minimum
value, then increases gradually and finally increases rapidly with excess base.

Aluminium ions react with hydroxide ions to form insoluble aluminium hydroxide.
̅
The reaction reduces the concentration of aluminium ions in solution and conductivity
decreases to a minimum on complete precipitation.
The aluminium hydroxide reacts with more hydroxide ions to form a soluble complex
of tetrahydroxoaluminate(III) ions hence a gradual increase in conductivity.
̅
The conductivity then increases rapidly due to excess mobile highly conducting
hydroxide ions.
Questions
1. The conductivity of of copper(II) sulphate solution varies with the volume of
0.1M sodium hydroxide solution added as shown by the graph below;
P
R
Electrolytic
conductivity
20.0
|
Volume of sodium hydroxide solution 𝒄𝒎𝟑

724
(a) Define the term electrolytic conductivity

(b) Give a reason why:
(i) conductivity is high at point P.
(ii) conductivity increases along QR
(c) Calculate the initial concentration of copper(II) sulphate solution
(d) (i) The electrolytic conductivity at P was at ℃.
Determine the molar conductivity of the copper(II) sulphate solution.
(ii) State and explain the effect of dilution on the answer in d(i) above.
2. The molarity of a sample of hydrochloric acid about 0.1M was determined accurately
by measuring the conductivity of the solution as 1.0M sodium hydroxide solution was
added to of the acid. The results were as shown below:
Conductivity 4.1 3.3 2.4 1.7 1.5 1.8 2.2 2.5
Volume of 1.0M sodium hydroxide 1 2 3 4 5 6 7 8

(a) Plot a graph of conductivity against volume of 1.0M sodium hydroxide
(b) Determine from the graph, the volume of sodium hydroxide used to reach end
point
(c) Calculate the molarity of hydrochloric acid
(d) Explain the shape of the graph
(e) (i) Distinguish between solubility and solubility product.
(ii) Describe an experiment to determine the solubility product of calcium
phosphate in the laboratory.
3. The table below shows the conductivity of a solution of when a small volume of
sodium hydroxide solution was added to of 0.1M hydrochloric acid.
Volume of sodium 0 1 2 3 4 5 6 7 8 9 10
hydroxide
Conductivity 3.90 3.35 2.80 2.27 1.72 1.11 0.62 0.76 1.19 1.62 2.0
(a) (i) Plot a graph of conductivity against volume of sodium hydroxide

(ii) Use your graph to determine the volume of sodium hydroxide used to
neutralize the acid
(iii) Calculate the molarity of sodium hydroxide
(iv) Explain the shape of the graph
(b) State one other application of conductivity measurements.
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4. (a) The ionic radii and ionic conductivities at infinite dilution of some ions are shown
in the table below:
Ion Ionic radius Ionic conductivity

0.060 38.7
0.095 50.1
0.133 73.5
Explain the results in the table
(b) The diagram below shows curves A and B obtained when aqueous sodium
hydroxide was gradually added separately to equimolar
solutions of hydrochloric and ethanoic acid separately

Molar conductivity
Volume of sodium hydroxide added

Explain the shape of the curves:
(i) Curve A
(ii) Curve B
5. (a)The conductimetric curve for titration of ethanoic acid and ammonia solution is
given below:
Conductivity
Y Z
W
X
Volume of ammonia solution 𝒄𝒎𝟑
Explain the shape of the graph.

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(b) The molar conductivities of nitric acid, sodium bromoethanoate and sodium nitrate
are and respectively at infinite dilution at 25℃.
Calculate the:
(i) molar conductivity of bromoethanoic acid at infinite dilution
(ii) dissociation constant, , of a 0.1M bromoethanoic acid solution.
(Electrolytic conductivity of bromoethanoic acid is
6. (a) The conductimetric curve for the titration of ethanoic acid and sodium hydroxide
is given below.
S
Electrolytic
conductivity
𝟏 R
𝒄𝒎 𝟏

P
Q
Volume of sodium hydroxide solution added 𝒄𝒎𝟑
Explain the shape of the curve PQRS
(b) The molar conductivity of silver nitrate, potassium nitrate and potassium
chloride are 134.0, 143.2 and 140.8 respectively at infinite
dilution and 25℃. Calculate the:
(i) molar conductivity of silver chloride at infinite dilution at 25℃
(ii) solubility product, Ksp of silver chloride at 25℃ .(The electrolytic
conductivity of water and that of a saturated solution of silver chloride are
respectively)
(c) The molar conductivities of sodium bromoethanoate, hydrochloric acid and
sodium chloride are and respectively at infinite
dilution at 25℃. Calculate the:
(i) degree of ionization of 0.1M bromoethanoic acid solution at 25℃.
(The molar conductivity of 0.1M bromoethanoic acid solution is
)
(ii) ionisation constant, , of a 0.1M bromoethanoic acid solution at 25℃.
(i) electrolytic conductivity
(ii) molar conductivity
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(b) Draw a sketch graph to show how molar conductivity varies with concentration
for:
(i) hydrochloric acid
(ii) ethanoic acid
(c) Explain the shape of the curve in each case.
(d) 25 of 0.1M ethanoic acid was titrated with sodium hydroxide solution.
(i) Draw a sketch graph to show how conductivity of the solution changes
when sodium hydroxide is added to the acid
(ii) Explain the shape of the graph.
ELECTRODE POTENTIAL AND ELECTROCHEMICAL CELLS
ELECTRODE POTENTIAL

A metal rod consists of metal ions and a cloud of delocalized valence electrons. If the
metal is dipped in a solution of its ions, some of the cations dissolve leaving up an excess
of electrons on the surface of the metal.
The metal will become negatively charged with respect to the solution sorrounding it.
The tendency of the metal to lose ions to the sorrounding solution is known as
electrolytic solution pressure.
Metal rod(negative electrode potential)
+ +
+ +
+ + Solution of the metal ions
+ +
++++
Alternatively, metal ions may take electrons from the strip of the metal and get
discharged as metal atoms.
In this case, the metal becomes positively charged with respect to the solution
surrounding it.
The tendency of the ions to deposit on the metal from a solution is called the deposition
pressure.
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Metal rod(positive electrode potential)
+ +
+ +
+ + Solution of the metal ions
+ +
+
The potential difference between the strip of the metal and the solution depends on the
nature of the metal and on the concentration of the ions in equilibrium with the metal
surface.
For a zinc rod dipped in a solution of zinc ions, the zinc has a negative electrode
potential because it has a greater tendency to dissolve to form ions (greater electrolytic

solution pressure) and a smaller tendency to be deposited as a metal (lower deposition
pressure). The zinc rod is said to be a negative electrode.
For a copper rod dipped in a solution of copper(II) ions, the copper has a positive
electrode potential because it has a greater tendency to be deposited as a metal (higher
deposition pressure) and a smaller tendency to dissolve to form ions (lower electrolytic
solution pressure). The copper rod is said to be a positive electrode.
An equilibrium is established when the rate at which electrons are gained is equal to the
rate at which electrons are lost.
The position of equilibrium differs for different combinations of metals placed in

solutions of their ions.
Electrode potential is the potential difference developed between a metal placed in

contact with a solution of its ions.
Its symbol is (measured in volts, ).
By IUPAC convention, the term electrode potential means reduction electrode potential.
Therefore in most of the work hereafter we shall deal with reduction potentials.
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Electrochemical series
The electrochemical series is an arrangement of elements in increasing order of their
electrode potential. Reduction potentials are used in the arrangement.
Reduction equation Electrode potential,

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730
Note:
1. The elements with more negative values of electrode potential are highly
electropositive metals i.e. Lithium, potassium, sodium and magnesium.
2. The elements with more positive values of electrode potential are strongly
electronegative elements i.e. Bromine, chlorine and fluorine.
3. From the half-cell reactions, any reagent on the right is a reducing agent and any
reagent on the left is an oxidizing agent.
4. Any species on the right for a reaction with a lower (more negative) electrode
potential is a stronger reducing agent than a species with a higher(less negative or
more positive) electrode potential. Lithium is the strongest reducing agent and the
fluoride ion is the weakest reducing agent. On the other hand, fluorine, with a more
positive electrode potential is the strongest oxidizing agent and the lithium ion is the
weakest oxidizing agent.
5. The more positive (or less negative) the electrode potential, the easier it is to reduce

the ions on the left. So the metal on the right is relatively unreactive and is a relatively
poor reducing agent. For example:
6. The more negative (or less positive) the electrode potential, the more difficult it is to
reduce the ions on the left. So the metal/ species on the right is relatively reactive and
is a relatively good reducing agent. For example:
7. The Lithium electrode can as well be written as . The process is a

reduction and the electrode potential is a reduction potential.
Question
The standard electrode potentials of some half-cell reactions are given below:
State which species is the:

(a) strongest reducing agent
(b) strongest oxidizing agent
(c) most difficult to reduce
(d) most reactive metal
(e) easiest to reduce
|
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Absolute and relative electrode potential

Absolute electrode potential is the potential difference developed between a metal surface
and the solution with which it is in contact.
The relative electrode potential is the potential difference developed between a metal
surface and the solution with which it is in contact relative to a reference electrode. The
standard hydrogen electrode is the commonest reference electrode used.
Other reference electrodes include the saturated calomel electrode, the quinhydrone
electrode, the silver/ silver chloride electrode and the glass electrode.
It is impossible to measure the absolute potential difference of a metal with respect to
its solution because it is necessary to have a second electrode which also has its own
potential difference with respect to its solution.
The structure and functioning of the Standard Hydrogen Electrode (SHE)

Structure
Platinum wire

Hydrogen gas at 298K and
1 atm
Platinised platinum
1M hydrochloric
acid solution
The standard hydrogen electrode consists pure hydrogen gas continuously bubbled over
the surface of a platinum foil coated with platinum black at 298K and 1 atmosphere.
The platinized platinum is dipped in 1M solution of hydrogen ions.
Functioning
The hydrogen is adsorbed on the platinum black and equilibrium is set up between the
adsorbed layer of hydrogen and the hydrogen ions in the solution.
The platinum black is inert hence does not take part in the reaction and is finely divided
platinum to catalyse the set up of this equilibrium. There will be an electrode potential
between the adsorbed hydrogen and the solution which is arbitrary taken as .
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This fixes a scale against which other standard electrode potentials are measured by
combining the standard hydrogen electrode with other electrodes and measuring the
emf of the cell formed.
Standard electrode potential,

When the standard hydrogen electrode is used in conjunction with a metal electrode
placed in a solution containing 1M of the ions of the metal at 298K and 1 atmosphere, the
electromotive force (emf) obtained is called the standard electrode potential.
Standard electrode potential is the potential difference or reduction potential
established when a metal electrode is dipped in a 1 molar solution of its ions measured
relative to the standard hydrogen electrode at 25 oC and 1 atmosphere.
Experiment to measure standard electrode potential of a metal
Considering an iron electrode;
Potentiometer

Hydrogen gas at 1 Iron rod
atm and 298K Salt bridge
1M solution of hydrogen
ions
1M Iron(II) sulphate
Platinised 298K solution
platinum
An iron rod is dipped in a 1molar solution of iron(II) sulphate
The iron half-cell is connected externally by electric wires to a standard hydrogen
electrode via a high resistance voltmeter or a potentiometer to measure the emf of the
cell.
The iron half-cell is connected to the standard hydrogen electrode internally by means of
a salt bridge to allow exchange of ions without mixing of the two solutions in the half-
cells.
The temperature of the solution is maintained at 298K
Since the standard hydrogen electrode has a standard electrode potential of , the
reading on the voltmeter/ potentiometer is the standard electrode potential of the iron
electrode.
|
733
NOTE:
(i) The emf of the cell is measured without passing any current so that the
composition of the chemicals in the cell is not changed.
(ii) The salt bridge consists of a bent glass tube containing some inactive solution
such as saturated potassium chloride or a folded filter paper saturated with
potassium chloride.
(iii) A standard hydrogen electrode is not easy to use because it is bulky, slow to
reach equilibrium and susceptible to presence of impurities. It is also not easy to
maintain a stream of hydrogen at 1 atmosphere.
(iv) Electrode potentials of other metals are measured in the same way
(v) A porous partition may be used instead of a salt bridge
Factors affecting magnitude of electrode potential

When a metal rod is dipped or a gas is bubbled in/through a solution of its ions, it
undergoes the energy changes. First, it‟s converted to free gaseous atoms. Electrons are

then removed from the gaseous atoms to form gaseous ions. The gaseous ions then
combine with water molecules to form hydrated ions. The energy changes involved are
summarized below for a divalent metal, ;
→ → →
Therefore the enthalpy change associated with the reaction;
Therefore the factors that affect the magnitude of electrode potential include;
(i) Atomization energy
(ii) Ionization energy
(iii) Hydration energy
(iv) Concentration of the solution of the electrolyte
Note that any endothermic process decreases the electrode potential (makes it less
negative or more positive) and any exothermic process increases the electrode potential
(makes it more negative or less positive.
(i) Atomization energy
Atomisation energy is endothermic. The higher the atomisation energy, the lower (more
positive ) the electrode potential. This is because it becomes difficult to convert an
element into its gaseous atoms.
|
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(ii) Ionization energy

Ionization energy is endothermic. The higher the ionization energy, the lower (more
positive) the electrode potential. This is because it becomes difficult to form gaseous ions
from gaseous atoms.
(iii) Hydration energy.
Hydration is an exothermic reaction. The higher the hydration energy the higher(more
negative ) the electrode potential. This is because more energy is given off when gaseous
ions are completely surrounded by water molecules.
Variation of electrode potential in group II and period 3

1. The table below shows the standard electrode potential values of Group II
elements.
-1.70 -2.37 -2.87 -2.89 -2.90

Standard electrode potential( ) (Volts) for
(a) Name with reasons;

(i) the strongest reducing agent
(ii) the weakest reducing agent
(b) Explain the general trend in standard electrode potential of the elements
(c) explain why beryllium has an abnormally less negative value
(a) (i) Barium (but not Ba) Because it has the most negative standard electrode potential
(ii) Beryllium (but not Be) Because it has the least negative standard electrode potential
(b) Standard electrode potential generally becomes more negative from beryllium to
barium because ionic radius increases, ionisation energy decreases, atomisation
energy decreases and hydration energy also decreases. However, the decrease in
ionisation energy and atomisation energy is more rapid than decrease in hydration
energy.
(c) Beryllium has an abnormally less negative value because the beryllium ion has the
smallest ionic radius, highest charge density and highest polarising power, thus
attracting many water molecules, giving off highest amount of hydration energy that
counterbalances its high positive ionization energy and its high atomisation energy.
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735
2. The table below shows the standard electrode potential values of some of the
elements in Period 3 of the Periodic Table.
Element Na Mg Al Cl
Standard electrode potential( ) (V) for -2.71 -2.37 -1.66 +1.36
(a) State;
(i) the factors that affect the magnitude of standard electrode potential
(ii) with a reason, name the strongest reducing agent
sodium because it has the most negative standard electrode potential
(iii) with a reason, name the strongest oxidizing agent
chlorine because it has a positive standard electrode potential
(a) Explain the trend in standard electrode potential of the metallic elements
Standard electrode potential becomes less negative(decreases) from sodium to

aluminium because ionic radius decreases, ionization energy increases, atomization
energy increases and hydration energy also increases. However, the increase in
ionization energy and atomization energy is more rapid than increase in hydration
energy.
3. Although standard electrode potentials of alkali metals and alkaline earth metals
become more negative down the groups, the standard electrode potentials of
Lithium and beryllium are most negative in the respective groups.
ELECTROCHEMICAL CELLS
An electrochemical cell is a cell that converts chemical energy into electricity. Examples
of electrochemical cells include a Daniel cell, dry cells, Lead-acid battery cell and fuel
cells.
The cell consists two metal/ metal ion convention half cells.
Metal/ metal ion convention cells (RHE and LHE)
When a metal rod is dipped in a 1 molar solution of its ions, the cell generated is called a
half cell.
A magnesium half-cell is made by dipping a pure magnesium rod in a 1M solution of
magnesium ions ( for example a 1M magnesium sulphate solution) at 298K. The
magnesium half-cell is represented as
A silver half-cell is made by dipping a pure silver rod in a 1M solution of silver ions ( for
example a 1M silver nitrate solution) at 298K. The silver half-cell is represented as;
|
736
The Magnesium half cell

Magnesium rod
1M solution of magnesium ions.
The Silver half cell

Silver rod
+
+
+

1M solution of silver ions.
To construct an electrochemical cell, the two half cells above are made by dipping the
metal rods in 1 molar solution of their ions in separate beakers.
The two half cells are then connected using electric wires to connect the metal rods via a
high resistance voltmeter.
A salt bridge is used to complete the internal circuit and allowing the movement of ions
between the two half-cells so that ionic balance is maintained.
How do you come up with the conventional arrangement of the cell?

The reduction equations and reduction potentials for the half-cells can be represented by
the following half-equations:
The relative values of these voltages show that ions are more difficult to reduce
than ions. So ions will accept electrons from the half-cell
and magnesium will lose electrons to the half-cell.
By convention, the electrode with a negative standard electrode potential constitutes
the Left Hand Electrode (LHE). This electrode is also called the negative electrode or
the anode.
The electrode with a positive standard electrode potential constitutes the Right Hand
Electrode (RHE). This electrode is also called the positive electrode or the cathode.
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737
The electrochemical cell can be drawn as shown below:

Flow of electrons
Voltmeter
Magnesium rod Silver rod

(anode(-)) Salt bridge (cathode(+))
1M magnesium
1M Silver
sulphate
nitrate solution
solution
If a porous partition is used instead of a salt bridge, then the cell has the structure
below:
Porous partition

Magnesium rod Silver rod
(anode(-)) (cathode(+))
1M magnesium 1M Silver
sulphate nitrate solution
solution
Construction of a Daniel cell

A Daniel cell consists of a zinc half-cell made by dipping a pure zinc rod in a 1M
solution of zinc ions and a copper half-cell made by dipping a pure copper rod in a 1M
solution of copper(II) ions in separate beakers at 298K.
The two half cells are then connected using electric wires to connect the metal rods via a
high resistance voltmeter.
A salt bridge is used to complete the internal circuit to allow the movement of ions
between the two half-cells without the two solutions mixing.
The zinc electrode constitutes the Left Hand Electrode and the copper electrode
constitutes the Right Hand Electrode.
Electrons move from zinc rod to copper rod. The sulphate ions move from the cathode to
the anode to maintain the charge balance throughout the cell
|
738
The Structure of the Daniell cell:
High resistance voltmeter

Porous partition
Zinc rod (-) Copper rod (+)
1M Zinc sulphate 1M Copper(II) sulphate

solution solution
The cell notation/cell convention

Symbolic representation used to represent an electrochemical cell is called the cell
notation.
The following steps are followed to come up with a cell notation of any cell:

1. Make sure the electrode potentials given are reduction potentials. i.e. The equations
show reduction( electrons on left hand side). If instead oxidation potentials are
given, reverse the reactions to make them reduction equations and also the sign of
electrode potential. For example;
The electrode potentials given above are reduction potentials and require no
changes.
The electrode potentials given above are oxidation potentials and both equations
and the values should be reversed to make them reduction reactions and potentials
as shown below;
Recall:
OIL RIG – Oxidation is loss of electrons, Reduction is gain of electrons
LEORA says GEROA- loss of electrons is oxidation (Reducing agent). Gain of
electrons is reduction (Oxidising agent)
In some cases, one electrode potential can be given as reduction and the other
oxidation. In such a case, only one equation is reversed.
|
739
2. Identify the reaction that takes place at the anode (left hand electrode, negative
electrode) and the cathode (right hand electrode, positive electrode). Use the table
below to guide you.
Given two reduction potentials and equations;
One reduction potential Negative electrode potential Represents reaction at

positive and one negative anode(LHE)
Positive electrode potential Represents reaction at
cathode(RHE)
Less positive electrode Represents reaction at
Both reduction potentials potential anode(LHE)
positive More positive electrode Represents reaction at
potential cathode(RHE)
More negative electrode Represents reaction at
Both reduction potentials potential anode(LHE)
negative

Less negative electrode Represents reaction at
potential cathode(RHE)
3. After step 2, write down the equation at the anode (negative electrode) and equation
at the cathode (positive electrode). Equation at the anode should be oxidation (gain
of electrons)and that at the cathode should be reduction(loss of electrons)
RED CAT and AN OX- Reduction occurs at the cathode, Anode is for oxidation.
Consider the reactions;
Following step 2 shows that;

Anode(LHE)
Cathode(RHE)
Equation at anode (oxidation reaction) is
Equation at cathode (reduction reaction) is
4. Write cell notation following the following guidelines;
(i) Use a vertical line to separate different phases e.g. (aq) from (s) , (s) from
(l), (aq) from (g) or (s) from (g). However, (l) and (aq) are the same phase
and cannot be separated by a line.
(ii) Use a comma to separate similar phases e.g (s) from(s) or (aq) from (l)
(iii) Double vertical lines show the salt bridge
(iv) The anode is written on the left and the cathode on the right
(v) For half-cells that do not contain a solid metal electrode, platinum, is
introduced as an inert electrode.
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740
Using the equations above, the cell notation is:

𝑷𝒕 𝒔 𝑺𝒏𝟐 𝒂𝒒 𝑺𝒏𝟒 𝒂𝒒 𝑩𝒓𝟐 𝒍 𝑩𝒓 𝒂𝒒 𝑷𝒕 𝒔
The cell notation, if well written can guide you on how to draw a well labelled diagram
of the electrochemical cell.
More examples
1. The standard electrode potentials of two half cells are given below.
(a) Write ionic equation for the:

(i) reaction at the cathode
(ii) reaction at the anode
(iii) overall equation for the reaction

(b) Write the cell notation for the cell made by combining the two half cells.
Hint: The negative electrode potential shows the reaction that will take place at the anode,
where oxidation (loss of electrons) should occur. The other reaction obviously should occur at the
cathode and should be reduction (gain of electrons)
(a) (i)
(ii)
( )
(iii)
(b)
2. The Daniell cell has copper and zinc half cells as shown below:

(i) reaction at the negative electrode
(ii) reaction at the positive electrode
(b) Write the cell notation for the Daniell cell.
Hint: The negative electrode potential shows the reaction that will take place at the negative
electrode (anode), where oxidation (loss of electrons) should occur.
(a) (i)
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741
(ii)
(iii)
(b)
3. The electrode potentials of some half cells are given below.

(i) reaction at the cathode
(ii) reaction at the anode
(b) Write the cell notation for the cell made by combining the two half cells.

Hint: The electrode potentials given are oxidation potentials as there in increase in oxidation state in
each case. Standard reduction potentials should be obtained first reversing the equations and the
symbols of the electrode potentials too.
(a) (i)
(ii)
(iii)
(b)
The platinum electrode is introduced as an inert electrode in the cathode half-cell because
there is no solid metal electrode.
4. The convention of a cell is given below

.
(a) Write equation for the half-cell reaction at the:
(i) anode
(ii) cathode
(b) Write the overall equation for the cell reaction
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742
Hint: When the cell notation is already given, well balanced half-cell equations are written directly
from it.
(a) (i)
(ii)
(b)
Calculation of cell emf and prediction of spontaneity/feasibility of a

reaction
The emf of a cell, is given by the expression;
The values substituted in the above expression must be reduction potentials.

The final answer should have a charge which should never be a superscript or subscript.
Wrong answers Correct answers

-
-1.20, 1.20V, -1.20V
+0.45, +0.45V, +0.45V
 If the calculated value of emf is positive, the reaction is spontaneous/ feasible

 If the calculated value of emf is negative, the reaction is not feasible
Examples
1. The standard electrode potential for some half cells are shown below:
(a) What is meant by the term standard electrode potential

(b) (i) Write the cell convention and the equation for the overall reaction that
occurs when electrode potentials in (a) are combined.
(ii) Calculate the overall electrode potential for the cell
(iii) State whether the reaction in b(i) is feasible or not. Give a reason for
your answer.
Hint: Electrode potentials are both positive. The less positive electrode potential shows the
reaction that will take place at the anode, where oxidation (loss of electrons) should occur. The other
reaction obviously should occur at the cathode and should be reduction (gain of electrons)
(b) (i)
Overall equation;
(ii)
(iii) The reaction is feasible, because the emf of the cell is positive.
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743
(a) Write the:

(i) cell convention
(ii) equation for the reaction that takes place at the anode and cathode
(iii) equation for the overall cell reaction
(b) (i) Calculate the emf of the cell.
(ii) State whether the reaction in a(iii) is feasible or not. Give a reason for
your answer.
(a) (i)
(ii)
(iii)
(b) (i)

(ii) The reaction is feasible because the emf of the cell is positive.
(a) Write the cell notation

(b) Calculate the emf for the cell
(c) State whether the cell reaction in (a) is feasible or not. Give a reason for
your answer.
Hint: The negative electrode potential shows the reaction that will take place at the anode.
The other reaction obviously should occur at the cathode and should be reduction (gain of electrons)
(a)
(b)
(c) The reaction is feasible, because the emf of the cell is positive.
4. A galvanic cell consists of the following electrodes.
At 25℃, the emf of the cell was found to be .

(i) Write the overall cell equation
(ii) Calculate the standard electrode potential for the
electrode.
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744
Note; The reactions given are already reactions at the electrodes. However for calculations, the
electrode potential at the LHE should be made a reduction one.
(i)
(ii)
Gibb’s free energy, , as a measure of spontaneity

The Gibb‟s free energy, of a cell is given by the expression;
where is number of electrons taking part in the process

is the Faraday‟s constant
is the emf of the cell
 The value of n is simply the number of electrons involved in writing the overall
reaction.

 If the calculated value of is negative, the reaction is spontaneous/ feasible
 If the calculated value of is positive, the reaction is not feasible
 Gibb’s free energy is also a measure of maximum useful work done by the cell.
Examples
1. The electrode potentials of and are
and respectively.
(a) Write an equation for the reaction that occurs at the:
(i) anode
(ii) cathode
(b) Write the:
(i) cell notation
(ii) overall cell reaction
(c) Calculate the :
(i) emf of the cell generated from the cell reaction in c(ii) above.
(ii) Gibb‟s free energy for the cell
(iii) State whether the above cell reaction is feasible or not. Give a reason
for your answer.
(a) (i)
(ii)
(b) (i)
(ii)
(c) (i)
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745
(ii)
(iii) The reaction is feasible because the value of Gibb’s free energy of the cell is
negative.
2. The convention of a cell was set up as shown below

.
(a) Write equation for the half-cell reaction at the:
(i) anode
(ii) cathode
(b) Write the overall equation for the cell reaction.
(c) The reduction potentials for the reactions in (a)(i) and (ii) above respectively
are and respectively. Predict the spontaneity of the cell
reaction.
(a) (i)
(ii)

(b)
(c)
Since the emf of the cell is negative, giving a positive value of Gibb’s free energy, the reaction
is not spontaneous.
Applications of electrode potentials

(i) Predicting feasibility of a reaction
(ii) Calculating emf of electrochemical cells
(iii) Determining equilibrium constant
(iv) Determining solubility of a sparingly soluble salt.
Questions
1. The diagram below shows an electrochemical cell designed to calculate the standard
electrode potential of zinc.
(a) Name the apparatus labeled A and state a characteristic it should have
(b) (i) Name B and state its purpose.
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746
(ii) State how part B is prepared

(c) Identify C
(d) Name part D and explain its function.
(e) State three standard conditions for measuring of standard electrode potential.
2. The figure below shows a voltaic cell set up between two electrodes
Zinc
1M Iron(III) chloride solution
1M Zinc sulphate solution
Platinum
(a) (i) Define the term voltaic cell

(ii) Name Y and state its role in the above set up
(b) The reading on the voltmeter above was volts.
(i) Write the equation for the redox reaction that takes place
(ii) State whether the reaction in b(i) is feasible . Give a reason for your
answer.
(c) Calculate the electrode potential of the left hand electrode if the electrode potential
of the right hand electrode is
(d) Write the cell convention of the voltaic cell above.
3. Calculate the emf, write the cell notation, equation at each electrode and overall
equation for each of the following cells
(a)
(b)
(c)
(d)
(e)
(f)
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747
(g)
̅
(h)
4. (a) State factors that can affect standard electrode potential of an element.
(b) The standard electrode potential for group II elements are given in the table below
Electrode potential
(i) State and explain the trend in variation of standard electrode potential
(ii) Explain why the values of standard electrode potentials are negative
(c) Electrode potentials for some half cells are given below:
Half cell

(i) Write the equations for the reactions that take place at anode and cathode
(ii) Write the overall cell reaction
(iii) Calculate the emf of the cell
(d) State whether the reaction in c(iii) is feasible or not. Give a reason for your
answer.
5. Calculate the standard electrode potential of the electrode if the
electrode potential of the cell given below is . .
6. Two half cells are given below where combined:
(a) State which half-cell is suitable to make the:

(i) negative electrode
(ii) positive electrode
(b) Write the equation for the cell reaction.
(c) If the emf of the cell is and . Calculate the
standard electrode potential for the cobalt half-cell.
7. Equations for some half-cell reactions are given below.
(a) Write the convention for the cell.

(b) Write equation for the overall reaction.
(c) Calculate the cell voltage.
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748
8. Half equations for some cell reactions and the electrode potentials are given below:
(a) Write:
(i) the cell notation of the cell formed when the half cells are combined.
(ii) the overall cell reaction
(b) Calculate the emf of the cell
(c) Predict the feasibility of the reaction and give a reason for your answer.
9. The standard electrode potentials for some half cell reactions are given below:
(a) Write the overall equation for the cell reaction that occurs when the half cells are
combined.
(b) (i) Calculate the Gibbs free energy for the cell reaction.

(ii) State whether the cell reaction is feasible or not and give a reason for your
answer.
10. (a) Explain what is meant by the terms
(i) standard electrode potential
(ii) standard hydrogen electrode
(b) The standard electrode potentials for some half-cells are shown below.
Half cell
State what is observed at the:

(i) positive electrode
(ii) negative electrode
(c) Write:
(i) the cell convention for the combined cell
(ii) the equation for the cell reaction that would take place if the half cells are
combined.
(d) Calculate;
(i) the electrode potential for the cell
(ii) the work done by the cell
11. The following half-cell reactions are given:
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749
(a) Write the cell notation for the cell formed by combining the two half cells.
(b) State what will be observed and write equations for the reactions that take place at:
(i) anode
(ii) cathode
(c) Calculate the emf of the cell.
12. The standard electrode potentials for some half cells, in volts are shown below:
A.
B.
C.
D.
E.
F.
G.
H.

(a) State the species that is the most powerful oxidizing agent and give a reason for
your answer.
(b) State what would be observed and write equation for the reaction that would take
place if the half cells:
(i) A and E are connected
(ii) B and G are connected
(c) Calculate the emf of the cell in a(i)
(d) Write the cell notation for the cell in (b)(ii) above
(e) Explain why hydrochloric acid is not used to acidify titrants in volumetric
analysis involving potassium manganate(VII) solution.
(f) Write the cell convention when half cells C and D are combined.
13. (a)(i) Distinguish between electrolytic conductivity and molar conductivity of
a solution.
(ii) Write the equation to show the relationship between electrolytic
conductivity and molar conductivity of a solution.
(b) The table below gives the molar conductivity of a solution of ethanoic acid at
298K.
[ ] 0.001 0.01 0.1
Molar conductivity 50 16 5
(i) Give a reason for the decreasing values of molar conductivity of ethanoic acid
with increase in concentration.
(ii) Calculate the and ionization constant, of 0.01M ethanoic acid.
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750
(The molar conductivity of ethanoic acid at infinite dilution is

)
(c) (i) Define the term standard electrode potential.
(ii) Discuss the factors that affect the value of standard electrode potential.
(iii) State two applications of standard electrode potential.
(d) The standard electrode potentials of systems, and
are and respectively.
(i) Write equation for the overall cell reaction.
(ii) Calculate the maximum energy obtained from the cell.
14. (a) State three factors which determine the magnitude of electrode potential of a metal
(b) The standard electrode potentials for the following reactions are given

Write;
(i) the cell notation for the cell formed when the two half cells are connected.
(ii) the equation for the overall cell reaction
(c) (i) Calculate the emf of the cell.
(ii) What deduction do you make from your answer in (c)(i)?
(d) When dilute sulphuric acid is added to copper(I) oxide, a brown solid and a pale blue
solution were formed. Explain the observation.
15. The standard redox potentials of and are
and respectively.
(a) Write the cell convention for the combined cell
(b) Write an equation for the half-cell reaction at the:
(i) cathode
(ii) anode
(c) Write the overall cell reaction equation.
(d) State two conditions under which the electrode potentials above are measured
(e) Deduce if the overall reaction is feasible or not. Give a reason for your answer.
(f) State one application of electrode potentials
16. The standard electrode potentials for some systems are given below:
(a) Write the convention for the cell

(b) Write the equation for the overall reaction
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751
(c) (i) Calculate the cell voltage

(ii) What conclusion can you draw from the emf value in c (i) above
17. The standard electrode potentials of lead and magnesium are given below:
(a) Write the convention for the cell that can be formed
(b) Write the equation;
(i) for the reaction taking place at each electrode
(ii) for the overall reaction
(c) Calculate the emf of the cell
18. (a) (i) Define the term standard electrode potential.
(ii) Give reasons why it is not possible to measure standard electrode potential
absolutely.
(iii) Explain the factors that affect the value of standard electrode potential.

(b) Describe:
(i) the structure of a standard hydrogen electrode.
(ii) how you would measure standard electrode potential of magnesium in a
solution of its ions.
(c) The standard electrode potential of copper and zinc are given below.
Write the cell notation for a zinc-copper cell and calculate the emf of the cell.
(d) State two ways by which an electrolytic cell differs from an emf cell.
19. Given the following electrode potentials.
(a) Arrange the electrodes in order of reducing power starting with the least reducing
(b) (i) Which two electrodes will form a cell of maximum emf ?
(ii) Write the cell notation for the cell you gave in b(i) above.
(iii) Write the overall cell reaction for the cell in b(i).
20. (a)(i) What is meant by the term “standard electrode potential”?
(ii) Write down the factors that affect the magnitude of standard electrode
potential.
(b) (i) With the aid of a labeled diagram, describe how the standard electrode potential
of a metal can be measured.
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752
(ii) State two applications of standard electrode potentials.

(c) Some half equations and their standard electrode potentials are given below:
(i) Name the species that is the strongest reducing agent. Give a reason for
your answer.
(ii) Write the cell notation of the cell made by combining half cells of
dichromate(VI) and chlorine and calculate the emf of the cell. Draw a well
labeled diagram for the cell arrangement.
(iii) Calculate the energy given out by the cell in (c)(ii) above. Comment on
your answer.
(iv) Using the standard electrode potentials given, explain why hydrochloric
acid cannot be used to acidify aqueous manganate(VII) solutions.

21. Draw a well labeled diagram of a half cell consisting of;
(a) a half-cell and a half-cell.
(b) a half-cell and a half-cell.
22. (a) The molar conductivity of a carboxylic acid, at infinite dilution at ℃
is and the acid dissociation constant, .
(i) Define the term molar conductivity
(ii) Calculate the molar conductivity of a 0.01M solution of .
(b) The zinc/ silver oxide cell used in hearing aids and electric watches has the
following electrode potentials.
̅
(i) Calculate the emf of the zinc/silver oxide cell
(ii) Write the overall redox reaction that generates the emf calculate in b(i) above
(iii) Draw a well labeled diagram to show the zinc/ silver oxide cell can be set
up and the emf measured.
23. (a) State and discuss three factors that affect the value of standard electrode potential
(b) Draw a well labeled diagram to show how the standard electrode potential of the
zinc electrode can be determined.
(c) The electrode potentials of some half cells are given below;
Write the:
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753
(i) cell notation for the cell formed when the two half cells are combined.
(ii) equation at the anode, cathode and overall cell reaction.
(d) Calculate the emf of the cell in (c)(i)
(e) (i) State Faraday‟s law of electrolysis.
(ii) How long will it take of hydrogen at room temperature and
pressure when acidified water is electrolyzed using a current of .
Assignment:
Batteries
 Research, read and make notes about batteries (dry cells, mercury cell, Nickel-
Cadmium cell and fuel cells)
 Uses of batteries
 Explain the functioning of a battery
 Explain the conversion of one form of energy to another

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754

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DEMYSTIFYING PHYSICAL CHEMISTRY (A‟LEVEL)

A simplified, well elaborated and illustrative approach to the

Joseph Jobs Kayiira,

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

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muon neutron kaons

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An electron has a mass of ⁄ of a proton, therefore its mass is said to be

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DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

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(iv) Formation of the oxonium ion.

b) Negative ions (anions)

(i) Formation of a chloride ion.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

2. Monoatomic cations are simply given the name of corresponding element

Monoatomic cation Name

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DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

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Diagram showing the essential parts of a modern mass spectrometer

Hot tungsten filament

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

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DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Uses of a mass spectrometer

Advantages of a mass spectrometer over other methods of determining

1. It gives more accurate values

The mass spectrum

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DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

gaseous atoms by electrons as shown below;

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Consider the mass spectrum for bromine below;

Peak at ⁄ value of; Formula of ion

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Consider the mass spectrum below for pentane

The use of a mass spectrum

Average atomic mass

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Relative atomic mass(Ar)

Relative molecular mass(Mr)

an atom of the carbon-12 isotope.