Fundamentals of Inorganic Chemistry Lect

Fundamentals of Inorganic Chemistry (Chem1011): Lecture Note, 12-14-2015
Unit One
Fundamental Laws of Chemical Combinations
1. Introduction
1.1. Development of atomic theory

Atomic theory is the study of atoms and the force which hold them together.
 Philosophers and scientists did not arrive at the atomic theory alone. It is the contribution
of each succeeding persons would build the concept from a previous ideas.
 The nature of matter stated by Arstotile, is that solid body can be divided and subdivided
into smaller pieces without limit. This view is known as the continuous theory of matter.
 The Greek philosopher, Democritus, suggested that matter is made of up of particles so
small and indestructible that they can`t be divided into anything smaller. This view is
known as discontinuous theory of matter. Democritus called such indestructible particles
as atoms: from Greek word indivisible or indestructible.
 The English man, Robert Boyle (17th century), who did research on the behavior of gases,
provided clear evidence for the atomic make up of matter. He defined an element as a
substance that cannot be chemically broken down further. He believed that a number of
different elements might exist in nature.
1.1.1. Dalton’s Atomic Theory (DAT)
Thus the main postulates of Dalton’s Atomic Theory can be stated as follows:
 Matter is discrete (discontinuous) and made up of very small particles called atoms. An
atom is the smallest indivisible particle of an element which can take part in a chemical
change.
 Atoms are neither created nor destroyed during chemical reaction. Chemical reactions
only rearrange the way that atoms are combined; the atoms themselves are unchanged.
 Atoms of the same element are identical in all respects, having the same size, shape and
structure, and especially mass. Atoms of different elements have different properties and
different masses.
By: Bezabih Kelta(M.Sc. Inorg. Chem) -1- Department of Chemistry, Wolaita Sodo University
 Atoms of different elements can combine in a fixed ratio of small
whole numbers to form compounds.
Drawbacks of Dalton's theory
In light of the current state of knowledge in the field of Chemistry (according to the modern
atomic theory), Dalton’s theory had a few drawbacks. According to Dalton’s postulates:-
 An atom is the smallest indivisible particle of an element. However, it is now known that
atoms can further be subdivided into elementary particles like electrons, protons, and
neutrons.
 Atoms of the same element are identical in all respects, having the same size, shape and
structure, and especially mass. Today, we know that atoms of the same element can have
slightly different masses. Such atoms are called isotopes. Atoms of different elements
have different properties and different masses. However, different elements do exist
whose atoms have the same mass. Such atoms are called isobars.
Activity 1.1
1. Briefly discuss the difference between isotopes, isobars and isotones and give two
examples for each.
2. What are the importances of Dalton’s atomic theory? Discuss briefly.
1.2. Laws of Chemical Combination

a) The law of conservation of mass (Lavoisior, 1789) – states that in chemical reaction, the
mass of the system (reactants and products) remains constant. Hence matter is neither created
nor destroyed in a chemical reaction.
Example: Hydrogen + oxygen water
2H2 + O2 2H2O
2 molx2 g/mol + 1 molx32 g/mol = 2 molx18 g/mol
4 g + 32 g = 36 g
36 g = 36 g
b) The law of definite (constant) proportions (Proust, 1799) - This law states that, in a pure
chemical substance, the elements are always present in definite proportions by mass.
Example: In the substance sodium chloride (NaCl), for instance, the ratio of the mass of
sodium to the mass of chlorine is always 23:35.5, regardless of the source of the salt.
c) The law of multiple proportions (Dalton, 1805).
 When two elements combine to form more than one compound, the mass of one element
that combine with a fixed mass of the other element are in the ratio of small whole number.
Example: H2O  2: 16 or 1: 8 H2O2 2:32 or 1: 16

The two masses of oxygen are simple whole numbers ratio, 8:16 1:2
Review Activity
1. Silicon dioxide (SiO2), made up of elements silicon and oxygen, contains 46.7% by mass
of silicon. With what mass of oxygen will 10g of silicon combine?
2. 2.16 g of mercuric oxide gave on decomposition 0.16 g of oxygen. In another experiment
16 g of mercury was obtained by the decomposition of 17.28 g of mercuric oxide. Show
that these data conform to the law of constant composition.
3. In an experiment 34.5 g oxide of a metal was heated so that O2 was liberated and 32.1 g of
metal was obtained. In another experiment 119.5 g of another oxide of the same metal was
heated and 103.9 g metal was obtained and O2 was liberated. Calculate the mass of O2
liberated in each experiment. Show that the data explain the law of multiple proportions.
Unit Two
Structure of Ionic Solids
2.1. Introduction
In crystalline solids the atoms or ions are arranged in a periodic fashion and have long range
order. By translating atoms or group of atoms in three dimensions, a crystal structure is formed.
The crystal structure of a material is based on the crystal lattice, which is an imaginary point in
space. This array of points are not arbitrary but follows a set of rotational and translation rules.
Unit cell – is the smallest group of lattice points that displays the full symmetry of the crystal
structure. The unit cell has all the properties found in the bulk crystal.
Fig.2.1 The three dimensional unit cell

 Ionic compound has a giant ionic structure in which there are strong ionic bonds between
cations (positively charged ions) and anions (negatively charged ions).
 Common ionic compounds include: salts, oxides, hydroxides, sulphides and the majority
of inorganic compounds, which are held together by the electrostatic force of attraction
between the positive and negative ions.
 The attractive force becomes maximum when each ion is surrounded by the greatest
possible number of oppositely charged ions.
 The number of ions surrounding any particular ion is called the coordination
number(CN).
The possible geometry and CN of ionic solids can be predicted by radius ratio calculation.
2.2 Radius Ratio Rule
An ionic solid should achieve maximum electrostatic stability when:
(i) each ion is surrounded by as many as possible ions of opposite charge,
(ii) the anion cation distance is as short as possible.
 The cation-anion radius ratio is the ratio of the ionic radius of the cation to the ionic
radius of the anion in a cation-anion compound. This is simply given by:-
Radius ratio= r+/r- , where: r+ = radius of cation & r- = radius of anion
Table 2.1The radius ratio values with their respective geometrical arrengments
Radius ratio(r+/r-) CN Geometry Example
<0.155 2 linear Rare
0.155-0.225 3 triangular Ba2CO3
0.255-0.414 4 tetrahedral Wurtzite(ZnS)and Zink blende(ZnS)
0.414-0.732 6 octahedral Rutle(TiO2) and Sodium Chloride(NaCl)
0.732-1.000 8 cubic Cecium chloride(CsCl) and Fluorite(CaF2)
EXAMPLE-1: The relative sizes of the anions and cations required for a perfect fit of the close
packed structure is given by the following diagram. Calculate the radius ratio and predict the CN
and geometry.
d = 2r- +2r+  r - +r+ = .r-
d2 = (2r -)2 + (2r -)2 r+ = r -( -1)
d=  r+/r - = 0.414
2(r - + r+) = Fig.2.2
The geometry is tetrahedral and the CN is 4.

Activity 2.1
For the solid whose three dimensional structure shown in the figure 2.3 below, calculate radius
ratio and determine the geometry and the corresponding coordination number.
Fig.2.3
2.3. Close Packing

Close Packed Structures
 Close-packed structures are ones that fill space most efficiently.
 The packing of spheres can describe the solid structures of crystals. In a crystal
structure, the centers of atoms, ions, or molecules lie on the lattice points.
 Atoms are assumed to be spherical to explain the bonding and structures of metallic
crystals
 The term "closest packed structures" refers to the most tightly packed or space-
efficient composition of crystal structures (lattices).
 Imagine an atom in a crystal lattice as a sphere. While cubes may easily be stacked to fill
up all empty space, unfilled space will always exist in the packing of spheres. To
maximize the efficiency of packing and minimize the volume of unfilled space, the
spheres must be arranged as close as possible to each other.
 There are two types of close packing: Hexagonal and Cubic Close Packing
a. Hexagonal Close Packed (hcp)
 The hexagonal close packed structure can be made by piling layers in the A - B - A - B -
A - B . . . . . sequence. An alternative sequence would be A - C - A - C – A-C…
(a) (b) (c)

Fig.2.4 The hexagonal close packing: (a) space filling structure (b) ball and stick
modeling (c)hcc unit cell
 In hexagonal close packing, having placed two layers, labeled A and B, there are
alternative positions for the spheres in the third layer. They could be placed directly over
spheres in the first layer A to give a sequence denoted ABA.
 This arrangement is 74% efficient and only 26% is empty space (hole).
 The CN of each atom in the hcc is 12(see fig.2.4 b).
b. Cubic Closest Packed (CCP)
 Similar to hexagonal closest packing, the second layer of spheres is placed on two of half
of the depressions of the first layer. The third layer is completely different than those first
two layers and is stacked in the depressions of the second layer.
 The Cubic close packed structure can be made by filling layers in the A - B - C – A-B –
C- A - B -C. . . . . sequence.
 It repeats at fourth layer.
(a) (b)
Fig.2.5 The Cubic close packing: (a) space filling structure (b) Space filling model of ccp
using spheres as letters
The ccp structures are further classified as:
 Simple cubic close packing (scc)
 Body centered cubic close packing (bcc) and
 Face centered cubic close packing (fcc).
i) Simple cubic close packing
 Spheres are placed so as to define a network of cubic frameworks.
 In the extended lattice, each sphere has a coordination number of 6.
 The hole within each cubic unit is not large enough to accommodate a sphere equal in
size to those in the array,
 Atoms are placed at the eight corners.
 There is no contact between spheres along face-diagonals or body-diagonals.
 Known to be not close packed - primitive or simple cubic cell.
 The number atoms per unit cell is = 1.
 Least efficient method of packing (52%).
 The atoms are in contact along the cell edge. Therefore a = 2r.
Fig.2.6 Unit cell of a simple cubic structures

Packing efficiency (PE) or density of close packing:- refers to the ratio of the volume
occupied by atoms in a unit cell to the volume of unit cell multiplied by 100%.
PE=
- The ratio is known as packing fraction (PF) and thus,
PF = where the volume of atoms per unit cell
V = the volume of unit cell

For a simple cubic unit cell,
 The volume of unit cell is V= a3
 Number of atoms per unit cell is n = x8 corners) = 1
 The lattice parameter is a = 2r  r =
Then, PF=
But =
 =
 =
 = a3 then,
PE= x 100%  PE =
 PE =
 PE =
 PE =
PE =
 PE 
Therefore, simple cubic close packing is only 52% efficient and 48% remains hole.
ii) Body centered cubic close packing
 The eight spheres in the cubic cell are pulled apart slightly; another sphere is able to fit
inside the hole.
 The coordination number of each sphere in a bcc lattice is 8.
 Each corner atom in this structure is shared by eight cells.
 The CN of each species at lattice point is 8; i.e., each ion in the lattice point is in contact
with 8 opposite ion.
 An additional atom sits at the body centre within the unit cell touching the eight corner
atoms along the body diagonal and not along the edges as discussed in scc structure.
Fig.2.7 The unit cell of body centered cubic structure

To calculate the Packing efficiency (PE) of bcc structure,
 Let us consider triangle ABC which is right angle at B. Thus,
(AC)2 = (AB)2 + (BC)2
 x2 = a2 + a2
x =
 Now let us consider triangle FAC which is right angled at A. Then,

(CF)2 = (FA)2 + (AC)2
 (4r)2 = a2 +x2
(4r)2 = a2 +( )2
16r2 = a2 + 2
r=
Fig.2.8
 Total No of atoms (n) in bcc structure is 2 (i.e., 1/8x8 corners + 1 atom at cube
center).
 Now, PE=
But =
 =
 =
 =
Then, PE=  PE = x100%
 PE =
 PE = 68%
iii) Face centered cubic close packing
 This is the closest packed cubic solid structure whose packing efficiency is 74%.
 Here the lattice points (or ions) are situated at all the eight corners as in the previous two
cases, but also at the centers of the six faces.
 The face centre atom shares with two unit cells. Hence the number of atoms in a unit cell
(n) is ( x 8 corners + x6 faces) = 4.
 The atoms touch along the face diagonals.

 The coordination number in fcc is 8.
Fig.2.9 The unit cell of face centered cubic close packed structure
Activity 2.2 Show that PE for fcc solid structure is 74%.

2.4 Holes in close packed structures
 Close-packed structures contain octahedral and tetrahedral holes (or sites).
 There is one octahedral hole per sphere, and there are twice as many tetrahedral as
octahedral holes in a close-packed array.
 The octahedral holes are larger than the tetrahedral sites.
 A tetrahedral hole can accommodate a sphere of radius 0.23 times that of the close-
packed spheres, where as a sphere of radius 0.41 times that of the close-packed spheres
fits into an octahedral hole.
(a) (b)
Fig.2.10 Tetrahedral and octahedral holes in close packed structure
Figure 2.10 (b) shows that between adjacent close-packed layers are octahedral and tetrahedral
holes (labeled O and T) such that atoms of another kind occupying these sites would be
octahedrally or tetrahedrally coordinated. For ionic compounds we can imagine the larger ions
(usually the anions) forming the close-packed array, and cations occupying some of the holes. In
either hexagonal (hcp) or cubic close-packed (ccp or fcc) arrays of B there is one octahedral and
two tetrahedral holes per B atom.
2.5 Classification of Ionic Structures (MX & MX2-Types)
i) Ionic compounds of the type MX

 In the ionic solids of MX type the coordination number of M and X must be equal.
 Ionic compounds of the type MX have three types of crystalline structures: (A) ZnS type
(B) NaCl types (C) CsCl types.
A) Zinc sulphide(ZnS) structure
 Zinc(II) sulfide occurs naturally both as zinc blende (also called sphalerite) and
wurtzite, although the former is more abundant and is the major ore for Zn production.
Zinc blende has cubic structure where as wurtzite is hexagonal. Such structures are said
to be polymorphs.
 In both structures, the Zn to S ratio is maintained to be 1:1. Thus the difference between
wurtzite and zinc blende lies in the different arrangements of layers of ions.
 Although zinc blende is thermodynamically favored at 298K by 13 kJ mol-1, the
transition from wurtzite to zinc blende is extremely slow, allowing both minerals to exist
in nature.
B) The rock salt (NaCl) lattice
 The larger Cl- ions (rCl- = 181 pm) define an fcc arrangement with the Na+ ions (rNa+ =
102 pm) occupying the octahedral holes. Thus, the radius ratio (rNa+/rCl- = 0.563)
indicates that NaCl structure has the octahedral geometry with the CN of 6 for sodium
and chloride ion. i.e., each Na+ ion si surrounded by 6 Cl- ion and vice versa.
Fig. 2.11 The rock salt (sodium chloride, NaCl) lattice

 There are many ionicly bonded molecules that take this structure including all other
halides of Na, Li, K and Rb. CsF, AgF, AgCl, BaO, CoO, and SrS are also among many
that will form similar structures to NaCl.
Activity 2.3: Determine total number of Na+ ion and Cl- ion per a unit cell of Sodum
chloride structure.
C) The caesium chloride (CsCl) lattice
 The structure of CsCl can be seen as two interpenetrating scc structures, one of Cs+ and
one of Cl-.
 Anions and cations have similar sizes.
 Each Cs+ is surrounded by 8 Cl- at the corners of its cube and each Cl- is also surrounded
by 8 Cs+ at the corners of its cube. The cations are located at the center of the anions’
cube and the anions are located at the center of cations’ cube.
a) b)
Fig.2.12 The CsCl lattice: (a) the unit cell of CsCl (b) the interpenetrating simple cubic
structures of Cs+ ions and one of Cl- ions.
 The CsCl structure is relatively uncommon but is also adopted by CsBr, CsI, TlCl and
TlBr.
ii) Ionic compounds of the type MX2
 In salts of formula MX2, the coordination number of X must be half that of M.
 fluorites, CaF2 and rutile, TiO2 and mainly diflourides and dioxides have one of these
structures. Another fairly common structure is one form of SiO 2 called β-cristobalite.
A) FLUORITE (CaF2) STRUCTURE
 Ionic radius Ca2+ = 1.12Å; radius F- = 1.31Å; radius ratio = 0.85 cubic coordination.
 One Ca2+ ion is surrounded by 8 F- ions and one F- ion is surrounded by 4 Ca2+ ions.
 Other examples: ZrO2 & BaCl2.
Fig.2.13 The fluorite (CaF2) structure
B) The rutile (TiO2) Structure

 The mineral rutile occurs in granite rocks and is an important industrial source of TiO2.
 The coordination numbers of titanium and oxygen are 6 (octahedral) and 3 (trigonal
planar) respectively, consistent with the 1:2 stoichiometry of rutile.
 Two of the O2- ions shown in Figure 2.14 reside fully within the unit cell, while the other
four are in face-sharing positions.
Fig.2.14 The unit cell of rutile (one polymorph of TiO 2)

C) The -cristobalite (SiO2) lattice
 Because of its component: glass, silicon dioxide is a very common and important
molecule in the construction industry.
 There are many different forms of SiO2 derived from quartz: β-cristobalite, alpha-
cristobalite, beta-quartz, alpha-quartz, beta-tridymite, alpha-tridymite and many more.
 The alpha and beta stands for the temperature range. Alpha molecules have low
temperature while beta molecules have high temperature.
 -Cristobalite is one of several forms of SiO2 which exists at high temperature.
Review Activities
1. The rotatable structure opposite shows the ZnS (zinc blende) structure in which the
Zn2+ ion is surrounded by 4 S2- ions. The distance from the centre of the tetrahedron to
the corner, d, is: d = r + + r – and anion-cation-anion bond angle,  = 109.5o as shown in
the diagram below.
Fig.2.15
Calculate the radius ratio and predict the CN and geometry of zinc blende structure.
2. Outline the similarities and differences between cubic and hexagonal close-packed
arrangements of spheres, paying particular attention to (a) coordination numbers, (b)
interstitial holes and (c) unit cells.
3. State the coordination number of a sphere in each of the following arrangements: (a)
ccp; (b) hcp; (c) bcc; (d) fcc; (e) simple cubic.
4. (a) Lithium metal undergoes a phase change at 80K (1 bar pressure) from the a- to b-
form; one form is bcc and the other is a close-packed lattice. Suggest, with reasons,
which form is which. What name is given to this type of structural change? (b) Suggest
why tin buttons on nineteenth-century military uniforms crumbled in exceptionally
cold winters.
Unit Three
Acid-Base Theories and the Solvent System
3.1 Introduction
 The word "acid" comes from the Latin word acidus, meaning "sour" or "tart," since
water solutions of acids have a sour or tart taste.
 Lemons, grapefruit, and limes taste sour because they contain citric acid and ascorbic
acid (vitamin C).
 Common properties of acids include: acids produce hydrogen gas when reacted with
active metals like Na, K, Mg, Zn etc., change color of indicators (litmus paper is red in
acids), they have sour taste, neutralize bases and form salt and water, etc.
 Bases are chemical opposite of acids.
3.2 Definitions of Acid and Base
Different researchers defined acids and bases in different perspectives.
3.2.1 Arrhenius Acids and Bases
In the Arrhenius acid-base definition, acids and bases are classified in terms of their formulas
and their behavior in water:
 An Arrhenius acid is a substance that has H in its formula and when added to water
increases the concentration of H+ ions present.
 An Arrhenius base is a substance that has OH in its formula and when added to water
increases the concentration of OH- ions present.
Illustrations : HCl H+(aq) + Cl-(aq)

NaOH(aq) Na+(aq) + OH-(aq)
 Some typical Arrhenius acids are HCI, HNO3, and HCN, and some typical bases are
NaOH, KOH, and Ba(OH)2.
 Thus the acids increase the H+ ion and bases increase OH- ion concentration when
dissolved in it.
 The H+ ion produced by an Arrhenius acid is always associated with a water molecule to
form the hydronium ion, H3O+ (aq).
Limitations to the Arrhenius Theory

1) The theory defined an acid or a base in terms hydrogen or hydroxyl compounds only.
However, this does not explain the weak base ammonia (NH3), (that does not contain
OH- itself), which in the presence of water, releases hydroxide ions into solution.
NH3 NH4OH NH4+ + OH-

2) It offered no satisfactory explanation for the acid property of various substances such as
AlCl , NH NO etc.
3 4 3,
3) A bare proton cannot exist in solution.
4) The theory does not include non-aqueous solvents.
3.2.2 Brønsted-Lowry Acids –Bases Theory
In the Lowry-Brønsted definition:-
 An acid:- is a hydrogen ion(proton) donor;
 A base: - is a hydrogen ion (proton) acceptor.
The transfer of a proton to a proton acceptor is an acid-base reaction under the Lowry-Brønsted
definition. A general equation expressing proton transfer in aqueous solutions is:
AH(aq) + B(aq)→ A-(aq)+ BH+(aq)
Acid base
Example:
Acid-Conjugate base and Base-conjugate acid pairs

According to Lowry and Brønsted, when acid reacts with a base, there are two conjugate acid-
base pairs i.e., for every acid there exists a base which is produced when the acid loses its proton
and for every base there exists an acid which is produced when the base accepts proton.
An acid is one proton (hydrogen ion, H+) than its conjugate base and a base is one
proton less than its conjugate acid.
AH(aq) + B(aq) → A-(aq) + BH+(aq)
Acid1 Base2 base1 Acid 2
In the above illustration, acid 1 and base1 are conjugate pairs and, similarly, acid 2 and base 2
are conjugate pairs.
Example: NH3(aq) + H2SO4(aq) NH4+(aq) + HSO4-(aq)
Base1 Acid 2 Acid 1 Base2
Thus, in the above example, H2SO4 and HSO4- are acid-base conjugate pair; and NH4+ and NH3
are acid- base conjugate pairs.
Note:
A strong acid always has a weak conjugate base.
A weak acid always has a strong conjugate base.
Activity 3.1
1. Write at least three acid-base conjugate pair reactions.
2. Write:
a) Conjugate acids for the bases: CO32-, NH3, H2O, OH-, SO42- and H2PO4-.
b) Conjugate bases for acids: HPO42-,H2O, HCl, CH3COOH, H3O+,HS-,NH3 and H3PO4.
3. Label each acid-base conjugate bair in the following reaction
H3O+(l) + F-(aq) OH-(aq) + HF(aq)
3.2.3 Lewis definition of Acids and Bases
According to this theory:
 Acid: an electron pair acceptor.
 Base: an electron pair donor.
It turns out that it may be more accurate to say that "Lewis acids" are substances which are
electron-deficient (or low electron density) known as electrophiles and "Lewis bases" are
substances which are electron-rich (or high electron density) - known as nucleophiles.
Several categories of substances can be considered Lewis acids:
 positive ions;
 having less than a full octet in the valence shell;
 polar double bonds (one end);
 expandable valence shells.
Several categories of substances can be considered Lewis bases:
 negative ions;
 one of more unshared pairs in the valence shell;
 polar double bonds (the other end);
 the presence of a double bond.
The product of any Lewis acid-base reaction is called an adduct, a single species that
contains a new covalent bond:
3.2.4 Solvent System Definition of Acids and Bases

According to the solvent system definitions:
 A solute that causes an increase in the concentration of the solvonium ions (positive
ions) and a decrease in the concentration of solvate ions of solvent (negative ions) is
defined as an acid.
 A solute that causes an increase in the concentration of the solvate ions and a decrease in
the concentration of the solvonium ions of solvent is defined as a base.
Example: In liquid ammonia, KNH2 (supplying NH2 −) is a strong base, and NH4NO3 (supplying
NH4+) is a strong acid. In liquid sulfur dioxide (SO2), thionyl compounds (supplying
SO2+) behave as acids, and sulfites (supplying SO32−) behave as bases.
 The solvents which contain hydrogen and from which proton can be derived are known
as protic solvents, e.g. water, liquid ammonia and hydrogen fluoride. Solvents which
have no tendency to accept or release protons are known as aprotic solvents, e.g.
benzene, chloroform, CCl4, etc.
Review Activity 3
1. Discuss briefly the advantages of Arrhenius definition of acids and bases.
2. List at least 3 limitations of Arrhenius definition of acids and bases.
3. All Arrhenius acids are also Brønsted-Lowry acids and vice versa (True/False).
4. If the pH of a solution is 9.55 at 25oC, what is the hydroxide-ion concentration in the
solution?
5. For each of the following pairs, give the stronger acid. Explain your answer.
a) H2S, HS- b) H2SO3, H2SeO3 c) HBr, H2Se d) HIO4, HIO3 e) H2S, H2O
6. For the following reactions, label each species as an acid or a base. Indicate the species
that are conjugates of one another.
A) HPO42- + HCO3- PO43- + H2CO3
B) F- + HSO4- HF + SO42-
C) HSO4- +HSO4- + H2O SO42- + H3O+
D) HS- +CN- S2- + HCN
7. Arrange the following protic acids in increasing acidity
a) HBr, HI, HF and HCl
b) H Se, H Te, H O and H S
2 2 2 2
8. Decide whether each of the following is an acid or base in liquid ammonia:

a) NH2CONH2 b) NH4C1 c) NaNH2 d) PbNH
Unit 4
Structure of Atoms
4.1 Introduction
Electromagnetic radiation (EMR)

 Radiation is the emission and transmission of energy through space in the form of waves.
 A feature common to all electromagnetic waves is the speed with which they travel:
3.00x108 m/s, which is the speed of light in a vacuum.
 Electromagnetic radiation (EMR) can be described as a wave composed of oscillating,
mutually perpendicular electric and magnetic fields propagating through space.
 Light is an electromagnetic radiation-type of energy embodied in oscillating electric
and magnetic fields.
 A particular wave is characterized by:

 wavelength ()
 frequency ()
 amplitude (intensity)
 wave number, , which is the reciprocal of .
Fig 4.1 A particular wave
 The wavelength, denoted by Greek letter  (lambda), is the distance between any two
adjacent identical points of a wave.
 The frequency of a wave, denoted by Greek letter  (nu), is the number of wavelengths of
that wave passes a fixed point per unit time (usually one second). It is the number of
oscillations or waves per second.
Fig 4.2 Waves of different frequencies: a) 4Hz; b) 8Hz and c) 16Hz

 The speed of a wave is given by /t. If one complete oscillation takes place in t seconds,
the number of oscillations (cycle) in one second is .
 C=   = C/ = 1/ = ν/C
Where C = Speed (velocity of the radiation)

 C
 = wavelength = frequency
Units: (wave length) = meter, centimeter ( 10m-2), millimeter ( 10 -3 meter) nanometer ( 10-9
meter), Angstrom ( A0) = 10-8 cm or 10-10 m or 0.1nm.
(wave number) = cm-1
 (Frequency) = s-1, Hertz ( Hz), Kilocycles, KHz or 103 cycles, megacycles or 106 Hz
Note: 1s-1 =1Hz
Examples:
1. A radio operator broad casts at a frequency of 14.2 MHz. calculate the wavelength of the
radiation.
Given:  = 14.2 MHz = 14.2 x 106 Hz = 14.2 x 106 s-1

C = 3.0 X 108 m/s
Required  = ?
Solution we know that  = C/
= = 21.1m
2. What is the wavelength, in nanometers, of green light having a frequency of 6.67x 10 14 Hz ?

Given: C = 3.0 x 108 m/s
 = 6.67 x10-14 s-1
Required:  Solution We know that  = C/
= 4.5 x107 m x 10-14

= 4.5 x 10-7 m
 To convert from meters to nanometres we multiply by 10 9 nm/m.
Therefore,  = 4.5 x 10-7m x 109 nm/m
= 4.5 x102 nm
= 450 nm
Practice – Calculate the wavelength of an FM radio signal at Wolaita Sodo with a frequency of
99.9 MHz ( Ans:  = 3x109 nm ).
4.2 Electromagnetic spectrum
 The complete range of wavelengths or frequencies of EMR is known as the

electromagnetic spectrum. The electromagnetic spectrum is largely invisible; we see
only a tiny portion near the middle of the range.
 When a white light from an incandescent lamp passes through a narrow slit and then
through a glass prism, it separates into a spectrum. This spectrum is continuous in that
each color merges into the next without a break, like a rainbow.
 If light passed through the prism comes from an electric spark passing through a tube
containing a gas such as hydrogen or sodium vapor, the spectrum produced looks quite
different. Instead of a rainbow colors, only a few colored lines are seen. Because of the
appearance of the spectrum, it is often called discontinuous or line spectrum. The line
spectrum is characteristic of a particular gas in the tube.
Fig.4.3 The electromagnetic spectra
Visible spectrum
 Visible spectrum contains only very small portion of EMR; only wave length range of
about 400nm-750nm.These spectrum are the only radiations visible to human naked eye.
The spectrum consists of seven main colors.
Table 4.1 Visible spectrum
Activity
a) List all the regions of the electromagnetic spectra. Arrange these radiations in
order of increasing wavelength.
b) Which part of the spectrum is visible to the human eye?
c) Arrange the following spectra in the order of increasing wavelength:Yellow,
blue, orange, green, red, orange, indigo
4.3 Atomic Spectra and the Bohr Model of the Hydrogen Atom
4.3.1 Atomic spectra
Much of information regarding the detailed structure of the atom comes from spectral
analysis.
When sunlight is dispersed by passing through a prism a continuous spectrum is obtained.
On the other hand, the dispersion of light from flame of vaporized compound is
dispersed in a similar manner, only certain wavelengths of light are emitted. These
emitted lights are characteristic of that particular element. These produce line (atomic)
spectra.
This is why flame tests can be used for identifying species (elements), because every element
produces characteristic flame, which upon dispersion produces unique line spectra.
4.3.2 The hydrogen atom spectrum
Each of the elements gives a characteristic set of lines which is different from that of any
other element. Calcium, for instance produces a strong red color when put into a non
luminous laboratory flame. This may serve as a qualitative test for the presence of the
element.
Since light is a form of energy these lines emitted by the atoms of an element are due to a
loss of energy by the atoms.
Specifically it is the electrons which gain energy and then give out this excess energy again in
the form of radiation. The loss of energy is in the form of a precise energy value (quanta).
The first person to notice a pattern in the lines of the visible region of the spectrum was John
Balmer. In 1885, he noticed that the wavelength in the visible spectrum of hydrogen could be
reported by the simple formula:
= RH [ where n = 3,4,5…
Later on more lines were discovered. The Swedish scientist Johan Rydberg noticed that all the
spectral lines could be predicted from the expression
where n = 1,2,3 and n2> n1
1  1 1  R is Rydberg’s constant =109,678cm-1
 1.097 107 m -1  2  2 
  n1 n 2  = 1.097x107 m-1
Series n1 n2 Spectrum region
Lyman 1 2,3,4,… Ultraviolet
Balmer 2 3,4,5,… Visible
Paschen 3 4,5,6,… Infrared
Brackett 4 5,6,7,… Far IR

Pfund 5 6,7,8…. Far IR
Table 4.2: Various series in atomic hydrogen emission spectrum
Examples:
Calculate the wavelengths of the radiations by a hydrogen atom when an electron makes the
following transitions: a) n2 = 2 to n1 = 1 b) n2 = 4 to n1 = 2
Solution
a) 1/ = R(1/n12 – 1/n22) b) 1/ = R(1/n12 – 1/n22)
1/ = R(1/12 – 1/22) 1/ = R(1/22 – 1/42)
1/ = 109678cm-1(1 – 1/4) 1/ = 109678(1/4 – 1/16)
1/ = 109678(3/4) 1/ = 109678(3/16)
 = 4/3x109678  = 16/3x109678
= 6.38x10-6 cm  = 3.65x10-5 cm
Activity
1. Calculate the wavelengths of the radiations by a hydrogen atom when an electron makes the
following transitions.
a) n2 = 3 to n1 = 2 b) n2 = 4 to n1 = 1
c) n2 = 5 to n1 = 2
2. The wavelength of which of the above transitions is (are) in the visible region?
3. Discuss in groups about the limitations of Rutherford’s atomic model
4.3.3 Postulates of Bohr

In 1913, Niels Bohr proposed a theory of hydrogen atom which not only explained the origin of
hydrogen spectrum but also led to an entirely new concept of atomic structure. The three
postulates on which Bohr model was based are described:
1. In a hydrogen atom, the electrons revolve around the nucleus in certain definite circular
paths called orbits, or shells.
2. The atom does not radiate energy while in one of its stationary states. That is even
through it violates the idea of classical physics the atom does not change energy while the
electrons moves with in an orbit. Each shell or orbit corresponds to a definite energy.
3. The electrons present in an atom can move from a lower energy level (E lower) to a level of
higher energy (Ehigher) by absorbing the appropriate energy. Similarly, an electron can
jump from a higher energy level (Ehigher) to a lower energy level (Elower) by losing the
appropriate energy. The energy absorbed or lost is equal to the difference between the
energies of the two energy levels, i.e., ΔE=hv= E higher - Elower
The state of atom with the lowest energy is called is ground state. The states with higher energies
are called excited states. Thus the energy of a hydrogen atom in the ground state is - 13.6 eV and
in the first excited state = -3.4eV.
Fig 4.4 Energy level diagram for the electron in the hydrogen atom
Activity
Using the Fig 4.4 and the previous concepts do the following questions.
a) Calculate the frequency of electromagnetic radiation emitted by the hydrogen atom in
electron transition from n = 4, to n = 3.
b) The first line of the Lyman series of the hydrogen atom emission results from a transition
from the n = 2 level to then = 1 level. What is the wavelength of the emitted photon?
Using figure 4.2 describe the region of the electromagnetic spectrum in which this
emission lies.
c) What is the difference in energy between the two levels responsible for the ultraviolet
emission line of the magnesium atom at 285.2 nm?
d) Calculate the shortest wavelength of the electromagnetic radiation emitted by the
hydrogen atom in undergoing a transition from the n = 6 level.
Limitations of Bohr’s model
i. The only 'success' was with the hydrogen atom and similar atoms i.e. those with one
electron like: He+, Li++ etc. Thus, it does not explain the properties of multi electronic
atoms.
ii. It does not show conformity to the uncertainty principle, which states that it is not
possible to know precisely both the energy and position of the electron at the same time.
If the energy is known, the position cannot be determined with certainty. He used the
classical physics concepts to determine the electrons around the nucleus of an atom and
considered an electron as macro objects.
The Energy states of Hydrogen Atom
A very useful result from Bohr`s work is an equation for calculating the energy levels of an
atom:
ΔE = Efinal-Einitial = -2.18x10-28J
Note that if we combine the above equation with plank`s expression for the change in an an
atom`s energy, we obtain the Rydberg’s equation:
ΔE = hυ = = -2.18x10-28J
Therefore, = -2.18x10-28J
 =
 =
Where nfinal = n2, ninitial = n1 and 1.097x107m-1 is the Rydberg’s constant.

Activity
The line spectra in H-atom has wavelength of 1212.7Ao (use 1Ao = 10-10 m). The line result from
transition to n2 = 2. Then determine n1. (Use R= 1.097 X10-7 m-1)
4.4 Quantum numbers
 Quantum numbers designate main energy levels, shapes of sub-shells, orbitals, and
spins of electrons.
 A total of four quantum numbers were developed to better understand the electronic
structure of an atom.
 Each quantum number indicates an electron's trait within an atom, which satisfies to
explain the movement of electrons as a wave function, described by the Schrodinger
equation.
 Each electron in an atom has a unique set of quantum numbers; no two electrons can
share the same combination of four quantum numbers. Quantum numbers are very
significant because they can determine the electron configuration of an atom and a
probable location of the atom's electrons. They can also aid in graphing orbitals.
 Quantum numbers can help to determine other characteristics of atoms, such as ionization
energy and the atomic radius.
There are a total of four quantum numbers:
 the principal quantum number (n)
 the angular momentum quantum number (ℓ)
 the magnetic quantum number (mℓ)
 and the electron spin quantum number (ms)
1. The principal quantum number (n)
- n can be any positive integer values (1,2,3…etc)
- The principal quantum number, n, designates or describes the principal electron
shell (the main energy levels). i.e n=1=K , n=2=L , n=3=M ….etc.
- It also describes the most probable distance of the electrons from the nucleus,
the larger the number n is, the farther the electrons are from the nucleus, the larger
the size of the orbital, and the larger the atom is.
- n can be starting at 1, as n=1 designates the first principal shell (the innermost
shell). The first principal shell is also called the ground state, or lowest energy
state. n = 3 designates the third principal shell, n=4 designates the fourth
principal shell, and so on. n=1, 2, 3, 4…
- As energy of the electron increases, so does the principal quantum number.
- The maximum number of sub-shells permitted for a particular shell is equal to n2.
- The maximum number of electrons permitted in a particular shell is equal to
2xn2.
- This explains why n can’t be 0 or any negative integer, because there exists no
atoms with zero or a negative amount of energy levels/principal shells.
2. The Angular momentum quantum number (azimuthal quantum number) (ℓ)

 ℓ describes the shape of the orbital. Orbitals have shapes that are best described as
spherical (l = 0), polar (l = 1), or cloverleaf (l = 2).
 The quantum number that designates the “sub-shell” an electron occupies.
 It is an indicator of the shape of an orbital in the sub-shell. Each value of ℓ indicates a
specific s, p, d, f subshell (each unique in shape.)
 It has integer values from: 0 to n-1. i.e. ℓ = 0, 1, 2, 3, …, n – 1
 The value of ℓ is dependent on the principal quantum number n. Unlike n, the value of ℓ
can be zero. It can also be a positive integer, but it cannot be larger than one less than the
principal quantum number (n-1): i.e. ℓ = 0 to (n-1)
3. Magnetic quantum number (mℓ)
 There is only one way in which a sphere (l = 0) can be oriented in space. Orbitals that
have polar (l = 1) or cloverleaf (l = 2) shapes, however, can point in different directions.
 The magnetic quantum number (m), to describe the orientation in space of a particular
orbital. (It is called the magnetic quantum number because the effect of different
orientations of orbitals was first observed in the presence of a magnetic field.)
 It is an integer from –  through o to +  .

 The possible numbers of an orbital magnetic quantum numbers are set by its azimutal
quantum number (that is,  determines mℓ).
 The possible permitted values of mℓ for a particular sub-shell (ℓ) is equal to 2ℓ + 1.
Activity
1) List the values of n,  , and mℓ in the following sub-shell.
i) 3d ii) 4s iii) 3p iv) 4f v) 6d vi) 7d
2) What is the maximum number of electrons that can be present in the following expressions?
a) n =3,  = 2, ml =0. b) n= 3,  = 2 c) n = 5,  = 1 d) n = 2,  = 0 e) n =4,  = 3
3) Give the notation for the sub-shells denoted by the following quantum numbers.
i) n = 3,  = 1 ii) n = 4,  = 2 iii) n = 4,  = 0 iv) n = 5,  = 3
4. Spin Quantum Number (ms)
 Unlike n, ℓ , and mℓ, the electron spin quantum number ms does not depend on
another quantum number.
 It designates the direction of the electron spin and may have a spin of +1/2,
represented by↑, or –1/2, represented by ↓. This means that when ms is positive the
electron has an upward spin, which can be referred to as "spin up." When it is
negative, the electron has a downward spin, so it is "spin down." ms = +1/2 or ms = -
1/2
 The significance of the electron spin quantum number is its determination of an
atom's ability to generate a magnetic field or not.
Now we can write a set of four quantum numbers for any electron in the ground state of any
atom.
Example
Boron atom has a total of five electrons. Write the four quantum numbers for each of the five
electrons in the ground state.
Solution
Start with n = 1, so  = 0 , a sub shell corresponding to the 1s orbital. This orbital can
accommodate a total of two electrons. Next, n = 2, and .  may be either 0 or 1. The  = 0 sub
shell contains one 2s orbital, which can accommodate a total of two electrons. The remaining
one electron is placed in the .  =1 sub shell, which contains three 2p orbitals. The orbital
diagram is
5B   
1s2 2s2 2p1
The results are summarized in the following table:
Electron n  ml ms Orbital
1 1 0 0 +1/2 1s
2 1 0 0 -1/2
3 2 0 0 +1/2 2s
4 2 0 0 -1/2
5 2 1 0 -1/2 2px
The placement of the fifth electron in the orbital labeled ml = 0 , is arbitrary. It would be equally
correct to assign it to ml=-1 or ml=+1.
Note : Each main energy level has n2 orbital
n  ml Number of Atomic orbitals
orbitals
1 0 0 1 1s
2 0 0 1 2s
1 -1,0,+1 3 2px,2py,2pz
3 0 0 1 3s
1 -1,0,+1 3 3px,3py,3pz
2 -2,-1,0,+1,+2 5 3dxy,3dyz,3dxz,3dx2-
y2,3dz2
Activity
1. What is the electron capacity of the third energy level?
2. Assign the four quantum numbers for all electrons added to fluorine atom.
3. Can the two electrons in the same orbital have the same spin quantum numbers? Explain in
groups.
4. Explain why each of the following sets of quantum numbers would not be possible for an
electron, according to the rules for quantum numbers.
a) n = 1, .  = 1, ml = 0, ms = +1/2 f) n =3, .  =1, ml =+3 , ms = +1/2
b) n = 1, .  = 0, ml = 0, ms = +1 g) n =4, .  =3, ml =-3 , ms = -1/2
c) n = 3, .  = 2, ml =+3, ms = -1/2 h) n =2, .  =2 ml =-1, ms = -1/2
d) n = 2, .  = 1, ml = -1, ms = +3/2 i) n =5, .  =0, ml =0 ,ms =-1/2
e) n = 0, .  = 1, ml = 0, ms = +1/2 j) n =3, .  =3, ml =-1, ms = +1/2
Unit Five
Chemical Bonding and Structure
5.1 Introduction
Why do atoms combine?
 Everything wants to be more stable. It is easy to lie down than stand up; bonding is
natural way of allowing the elements to lie down. Chemical bonds form to lower the
energy of the system, the components of the system becomes more stable through the
formation of bonds.
 In general atoms are bonded together to:
- attain noble gas electronic configuration.
- have stability.
- have lowest possible energy.
Octet rule
- Octet rule - States that an atom tends to gain, lose or share electrons until there
are eight electrons in its valence shell (the nearest noble gas configuration at its
row).
Example: Na+ = 1s22s22p6 = 2:8  Configuration of Ne.

Cl- = 1s22s22p63s23p6 = 2:8:8  Configuration of Ar.
Note: - Hydrogen follows a special configuration called Duet rule (2 electrons in its outer most
shell).
What is chemical bonding?

 Chemical bond is the process of combination involves the reunion of two or more atoms
through redistribution of electrons in their outer shells either by the process of sharing of
electrons among themselves so that all the atoms acquire the stable noble gas
configuration of minimum energy or transfer of electron from the electropositive atom to
most electronegative atoms.
Fig. 5.1 Potential-energy curve for H2: The stable molecule occurs at the bond distance
corresponding to the minimum in the potential-energy curve
5.2 Major types of chemical bonds
 The two extreme cases of chemical bonds are:

i) a bond formed when two atoms of different electronegativity(metal & nonmetal) -
ionic bonding.
ii) a bond formed when two atoms of similar electronegativity:
 nonmetals with nonmetals- covalent bonding.
 metal with metal( two electropositive atoms)- metallic bonding.
5.2.1 IONIC BONDING
 In ionic bonding, electrons are completely transferred from one atom to another. It is
formed between metals and nonmetals.
 In the process of either losing or gaining negatively charged electrons, the reacting atoms
form ions.
 The electrostatic force of attraction between oppositely charged ions results in the
formation of ionic bond or electrovalent bond.
 Examples of ionic compounds include: NaCl, MgO, MgBr 2, CaC2, HCl, Li3N…
Example: Consider the formation of some ionic bandings in the following examples:
Ionic Compounds
 Compounds involve in ionic bond are known as ionic compound or electrovalent
compound.
 In naming simple ionic compounds, the metal is always first, the nonmetal second (e.g.,
sodium chloride).
General Properties of Ionic Compounds
 Ionic compounds usually exist in the form of crystalline solids.
 Ionic compounds have high melting point and boiling point due to strong attraction of
force between ions.
 Ionic compounds are generally soluble in water and other polar solvents having high
dielectric constants.
 Ionic compounds are good conductors of electricity in the solutions or in their molten
states.
 In ionic - compounds, each ion is surrounded by oppositely charged ions uniformly
distributed all around the ion.
5.2.2 COVALENT BONDING
 Covalent chemical bonds involve the sharing of a pair of valence electrons by two
atoms, in contrast to the transfer of electrons in ionic bonds.
 When two atoms have a small difference in their tendencies to lose or gain electrons, we
observe electron sharing and covalent bonding.
 This type of bonding most commonly occurs between nonmetal atoms (although a pair of
metal atoms can sometimes form a covalent bond).
Example:
Multiple covalent bonds are common for certain atoms depending upon their valence
configuration. For example, a double covalent bond, which occurs in ethylene (C2H4), results
from the sharing of two sets of valence electrons. Atomic nitrogen (N 2) is an example of a triple
covalent bond.
Covalent double bond
Covalent triple bond
 The polarity of a covalent bond is defined by any difference in electro-negativity

between the two atoms participating in the covalent bond formation.
 Bond polarity describes the distribution of electron density around two bonded atoms.
 For two bonded atoms with similar electronegativities, the electron density of the bond is
equally distributed (shared) between the two atom, this is a non-polar covalent bond.
 The electron density of a covalent bond is shifted towards the atom with the largest
electro-negativity. This results in a net negative charge within the bond favoring the more
electronegative atom and a net positive charge for the least electronegative atom.
Example: HBr = H2 =
Polar covalent bond Non- polar covalent bond
Coordinate Covalent
 A coordinate covalent bond (also called a dative bond) is formed when one atom
donates (contribute) both of the electrons to form a single covalent bond.
Example: BF3 + :NH3 H3N-BF3
 As boron does not have a full outer shell, it is able to accept an electron pair from
ammonia.
Properties of covalent compounds
 The covalent compounds do not exist as ions but they exist as molecules.
 The melting and boiling points of covalent compounds are generally low.
 Covalent compounds are generally insoluble or less soluble in water and other polar
solvents. However, these are soluble in non- polar solvents.
 Since covalent compounds do not give ions in solution, these are poor conductors of
electricity in the fused or dissolved state.
 Molecular reactions are quite slow because energy is required to break covalent bonds.
 Since the covalent bond is localized in between the nuclei of atoms, it is directional in
nature.
5.2.2.1 THEORIES OF COVALENT BONDING
5.2.2.1.1 Lewis Theory of Covalent Bonding
 The Lewis structure (or Lewis formula)- is two-dimensional structural formula consists
of electron-dot symbols that depict each atom and its neighbors, the bonding pairs that
hold them together, and the lone pairs that fill each atom's outer level (valence shell) -
octet rule.
 The octet rule guides us in allotting electrons to the atoms in a Lewis structure; in a few
cases, however, we set the rule aside.
The procedure for doing this can be summarized in the following steps:
i. Write the electron configuration of the combining atoms and determine the valence shell
electrons of each atom.
ii. Add the valence shell electrons of all combining atoms (charge on the molecule: if the
molecule is positively charged, subtract the number of charges from the total valence
electrons and if the molecule is negatively charged add the number of charge to the total
valence shell electrons of the molecule).
iii. Decide the central atom:
In many instances the arrangements of atoms can be inferred from the formula, followed by the
atoms that surround the central atom. This is true for compounds like CO 2, NH3, NO2, NO3-,
SO3, CO32-, & SO42-. This is not true for molecules such as HClO, or ions like SCN -. Once we
know the arrangement of atoms in the molecule, we can go about distributing the valence
electrons.
The rules to decide the central atom
a) The atom with fewer numbers is taken as central atom.
b) Large sized and relatively electropositive atoms are always selected as central atom.
c) H, O and halogens are always selected as surrounding atoms.
d) O and C have a tendency to form O-O and C-C chain respectively.
iv. Share a pair of electron between central atom and surrounding atom (form a temporary single
bond).
v. Complete the octet starting from the surrounding atom
vi. Put any electron that is not shared between central and surrounding atom as after the
surrounding atoms complete their octet is put as lone pair on the central atom
vii. If the central atom has less than an octet, you must form multiple bonds so that each atom has
an octet.
Example: What is the Lewis structure for CCl4?
Solution: First we need the arrangement of atoms. The formula suggests that it is
 We count the valence electrons
Carbon group IVA contributes 4e-
Chlorine Group IIIA contributes 7e each 28e-

32e-
 Distributing electrons by placing pairs in each bond gives
Cl
Cl C Cl
Cl
 This has used 8e- so there are 32 - 8 = 24e- left. Complete the valence shells of Cl atoms.
Cl Cl
Cl C Cl or Cl C Cl
Cl Cl
 -
This has used 24e , non are left. Each atom has an octet & therefore, this is the Lewis
structure for CCl4
Example 2: What is the Lewis structure for SF4?
Soln. The formula provides the arrangement to be
 Next we count valence electrons, 6 from S & 7 from each F atoms gives a total of 6 + 28
= 34e-. We start by placing a pair of electrons in each bond.
F
F S F
F
 This leaves us with 34 - 8 = 26e-. Next we complete the valence shell of fluorine. This
has used 24e-, so 2e- left. These are placed to S atom rearranging the fluorines to make
room for the extra dots on s gives us the dot structure for SF4.
F F
F S F
or F S
F
F F
Example 3: What is the Lewis structure for the carbonate ion, CO32-?
Solution: This time we have an ion whose formula suggests the atom arrangement
O
O C O
 Counting valence electrons; carbon supplies 4e -, each oxygen supplies 6e -, & the negative
charge adds Ze-, the total is 4 + 18 + 2 = 24e-. Placing a pair in each bond gives.
O
O C O
This has used 6e-, leaving 18e-. The 18 electrons are used to complete the octet around oxygen.
O
O C O
 This time we've run out of electrons, but C doesn't have an octet. What we must do now
is move one of the unshared pairs on oxygen into one of the bond.
 Notice that the oxygen hasn't lost the
pair, but carbon completes its octet by sharing it. Finally we should be sure to indicate the
charge on the ion by enclosing the Lewis structure in brackets with the charge outside.
2-
O
C
O O
Q. Is it all about the Lewis structure of carbonate ion? Discuss other possibilities.
Activity
 Write the Lewis structure for:
A. H3PO4
B. H2SO4
C. BFCl2
D. In A and B decide the most likely structure after calculating the formal charges.
E. How many electron pairs are there in the central atom of each of the above molecules?
Limitations of Lewis Structure (Exceptions to the Octet Rule)

1. Electron deficient molecules:
 Gaseous compounds containing either beryllium or boron are often electron deficient,
that is they have fewer than eight electrons around Be or B atom.
2. Odd electron molecules: A few molecules contain an odd number of valence electrons,
so they cannot possibly have all their electrons in pairs. Such species, called free
radicals, contain a lone (unpaired) electron, which makes them paramagnetic and
extremely reactive. Most odd electron molecules have a central atom an odd numbered
group, such as N (group VA) or Cl (group VIIA).
Activity:
 Draw the Lewis structure for NO2 and predict the numbers of electron pairs in the
central atom.
 Free radicals can react with each other to pair up their lone electrons. When two NO 2
molecules collide, for example they form dinitrogen tetraoxide, N 2O4, and each N attains
an octet.
O O O O
N + N N N
O O O O
3. Expanded valence shells:

 Many molecules or ions have more than eight valence electrons around the central atom
from period 3 or higher, those in which d orbitals are available.
In activity below you see that the central atom forms bonds to more than four atoms.
Activity:
1. Draw the Lewis structure for PCl5 and SF6. How many electron pairs are there in the
central atom of each of the molecules above?
2. Draw the Lewis structure for the following molecules and polyatomic ions.
a. ClF3 b. IBr5 c. BrCl4 -
But there are many cases of expanded valence shells in which the central atom bonds to four or
fewer atoms.
RESONANCE
Some molecules have structures that are not expressed correctly by single Lewis structure. For
example consider nitrate ion, NO3 -, which as potassium nitrate, is used in fireworks and
fertilizers. The three Lewis structures shown in figure below differ only in the position of the
double bond.
O O O
N N N
O O O O O O
 All are valid structures, and all have exactly the same energy.
 However, measurements of the bond lengths in the nitrate ion show that none alone is
correct structure. A double bond between two atoms is shorter than single bond between
two atoms and it is longer than double bond between the same types of atoms. If one of
the pictured structures were correct, we would expect two long single bonds and one
short double bond. However, the experimental evidence is that the bond lengths in nitrate
ion are all the same. i.e., 124pm, longer than typical N=O double bond (120pm) but
shorter than a typical N-O single bond (140pm).
 The bonds in the nitrate ion have a character intermediate between a pure single bond
and a pure double bond.
Note: Because all three bonds are identical, a better model of the nitrate ion is a blend (hybrid)
of all three Lewis structures. This blending of structures, which is called resonance, is
depicted in figure below by double-headed arrows.
O O O
N N N
O O O O O O
Resonance structure of nitrate ion, NO3+
Activity :
Stratospheric ozone, O3, makes an important contribution to life on earth by absorbing harmful
ultraviolet radiation from the sun. Suggest two Lewis structures that contribute to the resonance
structure for the O3 molecule. Experimental data show that the two bond lengths are the same.
Formal Charge (Cf)
Formal Charge (Cf) is the difference between the number of valence shell electrons in the free
atom and the number of electrons assigned in Lewis structure.
Cf = x-(y + )
Where
X= number of valence shell electrons of free atom.

Y= Number of lone pair (unshared) electrons of an atom in the Lewis structure.
Z = Shared electrons (bonded electrons)
A particular Lewis structure is said to be stable iff:
 The formal charges of each atom are as close to zero as possible.

 Any negative formal charge is assigned on relatively electronegative atom in the
structure.
 Relatively with least charge difference.
Lewis structures typically have the lowest energy when the formal charges of the individual non-
metal atoms are closest to 0. The low formal charges indicate that atoms in the preferred
structures have undergone the least redistribution of electrons relative to the free atoms.
Example 1: Decide the most acceptable Lewis structure of methanol (CH 3OH) between the
following possible structures using the formal charge calculation.
Structure a) Structure b)
C , x = 4 ; y = 0 and z = 8 C , x = 4 ; y = 2 and z = 6
Cf = x-(y + ) Cf = x-(y + )
Cf = 4-(0 + ) Cf = 0 Cf = 4-(2 + ) Cf = - 1
O, x = 6; y = 4; z = 4 O, x = 6; y = 2; z = 6
Cf = 6-(4 + ) Cf = 0 Cf = 6-(2 + ) Cf = 1
H, x = 1; y = 0; z = 2 H, x = 1; y = 0; z = 2
Cf = 1-(0 + ) Cf = 0 Cf = 1-(0 + ) Cf = 0
 Since O is more electronegative than C, the negative formal charge assigned on C and positive
formal charge assigned on O on structure (b), structure (b) could not be acceptable. Moreover, all
the atoms in structure (a) have formal charge of zero and minimum charge separation on
structure (a) makes it be most acceptable structure.
Activity:
1. Decide the most acceptable Lewis structure of Boron trifluoride (BF3) between the
following possible structures using the formal charge calculation. Give the reason why
one structure is acceptable and another is not acceptable.
2. Calculate the formal charges for the two Lewis structures of the phosphate ion shown in
figure below. Which of the two structures has lowest energy?
3- 3-
O O
O P O O P O
O O
(a) (b)
3. Write the Lewis structures with different atomic arrangement for thiocyanate ion NCS -
and suggest which one is likely to be the most plausible structure.
N C S C N S C S N
5.2.2.1.2 Sidwick-powell theory
This theory is very useful in predicting the geometry or shape of a number of polyatomic
molecules or ions of non-transition elements. This theory was proposed for the first time by
Sidwick and Powell in 1940 and developed by Gillespie and Nyholm in 1957.
According to this theory: - “The shape of a given species (molecule or ion) depends on the
number and nature of electron pairs surrounding the central atom/ion of the species.” The
Valence Shell Electron Pair Repulsion theory that we are going to study in the next portion is the
extension of this theory.
5.2.2.1.3 Valence Shell Electron Pair Repulsion (VSEPR) Theory and Molecular Geometry
Molecular Geometry is the general shape of a molecule as determined by the relative position
of atomic nuclei. The determination of molecular shape involves determining bond angles.
There is a very simple theory of molecular shape, which only requires Lewis electron dot
structures and simple electrostatic ideas; this is called Valence Shell Electron Pair Repulsion
Theory (VSEPR).
The VSEPR theory predicts the shape of covalent compounds in which valence shell electron
pairs are arranged about each atom so that electron pairs are kept as far away from one another as
possible, thus minimizing the electron pair repulsion.
The basic principles of VSEPR theory
1. Electron pairs will arrange themselves to be as far apart as possible so that the repulsion
between them is at minimum.
2. Lone pair of electrons takes more room on the surface of atom than that of bonding pairs.
According to the VSEPR theory, the repulsion of electron pair is in the following order:
Lone pair-Lone Pair > Lone Pair- Bond Pair > Bond Pair- Bond Pair
3. The repulsive force decreases sharply with increasing bond angle.
 The geometries that minimize the repulsion between groups of electrons have been
mathematically established.
Rules for predicting the molecular geometry of covalent compounds
1. Write the Lewis structure of the molecule or compound and count the number of electron
pairs around the central atom (count a multiple bond as a one pair).
2. Count the region of high electron density (lone pairs and bonding pairs).
3. Identify the most stable arrangement of these electron densities as linear, trigonal planar,
tetrahedral, trigonal bipyramidal or octahedral.
4. If more than one arrangement of unshared electron pairs and bonding pairs of electrons,
select the one that reduces the repulsion.
Table: The basic sets of five geometries, general formula of molecules, bond angles and
examples.
Geometrical General Angles Examples 3-dimemensional Two dimensional
description formula view of geometry view
Linear AX2 1800 BeCl2,
CO2, CS2
Trigonal-
planar AX3 1200 BCl3,CO32,
(Equilateral SO3
triangle)
Tetrahedron AX4 109.5 CH4,CCl4,

NH4+,SiF4,
BF4 -,ClO4 -
,PO43-
Trigonal AX5 900,1200 PF5,

bipyramid PCl5,AsF5
Octahedron AX6 900 SF6,SeF6,P

F6 -,SiF62-
 The molecular geometry is conventionally considered to be the geometry of the atoms,

not the geometry of the electron groups. Generally the molecular geometry depends on
the number of bonding pairs around central atom.
 However, the electron pair geometry depends on both bonding and lone pair electrons
around central atom.
The following table summarizes the electron pair geometry and molecular geometry.
Electro pairs Electro pair Molecular Example Other

Total Bondingpair Lone geometry Geometry Examples
pair
2 2 0 Linear Linear BeF2,

HCN, CS2,
CO2
3 3 0 Trigonal Trigonal SO3, NO3-,

planar planar CO32-
2 1 Trigonal Bent(V- SO2, PbCl2,

planar shape) SnBr2, O3
4 4 0 Tetrahedral Tetrahedral SiCl4,

SO42-,
ClO4 -
3 1 Tetrahedral Trigonal PF3, ClO3-,

pyramidal H3O+
2 2 Tetrahedral Bent(angular) OF2, SCl2
5 0 Trigonal Trigonal PF5, AsF5,

bipyramidal bipyramidal SOF4
4 1 Trigonal Distorted SF4,
bipyramidal tetrahedral(Se XeO2F2,
e Saw) IF4+, IO2F2-
3 2 Trigonal T-shape ClF3,

bipyramidal BrCl3
2 3 Trigonal Linear XeF2, IF2-

bipyramidal
6 0 Octahedral Octahedral IOF5, SCl6
5 1 Octahedral Square TeF5-,

pyramidal BeF5,
6 XeOF5
4 2 Octahedral Square planar ICl4-
Knowing the shape (geometry) of covalent molecules is a key to understand its physical and
chemical behavior. One of the most important and far-reaching effects of molecular shape is
molecular polarity, which can influence melting and boiling points, solubility, chemical
reactivity, and even biological function.
5.2.2.1.4 The Valence Bond Theory (VBT) and Orbital Hybridization
 The VBT was proposed by Heitler and London to explain the formation of covalent bond
quantitatively using quantum mechanics. Later on, Linus Pauling improved this theory by
introducing the concept of hybridization.
The main postulates of this theory are as follows:
 A covalent bond is formed by the overlapping of two half filled valence atomic orbitals
of two different atoms.
 The electrons in the overlapping orbitals get paired and confined between the nuclei of
two atoms.
 The electron density between two bonded atoms increases due to overlapping. This
confers stability to the molecule.
 Greater the extent of overlapping, stronger is the bond formed.
There are two types of covalent bonds based on the pattern of overlapping as follows:
(i) σ-bond:
 The covalent bond formed due to overlapping of atomic orbital along the inter-nucleus
axis is called σ-bond (sigma bond).
 It is a stronger bond and cylindrically symmetrical. The σ-bond (overlapping) is further
classified as σs-s overlapping, σs-p overlapping and σp-p overlapping (See the following
figure).
a)
(b) (c)
Fig.5.2 (a) σs-s overlapping on the formation of H2 molecule ( b) σs-p overlapping on the
formation of HF molecule and (c) σp-p overlapping on the formation of F2 molecule
(ii) π-bond:
 The covalent bond formed by sidewise overlapping of atomic orbitals is called π-
bond.
 In π- bond, the electron density is present above and below the inter-nuclear axis.
It is relatively a weaker bond since the electrons are not strongly attracted by the
nuclei of bonding atoms.
 Thus, the old version of valence bond theory is limited to diatomic molecules only. For
example, the covalent bond in H2, O2, Cl2, N2, HCl, etc. molecule can be explained by the
orbital overlapping of the two atoms. It could not explain the structures and bond angles of
molecules with more than three atoms.
E.g. It could not explain the structures and bond angles of H 2O, NH3 etc.
In order to explain the structures and bond angles of molecules, Linus Pauling modified the
valence bond theory using hybridization concept.
Hybridization
What is hybridization?
Definition: The intermixing of two or more atomic orbitals of with almost same energy to give
same number of identical and degenerate new type of orbitals is known as hybridization.
What are the requirements for atomic orbitals to undergo hybridization?
 The atomic orbitals of same atom with almost same energy can only participate in the
hybridization.
 The full filled or half filled or even empty orbitals can undergo hybridization provided
they have almost equal energy.
Note: No hybridization of atomic orbitals of different atoms can take place! The combination of
orbitals belonging to different atoms is called bonding.
What are the characteristics of hybrid orbitals?
 The new orbitals that are formed due to intermixing of atomic orbitals are also known as
hybrid orbitals, which have mixed characteristics of atomic orbitals.
 The shapes of hybrid orbitals are identical. Usually they have one big lobe associated
with a small lobe on the other side.
 The hybrid orbitals are degenerate i.e., they have similar energy.
 The number of hybrid orbitals formed is equal to the number of pure atomic orbitals
undergoing hybridization. Example: if three atomic orbitals hybridize,the number of
hybrid orbitals formed will be equal to 3.
 The hybrid orbitals are filled with those electrons which were present in the pure
atomic orbitals forming them.
 The filling up of electrons in them follows Pauli's exclusion principle and Hund's rule.
 The hybrid orbitals participate in the σ bond formation with other atoms.
 The hybrid orbitals are oriented in space so as to minimize repulsions between them.
This explains why the atomic orbitals undergo hybridization before bond formation.
Remember that the hybridization is the process that occurs before bond formation.
 The bond angles in the molecule are equal to or almost equal to the angles between the
hybrid orbitals forming the σ bonds. The shape of the molecule is determined by the type
of hybridization, number of bonds formed by them and the number of lone pairs.
Types of Hybrid Orbitals
sp hybridization: When two electron groups surround the central atom, we observe a linear
shape, which means that the bonding must have a linear orientation. VB theory explains this by
proposing that mixing two nonequivalent sp hybrid hybrid orbitals that lie 180 0 apart, as shown
in figure below. Characterized by the central atom of linear molecules.
Example: CO2, BeCl2 etc
Fig.5.3 The sp hybrid orbitals
sp2 Hybridization: - In order to rationalize the trigonal planar electron group arrangement and
the shapes of molecules based on it, the mixing of one s and two p orbitals of the central atom to
give three hybrid orbitals that point toward the vertices of equilateral triangle , their axes at 1200
apart are used. These are called sp2 hybrid orbitals.
Fig.5.4 The sp2 hybrid orbitals
VB theory proposes that the central B atom in the BF3 molecule is sp2 hybridized. The figure
below shows the three-sp2 orbitals in the trigonal plane, with the third 2p orbital unhybridized
and perpendicular to this plane. Each sp2 orbital overlaps the 2p orbital of an F atom, and the six
valence electrons- three from B and one from each of the three F atoms-form three bonding
pairs.
sp3 Hybridization: - VB theory proposes that the one s and all three p orbitals of the central
atom mix and form four sp3 hybrid orbitals, which point toward the vertices of a tetrahedron.
As shown in figure below, the C atom in methane is sp3 hybridized. Its four valence electrons
half fill the four sp3 hybrids, which overlap the half-filled 1s orbitals of four H-atoms and form
four C-H bonds.
sp3 sp3
sp3 sp3
Fig.5.5 The sp3 hybrid orbitals
The shapes of molecules with trigonal bipyramidal or octahedral electron group arrangements are
rationalized with VB theory through similar arguments. The only new point is that such
molecules have central atoms from period 3 or higher, so atomic d orbitals as well as s and p
orbitals, are mixed to form the hybrid orbitals.
sp3d Hybridization: - To rationalize the trigonal bipyramidal shape of molecules such as PCl5
molecule, the VB model proposes that the one 3s, the three 3p, and one of the five 3dorbitals of
the central P atom mix and form five sp3d hybrid orbitals, which point to the vertices of a
trigonal bipyramid. Each hybrid orbitals overlaps a 3p orbital of a Cl atom, and the five valence
electrons of P, together with one from each of the five Cl atoms, pair up to form five P-Cl bonds,
as shown in figure below.
Fig.5.6 The sp3d hybrid orbitals
Sp3d2 Hybridization: - To rationalize the shape of SF6, the VB model proposes that the one 3s,
the three 3p two of the five 3d orbitals of the central S atom mix and form six sp3d2 hybrid
orbitals, which point to the vertices of an octahedron.
Fig.5.7 The sp3d2 hybrid orbitals
5.2.2.1.5 The Molecular Orbital Theory (MOT)
Molecular orbital: is a region where electrons are most probably found around the nuclei of
two or more atoms. Molecular orbitals are formed by the overlap of atomic orbitals.
In contrast to valance bond theory, in which one bonding orbital is formed because of the
interaction of two atomic orbital, in MOT two molecular orbital results from the combination of
two atomic orbital. For example: when two H nuclei lie near each other, as in H2 their AO’s
overlap. The two modes of combining the AO’s are as follows:
There are two types of molecular orbitals.
a) Bonding molecular orbital (BMO):
 Is the combination of atomic orbital of the same sign to form molecular orbit:
ψ A + ψ B = ψ AB (BMO) where ψ (psi) is a wave function of
atomic or molecular orbital.
 The energy of BMO is lower than the energy of atomic orbital in an isolated
atom.
 The electron density is concentrated b/n the two nuclei.
 Formation of BMO is exothermic process and stabilizes the molecule.
b) Anti Bonding molecular orbital (ABMO):
 Is formed by subtraction of atomic orbital that overlap.
ΨA _ ψB = ψ* AB (ABMO)
 This combination forms an antibonding MO, which has a node between the
nuclei, a region of zero electron density.
 The energy of ABMO is higher than the energy of isolated atomic orbitals.
 The electron density is concentrated away from the region between the two
nuclei.
 If the electron occupies the ABMO, the molecule becomes less stable than
the isolated atom.
Types of Orbital Combination
i) s-s Combination
When 1s- orbital from two different atoms A and B with the same size approach each other, they
overlap to form sigma 1s- bonding molecular orbital (δ 1sAB )
1sA + 1sB (δ 1sAB )
. +A + . +B A.+ +
.B .A .B
A sigma bonding MO
Fig.5.8 Formation of BMO from addition of two 1s atomic orbitals
When 1s – orbital from two different atoms, A and B with opposite sign approach each other,
they form sigma anti bonding 1s molecular orbital (δ * 1sAB)
1sA _ 1sB (δ* 1sAB)
. +A _ . +B A.+ _
.B
+
.A .B -
A sigma antibonding MO
Fig.5.9 Formation of ABMO from subtraction of two 1s atomic orbitals
ii) p – p Combination
There are two types of P-P combinations
a) overlap of 2p atomic orbitals along the internuclear axis (head on overlap)
δ* 2px
2px + 2px δ 2px
ABMO (δ* 2px)
2px 2px BMO(δ 2px )
Fig.5.10 Head on combination of P- P atomic orbitals
b) Lateral (side way) overlap of 2p atomic orbitals
л*2py
2py + 2py л 2py
+ -
- +
Л*2py (ABMO)
-
2py 2pz л 2py (BMO)
Fig.5.11 Sideway combination of P-P atomic orbitals
 2py and 2pz atomic orbital from two atoms lie perpendicular to the internuclear axis and
to each other. They overlap laterally (side to side) to form л- bonding molecular orbital
(л2py, л2pz) and л-anti bonding molecular orbitals (л*2py,л*2pz).
Electronic configuration in MOT
The electronic configuration in MOT depends on;
1) The Aufbau Principle: fill electrons in to molecular orbital starting from lower
energy molecular orbital.
2) Pawl’s Exclusion Principle: each molecular orbital can contain a maximum of
two electrons with opposite spin.
3) Hund’s rule: if the molecular orbitals are degenerates (molecular orbitals with the
same energy), electrons are filled in to degenerate molecular orbital singly with
the same spin before pairing.
Example
MOT explanation of bonding in H2.
H2 has electronic configuration of H2 = δ1s2
A.O M.O A.O
δ*1s
energy erg
1s1 1s1
H δ1s H
Energy
Fig.5.12 Molecular orbital energy level (diagram) for H2- molecule

energy
The molecular orbital electronic configuration for simple homonuclear diatomic molecule is in
the increasing order of :
δ1s2 , δ*1s2 , δ2s2 , δ*2s2 , δ2p2x, л2p2y , л* 2p2y , δ* 2p2x , δ3s2 , δ*3s2
л2p2z л* 2p2z
δ2px is lower in energy than л2py and л2pz molecular orbital, because sigma overlap is stronger
than л- overlap.
Bond Order of Molecules
Bond order (B.O.): is the number of bonding electron pairs between two atoms with in a
covalent molecule.
 electrons in BMO  electron s in ABMO 
Bond order =  
 2 
 molecules with bond order ½ or greater will be stable with respect to their atoms.
 molecules with bond order zero will be unstable.
 The greater the bond order the more stable the molecule is.
Example
Determine the electronic configuration, bond order, stability, and draw molecular orbital energy
level for:
a) H2+
Total number of electron: 2-1=1
Electronic configuration = δ1s1
Bond order = ½ ( number of electrons in BMO – number of electrons in ABMO)
1 1
= (1-0) =
2 2
Stability: the molecule is stable because bond order  0
b) He2
Total electron = 2+2=4
Electronic configuration = δ1s2, δ*1s2

22
= =0
2
Stability : Unstable. Because B.O =0, Hence He2 molecule does not exist.
c) He2+
Total electron = 2+1= 3
Electronic configuration = δ1s2 , δ*1s1
2 1
= =½
2
Magnetic Property
One of the advantages of molecular orbital theory over valence bond theory is its ability to
explain the magnetic properties of covalent molecules.
 If the electronic configuration of a molecule contains unpaired electrons, the

molecule is said to be paramagnetic.
 If the electronic configuration of a molecule contains all electrons paired, the

molecule is said to be diamagnetic.
Example
Determine the electronic configuration, bond order, stability, magnetic property and sketch
molecular orbital energy level for :
a) Li2+
Total number of electrons = 3+3-1=5
Electronic configuration = δ1s2 , δ*1s2 , δ2s1
32
= =½ Stability: Stable because B.O  0
2
Magnetic property : Paramagnetic because there is unpaired electron.
b) N2
Total number of electron 7+7=14 л2p2y
Electronic configuration = δ1s2, δ*1s2, δ2s2 , δ*2s2, δ2p2x, л2p2z
Bond Order = ½ ( number of electrons in BMO – number of electrons in ABMO)
10  4
= =3 Bond Order = 3  triple bond.
2
The molecule is stable.
The molecule is diamagnetic  no unpaired electron.
Activity
1. Determine the electronic
configuration, bond order, stability, magnetic property and sketch molecular orbital energy
level for:
a) O2 b ) F2 c) O2- d ) CO e) O 2+
2. Explain the advantages of MOT over VBT.
3. Explain why O2 is paramagnetic but N2 is diamagnetic.
5. 2. 3 Metallic bonding
As the name implies, metallic bonding usually occurs in metals, such as copper, iron, silver
etc. A piece of a particular metal has a certain arrangement of metal atoms.
The electron sea model of metallic bonding
 The valence electrons of metal atoms are free to move about the piece of metal and are
attracted to the positive cores of the metal atoms, thus holding the atoms together.
 In metallic bonding, the positive nucleus of each atom is considered to be immersed in
the sea of valence shell electrons of the entire atoms in the arrangement.
 This is known as the electron sea model. For example: Consider the metallic bonding in
silver.
Fig.5.13 The electron sea model of metallic bonding in silver
Properties of metals
Property of metal Explanation in relation to metallic bonding
Metals are dense The particles present in metals are tightly packed in
the lattice.
Strong forces of attraction exist between particles. A
Metals have high melting and boiling large amount of thermal energy is required to
points overcome the strong electrical forces between the
positive nucleus and the delocalized electrons. These
forces operate throughout the lattice.
Metals are good conductors of heat. Delocalized electrons transmit the heat energy from
one atom to its neighbors.
Mobile delocalized electrons within the lattice flow in

Metals are good conductors of electricity. at one end, and the same number flow out the other
end.
Metals are malleable and ductile. The distortion does not disrupt the metallic bonding.
Metals are lustrous. The presence of free electrons causes most metals to
reflect light (non-metals are transparent).

Fundamentals of Inorganic Chemistry Lect

Uploaded by

Copyright:

Available Formats

Fundamentals of Inorganic Chemistry Lect

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Fundamentals of Inorganic Chemistry Lect

Uploaded by

Copyright:

Available Formats

Fundamentals of Inorganic Chemistry (Chem1011): Lecture Note, 12-14-2015

1.1. Development of atomic theory

Drawbacks of Dalton's theory

1.2. Laws of Chemical Combination

Example: H2O  2: 16 or 1: 8 H2O2 2:32 or 1: 16

Fig.2.1 The three dimensional unit cell

d2 = (2r -)2 + (2r -)2 r+ = r -( -1)

2(r - + r+) = Fig.2.2

The geometry is tetrahedral and the CN is 4.

2.3. Close Packing

(a) (b) (c)

Fig.2.6 Unit cell of a simple cubic structures

- The ratio is known as packing fraction (PF) and thus,

PF = where the volume of atoms per unit cell

V = the volume of unit cell

 The lattice parameter is a = 2r  r =

 Each corner atom in this structure is shared by eight cells.

Fig.2.7 The unit cell of body centered cubic structure

 Now let us consider triangle FAC which is right angled at A. Then,

Then, PE=  PE = x100%

(n) is ( x 8 corners + x6 faces) = 4.

 The atoms touch along the face diagonals.

Activity 2.2 Show that PE for fcc solid structure is 74%.

i) Ionic compounds of the type MX

Fig. 2.11 The rock salt (sodium chloride, NaCl) lattice

Fig.2.13 The fluorite (CaF2) structure

B) The rutile (TiO2) Structure

Fig.2.14 The unit cell of rutile (one polymorph of TiO 2)

Illustrations : HCl H+(aq) + Cl-(aq)

Limitations to the Arrhenius Theory

NH3 NH4OH NH4+ + OH-

Acid-Conjugate base and Base-conjugate acid pairs

3.2.4 Solvent System Definition of Acids and Bases

8. Decide whether each of the following is an acid or base in liquid ammonia:

Electromagnetic radiation (EMR)

 A particular wave is characterized by:

Fig 4.1 A particular wave

Fig 4.2 Waves of different frequencies: a) 4Hz; b) 8Hz and c) 16Hz

 C=   = C/ = 1/ = ν/C

Where C = Speed (velocity of the radiation)

Given:  = 14.2 MHz = 14.2 x 106 Hz = 14.2 x 106 s-1

2. What is the wavelength, in nanometers, of green light having a frequency of 6.67x 10 14 Hz ?

= 4.5 x107 m x 10-14

4.2 Electromagnetic spectrum

 The complete range of wavelengths or frequencies of EMR is known as the

Fig.4.3 The electromagnetic spectra

Table 4.1 Visible spectrum

Series n1 n2 Spectrum region

Lyman 1 2,3,4,… Ultraviolet

Balmer 2 3,4,5,… Visible

Paschen 3 4,5,6,… Infrared

Brackett 4 5,6,7,… Far IR

Table 4.2: Various series in atomic hydrogen emission spectrum

1/ = 109678cm-1(1 – 1/4) 1/ = 109678(1/4 – 1/16)

1/ = 109678(3/4) 1/ = 109678(3/16)

3. Discuss in groups about the limitations of Rutherford’s atomic model

4.3.3 Postulates of Bohr

Limitations of Bohr’s model

Where nfinal = n2, ninitial = n1 and 1.097x107m-1 is the Rydberg’s constant.