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I '
CHEMISTRY

rtil/t,wt Learning Corner

~peT'iod 2000 to 2012
This section reveals the extra/relevant information
that are not required as part of the model answers KO~contents June & November, P2 & P4,
but to expand the student's knowledge in the re- Worked Solutions
spective fields. At the same time, it induces eagerness ~foT'm Topic By Topic
and interest into their learning process.
]:#'>compiled AS and A Levels
foT'
~ <pecial Learning Corner
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 SYALLABUS
C 0 :X70 X7cS CHEMISTRY (9701)
A & AS Level
rr SYLLABUS
Candidates for Advanced Subsidiary (AS) certification will take Papers I, 2 and either 31 or 32 at a
single examination session.
PHYSICAL CHEMISTRY Candidates who, having received AS certification, wish to continue their studies to the full
Atoms,. Molecules and Stoichiometry Advanced Level qualification may carry their AS marks forward and take just Papers 4 and 5 in the
Topic 1
Atomic Structure examination session in which they require certification.
Topic 2
Chemical Bonding Candidates taking the complete Advanced Level qualification at the end of the course take all five
Topic 3 papers in a single examination session.
Topic 4 States of Matter
Topic 5
Chemical Energetics Candidates may not enter for single papers either on the first occasion or for re-sit purposes.
Electrochemistry Candidates may only enter for the papers in the combinations indicated above.
Topic 6
Topic 7 Equilibria
Topic 8
Reaction kinetics I Type of Paper I
INORGANIC CHEMISTRY Multiple-choice I hour 40 31%
I 15%

Topic 9.1
The Periodic Table: Chemical Periodicity 2 AS structured questions I hour 15 min 60 46% I 23%

Group II 31132 Advanced Practical Skills 2 hours 40 23%

Topic 9.2
Topic 9.3 Group IV 4 A2 structured questions 2 hours 100 I 38%
Topic 9.4 Group VII Planning, Analysis and
An Introduction to the Chemistry of Transition Elements 5 I I hour 15 min I 30 I I 12%
Topic 9.5
Nitrogen and Sulfur
I 1
Evaluation

Topic 9.6
Paper 1
ORGANIC CHEMISTRY This paper will consist of 40 questions, thirty of the direct choice type and ten of the multiple comple-
Introductory Topics tion type, all with four options. All questions will be based on the AS syllabus. Candidates will answer
Topic 10.1 all questions.
Topic 10.2 Hydrocarbons
Topic 10.3
Halogen Derivatives Paper 2
Topic 10.4
Hydroxy Compounds This paper will consist of a variable number of structured questions of variable mark value.
Topic 10.5
Carbonyl· Compounds All questions will be based on the AS syllabus. Candidates will answer all questions. Candfdates will
Carboxylic Acids and Derivatives answer on the question paper.
Topic 10.6
Topic 10.7 Nitrogen Compounds Paper 31/Paper 32
Topic 10.8 Polymerisation In some examination sessions, two versions of the Advanced Practical Skills paper will be available,
i
identified as Paper 31 and Paper 32. In other sessions only Paper 31 will be available. .i
APPLICATIONS OF CHEMISTRY Paper 31 and Paper 32 will be equivalent and each candidate will be required to take only one of them.
This is to allow large Centres to split candidates into two groups: one group will take Paper 31, the other
Topic 11.1
The Chemistry of Life
group will take Paper 32. Each of these papers will be timetabled on a different day.
Applications of Analytical Chemistry
Topic 11.2
Topic 11.3
Design and Materials
Each paper will consist of two or three experiments drawn from different areas of chemistry.
The examiners will not be restricted by the subject content. Candidates will answer all questions. ~"
Candidates will answer on the question paper.
1\
REVISION
June I November 2011 Paper 2 & 4 J
June I November 2012 Paper 2 & 4
 PAGE II SYLLABUS PAGE Ill
SYLLABUS

5. To promote an awareness that:

Paper 4 the study and practice of science are co-operative and cumulative activities, and are subject to
This paper will consist of two sections. social, economic, technological, ethical and cultural influences and limitations
Section A (70 marks) will consist of questions based on the A2 core syllabus but is not restricted to the applications of science may be both beneficial and detrimental to the individual, the
the A2 syllabus and may include material first encountered in the AS syllabus. community and the environment
the use of information technology is important for communication, as an aid to experiments and
Section B (30 marks) will consist of questions based on the section "Applications of Chemistry" but
as a tool for interpretation of experimental and theoretical results.
may include material first encountered in the core (AS and A2) syllabus.
Both sections will consist of a variable number of structured and free response style questions of 6. To stimulate students, create and sustain their interest in Chemistry, and understand its relevance
variable mark value. Candidates will answer all questions. Candidates will answer on the question paper. to society.

Paper 5
This paper will consist of a variable number of questions of variable mark value based on the practical
skills of planning, analysis and evaluation. The examiners will not be restricted by the subject content. Assessment Objectives
Candidates will answer all questions. Candidates will answer on the question paper. The assessment objectives listed below reflect those parts of the Aims which will be assessed.

A Knowledge with understanding

Candidates should be able to demonstrate knowledge with understanding in relation to:
scientific phenomena, facts, laws, definitions, concepts, theories
Aims
scientific vocabulary, terminology, conventions (including symbols, quantities and units)
These are not listed in order of priority. The aims of a course based on this syllabus should be to:
scientific instruments and apparatus, including techniques of operation and aspects of safety
J. To provide, through well designed studies of experimental and practical chemistry, a worthwhile scientific quantities and their determination
educational experience for all students, whether or not they go on to study science beyond this scientific and technological applications with their social, economic and environmental implications
level and, in particular, to enable them to acquire sufficient understanding and knowledge to
present reasoned explanations for phenomena, patterns and relationships.
become confident citizens in a technological world, able to take or develop an informed interest
The subject content defines the factual knowledge that candidates may be required to recall and
in scientific matters
explain. Questions testing these objectives will often begin with one of the following words: define,
recognise the usefulness, and limitations, of scientific method and to appreciate its applicability
state, describe, explain or outline.
in other disciplines and in everyday life
be suitably prepared for employment and/or further studies beyond A level. B Handling, applying and evaluating information
~andidates should be able- in words or by using symbolic, graphical and numerical forms of presenta-
2. To develop abilities and skills that
tiOn- to:
are relevant to the study and practice of science
locate, select, organise and present information from a variety of sources
are useful in everyday life
handle information, distinguishing tbe relevant from the extraneous
encourage efficient and safe practice
encourage the presentation of information and ideas appropriate for different audiences and manipulate numerical and other data and translate information from one form to another
.I
analyse and evaluate information so as to identify patterns, report trends and draw inferences
purposes
develop self motivation and the ability to work in a sustained fashion. construct arguments to support hypotheses or to justify a course of action
apply knowledge, including principles, to new situations
3. To develop attitudes relevant to science such as: evaluate information and hypotheses.
accuracy and precision These assessment objectives cannot be precisely specified in the Subject Content because questions
objectivity testing such skills may be based on information which is unfamiliar to the candidate. In answering such
integrity questions, candidates are required to use principles and concepts that are within the syllabus and
apply them in a logical, reasoned or deductive manner to a new situation. Questions testing these
enquiry
objectives will often begin with one of the following words: predict, suggest, construct, calculate or
initiative
determine.
insight.

4. To stimulate interest in, and care for, the environment.

 SYLLABUS
PAGE IV PAGE v
SYLLABUS

Structure of the Syllabus

C Experimental skills and investigations
The syllabus has been constructed with a compulsory Advanced Subsidiary core.
Students should be able to:
That part of the core syllabus which will be examined only in the full Advanced Level qualification is
plan investigations
indicated in bold type.
use techniques, apparatus and materials
make and record observations, measurements and estimates A full Advanced Level qualification requires the study of further core material, together with section II,
Applications of Chemistry. The Applications of Chemistry section represents about 12% of the full
interpret and evaluate observations and experimental results
Advanced Level course, or 23% of the A2 course.
select techniques, apparatus and materials
Candidates can take the course either as an AS Level, A Level or staged assessment to A Level.
evaluate methods and suggest possible improvements.
Practice of experimental skills

Candidates should be directed towards the practice of experimental skills throughout the whole period
of their course of study. Candidates' experimental skills will be tested in Paper 31/32 and Paper 5.
Weighting of Assessment Objectives
The table below gives a general idea of the allocation of marks to the assessment objectives, though Paper 31132 is a practical examination that will test the skills of manipulation of apparatus, presentation
of data, analysis and evaluation.
the balance on each paper may vary slightly.
Paper 5 is a written examination that will test the higher-order experimental skills of planning, analysis
and evaluation. It should be stressed that candidates cannot be adequately prepared for this paper
Weighting Assessment components
' Assessment Objective without extensive laboratory work throughout the course of their study.
(%)
Papers I, 2 and 4 Section II Applications of Chemistry
A: Knowledge with understanding 46* :

8: Handling information and solving problems 30 Papers I, 2 and 4 l This section of the syllabus is designed to allow candidates to use the chemical knowledge gained in
the core syllabus to explore key areas of modem chemical science. The course provides opportunities
24 Papers 31 /32 and 5 to revise content from the core syllabus, as well as introducing candidates to some new chemistry. It
C: Experimental skills and investigations
focuses on the applications of chemistry in research, industry and everyday life, and raises awareness
of the associated ethical issues. The teaching of this section will incorporate practical work.
*Approximately 27% is allocated to recall and 19% to understanding Applications of Chemistry has three parts, all of which are compulsory:

The overall proportion of marks allocated to physical, inorganic and organic chemistry in Papers I and 11.1 The chemistry oflife
2, taken together, and in SectionAofPaper 4 will be in the approximate ratio 3:2:3. 11.2 Applications of analytical chemistry
113 Design and materials
Teachers should note that there is a greater weighting (54%) for skills (including handling, applying and
evaluating information, experimental and investigative skills) than for knowledge with understanding Each section also covers aspects of environmental chemistry. Examination questions will focus on the
chemical concepts and techniques, rather than on the recall of specific examples. All necessary informa-
(46%).
tion about the context will be given in the question, and candidates will be expected to apply their
knowledge both from the core syllabus and from this section to new situations.
Teachers' schemes of work and learning activities should reflect this.
A booklet covering Applications of Chemistry can be purchased from CIE or obtained free of charge
from CIE's Teacher Support site teachers.cie.org.uk.
 topic 1 Atom, Molecules & Stoichiometry
Page 1

7opic 1 :P.hysicaf 0./iemislry ~CORNER

qjl/i)} fP) (/ 4J
!7floms, !Jl(ofecufes and dloichiomelry f-i \.!!,/ t.r /.J \!;;a '?}Jening ....... .
Question 1

Sulphur forms two oxides, so2 and SO,.

Content
Relative masses of atoms and molecules. (c) ~~~~~~~; ~~~7~~:ss~~~~t~~~~:r ,greenhouses to rid the~
of pests and
dioxide of 50 ppm ( rt . . e · A gaseous concentration of sulphur
2 The mole, the Avogadro constant. pa s per milhon) by volume is effective
Calculate how many gra f ·
3 The detennination of relative atomic masses, A, , and relative molecular masses, M, . to produce a concentrati~ns ~ ;~~~~~ af g;~de~er neeqs to burn in order
sures 2m x 3m x 4m. . 0 . 2 In a greenhouse that mea-
from mass spectra.
{c) Volume of so, to produce a
4 The calculation of empirical and molecular fonnulae. [Volume of 1 mol of gas = 24 dm' {0.024 m') at r.t.p.] concentration of 50 ppm
[4]
5 Reacting masses and volumes (of solutions and gases). [JOOIP1/Q5) = 50 x1o-6 x 24000 dm 3
Suggested Solution:
=1.2dm 3
Learning Outcomes (c) Volume in the green house= 2x3x4 m3 =.24000 dm3 No. of mol so, to produce
[The tenn relative fonnula mass or M, will be used for ionic compounds.] No. of mol of gaseous molecules to occupy this volume=~= 1000 this volume = .!:.?. = 0 05
24 24 .
Candidates should be able to: No. of mol of S02 to give a concentration of 50 ppm= 50 x1o-s x 1000 = 0 05
(a) define the tenns relative atomic, isotopic, molecular and formula masses, based on the No. of mol of S needed= No. of mol of S02 = 0.05 . No. of mol of S needed
12
C scale Mass of S needed= 0.05 x 32.1 = 1_605 g
=no. of mol of so,= 0.05
(b) define the tenn mole in tenns of the Avogadro constant Mass of S needed
(c) *analyse mass spectra in terms of isotopic abundances and molecular fragments [knowl- Question 2 = 0.05 X 32.1 =1.605 Q
edge of the working of the mass spectrometer is not required]
The use of the Data Booklet is relevant to this question.
(d) calculate the relative atomic mass of an element given the relative abundances of its
Nitrogen exhibits a range of oxidation numbers in its compounds
isotopes, or its mass spectrum
{a) Complete the table below wh· h 1 . ·
(e) define the tenns empirical and molecular formulae nitric acid. IC re ers to possible reduction products of

(f) calculate empirical and molecular fonnulae, using combustion data or composition by mass formula of oxidation number
(g) *write and/or construct balanced equations product of nitrogen
(h) perfonn calculations, including use of the mole concept, involving: N0 2

(i) reacting masses (from formulae and equations) N20

(il) volumes of gases (e.g. in the burning of hydrocarbons) NH20H
(iii) volumes and concentrations of solutions
NH;
When perfonning calculations, candidates' answers should reflect the number of sig- [2]
nificant figures given or asked for in the question. When rounding up or down, can- (b) {i) Copper can reduce nitric acid to NO w·
this reaction. 2· nte a balanced equation for
didates should ensure that significant figures are neither lost unnecessarily nor used
beyond what is justified (see also Practical Assessment, Paper 31132, {ii) Aluminium can reduce nitric acid to NH • .
for this reaction. ' · Wnte a balanced equation
Display of calculation and reasoning)
(i) deduce stoichiometric relationships from calculations such as those in (h) (Iii) ~~g;:cs~ ~r~~=~~ ~: ~=t r~duction products of nitric acid are different
aa ~
 Page2 topic 1 Atom, Molecules & Stoichiomet!Y_
topic 1 Atom, Molecules & Stoichiometry Page3
.~CORNER
(c) The compound NH,OH is oxidised by Fe'•(aq), which is itself reduced to Suggested Solution: ~CORNER
Fe'•(aq). (b) (i) 2H2 S(g)+ 302 (g)-->2H2 0(g)+ 2S0 (g)
2
In an experiment, 25.0 em' of 0.100 mol dm·' NH,OH required 25.0 em' of
0.200 mol dm"" Fe'• for complete reaction. CS 2 (g)+ 3 0 2 (g)__. C0 2 (g)+ 2 S0 2 (g)
(i) How many moles of Fe'• react with one mole of NH,OH?
(ii) Let no. of mol of CS 2 be y.
(ii) What change in oxidation number does the nitrogen in NH,OH
No. of mol of H2 S = 5y
undergo?
(iii) Which formula from the table in (a) corresponds to th nitrogen-contain- ·i No. of mol of S0 2 formed from H2 S = 5y
ing product of this reaction?
i No. of mol of S0 2 formed from CS 2 = 2y
(iv) Construct an equation for the reaction of NH,OH with Fe'·. [4]
No. of mol of C0 2 formed from CS 2 = y
[JOOIP2103]
HenceratioofS02 to C0 2 =(5y+2y):y =7:1

Suggested Solution: (b) The fact that aluminium (iii) so~- and co~--
reduces nitrates to ammo-
(a) oxidation number nium ions is used to test for
formula of
product of nitrogen nitrates. When a nitrate (or Question 4
nitrite) is warmed with AI
N02 +4 foil (or Devarda's alloy), it is
69 71 Ga
converted to ammonium- (a) Gallium exists as two isotopes Ga (65%) and (35%).
N2 0 +1
ion. If the reaction takes (i) Calculate the relative atomic mass of gallium.
NH 2 0H -1 place in an alkaline medium
(ii) Define the term relative atomic mass. [3]
eg. by the addition of aq.
NH'4 -3
NaOH. ammonium is con- (b) Gallium nitride could revolutionise electric light bulb design as only a small
------- verted to ammonia gas filament is needed to give a bright light.
(b) (i) Cu(s)+4HN0 (aq)--> CU(N0 3)2 (s)+2N0 2 (aq)+2H 20(/)
3 which can be detected by Gallium reacts with nitrogen gas to form gallium nitride.
3
(ii) 8AI(s)+3HN0 (aq)+27W(aq)--> 8AI '(aq)+3NH: (aq)+9H 20(/)
a
using piece of moist red
(i) Write an equation for the formation of gallium nitride.
3 litmus paper which will turn
(iii) Aluminium and copper have different reducing power. Aluminium is a blue in its presence. (ii) Calculate the volume of nitrogen at room temperature and pressure
stronger reducing agent than copper and reduces nitric acid to ammo- which will react with 10.0 kg of gallium. [3]
(c) For the reaction.
nium ions but copper can only reduce nitric acid to nitrogen dioxide. (c) (i) If it is assumed that gallium nitride is ionic, give the formula and the
3 total no. of mol of e· lost by electronic configuration of the gallium ion.
(c) (i) No. of mol of NH20H =25 x 10-3 x 0.1 =2.5x 1 o- NH,OH =total no. of mol of
3 3 (ii) Give the formula and the electronic configuration of the nitride ion.
No. of mol of Fe 3' that is used= 25 x 1o- x 0.2 = 5.00 x 1 o- e- gained by Fe".
3
[2]
5 DO 10- One mol of NH,OH reacts
No. of mol of Fe 3' that reacts with 1 mol of
.
N~OH = · x
2.5x10'
3
2
with two mol of Fe".
[N03/P2/03]

(ii) Change by +2. Total no. of mol of electrons Suggested Solution:

gained by two mol of
•.!.
(iii) N20 Fe"= 2 mol (a) (i) A,= 0.65 x 69 + 0.35 x 71 = 69.7
(iv} 2NH 0H(aq)+4Fe 3' (aq) - - > 4Fe 2 ' (aq) +N 20(g) +H 20(/) +4H' (aq) Total no. of mol of electrons (ii) Relative atomic mass of an element is the average mass of an atom of (a) (i) Note that A, has no
2
units.
Question 3
lost by one mol of NH,OH
= 2 mol
the element relative to 1 1 the mas~ of a 12 C atom.

Hence, change in oxidation (b) (i) 2Ga+N2 - - > 2GaN

The gases given off during the eruption of a volcano include hydrocarbon such (b) (i) Ga is a Group Ill el-
as ethane and ethene, also sulphur-containing molecules such as hydrogen state of NH 20H =+2. 3 ement. Therefore, it readily
(")
11
10.0x10
na.=--- mo 1
sulphide, H,S. and carbon disulphide, CS,. 69.7 loses its 3 valence electrons
(b) Analysis of a sample of a mixture of the two sulphur-containing gases to form Ga" which aN atom
1
showed that hydrogen sulphide and carbon disulphide were present in a nN, = 2nGa accepts the 3 electrons to
5:1 mole ratio. During analysis, this mixture was burned in an excess of form N'·.
VN,=nN2 x24.0
oxygen.
(i) Write a balanced equation for the complete combustion of H,S and of 10 0 103
=_1_x · x x24.0 = 1722 dm3 (c) (i) Ga: 1s' 2s 2 2p' 3s' 3p'
cs,. 2 69.7 3d" 4s' 4p'.
(ii} Calculate the so,: co, mole ratio in the mixture obtained after com-
bustion. (c) (i) Ga 3 ' : 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 On forming Ga". it loses its
(iii) The so,
and CO, misture dissolves in aqueous NaOH. Give the for- 3 valence electrons in the 4s
mula of an anion produced from each of these oxides. [4] (ii) N3- : 1s 2 2s 2 2p 6 and 4p orbitals.
[NOOIP2!03b]
 Pa e 4 topic 1 Atom, Molecules & Stoichiometry Page 5
to ic 1 Atom Molecules & Stoichiomet
~CORNER
Add in sufficient (say 10cm 3) of dilute H,SO, using a measuring cylinder.
~CORNER
Add in a few drops of ferroin indicator. The solution should appear or-
ange-red.
Question 5
. . rtant industrial chemical, many thousands Titrate the solution with K2Cr20 7 from a burette until the colour of the solution
(a) Sodium chlorate (V) IS an lmpo f cture chlorine dioxide bleach for turns greenish-blue.
b · used each year to manu a . .
of tonnes e1ng . lly by the electrolysis of bnne m From the titre value, we can determine the concentration of Fe'• in the
the paper industry. It is made c;:a~7:~1asolutions at the anode and the solution, and the actual mass of FeSO, can then be calculated.
a cell with no diaphragm, so
cathode mix. . r s· 10 50
The overall process can be represented by the followmg equa IOn . (ii) n = 0 025x ·
c,, o~- · 1000
Cr+6PW-6e- ____. CI03+3H20 = 2.625x10-4 mol
6H,O + 6e- ____. 3H2 + 60H-
nFfl+ = 6 x ncr2 o~-
(i) Calculate the current needed to produce 1 tonne (1 x 10' g) of NaCIO,
= 1.575 x 10"3 mol = nFe
per day (24 hours). d
(ii) Calculate the volume of hydrogen (measured at room temperature a~6] f11r,, = nFe x 55.8
pressure) that is also prduced.
[N05/P3/02a] = 8.79x10-2 g

Suggested Solution: Question 7

(a) (J)
1
nNaCIO, = 23 + 35.5 + 3(16)
°6
= 9390 mol Most submarines travel under water using electrical power from batteries. The
German engineer Helmut Walter designed a diesel engine that could be used
to propel a submarine beneath the surface of the sea. Instead of taking air from
ne_= 6 xnC/03- = 56340 mol above the surface of the sea, Walter's engine used hydro!Jen peroxide, H20 2 ,

Q=

Q
n
.-
, F = 56 340 x 96500 = 5.437 x 1o• C

5.437 X 1o• 6.29 x1 04 A

to provide oxygen for a conventional diesel engine.
Hydrogen peroxide may be catalytically decomposed to give water and oxygen .
(a) (i) What is meant by the term catalyst?
I = T = 24 X 60 X 60 (ii) Construct a balanced equation for the decomposition of H2 0 2 • [3]
..) _ xn = 3x9390 = 28170 mol Diesel fuel may be considered to consist of the hydrocarbon C15H32 which reacts
(11 n H 2- 3 NaC/03
completely with oxygen according to the following equation.
5 d 3
V =n x 24 dm3 =28170x24=6.76x10 m
H2 H2 C, 5H32 +2302 ~15C0 2 +16H2 0
(b) (i) To which homologous series does C15 H32 belong?
Question 6 . (ii) Use the equation above and your answer to (a)(ii) to calculate the
(c} Potassium dichromate(VI) is a usef~l oxidising agent, acidified solutions of amount, in moles, of H2 0 2 , that will provide sufficient oxygen for the
complete oxidation of one mole of C15 H32 • [3]
which can be used to titrate reduc1ng agents. . .

~:~~:~gs~Ju~~~bl:n~d~~~~o~niso:i~~~=~l:dJ~i~~~=;~o~:·s:r~~:~si~~~~n~
A submarine equipped with a Walter engine used 212 tonnes of diesel fuel
(i) during an underwater voyage. The submarine also carried concentrated
the pracitcal details ~ou would need to follow In ~~~~ ~a~s of iron(ll)
aqueous H,O,. [1 tonne = 1O' g]

sulphate FeSO , In an lron-supp emen a ·

:0
dard solution Of po~aSSIU~ diChro~ate(V~ ;~a~U~U should include an
icals ou
(c) (i) Calculate the amount, in moles, of diesel fuel used during the under-
water voyage.
equation' for the' titration reaction, and name any ot~e;. chem y (il) Use your answers to (b)(ii) and (c)(i) to calculate the mass, in tonnes,
would use. Do not include any details of the calcu a IOn. . of hydrogen peroxide used during .the underwater voyage. [4]
. . wire is dissolved in acid and titrated With
(ii) When a 11 dcm,leKngcth Oof lr1o; 50 em' of oxidant solution is required to (d) The exhaust products of the Walter engine were passed ihto the sea.
0 025 mo m , r, ,, · · · th · [7]
r~ach the end point. Calculate the mass of Iron In e Wire. What would happen to them? [1]
[N05/P3/04c] [NOB/P210 1)

Suggested Solution:
Suggested Solution:
(c) (i) 2
6Fe 2' +Cr20,-+14 H' ~ ~ 6Fe3' + 2Cr 3' + 7H20 (a) (i) It is a substance that speeds up a chemical reaction by lowering activation
energy without being used up in the process.
Additional chemical required:. dilute sulphur!~ ac~dd dissolve it in a volu-
Grind the tablets into powder. We1gh a samp e a j (ii) 2H,02{aq) ~ 2H20{1)+02(g)
metric flask. .
Pipette 25.0 em' of the FeSO, solution into a comcal flask.
ll
.~
topic 1 Atom, Molecules & Qtoichiometry Page6 topic 1 Atom, Molecules & Stoichiomet!'f_ Page 7
~CORNER
(b) (i) Alkanes 5
~CORNER
(b) (i) n(CO) = PV = (1.01x 10 )(140x10-3) =3 .78 moles
(ii) C H needs 23 moles of oxygen for combustion. RT 8.31x450
15 32

2 moles of H,O, can provide 1 mole of 0 2 . 3 78

(ii) n(SaS04 ) = n(CO) = · = 0.945 moles
4 4
So one mole of C 15H 32 needs 46 moles of H,O,.
(iii) M,(SaS0 4 ) = 137 + 32 + (16x 4) = 233
(c) (i) C15 H32 = 212
mass of SaS0 4 = 0.945 x 233 = 220.2 g
6
212 X 10
n(C,sH32) = ~ . 220.2 .
%ofSaS0 4 more= x100=88.1%
6 250
amount of diesel fuel; 1x 10 mol
(c) (i)
6
(ii) n(H20 2) required= 46 x 10 mole
6 Ba''(g) + S(g) Ba''(g)+ s'-(g)
mass of H20 2 = 34x46x10

l
(d) The exaust products are
9
= 1.564 X 10 = 1564 tonneS C0 2 and H20. both are 1st IE -200 kJ mor' )2nd IE
soluble in water. of sulphur of sulphur
Heat of atomisation +279 kJ mar' +640 kJ mor'
(d) They would dissolve.
of sulphur Ba''(g) + s·(g)
Ba''(g) + S(s)
Question 8

I Describe and explain qualitatively the trend in the solubilities of the sulfates
(a) of the Group II -elements. [3]
1st & 2nd IE 1+1468 kJ mar'
of barium
The major ore of barium is barytes, BaSO ,. This is very unreactive, and so
I (b)
other barium compounds are usually made from the sulfide, BaS. This is
Ba(g) + S(s)
obtained by heating the crushed ore with carbon, and extracting the BaS
with water.
BaS0 4 (s) + 4C(s)--->BaS(s) + 4CO(g)
Heat of atomisation)+ 180 kJ mar'
When 250 g of ore was heated in the absence of air with an excess of of barium
3
carbon, it was found that the CO produced took up a volume of 140 dm
at 450 K and 1 atm. Lattice energy
Ba(s) + S(s)
(i) Calculate the number of moles of CO produced.
(ii) Calculate the number of moles of BaSO, in the 250 g sample of the ore.
(iii) Calculate the percentage by mass of BaSO, in the ore. [4] Heat of formation -460 kJ mar'
of BaS
(c) (i) Use the following data and data from the Data Booklet to construct a BaS(s)
Born-Haber cycle and calculate the lattice energy of BaS.

-460 kJ mol·'
LIH!om(Ba) + Ll~ 1st&2ndBa(g) + LIH::iom(S) + ~~~ 1s1(S) +LI~2nd(S) + LI~(BaS) = LI~BaS(s))
standard enthalpy change of formation of BaS(s)
standard enthalpy change of atomisation of Ba(s) +180 kJ mor'
180 + 1468 + 279 + 640- 200 + Lattice energy = -460
+279 kJ mol·'
standard enthalpy change of atomisation of S(s) 2367 +Lattice energy= -460 (c) (iij S'· ion being larger in
-200 kJ mol·' size than 0 2- ion, its
electron affinity of the sulfur atom Lattice energy= -2827 kJmor' charge density will be less
+640 kJ mol-'
electron affinity of the s- ion than that of 0 2- ion,
(ii) Lattice energy of BaS will be less than SaO, since the size of S'- ion is therefore LE of BaS will
(ii) Explain whether the magnitude of the lattice energy of BaS is likely to bigger than oz- ion. be less than BaO.
be greater or less than that of SaO. [4]
[N09/P4!01]
Question 9

Suggested Solution: In 1814, Sir Humphrey Davy and Michael Faraday collected samples of a flam-
(a) Solubilities of the sulphates decrease down the group. As the cationic size mable gas, A, from the ground near Florence in Italy.
increase down the group, therefore both lattice energy and hydration energy They analysed A which they found to be a hydrocarbon. Further experiments
decrease. The decrease in hydration energy is more than the decrease in were then carried out to detemnine the molecular formula of A.
lattice energy. (a) What is meant by the term molecular formula? [2]
 Pa e 8
to ic 1 Atom Molecules & Stoichiomet ~CORNER
f
of A by exploding it with an excess
1

2
D and Faraday deduced the ormu a .
avy and analysing the products of combustiOn. .
of oxygen 1 t combustiOn 'Jopic
(b) Complete and balance the following equation for the comp e e
of a hydrocarbon with the formula C, H, ·

c,Hy +( x +~ )o2-> .......................... + ......................... .

[2] :7/lomic dlruclure
- d temperature with 50 em' of oxygen
(c) When 10 em' of A was mlxe a1 room · d after cooling the
(an excess) and exploded, 40 em' of gas remame
apparatus to room temperatur~a~:~ ~;~s:~r:.xcess of aqueous potassium
When this 40 em' of gas was s . . Content
hydroxide, KOH, 30 em' of gas still remamed. .
The nucleus of the atom: neutrons and protons, isotopes, proton and nucleon numbers.
(i) What is the identity of the 30 em' of gas that remained at the end of
the experiment? 2 Electrons: electronic energy levels, ionisation energies, atomic orbitals, extranuclear
(ii) The combustion of A produced a gas that reacted with the KOH(aq). structure.
What is the identity of this gas?
(Iii) What volume of the gas you have identified in (ii) was produced by the
Learning Outcomes
combustion of A?
d ·n the combustion of A? [4] Candidates should be able to:
(iv) What volume of oxygen was use up I .

(d) Use your equation in (b) and your results from (c)(iii) and (c)( IV) to calculate (a) *identify and describe protons, neutrons and electrons in terms.oftheir relative charges
the molecular formula of A. [3] and relative masses.
Show all of your working. (b) *deduce the behaviour of beams of protons, neutrons and electrons in electric fields.
[N 1O!P210 1}
(c) describe the distribution of mass and charges within an atom.
(d) deduce the numbers of protons, neutrons and electrons present in both atoms and ions
Suggested Solution: t given proton and nucleon numbers (and charge).
(a) The molecular formula specifies the actual number of atoms of each elemen
(e) (i) describe the contribution of protons and neutrons to atomic nuclei in terms of
in one molecule of a compound.
proton number and nucleon number.
Y)o ~ xC0 2 + l'.Hp
{b) C,Hy+ ( X+4 2 2 (ii) distinguish between isotopes on the basis of different numbers of neutrons present.
(f) *describe the number and relative energies of the s, p and d orbitals for the principal
(c) (i) Oxygen gas (0,)
quantum numbers I, 2 and 3 and also the 4s and 4p orbitals.
(ii) Carbon dioxide gas (CO,)
(g) *describe the shapes of s and p orbitals.
(iii) 10 em'
(h) state the electronic configuration of atoms and ions given the proton number (and
(iv) 20 em' charge).

(d) c,Hy + (x+*)o2~ xC02 + ~H20 (d) For gaseous hydrocarbons

their number of moles are
{i) (i) explain and use the term ionisation energy.
(ii) explain the factors influencing the ionisation energies of elements.
10cm3 20cm3 ~ 10cm3 directly proportional to their
volumes Voc n. hence their ·(iii) *explain the trends in ionisation energies across a Period and down a Group of
1 mol of C,Hy gives 1 mol of COz. hence x = 1 volumes are directly ratioed the Periodic Table (see also Section 9).
as the·lr moles.
Y) 2 hence y=4 OJ deduce the electronic configurations of elements from successive ionisation energy
1 mol of c,Hy reacts with 2 mol of 0 2 or ( x +4 = •
data.
.. molecular formula of A= CH• (CH• + 20z -> COz + 2Hz0)
(k) *interpret successive ionisation energy data of an element in terms of the position of
that element within the Periodic Table.
 Page 1 toe.!.£1 Atomic Structure
togic 2 Atomic Structure
~CORNER Page2
(c) (i) The polarity of plate A is"-" since positively charged 'Hand 'He nuclides
are attracted towards it.
~CORNER
'1f/i)) !N (J ;lJ (ii) The deflection is dependent on the charge/mass(;;.) ratio. 'H has a;;.

1.1 '&If IJ \!;II qpening ....... .

ratio· of ~1 =1 while 'He has a .!...
m
ratio of ~ =_!_,
4 2
Hence 'H is deflected twice
as -much as 'He.
fl_uestion I
(iii) !.... ratio of 2H = _!_ = !.... ratio of 4He.
(a) Define the terms m 2 m
2
(i) isotope, :::::> angle of deflection of H =angle of deflection of 4He = 2°.
[2]
(ii) isotopic mass. !.... ratio of 3
He = ~ = ~x!.... ratio of 1H
m 3 3 m
(b) (i) Give the symbols (showing the nucleon numbers and charges) of the

angle of deflection of He = ~ x angle of deflection of 1H = ( ~)".

following three particles. 3
:::::>

protons neutrons electrons

particle
p 6 8 6
Question 2
7 10
a 7
8 7 7 (a) The use of the Date Booklet is relevent to this question.
R
(i) Sketch how the first ionisation energies of the elements change from
(ii) Use the Data Booklet to identify which are not the usual isotopes of. lithium to neon.
the elements concerned. [6]
(c) A plasma is a gaseous mixture in which the atoms have been completely
stripped of their electrons, leaving bare nuclei. Because of possible use in
controlled nuclear fusion reactions, plasma behaviour has been intensively first
studied. When passed between two plates carrying a certain electric charge, ionisation
'H and 'He nuclei are deflected as follows. energy

_1_ 'H

~'He 0
G 5
proton number
10
source

Giving reasons for your answer, suggest

r (ii) Give the equation that represents the first ionisation energy of nitrogen.
(iii) Explain why the first ionisation energy of oxygen is less than that of
nitrogen. [4]

(i) the polarity (+ or -) of plate A, (b) (i) State the electronic configuration ?f nitrogen.
(ii) Why 'H is deflected twice as much as 'He, (ii) Draw and label the shapes of the two types of electron orbital found
in nitrogen atoms. [3]
(iii) the angles of deflection of
.fJOOIP2/02]
1. 'H nuclei,
[4]
2. 'He nuclei. Suggested Solution:
[JOO!P1/Q1~
(a) (i) 2500

>-
E" 2000
Suggested Solution:
"c:
(a) (i) Isotopes are atoms of the same elements and have the same number of "'
c: 1500
protons but different number of neutrons. Hence isotopes have the same (b) (ii) P is actually carbon .Q

atomic nmber but different mass number.

(ii) Isotopic mass is the mass of a particular isotope of an element.
whose usual isotope is
carbon-12 and not carbon- '"
.!!l
c:
.Q
1000

14 and R is actually oxygen

whose usual isotope is ~ 500
(b) (i) ':P; 'ja 3 -; ~~ • oxygen-16 and not oxygen- i o+-.--r-.~~-,~--r-~
(ii) Unusual isotopes : P and R
15. ~ 0 1 2 3 4 5 6 7 8 9 10
-~ proton number
"'
:~
,..... Page 4
topic 2 Atomic Structure

Page3 ~CORNER
topic 2 Atomic Structure ~CORNER Question 4
Sir James Jeans, who was a great populariser of science, once .described an
(ii) N(g) ----> N' (g)+ e- . . (a) (i~ Rememberloshowthe
. d. Table with a p' configuration. The atom of carbon as being like six bees buzzing around a space the size of a
stale symbols for both Nand
iii) Oxygen is in Group VI of the Pe_no 'lc s the removal of an electron from w. First IE of an element is football stadium.
( . . . . rgy of oxygen mvo ve h
first 1on1sat1on ene . . due 10 the presence of anot er defined as the energy re- (a) (i) Suggest what were represented by the six bees in this description.
1
a paired orbital. THe. ele?tr~mc_ repu SIOn of ox en to be lower than that quired to remove 1 mol of
electron causes the first IOmsaliOn energy ov~~ from a singly occupied valence electrons from 1mol
(ii) Explain (in terms of an atom of carbon) what stopped the bees from
of nitrogen in which the f1rst electron IS rem flying away from the space of the .football stadium.
of gaseous atoms of that
(iii) What is missing from Jeans' description when applied to an atom of
orbital. element to form 1 mol of
carbon? [3]

o8
positive ions.
(b) (i) ts' 2s' 2p' (b) The diagram below represents the energy levels of the orbitals in atoms
(iii) In general, a Group VI
of the second period, lithium to neon.
(ii) porbital element has a lower first IE
s orblla
· 1
than the Group V element in (i) Label the energy levels to indicate the principal quantum numoer and
the same period despite its the type of orbital at each energy level.
higher nuclear charge. This
is because the electron is
removed from apaired orbital
in the Group VI element (with
Question 3 [1] ap' configuration) and is thus
(a) State the full electronic config~ration of krypton, 36Kr. aided by electronic repulsion.
[1]
(b) Explain what is meant by the term isotope. .
nucleus
N tural samples of kryptor consist of misture of isotopes. A particular sample
(c) p:Cduced the following peaks in its mass spectrum. (ii) In the space below, sketch the shapes of the two types of orbital.
(iii) Complete the electron configurations of nitrogen and oxygen on the
nucleon relative energy level diagrams below, using arrows to represent electrons.
number abundance (%)

80 2.4

82 11.7

83 11.6

84 56.9

86 17.4

nitrogen oxygen
i) Calculate its average A, from these data. .
( t and neutrons present 1n the
(ii) State the number of electrons, pro ons [4] (iv) Explain, with reference to your answer to (iii), the relative values of the
atoms with nucleon number 83 and 86. first ionisation energies of nitrogen and oxygen. The values are given
[J01/P1101]
in the Data Booklet and should be quoted in your answer. [6]

(c) (i) State the formulae of the negatiVely charged ions formed by these
suggested Solution: elements in simple binary compounds (nitrides and oxides).
(ii) Why do nitrogen and oxygen form negative ions, but not positive ions,
(a) 1s' 2s' 2p' 3s' 3p' 3d" 4s' 4p'
in simple binary compounds? [2)
I ntaining the same number of protons
(b) Isotopes are atoms of the same elemHen cothey have the same proton number {J02/P2101]
but different number of neutrons. ence
but different nucleon number.
Suggested Solution:
24 11.7 1 1 · 6 x83+-"-x84+--x86=
56 9 17.4 83 9
·
1 ~0
82 (a) (i) Electrons
(c) (i) Average A,= x80+Wox +Wo 100 100
(ii) Electrostatic attraction between the positively charged protons in the
(ii) For the atom with nucleon number 83: nucleus and the negatively charged electrons.
no. of electrons = 36, no. of protons = 36 and no. of neutrons = 47 (iii) The nucleus containing protons and neutrons are missing from Jean's
description. Also the electrons are not free to move everywhere in the
For the atom with nucleon number 86:
atom but are confined in regions of space called orbitals.
otons = 35 and no. of neutrons = 50
no. of electrons = 36, no. Of Pr
.......-
topic 2 Atomic Structure Page6
PageS
topic 2 Atomic Structure ~CORNER
(c) Which of the above ions would be deflected the most when a beam is ~
(b)
CORNER
passed through an electric field? [1]
(b) (i) ~
(d) Which of the above ions would be deflected the least when a beam is ' :t;l~l~l~
_22.- passed through an electric field? [1]
>1e> -
~
(I)
c: [N02/P3/Q 1]
(I)
_j§_
I nucleus Suggested Solution:
~~
-
..--

'
~ 1~1~1~

8
(ii) (a) Ionisation energy generally decreases down the group. This is because the

o·
~~
valence electron to be removed is further from the nucleus. Also, there is an -
increase in the number of filled inner quantum shells down the group so that h_tl~l~
the valence electron to be removed is more greatly shielded and effective - ~ ~
nuclear charge decreases down the group. Thus, despite the greater number ~
p orbital (dumbbell shape) " " "
0
s orbital (spherical shape) of protons, ionisation energy decreases down the group. ~ ,~
~ ~ I ~c.
(iii)
_LL _L __L (b) (i) nv'-; T~x'-: T~z-
"'
0.. "'
0
z0
0
0
z
0
0
z
_L _L _L (ii) T~v'-: T~x'-: T~v­
_u_ (i) tsoelectronic =:> same
_ll (c) (iQ When a metal and non· (iii) T~ v'-: T~w'-: T~v-
number of electrons

__ll
_u_ metal combine to form a
binary compound, the metal
~ ~~v 3 -; ~~x 2 ~; tiz-
(c) T~v'-
oxygen which usually has three or (iii Isotonic=> samenum·
nitrogen tess valence electrons loses ber of neutrons
(d) T~z-
(iv) The first ionisation energies of nitrogen and oxygen are 1400 and 1310
kJ mot-' respectively. The first ionisation energy of oxygen is tower than
electrons to form ppsitive
ions while the non-metal
=> ;;v'-: iix'-; ;;v-
that of nitrogen despite its higher nuclear charge because the electron to wh'tch usually has five or (iii) Isotopic => samenum·
be removed in oxygen is found in an orbital containing a pair of electrons. more valence electrons Question 6 ber of protons
The electron repulsion due to the presence of another electron in the gains electrons to form
same orbital causes less energy to be required tor the electron to be negative ions. The ionisation This question is about the elements in Group II of the Periodic Table, magne- => ;iv'-; ;;w'-; :iv-
energy and electron affinity sium to barium.
removed in oxygen. required are compensated
V" and Y· are not truly
(a) Complete the table below to show the electronic configuration of calcium isotopic. They are the same
(c) (i) N'- and 02-. by the exothermic lattice atoms and of strontium ions, Sr'•. isotope since they have the
(ii) To achieve a stable electronic configuration of that of a nobal gas, nitro- energy which arises from
same mass number.
gen and oxygen can gain three or two electrons respectively or lose five or the electrostatic attraction
six electrons respectively. Since it is energetically more demanding to lose between the resultant posi· 1s 2s 2p 3s 3D 3d 4s 4p 4d (c) & (d) Since all the particles
such a high number of electrons tor both nitrogen and oxygen, they tend to live and negative ions. The shown are negatively
gain electrons to form negative ions than to lose electrons to form positive ions first electron affinity is usu· Ca 2 2 6 charged, they will be de-
ally exothermic while the flected towards the positive
in binary compounds. subsequent electron affini· sr'· 2 2 6 plate. The angle of deflec-
ties are endothermic. [2] tion of a charged particle in
(b) Explain the following observations. an electric field is depen-
Question 5 (i) The atomic radii of Group II elements increase down the Group. dent, on the ratio elm, where
(a) Describe and explain briefly the general trend in ionisation energy down e and m are the charge
(ii) The strontium ion is smaller than the strontium atom.
a group. [2] and mass of the particle
(iii) The first ionisation energies of the elements of Group II decrease with respectively. Since V" has
Atoms or ions that contain the same number of electrons are called isoelec- increasing proton number. [4] the highest elm ratio, it is
tronic. Those that contain the same number of neutrons are called isotonic.
{J07/P2/Q3] deflected the most. Since
Those that contain the same number of protons are called isotopic.
z- has the lowest elm ratio,
The rest of this question is concerned with various properties of the following it is deflected the least.
Suggested Solution:
five ions.
~~v 3 -, ~~w 2 -, ~~x 2 -, ~~v-, ~~z- (a)
15 2s 2p 3s 3o 3d 4s 4p 4d
(N.B. the symbols V, W, X, Y and Z are not the atomic symbols of the elements
Ca 2 2 6 2 6 0 2 0 0
concerned.)
(b) Which of the above ions are sr'· 2 2 6 2 6 10 2 6 0
(i) isoelectronic,
(ii) isotonic, [6]
(iii) isotopic?
.1'1
r topic 2 Atomic Structure
Page7
~CORNER
topic 2 Atomic Structure PageS
~CORNER
(c) (i) AI and Mg.
(b) (i) Number of energy levels increase down the group, therefore, atomic size In AI outemnost electron is in 3P rather than 3S
(b) (ii) Greater nuclear ···l 3P electron is at higher energy ' so I.1 .IS f urther away
· ·
from Nucleus (c) (i) ,3Al: 1S2, 2S2, 2P', •.
increases.
(ii) Outermost shell is removed and nucleus has more protons than electrons. charge attracts remaining P and S. · 3S2, 3P'
(l
electrons more strongly,
(iii) Number of shells increase and valence electrons are further away from For P' 3P subshell is singly filled and for S ,Mg: 1S'. 2S 2, 2P'. 3S'
therefore reducing its size. electrons. Paired electrons repel. • one 3P orbital has paired
nucleus. The shielding effect increases and effective nuclear charge
3P .orbital is away than 3S ':
decreases causing decrease in first ionisation energies.
(d) (i) & (ii) from the Nucleus. So less .
energy is required to re· ·
element Na Mg Ai Si p s move electron from 3P •·
Question 7 than 3S.
melting point low high high high low low
The Periodic Table we currently use is derived directly from that proposed by Mendeleev (d) Na, Mg and AI are metals.
in 1869 after he had noticed patterns in the chemical properties of the elements he conductivity high high high moderate low low Metallic bonds strength
had studied. mcreases from Na to AI
The diagram below shows the first ionisation energies of the first 18 elements (e) Because they had not been discovered. as the number of valence
of the Periodic Table as we know it today. electron increases, so
melting point increases.
2500
Ne
Question 8 Si is non-metal and form
2000 giant covalent molecule so
consist of a positive, heavy ~ucfenme~~al results showed scientists that atoms
In lhe 19th and 20th centuries ex · · melting point is high.
first Ar
ionisation
energy
1500 Then in the 20th century, theor:t~:alws lchIS surrounded by electrons.
P, and S, are simple cova·
lent molecuies and their
/kJ mol· 1 H arranged in orbitals around atoms. Clentlsts expla.ned how electrons· are
1000 melting point is low.

atoms of the second period (Li to N~) rgy levels of the orbitals present in
(a) The diagram below represents the ene .
sao Li
(i) Label the energy levels to indicat." the . .
lhe type of orbital at each pnnclpal quantum number and
1 2 3 4 5 6 7 8 9 101112131415161718 energy level.
proton number
(a) Give the equation, including state symbols, for the first ionisation energy of
fluorine. [2]
(b) Explain why there is a general increase in first ionisation energies from
sodium to argon. [3]
(c) (i) Explain why the first ionisation energy of aluminium is less than that

type (shape) of orbital that is occ . ~gbram of one of each different

of magnesium. (ii) 0 n the axes below, draw a sketch di
(ii) Explain why the first ionisation energy of sulphur is less than that of
period element. uple Y the electrons in a second-
phosphorus. [4]
The table below refers to the elements sodium to sulphur and is incomplete. Label each type.

~-f~ro:< *'
Si p
Na Mg A/
element
high
melting point
high
conductivity

(d) (i) Complete the. 'melting point' row by using only the words 'high' or
'low'.
(ii) Complete the 'conductivity' row by using only the words 'high', 'mod-
Wol wM ,
atoms on the energy level di~g~~~~sb~io:trogen atoms and oxygen
erate' or 'low'. [5] Use arrows to represent electrons. .
(e) When Mendeleev published his Periodic Table, the elements helium, neon
and argon were not included. Suggest a reason for this. [1] (a) Ionisation energy is defined
[JOB!P2102]
as the amount of energy
required to remove one ~
mole of electron from one "'c
Suggested Solution:
mole of gaseous atom to
"'
form one mole of gaseous
(a) F191 -> F1~ 1 + e·
'1011. nitrogen
(b) From Na to Ar, electrons are added to the same quantom shell, so there is
no change in shielding. Nuclear charge also increases and radius decreases.
 topic 2 Atomic Structure
Page 9 Page 10
top_ic 2 Atomic Structure
~CORNER ~CORNER
(b) (i) Nitrogen: 1400 kJ mol-• Oxygen: 1310 kJ mol-•

(ii) In nitrogen each p-orbital is half filled which is relatively stable configu-
>- ration as compared to p' configuration in oxygen. In case of oxygen pairing
e'
Q)
cQ) starts in p-orbitals as a result interelectronic repulsions are dominant and
_l_l it is easier to remove electrons hence oxygen has less 1st ionisation
energy than nitrogen.

oxygen [6]

(b) (i) Use the Data Booklet ·to state the value of the first ionisation energy
of nitrogen and of oxygen.
(ii) Explain, with reference to your answer to (a)(iii), the relative values of
i these two ionisation energies. [3]

i\ [J10/P2/01}

I Suggested Solution:
! (a) (i) ~~~
(a) (Q All P orbitals of same
quantum shell are of equal
energy.
>·
Ol
Q; ~
c:
Q)
__1_s_

(ii) p,, P,. P, are similar

i!

';"*' W·
z in shape but their alignment
:!~
1;. in space is different. They
::~
are in different directions

:';i w.r.t. each other.

I'·
li'l

~ii]c' '
:1
·i

s-orbital is p-orbital is
spherical in shape bilobed or dumb-bell
shaped
(iii) In nitrogen atom
?e-s are arranged as
(iii)

>-
e'
• _L

__LL
_L __1_ 1s' 2s2 2p'

[tltltl
1! Px Py p,
Q)
__u_ half filled p-orbital.

In oxygen atom ae- s are

nit(ogen
arranged as 1s' 2s2 2p'

lui t I tJ
• __LL _L __1_
2Px 2py 2p,

_u_ Hence one of p-orbital is

f\ __u_
paired.

oxygen
7opic 3 (k) *describe, interpret and/or predict the effect of d"ffi
ing, covalent bonding, hydrogen bond in
.
h I . erent types of ?ondm~ (ionic bond-
bonding) on the physical propert·l f g, bot er mterrnolecular mteractJOns, metallic
es o su stances.
C.£emicaf !7Jondiny (I) deduce the type of bonding present from given information.
(m) show understanding of chemical reactions in
the breaking and making of chemical bonds. terms of energy transfers associated with

Content
I

2
Ionic (electrovalent) bonding.
Covalent bonding and coordinate (dative covalent) bonding
(i) The shapes of simple molecules.
I
(

3
4
(ii) Bond energies, bond lengths and bond polarities.
Intermolecular forces, including hydrogen bonding.
Metallic bonding.
'
5 Bonding and physical properties.

Learning Outcomes
Candidates should be able to:
(a) *describe ionic (electrovalent) bonding, as in sodium chloride and magnesium oxide,
including the use of 'dot-and-cross' diagrams.
(b) *describe, including the ~.e of 'dot-and-cross' diagrams,
(i) covalent bonding, as in hydrogen, oxygen, chlorine, hydrogen chloride, carbon
dioxide, methane, ethene.
(ii) co-ordinate (dative covalent) bonding, as in the formation of the ammonium ion
and in the AI2CI6 molecule.
(c) *explain the shapes of, and bond angles in, molecules by using the qualitative model
of electron-pair repulsion (including lone pairs), using as simple examples: BF3 (trigo-
nal), C02 (linear), CH, (tetrahedral), NH 3 (pyramidal), H,O (non-linear), SF, (octahedral).
(d) *describe covalent bonding in terms of orbital overlap, giving cr and 11 bonds.
(e) *explain the shape of, and bond angles in, the ethane, ethene and benzene molecules
in terms of cr and 11 bonds (see also Section I 0.1 ).
(j) predict the shapes of, and bond angles in, molecules analogous to those specified in
(c) and (e).
(g) describe hydrogen bonding, using ammonia and water as simple examples of molecules
containing N-H and 0-H groups.
(h) explain the terms bond energy, bond length and bond polarity and use them to compare
the reactivities of covalent bonds (see also 5b(ii)).
(i) *describe intermolecular forces (van der Waals' forces), based on permanent and
induced dipoles, as in CHC/ 3(1); Br2(1) and the liquid noble gases.
OJ describe metallic bonding in tenns of a lattice of positive ions surrounded by mobile
electrons.
 topic 3 Chemical Bonding_
Pa2:e 2
toQic 3 Chemical Bonding Page l
~CORNER (c) (i) The enthalpy factors are ~CORNER
(1) the lattice energy of aluminium fluoride (which needed to be over
(b) Dative covalent bonding is
come);
'- indicated by a lone pair of

r;;ffl(j)) rN (J ;lJ {2) enthalpy change of hydration of aluminium and fluoride ions. electrons on the donor atom
and an arrow from the
Aluminium fluoride is made up of small and highly charged aluminium
IJ \!!/If IJ \.!;;~ qpening ....... . ions and small fluoride ions so that lattice energy of aluminim fluoride is
donor to the acceptor. A
wedged line(........_) is used
highly exothermic and hard to overcome. Even though the enthalpy change
to _indicate bonds protru-
of hydration of aluminium and fluoride ions is also exothermic, it is not
ding out of the page while a
exothermic enough to compensaie for the very exothermic lattice energy
Question I
of aluminium fluoride. Hence, aluminium fluoride is insoluble in water. dolled line (I i '' .) is used
(a)" Boron trifluoride, BF,."and aluminium fluoride, AIF 3 , differ markedly in their 3 to indicate a bond protru-
(ii) At •(aq)+30H"(aq)-----. AI{OH) (s) ding into the page. The
physical properties. 3
angles of 109.5" are labell-
compound melting point/ "C AI{OH)3 {s) + OH"(aq) ---> [ AI{OH) 4 J (aq) ed to indicate that the
shape around B and N is
BF3 -144 tetrahedral.
Question 2
AIF3 1291
(c) (i) ilH 50 , = ilHh,,- L.E.
(a) Define the term relative atomic mass. [2]
Deduce the type of bonding in each of these compounds and draw 'dot-
A more exothennic enthalpy
and-cross' diagrams to illustrate this bonding. [4] (b) The mass spectrum of krypton consists of several peaks, due to the exist-
change of hydration
ence of isotopes. Calculate the relative atomic mass of Kr to 1 decimal
(b) Boron trifluoride forms a compound with ammonia. Describe the type of (ilHh,,) favours solubility

I
place using the following data.
bond that is formed during this reaction. Draw a diagram to illustrate the

c~~ """'~· "'~""""""=

of an ionic compound by
shape of and bonding in the product. [2]
making the enthalpy cha-
(c) Aluminium fluoride is almost completely insoluble in cold water, but alu- 80 2.6 nge of solution (t;H ,)
minium chloride dissolves to give a clear solution. The addition of aqueous 501
sodium hydroxide to this solution produces a white precipitate which dis- 82 11.6 more exothennic. Similarly,
a less exothermic lattice

I
solves in an excess of aqueous sodium hydroxide forming another clear 83 11.5
solution. (L.E.) also favours dissolu-
84 56.9 tion of an ionic compound
(i) What enthalpy factors are involved in process of dissolving an ionic salt
86 17.4 in water. However factors
in water? Use these factors to suggest a reason why AIF, is so in- [2] {high charge and small
soluble. [4] (c) Krypton reacts with fluorine to form a fluoride A. A mass of 0.100 g of A ionic size) that make
(ii) Suggest equations for the formation of the white precipitate and for its (a) The low melting point of occupies 104 em' at 2.00x1 0' Pa and 305 K. Calculate the relative molecu-
ilHhyd more exothermic
dissolving in an excess of aqueous sodium hydroxide. [2] BF, shows that weak inter- lar mass of A, and hence suggest its formula. [2]
(N01/P1/Q1} molecular forces exist {which favours solubility)
(d) Another noble gas, xenon, forms a tetrafluoride XeF,.
also make L.E. more exo-
between particles of BF,
(i) Suggest a dot-and-cross diagram to show the bonding in XeF,. thermic {which does not
so that BF, is a simple
Suggested Solution: covalent molecule and the
favours solubility). Hence
(ii) Use your diagram to suggest the shape of XeF,.
(a) The bonding in BF is covalent bonding and the bonding in aluminium fluoride whether an ionic com-
3 bonding in BF, is covalent
(iii) When added to water, XeF, reacts according to the following equation. pound is likely to be soluble
is ionic bonding. bonding. The high melting
Deduce· the values of a, b and, c in this equation. in water or not depends on

..
Dot and cross diagrams:

:FXBXF:
.. 3+ r. •• ]-
point of AIF, and the fact
that AIF, is made of metallic
aluminium and non-metallic
6 XeF4 + 12 H2 0 ----> a Xe0 3 + b Xe + 30 2 + c HF [4] therelativevaluesof ilHhyd
and L.E.
3r!.:
... [ AI ]
•• • X •• fluorine indicates that the {N04/P3/Q1}
: F: bonding in AIF 3 is ionic. {ii) Aluminium hydroxide
Suggested Solution: is an amphoteric hydroxide
BF, AIF, and dissolves in excess
(a) The relative atomic mass of an element, A,, is defined as aqueous sodium hydroxide
(b) The type of bonding in the compound formed between boron trifluoride (BF ,)
to form the soluble comp-
and ammonia (NH,) is dative covalent bonding (or co-ordinate bonding). Boron A = 12 x Average mass of one atom of the element
in BF has only si" valence electrons and has a vacant orbital while N in NH 3
' · Mass of one atom ot 12 C lex [ AI(OH) 4 J.
3
a
has lone pair of electrons. The dative covalent bond is formed by the donation
of the lone pair of electrons on N to the vacant orbital of B in BF,. The attrac-
tion between the shared electrons and the Band N nuclei hold BF, and NH 3 ( b) A = 80x2.6+82x11.6+83x11.5+84x56.9+86x17.4 _ Common Error
' . 100 83 9
to form an addition compound. {b) When using pV =nRT, St
F 109.5° H units are used. The units

F"»--~::(·•H
for V is m' (not em').

I 109.5° H
Note that M, has no units.

The product is tetrahedral around B and N.

 topic3 Chemica/Bonding Pa e 4

~CORNER
Page3
topic3 Chemica/Bonding ~CORNER isotope m/e accurate isotopic mass

(c) Assume ideal gas behaviour,

••s 10 10.013
(d) (i~ In XeF ,. there are 6 "B 11 11.009
pV =nRT
regions of electron clouds. 35C/ 35 34.969
(2.00 x 104 )(1 04 x1 O..s) = n x 8.31 x 305 To minimise electronic
repulsion, they are directed 3'CI 37 36.966
n = 8·.21 x 1o_. mol
octahedrally.
Part of the mass spectrum of BCI3 is shown bel ow.
M=~=122
4
mor' ;"(+,/:
8.21x10 g : Xe : 12
Hence, the relative molecular mass of A is 122. /..,..\:
Since there are 21one pairs relative · 10
122-83.9 = 38.1 abundance
of electrons (they occupy
This is equivalent to 2 F atoms (2x19). oppostte each other), XeF, is 8

Hence, A is KrF 2 . square planar.

6
F'-.. i·/F
(d) (i) :F.
• • • )()C.)(
'F'
• ••
Xe
F/ -/· '--F
4
Xex

.·
• •F . ) ( ) ( ) (

•, ·...F·
x, Kr and Xe are in periods 4
and 5 respectively. They
are able to expand their
2

OT-~,-~~~~·~~L_
(ii) Square planar. octet electronic configura· 45 46 47 48 ,
tion. This is observed when m/e
(iii) To balance 0, a= 2.
they react with F (a very
To balance Xe, b =4. reactive element) to form
(ii)
... state the identity of each peak in th e mass spectrum shown
To balance F (or H). c =24. compounds such as KrF 1• (.ut) Calculate the accurate mass of th e pea k at m/e=46 .
XeF 1 and XeF ,. (tv) Use the spectrum to determine the .
curring boron, and hence calculate t~encentage of ··~ in naturally oc-
Question 3 of boron, quoting your answer to 2 de ac~ulrate relattve atomic mass
ecmta places. [5]
Fluorine, the first member of Group VII, does not occur in nature as the element.
[N06/P3/02]
The main sources of fluorine are the ionic compounds fluorspar, CaF,, and ,.
cryolite, Na3 AIF ,. Suggested Solution:
(a) Fluorspar, CaF ,. is a simple ionic compound. Draw a 'dot-and-cross' dia-
(a) (i) T~e.re. are
mtntmtse eleptronic repulsion: they are d_arotu~d· B (~tth no lone pair). To
gram to show the bonding in fluorspar. [1] 3. region of electron clouds .
[N06/P2101 a]
Hence, BF3 is trigonal planar. tree e tn a tngonal planar manner.

Suggested Solution:
:nB~F:
(a) [ oo J- [ Ca 2+ [
~fo~
00 J- •• •X
: F:
''

~F ~
00 J (ii) A dative bond is formed between rf ,
electrons, while B has a vacant orb"at nld B where N uses its lone pair of
1 a to accept it.

Question 4
(a) Boron forms simple trihalides of formula BX3 with all the halogens. BF 3 and ~ :N
ecH '
BC/ are the most common. Both find uses as Friedei-Crafts catalysts since \.
CH,
3
they readily react with electron pair donars.
;~: (i) Describe and explain the shape of BF 3 molecule.
(b) (i) Relative atomic mass is the ratio of the average mass of an atom to
(ii) BF and trimethylamine, (CH 3) 3N, react in a I :1 ratio to give a white
3
crystalline solid. Draw a diagram to show the bonding within a mol- the mass of a 12c isotope. 12
ecule of this solid, explaining the type of bonding involved. [5]

(b) (i) Define the term relative atomic mass.

Naturally occurring boron has two stable isotopes, "B and "B. Chlorine
also has two stable isotopes, 35 C/ and 37 CI. The accurate masses of these
isotopes are given in the table.
 Page 5 topic 3 Chemical Bonding_
top_ic 3 Chemical Bonding Page6

(ii) mle
45
46
'
0

"s"cr
--
Ion
s"cr
~CORNER
(e) When aqueous hydrazine is reacted with HC/, a solid compound of formula
N,H,C/ may be isolated. When an excess of HC/ is used, a second solid,
N,H,C/2 , is formed.
(i) Suggest what type of reaction occurs between hydrazine and HCI.
~CORNER

47 'oB3'CI' (ii) What feature of the hydrazine molecule enables this reaction to occur?
48 "s"'cr (iii) Suggest why one molecule of hydrazine is able to react with one or
two molecules of HC/. [3]
(iii) mass= 11.009 + 34.969 = 45.978 (g mol-') {J07/P2101]

(iv) Let x be the fraction of "B. Suggested Solution:

Using peaks at m I e = 45 and 46, (a) (i) between 117' and 120' (a) (i) Each carbon in ethene
is sp' hybridised making
abundance of m I e = 45 x 3 trigonal planer structure
(ii) Hx·N .. N•xH
abundance of m I e =46 = (1- x) = 1z • electron of nitrogen
around carbon atom.
12x = 3(1-x) HH x electron of hydrogen H-C-H angle is little less
x = 0.2 or 20% than 120 'C.
(iii) between 107' and 109•
(iii) Eachnitrogenhasthree
Reiative atomic mass of boron= 0.2 x 10,013 + O.B x 11.009 = 1O.B 1
(b) Ethene molecules offer vander wall's forces and hydrazine has hydrogen bonds bond pairs and a lone pair,
among these molecules. Hydrogen bonds are stronger than vander wall's H-N-H is about 107 'C.
forces, therefore, melting point and boiling points of hydrazine are much higher
Questio'!_l. than those of ethene.
Ethene, .C,H,, and hydrazinc, N,H,, are hydrides of elements whi<;h are adja- (c) Etha~ol and hydrazine have dipoles as shown. (c) Hydrazine & ethanol offer
cent in the Periodic Table. Data about ethene and hydrazine are given in the hydrogen bonding making
CH 3
table below. """-._ ,_ 0+
H"",o,· ;;,./H
li+
hydrazine very soluble in
N,H,
o· and N-N elhanol.
c,H, H'y"' Hsy "'-H''
melting
poinV'C
I -169 I +2 Oxygen atom of alcohol and hydrogen of hydrazine bond together.

boiling I H C/
I -104 +114
poinV'C
(d) (i)
I I
--- CH 2=CH2 + HCI......,. CH:r-CH
2
solubility in I insoluble I high (d) (i) Addition reaction takes
water (ii) Electrophilic addition place across the double
bond in ethene.
solubility in 1 high I high (iii) C,H,C/ molecule is a saturated compound and there is no possibility of
ethanol further addition.
(e) (i) acid - base reaction
Ethene and hydrazine have a similar arrangement of atoms but differently

!"'
shaped molecules. (ii) Nitrogen atom has a lone pair of electrons to make dative bond with H• (e) (i) Nitrogen of hydrazine
ion.
(i) What is the H-C-H bond angle in ethene? donates a lone pair to
(ii) Draw a 'dot-and-cross' diagram for hydrazine. (iii) There are two nitrogen atoms in hydrazine and each nitrogen atom has proton of HC/, therefore
a lone pair of electrons to make a dative bond with H• ion. acts as a base.
(iii) What is the H-N-H bond angle in hydrazine? [4]

I (b)
The melting and boiling points of hydrazine are much higher than those of
ethene. Suggest reasons for these differences in terms of the intermolecu-
Question 6
lar forces each compound possesses. [3] I
I This question is about the bonding of covalent compounds.
(c)
Explain, with the aid of a diagram showing lone pairs of electrons and ·.i,. (a) On the axes below, sketch the shapes of a 1s, a 2s, and a 2p, orbital.
dipoles, why hydrazine is very soluble in ethanol. [3] ·,!
z z z
;\

-¥· -¥· -¥·

Ethene and hydrazine each react with HC/.
·.·)

,;!', (d) When ethene is reacted with HC/, C,H,C/ is the only product. ;~~ i
(i) Using structural formulae, give an equation for the reaction between
ethene and HC/.
(ii) What type of reaction occurs between HC/ and ethene?
(iii) Explain why there is no further reaction between C,H,C/ and HC/. 1s 2s
[3] 2px
[3]

r
 topic3 Chemica/Bonding Page 8
Page 7
topic 3 Chemical Bonding ~CORNER (b) (i) Electrostatic attraction between bonding electrons and positive nucl!)i of
~CORNER
wo atoms share a pair of electrons. Co· the atoms.
(b) Covalent bonding occurs when t "b d in terms of orbital overlap with the

m
valent bonding may also be descn e (ii)
formation of" bonds.
. I nt bond held together? In your answer,
(i) How are the two atoms In a cava ed another and the nature of the
state which particles are attracte to one
force of attraction. d. ·
(ii) Draw sketches to show orbital overlap that produces the a bon lng In HCL
the H, and HCI mo~ecules.
(c) (i) Two different non·
(c) (i) When bonding electrons are unequally shared, the molecule has a dipole metallic atoms make cova-
character. lent bond. Due to difference
(ii) Chlorine atom being more electronegative than hydrogen, gets a partial in electronegativities of
negative charge and hydrogen atom gets partial positive charge. the atoms, the bond
becomes polar.
(d)
HCL
[4]

(c) The bond in the HCI molecule is said to be 'polar'.

(e) tJ.H1(C2 H4 ) = !J.Hc(Rl- tJ.Hc(P)
(i) What is meant by the term bond polarity? [2]
(e) If combustion data is pro·
(ii) Explain why the HCI molecule is polar. . =[2tJ.Hicl + 2tJ.Hc(H 2 )]- [tJ.Hc(C 2 H.)j vided the formula is given
. . be described as a mixture of" and • bonding. = [2(-393.7) + 2(-285.9)]-[-1411.0] as below
(d) The bondmg m ethene may h below
Ethanlpy offormation
Each carbon atom in ethene fonns three " bonds as s own . =51.80
H tJ.Ht = 51.80 kJ mol-' = LoH, (R) - l.uH, Products
(P)
H-···-~
c - c/~
Reactants

H
/ ~H Question 7
On the diagram, sketch the • bond that is also present in ethene. [1] The structural formulae of water, methanol and methoxymethane, CH,OCH,,
(e) Carbon, hydrogen and ethene each bum exothermically in an ex:ess of air. are given below.
0 0 0
tJ.H~ = -393. 7kJ mol-
C(s)+0 2(g) ~ C02(g) / \. /\. / \.
tJ.H~ =-285.9kJmor' H H H
H2(g) + ,)f02(g) ~ Hp(l)
tJ.H~ = -1411.0kJmol-' (a) (i) How many lone pairs of electrons are there around the oxygen atom
~ 2C02(g) + 2H20(1)
I.
C2H4(g) + 302(g) I
in methoxymethane?
enthalpy change of formation, I
Use the data to calculate the standard (ii) Suggest the size of the C-0--c. bond angle in methoxymethane. [2]
tJ.Ifi, in kJmor', of ethene at 298 K. The physical properties of a covalent compound, such as its melting point,
[3] boiling point, vapour pressure, or solubility, are related to the strength of attrac-
2C(s) + 2H2(g) ~ C2H•(g) tive forces between the molecules of that compound.
[N07!P2104]
These relatively weak attractive forces are called intennolecular forces. They
differ in their strength and include the following.
l,,
Suggested Solution: A interactions involving permanent dipoles
z B interactions involving temporary or induced dipoles
(a) z
z C hydrogen bonds

*' 1s
#· *' 2s

larger spherical
2p,
double lobe~ along
the x-axis
1
~~
d
~~
~~
~~
(b) By using the letters A, 8, or C, state the strongest intermolecular force
present in each of the following compounds.
For each compound, write the answer· on the dotted line.
ethanal
ethanol
methoxymethane
CH,CHO
CH,CH 2 0H
CH,OCH,
spherical
~1 2-methylpropane (CH,) 2CHCH, [4]
~
 Page9
top_ic 3 Chemical Bonding

(c) Methanol and water are completely soluble in each other.

~CORNER
:Jopic 4
(i). Which intermolecular force exists between methanol molecules and
water molecules that. makes these two liquids soluble in each other?
Oi) Draw a diagram that clearly shows this intermolecular force. Your
diagram should show any lone pairs or dipoles present on either
dlales of !Jl(afler
molecule that you consider to be important. [4]

(d) When equal volumes of ethoxyethane, C,H,OC 2 H5 , and water are mixed,
shaken, and then allowed. to stand, two layers are formed. 1

Suggest why ethoxyethane does not fully dissolve in water. Explain your
Content
answer. [2] . The gaseous state:
[JOBIP2101]
(i) Ideal gas behaviour and deviations from it.
(a) (i) ~~
(ii) p V = nRT and its use in determining a value for M,.
Suggested Solution:
x•~xC-H
H-C 1"'-H 2 The liquid state
(a) (i) 2 H/1 H
H The kinetic concept of the liquid state and simple kinetic-molecular descriptions of
(ii) 104.5" changes of state.
(iQ When there are two
(b) ethanal : A lone pairs and two bond 3 The solid state
ethanol : c pairs, the angle is 104.5'. Lattice structures.
methoxymethane : A 0
2-methylpropane :B II
(b) In case of CH,- C -- H Learning Outcomes
(c) (i) Hydrogen bonds. and CH 3 --Q-CH,. Candidates should be able to:
hydrogen is not direclly
(ii) CH 3 H (a) state the basic assumptions of the kinetic theory as applied to an ideal gas.
bonded with oxygen. So
I I
:o:········H-O-CH3
hydrogen bonding is
(b) explain qualitatively in terms of intermolecular forces and molecular size:
:o:·········H-0-H or absent. But in case of
I I
H
CH,CH 2-0H, hydrogen (i) the conditions necessary for a gas to approach ideal behaviour.
H bonding is present.
(ii) the limitations of ideality at very high pressures and very low temperatures.
(d) Hydrogen bonding exist between H20 molecules. In case of (CH 3) 2CHCH,
polarity is absent. So (c) state and use the general gas equation pV = nRT in calculations, including the deter-
Hydrogen bonds can not form between C2 H5 - 0 - C2 H5 molecules because
Vander waal forces oper- mination of M,.
oxygen and hydrogen are not directly bonded.
ate. , (d) *describe, using a kinetic-molecular model: the liquid state, melting, vaporisation, vapour
pressure.
(e) *describe; in simple terms, the lattice structure of a crystalline solid which is:
(i) ionic, ,as in sodium chl~ride, magnesium oxide.
(ii) simp!~ molecular. as in iodine.
(iii) giant molecular, as in silicon(IV) oxide and the graphite and diamond allotropes of
carbon.
i :.
\'
I\i' (iv) hydrogen-bonded, as in ice.
II
(v) metallic, as in copper.
II!,
[the concept of the 'unit cell' is not required]
\·
1~:,,, (f) explain the strength, high melting point and electrical insulating properties of ceramics
in terms of their giant molecular structure.
(g) relate the uses of ceramics, based on magnesium oxide, aluminium oxide and silicon(IV)
oxide, to their properties (suitable examples include furnace linings, electrical insulators,
glass, crockery).

-•••••~· ~•·•c=•-o..-"7"~-J'>,..,..."''"-""'-"T~~~
:~
 topic 4 States of Matter Page I

~CORNER
describe and interpret the uses of the metals aluminium (including its alloys) and copper
(h)
(including brass), in terms of their physical properties.

(i)
understand that materials are a finite resource and the importance of recycling pro-
qjl(j)) fP) {/ 4J
cesses.
outline the importance of hydrogen bonding to the physical properties of substances,
t.lv \!// !J 1J \!oil qJJening ....... .
(j)
includina ice and water.
~ . a
suggest from quoted physical data the type of structure and bonding present m Question I
(k)
substance .. Carbon dioxide is used as a coolant gas in some nuclear reactors. Unlike
hydrogen or helium, carbon dioxide shows marked deviations from the ideal
behaviour that is predicted by the kinetic theory of gases.
·(a) State two assumptions of the kinetic theory, and use these to explain why
you mighi expect the behaviour of carbon dioxide to be less ideal than that
of hydrogen. [3)
{b) Under what conditions of temperature and pressure would you expect the
behaviour of carbon dioxide to be most like that of an ideal gas? [2)
(c) The volume of 1 mol of carbon dioxide was measured at various pressures
but al a constant temperature of 285 K. The following results were obtained.

pressure, p volume, V pressure x volume, pV I m3

/Pa /m 3 Pa

4.0x10 5 5.80 x 1o- 3 2320

B.Ox10 5 2.85 X 10-3

15.0x 10 5 1.46x 10-3

20.0x10 5 1.07x10-3

(i) Complete the calculations for the third column and use these data to
plot a graph of the product pV against pressure p.
(ii) State how the value of the product pV should change with pressure for
an ideal gas.
(iii) Use the graph to calculate the volume of 1 mol of carbon dioxide at
a pressure of 10 x 10 5 Pa. Calculate the volume at 285 K that the ideal
gas equation predicts for this pressure and comment on the difference
between two values. [7)
[JOOIP1/Q2}

Suggested Solution:
(a) Two assumptions of Kinetic Theory:
1. Attractive forces between particles are negligible. (b) Under higher temperature
2. Volume occupied by particles are negligible. condilions, particles have
high kinetic energy so that
Since CO, has a larger electron cloud size than H,, attractive forces between.
attractive forces between
CO, molecules is greater than that between H, molecules.
particles are negligible.
Also since C02 is a larger molecule than H, molecule, the volume. occupied
by CO, molecules is larger than that of H, molecules. Under low pressure condi·
lions, particles are far apart
Hence behaviour of C0 2 is less ideal than that of H,.
so that volume occupied by
{b) High temperature and low pressure conditions. particles is negligible com-
pared to the total volume of
the system.
 Page2 top_jc 4 States of Matter Page3
top_ic 4 States of Matter
~CORNE~ Use the following data on critical temperatures to suggest an explanation ~CORNER
(c) (i) pressure, p volume, V pressure x volume, pV I m' _ for this. ·
/Pa 1m3 Pa
gas formula M, r,1·c
4.0' 10
5
5.80' 10"
3 2320 I
·- methane CH4 16 -82
8.0x10 5 2.85 X 10-3 2280
ammonia NH 3 17 133
15.0x105 1.46x 10-3 2190 steam H2 0 18 374
[2]
20.0x10 5 1.07x10-3 2140
-
{N02/P3!02]

2500 Suggested Solution:

2400 (a) Two assumptions of the kinetic theory of gases are,
"'
Q_

'"E 2300 1. Gases consist of small particles of negligible volumes.

~ 2200 2. The gas particles exert no attractive forces on each other.
2100
(b) Gases behave more ideally under conditions of low pressure and high tem-
2000. perature.
0 10 20 30
5 At low pressure, the molecules are far apart and there are relatively few
p/Pa x 10 molecules. Hence, the volume occupied by the gas particles and the attractive
(ii) For an ideal gas, pV remains constant even when pressure changes at forces of attraction are negligible.
At high temperature, the gas particles have large kinetic energies so that (e) Methane has such low
a fixed temperature.
attractive forces between them are insignificant. intermolecular forces of at-
(iii) From the graph, when p =10 x 105 Pa, 3
pV = 2256 m Pa. traction that above -82 ·c.
(c) When air is expanded into a region of low pressure, the molecules are further the particles have enough
2256 apart from each other. Energy needed to be taken in to overcome some kineticenergynot to beheld
v= =2.256 x 1o-3 m
3
intermolecular attractive forces. Thus, the expansion of air into a region of low in fixed volume by the weak
10x 10 5
pressure is an endothermic process. intermolecular forces even
For the ideal gas, p V = nRT.
(d) Increasing pressure causes the gaseous particles to be closer together so that under high pressure condi-
1 1
For n = 1 mol, T = 285 K, R = 8.31 JK- mol- ,
attractive forces between particles become more significant. When the pres- tions. However, ammonia
3 sure is high enough, the attractive forces between the particles are so great and steam have stronger
pV=1x8.31x285=2368m Pa forces of attraction and can
that the particles are no longer free to move anywhere in the container. The
2368 3 gas has condensed into a liquid and the particles can only move within the be liquified by an increase
v= = 2.368 x 1o-3 m in pressure unless the tem-
10x105 volume of the liquid.
i :: perature is so high that
~~! The volume for co, if it were ideal is greater than the actual volume of (e) The average kinetic energy of a gas is dependent on the temperature. Above their strong forces of
CO,. The attractive forces between co, at the relatively low temperature a certain temperature, the critical temperature, the average kinetic energy of attraction cannot hold the
ii:' of 285 is not negligible so that the CO, molecules are attracted to each a gas is so great that the particles can not be held within the volume of a liquid particles in a fixed volume
other and the volume of gas is smaller than the ideal situation. even though the increasing pressure is bringing the particles closer together. due to high kinetic energy.
ii!f
1: The increased attractive forces of attraction due to particles being forced closer Steam has a higher critical
together are hot sufficient to hold the particles within a fixed volume due to temperature than ammonia
Question 2 high kinetic energies which the particle's possessed above the critical tem- as hydrogen bonding is
perature. stronger and more exten-
[2]
(a) State two assumptions of the kinetic theory of gases. Different gases have different critical temperatures as they have different inter- sive between H, 0 mol-
u_i
(b) Under what conditions of temperature and pressure do gases behave most molecular forces. A gas with low intermolecular forces such as methane has a ecules than !Jetween NH,
ideally? Give reasons for your answer. [3] low critical temperature than ammonia and steam. Methane has relatively weak molecules.
instantaneous dipole induced dipole interactions while hydrogen bonding oc-
In the industrial liquefaction of air, high-pressure air is pre-cooled in a coil curs in both ammonia and steam.
surrounded by cold water. It is then allowed to expand into a region of low
pressure, where upon it cools down by a large amount. An ideal gas does not
show this behaviour. Question 3
(c) Suggest why the expansion of air into a region of low pressure is an (a) Describe the bonding within, and the shape of, the carbon dioxide mol-
endothermic process. · [2] ecule. Include a dot-and-cross diagram in your answer. [3]
(d) Gases like carbon dioxide can be liquefied at room temperature just by ·-r (b) Describe the type of attractions that might occur between carbon dioxide
pressurising them. Why does the application of pressure cause the gas to molecules. [1]
liquefy? [1]
(c) Cylinders of pressurised carbon dioxide are used to produce carbonated
(e) Gases can only be liquified by pressure alone if their temperature is below drinks. One such cylinder has an internal volume of 2.5 dm 3 , and contains
their 'critical temperature', T,. Above the critical temperature no amount of 2. 3 kg of carbon dioxide.
pressure will liquefy a gas.
/;J
7

topic 4 States of Matter Pa e 5

Page 4
topic 4 States of Matter ~CORNER ~CORNER
(i) Calculate the amount of carbon dioxide (in moles) in the cylinder.[1] Question 4
(ii) Using the ideal gas equation pV = nRT, calculate the pressure (in (a) State two assumptions of ideal gas behaviour. [2]
pascals) the carbon dioxide would exert inside the cylinder at room
temperature (298 K). [1 m' = 10' dm'] [2] Use of the Data Booklet is relevant in (b) and (c). .
(b) The ideal gas equation is pV- RT E 1 •
(iii) In fact, the pressure inside the cylinder is 2.2 x1 0' Pa under these
conditions. Explain why this differs from the pressure you calculated in of the following terms, and g~v: th~ ~~i~nf:rs ~~~ ~s you can the m~aning
value of R given in the Data Booklet o correspond w1th the
~
(ii). [1] I
(iv) A glass of cola is fizzy because carbon dioxide has been dissolved in OOOMt en, an
.
evacuated glass bulb of volume 63.8 em' is filled with a as
~h 24 C ~nd 99.5 ~Pa, t.he mass increases by 0.103 g. Deduce whet~er
I
it under pressure. WhEln the cola is poured out of the can, the carbon
dioxide is gradually released as bubbles of gas. The cola will even- e gas IS atnmoma, mtrogen or argon. .· .
tually go flat, as the concentration of dissolved carbon dioxide decreases
I (ii) E
fr~~a:~e:~yg=:~~~~~i~u~~e most likely of thes~ three gases to deviate
I
to its saturation level.
A 500 em' can of cola has 2.0 g of carbon dioxide dissolved in it under I [5]
pressure. Calculate the volume of carbon dioxide that is released to the 'I,. [J04/P2/Q 1]
atmosphere as it goes flat. I
[A saturated solution of carbon dioxide at room temperature contains
1 :S g dm~. Assume carbon dioxide behaves as an ideal gas under I Suggested Solution:

these ~ondilions.] [2]

l! (a) (i) Thethevolume
of gas. of gas mol ecu 1es IS
• negligible
•• as compared to total volume
{N03/P3!01]
(ii) There are no intermolecular forces between gas molecules.

Suggested Solution: (b) p: It is the pressure exerted by the gas measured in pa?cals (Pa).

(a) :o::c::o: O=C=O

V: The
(m'). volume of gas • m eans vorume
, of the container ·
qf gas measured in ·

C0 2 is linear. (c) (i) When using the

T: The absolute temperature measured in kelvin (k).
Each 0 atom is bonded to the central C atom by a covalent double bond m
formula n = M' the mass
(which contains a a bond and a " bond)
(c) (i) pV = !!!...Rr
(b) Van der Waals' forces of attraction. of CO, should be in units M,
of g (not kg).
M, = mRT
(c) (i) M, ofC0 2 =12+2x16=44 (ii) When using pV= nRT, pV
2.3x10
3 the volume should be in 0.1 03x 8.31x 297
nco, =~ =52.3 mol units of m' (not dm'). 99.5 X 10 3 X 63.8x 1o-S
(iv) Alternatively, Vcanbe =40.0 gmol"'
nRT 52.3x8.31x298 = 5 . 18 x 107 Pa calculated using the molar
(ii) p=-v 2.5 X 10-J volume at rtp = 24 dm' This gas is argon.
7
mol·'.
most from ideal behaviour while i~un~:r Y regen bonds hence deviates
(iii) The actual pressure is lower than the ideal gas pressure of 5.18 x 10 Pa. (ii) Ammonia molecules have intermole 1 h d
Under this high pressure, the gas does not behave ideally. The gas
moiecules are close enough to each other and exact intermolecular at-
i.e. V=nxVm waal's forces of attraction are present b~T!:e~n~o~~~~~swe;~k van der
traction. This reduces the forces the molecules exert on the cylinder wall
=0.02841x24
and hence a lower pressure. =0.682 dm3
=682 cm
3 Question 5
. )
( IV Mass o
f c0 .1n 500 em 3 at saturation=
. 500
1.5 x - - = 0.75 g
2 1000 The PtabledbeTiow gives data on some oxides of elements ,·n
eno 1c able. Period 3 of the
Mass of C0 2 evolved= 2.0-0.75 = 1.25 g

1 25 oxide Na,O MgO A/203 Si02 P.0 10 so,

nco evolved= · = 0.02841 mol
2 44 melting point/ K 1193 3125 2345 1883 853 290
Assume ideal behaviour at rip, boiling point 1 K 1548 3873 3253 2503 318

~i~~~~no:i~~at1on for the reaction of aluminium with oxygen to form alu:

V = nRT 0.02841 x 8.31 x 298
5 (a)
p 1.01x10
[1]
3
=6.97x10-4 m (b) Drawing diagrams where appropriate, suggest in terms
3
bond1ng, explanations for the following. of structure and
= 697 cm

j
 togic 4 States of Matter Pal!e 7

4 States of Matter
Page6
~CORNER
top_ic
~CORNER Suggested Solution:

(i) the high melting point and boiling point of A/20 3 (a) H • • C =~Co • H
(ii) the low boiling point of sO,
[7] (b) pV = nRT
(iii) The melting point of Si0 2 is much higher than that of P,O.,,
3 3
Pv (1515x10 )x(76x10- ) =46.5moles
.(c) Water was added to each of the oxides in the table. n=--
RT 8.31x298
Choosing a suitable oxide in each case, write an equation for the formation
of (c) (i) CaC 2 +2H 2 0--> Ca(OH) 2 +C 2H2 .
(i) an alkaline solution,
[2) (ii) n(C 2 H2 )=n(CaC 2 ) = 100x46.5
(ii) an acidic solution. =100x46.5x64
(N04/P2!02] massofCac;
= 297570 g
= 297.6 kg
Suggested Solution:

(a) 4 AI (s) + 30 2 ---> 2 A/20 3 Question 7

(b) (i) A\ 0 has giant ionic crystal \attic structure, oppositely charged ions held
3
by2 strong electrostatic forces of attraction. Hence very high melting point. Copper and iodine are both solids which have different physical and chemical
properties. Each element has the same face-centered crystal structure which
(ii) SO, is simple molecular covalent compound with weak van der waal's is shown below.
forces of attraction between molecules hence low boiling point.
(iii) Si0 is macromolecular covalent compound with large number of strong
. inter2 atomic covalent bonds which are very difficult to break t1ence high
melting point. While P,0 is simple molecular with very weak intermo-
16
lecular forces between molecules hence its melting point is less than
Si0 2•
(c) (i) an alkaline solution: Nap+HP--> 2NaOH

(ii) an acidic solution: 50 2 + H20 --> H2 S0 3

Question 6 The particles present in such a crystal may be atoms, molecules, anions or
The unsaturated hydrocarbon elhyne (acetylene), C,H,, is widely used in 'oxy- cations.• In the diagram above, the particles present are represented by !8·
acetylene torches' for cutting and welding metals. In the torch, ethyne is burned
in oxygen to produce a flame with a temperature of 3400 K. (a) Which type of particles are present in the iodine crystal? Give their formula.
[2)
(a) Ethyne. is a linear molecule with a triple bond, C;C, between the two
(b) When separate samples of copper or iodine are heated to 50 oc, the copper
carbon atoms. [1) remains as .a solid whil.e the iodine turns into a vapour.
Draw a 'dot-and-cross' diagram of an ethyne molecule.
(i) Explain, in terms bf the forces present in the solid structure, why copper
(b) When used for cutting or welding, ethyne is transported in cylinders which remains a solid. at 50 °C.
contain the gas under pressure. A typical cylinder has a volume of 76 dm'
and contains ethyne gas at 1515 kPa pressure at a temperature of. 25 °C. (ii) Explain, in terms of the forces present in the solid structure, why iodine
turns into a vapour when heated to 50 oc. [4)
Use the general gas equation, pV= nRT, to calculate the amount, in moles,
of ethyne in this cylinder. [2) (c) (i) Although copper is a relatively unreactive metal, when it is heated to
a high temperature in an excess of chlorine, copper(\\) chloride is formed.
(c) In some countries, elhyne is manufactured from calcium carbide, cac,;
which is produced by healing quicklime and coke together at 2300 K. How ooes chlorine behave in this reaction?
(ii) When a mix1ure of copper and iodine is heated to a high temperature,
CaO +3C -~ CaC 2 +C0
no reaction occurs.
When water is added to the CaC , calcium hydroxide, Ca(OH) 2, and ethyne, Suggest a reason for this difference. [2)
2

c,H,, are produced. {N06/P2102]

(i) Construct a balanced equation for the formation of ethyne from calcium
carbide.
(ii) Use this equation and your answer to part (b) to calculate the mass of
CaC which will react with an excess of water to produce enough ethyne \
2
to fill 100 cylinders of the gas. [3) :
{J061P2102 a,b,c] .!
\
-~ •• <:
 topic 4 States of Matter Page 8
~ic 4 States of Matter
Suggested Solution:
~CORNER Page9

~CORNER
{b)
{a) particle: Simple molecules.
formula: 12
{b) (i) Copper has metallic bond with strong electrostatic forces of attractions
between copper cation and sea of electrons hence high melting point and (b) At least one Si - o _ Si
remains solid at 50 oc. bond must be shown.
(ii) Iodine is simple molecular covalent compound with weak van der waal's e:o (c) (i) AHematively:
forces of attraction between molecules hence low melting point, boiling
point and easily vaporizes at 50 oc. e: si • the molecules behave
as rigid spheres.
(c) {i) Chlorine is acting as oxidizing agent.
• there are no inter-molecu-
(ii) Iodine is weaker oxidizing agent than chlorine hence can not oxidize lar forces between the·
(c) (i) • Mol 1
copper solid to copper ions. ecu es have weak intenmolecular forces between molecules molecules.
The II' · ·
co IS/on between the molecules are perfectly elastic. • molecules move in
The volume of molecule is negligible. straight line until they
Question 8 collide with other molec-
The kinetic energy of molecules is directly proportional to the tempenatu ules.
The elements carbon and silicon are both in Group IV of the Periodic Table.
Carbon is the second most abundant element by mass in the human body and
~ pressure exerted by the gas is due to the collision between the
mo ecules and the walls of the container.
g:· s
(ii) Induced dipole infer
silicon is the second most common element in the Earth's crust. action is present which
The molecules move in random motion.
Carbon and silicon each form an oxide of general formula XO,. causes deviation from ideal
{ii) Inte_r-molecular forces among CO I I gas behaviour.
At room temperature, C02 is a gas while Si02 is a solid with a high melting point. dev t f mo ecu es are strong enough to
Ia e rom ideal gas behaviour. '
(a) Briefly explain, in terms of the chemical bonds and intermolecular forces (e) (i) An~mafive/y
present in each compound, why CO, is a gas and Si02 is a solid at room {d) Each carbon atom is c I I . .
free electron which i o~~ ent ~ bonded With three carbon atoms, hailing one Si02+3C~SiC+2CO
temperature. [3]
• s e ocalised to make it conductor of electricity.
{b) Draw a simple diagram to show the structure of Si02 • Your diagram should {e) (i) 2C + Si02 ~SiC+ C02
contain at least two silicon atoms and show clearly how many .bonds each
atom forms. [2] (ii) form: diamond.
C02 does not behave as an ideal gas. reason: Si and C bo d I
makes it hard. n a ternately to give diamond like structure, which
(c) {i) State the basic assumptions of the kinetic theory as applied to an ideal
gas.
{ii) Suggest one reason why CO, does not behave as· an ideal gas. [5]
Question 9
Carbon exists in a number of forms, one of which is a conductor of electricity
and one of which is a non-conductor of electricity. Silicon is the main compo- Copper, proton number 29 and
nent of most semi-conductors.
have different ph . I ' a~gon, proton number 18, are elements which
YSICa and chem1cal properties.
{d) Graphite is the form of carbon that is a conductor of electricity. Give a In the solid state each ele
lure which is sh~wn belowment has the same face-centred cubic crystal struc-
simple explanation for this property. [1]
When carbon and silicon(IV) oxide are heated together at about 2000 oc, sili-
con carbide, SiC, is formed. Silicon carbide is a hard material which is widely
used as an abrasive and in ceramics.
{e) (i) Construct an equation for the reaction of carbon and silicon(IV) oxide.
(ii) SiC has a similar structure to one of the common forms of carbon.
Which form is ihis? Give a reason for your answer. [2]
[N09/P2/Q 1]

Suggested Solution: (a) C02 is a linear non-polar

molecule and SiO 2 has 3-D The particles present in such a c st
(a) Carbon dioxide is a simple covalent molecule. There are weak intermolecular cations In the d' ry al may be atoms, molecules, anions or
forces i.e. induced dipole - induced dipole interactions, between molecules. structure with Si and 0 al-
·. lagram above, the particles present are represented by n
ternately bonded to give
Si02 has a giant covalent macro molecular structure. That is why C02 is a gas {a) Which types 0 f . •·
diamond like structure. particle are present in the copper and
and Si0 2 is a solid at room temperature. In each case, give their formula. argon crystals?
 Page 8
toQic 4 States of Matter Page9
toQ_ic 4 States of Matter ~CORNER (b) ~CORNER
Suggested Solution:
(a) particle: Simple molecules. (b) At least one Si - 0 - Si
formula: 12 bond must be shown.
(b) (i) Copper has metallic bond with strong electrostatic forces of attractions
(c) (i) Affematively:
between copper cation and sea of electrons hence high melting point and e:o
• the molec~les behave
remains solid at 50 "C.
(ii) Iodine is simple molecular covalent compound with weak van der .waal's
e: si as rigid spheres.
forces of attraction between molecules hence low melting point, boiling • them are no inter-molecu-
point and easily vaporizes at 50 °C. lar forces between the
molecules.
(c) (i) Chlorine is acting as oxidizing agent. (c) (i) • Molecules have weak intermolecular forces between molecules.
• molecules move in
(ii) Iodine is weaker oxidizing agent than chlorine hence can not oxidize The collision between the molecules are perfectly elastic. straight line until they
copper solid to copper ions. The volume of molecule is negligible. collide with other molec-
ules.
The kinetic energy of molecules is directly proportional to the temperature.
The pressure exerted by the gas is due to the collision between the gas (i~ Induced dipole inter
Question B. molecules and the walls of the container. action is present which
The elements carbon and silicon are both in Group IV of the Periodic Table. causes deviation from ideal
The molecules move in random motion.
Carbon is the second most abundant element by mass in the human body and gas behaviour.
silicon is the second most common element in the Earth's crust. {ii) Inter-molecular forces among CO, molecules are strong enough to
(e) 0) Affemative/y:
deviate from ideal gas behaviour.
Carbon and silicon each form an oxide of general formula XO,.
Si0 2 + 3C ~SiC+ 2CO
At room temperature, co,
is a gas while SiO, is a solid with a high melting point. (d) Each carbon atom is covalently bonded with three carbon atoms, having one
(a) Briefly explain, in terms of the chemical bonds and intermolecular forces free electron, which is delocalised to make it conductor of electricity.
present in each compound, why CO, is a gas and Si0 2 is a solid at room
(e) (i) 2C + Si0 2 ~SiC+ C0 2
temperature. [3]
(b) Draw a simple diagram to show the structure of Si0 2• Your diagram should (ii) form: diamond.
contain at least two silicon atoms and show clearly how many bonds each reason: Si and C bond alternately to give diamond like structure, which
atom forms. [2] makes it hard.
C0 does not behave as an ideal gas.
2
(c) (i) State the basic assumptions of the kinetic theory as applied to an ideal
Question 9
II gas.
(ii) Suggest one reason why CO 2 does not behave as· an ideal gas. [5]
Copper, proton number 29, and argon, proton number 18, are elements which
~ Carbon exists in a number of forms, one of which is a conductor of electricity have different physical and chemical properties.

II and one of which is a non-conductor of electricity. Silicon is the main compo- In the solid state, each element has the same face-centred cubic crystal struc-

, nent of most semi-conductors. ture which is shown below.

II' (d) Graphite is the form of carbon that is a conductor of electricity. Give a
II simple explanation for this property. [1]
rl~I. When carbon and silicon(IV) oxide are heated together at about 2000 oc, sili-
con carbide, SiC, is formed. Silicon carbide is a hard material which is widely
used as an abrasive and in ceramics.
'li
1.,

it tl
(e) (i) Construct an equation for the reaction of carbon and silicon(IV) oxide.
(ii) SiC has a similar structure to one of the common forms of carbon.

'iiI
I Which form is this? Give a reason for your answer. [2]
[N091P210 1} i

I (a) C0 is a linear non-polar

2
molecule and Si0 2 has 3-D
The particles present in such a crystal may be atoms, molecules, anions or
cations. In the diagram above, the particles present are represented by g.
Suggested Solution: structure with Si and 0 al-
(a) Carbon dioxide is a ·simple covalent molecule. There are weak intermolecular

' ternately bonded to give (a) Which types of particle are present in the copper and argon crystals?
I forces i.e. induced dipole - induced dipole interactions, between molecules.
diamond like structure. In each case, give their formula.
SiD, has a giant covalent macro molecular structure. That is why C0 2 is a gas
and SiD, is a solid at room temperature. \
'(
;:l

':1 ~
 topic 4 States of Matter Page 10

~ ~CORNER
element particle formula
copper
argon [2]

er is a solid while argon is a gas.

AI room temperature, copp
(b) Explain these observations in terms of the forces presen1
in each solid
[4]
G.£emicaf 0neryelics
structure. h n it is heated to a high
. 1 r ely unreactive element, w e . d
Although copper IS a rea w . copper(ll) chloride IS forme .
temperature in an excess ol chlonn~, . h ted to a high temperature, no
Content
When a mixture of argon and chlonne IS ea
reaction occurs. . . ron with copper? Enthalpy changes: l:o.H of fonnation, combustion; hydration, solution, neutralisation
. ow does chlorine behave In liS reac I d and atomisation; bond energy; lattice energy; electron affinity.
(c) (1) H
(ii) Suggest a reason for the lack of a reaction between argon an[2] 2 Hess' Law, including Bom-Haber cycles.
chlorine. . below
The meltin g pOl"nts of the noble gases neon to xenon are given . Learning Outcomes

Ne Ar Kr Xe Candidates should be able to:

melting point /K 25 84 116 161

(a) * explain that some chemical reactions are accompanied by energy changes, principally
in the form of heat energy; the energy changes can be exothermic (l:o.H; negative) or
(d) Explain why there .IS an .Inc rease in melting point from neon to [J10IP2/Q2]
xenon. [2] endothennic.

,, (b) explain and use the terms:

),I
li
,1:'
Suggested Solution: (i) enthalpy change ofreaction and standard conditions, with particular reference to:
formation, combustion, hydration, solution, neutralisation, atomisation.
(a) (a) Copper has metallic lattice
element particle formula (ii) bond energy (!:o.H positive, i.e. bond breaking).
structure in which metal
copper cations Cu2• cations are surrounded by (iii) lattice energy (l:o.H negative, i.e. gaseous ions to solid lattice).
sea of electrons. While Ar (c)
argon atoms or molecules Ar is simple moleculer covalent calculate enthalpy changes from appropriate experimental results, including the use of
the relationship.
ccmpound in which each
atom is monoatomic.
{b) In copper metal cations are surrounded k ~ander weal's forces of attractions
b sea of electrons to form strong enthalpy change = mcl:o.T
metallic bond while in case of argon wea {d)
b 1 een the molecules. explain, in qualitative terms, the effect of ionic charge and of ionic radius on the
are presented e w b copper is oxidised from numerical magnitude of a lattice energy.
(c) (i) Chlorine behaves as an OXI·d"ISing
· agent ecause (c) (i) CU+CI2 ~CuC/2 (e)
apply Hess' Law to construct simple energy cycles, and carry out calculations involving
such cycles and relevant en~rgy terms, with particular reference to:
o oxidation state to +2. most shell is completely Copper is oxidised by chlo-
(..11) Ar has very high first ionisa_tion energy. Its ou1er rinefrom aoxidation number
• · h" hly unreaclive. to +2.
filled and IS lg . d number of electrons (i) determining enthalpy changes that cannot be found by direct experiment, e.g. an
· f the molecule mcreases an f enthalpy change of formation from enthalpy changes of combustion.
(d) also
Fromincreases, hence SIZe
Neon to Xenon, o
strength of Vander
X waal's forces increases. There ore,
(i i) average bond energies.
melting point increases from Ne to e.
(iii) the formation of a simple ionic solid and of its aqueous solution.
{iv) Born-Haber cycles (including ionisation energy and electron affinity).
(f) construct and interpret a reaction pathway diagram, in terms of the enthalpy change
of the reaction and of the activation energy (see Section 8).

I
1.
Note: The additional learning outcomes to be studied by A2 candidates are shown in bold type. The A2
components will assess all learning outcomes and will not be limited to those in bold type.
r
topic 5 Chemical Energetics
Pa2e2
top_ic 5 Chemical Energetics ~e l ~CORNER (c) Angle ONO, e, is 120". ~CORNER
0 0
Angle NON, e, is less than 109f, e.g. 105". t t
c:f?(j}) !D) !1 ;jJ (d) N20 5 (g)+H,O(/) - > 2HN0 3 0
~
·~··
e. 0 a.
IJ ~If !J ~ qpening ....... .
Question 2

Question I 'Water gas' is an equimolar mixture of hydrogen and carbon monoxide. It is

used as an industrial gaseous fuel. It is produced when steam is blown through
Dinitrogen pentoxide, Np,, can be produced by the following reaction sequence.· white-hot coke in the following reaction.
t.H = +180 kJ mol-'
N (g)+0 2 (g) ~ 2NO(g) H2 0(g)+C(s) ~ H2 (g)+CO(g)
2
t.H =-57 kJ mol-'
NO(g) + ~O,(g) ~ N0 2 (g) Another widely-used industrial fuel is natural gas, which consists mainly of
t.H =-55 kJ mor' methane.
Ill 2N0 2 (g)+~0 2 (g) ~ N2 0 5 (g)
(a) (i) Use the following enthalpy changes of combustion to calculate the
(a) (i) Explain why reaction I occurs in car engines. volume of methane (measured at 25 "C and 1 atm) required to produce
(ii) Suggest why reaction I is endothermic. [3] 1 MJ (1000 kJ) of heat energy when burned.
(b) (i) What is meant by the standard enthalpy change of formation of a (ii) Calculate the volume of water gas (measured at 25 "C and 1 atm)
compound? required to produce the same amount of heat energy.
(ii) Write the equation which corresponds to the enthalpy change of for-
enthalpy change of combustion,
mation o! dinitrogen pentoxide. substance
There are three regions of t;H, I kJ mol-'
(iii) Use the data given to calculate the enthalpy change of formation of "~c)
etectr011 density around N
d~nitrogen pentoxide. [3] so thai N nas a trigonal
CH, -890
(c) Dinitrogen pentoxide is a covalent molecule. Draw a possible displayed planar electron geometry H, -242
formula for the molecule, and suggest the bond angles in the molecule. and e, is expected to be co
[3] -283
120".
(d) Suggest an equation for the reaction of dinitrogen pentoxide with water. There are four regions of (iii) Based on your calculation, or on other considerations, suggest two ad-
[1] electron density around 0 vantages (economic, safety or engineering) of using natural gas rather
[NOOIP2101] so that 0 has a tetrahedral than water gas. Give reasons for your answers. [7]
electron geometry and e,
(b) An industrially important source of hydrogen is the reaction below.
is expected to be 109 f. CH4 (g)+ 2H2 0(g) ==' C02 {g) + 4H2 (g)
Suggested Solution:
(a) (i) Due to the high temperature of the car engine, energy is provided for the However since lone pair I (i) Use the above enthalpy changes of combustion to construct an energy
exerts a greater repulsion
high activation energy need to break the strong N =N and 0=0 and also
than a bond pair, e, is less
!I cycle and use it to calculate the enthalpy change of this reaction.
favours the endothermic formation of NO.
(ii) Reaction I is endothermic because strong N ,. N and 0=0 bonds needed (d) l'rlaW$W1l<idation state of I
l (ii) Predict how the position of equilibrium might be affected by
+5 and Is an oxide of a non· I an increase in pressure,
to be broken and this is not compensated by the N=O bonds formed.
metal.ltisexpectedtoreact I II an increase in temperature. [5]
(b) (i) Standard enthalpy change of formation of a compound is the energy given
with water to fonn an acid
·of oxidation state +5 and
I [N01/P1/03]
out or taken in when one mol of that compound is formed from its ele-
ments in their normal states urider standard conditions of 298 K and 1 atm
pressure.
hence is expected to fonn
HNO,. Compare this with
other non-metal oxides such
I Suggested Solution:

as CO, and SO, which react (a) (i) CH 4 (g)+20 2 (g) ~ C0 2 (g)+2H2 0(g) t.H, = -890 kJ mo\" 1
(ii) N2 (g)+%0 2 (g)---tN 20 5 (g)
with water to fonn H,CO,
1 mol of CH, produces 890 kJ of heat on combustion.
and H,SO, respectively. i
(iii) N,(g)+%0,(g) t.H,[N,o,(g)] ~ N,O,(g) Notice that the oxidation No. of mol of CH, required to produce 1000 kJ of heat = 1000 = 1.124
1' -55 kJ mol-' number of C (or S) in its
j 890
.!- +180 kJ mol"'
3 1
oxide and acid are the same. I Volume of CH, at rtp = 1.124 x 24.0 dm' = 27.0 dm' (to.3 s.f.)
2NO(g) + -0 (g)
2 2 2x( -57) kJ mol"
, 2N0 2 (g) + -0 2 (g)
2
The reactions of these oxides
with water are thus not redox
I

l
reactions so that the products
t.H [N 0 (g)] = + 180 + 2 x (-57)- 55=+ 11 kJ mol-' have the same oxidation·
1 2 5
numbers as the reactants.

:I
:i ,,
 topic 5 Chemical Energetics Page 3 topic 5 Chemical Energetics
~CORNER Page4
(ii) CO(g) + ~0 2 (g)--> C02(g) t>Hc =-283 kJ mol- 1 (a) Calculate the st d d
an ar enthalpy change for the following reaction. ~CORNER
1 . 1 C2H• (g)+ H20 (I) ----> C2H 0H(I)
H2(g) +20 2(g)--> Hp(g) 6.H0 = -242 kJ mol- 5 [2]
(b) (i} Define the ter~ standard enthalpy change of combustion.
(ii) E I
1 mol of water gas contains ~ mol of CO and Y, mol of H,. xp ain ~hy the state symbols for water and ethanol iven in the
Amount of heat energy produced by 1 mol of water gas ;~~~~~~ In (a) have been changed from those quoted in ~e industrial
=;;;X (283) +X X (242)kJ = 262.5 kJ (iii) Write the equation for the complete combustion of ethanol. [4]
1000
No. of mol of water gas nellded to produce 1000 kJ of heat =262 _ =3.810 (c) Ethanol IS miSCible with water becau I h
5 molecules of ethanol and water Dra ~~ ydroge~ bonding between
0

Volume of water gas at rtp = 3.810 x 24.0 dm' = 91.4 dm' (to 3 s.f.) the hydrogen bonding betwee~ a w Ia lal grafm, lncludmg dipoles, to show
water. mo ecu e 0 ethanol and a molecule of
(iii) One advantage of using natural gas is that it is more economical than [2]
water gas. By comparing the volumes of methane and water gas in (a)(i)
{J02/P2102]
and (ii), it can be seen that the volume of methane is about 3.3 times
lower. Hence, the amount of natural gas required to produce the same Suggested Solution:
amount of heat energy is much lower than that of water gas. Also natural
gas is found naturally in some areas and does not need much processing (a) 8H"
C' H,(g) + H,O(l} ~ C,H,OH(l}
to be used while water gas needed to be produced by reacting steam with
hot coke. Hence production of natural gas is expected to be less costly
than water gas. 6.1-t:[C,H,(g~O, +3;iH; [C,H,OH(l}]
Another advantage of natural gas is safety. Water gas contains potentially (b) (iij The position of equilib- 2CO,(g) + 3H,O(l}
.explosive hydrogen gas and toxic carbon monoxide. CO combines with rium may be predicted by
haemoglobin in the blood strongly and inhibits respiration. The problem By Hess' Law,
using Le Chartertie~s Prin-
is worsened by the fact that it is colourless and odourtess. Natural gas
on the other hand is less toxic and less potentially explosive.
ciple. The system counter- t>H,~" = 6.Hc"[C2H,(g)]-6.Hc"[C 2H50H(/)]
acts the increase in pressure
byfavouring the reaction that = -1411-(-1367) kJ mor' (c) Hydrogen bonding arises
(b) (i) CH,(g) + 2H, O(g) ~ CO,(g) + 4H,(g) decreases pressure. Since = -44 kJ mol-1 from the electrostatic attrac-
pressure is proportional to
""'-+20,(g) ~20,(g) the number of gaseous mol-
(b) (i) Standard enthalpy change of combustion is the enthal
one mol of a substance is completely b . PY change when
tion between a H attached
to a small electronegative
t>.Ho[CH,~ /4t>HJHJ ecules under the conditions pressure. ~rn 1 In oxygen at 298 K and 1 atm atom such as N, 0 or Fand
CO,(g) + 4H,O(g) of constant temperature a lone pair of electrons on a
(ii) T
and volume, the reaction o apply Hess' Law and to make use of the sta d small electronegative atom
By Hess' Law, that produces less gaseous of combustion given •. the initial and final states ofnth'::'ds;~~~lpy
c~~ng~s such as N, 0 or F:
6.H1 = 6.Hc[CH 4]- 46.H0[H 2] = -890- 4(-242) = +78 kJ mol-' molecules (the backward ~:~~ standard conditions. Since under standard conditions of~~~ K oan~ J- cf+ 8-
reaction) is favoured. Thus
position of equilibrium for
of wat~;e:~~r:·t~~~~~~~te(~)a~~v~hbanol exhist as liquid~, t~e state symbols X- H ........... : y
(ii) With an increase in pressure, position of equilibrium shifts to the left which
has less total number of gaseous molecules. the reaction shown shifts (iii)
een c anged to liqUid. """""
X = N, 0 or F; y = N, 0
left. C2HsOH(/)+302(g) -----> 2C02(g)+3H20(1} or F.
With an increase in temperature, the position shifts to the right since the
forward reaction is endothermic. With an increase in tem- (c) Between water and ethanol
H
~' the H bond may arise fro~
perature, the system coun-
I 0-
5+
Question 3
teracts the change by
favouring reaction that ab-
sorbs heat, i.e. the endother-
CH,-C-O
\ \5;- 0-H
H H-----·· /
..o,
or CH
H
I •• 0- 5+/0
,-c-o:·----
\ \
H 0-
the attraction between o
on
J+
Ethanol, C,H,OH, is a most important industrial chemical and is used as a mic reaction (the fmward H H H5+ ethanol and H of water or
solvent, a fuel and an intermediate in large scale organic synthesis. reaction). Thus position of 5+ J-
Ethanol is prepared industrially by the reaction of ethene and steam in the equilibrium for the reaction between 0 of water and
presence of a catalyst. shown shifts rights. 6+
Question 4
H of the hydroxyl group in
C 2H4 (g)+ H20(g) -----+ C2H50H(g)
(a) (i) Explain what is meant by the tt· ethanol.
The standard enthalpy change of the reaction can be determined by using the . 1a ICe energy of an ionic compound.
(ii)
standard enthalpy changes of combustion, t>H;' , at 298 K. Wnte an equation which represents the lattice energy of calcium oxide.

t>H;' I kJ mot·· (b) (i) Write one equation 'th 1 t . [3]

second ionisation ~n:'rgi:s a ~ %_m,cbols, Which represents the first and
C2H,(g) -1411 I 1um.0
(ii)

I
C2HsOH(I) -1367 Use the Data Booklet to calculate this energy change.
[2]

il:;,.
 Page 5 topic 5 Chemical Energ_etics
Page6
to£ic 5 Chemical Energetics
~CORNER
On the opposite page, use the grid to construct a Born-Haber cycle \
(c) (i) energy+ ~-CORNER
(c) (i) Ca"(g) + o'-(g)
which can be used to calculate the lattice· energy of calcium oxide.
Extra Information
Label each energy -level of your cycle, and draw arrows representing
the energy terms involved. Use words or symbols to represent these Ca''(g) + O(g) tEA,+ EA, = 657 kJ
(c) (i) EA, of 0 is exothermic
energy terms. since 0 has a strong affinity
(ii) Calculate the lattice energy of calcium oxide using the following data Ca(g) + O(g) frE, +IE,= 1740 kJ for electrons. However, its
LE[CaO] EA, is positive because
~ O,(g) f.iH,-[0] = 249 kJ
and the ionisation energy value you obtained in (b)(ii).
Ca(g) + energy is required to add.a
enthalpy change of formation of calcium oxide = -B35 kJ mot-• negativelychargedeleclron to
enthalpy change of atomisation of calcium = +178 kJ moi-' the negatively charged o-.
enthalpy change of atomisaticn of oxygen =
+249 kJ mot-• of oxygen atoms Ca(s) + 1 O,(g) t.H,_[Ca] = 178 kJ
0 2
sum of first and second electron affinities of oxygen = +657 kJ mot-• [7]

energy t.H,[CaO(s)] = -635 kJl

Ca''O''(s) ,

(ii) 178+249 + 1740 +657 +LE = -635

LE = -3459 kJ mol-'
(d) For Ca, its lattice energy is related to the enthalpy change of atomisation.

Ca(g) ------> Ca(s) L[ = -t.H alom!Ca]

Thus, the lattice energy depends on the strength of the metallic bond that
binds the metal atoms in the crys)al lattice. This is weaker tt1an the strong ionic
bonds that hold Ca'•02- together in its crystal laflice. The relatively stronger
0~---------------------- ionic bond could be explained by the higher negative charge (-2) on 0 2- in
CaO compared to that of the electrons (e-) in Ca. Hence, the lattice energy
of Ca is less exothermic than that of GaO.

Question 5
(d) The lattice energy of a metal is small compared with that oi an ionic com- (a) Define the term standard enthalpy change of neutralisation. [1]
pound. The value for the lattice energy' of calcium is -178 kJ mol-'.
Solutions of carbonates and hydrogen carbonates react with acids as fol-
Comment on and suggest reasons for the difference between this value for lows.
calcium and the value you obtained in (c)(ii) tor calcium oxide. [4]
C0 3 -(ilq)+2H•(aq) ~ H2 0(i)+C02 (g)
2
[N03/P2102] reaction 1
HC03 -(aq) + W(aq) ~ H2 0(i) + C02 (g) reaction 2

Suggested Solution: (b) The standard enthalpy change of reaction 2 was determined experimen-
tally by mixing known volumes of 1.0 mol dm-o NaHCO,(aq) and 1.0 mol
(a) (i) The lattice energy of an ionic compound is the energy released when 1
dm-o HC/(aq). The following results were obtained.
mol of the ionic crystalline solid is formed from its constituent gaseous
ions. volume of NaHCO,(aq) used = 40.0 em'
MP•(g)+ xq-(g) - - t MqXp(s) t:.H = lattice energy volume of HC/(aq) used = 40.0 em'
change in temperature = -0.5 oc
(ii) Ca2 •(g)+0 2 -(g} - - t CaO(s} Use the data given to calculate the standard enthalpy change for the re-
action (Assume the heat capacity of all solutions = 4.2 J K-• cm-o]. [2]
2 (b) 0) Note that Ca is the
(b) (i) Ca(g) - - t Ca •(g}+2e- gaseousstate(notsolidstate). (c) (i) Use the data in the table below to calculate another value for standard
' ,\:i:;
1
enthalpy change of reaction 2. ·
(ii) t:.H = 590+ 1150 = 1740 kJ mor
\i:: species t.H,"ikJ mor'
!I ~ I
H2 0(i) -285.8
CO,( g) -393.5

t
HCO,-(aq) -692
W(aq) 0.0
(1]

()
 topic 5 Chemical Energetics Page 8

~CORNER
Page 7
topic 5 Chemical Energetics ~CORNER mass of butane used 3.4 g.
mass of water heated 500 g
(ii) Compare your answers in (b) and (c)(i) and suggest one possible 44 oc
temperature rise
reason for any difference. [11
(d) (i) The standard enthalpy change of reaction 1 is -2.3 kJ mor'. Use this figure
(i)ii) write a balanced equation for the combustion of butane. (11

and those in the table to calculate a value for t.H~ of COt(aq). [21
(
..
State one precaution you should observe
men! such as this one in orde t
.
. when carry1ng out an experi-
r o ga1n accurate results. 111
(ii) Use your answer to (d)(i) to calculate the standard enthalpy change of
(nl) Use the data given to calculate the
the reaction. butane. (Assume the heat cap . efnthalpy change of combustion of
ac11Y o water = 4.2 J K-' cm_, 1 21
2HC0 - (aq) ----> C0 32- (aq) + H20(1) + C02(g)
3 (iv) The standard enthalpy chan . · [
and hence predict the effect of heat on an aqueous solution of NaHCO,. mol-'. Suggest an ex lanatio ge of com.bustJon of butane is -2877 kJ
value in (iii). p n for the difference between this and your
Explain your answer. · [31 111
[N031P3!03 Either]
(c) (i) Use the bond energies given in the o
value for the standard enthalpy chan ata Booklet to calculate another
a value of 805 kJ mol-• for the b dge of combustion of butane. [Use
on energy of C=O in CO21 131
Suggested Solution:
(a) Standard enthalpy change of neutralisation is the heat evolved when 1 mole (ii) Suggest a reason for the discrepancy between !his
in (b) (iv). . value and that• quoted
of water is formed when an acid reacts with a base under standard conditions. (b) s·mce the temperature
(11
change is negative, the tem-
perature of the solution [N03/P3/Q3 Or]
40
(b) nNaHCO, =1.0 X 100o =0.0400 mol dropped and the reaction is
endothermic i.e. tl.H is posi- Suggested Solution:
40
nHCI =1.0 1QOo
X =0.0400 mol tive. (a) Standard enthalpy change of combustion .
when 1 mole of the substance at it t of a substance IS the heat evolved
The same amount of NaHC0 3 and HCI were used. oxygen under standard conditions osfs1 antdard state is completely burned in
am and 298 K.
nH,0 = 0.04 mol
Q = 4.2x (40 + 40) x 0.5 = 168 J absorbed (b) (i) C4H10(g) + ~3 Oz(9) -----t 4COz(g)+5HzO(/)
(b) (iQ The water should be
t;.H; = +~= +4200 J mor' or +4.2 kJ mol-' (ii)
... The beaker should be 1agge d and covered to minimise heat lost stirred continuously to mix
0.04 the water well. The expert-
(111) Assume water has a density of 1 gem _, . ·
men! should be done in a
(c) (i) !J.H; = !J.H,O(products)- t;.H,O(reactants) 3
(c) (iQ The reason given has VH,o = 500 cm drought-free environment
= [(-285.8) + (-393.5)- (-692) = + 12.7 kJ mol-' to be specific as to WhY (b) to minimise heat lost during
Q = 4.2 x 500 x 44 = 9.24 x 1o• J evolved transferlromthecombustion
(ii) Heat absorbed from the surrounding. Otherwise, the temperature drop is lower than (c)(i). Reason
such as the container was M, of C4H10 = 4x12 + 10x1 =58 of butane to the beaker of
could be more. not lagged is too general water.
tl.Ht = t;.Ht'(H20) + tl.H,O(C02)- t;.H,O(CO/-l- 2 X t;.H,O(W) and not acceptable. nc,H, = 3 .4-
- 5.86 x 10-2 mol
(d) (i) (iii) Since the temperature
58
-2.3 =(-285.8) +(-393.5)- t;.H,O(CO/-l increases, the reaction
!J.H= 9.24x10 4 J'f.·
tl.H,O(CO/-l =-677 kJ mor' 5.86 x 1o-2 = -1.58x 1 os J mol-' or -1580 kJ mol-' is exothermic i.e. !J.H is
negative.
(ii) t;.H" = t;.H,O(CO/-) + !J.Ht (~0) + tl.H,0(C02)- 2 X tl.Ht'(HC03-) the water in the beaker The h Is. n~t completely transferred to heating
(iv) The heat of combustion of butane i .
· ea IS ost to the surrounding.
= (-677)+(-285.8)+(-393.5)-2x(-692) = +27.7 kJ mol-'
Heating will facilitate decomposition of HCO,- into co;-
and co,
since (c) (i) CH3CH2CHzCH3(g)+ 1:02(g) -----t 4C02(g)+5H20(/)
the reaction is endothermic. The equilibrium will shift to the right when
heat is supplied, according to Le Chatelie~s Principle, so as to remove
the excess heat. t;.H: =10BE(C-H)+3BE(C-C)+~BE(0=0)-4
. 2 x 2 xBE(C=0)-5x2xBE(H-O)

13
=10x410+3x350+ 2 x49 6-8x805-10x460 = -2666 kJ mor'
Question 6
[11
(a) Define the term standard enthalpy change of combustion. I (
ii)T
he bond energies used are avera es
.
(b) An experiment was carried out as follows to determine the standard en- I energies of the bonds in the com g .dThey may not be the actual bond
poun s e.g. C - C and C - H bonds.
thalpy change of combustion of butane, contained in the gas cylinder of a
camping gas stove.
I
A large beaker of water was placed on the stove and heated. The tempera-
ture rise was recorded. The cylinder was weighed before and alter the
experiment to determine the mass of gas used. The following results were
l
I
obtained.
I
,L,
topic 5 Chemical Energetics Page9
to~ Chemical Energ_etics
~CORNER Pag_e 10
Suggested Solution:
Question 7
(a) On the incomplete outline below sketch the Bom-Haber cycle which in-
{a) Energy ~CORNER
cludes the standard enthalpy change of formation, !!.H,.. , and the lattice Ca''(g) + s'-(g)
ene.rgy of calcium sulphide. Label all the enthalpy changes involved a!ld EA,+ EA, of S
the chemical species at each slage. [Abbreviations can be used, as in part Ca''(g) + S(g)
(b).] IE,+ IE, of Ca
Ca''(g) + s'-(g)

~..,)
Ca(g) + S(g)
t>.l-t:{S)
Ca(g) + S(s)
t>.H:(Ga)
Ca(s) + S(s)

lt>.H:CaS(s) CaS(s) Latt ce Energy (CaS(s))

(b) -487 = 178 + 279 + (590 + 1150) + 337 +Lattice energy

~ Lattice energy = -3021 kJ·mol-'
Ca(s) + S(s) Extra Information
(c) (i) EA 1 +EA 2 = 337
(c) The 2nd electron affinity of
EA 2 = 337- EA 1 an element is always endot-
hermic. This is because the
= 337- (-200) process involves the addi-
CaS(s)
= +537 kJ mor' tion of a negatively charged
(b) The standard enthalpy changes of atomisation, [5] electron to a negatively
(ii) s-(g) + e- --7 s 2 -(g) t'.H = EA charged ion, and like
t.H: of calcium= 178 kJ mol- 1, 2 charges repel.
t.H: of sulphur= 279 kJ mol- 1• EA, involves the addition of a negatively charged electron to a negatively M-(g)+e- -->M 2-(g) l'>H=EA
charged anion. The like charges repel and this makes the process difficult 2
The sum of the first two electron affinities of sulphur = 337 kJ mol-'. to take place. Hence, the process is endothermic, unlike EA,. (d) Since 0'- is smaller than S'-

Iq+q-1
The standard enthalpy change of formation,
1 , the ionic bond in Ca'-01- is
t.Hj, of calcium sulphide= -487 kJ mol-
(d) !Lattice energy! oc stronger than thai in Ca"S'·
The other enthalpy change values are to be obtained from the Data Book- r+ + r_ . It is therefore more difficuH
let. to separate the cations and
Use these values to calculate the lattice energy of calcium sulphide. [2] Since 0'- is smaller than S'-. the lattice energy of CaO would be more exo- anions of Ca''O'- and
thermic than that of CaS.
(c) (i) The first electron affinity of sulphur is -200 kJ mol-'. Calculate the value hence they have a more
of the second electron affinity of sulphur. exothermic lattice energy.
(ii) Comment on or explain the difference between these two values. [2] Queslion 8
(d) Suggest and explain how you would expect the value of the lattice energy
of calcium oxide to compare with the value you obtained in (b). [2] (a) What do you understand by the term lattice energy?
(b) Write equations to represent
[1]
[N04/P2102}
(i) the lattice energy,
(ii) the enthalpy change of formation,
of magnesium oxide, MgO. [2]
.'I'
,:[
(c) Use the following data, together with appropriate data from the Data Book-
let, to calculate the lattice energy of magnesium oxide. :i
i:!
first electron affinity of oxygen (O(g)+e·· ----.o-(g)) -140kJ mol-
1
second electron affinity of oxygen (0-(g) + e- ----->0 2 -(g)) +798kJ mol- 1
II'
I I enthalpy change of atomisation of Mg
enthalpy change of formation of MgO(s)
+148kJ mol- 1 I
'

L
-602kJ mor'
[3]
!l
,·,'I

~I
topic 5 Chemical Energetics Page 11 topic 5 Chemical Energetics

~CORNER Page 12
(d) How would you expect the lattice energy.of GaO to differ from that of MgO? suggest a reason for the discrepancy between the .
Explain your answer. [2]
(i)
calculated in (b)(il) and that given in the table. C>Hc for octane- you
~CORNER
(e) What effect do. the relatively high lattice energies of the Group II oxides
have on their physical properties ? Give one example of a use of these (ii) s uggest what the regular increase in the values of
oxides that relies on its high lattice energy. [2] table represents. t>Hc given in the
[N05/P3/03 Either] (d) The enthalpy change of combustio . [2]
~ensities of ethanol and octane ar: ~~ 7~hanol~s -1367 kJmol·', and the
lively. Calculate the heat produced by th gem and 0.70 gem"' respec-
Suggested Solution: of each fuel. - e complete combustion of 1.0 dm'

(a) Lattice energy is the energy released when 1 mole of an ionic compound is [3]
formed from its constituent gaseous ions. [N051P3103 Or]
Suggested Solution:
(b) (i) Mg 2'(g)+0 2-(g)--> MgO(s) t>H=LE.
(a) The bond energy is th
(ii) Mg(s)+~0 2 (g) --> MgO(s) t>H=t>H 1 bond. e average energy required to break 1 mole of a covalent

1
(c) 6~(Mg0) = t>H,10m(Mg) + IE1(Mg) + IE 2(Mg) + -BE(0 2)+EA1(0) + EA 2(0) + l.E. (b) (i) CaH,a +~5O, ------> 8CO, + 9H,O
2
r
-602 = 148 + 736 + 1450+ _!(496) -140 + 798 + L.E.
2
(iiJ
t>Hc = L18xBE(C-HJ+ 7BE(C-CJ+ ~5 BE(O = 0)]
LE. =-3842 kJ mor' -[8x2BE(G =0)+9x2BE(O-HJ]
(d) Lattice energy of GaO is less exothermic than that of MgO because Ca'' is
larger than Mg''. =(18x41 0 + 7x 350+ ~5 x496) -(16x 740+18x460)
jLE.j oc ,Q. q_, = -4090 kJ mol-1
r+ +r_
(c) (i)
When the interionic distance is bigger, the ionic bond is weaker and the The bond energies used are only average values.
magnitude of lattice energy is smaller. (ii) H
t> associated with the combustion of a GH .
2 Untl.
(e) Due to their relatively high magnitude of lattice energy, Group II oxides have
(d) Ethanol: n = .,...._...:7..:9::._0_ _
high melting points due to strong ionic bond. 17.17 mol
2x12+6x1+16
MgO is used in furnace lining.
Heat produced = n x t>H ;""

=17.17x1367=2.35x104 kJ
Question 9
Octanol: n 700
One of the most important uses of alkanes is for fuels. In some countries, where Bx12+18x1+16 =5.385 mol
crude oil is either scarce or expensive, bio fuels such as ethanol are increas-
ingly being used for fuels instead of hydrocarbons.
Heat prqduceq = n X llH:

(a) What do you understand by the term bond energy? [1] = 5.385 X 5470 = 2.95 X 104 kJ

(b) (I) Write an equation for the complete combustion of octane, C,H,..
(ii) Use the bond energies given in the Data Booklet to calculate a value Question 10
for the enthalpy change of combustion of octane. [4J
(d) The equation for the complete combustion of e . .
(c) The accurate experimental enthalpy changes of combustion of three hydro-
Use appropriate bond ener d t y1hne IS gtven below.
carbons are given in the table below.
value for the enthalpy changg~ ~a from t~e Data Booklet to calculate a
o combustion of ethyne
5 0

alkane formula t>H0 /kJmor-'

C,H,(g)+20,(g) -t 2CO,(g)+H,O(g) [3]
heptane c;H,6 -4817 (e) The value for the standard enth I
-1300 kJ mot-•. apy change of combustion of ethyne is
octane CaHta -5470 (i) D f
ii) e ine the term standard enthalpy change of combustion
( Explatn why your answer to (d) d0 . -
nonane GgH2o -6125
standard enthalpy change of ~ 5 not have the same value as the
com ust1on. [ ]
3
{J06/P2102 d,e]
 Page 13 topic 5 Chemical Energetics Page 14
top_ic 5 Chemical Energetics
~CORNER ~CORNER
Suggested Solution: Question 12
(d) H-C:=C-H +~0=0---l> 20=C=O + 0
1\ Fluorspar reacts with concentrated sulphuric acid to form hydrogen fluoride
H H gas.
Bond Breaking
CaF2 +H2S0 4 --> CaS0 4 +2HF
Bond Energy of 2 x C-H;, 2x410
Borid Energy of C =C = 840 Data about HF, HC/, HBr, and HI are given below.

Bond Energy of ~x 0 = 0 = ~x496 HF HC/ HBr HI

2 2
boiling point I 'C +20 -85 -67 -35
Total = 2900 kJ mor1 bond energy I kJ mol-1 562 431 366 299
1
t>Ht' /kJmor -269 -92 -36 +26
Bond Making
Bond Energy of 4 xC= 0 = 4x 740 (c) (i) Explain why the boiling points of HCI, HBr, and HI increase down the
=2980 Group.
Bond Energy of 2x0-H = 2x480 (ii) Suggest why the boiling point of HF is much higher than those of the
=920 others.
[3]
1 {N06/P2/01 (c)]
Total = 3880 kJ mor

AHc =Bond Breaking- Bond Making Suggested Solution:

= 2900 - 3880 = -980 kJ mol-
(c) (i) As the molecular size increases from HC/ to HI, the number of electrons
(e) (i) It is the enthalpy change when one mo!e of a compound is completely per molecule increases and the strength of VOW forces between the
burnt in oxygen at standard conditions of temperature and pressure (298 molecules increases. Hence, the boiling point increases.
K and 1 atm.) (ii) There is strong intennolecular hydrogen bond between HF molecules.
(ii) Calculations in (d) includes water in gaseous form while AHc involves
water in liquid fonn. Hence some of the energy is used to convert liquid
Question 13
water to gaseous state.
Ketene, C,H,O, is a member of a class of unsaturated organic compounds that
is widely used in phannaceutical research for the synthesis of organic com-
Question 11 pounds.

Monuments made of marble or limestone, such as the Taj Mahal in India and
CH, =C = 0
the Mayan temples in Mexico, are suffering erosion by acid rain. The carbonate ketene
stone is converted by the acid rain into the relatively more soluble sulphate. (c) (i) Define the term standard enthalpy change of formation.
CaC0 3 (s) +H2S0 4 {aq) ~ CaS04 (s)+HP(I)+C0 2(g) (ii) Use the.data below to calculate the standard enthalpy change of fonnation
of ketene.
acid rain
(c) (i) Explain what is meant by the tenn lattice energy. t.H" lkJ mol- 1
(ii) Predict, with a reason, how the lattice energy of BaSO, might compare standard enthalpy change of
with that of MgSO,. [3] formation of C02 -395
{J06/P4/Q2 (c)]
standard enthalpy change of
combustion of H2 -286

Suggested Solution: standard enthalpy change of

combustion of CH2=C=0 -1028
(c) (i) Lattice energy is the heat evolved when one mole of an ionic compound [6]
is formed from its gaseous ion (at 298 K, 1 atm). (d) Ketene can be converted directly into ethanoic acid, CH,CO,H, by reaction
(ii) Lattice energy of MgSO, is greater as compared to BaSO, because ol with a compound A. Suggest the identity of A. [1]
larger ionic radius of Ba'• ions as compared to Mg'• ions. [N08/P2/02(c,d)]

Lattice Energy oc q• q-
r+ +r-
,.
topic 5 Chemical Energetics Page 11 topic 5 Chemical Energetics
~CORNER Page 12
(d) How would you expect the lattice energy of GaO to differ from that of MgO? s .
Explain your answer. [2)
(i)
uggest a reason for the discrep_ancy between the
calculated in (b)(ii) and that . . tlHc for octane· you
~CORNER
(e) What effect do. the relatively high lattice energies of the Group II oxides g1ven 1n the table.
have on their physical properties ? Give one example of a use of these (ii) s
uggest what the regular increase in th I
oxides that relies on its high lattice energy. [2) table represents. e va ues of t.Hc given in the
[NOSIP3/Q3 Either} (d) The enthalpy change of combust" . 121
~ensifies of ethanol and octane ~~: ~f 7~hanol~s -1367 kJmo!-•, and the
lively. Calculate the heat produced b th gem and 0.70 gem""" respec-
Suggested Solution: of each fuel. Y. e complete combustion of 1.0 dm•
(a) Lattice energy is the energy released when 1 mole of an ionic compound is [3)
formed from its constituent gaseous ions. [NOSIP3!03 Or]

(b) (i) Mg 2•(g)+0 2-(g)--> MgO(s)

Suggested Solution:
tlH = L.E.
(a) The bond energy is th
(ii) Mg(s)+~02 (g) --> MgO(s) bond. e average energy required to break 1 mole of a covalent

1
(c) tlfit(MgO) = llH,1om(Mg)+IE 1(Mg) +IE2(Mg)+ -BE(0 2)+EA1(0)+EA2(0) + L.E. {b) (i) GsH,a+~502 _____, 8G02+9H20
2
-602 = 148+ 736+ 1450+~(496}-140+ 798+ L.E. 1
2
(iiJ
6~ =l18xBE(C-H)+ 7BE(C-G)+ ~5 BE(O =o)J
L. E. = -3842 kJ mol-1
-[8x2BE(C =0)+9x2BE(O-H)]
(d) Lattice energy of GaO is less exothermic than that of MgO because Ga'• is
larger than Mg'•. =( 18 X 41 0 + 7 X 350 + ~5 496)- (1 6
X X 740 + 18 X 460)
I
jL.E.j oc q+ q_,
r. +r_
= -4090 kJ mar'
(c) (i)
When the interionic distance is bigger, the ionic bond is weaker and the The bond energies used are only average values.
magnitude of lattice energy is smaller. (ii) t.H a ·
ssoctated with the combustion of a CH "t
2 Unt.
(e) Due to their relatively high magnitude of lattice energy, Group II oxides have
(d) Ethanol: n 790
high melting points due to strong ionic bond.
2x 12 + 6x 1+ 16 = 17.17 mol
MgO is used in fumace lining.
Heat produced = n x t.H:

= 17.17x 1367 = 2.35 x 104 kJ

Question 9
Octane\: n= 700
One of the most important uses of alkanes is for fuels. In some countries, where 8x12+18x1+16 =5.385 mol
crude oil is either scarce or expensive, bio fuels such as ethanol are increas- Heat prqduce(j = n X 6H:
ingly being used for fuels instead of hydrocarbons.
(a) What do you understand by the term bond energy? [1] = 5.385 X p470 = 2.95 X 104 kJ

(b) (I) Write an equation for the complete combustion of octane, G,H 18 •
(ii) Use the bond energies given in the Data Booklet to calculate a value Question 10
for the enthalpy change of combustion of octane. [4]
(c) The accurate experimental enthalpy changes of combustion of' three hydro- (d) 3he equatio~
for the complete combustion of eythne is given bela
carbons are given in the table below. se appropnate bond energy data fr w.
value for the enthalpy change of obm the Data Booklet to calculate a
com ust1on of ethyne
5 .
alkane formula tlH0 I kJmol- 1
C2H2 (g)+ 202 (g) --> 2C02 (g)+ H20 (g) [3]
heptane G7H1s -4817 (e) The value for the standard entha\
-1300 kJ mol·'. py change of combustion of ethyne is
octane GsH,s -5470 (i) D f
ii) e in~ the term standard enthalpy change of combustion.
( Explain why your answer to (d) d
nonane G9H2o -6125
standard enthalpy change of obes not have the same value as the
com ust1on
. [3]
[J06/P2102 d,e]
 Page 13 topic 5 Chemical Energetics
toQic 5 Chemical Energetics Page 14
~CORNER ~CORNER
Suggested Solution: Question 12
(d) H-C:=C-H +.§. 0=0~ 20=C=O + 0
2 /'\ Fluorspar reacts with concentrated sulphuric acid to form hydrogen fluoride
H H gas.
Bond Breaking
CaF2 +H2 S0 4 ----+ CaS0 4 +2HF
Bond Energy of 2 x C-H =2x410
Borid Energy of C =C = 840 Data about HF, HC/, HBr, and HI are given below.

Bond Energy of ~x 0 = 0 = ~x496 HF HC/ HBr HI

2 2
boiling point I 'C +20 -85 -67 -35
Total = 2900 kJ mar' bond energy 1 kJ mor1 562 431 366 299
1
!!.Ht' I kJ mol- -269 -92 -36 +26
Bond Making
Bond Energy of 4 x C= 0 = 4x 740 (c) (i) Explain why the boiling points of HCI, HBr, and HI increase down the
=2980 Group.
Bond Energy of 2x 0-H = 2x480 (ii) Suggest why the boiling point of HF is much higher than those of the
=920 others.
[3]
[N06/P2/Q1 (c)]
Total = 3880 kJ mar'

t;.Hc =Bond Breaking- Bond Making Suggested Solution:

= 2900 - 3880 = -980 kJ mar
(c) (i) As the molecular size increases from HC/ to HI, the number of electrons
(e) (i) It is the enthalpy change when one mo!e of a compound is completely per molecule increases and the strenglh of VOW forces between the
burnt in oxygen at standard conditions of temperature and pressure (298 1 molecules increases. Hence, the boiling point increases.
K and 1 atm.) I (ii) There is strong intennolecular hydrogen bond between HF molecules.
(ii) Calculations in (d) includes water in gaseous fonn while t;.Hc involves I
water in liquid fonn. Hence some of the energy is used to convert liquid
\ Question 13
water to gaseous state.
Ketene, C,H,O, is a member of a class of unsaturated organic compounds that
is widely used in phannaceutical research for the synthesis of organic com-
Question 11 pounds.

Monuments made of marble or limestone, such as the Taj Mahal in India and
= =
CH, C 0
the Mayan temples in Mexico, are suffering erosion by acid rain. The carbonate ketene
stone is converted by the acid rain into the relatively more soluble sulphate. (c) (i) Define the term standard enthalpy change of fonnation.
CaC0 3 (s) +H2S0 4 (aq)-? CaS04 (s)+HP(I)+C0 2(g) (ii) Use the .. data below to calculate the standard enthalpy change of fonnation
of ketene.
(,.' acid rain
:~~ :

~~; (c) (i) Explain what is meant by the tenn lattice energy. !!.H" lkJ mol-1
:~· (ii) Predict, with a reason, how the lattice energy of BaS0 4 might compare
il''· standard enthalpy change of
with that of MgS04 • [3] -395

~
'· ,,
..·..·'.· [J06/P4/Q2 (c)]
formation of C02
standard enthalpy change of
-286
\ combustion of H2
-
Suggested Solution: slandard enthalpy change of
.: combustion of CH2=C=0 -1028
(c) (i) Lattice energy is the heat evolved when one mole of an ionic compound [6]
[i:·: -

~~;~ is formed from its gaseous ion (at 298 K, 1 aim). (d) Ketene can be converted directly into ethanoic acid, CH,CO,H, by reaction
,I with a compound A. Suggest the identity of A. [1]
(ii) Lattice energy of MgSO 4 is greater as compared to BaSO 4 because of
larger ionic radius of Ba'• ions as compared to Mg'• ions. [NOBIP2/Q2(c,d)]

Lattice Energy oc q• q-
r+ + r-

.
i
1'.! ·.
.£L~
!:

6
Page 15
topic 5 Chemical Energetics
~CORNER 7opr"c
Suggested Solution: .
. . 1 mol of a compound is formed from its constrtuent
(c) (I) ;l~~~~{s ~~a~hge~r~~=~dard states under standard conditions.

(ii) 0/ec/rochemislry

Content
Redox processes:
electron transfer and changes·in oxidation number (oxidation state).
Applying Hess' law A.Hf' = A.H:; + A.H:; 2 Electrode potentials
A.H:; =A.Hf' - A.H:; (i) Standard electrode (redox) potentials, £-& ; the redox series.
= 2(-395) + (-286)- (-1028) = -48 kJmol-' (iO Standard cell potentials, E!J 1, and their uses.
A.H-e--
f - A.H-e-
s, =-48 kJ mer' (iii) Batteries and fuel cells.
(d) H20(g) (steam) 3 Electrolysis
(0 Factors affecting the amount of substance liberated during electrolysis.
Question 14 (ii) The Faraday constant:
[2] the Avogadro constant: their relationship.
(a) What is meant by the term bond energy? .
(b) Describe and explain what is observed when ~ r~~-ho~~~ea~s/~lnged rnto (iii) Industrial uses of electrolysis.

~e:;r:~: ~~~~~~~e~~~h:a~uaesse~~:f~r~~ Tn~~rpr~:in~s these obse~ations?

0

.·,i' [3] Learning Outcomes

(c) The following reaction occurs in the gas phase. Candidates should be able to:
3F2(g)+C/i(9)---72C/F3(g), A.H,e =-328 kJ mol-'
(a) describe and explain redox processes in terms of electron transfer and/or of changes
Use these and other data from the Data Booklet to calculate the averaf~ in oxidation number (oxidation state) (calculation of oxidation number is required).
bond energy of the CI-F bond in CIF,.
[N09/P4104] (b) explain, including the electrode reactions, the industrial processes of:
(i) the electrolysis of brine, using a diaphragm cell.
Suggested Solution: (ii) the extraction of aluminium from molten aluminium oxide/cryolite.
(a) The energy required to break one mole of bonds in the gas phase. (iij) the electrolytic purification of copper.
(b) With HCI. no change with HI purple fumes of iodine- are produced. (c) define the terms:
.,
1,.
H- Cl bond being strong does not brea k whereas H-I bond being weaker (i) standard electrode (redox) potential.
breaks into its elements.
(ii) standard cell potentiat
'ilrl
:,I
(d) describe the..standard hydrogen electrode.
(c) Bonds broken -Bonds formed= -328
(e) .describe methods used to measure the standard electrode potentials of:
=> 3BE(F -F)+ BE(CI-C/)-6BE(CI-F) = -328
;I'
(3x158)+ 244-6BE(CI-F) = -328 (i) metals or non-metals in contact with their ions in aqueous solution_
·: 718- 6BE(C/-F) = -328 (ii) ions of the same element in different oxidation states.
6BE(CI-F) = 1046 (/) calculate a standard cell potential by combining two standard electrode potentials.
I
I BE(C/-F) = 174.3 ,.174 (g) use standard cell potentials to:
(i) explain/deduce the direction of electron riow from a simple cell.
(ii) *predict the feasibility of a reaction_

.I
 topic 6 Electrocl]emist!J(_ Page 1
(h) construct redox equations using the relevant half-equations (see also Section 9.5).
(i) predict qualitatively how the value of an electrode potential varies with the concentra- ~CORNER
tion of the aqueous ion.
(j) state the possible advantages of developing other types of cell, e.g. the H,fO, fuel cell
and improved batteries (as in electric vehicles) in terms of smaller size, lower mass q?/ii) fP) !141
and higher voltage. ~ ~t.r IJ~ qpening ...... ..
(k) state the relationship, F= Le, between the Faraday constant, the Avogadro constant

(I)
and the charge on the electron.
·predict the iden~ity of the substance liberated during electrolysis from the state of
I1 Question I

electrolyte (molten or aqueous), position in the redox series (electrode potential) and
concentration.
I
i
(a) Draw a fully labelled sketch of how you would determine the standard
electrode potential of the Fe''(aq) 1 Fe''(aq) electrode system. [4]

(m) calculate: l (b) lron(ll) salts are often used as a dietary supplement to help cure some
forms of anaemia. The amount of iron in such a pill may be estimated by
(i) the quantity of charge passed during electrolysis. I titration with KMnO,(aq).

(ii) the mass and/or volume of substance liberated during electrolysis, including those I Use information in the Data Booklet to write a balanced equation for the

(n)
in the electrolysis ofH,SO,(aq), Na,SO,(aq).
describe the determination of a value of the Avogadro constant by an electrolytic method. ll reduction in acid solution of MnO,·(aq) to Mn''(aq) by Fe''(aq). [1]
(c) A dietary supplement pill was dissolved in 10 em' of dilute sulphuric acid
and titrated against 0.0200 mol dm"' KMn,O,. The E"'' was measured against
a standard hydrogen electrode and the following graph was obtained.
~
I y
I

'z
E~/V

X I
I
I

: 16.5 em'

O'
0
v
volume of KMnO, added/em'

Using suitable E" data listed in the Data Booklet, suggest approximate E
values, in volts, for the points X and Y. [3]
{d) Use the graph to calculate ·tiow many moles of Fe'' were contained in the
pill. [2] _... .·

(e) The end-point of this titration can be determined without using either a
voltmeter or an indicator. By deducing the colours of the solution at points
X, Y and Z, suggest how the end-point might be recognised. [2]
[NOOIP1/Q2}

Suggested Solution:
(a)

H2 (g) at 1 atm
and 25 'C

[H'(aq)]=1.0 [Fe 2'(aq)] =

moldm· 3
Temp at Fe 3'(aq)] = 1.0
25 'C mol dm·3

Note: The />2. parts of the syllabus, which will be examined only in the full Advanced Level qualification, are (b) MnO;(aq)+BH'(aq)+5Fe2'(aq) ---> Mn 2'(aq)+4H20(/)+5Fe 3'(aq)
indicated in bold type.

:~~"'-
 topic 6 Electrochemistry Page 3
Page2
topic 6 Electrochemistry
~CORNER Suggested Solution:
~CORNER
(c) At X, Fe'', Fe"' and Mn'• are present. No MnO,- is present since equivalence (c) Note that the answer only
point is not reached. The cell is assumed to be similar to that of a Fe'• I Fe"' (a) (i) 2HN03 + 2802 + H20 ~ N 20 3 + 2H 2 so·4
I'€ quires an approximation of

half-cell. the Evalues at XandY. The ~nu~:e~bove reaction only N and S undergo changes in their oxidation
From the data booklet, values of Eat XandY may
E" = +0.77 v not be equal to E~ell since Let the oxidation no. of N in HNO, be a.
+1+a+3(_:2},=0 ::;:, a=B- 1=+5 _
Ecell "'E~11 = E&, , -E& =+0.77 -0 = +0.77 V conditions are not standard
Fe +/Fe.. H"IH 2

AI Y, Fe"', MnO,- and Mn'• are present. No more Fe'• is present since equiva-
at these points. It is possible Let lhe oxidation no. of N in N20 3 b~ b•
to calculate the exact E
lence point is exceeded. The cell is assumed to be similar to that of a MnO; values but the method is 2(b) + 3(-2) =·0 ::::> 2b = 6 and hence b = +3.
beyond that of the A-level Since oxidation no. of N decreases in the reaction, N is reduced.
IMn'' half-cell.
syllabus.
From the data booklet, Let the oxidation no. of s in so, be c.
(d) The graph is called a redox
tffraffon curve. It is similar to c+2(-2)=0 ::;:, C=+4
. & & E& V
that of a pH titration curve Let the oxidation no. of s in H,so, be d.
Ecell "'Ecell = EMrlO,-/Mn'' - H'/H, = + 1.52-0 = +1.52 except that the y-axis is
electrode potential, E. 2(+1)+d+4(-2)=0 ::::> d=8-2=+6
(d) From the graph, the volume of MnO; needed to exactly react with the amount instead of pH. The volume at
Since oxidation no. of S increases in the reaction, S is oxidised.
of Fe'• present = 16.5 em'. which there is a great in-
crease in E is the volume
Amount of Mn04 = ~x0.0200 mol= 3.30x10-4 mol (ii) FeO• 2 -+Mn02+4H' ----+Fe2'+Mn04 -+2H2 0
needed for equivalence
1000
point to be reached. i.e. the In the above reaction , only Fe an d Mn undergo changes in their oxidation
numbers.
No. of mol of Fe'' = 5 x no. of mol of MnO; = 1.65 x 10-" volume that contains the
amount of MnO,-needed to Let the oxidation no. of Fe in FeO;' be e.
(e) At X, Z andY, the colour of the solution is yellowish green, orange and purple exactly oxidise the Fe''
respectively. Hence the end-point might be recognised by a change in colour present. Hence at equiva- e+4(-2)=-2 ::::> e=-2+8=+6
of the solution from yellowish green to orange. lence point, no. of mol of Oxidation no. of Fe in Fe'• = +2
Fe>' = 5 x no. of mol of
Since oxid.atio_n no. of Fe decreases in the reaction, Fe is reduced.
Mno,-.
Let the oxrdatron no. of Mn in MnO, be f.
Question 2 (e) AI X, about equal amounts
of Fe'' and Fe~ is present f +2(-2) = 0 ::::> f = +4
(a) By calculating the oxidation numbers of the relevant elements on each side
of the following equation,. slate which atoms have been oxidised and which so that the colour of solution Let the oxidation no. of Mn in MnO; be g.
at X is yellowish green.
reduced. Show all"your working. g+4(-2)=-1 ::::> g=-1+8=+7
1 AI Z, a slight excess of the
(i) 2HN03 + 2S02 + HP ~ N 203 + 2H2S04 purple Mno,- is present. A Since oxidation no. of Mn increases in the reaction, Mn is oxidised.
[4] miXture of the light purple
· (ii) Fe0 2- +Mn0 2 +4W ~ Fe ' +Mn0 4- +2HP
3
4 colour of that small amount · (b) (i) The experimental set-up is shown in the diagram below:
(b) (i) Describe the experimental procedure you would use to measure the of MnO,- with the yellowish
Fe>' causes the colour of Temperature= 25 oc,----{VV'}----
standard electrode potential of the l,(aq)ll·(aq) system. voltmeter
the solution to appear salt bridge
(ii) What effect would an increase in the concentnation of iodide ions have -H, (g) at 1 aim pressure (b) (iQ From the Data Book·
on the E.,., of this system? [4]
Ot<Jl99. let,
AI Y, a relatively large ex-
(c) Use the Data Booklet to predict the reactions that would occur when the E.. of 1 (aq) + 2e· ~
cess of MnO,- which is in- 1.0 mol dm'' of 1.0 mol dm''of H' (aq) 2

following pairs of solutions are mixed. Calculate theE:, and write an equa- tensely purple is present so I, (aq).and r (aq) PI electrode 2l·(aq) is -1{).54 v.
that tts colour dominates In connecting the l,(aq)
tion for each reaction. that of the yellowish Fe~ so The temperature is maintained at 25 oc. /1-(aq) half-celllo the stan-
(i) aqueous iron(ll) sulphate and acidified dichromate(VI) that the colour of the solu- dard hydrogen electron, 1,
[4] tion is purple. To determine the standard electrode potential f 1h
(ii) acidified manganate(VII) and aqueous sulphur dioxide a solution containing iodine and pot . . d? e l,(aq)!l-(aq) system, rs reduced while H2 is
1 mol dm"') is r . assrum 10 rde (each of concentration oxidised. Hence
{J01/P1!03]
This is the l,(~}~l~~;rh:l~:::~um electrode is dipped into this solution.
E"" =E111
2
_ =E.
H IH 2

~~~~:!:~:~~i:~~~:~~~~~~o~~:~~~~e~o~~i=~ss~n~a~~~~~~~~g~~~~~~
lion 1 mol dm' and h d nrng Y regen rons of concentra-
Increasing [l·(aq)] decrea·
ses E,
1 11
_ so that E., dec-
connected as shown io ~~~~~d ~~! ~~~~ pres~ure of 1 atm. A voltmeter is reases.
bridge is used. · age. 0 complete the circuit, a salt
j

rl
 Page 4 topic 6 Electrochemist!Y._
to_p_ic 6 E/ecjrochemistry Page 5
~CORNER
The reading on the voltmeter y V is noted. If electrons flow from the. l,(aq)/
Suggested Solution: ~CORNER
1-(aq) half-cell to the standard hydrogen electrode, the standard electrode (a) Bauxite
potential of the l,(aq)/1-(aq) system is -y V. If electrons flow from the stan-
dard hydrogen electrode to the 12(aq)!l-(aq) half-ceil, the standard elec- (b) (i)
trode potential of the l,(aq)/1-(aq) system is +Y V. (b) (i) The aluminium obtai-
ned by this method is 99%
(ii) An increase in the concentration of the iodide ion causes the E""' of the pure. The cryolite remained
system to decrease. Bauxite dissolved~---­ unchanged so that only
in molten cryolite bauxite needed to be
(c) (ij From the Data Booklet added as required. Due to
~-Molten aluminium the reaction with oxygen,
Cr 0/- + 14W + 6e- ~- 2Cr
3
2
• + 7H20 E" = + 1.33 V the graphite anode gets
Fe 3... + e- ~ Fe 2 + E" = +0.77 v burned away and has to
Bauxite (impure AI,O,) is first treated chemically to obtain pure Al 0 which be replaced, usually after a
2 3
For the reaction between Fe'• and acidified Cr,o;-, is then dissolved in molten cryolite (Na3 AIF,) and electrolysed. Cryolite is period of twenty days.
added to lower the melting point of the mixture and to increase the elec-
E:, =+ 1.33-0.77 =+0.56 V > 0 V
11
=> reaction is energetically feasible. trical conductivity of the molten mixture. Molten aluminium i.s obtained at
3 the graphite cathode and being denser than the bauxite and cryolite
Fe 2 • is oxidised to Fe 3• while Cr20/- is reduced to Cr •. mixture, sinks to the bottom and is tapped off separately. Oxygen is pro-
3 3 duced at the araphlte anode.
Cr 0/-(aq)+ 6Fe 2•(aq)+14H•(aq)----> 2Cr •(aq)+6Fe •(aq) + 7H20(1)
2

{ii) From the Data Booklet (ii) At the cathode: Al 3 + (/) + 3e- ----t AI(/)

MnO - + BH' + 5e- ;:----' Mn2 • + 4H 20 _E" ~ +1.52 V At the anode: 20 2 -(1) ----t 0 2 (g) + 4e-
4

so/· +4H' +2e- ~ so 2 +2H20 E" = +0.17 v (iii) Under the high temperature of the reaction, the oxygen produced reacts
with the graphite anode to give carbon dioxide:
For the reaction between SO,(aq) and acidified Mno,-.
0 2 (g)+C(s) ----t C0 2 (g)
E:, 11
= + 1.52-0.17 = + 1.35 V > 0 V => reaction is energetically feasible.
(c) Two advantages of using aluminium in the making of vehicles:
2
S0 is oxidised to SO/- while MnO 4 - is reduced to Mn •. 1. Aluminium is corrosion resistant due to protection by a layer of dense and
2
inert aluminium oxide.
'!:i 2Mn0 -(aq} + 5S0 (aq) + 2H 20(/) ----> 2Mn2 •(aq) + 5SO/-(aq) + 4W(aq)
;ji: 4 2
2. Aluminium is lighter than steel.
.. ::11

'·II
i,l!'l Question 3 Question 4
!fill
i,~ Aluminium is the third most abundant element in the Earth's crust, occurring
Architectural and other models are often made from brass. The pattern of, say,
combined in many minerals. a window frame is drawn on the brass using a special ink and the unprotected
(a) Name a mineral from which aluminium may be extracted. [1) brass removed by etching. The outline of the window frame remains.
(b) (i) Describe with the aid of a diagram, the electrolytic extraction of alu- (a) Brass is a mixture of copper and zinc. When a piece of brass is placed in
minium from purified aluminium oxide. State what the electrodes are dilute hydrochloric acid, only one of the metals present dissolves.
made of.
(i) ·.t\rrite an equation for this reaction.
(ii) Give an ion-electron equation for the electrode process
(ii) Use the Data Booklet to explain why one metal dissolves and one
at the cathode, .metal does not dissolve in dilute hydrochloric acid. [3]
at the anode.
i; [8) (b) The process of etching brass involves dissolving the unprotected brass in
..1 (iii) What further reaction takes place at the anode? a suitable .reagent. In practice, the sample is placed in aqueous iron(lll)
(c) Much of the bodywork of trains, aircraft and ships is made from aluminium chloride until all of the unwanted brass has been removed.
rather than from steel. State two advantages of using aluminium in the
![,, making of vehicles. [2) (i) By using the relevant £" values, explain why both the components of
[J02/P2/Q3} brass are soluble in aqueous iron(lll) chloride.
(ii) Write an ionic equation with state symbols for the reaction between
copper and aqueous iron(lll) chloride. [3)
 topic 6 Electrochemistry Page7

~CORNER
Page 6
topic 6 Electrochemistry ~CORNER
For the reaction between Cu and H•, E~n = 0-0.34 V = -0.34 V < 0. Thus (a) & (b) For a redox reaction to
. the two electrodes in a Daniell cell. The cell is set up be energetically feasible under st-
(c) Copper and z1nc are reaction is not energetically feasible under standard conditions and Cu andardconditions, E;,=E:-E~
as below. does not dissolve in "dil HCI. should be positive (where
voltmeter Ef: =standard electrode poten-
(b) (i) E" values for reduction of Fe"' to Fe'' is +0.77 V. tial of substance reduced and
zinc rod
copper strip For the reaction between Zn and Fe"', E:.,, = 0. 77- (-0. 76) V = +1.53 V> 0. Et = standard electrode poten-
tial of substance oxidised.)
Thus reaction is energetically feasible. under standard conditions and Zn Thus, Ef: must be greater
is reduced by Fe'' to Zn''. Since zinc chloride is soluble, Zn is soluble than Et for a reaction to be ener-
1.0moldm-• in aq Fe"'. getically feasible under standard
t.Omoldm- 3 copper(ll) sulphate corxf4K>ns.
zinc sulphate
For the reaction between Cu and Fe"', E:.u = 0.77-0.34 V = +0.43 V > 0. Since E.. of H" is greater than
Thus reaction is energetically feasible under standard conditions and Cu
is reduced by Fe"' to Cu2'. Since copper(\1) chloride is soluble, Cu is E.. of Zn, reaction between H·
porous partition soluble in aq. Fe'•. and Zn is energetically feasible
under standard conditions and H·
!rode processes that occur. (ii) Cu(s)+2Fe 3'(aq) ~ Cif'(aq)+2Fe 2'(aq)
(i) State half equations for the two e1ec oxidises Zn. Since E.. of H" is
copper electrode (c) (i) copper electrode: Cif'(aq)+2e- ~ Cu(s)
smaller than E.. of Cu. H" does
Zinc electrode . .?
• the external c~rcu1t. zinc electrode: Zn(s)- Zn2'(aq)+2e- not react with Cu.
(ii) In which direction will the electrons 11 ow In
(ii) from zinc electrode to copper electrode .Since E.. of Fe" is greater than
from ................................................... to···················································
E.. of both Zn and Cu. Fe3•
h w in the above cell? [31 (iii) +1.10 v
(iii) What voltage should the voltmeter s o . oxidises both Zn and Cu.
ents are often soldered together. Dunng (d) (i) Water (or H' from self-ionisation of water) is reduced at the brass elec- (c) Electrons flow from the
{d) Models made fr~m bra~s compon hos horic acid, are used in order to_ help trode which is the cathode. anode (zinc electrode where oxi-
soldering, ac1d1c fluxes • such as_ P P !ten leaves the brass tam1shed dation takes pla1=9 and electrons
the solder form a strong joint. ThiS process o (ii) The bubbling of hydrogen gas at the brass cathode dislodges the impu- are produced) to the cathode
rather than shiny. d b setting up the following cell. rities from the brass and hence cleans the brass and restores its shine. (copper electrode where reduc-
Such a model can be cleane Y (iii) To neutralise the acidic fluxes that are used.
tion takes place and electrons are
connecting taken in).
E:n=E~~E;

zinc
Question 5 =+{).34-(-0.76) =+1.10 v
brass model (a) What do you understand by the term standard electrode potential? [2] (d) 0) Since brass contains
copper which is less easily oxidi-
(b) The following cell was set up between a copper electrode and an unknown sed than zinc, the zinc electrode
aqueous
metal electrode M'•(aq) /M(s). The standard cell potential was found to be is the enode where oxidation
aqueous sodium
carbonate 0.76 V, and the copper foil was the positive electrode. takes place while brass elect-
sodium rode is the cathode where· reduc-
carbonate
tion takes place. Electrons flow
direction of electron flow
from the zinc anode to the brass
porous partition cathode, The electrolyte contains
Na·, CO,>-, H" (from self-ionisation
(I) Suggest a reason why hydrogen is given off at the bras~ electrod=~t of water) and OH· (from se~­
ionisation of water and hydroly-
(ii) During soldering with the flux the brass mo~el be~~:~~i~~Y-
Sugg r-------;V!-------- sis of the weak base CO,>-) and
why this process cleans the brass and res ores . . of course water. The three sub-
"t e as an electrolyte, tor us1ng stances which can be reduced
(iii) Suggest one reason, other ~han 1s us [3] unknown metal
copper foil
are Na·, H" and H,O. Na· is not
aqueous sodium carbonate In the cell. wire,M reduced as it has a very low E"
[N02/P2!01]
value. H" may be reduced to H,
(2H· + 2e- --> H,) or H20 may
CuS04{1 mol dm-") be reduced (2 H, 0 + 2e· --> H,
suggested Solution: + OH·). Both .reaction gives out
H, and may be acceptable as an
(a) (i) Zn(s)+2HCI(aq)----> ZnCI2(aq)+H2(g) . answer. ·
-0 76 v 0 v and +0.34V respectively.
{il) E" values for Zn, H and Cu are . '
d H• E" - 0-(-0 76) V = +0.76 V > 0.
For the reaction between Zn an • cell - •
(I) Use the Data Booklet to calculate the standard electrode potential of
Thus reaction is energetically feasible under standard conditions and Zn the M''(aq) /M(s) system.
dissolves in dil HCI, forming soluble ZnCI,.
 PageS topic 6 Electrochemist['f_
Page 9
toQic 6 Electrochemistry
~CORNER
(ii) Draw an arrow over the voltmeter symbol in the above diagram to show
II. The metal will dissolve and effervescence will occur. ~CORNER
the direction of electron flow through the voltmeter. M{s)+ 2W(aq)----. M2 +(aq)+H2 (g)
(iii) Predict the outcomes of the following situations. Describe what you Metal M will react with H· to form H, gas.
might see and write ionic equations for any reactions that occur.
(c) (i) d.c. source
A rod of metal M is dipped into a solution of 1 mol dm"" CuSO ,.

II
electrolyte: aqueous copper( II) sulphate
Dilute sulphuric acid is added to a beaker containing a powdered
sam~le
of metal M. [6]
2
(c) Because of its increased scarcity, cheaper copper ornaments are no longer (ii) Cu +(aq) + 2e- -----> Cu(s)
made from the solid metal, but from iron that has been copper plated. 0.500
(i) Complete the following diagram showing the set-up for a copper elec-
ncu = 64 = 0.007813 mol

troplating process. Show clearly the polarity (+/-) of the power source, n9 • ~ 2 x ncu ~ 0.01563 mol
and suggest a suitable electrolyte.
d.c. source
Q ~n
.- xF ~ 0.01563x96500 ~ 1507 C

t~9.= 0.500
1507
~3015s~50min16s
Q'
Questiou 6

(a) By means of a fully labelled diagram, describe how the standard electrode
potential of the Fe"•/Fe'+ system can be measured by using a standard
!object to be plated hydrogen electrode. [4]
electrolyte:
(b) Hydrogen peroxide and an acidified solution of tin(ll) ions react according
to the following equation.
(b) (i) Since Cu is the posi-
2
tive electrode. it is a cathode Hp2 (aq)+2W(aq)+Sn +(aq)-----> Sn4 +(aq)+2Hp(l)
where reduction takes place. For this reaction
(ii) A current of 0.500 A is passed through the electroplating cell. Calculate
the time required to deposit a mass of 0.500 g of copper on to the Cu2+ + :ie- --> Cu (i) calculate the changes in oxidation numbers that occur, and
ornament. [5] Hence, metal Mis the nega-
(ii) use the Data Booklet to calculate the E_;:, 11 of the reaction.
[J03/P4!01] tive anode where oxidation

~1\:
takes place. Hence predict wheliher the reaction is feasible in the left--> right direction. [2]
M--> M2+ +2e-

~
(c) For each of the following situations, use E" data to predict what might
i Suggested Solution: When the 2 half-cells are
I happen when solutions of the two reagents are mixed together. Write
(a) The standard electrode potential, E&, of an element is defined as the poten- coupled, the E! can there- balanced equations for any reactions that occur.
·~:1
11
tial difference between a .standard hydrogen half-cell and a half-cell of the
lore be computed by.
element in a solution of its ions at 1 mol dm"" and at 298 K and 1 atm. (i) Ag+(aq)+Fe2 •(aq) ----7
i!
E~ 8 = E~1 • 1 eu- E;. 1M
11\ (ii) V3 +(aq)+Cif+(aq)----->
:~j! E"cell =E" (4]
(b) (i) eu'" /Cu -E·"
M'" /M (iij Electronsflowfromthe
negative electrode to the [N04/P3!02]
0.76 = 0.34- E:,.,M posttive electrode in the

I
ii!l!.
l:!i
E;,. /M = -0.42 v external circuit. Suggested Solution:
(a) (a) The required conditions for
t
1.:: (ii) electron flow )
(ti) Frorn the e· ;we can
see that Mis 3 more reactive Hydrogen
standard electrode poten-
tial are
jii metal· compared to cu. gas (1 atm)

~ji\[ -0- Hence, it will reduce Cu'" to

· Cu and itself being oxidised 1 mol dm-•
Platinum 0

o
T=298K
concentration of ions =1
(iii) I. A pink coat of copper on metal M will be formed. to M'". Depending on the W(aq) mol dm"'
5 1 mol dm-• Fe3 +
~
3
j I
The blue colour of the solution will lade. extent of the reaction (the
reaction stops when M is
Platinum
..........- ....:r,.:;;
~~~:=~~;,:Jh-,~
1 mol dm- Fe 2+
o pressure of gas = 1 atm
2
M(s) + cJ+ (aq)---> M +(aq) + Cu(s) completely covered by Cu), (NOT pressure of
the solution may remain blue 298 K atmosphere)
Metal M will displace Cu from the solution.
or take the colour of M'". The reading on the voltmeter gives the electrode potential of Fe 3+/Fe'+.

'-!;.
b"J;·
 topic 6 Electrochemistry Page 11
Page 10 ~CORNER
topic 6 Electrochemistry ~CORNER
Question 8
(b) (i) Sn : Increases from +2 lo +4 by 2 units. Zinc chloride is one of the most im . .
cell _batteries, as a flux for solderfnort:nt c~m~ounds of zinc. It is used in d
0 : decreases from -1 to -2 by 1 unit.
cooling towers and in the manufactugr ndf !Jnnmg, as a corrosion inhibitor
e o rayon.
~
(ii) £~1 = 1.77-0.15 = +1.62 V >0 extra information
hydrogen electrode to measure the ~w ~ow you could use a standard
The reaction is energetically feasible under standard conditions. (a) Draw a fully labelled diagram to sh
(c) (i) The reaction does not zmc. s an ard electrode potential, E" , of

(c) (i) Ag•(aq)+Fe2•(aq) ~ Ag(s)+Fe "(aq)

3 go to completion since E:, 6

is near zero. As the reacflon (b) The electrolysis of zinc chlorid [ ]

depending on the conditions usedcan give different electrode products
E:u = 0.80-0.77 = +0.03 V > 0
Ag" will oxidise Fe". to· Fe.. while itself is reduced to metallic Ag.
proceeds, both [Fe"] and
[Ag"] decreass. Hence,
Suggest the products formed at :a~h electrode in the followJ·ng cases. One'
space has been filled in for you.
2 E"'J"IAg decreases and
(ii) 2V 3•(aq)+Cu2•(aq)+2HP(ll---> 2V0 •(aq)+Cu(s)+4H•(aq) conditions product at anode product at cathode

EF•'" IF•'" increases, and ZnCk(1) chlorine

E:u = 0.34- 0.34 = 0 V 3 2

;:zZ,n~C~k~(dfflil~ut~e~a~q~u~eo;u~s~)~:=~-t--------------t------------=~
Since E:u = 0 V, no reaction takes place when v • and Cu • are mixed. ZnCk (concentrated aqueous)
E.,, decreases and be-
comas 0 eventually. When I
this happens, a state of 3
Question 7 dynamic equilibrium is
(c) Use the following data 10 eth . fl
(a) Predict the products formed at the anode, and at the cathode, when the attained and the 4 species to construct a Born-H~be?cyc::; ~~h r~le~ant data from the Data Booklet
exist in equilibrium. of zmc chloride. ca cu ate a value for the lattice energy
following liquids are electrolysed using inert electrodes.

(i) NaBr(l)
(iQ Since E:, = 0, there standard enthalpy change of formation of ZnCk 415 kJ mot·'
1
is no driving force lor the
(ii) NaBr(aq) reaction to proceed. Simi- standard enthalpy change of atomisation of Zn(s) + 131 kJ mot·'
(iii) CuF,(aq) larly, if Cu and VO'" are
electron affinity per mole of chlorine atoms 349 kJ mot·'
In each case explain your reasoning, using data from the Data Booklet. [6] mixed, the reverse will not
[N06/P3/Q 1] [3]
take place either.
{J07/P4/Q1{a,b,c)]

Suggested Solution: Suggested Solution.

NaBr(aq) CuF2(aq)
(a) NaBr(l) (a)
H, Cu
Cathode Na
0, (a) To complete the diagram
Br2 02
Anode following Hems should be
shown:
(I) In NaBr(l), the ions present are Na· and Br. Hence,
salt bridge, voltmeter zinc
Na•+e· ~ Na
metal in Zn'" and H' 'in H·
Zn 2• (aq)
sr· ~ 2-sr2 +e· Platinised · 1 mol dm.,
and PI electrode, all solu-·
2 platinum lions at 1 mol dm"', 298K &
electrode one aim pressure.
(il) In NaBr(aq), the ions present are Na., Br, H+ and OH-.
H• is discharged due to its higher £" (0 V) compared to Na• (-2.71 V). W(aq)
1 mol dm-3
1
W +e - ~2 H2
(b)
OH- ion is discharged preferentially over Br due to its lower£" value
I conditions product at anode I product at cathode
ZnCk(1) chlorine Zinc
(OH- : +0.40 V, Br : + 1.07 V).
40H- ~ 2H 20+0 2 +4e· ZnCk (concentrated aqueous) Chlorine hydrogen

(iii) In CuF,(aq), the ions present are Cu'•, F·, H• and oH·. ZnCk (dilute aqueous) Oxygen hydrogen
Cu"• is discharged since ~ has a more positive £" (+0.34 V) compared to H•

(0 V).
Cu2• +2e- ~ Cu
OH· is discharged since tt has a more negative E" (+0.40) compared to Fe

(+2.87 V).
40W --> 2H 20 + 0 2 + 4e·
 Page 12 topic 6 E/ectrochemist!Y__
top_ic 6 Electrochemistry Pa_ge 13
~CORNER
(c)
gas phase ions
(c) Two labelled routes of the
Suggested Solution:
~CORNER
(a) (I) A: C/2 (chlorine)

lA reaction must be shown to

[' cr (aq)
create a relationship. B: NaC/ or HC/ or (a) (i) Salt Bridge connects
elementsr B = t>H, (ZnC/1) = - 415 C: Salt bridge or KNO, (aq) the lwo half cells. It com-
kJ mol·'- 0: Platinum I PI pletes the circuit by allowing
the passage of electricity
A =~H~ton.isatton of zinc E: Mixture of Fe'· + Fe'' salts. 1 moldm-3 concentration. between electrodes but
ZnC/2 (s) = + 131 kJ mol.
(ii) E !,, = E !UCIJon- Eo:oti~n
physically separates the
A+LE = B =0.77-1.36 = -0.59 V. lwo ha~ cells.
LE =8-A 6.~st & 2nd. ionisation energy Direction of electron flow: from right to left
The standard cell
= (-415) --(131 +9os+ 1730) -{244 + 2(-349)} = (908 +i730) kJ mol·'-
(b) (i)
= -415-2315 = -2730 + potential E! , is a
1
liH,;.,nd ene•gy (C!-Cij = measure of the tendency
Lattice Energy= 2730. kJ mor
+ 244 kJ mol·' of electrons to flow
through the external circuit
l'i~ A (CJ atom) = - 349 kJ under standard conditions
Question 9 mol·'- of 25"C and 1 atmospheric
Chlorine gas and iron(ll) ions react together in aqueous solution as follows. pressure and 1 mol dm-3
LE= concentration. It is the
C/ + 2Fe'' --> 2CJ- + 2Fe"
Hi AH~IomisationCZn)
2
[A (ZnC/ ) -
maximum potential
(a) The following diagram shows the apparatus needed to measure the E:,, 2 Applying Hess' law
difference between the
• f !
for the above reaction; .+AH1s1 & 2nd I.E. -\AHa F. iG1--Ch t.H ~ = b.H:.+t,H-:;_ electrodes. E!; =E-:- -E~
+2(t.HtA(CJ))}] t>H:;_= t>H~-b.H:. i.e. E!', =E!...., -E,!.,..,
A put-the values and calculate
= [(-48.5) + 3(-167.2}] -(-399.5)

-lll~~~\~
LE as given in answer.
E = -550.1 + 399.5 = 150.6 kJ/mol- 1
c (ii} 2Fe
3
' +Cu-+ 2Fe 2 • +Cu 2 •
D E~ = 0. 77- 0.34 = +0.43V
~---_;--:::-_ - ------
B
(i) In the spaces below, identity what the five fetters A- E in the above
Question 10
il diagram represent.
(ii) Use the Data Booklet to calculate the E!,, for this reaction, and hence
IrI decide which direction (tell to right, or right to left) electrons would flow
through the voltmeter V when switch S is closed. [7]
Chlorine gas is manufactured by the electrolySis of bnne using a diaphragm
cell.
(a) Write ha\1-eq!Jations, including state symbols, for the reac.tions occurring at

I each of the electrodes of a diaphragm cell.

(b) lron(ll\) chloride readily dissolves in water.
I
FeCI (s)--> Fe''(aq) + 3CJ·(aq) anode ...............................................................................................................................
~ 3

Il
(i) Use the following data to calculate the standard enthalpy change for this cathode ....................................................................................................................... [2]
process. (b) In the diaphragm cell, the anode is made of titanium and the cathode is
1 made of steel.
species b.Ht /kJmol-
Suggest why steel is never used for the anode. [1]
~~ FeCI3(s) -399.5
Fe 3'(aq) -48.5 (c) One important product made in the diflphragm cell is formed in aqueous
00 solution.
'\~t1 1 Cr{aq) -167.2
(i) What substance is produced in aqueous solution in the diaphragm
~
t (ii) A solution of iron( Ill) chloride is used to dissolve unwanted copper from cell?
~ printed circuit boards.
II'
d When a copper-coated printed circuit board is immersed in FeCI3(aq), (ii) Explain, with the aid of appropriate half·equation(s), how this compound
~ the solution turns pale blue. is formed by electrolysis. [3]
w
il'
Suggest an equation tor the reaction between copper and iron(ll\) chlo-
ride and use the Data Booklet to calculate the E. for the reaction. [4]
[J08/P4/01]

~LIH.
 topic 6 Electrochemistry .Page
. 14 topic 6 Electrochemistry

. an d will form compoun ds by direct comb1nat1on

(d) Chlorine is very reactive
~CORNER Page 15
Suggested Solution:
with many eiements.
Describe of
what you wou ld see when
. . assed over separate heated
horu schlonne IS P · for the (a) NaCI(s): observation: Dense white fumes ~CORNER
samples sodium and phosp . In each case write an equation [4]
equation: 2NaC/ + H2S04 -+ Na S0 + 2HC/
2 4 (a) Slrong H,so, Will displace
reaction. hi "de SiC/ each dissolve NaBr(s): observation: Brown fumes weak aCids i.e. HC/ &HBr,
.
(e) Magnes1um chi on"de • MgCI,. and silicon tetrac on , ,.
but HBr Will further react
in or react with water. t· formed in each case. equation: 2Na8r + 3H2SO4 -+ 2NaHSO + 2H 0 + S0 + Br with H,so, to produce so,
· te pH of the so 1u Jon
Suggest the approxJma
4 2 2 2 & Br,
(b) E..,. values: Cf,! Ct = 1.36, Br I Br- "' 1.07.
2
2HBr + H,SO,--> S0 + Br,
·····.·th···;~~-~i~·~;·~~-~quation, valu~~j
.......... SiC/,................... . ............ .
MgC/,. the difference between the two
E..,.be
not q
of oxidised
is more positive, and stronger oxidising agent therefore HC/ will
to chlorine. + H,O
1

Expla1n, WI
(c) Suitable reductant: Sn4• /Sn 2 +,
E ... = 0.15 V
[N08/P2103] 2
Equation: Sn • + Br2 -+ Sn'• + 2Br-
(c) Any reductant having
Suggested Solution: E ..,. =reduction - oxidation E ..,. value less than 1.07
v will reduce Br, lo Br ion.
(a) anode: -
C1(aq) ~ ..!.ct
2 2 <g1+ e-
= 1.07-0.15 = 0.92

cathode: Hiaql + e- ~ 21 H2 <gl Question 12

(b) Because the iron in steel will react with chlorine. Iron metal and its compounds are useful catalysts in certain reactions.
(a) Apart from its catalytic activity, state two properties of iron or its
(c) (i) Sodium hydroxide (NaOH) compounds that show that it is a transition element. [2]
(ii) 2H20 + 2e- ~ H2 + 20H- (b) You are provided with a solution of KMnO, of known concentration in a burette.
Outline how you could use this solution to find out the concentration of
Ieaving OH- in solution as NaOH . Fe'•(aq) in a solution. You should include relevant equations for any
reactions you describe. [4]
(d) sodium: Sodium burns with a yellow flame an d forms a white solid. (c) For each of the following equations, write the oxidation number of the
(d) p bums on heating to give
element printed in bold underneath its symbol, and balance the equation
2Na + C/2 ~
2NaC/
hosphorus: Phosphorus bums with
a white flame and forms a colourless
PCIJ" With excess of Cl,,
PCI, is oxidised to PCI,.
by adding appropriate numbers before each species.

~quid(PC/,) OR a white solid PC/,.

(e) MgC/3 is an ionic co~­ (i) ···-·· Mno.; + ...... S02 + ...... H2 0-+ -····· Mn 2 • + ...... so~-+ ...... w
P4 + 6C/2 ~ 4PC/3 pound. When dissolved m oxidation numbers:
water the solution is
PC/3 + C/2 ~ PCis slightly acidic (pH = 6.5). (ii) ...... Cr2 o~- + ...... N0 2 + ...... w ~ ··-··· Cr3• + ...... No;+ ...... H 0
oxidation numbers: 2
(e) MgCI,: 6.5 SiCI,: 2 . SiCI, is a covalent co_m-
MgCI dissolves with?ut reaction pound & hydrolyse to g1ve
fumes of HC/ gas, and so- [6]
SiC/ 'reacts with water (Hydrolyse) (d) Outline the role that Fe,. ions play in catalysing the reaction between iodide
~ Si02 + 4HCI
lution is acidic (pH = 3). ions and peroxydisulfate(VJ) ions.
SiC;, + 2Hp

[2]
Question 11 If · cid [N09/P4103]
Suggested Solution:
(a) Describe the observations_ you ~o~ C/ (s) and NaBr(s). Write an equatJon
. d make when concentrated su unc a.
is added to separate portions o a [4] (a) (i) variable oxidation status
for each reaction that occurs. D I Booklet, explain how the (ii) able to form complex ions
(b) By quoting relevant E..,. d~ta fr~m ~hr:lat! t~ the relative oxidising power
observations you have descnbed a ov [2] (b) equation: Mno:; + BW + 5Fe 2 • -+ Mn 2• + Fe 3• + 4H 0
of the elements. 2
method: Measure a known volume of Fe'• (aq) with the help of a pipette and
..,. data choose a suitable reagent to convert Br, place in conical flask. Add an excess of dilute H SO,. Titrate the mixture against
(c) By referring to relevant E I t the E..,. for the reaction. [3] 2
ation and calcu a e Mno,- solution of known concentration till permanent pink colour appears.
into Br. Write an equ (J09/P4/Q2]
Note the volume
consistent readings.of MnO,- (aq). Repeat the titration and take average of
!
l
 topic 6 Electrochemist,Y Page 17
Page 16
to11ic 6 Etectrochemist!;L ~CORNER
(i) Calculate the following, using appropriate data from the Data Booklet.
~CORNER
... ?.. MnO~ + ...~.. 50 2 + ...?.. H20--> ..?... Mn ' so~-+ ..~... H' number of moles of copper produced at the cathode
2
+ .. !?..
(c) (i) number of moles of electrons needed to produce this copper
+4 +2 +6
number of moles of electrons that passed through the cell
oxidation numbers: .~! (ii) Hence calculate the percentage of the current through the cell that has
Cr 0~- + .. ~.. N0 +-~··· H'--> .?... Cr +-~··· N03 ..... ~., H 0
2
3 2
.}... ' been 'wasted' in dissolving the impurities at the anode. [4]
2
(ii)
.:1:.~. :!:~.
(c) Nickel often occurs in ores along with iron. After the initial reduction of the
oxidation numbers: .:1:!?. :!:?.. ore with coke, a nickel-iron alloy is formed.
Use data from the Data Booklet to explain why nickel can be purified by
a similar electrolysis technique to that used for copper, using an impure
is a homogeneous catalyst
(d) Fe 3' 2
nickel anode, a pure nickel cathode, and nickel sulfate as the electrolyte.
oxidises 1- to 12 and reduces itself to Fe ' Explain what would happen to the iron during this process. [2]
Fe 3 '
2 [N10/P4/03]
2Fe 3' + 21- --> 2Fe ' + 12
sp~- to so~- and oxidises itself to Fe '
3
reduces
Fe2 "'"
2Fe2 ' + sp~- --> 2Fe + 2SO~-
3
'
Suggested Solution:
(a) (i) Cu(s) --> Cu2 ' + 2e-

(ii) E~ for Ag•/Ag is O.BOV more positive than 0.34V for Cu'' /Cu(s) . Hence
silver is less reactive than copper and will not oxidise.
Question 13
The electrolytic purilication of copper can be carried out in an apparatus similar (iii) E~ for Ni'•/Ni is -0.25V. Nickel will readily oxidise and forms solutions
to the one shown below. of Nickel ions.
- . ~~-_, (iv) Cu 2' (aq) + 2e- --> Cu(s) (Pure copper)

pure copper cathode (v) E~ for Zn 2' /Zn is -Q.76V. Hence Zn 2' will not reduce at cathode.

impure copper anode~ (vi) Cu''(aq) are reduced at cathode to copper solid. Thus blue solution fades
v VCuS04 (aq)
away leaving Zn'• and Ni 2 ' in solution.

anode 'sludge'~ 225

(b) (i) Amount of copper=
63.5
= 3.5433 =3.54 mol
The impure copper anode contains small quantities of metallic nickel, zinc and Number of electrons needed= 2 x 3.5433 = 7.087 = 7.09 mol
silver, together with inert oxides and carbon resulting from the initial reduction

of the copper ore with coke. No. of coulombs= lxl = 20x10x60x60 = 720000 C
The copper goes into solution at the anode, but the silver remains as the metal
and falls to the bottom as part of the anode 'sludge'. The zinc also dissolves. 96500 C of charge is earned by 1 moles of electrons.
720000
(a) (i) Write a half equation including state symbols for the reaction of copper l 720000 C of charge is carried by = 7.461 moles of electrons.
at the anode.
~ 96500
(ii) Use data from the Data Booklet to explain why silver remains as the
i 7.46 moles of electrons passed through the cell.

metal.
(iii) Use data from the Data Booklet to predict what happens to the nickel
I 7 461 7 087
(il) Percentage wasted= < · - · ) x100 = 5.01%

at the anode.
(iv) Write a half equation including state symbols for the main reaction at ll (c) E~ for Ni'' / Ni = -Q.25V
7.461

the cathode.
(v) Use data from the Data Booklet to explain whY zinc is not deposited

on the cathode.
I (
E~ for Fe'• I Fe = -Q.44V

Iron in the alloy will dissolve because Iron is more reactive than Nickel.
(vi) Suggest why the blue colour of the electrolyte slowly f;3.des as the ~
electrolysis proceeds. ·
(b) Most of the current passed through the cell is used to dissolve the copper
at the anode and precipitate pure copper onto the cathode. However, a
(7l

small proportion of it is 'wasted' in dissolving the impurities at the anode

lI
which then remain in solution.
When a current of 20.0 A was passed through the cell for 10.0 hours, it was
found that 225 g of pure copper was deposited on the cathode. I
~~-~
 :Jopic 7 (1)
explain qualitatively the differences in behaviour be
bases and the pH values of the.
tion.
.
. .
_tween strong and weak ac1ds and
lr aqueous solutwns m terms of the extent of dissocia-

(j) explain the terms pH K pK K d

' •' •' .. an use them in calculations.
(k) calculate [H•(aq)) and H I
. p va ues for strong and weak acids and s t rong bases.
{I)
"' :xplal~ the choice of suitable indicators for acid-base titrations, given appropriate data.
lj {m)
descnbe the changes in pH during acid-base titra i
terms of the strengths of the acids and bases.
.
t ons and explam these changes in
Content !. (n)
(/) ~xplain how buffer solutions control pH.
Chemical equilibria: reversible reactions; dynamic equilibrium j (ii) d
I . escribe and explain their uses, including the role of HCO - . .
(i) Factors affecting chemical equilibria. m blood. , m controlling pH
(ii) Equilibrium constants.
i (o) calculate the pH of b r~ I . . .
u •er so ubons, giVen appropriate data.
(iii) The Haber process; the Contact process. (p) show understanding l d
o 'an use, the concept of solubility product, K .
2 Ionic equilibria (q) calculate K from t · · ,.
'P concen rations and vice versa.
(i) Bmnsted-Lowry theory of acids and bases. (r)
show understanding of the common ion effect.
(ii) Acid dissociation constants, K, and the use of pK,.
(iii) The ionic product of water, Kw.
(iv) pH: choice of pH indicators.
(v) Buffer solutions.
(vi) Solubility product; the common ion effect.

Learning Outcomes
Candidates should be able to;
(a) *explain, in terms of rates of the forward and reverse reactions, what is meant by a
reversible reaction and dynamic equilibrium.
(b) *state Le Chatelier's Principle and apply it to deduce qualitatively (from appropriate
information) the effects of changes in temperature, concentration or pressure, on a
system at equilibrium.
(c) deduce whether changes in concentration, pressure or temperature or the presence of
a catalyst affect the value of the equilibrium constant for a reaction.
(d) deduce expressions for equilibrium constants in terms of concentrations, Kc, and partial
pressures, K,
[treatment of the relationship between K, and Kc is not required].
tli
rot,
(e) calculate the values of equilibrium constants in terms of concentrations or partial pres-
],'
II sures from appropriate data.
:H: (j) calculate the quantities present at equilibrium, given appropriate data (such calculations
11 1
"tiIll1
will not require the solving of quadratic equations).
~~~~
.J!!I
(g) describe and explain the conditions used in the Haber process and the Contact process,
l:i
,II
as examples of the importance of an understanding of chemical equilibrium in the chemical
1;!1,,1 industry (see also Section 9.6).
Note: The additional teaming outcomes to be studied b A2 .

~
(h) show understanding of, and use the Bmnsted-Lowry theory of acids and bases.
topic 7 Equilibria Page 1 topic 7 Equilibria
~CORNER Page2
Suggested Solution:
2
~CORNER
(a) Mg '(aq)+20W(aq)--. Mg(OH) (s)
q?fil) rN (] dJ
2

(b) No. of mol of OH- needed to react with Mg'•

!J \91J fJ \!;a qpening ...... .. = Volume of NaOH required for equivalence point x [OH-(aq)] (b) From the graph, it can be
= 20 X 10-" X 1.0 = 0.02 seen that pH is maintained
2 at9desp~etheadditionolaq.
Question I No. of mot of Mg ' = .!.x no. of mol of OW= 0.01
2 . NaOH to the mixture (lor
volume of aq. NaOH rang-
In an experiment, 50.0 em' of aqueous magnesium chloride were titrated with 0 012
[MgC/2 (aq)] = [Mg ' (aq)] = ' -,"l = 0.2 mol dm-3 ing from 2.50 em' to 17.50
1.00 mol dm.., sodium hydroxide. The pH of the solution changed as in the · 50x10 em'). This is because OH-
diagram. · ·· (aq) is removed by precipi-
(c) (i) [OW(aq)] = 1 o-(''·PH! = 1x 1o-s mot dm-3 tation wnh Mg,.(aq) to form
insoluble Mg(OH) • After
concentr~tion = .!.x
2 2
14 (ii) [Mg ' (aq)] =.!. x original 0.2 = 0.1 mol dm' 3 about 17.50cm'ofaq. NaOH
2 2
have been added, almost all
2 Mg,.(aq) has been precipi-
(d) (i) Ksp = [Mg '(aq)][OH- (aq)f
.. _.,; tated out so that pH
changes rapidly. Theequiva-
(ii) Ksp =0.1x(1x10~) 2 =1x10'11 mol3 dm-9
tence point occurs when
20.00 em' of aq. NaOH is
(e) No. of mol of excess OH- = (30 - 20) x 10.., x 1.0 = 0.01 added and the amount of
0 01 OH· added just precipitates
[OW(aq)] = · ., 0.125 mol dm-3 out all the Mg,._
(30+50)x10 ·

pOH = -log[OH-(aq)] = 0.90

pH= 14-pOH = 13.1
9

8 Question 2

Nitrogen dioxide, NO,, is a brown gas that is a constituent of smogs caused

7 by cars in cities.

(a) Suggest how NO, is formed in a car engine and how it may be removed
6 from exhaust gases. [2]

(b) In the gaseous state, NO, can dimerise as follows.

1
2N02 (g) ~ N2 0 4 (g) 6.H =-58 kJ mot·'
volume of 1.00 mol dm.., NaOH(aq) added/em'
(i) Explain, with reasons, whether the above dimerisation is favoured by
(a) Write an equation (Ionic or molecular) for the reaction between aqueous high or low pressure,
MgC/ and aqueous NaOH. Include state symbols so that any precipitation ,
2 high or low temperature.
is clearly indicated. (1] ,
(ii) The NO, molecule has an unpaired electron on its nitrogen atom but
(b) Calculate the concentration, in mol dm..,, of the aqueous MgC/2 • (1]'
the N,o, molecule does not. Suggest a shape for the NO, molecule
(c) When 10 em' of aqueous N::~OH were added, and suggest a structural formula for N,o,. [5]
(i) calculate the hydroxide ion concentration from the pH of the mixture,
(c) At a temperature of 320 K and a pressure of 1.0 x 1O' Pa (1.0 atm), 0.50g
(ii) estimate the hydrated magnesium ion concentration, assumir.g that it of the gaseous, NO,fN,O, mixture takes up a volume of 190cm'.
is half the original concentration. [2]
Calculate the average M, of the mixture.
(d) (i) Write an expression for the solubility product, K.,, of magnesium hydroXide. (2]
(ii) Use your values from (c) to calculate this K... including the units. [2]
(d) At another temperature, it is found that the partial pressures of NO, and
N,O, at equilibrium are 0.4 atm and 0.6 atm respectively.
(e) Show by calculation why the pH after the addition of 30 em' of aqueous
Write an expression for K, and calculate its value, giving units. [3]
NaOH should be 13.1. [1]
[JOOIP210 1I [NOOIP1/01]
 PageS topic 7 Equilibria Page6
topic 7 Equilibria
~CORNER (ii) Let HA represent lactic acid. ~CORNER
Alternative Method: (c) (iij Whether the common
[H•(aq)] in the solution of lactic acid= 10-<>" = 3.715 x 10-<~ mol dm"".
Since the total pressure at equilibrium is 1.9 and the remai?ing partial indicators of methyl
pressure of steam is 0.1, the partial pressures of H, and CO IS 1.9-0.1 HA(aq) ~ H'(aq)+A-(aq) orange and phenolphthalein
can be used for an acid -
= 1.8. . [A-]= [H'] = 3.715x 10·3 mol dm- 3
Since the same amounts of H, and CO are produced in the reaction, base titration depends on the
partial pressure of H2 = partial pressure of CO = * x 1.8 = 0.9 atm. [HA] = 0.10-3.715x10-3 = 0.09683 mol dm-3
3
strength of the acid and the
base. Forstrongacid-strong
3
K =[H'](A-] (0.715x10- )(3.715x10" )=1. x10-4 ld -3 {t f) base titration, both methyl
43 0 3 s. ·
PH.. x Pco 0.9 x 0.9 • [HA] {0.09683) · mo m
K = - · - - = - - - =8.1 orange and phenolphthalein
p PH,O 0.1 can be used. However for
(iii) Since the titration is a weak acid - strong base titration, a suitable indicator
is phenolphthalein. weak acid - strong base ti-
tration, phenolphthalein but
{iv) No. of mol of NaOH used = 22.2 x 1O"" x 0.500 = 0.011 not methyl orange is a suit-
Question 4 No. of mol of lactic acid = No. of mol of NaOH = 0.011 able indicator while for a
(a) Outline the Bronsted·Lowry theory of acids and bases. [2] 1 00 strong acid - weak base
M, of lactic acid = · = 90.1
(b) The following is a list of compounds that react with or dissolve in water: 0.011 titration, methyl orange but
not phenolphthalein is a
sodium chloride, hydrogen chloride, silicon tetrachloride, ammonia, metha-
suitable indicator. Both
nol. Question 5
methyl orange and phenol- ·
water can react as either an acid or a base. Choose a compound from the
Sulphuric acid is used in many industrial processes of major importance. phthalein are unsuitable
above list with which water acts as
indicators for weak acid-
(i) a Bronsted base. The first stage in the manufacture of sulphuric acid is to pass air over burning
weak base titration .
sulphur.
(ii) a Bronsted acid. (iv) M,, relative molecular
The emerging gas has the following composition by volume.
Construct a balanced equation for each reaction. [3] mass, is a ratio and has no
sulphur dioxide 10% units.
(c) Lactic acid is a monoprotic acid which is an important flavouring com~o­ sulphur trioxide 0.2%
nent of many foods such as cheese, yoghurt and pickled cabbage. A solution oxygen 10%
of lactic acid in water containing 0.1 0 mol dm"" has a pH of 2.43.
nitrogen etc. 79 - 80%
(i) Is lactic acid a strong or a weak acid? Explain your answer.
{a) (i) Write an equation for sulphur burning in air.
(ii) Use the data given to calculate the value of K, for lactic acid.
(ii) Suggest why the air is passed so fast that only ha~ the oxygen is used. (2]
'' (iii) Suggest a suitable indicator for the titration of lactic acid with aqueous
sodium hydroxide . The emerging gas is passed over a catalyst maintained at 450 - 550 oc in the
.! reaction chamber.
(iv) A sample of lactic acid having a mass of 1.00 g was dissolved in water
and titrated with 0.500 mol dm~ sodium hydr?xi~e. It was found that (b) Name the catalyst used in the Contact process. [1]
22.2 em' of hydroxide was reqUired for neutralisation. Calculate the M,
Sulphur trioxide is formed in 98% yield; 2% of sulphur dioxide remains unconverted.
of lactic acid. [7]
[N01/P1/Q2} t.H= -197 kJ mol-1
(c) The high yield is only achieved under certain conditions.
After each condition explain why this leads to an increased yield of sulphur
Suggested Solution: trioxide.

(a) The Bronsted-Lowry theory of acids and bases states that ~cids are pro!on {I) There needs to be an excess of air in the reacting gas mix1ure.
donors while bases are proton acceptors. Hence, an ac1d-base react1on (ii) The catalyst needs to be cooled.
involves the transfer of a proton from the acid to the base.
(iii) The air used to bum the sulphur must be as clean as possible. (3]
(b) (I) Water acts as a Bronsted base with hydrogen chloride: (d) In niodern plants, nearly all the SO,fSO, mix1ure is absorbed but up to
H2 0(/)+HCI(g) ~ H3 0'(aq)+Cr(aq) 0.05% by volume of so,
rnay be allowed to pass into the atmosphere
through a chimney stack.
(II) Water acts as a Bronsted acid with ammonia: Give two reasons why SO, should not be discharged into the atmosphere. (2]
H 2 0(1)+NH3 (aq) ~ NH/(aq)+OH-(aq) (c) ~) pH = -log[H"(aq)] (e) (i) When concentrated sulphuric acid is warmed with solid sodium chlo-
In 0.10 mol dm"' of lactic ride, misty fumes are produced.
(c) (i) Lactic acid is a weak acid. This is because it only under~oes parti?l acid,
dissociation. With a concentration of 0.10 mol dm-<~, the solut1on of lactic Identify the fumes .........................................................................................
(H"{aq)]= ~~ Write an equation for the reaction.
acid is expected to have a pH of 1 in water if lactic acid undergoes compl~te
dissociation. However, th~ solution of la~tic .acid has a pH of 2.44 wh1~ = 3.72 x 10"' mol dm"'
(il) When concentrated sulphuric acid is warmed with solid sodium iodide
shows that its hydrogen 1on concentration 1s less than 0.1 0 mold dm , < 0.10 mol dm"' purple fumes are produced. '
indicating that the dissociation of lactic acid is incomplete. => lactic acid does not dissoci-
,· Identify the fumes ......................................................................................... [3]
ate completely.
~: [J02/P2/04)
~·
~
topic 7 Equilibria Page 7 topic 7 Equilibria
PageS
~CORNER
Suggested Solution:
(e) Hydrogenhalides(HCI, HBr
(e) From the following list of indicators, put a tick in the box by the side of the ~CORNER
indicator you consider most suitable for this titration. · (1]
(a) (i) S(s) + 0 2 (g) ------> S0 2 (g) and HI) are gases at room
temperature and are more (c) The K, of NH, is t.74 x
indicator pH at which colour place one tlck·only 10.. mol dm"".
(ii) To reduce the possibility of nitrogen reacting with oxygen to form oxides volatile than H,SOr On re- changes
action of the appropnate solid in this column
of nitrogen.
halide (usually sodium or methyl violet 0.0-1.6 [OH"(aq)J; ,}Kb x[NH 3 ]
(b) Vanadium(V) oxide potassium halide)wilh cone. methyl orange
H,so,, the hydrogen halide 3.1-4.4 ;t87x10"3 moldm·'
(c) (i) An excess of air is needed. to provide excess oxygen to drive the position gas is produced as shown bromothymol blue
of equilibrium to the right so that a high yield of so, can be obtained. 6.0-7.6 pOH = -log[OH-(aq)] = 2.73;
(ii) The forward reaction is exothermic so that a lower temperature favours
by the following equation: 1 phenolphthalein 8.3-10.0
I
pH= t4- pOH = 1t.3
NaX(s)+H 2 S0 4(aq) l I
the forward reaction resulting in greater yield. Also the catalyst gets heated ~ (d) End point occurs when the
~
up and too high a temperature may denature the catalyst, causing it to (f) A solution containing NH,(aq) and NH,CI(aq) acts as a buffer solution,
indicator changes colour "'
function less efficiently. ;===:= NaHS0 4 (s)+HX(g) resisting changes in pH when acids or alkalis are added.
~ when no. of mol of HCI
(iii) Impurity poisons the catalyst and impurities such as water may cause the [X = Cl, Br or IJ .l Explain with the help of equations how this mixture acts as a buffer. [2) added exactly neutralizes the
formation of sulphuric acid mist when sulphur trioxide is formed. Besides ii
Being gaseous, the HX NH, present.
being harmful, this also -generates heat and not favour the forward exo- escapedfromthesystemthus ~ [J02/P4/01]
NH3 (aq) + HCI(aq)
thermic reaction.
(d) Sulphur dioxide damage_s the respiratory system and causes an increase in
driving the position of equilib-
riumtotheright.lodideismore
11 Suggested Solution: -t NH 4CI(aq)+H 20(1)
easily oxidised than chloride. l
asthma attacks. It stimulates. contraction of the airways, making it difficult to Concentrated sulphuric acid (a) Kw = [W(aq))[OH"(aq)] No. of mol of HCI al end
breathe. is strong enough an oxidising point = no. of mol of NH,
Sulphur dioxide is acidic and increases the acidity of rain. More seriously, it agent to oxidise the HI pro- {b) [OH"(aq)]; [NaOH(aq)]; 0.200 mol dm·3
can be oxidised to sulphur trioxide which dissolves in rain to form sulphuric duced to iodine and concen· ; _3Q__x 0.200; 4.00x to->
trated sulphuric acid is itse~ 1000
acid' which is a strong· acid. The formation of sulphuric acid increases the At 25 oc, Kw; 1x10-14 md dm"6 ; [W(aq))[OW(aq)]
acidity of rain greatly and acid rain causes many harmful environmental reduced to so,, S or H,S: Volume of HCI al end point
K 1 to·"
effects such as destruction of aquatic life and corrosion of buildings. [W (aq)]; _ _w _ ; _x_ _ mol dm- 3 ; 5 x 1o- 14 mol dm-3
e.g.: BHI+H,so,: no. of mol 4.00x1o-'
-t 41 2 + H2S+ 4H 20
[OH"(aq)] 0.200
= [Hci]; ----o:wo-
(e) (i) Hydrogen chloride fumes. pH; -log[H'(aq)] = 13.3
3
H2 S0 4 (aq)+NaCI(s)------> NaHS0 4 (s)+HCI(g) Thus sodium iodide reacts
= 0.04 dm = 40 em'
with concentrated sulphuric (c) NH, is a weak base and ionises incompletely in water to give OH- ions so
pH changes rapidly around
acid to give iodine rather that .the concentration of hydroxide ions in 0.200 mol dm"" of aq NH, is much the end point.
(ii) Iodine less than 0.200 mol dm"". Hence the pH of 0.200 mol dm"" of aqueous ammonia
than hydrogen iodide.
is less than that of 0.200 mol dm"" aq NaOH which is a strong base. The ammonium ion fonmed
Concentrated sulphuric acid
is not strong enough an hydrolyses in water so that
{d) 14
Question 6 oxidising agent to oxidise the pH at the end pont is less
chloride ion to chlorine gas than 7:
11.3
(a) Write an expression for K.. [1) so that chlorine is not fonmed
when sodium chloride is NHt (aq) + H20(/)
(b) Use your expression to help you calculate the pH of 0.200 mol dm"" NaOH(aq).
[2)
reacted with concentrated
sulphuric acid. pH 7 end-point
== NH (aq)+H 0'(aq)
3 3

(c) The pH of 0.200 mol dm"" NH,(aq) is 11.3. Explain why this answer differs The greater ease of oxidation [H"] at end point
from your answer in (b). [1) of iodide ions than chloride
ions is due to weaker attrac· ,jK, ofNH(x[NH(]
(d) A 20.0 em' sample of 0.200 mol dm"" NH,(aq) was titrated with 0.100 mol lion between the valence
dm"" HCI. electrons of iodide and its ; j__.!S.._x[NH(]
nucleus. Being shielded by Ol I I I ; I ~ VK, of NH3
On the following axes, sketch how the pH· changes during this titration. 0 10 20 30 40 50 60
more filled inner quantum
Mark clearly where the end point occurs. volume of added acid I cm3 1xt0"14 4x1o-3
shell, a valence electron in
iodide is more easily lost so (e) t.74xt0"5 x"""0:06
14
that iodide ion is more easily .indicator pH at which colour place one tick only
changes ;6.19xto-< moldm"";pH;5.21
oxidised since oxidation in this column
involves loss of electrons. methyl vi.olet 0.0-1.6 (e) The indicator chosen for a
methyl orange acid-base titration should
3.1 -4.4 ,/
change its colour at the
pH 7 bromothymol blue region where pH changes
6.0-7.6
rapidly.
phenolphthalein 8.3-10.0
Since the reaction is astrong
acid-weak base titration, pH
changes rapidly at pH less
o+---,---.---.---,----.---.- than 7 (in this case, around
0 10 20 30 40 50 60
pH 5). Thus the indicator
volume of added acid/cm3 [3) chosen is methyl orange.
'
 topic 7 Equilibria
Page9
topic 7 Equilibria
~CORNER Page 10
(f) On addition of a small amount of acid, NH 3 reacts with the H• added so that
[H'(aq)] remains approximately constant and pH is maintained:
~CORNER
(c) (i)
NH3 (aq)+W(aq) ~ NH/(aq)
On addition of a small amount of base, NH; reacts with the OH- added so
(li) Let Pso, • P,o, and Po, be partial pressures of SO,, SO, and 0 respectively.
that [OH·(aq)] remains approximately constant and pH is maintained: 2

NH/(aq)+OW(aq) ~ NH 3 (aq)+H2 0(/) At equilibrium, PS03 =4.7atmwhileP503 +P502 +POz -5 t

- 8 ffi.
The large reservoir of NH, and NH; in the buffer sufficiently copes with the
addition of the acid and the base. Thus, P,02 + P0 , =5-4. 7 = 0.3 aim, _; ___ (1)

Since a_ 2.: 1_ mixture of SO, and 0, is used and 2 SO reacts with 1 o

2
at eqUihbnum, the molar ratio of so, : o, = 2 : 1. ''
Question 7
The key stage in the manufacture of sulphuric acid is the reaction between => PSOz + 2Po2
I sulphur dioxide and oxygen. Substitute in (1) : 2P0 , + P0 , = 0.3 atm ~ P0 , = 0.1 atm
:;1
i t.H = -197 kJ mar' P, 0 , = 2x P0 , = 0.2 atm
i I
(a) Descnbe and explain the effect on the position of the equilibrium of increasing
i! ·" Substitute P, 0 z P = 0.1 atm and pso -4
= 0.2 atm 'Oz -
7 t · t K .
• 8ffifn0 p•
3
(i) the pressure,
IH (ii) the temperature. [4] p 2
K =--•_o,___ (4.7)
P p 2xP -( )2
2
3 -1
=5.52x10 atm (to3s.f.)
I
I,
(b) The reaction is carried out at a pressure of 5 atmospheres and a tempera- SOz o2 02
• X 0.1

~~~~- .

! (i) In what respects are these conditions not what you might have ex- Question 8
pected?
(ii) Suggest why these particular conditions are used. [3] (a) Ethanoic acid is a weak Bronsted acid.

(c) (i) Write an expression for K, for this reaction, giving its units. What do you understand by the terms in italics? [2]
(ii) When a 2:1 mixture of SO, and 0 2 was allowed to reach equilibrium (b) The dissociation constant for ethanoic acid, K,, is equal to 1.8 x 10"' mol dm"'.
at 500 'C and a total pressure of 5 atm, the partial pressure of SO, was
(i) Write an expression for K,.
found to be 4.7 atm.
Use your expression in (c)(l) to calculate the value for K,. [3] (ii) Us~ the v~lue of K, to calculate the [H'] in, and the pH of, a 0.10 mol
dm solut1on of ethanoic acid. [3]
{N02/P3/Q3(E:ither)]
(c) A solution containing ethanoic acid and its salt sodium ethanoate,
CH,CO,Na, acts as a buffer solution.
Suggested Solution: (b) Temperature affects both
rate of a reaction as well as (i) What do you understand by the term buffer solution?
(a) (i) Increase in pressure causes the position of equilibrium to shift to the right.
the yield for reversible reac·
By Le Chaterlier's principle, when pressure is increased, the system favours
lions. Even though exother·
(ii) Write ionic equations to show how this solution reacts with
the process that reduces pressure. Since the forward reaction produces
mic reactions are favoured I added H•(aq) ions,
less gaseous molecules than the backward reaction, pressure is reduced
by low temperature so that added OH-(aq) ions.
if the forward reaction is favoured. Thus, position of equilibirum shifts to a lower temperature results
the right with an increase in pressure. Conversely, the position of
in greater percentage of (iii) Use the v~lue of K, given above to calculate the pH of a buffer solution
equilibirum shifts left when pressure is lowered. product formed, a low tem- t~at conta1~s 0.50 mol of ethanoic acid and 0.20 mol of sodium ethanoate
(ii) Increase in temperature causes the position of equilibirum to shift to the perature also causes a dissolved 1n 1.0 dm' of water. [5]
left By Le Chatertier's principle, when temperature is increased, the sys- longer time for equilibrium
tem favours the process that reduces temperature. Since the backward to be established. Thus, for [N02/P3/Q3(0r)]
reaction is endothermic, heat is absorbed when the backward reaction is exothermic forward reac-
favoured so that the temperature is decreased. Thus, position of equilib- tions encountered in the Suggested Solution:
rium shifts to the left with an increase in temperature. Conversely, the Contact Process (manufac-
(a) A Bronsted acid is a proton [H•] donor.
position of equilibrium shifts right when temperature is lowered. ture of sulphuric acid) and
Haber Process (manufacture A weak acid is an acid which ionises partially in aqueous solution.
(b) (i) The temperature of 500 'C is rather high so that yield of SO, may be of ammonia), the tempera- !h us, the concentration of H• in an aqueous solution of a weak Bronsted acid
relatively low. The pressure of 5 aim is rather low. ture selected is a 'compro- IS 1ess than the concentration of the acid.
(ii) A high temperature is needed to ensure that the reaction proceeds at a mise'. It should be high
reasonable rate. The pressure need not be too high as high pressure enough for reaction to occur · (b) (i) K _ [CH3 Coo-(aq)J[W(aq)]
requires specialised vessels which can withstand high pressure and in- at a reasonable rate and low I a - [CH3 COOH(aq)]
creases cost. To ensure reasonable yield and speed, a moderate tem- enough for the yield to be·
perature and pressure is used. acceptable.
-I

topic 7 Equilibria Page 11 topic 7 Equilibria

Page 12
~CORNER
{il) Let [H•(aq)J : y mol dm"".
NH2 CONH2 + 20H-· -~ 2NH + C0
3 3
,_ ~CORNER
CH3COOH(aq) CH3 Coo-(aq) + W(aq)
NH 3 + HC/ ----> NH 4Ci
Initial conc./mol dm"" 0.10 0 0
When 0.1 00 g of a fertiliser was subjected to this procedure, the resulting
Eqm. conc./mol ·dm"" 0.10- y y y solution of ammonia required 14.0 em' of 0.200 mol dm--' HC/ for
neutralisation.

K. [CH3 Coo-(aq)][H'(aq)] :__L__: 1.8x10-5 Calculate the percentage of nitrogen in the fertiliser. [3]
[CH3COOH(aq)] 0.10-y
[N04/P3/Q3(Either)]
Since y « 0.10,
y2 (b) (iQ AHematively, (b)(ii) can Suggested Solution;
0.10- y"' 0.10 =>--"' 1.8x1o-s be solved without approxi-
0.10
mation: (a) A weak acid dissociates imcompletely in water to give H'.
=> y"' ,.f1.8x1 0-5 x 0,10:1.342 x 1o-a mol dm-3
y 2 :1.8x10-5 (0.10-y) HA(aq) <===== W(aq)+A-(aq)
pH: -log[H' (aq)]: -log(1.342 x 10-a) = 2.87 (to 3 s.f) => y 2 +1.8x10- 5y
CH3 C0 2H(aq) ~ H'(aq) +CH3C0 2 -(aq)
-1.8x10_. :Q
(c) (i) A buffer solution is a solution which maintains the pH when small amounts (b) (i) c, /mol dm""
Solvingthequadraticequation 0.100
of acids or bases are added to the solution. A buffer is usually made up
above, y = 1.333 x 10"-'. Ceqm /mol dm_, 0.100- X
of a mixture of a weak acid and its salt or a weak base and its salt. X X
pH = -log(1.333 X 10"-') K _ [H'][CH3 C02 -]
(iij 1: CH3 COO-(aq)+H'(aq) ~ CH3 COOH(aq) = 2.875 a - [CH C0 H]
3 2
2
II: CHJCOOH(aq)+OW(aq) ~ CH3 COO-(aq)+H2 0(1) 1.74x1o-s : __ x__
0.100-x
(iii) The presence of CH,Coo- suppresses the ionisation of CH,COOH.
Assume x « 0.1 00 since CH3C02 H is a weak acid.
Hence, [CH 3COOH(aq)]"' 0.50moldm- 3 and [CH 3coo-(aq)]"' 0.20moldm· 3 . 2
1.74x1o-s ,._x_
For a buffer solution, 0.100

[CH3coo-(aq)J 0.20 x = 1.319 x 1o-2 mol dm-3

pH= pK. +log -log(1.8x10-5 )+1og-: 4.35 (to 3 s.l)
[CH3COOH(aq)] 0.50 - pH= -lg[H'] = 1.88

(ii) pH (b) (iQ In this weak acid-

strong base titration, the
Question 9
equivalence point occurs at
(a) Ethanoic acid is a weak acid. What do you understand by the term in italics? an alkaline pH (i.e. pH > 7)
[1] at 20 em' of NaOH.
~end-point A suitable indicator is one
(b) The dissociation constant for ethanoic acid, K, = 1.74 x 10-s mol dm"". whereby its pH working
(i) Calculate the pH of a 0.100 mol dm"" solution of ethanoic acid. range is within the region of
7t------------ rapid pH change in atitration
(ii) Sketch the titration curve for the titration of a 20.0 cm3 sample of this curve. In this case, phenol-
solution with 0.200 mol dm"" sodium hydroxide. Label the end-point phthalein (9 -1 0) is suijable.
and suggest a suitable indicator from the following list.
t.88
pH at which
indicator
colour changes Indicator : phenolphthalein 20 Vol. of NaOH/cm'
methyl violet 0-1
. 14 -3
methyl orange 3-4 (c) nHCI =0.200x--=2.8x10 mol
1000
bromothymol blue 6-7 nN = 2.8x1o-~ mol
I
phenolphthalein 9-10
[6]
mN = 2.8x10-3 x14: 3.92x 10-2 g
(c) The nitrogen content of a urea-based fertiliser can be measured by boiling
3 92 1 2
a sample of known mass of the fertiliser with an excess of NaOH(aq),. % N: · x o- x100 = 39.2%
absorbing the gas evolved in water, and titrating the aqueous solution with 0.100
hydrochloric acid of known concentration.
T,. topic 7 Equilibria
topic 7 Equilibria Page 13 Page 14
~CORNER ~CORNER
[ HCo 3 - J 20
Question 10
[C02 ) =1 (d) (i~ SinceeachmolofC0
2
The main buffering agent in blood plasma is the carbon dioxide/hydrogen (c) % mass of N and HCO,- would contain 1
[ HC0 3 -] = 20[C0 2j molofC, lhetotalamountof
carbonate system.
HP+C02 == HC0 3 - +W K. = 7.90x10- 7 mol dm- 3
mass of N x 100%
mass of sample [ HC0 3 - ]+[C0 2) = 21[C0 2)
CO, + HCO,- would also
equal to the total amount of
carbon content.
(a) What is meant by the term buffet1 [2) 3.05 X 10-3
100 21[C02)
(b) Explain how the system above acts as a buffer when OH- ions are added
to the blood plasma. [1) 1000
(c) Use the data above to calculate the pH of normal blood plasma, if the [C02] = 1.45x10-3 mol dm-3
[HCO,-]I[CO,] ratio is 20:1. [2)
(d) The total CO,+ HCO,- content of blood plasma can be found by boiling a
plasma sample with an excess of dilute sulphuric acid and absorbing the Question 11
carbon dioxide evolved in a solution of barium hydroxide. The precipitated
barium carbonate can be filtered off, dried and weighed. {b) Although most chlorates are very soluble in water, iodates are much less
When a 100 em' sample of plasma was treated in this way, 0.600 g of so. The numerical value of the solubility products, K.... for strontium iodate(V),
barium carbonate was produced. Sr(IO,),, is 1.1 x 10....
(i) Write a balanced equation for the reaction between carbon dioxide and (i) Write an expression for K,. and state its units.
barium hydroxide.
(ii) Calculate [Sr''] in a saturated solution of Sr(IO,),. [4)
(ii) Use the data given to calculate the total number of moles of + co,
HCO,- in the blood plasma sample, and use the ratio given in (c) to [N05/P3/Q2{b)}
calculate the [CO,(aq)] in blood plasma. [5)
[N04/P3/Q3(or)] Suggested Solution:

(b) (i) K,P = [ Sr 2' J[ro; Jmol3 dm-9

Suggested Solution:
(a) A buffer is usually a mixture of a weak acid and its salt or a weak base and (ii) Let [ Sr2' ] = x.
its salt, and it is able to resist pH changes when a little acid or base is added
to it. Then [ro:;J = 2x
x.(2x) 2 = 1.1x 10"9
{b) OW+W ~H 2 0
x = 6.50x10-4 moldm-3
When OH- is added, it is removed by reacting with the H• in the system.
Hence, the pH does not increase.
Question 12
[H')[HC0 3 -)
(c)
[C0 2 ) {d) Dilute solutions of HF behave as weak acids. Aqueous HF of concentration
0.1 mol dm"" is only 8% dissociated into ions.
7 20
7.90x10" = [W]. (i) Calculate the pH of 0.1 mol dm"" HF,
1
[H') = 3.95 x 1o-s mol dm-3 (ii) By using data from the table, suggest why dilute solutions of HF be-
have as weak acids. [3)
:. pH= -lg[H') = 7.40
[N06/P2/Q 1(d)]

{d) (i) C0 2 + Ba(OH}2 ~ BaC0 3 +H2 0 (d) (i) Ba(OH),, otherwise Suggested Solution:
known as Baryta water,
(ii) M, of BaC03 = 137 + 12 + 3 x 16 = 197
behaves in a similar way as (d) (i) HF(aq} == H'(aq)+F-(aq)
lime water. Hence, it may
0.600
n8 aco, = 197 = 3.05 x 10
-3
mol also be used to detect the
[H'J = 0.08x 0.1
presence of CO,, where a = Bx1o-3 mol dm-3
nc = n8 aco, = 3.05 x 10-3 mol white precipitate of BaCO,
would be formed. pH= -lg[W] = 2.1
Hence, total amount of CO,+ HCO,- = 3.05 = 10"" mol.
(ii) T_he dissociation of HF involves breaking· the H-F bond. This process is
h1ghly endothermic as indicated by the high bond energy.
 topic 7 Equilibria Page 16
topic 7 Equilibria Page 15

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compound partial pressure
Question 13 I atm
N2o. 0.75
There are few naturally occurring organic compounds that contain fluorine.
NO 1.50
The South African plant Dichapetalum cymosum contains fluoroethanoic acid, N203 0.25
FCH2 C0 2 H. Data about ethanoic, fluoroethanoic and chloroethanoic acids are
;
given below. l (i) Write the expression for K,. including its units.
~

I 1 CH3C02H _j-FCH2C02H I ctCH2co2H] I (ii) Calculate a value for K, .. [3]

r pKa 1 4.76 1 2.57 1 2.87_ J ~

i
(c) Suggest, with an explanation, how the position of equilibrium might alter
when

(a) (i) Define the term pK,.

(ii) Define the term K,.
I
~
(i) the temperature is· increased,
(ii) the pressure is increased.
[4] I

I
[N06/P3/Q3(b,c)either]
{iii) Calculate K, for fluoroethanoic acid. [3]
{b) (i) State which is the strongest and which is the weakest of the three Suggested Solution:
acids.
! 2
~ atm-1
(ii) Suggest an explanation for the differences in acid strengths of the three
acids in terms of their structures and bonding. [4] t {b) (i) K =
P PN2 o.·P~o
[N06/P2/Q5] I 0.25 2
~
(ii) K
0 0.75 x 1.5' = 0.0370 atm-1
Suggested Solution: ~
(c) (i) According to Le Chatelie~s principle, when temperature increases, the
(a) (i) pK, = -lgK, position of equilibrium shifts to the left whereby the excess heat is re-
moved since the backward reaction is endothenmic.
(ii) For a weak acid, HA <==== W +A- (ii) When pressure is increased, according to Le Chatelier's principle, the
position of equilibrium shifts to the right where there is a reduction in the
K jw][A-] number of gaseous particles. This helps to reduce the increased pres-
a (HA) sure.

{iii) Ka = 10-2.57

= 2.69x 10-3 mol dm-3 Question 15

Alcohols and esters are important organic compounds which are widely used
(b) (i) FCH,CO,H as solvents.
CH,C0 2 H
Esters such as ethyl ethanoate can be fonmed by reacting carboxylic acids with
(ii) The presence of electronegative F and Cl withdraws negative charge away alcohols.
from -eo,- by inductive effective. This spreads the charge and stabilises CH3C02H+C2H50H <==== CH3C02C2H5 +H20
the anion. Hence, the acids FCH,CO,H and CICH,CO,H are stronger. F
is more electronegative than Cl. Hence, the stabilising effect is greater This reaction is an example of a dynamic equilibrium.
and FCH,CO,H is more acidic than CICH 2C0 2H.
{a) Explain what is meant by the term dynamic equilibrium. [1]
{b) Write the expression for the equilibrium constant for this reaction, K,. [1]
Question 14 {c) For this equilibrium, the value of K, Is 4.0 at 298 K.
A mixture containing 0.5 mol of ethanoic acid, 0.5 mol ethanol, 0.1 mol ethyl
When the gases dinitrogen tetroxide and nitrogen monoxide are mixed in a ethanoate and 0.1 mol water was set up and allowed to come to equilib-
1:2 ratio, the two gases slowly react to fonm the blue compound dinitrogen rium at 298 K. The final volume of solution was V dm'.
trioxide according to the following equilibrium.
Calculate the amount, in moles, of each substance present at equilibrium.
Np 4 (g)+2NO{g) <==== 2Np3(g) t:.H" = -26 kJ mol-
1
[4]
Alcohols may be classified into primary, secondary and tertiary. Some reactions
(b) A mixture containing a 1:2 ratio of N,O. and NO at an initial total pressure are common to all three types of alcohol. In other cases, the same reagent
of 3 atm was allowed to reach equilibrium. At equilibrium the following gives different products depending on the nature of the alcohol.
partial pressures were measured.·
{d) In the empty squares below give the structural fonmula of the organic
compound fonmed in each of the reactions indicated.
If no reaction occurs, write 'no reaction' in the space.
n 1
;: topic 7 Equilibria Page 17 topic 7 Equilibria Page 18
~CORNER
I

n{CH3C02 H) = n{C2H50H) = 0.5- x = 0.5-0.3 = 0.2

~CORNER
alcohol n{CH3 C02 C2H5 ) = n{H2 0) = 0.1+x = 0.1+0.3 = 0.4
(CH,)3COH
{d)
reagent(s)
conditions

j: {d) {i) Red phosphorus and

CH3Cfi,CH2CH,OH CH3CH2CH(OH)CH3 (CH,) 3COH iodine react with alcohols to
red phosphorus and
iodine
replace OH group by iodine.

heat under reflux {iQ Tertiary alcohol dehy-

drates to produce alkene. ·
{iii) Oxidation of primary
red phosphorus and
iodine alcohol produces carboxylic
acid, secondary alcohol pro-
heat under rellux duces ketone &tertiary alco-
heat
hol do not oxidise.

concentrated t;,so, CH,;-C=CH2

Cr2 o~-/l--t+ heat I
CH,
heat under reflux

[5) Cr2 o~-IH·

[J07/P2/02] CHpH2 CH2C02 H CH 3CH2COCH3 no reaction
heat under reflux

Suggested Solution:
(a) The rate of forward reaction equals the rate of backward reaction.
l
[ CH 3C0 2 C2H5 ][H2 0)
Question 16
[ CH3 C0 2H](C2Hs0H)
(a) Use the general formula of a carboxylic acid, RC02 H, to write equations to
(c) CH3 C02H + C2H50H ---:-" CH3C0 2C2H5 + H2 0 explain the following terms.
Initial moles 0.5 0.5 0.1 0.1 (i) K,
Let x be the number of moles of reactants used and that of products produced (ii) pK, [2)
equilibrium moles {0.5-x) {0.5-x) {0.1+X) {0.1+X) {b) The pK, values .of four carboxylic acids are listed in the table below.
{c) As the number of moles of
equilibrium reactants are equal to that acid formula of acid
{0.5-x) {0.5-x) {0.1+x) {0.1+x) pKa
concentration/ of products therefore K, has
mole dm-3 v v v v no units. 1 CHsCH,CO,H 4.9
2 CHsCHC.C02H 2.8

K _(~)(~) 3 CHsCCkCO,H 1.4

c - ( 0.5V- X)( 0.~- X) 4 CH,C.CH,CO,H 4.1

2 (i) Describe and explain the trend in acid strength shown by acids 1, 2
= {0.1+x) and 3.
4
{0.5 -x)2
(il) Suggest an explanation for the difference in the pK, values for acids
{0.5-44 = {0.1+x)2 2 and 4.
2{0.5- x) = {0.1+ x)
(iii) Calculate the pH of a 0.010 mol dm.., solution of propanoic acid
1-2x = 0.1 + x {acid 1). [6)
X =0.3
[N07/P4/01(a,b)]
 Page 19 topic 7 Equilibria Page 20

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topic 7 Equilibria
~CORNER
Suggested Solution: Question 18
(b) (Q Electron withdrawing
(a) (i) K = [RC02][W] effect of chlorine atom makes When hydrocarbons such as petrol or paraffin wax are burned in an excess of
' [RC0 2H] anion more stable or equilib- air in a laboratory, carbon dioxide and water are the only products.
rium moves to right hand When petrol is burned in a car engine, nitrogen monoxide, NO, is also formed.
(ii) pK, = -log 10 K 8 side, making more hydrogen
·ions available. (a) Explain how NO is formed in an internal combustion engine but not forined
(b) (i) Acid strength increases down the table. As the number of chlorine atoms when a small sample of petrol is burnt in an evaporating basin. [2] ·
increase, electron with-drawing effect increases making anion more stable. (iij As chlorine atom
(il) Chlorine atom is further away from 0 - H in number 4, so it has less moves away from functional The engines of modern motor cars have exhaust systems which are fitted with
influence upon -OH, .making acid to be weaker than in number 2. group, its electron with cataly1ic converters in order to reduce atmospheric pollution from substances
drawing effect decreases such as NO.
(iii) pH= .!_(pK8 -log 10 [Acid]) making acid weaker.
(b) (i) State three more pollutants, other than C02 and H20, that are present
2
0ii) Equation for dissocia- in the exhaust gases of a car engine.
=.!.(4.9 -log 10 0.01) tion of propanoic acid is:
2 (ii) What is the active materiaL present in the cataly1ic converter?
CH3CH,CO,H=='CH5CH 2C0i +W
' (iii) Write one balanced equation to shciir.inow-NO..Js removed from the
= .!.(4.9 + 2) = 3.45"' 3.5
i·
i 2 K _[ CH3CH 2C0i ]~ exhaust gases of a car engine by a cataly1ic conv;rter.· [4]
'- (CH3CH20 2H)
NO is also fomned when nitrosyl chloride, NOC/, dissociates according to the
""[CH 3CH 2C0i]=[H']
following equation.
Question 17 :. [H"]' =K,(CH3CH 2C02H)
2NOC/(g) ;==== 2NO(g)+C/2 (g)
Potassium manganate(VII) can be used to estimate the percentage of hydrogen ( H" )=[K,(CH3CH2C02Hl)J
peroxide in household bleach. The following unbalanced equation represents the Different amounts of the three gases were placed in a closed container and
reaction between them.
~~[W ]=-log(K, (CH 3CH2C02Hjjl allowed to come to equilibrium at 230'C. The experiment was repeated at 465'C.

pH = 1(pK, -log [CH3CH1C0 2HJ ) The equilibrium concentrations of the three gases at each temperature are
...... Mn04 + ...... H20 2 + ...... W ~ ...... Mn2 • + ...... H20 + ,.....0 2
2 given in the table below.
(a) Balance this equation by putting the appropriate numbers in the spaces above. 1
pH= '2(4.9+2) = 3.45 • 3.5
[1] concentration I mol dm.a

temperature I 'C NOC/ NO Ck

(b) Use data from the Data Booklet to calculate the E:.u for the reaction. [1]
230 2.33 x10-3 1.46 X 10-3 1.15 X 10-"
(c) When 0.020 mol dm"" KMnO,(aq) was added from a burette into an acidi-
fied 25.0 em' sample of H,O,. 15.0 em' of KMnO' was required to reach the 465 3.68 x10-4 7.63 X 10-3 2.14 X 10-4
-'-
end-point.
(i) Describe what you would see during this titration, and also at the end- (c) (i) Write the expression for the equilibrium constant, K, , for this reaction.
point. Give the units.
[4]
(ii) Calculate the concentration of H2 0 2 in the sample. (ii) Calculate the value of K, at each of the temperatures given.
[N07/P4105]
230 'C
465 'G
(iii) Is the forward reaction endothemnic or exothemnic? Explain your answer.
Suggested Solution:
[5]
(a) 2 Mn04 + 5 Hp 2 + 6 W ~ 2 Mn
2
• + 8 H20 + 5 0 2 (b) Mn04 +BW +5e- ~ (d) The temperature of the equilibrium was then altered so that the equilibrium
concentrations of NOC/ and NO were the same as each other.
Mn2+ +4Hp.
(b) E~ell = 1.52-0.68 = + 0.84 V What will be the effect on the equilibrium concentration of NOC/ when the
E' =+1.52 following changes are carried out on this new equilibrium? In each case,
(c) (i) Colour changes from purple to colourless explain your answer.
0 2 +2W+2e-~HP 2 (i) The pressure of the system is halved at constant temperature.
(ii) n(Mn04)=0.02x~=3x10-4
1000 E9 =+1l.68 (ii) A mixture of NOC/(g) and NO(g) containing equal numbers of moles
of each gas is introduced into the container at constant temperature.
since H20 2 : Mn04 = 5 : 2 Overall equation: [4]

~x 3x 10-4 = 7.5x 10_.

3
n(H 0 ) = in 25 cm 2 Mno:; +5 H20 2 +6 W {JOB/P2/Q3]
2 2
2 ~2 Mn2• +8 H20+5 0 2
-4 1000 -2 d -3
:. [H20 2 l =7.5x10 x--=3.0x10 mol m
25
topic 7 Equilibria Page21 topic 7 Equilibria
Page22
~CORNER
Suggested Solution: (ii) A m1'xt ure containing 0.50 mol of co,. 0.50 mol of H,, 0.20 mol-of co ~CORNER
(a) High temperature and pressure provide enough energy to break N = N bond.
(a) Bond dissociation energy
and 0.~? ~ol of H,O was placed in a 1.0 dm' flask and allowed to come
to eqwhbnum at 1200 K.
(b) (i) C, CO, hydrocarbons and SO, and H,S, NOx =
of N N is very large Calculate the amount, in moles, of each substance present in the
because this requires equilibrium mixture at 1200 K
(ii) PI or Pd and Rh
breaking of three covalent
bonds per molecule. So it C02 + H2 co + H20
does get affected readily ~-

at temperature greater initial 0.50 0.50 0.20 0.20

(c) (I) Kc = [NOf[C/2] unit: moldm-3 than 3000'C. moles
[NOC/]2 '-
(b) S is present in the fossil (6]
fuel. When it is burnt S02
gas is produced. Nitrogen {J09/P2/Q3}
(ii) 230 'C:
is present in air, when fuel
burns in air, N02 is pro- Suggested Solution:
Kc= (7.63x10-3fx(2.14x10"") = 9 _2 x 1o-2 moldm-3 duced.
465 'C: (a) 2CH3 0H + 302 ~ 2C02 + 4H20
(3.68 x 1o"" )2

(iii) Endothermic because K, increases with temperature. (b) Sulphur dioxide and Nitrogen dioxide

(c) 1. Low temperature

(d) (i) Equilibrium moves to R.H.S. because more moles on R.H.S.
As the forward reaction is exothermic at low temperature the reaction will
(ii) No change to equilibrium position. go forward to produce high yield of methanol. '
2. High pressure
As the forwa_rd reaction goes to fewer gas molecules, the reaction will go
Question 19 forward at h1gh pressure.
Concern over the ever-increasing use of fossil fuels has led to many sugges-
(d) (i) It helps to remove carbon dioxide from air which is responsible for green-
tions for alternative sources of energy. One of these, suggested by Professor house effect and global warming.
George Olah, winner of a Nobel Prize in chemistr}', is to use methanol, CH,OH. (ii)
which can be obtained in a number of different ways.
C02 + H2 ~
co + H20 ·
Methanol could be used instead of_petrol in a conventional internal combustion
engine or used to produce electricity in a fuel cell. initial 0.50 0.50 0.20 0.20
moles
(a) Constnuct a balanced equation for the complete combustion of methanol.
(1] equilibrium (0.5- x) (0.50- x) (0.20 + x) (0.20 + x)
When hydrocarbon fuels are completely burned in an internal combustion engine, moles
several toxic pollutants may be formed. equilibrium 0.5-x 0.50-x 0.20+X 0.20+X
(b) State two toxic pollutants that can be produced after complete combustion concentration 1 1
1 1
of a hydrocarbon fuel in an internal combustion engine. [2] moledm"'

Methanol may be manufactured catalytically from synthesis gas, a mixture of K _ (CO)[H20J

CO, CO, and H,. The CO is reacted with H, to form methanol, CH,OH. c - [co2J[H ]
2
CO(g) +2~(g)~CHpH(g) t.H = -91 kJ mo1'
1
:::;.
(0.20+ x) 2
1.44 :::;. X=0.18
(0.50-x) 2
(c) From your understanding of Le Chatelier's principle, state two conditions
that could be used in order to produce a high yield of methanol.
at equilibrium: moles of (C0 2) =moles of (H2) = 0.50 _ 0.18 = 0.32
In each case, explain why the yield would increase. [4]
moles of (CO)= moles of (H20) = 0.20 + 0.18 = 0.38
Carbon monoxide, which can be used to make methanol, may be formed by
reacting carbon dioxide with hydrogen.

C0 2 (g)+H 2 (g)~CO(g)+~O(g) Kc = 1.44 at 1200 K

(d) (i) It has been suggested that, on a large scale, this reaction could be
helpful to the environment.
Explain, with reasons, why this would be the case.
 Page23 topic 7 Equilibria
topic? Equilibria Page 24
~CORNER
(iii) 14 Tll-r-IT--,IT--rll-rT"""T-r,-,....,.-..,-, ~CORNER
Question 20
(a) Explain what is meant by the Bronsted-Lowry theory of acids and bases.
[2) (iii)
(b) The K, values for some organic acids are listed below. NaOH + CICH 2C0 2H
pH 7 I I l I I I I i I IJi I I I I I I I II --> C/CH 2C0 2Na + H20
acid K,./mol dm-3 As the concentration of acid
CH3CO,H 1.7 X 10..5 and alkali is same, equal
volumes are required for
CICH,CO,H 1.3 X 10..3
complete neutralisation i.e.
CI,CHCO,H 5.o x to"" oI I I I I I I I I I I I I I I I I I I I I 10 em'.
0 5 10 15 20 (c) 0) Acid present in buffer
(i) Explain the trend in K, values in terms of the structures of these acids. will react with OH· ion ff
volume of NaOH added I em'
(ii) Calculate the pH of a 0.10 mol dm"" solution of C/CH,CO,H. alkali is added.
(iii) Use the following axes to sketch the titration curve you would obtain (c) (i) CH3 C0 2 H +OW --> CH3 C0 2 - + H2 0 Ethanoate ion will react with
when 20 em' of 0.10 mol dm"" NaOH is added gradually to 10 em' of H· ion ff acid is added to the
CH3Co,- + W --> CH 3C0 2 H
0.10 mol dm"" CICH 2 CO,H. buffer solution.
14.-ro-rT<rT-rT<-ro-~-r~,.-.~ (ii) pK, =-log10 K, =-log10 1.7x1o-s =4.77

[Salt]
pH = pK, +log-(-.-
Acid 1
02
= 4.77 + !og · = 4. 77 + 0.30 = 5.07
0.1
pH 7 I I I I I I I I ! I I I I. I I I I I I I I

Question 21

(c) Calcium hydroxide, Ca(OH),. is slightly soluble in water.

oI I I I I I I I I I I I I I I I I I I I I (i) Write an expression for K,. for calcium hydroxide, and state its units.
0 5 10 15 20 (ii) 25.0 em' of a saturated solution of Ca(OH), required 21.0 em' of 0.0500
volume of NaOH added I em' mol dm"" HC/ for complete neutralisation.
[8) Calculate the [OH- (aq)] and the [Ca'• (aq)J in the saturated solution,
(c) (i) Write suitable equations to show how a mixture of ethanoic acid, and hence calculate a value for K,..
CH,CO,H, and sodium ethanoate acts as a buffer solution to control the
(iii) How would the solubility of Ca(OH), in 0.1 mol dm"" NaOH compare
pH when either an acid or an alkali is added.
with that in water?
(ii) Calculate the pH of a buffer solution containing 0.1 0 mol dm"" ethanoic Explain your answer. [6)
acid and 0.20 mol dm"" sodium ethanoate. [4]
[J10/P4/Q2 c)
[J09/P4/Q1]

(b) (iQ K, for monoprotic acid Suggested Solution:

Suggested Solution: (HX) is,
(c) (i) K,p = rca'• now]', units = mol 3 dm-9
(a) Acids are species that donate protons (hydrogen ions) when dissolve in water.
Bases are species that accept protons when dissolve in water.
[w][ x- J
K=--
• [Acid) (ii) Moles of acid (W) = 0.05 x __3..!_ = 1.05 x 1o-3
. 1000
(b)_ (i) When chlorine is substituted in ethanoic acid, K, value increases and acid
becomes stronger. It is due to electron withdrawing effect of chlorine making As [w]=[x-J same moles of OW are present in 21 cm3 moles in 25 cm3 of Ca(OH) 2 •
0 - H bond weaker causing more W ions to be free. 1000
[OW(aq)] = (1.05x10- 3 )x = 4.2x 10-2 (mol dm-3 )
K=-
[wJ 25
(ii) [H•] =~K,(Acid) • [Acid)
(Ca 2 •(aq))=.!x4.2x10-2 =2.1x10-2 (moldm-3) (c) 0ii) Ca(OH), has one ion
2
= ~(1.3 x 10-3)x 0.1 = 0.0114 mol dm-3 [wJ =K,(Acid) K,P =(2.1x10- 2
]x[4.2x10- 2 ] 2 =3.7x1o-s mol3 dm-9
common with NaOH,
hence its solubility dec-
J
-log[ W = -log0.0114 [ W ]= ~K,(Acid) reases by shifting equil·
(iii) Ca(OH), will be less soluble in 0.1 mol dm"" NaOH because of common ibrium in backward direc-
pH= 1.94 ion effect. tion.
topic 7 Equilibria Page 25

Question 22
~CORNER r:fopic 8
(c) Lead(ll) chloride is slightly soluble in water.

PbC/2 (s) <==== Pb2 •(aq)+2Cr(aq) K,. = 2.0x10-5 :J?eaclion Xnelics

(i) Write an expression for the solubility product, K,. for lead(ll) chloride
and state its units.
(ii) Calculate [Pb''(aq)] in a saturated solution of PbC/2 •
An excess of PbCI (s) is stirred with 0.50 mol dm...., NaC/ until equilibrium Content
has been establish~d. The excess PbC/2 (s) is then filtered off.
Simple rate equations; orders of reaction; rate constants.
(iii) Assuming [C/-] remains at 0.50 mol dm...., throughout, calculate the
[Pb'•(aq)] in the remaining solution. · 2 Effect of temperature on rate constants; the concept of activation energy.
(iv) Suggest an explanation for the difference between this value and the 3 Homogeneous and heterogeneous catalysis.
value that you calculated in (ii). [4]
[N10/P4104 c)
Learning Outcomes
Candidates should be able to:
Suggested Solution:

(c) (i) K,. = [Pb 2+ ] [cr J units= mol 3 dm-9

(a) explain and use the terms: rate of reaction, activation energy, catalysis, rate equation,
order of reaction, rate constant, halllife of a reaction, rate-determining step.
(b) *explain qualitatively, in terms of collisions, the effect of concentration changes on the
(ii) Suppose [Pb 2 + = x J rate of a reaction.

:::o J
[Pb 2• x [ cr J = (x)(2x) 2
(c) *show understanding, including reference to the Boltzmann distribution, of what is
meant by the term activation energy.
:::o K,. = 4x 3
(d) *explain qualitatively, in terms both of the Boltzmann distribution and of collision fre-
x=ff=~ · : - 2 0 10 5
2 quency, the effect of temperature change on the rate of a reaction.
:::o =L71x1o-
(e)* (i) explain that, in the presence of a catalyst, a reaction has a different mechanism,
i.e. one of lower activation energy.

5
(ii) interpret this catalytic effect in terms of the Boltzmann distribution.
(IIi) [Pb J=2x1o-
2
+- --=8.0x10-5 moldm
(0.5) 2
-3
(f) describe enzymes as biological catalysts (proteins) which may have specific activity.
(g) construct and use rate equations of the form rate= k[A)m[B]" (limited to simple cases
(lv) Solubility of PbC/2 is decreased because of common ion effect.
of single step reactions and of multistep processes with a rate-determining step, for
which m and n are 0, I or 2), including:
(i) deducing the order of a reaction by the initial rates method.
(ii) justifying, for zero- and first-order reactions, tile ord.e.r of reaction from ·
concentration-time graphs.
(iii) verifying that a suggested reaction mechanism is consistent with the observed
kinetics.

(iv} predicting the order that would result from a given reaction mechanism (and vice
versa).
(v) calculating an initial rate using concentration data.
[integrated forms of rate equations are not required).
(h) (i) show understanding that the half-life of a first-order reaction is independent of
concentration.
(ii) use the half-life of a first-order reaction in calculations.
·•''fl'"''

topic 8 Reaction Kinetics

(i) calculate a rate constant using the initial rates method. Page I

~CORNER
OJ devise a suitable experimental technique for studying the rate of a reaction, from given
information.
(k) outline the different modes of action of homogeneous and heterogeneous catalysis,
including: q?/ii) /F) fJ 4J
(i) *the Haber process.
~ \.!:/ tr IJ \!;;;I cy;ening ....... .
(ii) the catalytic removal of oxides of nitrogen in the exhaust gases from car engines
(see also Section 10.2). Questio11 1
(iii) the-catalytic role of atmospheric oxides of nitrog~n in the oxidation of atmospheric
(a) The kinetics of the reaction
sulfur dioxide.
(iv) catalytic role of Fe>+ in the J·fs,o:- reaction. 2NO(g) + Br2 (g) ~ 2NOBr(g) 1:1H = -23 kJ mor'
are second order with respect to (NO] and first order with respect to (Br,].
The reaction has an activation energy of +5.4 kJ mol-•.
(i) Write the rate equation for the reaction and state the units of the rate
constant.

(ii) Sketch and label a reaction pathway diagram for the reaction showing
all relevant energy changes.
(4]
(b) (i)
A bromoalkane, RBr, is hydrolysed by aqueous sodium hydroxide.
I Write a balanced equation for the reaction and suggest what type of
reaction it is.

(ii) The following results were obtained from two experiments on such a
hydrolysis. In each experiment, the overall (NaOH(aq)] remained virtu-
ally constant at the value given at the top of the column.

time/min (RBr]/mol dm-3 [RBr]/mol dm-3

"'!hen [OHl =0.10 mol dm-3 when [OHl =0.15 mol dm-3
0 0.0100 0.0100
40 0.0079 0.0070
80 0.0062 0.0049
120 0.0049 0.0034
160 0.0038 0.0024
200 0.0030 0.0017
240 0.0024 0.0012

Plot these data on suitable axes and use your graphs to determine the
following.
•.
I Use the half-life method to deduce the order of reaction wtih
respect to the bromoalkane.
II Use the initial rates method to deduce the order of reaction with
respect to sodium hydroxide.
III Construct a rate equation for the reaction and use it to calculate
a value for the rate constant.
[8]
[NOO/P1/Q3]

Note: The additional learning outcomes to be studied by A2 candidates are shown in bold type. The A2
components will assess all learning outcomes and will not be limited to those in bold type.
 I topic 8 Reaction Kinetics Page3
i
topic 8 Reaction Kinetics Page2 ~
Let g, and g2 be the gradients of the graph at t = 0 min. ~CORNER
~CORNER
Suggested Solution:
(a) (i) Rate = k(NO(g)]'[Br,(g)] where k is the rate constant.
l
i
When [OH·] = 0.10 mol dm"" and 0.15 mol dm"" respectively.
Initial rate when [OH-] is 0.10mol dm-3 ,
r, =-g,
Notice that the value of k
obtained by the above method
is slightly different from that
Unit of k = mot·' dm' s-• r -(0.00 79 - 0·01 OO) 5.25 x 1o-5 mol dm-3 min-1
of substituting in the values
(b) (iij 1 Alternatively, half- ~ for the initial rate, [RBr] and

I
(li} lives when [OH·] = 0.10 mol 40-0 (OH·]. One reaction could
dm" can be found and they be that it is hard to determine
are constant with the value Initial rate when [OW] is 0.15 mol dm- 3 , theinitialrateacouratelysince
Potential
Activation Energy= +5.4 kJ mor' of 117 min.
Energy '2 = -g2 its value is dependent on the

I
11 An alternative method to gradient of the graph which
find order of reaction w.r.t. -(0.00 68 - -0 ·01 OO) = 8.00 x 1o-5 mol dm-3 min" 1 is found by drawing the tan-
QH·: 40-0 .gent to the curve at t= 0min.
Let order of reaction w.r.t.
QH· be b. ~ Ratio of r2 to r1 = 8.00x10-5 : 5.25x10-5 = 1.5: 1

~
NOBr Hence rate= k[RBr][OH·]'. Since the rate also increases 1.5 limes when [OH-] is increased 1.5 times,
Substitute in values for rate, rate of reaction with respect to OH· is one.
[RBr] and [OH-J: li
L - - - - - - - - - - - - Reaction Coordinate M
~
Ill Rate = k [RBr][OH·]
5.25 X 10·5 =k(0.01 00)(0.10)'. . (1)
(b) (i) RBr+NaOH----> ROH+NaBr 8.00x10--' =k(0.0100)(0.15)0 ... (2) ~ Substitute initial rate = 5.25 x 1o-s mol dm"" min-•, [RBr] = 0.010 mol dm""
Nucleophilic substitution (2)(1): I
~
and [OH·] = 0.10 mol dm"" into the above equation : ·

5.25x10-5 =kx0.010x0.10
(ii) Graph of [RBr] is plotted against time:
8.00x10-
5.25x10- 5
5
=(~)'
0.10
f
~ => k =
5 25 10
· x -5 0.0525 mol-1 dm-3 min- 1•
0.011 0.010x0.10
·+- - 1.52=(1.5)' ~
0.01 blog1.5 = log1.52 ~
--[OHl = 0.10 M
0.009 b= log1.52 =1 ~ Question 2
g, -o-[OHl = 0.15 M 1Qg1.5 ~
0.008 The kinetics of the hydrolysis of a bromoalkane with aqueous potassium hy-
--1
(b) (iij Ill Alternatively k can~.~; droxide depend upon the chemical stnucture of the bromoalkane.
0.007 be solved by using inttial rate {b) & (c) Halogenoalkanes re-
1 = 8.00 x 10"' mol drrr' min·'. (a) Explain what is meant by the rate of a chemical reaction. [2]
E g, act via a nucleophilic sub-
'0 [RBr] = 0.010 mol dm" and The table below gives the order with respect to each pair of reagents in two stitution mechanism which
0.006
0 [OH·] = 0.15 mol dm". If so experiments. can either be bimolecular,
~ 0.005
m k 8.00x10-5 order with order with
S,2 or unimolecular, s, 1.
S,2 proceeds via a pen-
111 experiment reactants
!£ 1 tl\o= 0.010x0.15 respect to [RBr] respect to [OHl tavalent intermediate and
0.004 78min = 0.0533mol- 1 dm 3 min·'. A is favoured by primary
CH3 CH2 CH2 CH2 Br +OW 1 1 halo-genoalkanes where
0.003 Another method makes use thecarbon at which the
B (CH 3 )_sCBr+OW 1 0
of the fact that since (OH·] halogen attached is less
0.002 2"'t.= sterically hindered. S, 1
» (RBr], the reaction is a {b) (i) Write the rate equation for experiment A using the rate constants, k.
78min pseudo first order reaction proceeds via. a carboca-
0.001 (il) State the units of k. tion intermediate and is
and the rate equation. favoured by tertiary halo-
0 Rate = k(RBr][OH·] = (iiQ Suggest what the rate equation indicates about the mechanism of genoalkanes since the ter-
0 50 100 150 200 250 experiment A. [4] tiary carbocaticin formed is
k'[RBr] where I<' = k[OH-].
time/min {c) Suggest a mechanism for experiment B. relatively more stable than
[2]
k'=~ secondary or primary carbo-
cations.
Since OH· is used in great excess, the shape of the graph is dependent 1112 {J01/P2/Q2]
on the order of reaction with respect to RBr and not OH·. When (QH·] =0.15 mo, drrr', CH 3CH 2CH 2CH Br is a
t,. = 78 min, primary bromoa~ane and
From the graph, when [OH-] = 0.15 mol dm"", both the first and second Suggested Solution: undergoes reaction with
half-lives = 78 min = is a constant. ~ order of reaction With respect to RBr k'=~=8.887xW 3 min-' OH·ion via an S,2 mecha-

I
{. (a) The rate of a chemical reaction is defined as the
is one. 78 change in the concentration of reactants or prod- -.. . nism as shown below:
k'
k=--
[OH-1
ucts per unit lime.
HO
-
+
, yH,CH,CH,
ll+c~ &-
f H {-H,CH,CHj fast
slow H"-' B -+ ...C
yH,CH,CH,
+ 8(
"I ··sr -+ v- -- r HO' J'H
oO..., .,-• ...:•• -•
{b) (i) Rate= k[CH3 CH2 CH2 CH2Br][OW] HH H H
(ii) Unit of k is mot·• dm' s-•. pentavalent intermediate

!
~~~~! i I
Page 4
tooic 8 Reaction Kinetics topic 8 Reaction Kinetics PageS
~CORNER ~CORNER
(iii) The rate equation indicates that the rate-determining step in- Suggested Solution:
volves one CH,CH,CH,Br molecule and one OH- ion, i.e. it CH, slow yH,
is bimolecular. The reaction proceeds via an S,2 mechanism. o+/:. .,0-- - ):, + ar- (a) A suitable experimental technique is colorimetry. A sample of the ester' and
CH 3/ I 'Br CH, .CH, alkaline mixture is prepared and placed in a colorimetric cell. The cell is then (a) Since the product appears
CH3 yellow. it has absorbed the
(c) (CH 3 ),CBr--> (CH3 ),C+ +Br- slow tertiary carbocation intermediate placed in a colorimeter and the absoribances of a suitable wavelength of light
complementary colour of
~ yH, lasi yH, yH, at specific times (e.g. 1 minute intervals) are ·taken.
(CH 3 ) 3 C+ +OW - - > (CH 3 ),COH fast Ho- +c -+ ..c or c.. yellow which is violet.
Samples of the yellow product of known concentration are then prepared and
cH: 'cH, HO''' \'cH, CH: I ···oH Henoe asuitable wavelength
CH, CH, the absoribance of each S(lmple is measured. A graph of absoribance against that could be used to mea-
concentration is plotted so that the concentration of the yellow product at various sure absorbance will be
Question 3 (CH,),Br is a tertiary absoribance may be detemnined from the graph. around 420 nm.
bromoalkane and undergoes A graph of concentration of the yellow produci is plotted against time. Rate
The ester 4-nitrophenyl_ ethanoate hydrolyses in alkaline solution according to reaction with OH- ion via an of this reaction at time t will be the gradient of the graph at time t.
the following equation. s, 1 mechanism as shown

~
CHa-C-0- 0 -N02 + 20H- _____. CHa-c-o-+'i? -a- o- N0 2 + H20
above. (b)
0.001.:-------------------------,

0.0009
colourless yellow 0.0008 (b) The concentration of ester
(a) Suggest, and briefly describe, a suitable experimental technique for study- used is very much less than
"' 0.0007
ing the rate of this reaction. [4] E the concentration of hydrox-
~ 0.0006 ide ions. This is to keep the
(b) The reaction rate was studied using two solutions of different hydroxide ion [OH-] approximately con-
.§ 0.0005
concentrations. ~ stant and variation of rate of
~ 0.0004 reactionwitll [ester] may then
run A: [OH-] = 0.20 mol dm_,
run B: [OH-] = 0.40 rnol dm_, O.OC03 be determined.

The foli'owing graphs show how the concentration of the ester, 4-nitrophenyl 0.0002
ethanoate, varied over time in the two runs.
0.0001
0.001.----------------------------,
0
j .I ." I
.I I I I
I
'!: 0.0009
0 10: --
2u --
30 40
o
50 60
11
1 tlil 21'1dtl!l time/min

7 0.0007
(i) Initial rate of run A= (O.OOOS-0.00 1) mol dm-3 min-1
E
'0 0.0006 (10-0)
0
.§ 0.0005 = 4.00 x 1o-S mol dm-3 min-1
~
! 0.0004
0.0003 Initial rate of run B (0.0002 - 0 · 001 ) mol dm-,'3 min- 1
(10-0)
0.0002
0.0001
= 8.00 x 1 o-5 mol dm-3 min-1

oi0 10
1 1 ,
20
, 1 ,
30
, 1 ,
40
1 ,
50
, I
60
(ii) When concentration of OH- ions is doubled from run A to run 8, initial rate
is also doubled. Hence the order of reaction with respect to [OH-] is one.
time/min
(iii) Order of reaction with respect to [ester] is one.
(i) By drawing tangents on the graphs, measure and calculate the initial
rates of reaction during the two runs. Give the units in each case. (iv) For run 8, the first half-life of 11.5 min, while the second half-life is 24 -
initial rate of run A and initial rate of run 8 [3] 11.5 = 12.5 min. Since the two half-lives are approximately constant, the
order of reaction with respect to [ester] is one.
(ii) By using your results, calculate the overall order of reaction with re-
spect to [OH-]. [1] (v) The rate equation is : rate = k[ester][OH-].
(iii) From the curve of run 8, determine the order of reaction with respect
to [ester]. [1]
(vi) From run 8, when [ester] = 0.001 mol dm_, and [OH-] = 0.40 mol dm_.,

(iv) Explain how you arrived at your answer in (iii). [1] initial rate = 8.00 x 10-<> mol dm_,., min-•.

(v) Write a rate equation for the reaction. (1] .. 8.00 x 1 o-5 mol dm-3 min- 1 = k x 0.001 mol dm-3 x 0.40 mol dm-3
(vi) Use your rate equation and the initial rates to calculate a value for the 5
rate constant, including units. [2] k = (B.OO x 1o- ) mol-1 dm-3 min-• = 0.200 mol-' dm 3 min-'
(0.001)(0.40)
{J02/P4/02]
 topic 8 Reaction Kinetics Page 6 topic 8 Reaction Kinetics Page 7
~CORNER (ii) ~CORNER
. /1 Question 4
\
.. ,! ' \
:r• '''ilt--------------j--Experiment
0.005' ~Experiment 1
2·
_d (a) Explain in molecular terms how changing the concentrations of reactants
in a reaction can often affect its rate. [2] . (b) (iii) • It is more accurate
(b) A solution of vanadium(V) ions in 1 mol dm"" H,SO, slowly oxidises 0.004 to use experiment 1 to
arsenic(lll) oxide to arsenic(V) oxide, according to the following (unbal- ? determine the half lives and
E
anced) equation. 1J check~theyareconstant.ln
0 0.003 experiment 2, the drop in
As2 0 3 + vo; + H•
~
2 [VO,"] is not big enough for
----? As 2 0 5 + V0 • + H2 0
us to accurately determine
(i) Balance this equation. [1] ~ 0.002 2ha~life values for compari-
The rate of the reaction was followed by measuring the concentration of son.
remaining vanadium(V) ions after fixed time intervals. Two experiments were • In experiment 1, we
carried out, starting with different concentrations of arsenic(lll) oxide. The
0.001
l,n
.\
''
should not extend the graph
following results were obtained. (
!(
I'
)I \ ,
1,: ' beyond t = 90 min so as to
I )I '' determine the ha~ life from
Experiment 1, with Experiment 2, with 0 ' [V02'] = 0.0025 to 0.00125
[As203] =0.10 mol dm-3 0 15 30 45 60 75 90 105 120 135
time/minutes [As203] =0.05 mol dm-3 mol dm.J. Such determina-
time/min
tion is highly inaccurate as
[VO~]/mol dm-3 [VO~]/mol dm-3
the 1, 0 determined would
(iii) Using experiment 1, largely depend on how the
0 0.0050 0.0050
graph was extended.
15 0.0040 0.0045 from[ VOz' J=0.005 mol dm- 3
to 0.0025 mol dm-3 ,
• When determining
30 0.0032 0.0040 the 2ha~ lives in experiment
t112 =50s.
45 0.0026 0.0036 J
from[ vo 2 • = 0.003 mol dm-3 to 0.0015 mol dm-3 , 1, the initial [V02'] shouldbe
asfaraspossibletominimise
60 0.0021 0.0032
t ' 112 =51 s. error.
75 0.0017 0.0029
Since the two 1112 are relatively constant, the reaction is first order with • To determine the
90 0.0014 0.0026 respect to vo,-. order w.r.t. As,O,. we use
the initial rates where the
0 005
(ii) Using the same axes, plot graphs of [VO,•] against time for the two Initial rate for experiment 1 = · = 8.33 x 1o-s mol dm-3 min·' initial [V02·] are the same.
experiments. [2] 60 Any difference in the initial
0 005 rates can then be associated
(iii) Use your graphs to determine the order of reaction with respect to Initial rate for experiment 2 = · = 4.17 x 1o-s mol dm-3 min-' with the different [As,OJ.
[As,O,l and to [V02 •], showing your working clearly. Hence give the rate 120
equation for the reaction. [3] When [As,O,l is halved, the initial rate is also halved. The rate of reaction
(iv) Checking the units:
is first order with respect to As,O,.
(iv) Calculate the initial rate from experiment 1, and use it, together with
your rate equation, to calculate the rate constant for the reaction, in- mol dm-3 min-1 =[k]xmol dm-3
Hence, the rate equation is R = k[VO,•][As20 3].
cluding units. [2] xmol dm-3
(iV) 8.33 X j o-S = k X 0.1 0 X Q.QQ5Q [k]=(mol dm-Jr' min-'
[N03/P3/Q2}
(a) In the Collision Theory, when k = 0.167 (mol dm-3 ) min-' or dm3 mar-' min-'.
particles collide, they must
Suggested Solution: be oriented in an appropriate
(a) In the Collision Theory, the rate of a reaction depends on the frequency of manner and possess energy Question 5
effective collision between reactant particles. When the concentrations of greater than the activation
reactants are increased, there are more particles within a unit volume. Hence, energysothatareactioncan The equation for the partial decomposition of gaseous hydrogen iodide at
they are more likely to collide with each other. This in tum increases the rate take place. However, in this 400 oc is shown.
of the reaction. question, these 2condijions
are not required as answers. 2HI(g) === H2 (g)+l2 (g)

(b) (i) The2halfequationsare The values for the initial rates of decrease in hydrogen iodide concentration at
various initial concentrations have been determined. These are shown in the
AsP3 +2Hp table below.
-+AsPs +4W +4e-
Initial concentration
/mol dm-3 1.67 3.34 5.01 6.68
vo; +2W +e-
2 Initial rate
--+ vo • + H20 /mol dm-3 s·' 0:41 1.64 3.69 6.56
 top_ic 8 Reaction Kinetics PageS topic 8 Reaction Kinetics
Page 9
~CORNER
(a) (i) Determine the rate equation for this reaction. Give your reasoning.
Question 6
~CORNER
(ii) Calculate the rate constant for this reaction. Give the units. [4]
(b) (I) At 400 'C the activation energy for the forward reaction is 184 kJ mor' {a) The reaction between nitric oxide and oxygen is an important intermediate
and that for the reverse reaction is 163 kJ mot·'. In the space below step in the industrial production of nitric acid. It is also one of the reactions
sketch the reaction pathway diagram for this reaction. involved in atmospheric pollution from car exhausts.
(ii) Detennine and state the value of the enthalpy change which can be Kinetic studies have shown that the reaction is third order overall, and it
calculated from these data. · [3] has been suggested that the mechanism involves the following two steps.

(c) What will be the effects of increasing the temperature on the decomposition 2NO ~ N2 0 2
of hydrogen iodide? Give reasons to explain your answer. [3]

{d) In the presence of a ·gold catalyst, the activation energy for the reverse N2 0 2 +02 ~ 2N0 2
reaction is 85 kJ mol·'. On your sketch in {b)(i) draw the energy profile of (i) Construct a rate equation for this reaction.
the catalysed reaction. Label this clearly.
{ii) Explain the meaning of the following terms.
Suggest a value for the activation energy for the decomposition of. 2 HI
rate constant
under these conditions. [2]
order of reaction
[N04/P2/Q 1]
rate-determining step
[4]
{b) The decomposition of hydrogen peroxide is a first order reaction.
Suggested Solution:

(a) {i) R = k{HI]' H20 2 --> H2 0 + ~0 2 liH" = -98 kJ mor'

2
As the initial [1,] doubles from 1.67 to 3.34 mol dm"", the initial rate in- The uncatalysed reaction has an activation energy of 79 kJ mol-'. Both
creases by 4 times from 0.41 to 1.64 mol dm"" s·'. platinum and the enzyme catalase act as catalysts, and speed up the
reaction.
{ii) 0.41 = k. {1.67)2
(a) (iij Balancing the units, {i) Use the data provided to construct a reaction pathway diagram for the
k = 0.147 mol-' dm 3 s·' uncatalysed reaction.
moldm-3 s·'=k·(moldm-3) 2
(ii) Explain what is meant by the term activation energy.
{b) {i) Energy k =mol·' dm3 s·'
{iii) Describe how the activation energy is affected by the presence of a
catalyst, and explain how this increases the rate.
{iv) What effect will the presence of the catalyst have on the rate constant
for this reaction? Explain your answer. [6]

[N05/P3/Q1]

(c) A minor factor that leads to Suggested Solution:

an increase in rate of reaction
{a) (i) R = k[0 2 ][NO]"
due to an increase in tem-
reactant perature is the increase in (ii) In a reaction, aA+bB ~product.
frequency of collision of
' - - - - - - - - - - - - - ; . R e a c t i o n co-ordinate particles (since the particles Let the rate equation be R = k[ArfB]". Then , k is the rate constant.
are moving faster now). m is the order of reaction with respect to A,
{ii) nH = 184-163 = +21 kJ mor'
n is the order of reaction with respect to B,
(b), (d) In the sketch for both
{c) Since the forward reaction is endothermic, increasing the temperature causes catalysed and uncatalysed
m+ n is the overall order of reaction,
the equilibrium to shift to the right. According to Le Chatelier's Principle, it reactions, we assume a In the mechanism of a reaction, the slowest elementary step that deter-
shifts right to absorb the excess heat. In addition, the rate of reaction becomes one-step reaction. Otherwise, mines the overall rate of reaction is the rate detennining step.
faster since the molecules have greater average kinetic energy to overcome there will be more than 1
the activation energy. hump in the diagram and (b) (i) energy
the sketch will look more
{d) E. =85+21=106 kJ mol-' oomplicated.

products

reaction co-ordinate
 Page 10
topic 8 Reaction Kinetics
~CORNER topic 8 Reaction Kinetics Page 11
(ii) Activation energy is the minimum energy that particles must possess when
they collide for a reaction to take place. Suggested Solution: ~CORNER
(iii) The presence of· a catalyst provides an altemati_ve pathway for the reac-
tion to take place and this has a lower act1vat1on energy. Hence, m?re (d) (i) An instrumental method like a colorimeter is used.
particles have energy more than the activation energy and the react1on In a colorimeter absorbance at different wavelengths is measured to find the
rate increases. wavelength shift from 40~00 nm. Time taken for this change is noted.
number of 1
Ea : activation energy of Since the time is related to rate, i.e. rate a: -.--, the gradient of absorbance
particles uncatalysed reaction. t1me
over time gives the rate of reaction. The experiment is repeated with different
E;: activation energy of concentrations of [Zn'•(aq)], which gives relation between rate and concen-
catalysed reaction. tration of [Zn'•(aq)] and PAR.

(ii) Add aqueous bromine to PAR brown colour will decolorise to show
presence of phenol group.

(iv) The presence of a catalyst increases the rate constant. The rate _constant is a Question 8
function of activition energy. The lower the activtlion energy, the higher the rate
constant. In the late 19th century the two pioneers of the study of reaction kinetics, Vernon
Harcourt and William Esson, studied the rate of the reaction between hydrogen
peroxide and iodide ions in acidic solution.
Question 7 H20 2 +21-+2H' -->2H2 0+12
Zinc chloride is one of the most important compounds of zinc. II_ is use? _in d~
cell batteries, as a flux for soldering and tinning, as a corros1on 1nh1b1tor m This reaction is considered to go by the following steps.
cooling towers and in the manufacture of rayon.
step 1 H2 0 2 + 1· --> 10· + H2 0
(d) Zinc is an essential element for plant and animal life. It is often a_dminis-
tered in the form of a chelate, which is a complex between a metal 1on and step 2 10· + H' --> HOI
a polydentate ligand.
The rate of the reaction between zinc ions and the ligand 4-(2-pyridylazo)
step 3 HOI+H' i-r --> 12 +H2 0
resorcinol, PAR, has been studied. The general form of the rate equation is as follows.

rate= k[H2 0 2 ]a Wl" [H']"

(a) Suggest how the appearance of the solution rnight change as the reaction
takes place. [1]

(b) Suggest values for the orders a, b and c in the rate equation for each of
PAR Zn-PAR
the following cases.
Both PAR and its zinc complex absorb radiation in the UV-visible region.
The figure below shows their absorption spectra. numerical value
. case
1.4 a b c
1.2 r·-... step 1 is the slowest overall
., 1.0 I \
i step 2 is the slowest overall
.,c:
0
0.8
PAR \..--zn-PAR
€ step 3 is the slowest overall
0
CIJ
.D
[3]
"' \..•. A study was -carried out in which both [H2 0 2] and [H'] were kept constant at
..... 0.05 mol dm'', and [I"] was plotted against tirne. The following curve was ob-
tained.
600 700
wavelength/nm

(i) Devise a suitable experimental technique for studying how the rate of
this reaction varies with [Zn''(aq)].
(ii) Describe a reaction you could cany out to show that PAR is a phenol. [7)
(J07/P4/Q1(d)]
,--
topic 8 Reaction Kinetics Page 13
Page 12
8 Reaction Kinetics
~CORNER
to£ic
~CORNER (d)
0.001 0.001
0.0009 1\ 0.0009 1\
0.0008
'\ 0.0008 ~ (d) Half life is constant, so

[rion]/moldm-3
0.0007
0.0006
0.0005
"' ...._,
[r ion]/moldm-3
0.0007
0.0006
0.0005
1"\. 1st order w.r.t 1- ion.

0.0004
0.0003 "" .......,
...... r---...
0.0004
0.0003
""' ""'-· ""-..,
....... ....___
0.0002
0.0001
--!'---- ~
0.0002
0.0001
-.... .....___,
0.-.---- I I 1 , • 0
0 30 60 90 120 150 180 210 240 270 300 0 30 60 90 120 150 180 210 240 270 300
time is time/s

To gain full marks for the following answers you will need to draw relevant From the graph, Half life = 120 - 30 = 90 s.
construction lines on the graph opposite to show your working. Draw them
using a pencil and ruler. · (e) Line I and 2: as [H 2 0 2 ] increases by g:g~ =I .4 so does rate. So order w.r.t.
(c) Calculate the initial rate of this reaction and state its units. [2]
[H 20 2]=1.
(d) Use half-life data calculated from the graph to show that the reaction is first Line 1 and 3 increases in rate (1.8) is also increase in [H,O,J. So rate is
order with respect to [1-]. [2] independent of [H'].
(e) Use the following data to deduce the orders with respect to [H 20 2] and [H'], Order w.r.t. [H,O,l =1st order.
explaining your reasoning. · Order w.r.t. [H'] = zero order.
3 Relative rate
[H2~]/mol dm-
3 [H']/mo\dm-
(f) The 1st step. Equation: H2 0 2 + t- -4 to- + H2 0
0.05 0.05 1.0

0.07 0.05 1.4

Question 9
0.09 0.07 1.8
[2]
(a) The reaction between iodide ions and persu\fate ions, sp~-, is slow.
(f) From your results, deduce which of the three steps is the slowest (rate
determining) step. [I] 2r + s 2 o~- ---+12 + 2So~-
[NOBIP4/02]
The reaction can be speeded up by adding a small amount of Fe'• or Fe''
ions. The following two reactions then take place.

Suggested Solution: 21- + 2Fe 3 ' ---+ 12 + 2Fe 2' 2

(a) When r i,; oxidised to 12,
(a) Colourless to reddish brown. 2
reddish brown colour of 2Fe ' + S 2 o~----+ 2Fe 3 ' + 2So~- 3
I
(b) numerical value 12 is observed.
(i) What type of catalysis is occurring here?
case c
a b (ii) The rates of reactions 2 and 3 are both faster than that of reaction 1.
0 By considering the species involved in these reactions, suggest a reason
step 1 is the slowest overall 1 1
for this.·
1 1 1
step 2 is the slowest overall

1 2 2
step 3 is the slowest overall

3
(c) rate=7.5xlo-6 moldm- s-'
 topic 8 Reaction Kinetics Page 15
Page 14
topic 8 Reaction Kinetics
~CORNER ~CORNER
.
(iii) The following reaction pathway diagram shows the enthalpy profile of Question 10
reaction 1.
Phenacyl chloride has been used as a component of some tear gases. Its
lachrymatory and irritant properties are due to it reacting with water inside body
tissues to produce hydrochloric acid.
It undergoes a nucleophilic substitution reaction with NaOH(aq):

0
enthalpy
2r: s,o~- ~Cl
lUJ - +ow-

12 + 2SO~- phenacyl chloride

(a) Write the formulae of the products of this reaction in the two boxes above.
progress of reaction
[2]
Use the same axes to draw the enthalpy profiles of reaction 2 follo~ed When the rate of this reaction was measured at various concentrations of the
by reaction 3, starting reaction 2 at the same enthalpy !eve r4~ two reagents, the following results were obtained.
reaction 1.
experiment number [phenacyl chloride] (NaOH] relative rate
(b) The oxidation of SO, to SO, in the atmosphere is speeded up by the pres-
ence of nitrogen oxides. 1 0.020 0.10 1.0
(i) Describe the environmental significance of this reaction. 2 0.030 0.10 1.5
(ii) Describe a major source of SO, in the atmosphere. -
3 0.025 0.20 2.5
(iii) By means of suitable equations, show how nitrogen oxides speed ~~
this reaction. (b) (i) What is meant by the term order of reaction?
[J09/P4/04}
(ii) Use the above data to deduce the order with respect to each reactant.
Explain your reasoning.

Suggested Solution: (iii) Write the overall rate equation for the reaction.

(a) (i) homogeneous h (iv) Describe the mechanism for this reaction that is consistent with your
overall rate equation.
(ii) Ions in reaction 2 and 3 are oppositely charged, thus attract each ot er
and react easily. You should show all intermediates and/or transition states and partial
charges, and you should represent the movements of electron pairs by
(iii) curly arrows. (7]
(c) (i) Describe an experiment that would show that CH,COC/ reacts with
water at a much faster rate than phenacyl chloride. Include the
reagents you would use, and the observations you would make with
each chloride.
enthalpy
2r + s,o~- (ii) Suggest an explanation for this difference in reactivity. (4]
{J10/P4/Q1}

12 +2Sol· Suggested Solution:

(a)
progress of reaction

{b) (i) Sulphur trioxide dissolves in rain water to produce H,SO,, which damages
buildings ow-
(ii) The burning of fossil fuels.

(iii) S0 2 + N02 --> S03 +NO phenacyl chloride

NO+ .:!.o,--> NO,

2
toQ_ic 8 Reaction Kinetics Page 16

{b) {i) It is the power to which concentration is raised in the rate equation.

{ii) By comparing experiment 1 and 2, rate increases by the same ratio as

~CORNER :Joprc 9.1 gnoryanic G.h'emislry
concentration of R- Ct increases, hence Rate ex [primary haloalkane]. It
is observed in experiment 2 and 3 that rate is proportional to OH-. 7h'e :Periodrc 7ab'le: G.hem.rcal :Perioch"c.r'fy
{iii) Rate= K[R-CI][OW].

(iv) R
\~ c/ R ]- HO R
·. c:...----::___ __.
OH.~/\.
[
HO···::A:···CI -----. f~+ cr Content

H H H H Periodicity of physical properties of the elements: variation with proton number across
H H
the third period,(sodium to argon) of:
Primary haolalkane undergoes SN, mechanism (Bimolecular nucleophilic
(i) atomic radius and ionic radius.
substitution).
(ii) melting point.
0
II (iii) electrical conductivity.
(c) (i) Reagent to check relative reactivity of R-C/ and R-C-Ci is silver nitrate (iv) ionisation energy.
solution. Add dilute aq. AgNO, solution to each of the above halogen
0 2 Periodicity of chemical properties of the elements in the third period.
II
derivative, white precipitate of AgC/ are formed at once with R-C-C/. (i) Reaction of the elements with oxygen, chlorine and water.
R-C/ forms white ppt after some time as hydrolysis of R--C/ is slow. (ii) Variation in oxidation number of the oxides (sodium to sulfur only) and of the
chlorides (sodium to phosphorus only).

(ii) In acylhalide
R)
R-C~I, carbon atom is more positive as compared to
(iii) Reactions of these oxides and chlorides with water.
carbon atom in haloalkane. Hence acid halides undergo faster hydrolysis (iv) Acid/base behaviour of these oxides and the corresponding hydroxides.
as compared to haloalkane~.

Learning Outcomes
Candidates should, for the third period (sodium to argon), be able to:
(a) *describe qualitatively (and indicate the periodicity in) the variations in atomic radius,
ionic radius, melting point and electrical conductivity of the elements (see the Data
Booklet).

(b) explain qualitatively the variation in atomic radius and ionic radius.
(c) interpret the variation in melting point and in electrical conductivity in terms of the
presence of simple molecular, giant molecular or metallic bonding in the elements.
(d) explain the variation in first ionisation energy.
(e) describe the reactions, if any, of the elements with oxygen (to give Na,O, MgO, A/ 0 ,
2 3
P,0, 0, SO,, SO,), chlorine (to give NaC/, MgC/2, Al 1Cl 6 , SiC!,, PC!,) and water (Na
and Mg only).

(f) state and explain the variation in oxidation number of the oxides and chlorides in terms
of their valance shell electrons.
(g) describe the reactions of the oxides with water.
[treatment of peroxides and superoxides is not required].
(h) describe and explain the acid/base behaviour of oxides and hydroxides including, where
relevant, amphoteric behaviour in reaction with sodium hydroxide (only) and acids.
(l) describe and explain the reactions of the chlorides with water.
()) interpret the variations and trends in (/), (g), (h), and (i) in tenns of bonding and
electronegativity.
 to ic 9.1 The Periodic Table: Chemical Periodicit Pa<>e 1
(k) su<H•est the types of chemical bonding present in chlorides and oxides from observa-
ORNER
tio~~ of their chemical and physical properties.

In addition, candidates should be able to:

(I) predict the characteristic properties of an element in a given group by using knowledge
of chemical periodicity.
/
qJJening ....... .
(m) deduce the nature, possible position in the Periodic Tab!~, and ident~ty of unknown
elements from given information about physical and chem1cal properties. ,-----------~----;,- - - - - - - - - - - - - . , 7 " ' - , l . (b) : Ionic chloride do not un-
Question I j ! ! dergo hydrolysis but merely
J \ dissociate into metal ions
The chlorides of the elements sodium to phosphorous all dissovle in or react \ \and chloride ions. If t~'
with water. · \ metal ions have a hi
(a) State the formula of a chloride of each of these five elements. [2] \\ charge densny, they under
\ slig~l hydrolysis, e.g. Mg :
(b) Describe the reaction, if any, of the chlorides of sodium and silicon with
water, relating any differences to their bonding. Give equations of any ·Wg(HP) 6 ]2+( aq) + H20(/)
\
reactions and suggest the pH values of the resulting solution. (5] o=~Mg(Hp) 5 (0H))'(aq)
A chloride of a Group V element has the formula MCI •
3 *H 0',(aq)
3
(c) Draw a dot-and-cross diagram showing the arrangement of outer shell Hen~. an':·.aqueous solu-
electrons in MCI,. Suggest the shape of the molecule and draw a diagram tion of Mg~li has a pH of
to illustrate this. (3] about 6 and·,~~ not neutral.
The first step'irt, the hydroly-
(d) When 0.100 g of MCI, was added to water and the resulting solution titrated sis of covalent chlorides
with 0.0500 mol dm"" silver nitrate, it was found that 33.0 cm3 of aqueous involves the formation of an
silver nitrate were needed to p(ecipitate all the chloride ions. Use these intermediate by a water
data to calculate the A, of M arler-he.Q~e identify M. molecule donati~g a lone
pair of electrorlS to the
(Ag•(aq)+Cr(aq) ~ AgC/(s)] (2] central atom. ¢ovalent
[NOO/P1/04] chloride undergo ~ydroly­
sis if the central a m con-
tains low lying vaca t orbit-
Suggested Solution:

(a) NaG/. MgC/2 , A/C/3 , SiC/4 and PCI3 (or PC/5 ).

als the can accept the' lone
pair of electrons from water I
to form the intermediate.
Si is in period Ill and con-
(b) Sodium chloride does not react with water but merely issolves in water. The tain empty 3d'Or!Jitals which
bonding in sodium chloride is ionic and on addition t water, the ion-dipole can aocommodate the lone
interaction that the polar water molecules have with the sodium ions and pair of electrons from water
chloride ions is sufficient to overcome the strong ionic bonds between these to form the pentavalent in-
oppositely charged ions so that sodium chloride disso readily in water: termediate. Hence SiCI, un-
dergoes hydrolysis with
NaC/(s)+aq ----t Na'(aq)+Cr(aq) water. On the other hand,
Since Na• is not highly charged, it does not undergo acid hydrolysis. CCI, does not hydrolyse
Since Ct is the conjugate base of a strong acid, it does not hyi;lrolyse in water. in water because C is in
period II and cannot exp-
Hence a solution of sodium chloride in water is neutral and its pH is 7 at and its octet to form the
25 oc. Silicon chloride is a covalent chloride. Silicon has a lower electrone- pentavalent intermediate
gativity than chlorine and is attacked by the nucleophilic water molecules, with water.
undergoing hydrolysis: BCI, undergo hydrolysis even
through B is in period II because
SiC/4 + 4H,0(1} ----t Si0 2 .2 H2 0(s) + 4HC/(aq) B in BCI, only has 6 valence
The mechanism of the reaction is shown below: electrons so that it has a vacant
orbital to accept the tone pair of
electrons form water to form the
C/ intermediate.
I 3H,P
Si
/)'\
+ HC/ ---=-- Si(OH)4 • 4HC/
C/ C/ OH ~rearrangement

pentavalent intermediate Si0 2 2 H,P

Silicon is able to form the pentavalent intermediate because it can expand its
octet since it is in Period II I.
Due to the strong hydrochloric acid being formed, the resulting solution is
highly acidic with a pH of about 1.
 I!
i topic 9.1 The Periodic Table: Chemical Periodicity Page 2 topic 9.1 The Periodic Table: Chemical PeriodicitY..
Pag_e 3
~CORNER
(c) Shape of molecule is trigonal pyramidal
(a) & (b) 1st IE increases
Question 3
~CORNER
across the period and de-
:Ci:M:Ci: . M.,, creases down the group.
e e •

:ct:
X • e
/~ ''tct Hence of the elements The six elements in the third period from sodium to .sulphur show a change in
C! Ct shown, Cs has the highest their properties from metallic to non-metallic.
1st IE while Ne has the
lowest 1st IE. (a) Illustrate this statement by describing the variation in boiling point of the
33
(d) No. of mol of Ag• = x 0.0500 =1.65 x 1o-3 (c) Only compounds with H elements, and explaining this variation in terms of their structures and
1000 • bonded to N, 0 or F is ~~- ~ (a) ThestrongerVanderWaals
No. of mol of cr·formed from the hydrolysis of 0.100 g of MC/3 capable of forming intermo- forces ins, molecules com-
'' lecular H ,bonding. The (b) Choose one metallic and one non-metallic element from these six and, for
pared to P4 molecules is
each chosen element, describe what you would observe when
=no. of mol of Ag• =-1 .65 x 1o-3 attraction between the attributed to the larger num-
proton in the H of one mol-
li
;ji·
1
No. of mol of MC!3 = - x no. of mol of cr = 5.5 x 1o-• ecule and the lone pair of
(i) the element' reacts with oxygen,
(ii) its. oxide reacts with water containing universal indicator.
ber of electrons in s, which
gives rise to alarger electron
3 electrons of N, 0 or F con-
cloud which is more easily
stitute the H bond: Write equations for the reactions you describe. [6]
i·l•
.,·'·i'.i...· M ofMC/..= massofMC/3 ~= 18 1. 8 8- cr+ $·- .5+
distorted. DO NOT attribute
:II' ' o no. of mol of MC/3 5.5 x 1o-• :X-H----: X-H (c) Indigestion remedies often contain a suspension of magnesium hydroxide. the stronger Vander Waals
where X is N, 0 or F. When a typical dose of 10.0 em' of suspension was mixed with water and forces in s, to its large M,
\!j;: A, of M =M, of MC/3 - 3x A, of C/ =.181.8-3x 35.5 =75
The strength of the H bond titrated against 0.200 mol dm_, hydrochloric acid, 35.0 em' of acid were compared to P,.
:\::: required to neutralise it.
:.li! From the Periodic Table, M =As. thus depends .on how avail- (b) Besides Na, Mg can also be
•::i able the porton in H is able Calculate the mass of magnesium hydroxide in the dose. [3] chosen for discussion. Mg
to interact with the lone pair
of electrons on N, 0 or F and reacts with 0 2 to give MgO
[ Question 2 [J01/P1/04]
how available the lone pair so that Mg tarnishes on
is. standing in air. Since its
Part of the Periodic Table is shown below. Suggested Solution:
F has the highffit electrone lattice energy is exothermic
gativity and pulls the bonding due to high charge density
I B c N 0 F ~Je
electrons strongly towards (a) Sodium, magnesium and aluminium are metals. Metal consists of a lattice of of both Mg'' and O'- ions,
Na Mg A/ Si p s Cl nSetr. Thus the proton L1 the ions with the valence electrons forming a sea of delocalised electrons. Strong MgO does not react with
nucleus of Hin HF is the most electrostatic forces exist between the negatively charged sea of delocalised water appreciably. Thus that
Ti v Cr Mn Cu ·Br exposed to form a hydrogen electrons and the positive metal ions resulting in these metals having high pH of the resultant mixture
Ag Sn I bond wtth the Fin another HF boiling points. Boiling points increase from sodium to aluminium as the num- after adding water to MgO
molecule so that HF has the ber of valence electrons increases from one to three resulting in increasing is about 8 and universal
Cs Pb An strongest intermolecular H strength of metallic bonds from sodium to aluminium. indicator gives a bluish
- -
bonds.
Silicon also has very high boiling point as it has a gaint covalent structure. green colour in a mixture
From the elements shown in this table, identify one which (d) Mg(N03 )l' Cu(N03 )2 and containing water and MgO.
Strong covalent bonds exist between all the silicon atoms and require a high
Mn(N0 3) 2 on neating decom- temperature to overcome.
(a) has the lowest first ionisation energy, pose to the respective oxide, AI should not be used for
NO, and 0 2• Phosphorus and sulphur has relatively lower boiling point. Both have simple this discussion as AI is pro-
(b) has the highest first ionisation energy,
(e) Vanadium can exist as molecular structure with weak Van der Waals forces due to instantaneous tected by a layer of tena-
(c) has a hydride that forms the strongest intermolecular hydrogen bonds, cious oxide layer so that AI
+5 (Vo,·) and +4 (VO'') oxi- dipole-induced dipole interactions between the molecules. Such forces are
(d) has a nitrate of formula X(NO,), that evolves a brown gas when heated, dation states. easily overcome resulting in their low boiling point. The boiling point of sul- does not react with oxygen.
<n Ag(NHl),·. is formed when phur is higher than that of phosphorus. This is because sulphur exists as s, In addition, Al203 does not
(e) can undergo a reduction of the type react with water so that
excess aq. NH 3 is added to a molecules while phosphorus exists as P, molecules. Since an s, molecule
xo;(aq)+ 2W(aq) +e- ----> Xo 2 •(aq) + H2 0( I), silver salt such as silver chloride. has a larger number of electrons than a P, molecule, the Vander Waals forces universal indicator does not
(g) B has three valence elec- in sulphur are relatively stronger than that in phosphorus, resulting in sulphur change colour but remains
(f) has a monopositive ion which forms a complex with ammonia, trons. After sharing one electron having a higher boiling point. green.
each with three fluorine atoms, it Besides sulphur, phospho-
(g) has a trifluride with molecules of trigonal shape, has six valence electrons with (b) The metallic element chosen is sodium while the non-metallic element chosen rous can also be chosen for
(h) has an oxide used in ceramics and glass, three regions of electrons density is sulphur.
around it. Hence BF 3 hasa trigo- discussion. P reacts with 0 2
(i) is likely to have the most exothermic reaction with fluorine (per mole of X), nal shape. A/ is not accepted (i) Sodium reacts with oxygen readily at room temperature to give sodium to give white fumes of P,o,.
because AIF 3 is ionic. oxide: P,O, reacts with water to
.(j) has an insoluble chloride. [1 0]
(i) The metal that reacts with 4Na(s)+0 2 (g)--> 2Na 2 0(s) give H3PO, so that the
(NOO/P2/Q2] fluorine to give the ionic fluoride added universal indicator
with the most exothermic lattice Silvery sodium tarnishes readily to give a white coating of sodium oxide turns orange I red. Silicon
energy is likely to have the most when it is exposed to oxygen. Yellow sulpur bums in oxygen with a bright should not be used for this
Suggested Solution: exothermic reaction. Lattice en- blue flame to give sulphur dioxide which is a colourless gas with a char- discussion as Si reacts
(a) Cs (e) V (i) A/ ergy of AIF 3 is expected to be acteristic irritating smell: readily with oxygen only at
the most exothemnic so that AI
(f) Ag (j) Ag or Pb is likely to have the most exo- S(s)+0 2 (g)--> S0 2 (g) red heat. In addition, Si02
(b) Ne
themnic reaction with fluorine. does not react with water so
(c) F (g) B G) Silver or lead(ll) chloride that the added universal in-
is insoluble. dicator does not change
(d) Mg, Cu or Mn (h) Si
colour but remains green.
topic 9.1 The Periodic Table: Chemical Periodicity Page 4 topic 9.1 The Periodic Table: Chemical Periodicity Page 5
~CORNER ~CORNER
(ii) Sodium oxide dissolves in water to give the strong alkali aqueous sodium
Questio11 5 (b) (i) Sodium atoms has the
hydroxide:
In this question, a maximum of 4 marks is available for quality of language. elelctronic configuration of
Nap(s) + H2 0(/) -----> 2NaOH(aq)
1s'2s2 2p'3s'.ln becoming
Hence when sodium oxide is added to water containing universal indi- (a) What factors determine the size of an atom? [1]
the sodium ion, rr loses a
cator, the white soild dissolves readily turning the universal indicator from (b) (i) Explain why the ionic radius of sodium is far smaller than its atomic valence electron to give the
green to violet. Sulphur dioxide dissolves in water to give the weak sul- radius. electronic configuration of
phurous acid: (ii) Explain why the cations of Group I increases in radius with increasing 1s' 2s'2p'. Thus, a sodium
S0 2 (g) + H2 0(/) -----> H2 S0 3 (aq) proton number. · [2] ion has one valence shell
Jess than its atom. Less im-
Hence when sulphur dioxide is added to water containing universal in- (c) Explain why the atomic radii of the transition elements Cr to Cu are similar. portantly, the number of pro-
dicator, the gas dissolves readily turning the universal indicator from green [2] tons in a sodium atom and
to orange. its ion is the same, but the
{N01/P2101]
2
(c) Mg(OH) 2 (s)+2H'(aq)-----> Mg '(aq)+2Hp(i) ion has one less electron.
The attraction of the
Suggested Solution:
No of mol of H' ~ 35 0
· x 0.200 ~ 0.00700 protons for the electrons is
. 1000 greater in the ion than the
No. of mol of Mg(OH) 2 ~ i x no. of mol of H' ~ i x 0.00700 ~ 0.00350
{a) Radius of the valence electrons. A greater nuclear charge {more protons) and
less screening effect {by inner core electrons) reduce the size of an atom.
{b) (i) A sodium ion has one shell of electrons less than a sodium atom so that
atom. Thus, the ionic radius·
of sodium is much smaller
Mass of Mg(OHh = 0.00350 x [24.3 + (16.0 + 1.0) x 2] = 0.204 g than its atomic radius.
the ionic radius of sodium is far smaller than its atomic radius.
(c) For consecutive main
(ii) With increasing proton number, the number of filled inner shells also
group elements, a proton is
increases for Group I cations, so that the valence electrons are better
added to the nucleus while
Questio11 4 shielded ~nd are furth~r a':"ay from the nucleus. Thus, the radius of Group
electron is added to the same
In this question, a maximum of 4 marks is available for the quality of language. I catrons rncreases wrth rncreasing proton number. . . .
valence shell. Electrons
(a) State and explain the trend of the first ionisation energies for the Group I (c) In general, for each consecutive transition elements Cr to Cu, a proton is · added to the same valence
elements lithium to caesium. [2] added to the nucleus while an electron is added to the panultimate 3d-subshell. shells are poor shielders so
The electron added to the penultimate 3d-subshell (which is nearer to the nucleus that atomic radii generally
(b) Explain the trend of the first ionisation energies across the period sodium than the 4s-subshell) shields the 4s-e\ectron relatively effectively. Thus, even decrease across the period
to argon. [2] though the number of _protons increases from Cr to Cu, shielding provided by since number of protons in-
{J01/P2101] creases across the period.
the added 3d-electron rs suffrcrent to keep the effective nuclear charge approxi-
(b) The trend of increasing 1st IE mately constant. Hence, atomic radii of the elements Cr to Cu are similar. However for consective
is not observed consistently transrrion elements, electron
Suggested Solution:
across the period from Nato are NOT added to the
(a) The first ionisation energies for Group t elements de.crease down the group Ar. This is a disruption be- Questio11 6 valence shell but the inner
from lithium to caesium. This is because the valence electron is further from d-subshell. Compared to the
tween Mg & AI and P & S.
the nucleus and the number of inner filled quantum shell increases from lithium (a) Describe the reactions, if any, that occur when separate samples of sodium shielding by electrons in the
Despite having a higher ef- and phosphorus are
to caesium. The valence electron is more greatly shielded from the positively same valence shell, the d-
fective nuclear charge than
charged nuucleus progressively down Group I. As a result, Jess energy is Mg, AI has a lower 1st IE. (i) added to water, electrons are bellershielders
required to remove the valence electron down the Group resulting in the trend for valence electrons. Thus,
This is because the electron (ii) burned _in air, and water is added to the resulting oxide.
of decreasing first ionisation energies down Group I. to be removed in AI is a despite increasing the num-
higher energy p-electron fur- Write equations where appropriate and suggest the pH of any aqueous ber of protons, atomic radii
(b) Across the period from sodium to argon, the number of protons and electrons
ther from the nucleus while solution formed. [7] transrrion elements in the
increased by one each consecutively. There is a general trend of increasing
that to be removed from Mg same row are similar {com-
first ionisation energies across the period from sodium to argon. This is be- (b) Sodium per~xide, Na,O,. is us~d in submarines for absorbing atmospheric
is a lower energy s-electron pared to the varying atomic
cause the nuclear charge across the period increases as a proton is added carbon droxrde and regeneratrng oxygen. The reaction produces sodium
nearer the nucleus. radii of main group elements
to the nucleus but shielding remains approximately constant since the elec- carbonate as a by-product.
from the same period such
tron is added to the same valence shell. Effective nuclear charge increases Despite having a higher ef- (i) Write a balanced equation for this reaction, as sodium to chlorine).
across the period resulting in a general increase in first ionisation energies fective nuclear charge than
across the period from sodium to chlorine. P, S has a lower 1st IE. This (il) Calculate the mass of sodium peroxide needed per day to absorb the
is because the electron to be carbon dioxide produced by a crew of eight submariners, each of whom
removed in S comes from a exhales 600 dm' of C02 per day. [3]
p-<Jrbital with a pair of elec- [N02/P3/Q5 Either]
trons and is aided by repul-
sion while the electron to be
removed from Pcomes from
a singly occupied orbital, not
aided by repulsion. ·
 !'I
! topic 9.1 The Periodic Table: Chemical Periodicity_
topic 9.1 The Periodic Table: Chemical Periodicity Page 6 Page7
I ~CORNER
,I Suggested Solution: Suggested Solution: ~CORNER
l (a) (i) When sodium is added to water, much energy is given out and the sodium (a) The two common
allotropes of phosphorous
(a) (i) Oxidation number of aluminium in its chloride is +3 while oxidation num- (a) Metal ions with high
may ignite and bum with a yellow flame. Hydrogen gas and sodium ber of phosphorous in its chloride is +5. charge densily. eg AI~. Fe'"
are white and red phos· and Cr,. polarise lhe water
hydroxide are produced:
phorous. White phospho· 2AI(s)+3C/2 (g) ---> 2AJC/3 (s} .
2Na(s)+ 2H 2 0(/) --> NaOH(aq) + H2 (g) coordinated to them so
reus is very reactive and
2P(s)+ 5CI2 (g) ---> 2PC15 (g) greatly that their aqua com·
Phosphorus does not react with water. bursts spontaneously into
plexes hydrolyse readily in
flames if exposed to air. It is
(ii) Aluminium chloride dissolves in water to form aqueous aluminium chloride: water to give H3o· ions.
(ii) Sodium burns in air to give its oxide: normally stored underwater
to prevent it fmm reacting Hence, aqueous solutions
2Na(s)+0 2 (g) - - > l~a 2 0(s} AIC/3 (s)+aq--> A/ 3 .-(aq)+3Cr(aq) oltheir salts are acidic. The
with oxygen. Red phospho·
Sodium oxide diss·olves in water readily to give aq. NaOH: rous is much less reactive AI'· exists as a hexaaqua complex in solution : [AI(H,O),]"'. solutions are acidic enough
than white phosphorous to liberate C02 from aq.
Na 2 0(s) + H2 0(/) - - > 2NaOH(aq) AI'' is highly charged so that it polarises the water molecules coordinated
and does not need to be Na,CO, and their respective
Since NaOH is a strong base, 1he pH of the solution formed is around 13. stored under water. PI10S· to it greatly and hydrolysis occur to produce H,O•(aq): hydroxides are precipitated
'. ~~ :! phorous forms two oxides. out when aq. Na,co, is
Phosphorous burns in air to give phosphorous(V) oxide, P,O,:
P.O, and P.O.,:
3
[AI(H2 0)6 ] +(aq) + H2 0(/) <==== [AI(H2 0) 5 (0H)] 2+(aq) + H 0+(aq)
3 added to aqueous solutions
4P(s)+50 2 (g)--> P4 0 10 (s) containing their salts.
0 The formation H,O• causes aluminium chloride solution to be acidic and
Phosphorous(V) oxide dissolves in water to give phosphoric acid: II pH of an aqueous solution of aluminium chloride is around 3. Phosphorous forms two

P4 0 10 (s) + 6H 2 0(/) --> 4 H3 P0 4 (aq) o6

I
p
'-o
I
0
o'/ '-o
p,o,~
p
Phosphorous(V) chloride reacis with water to give phosphoric acid and
hydrochloric acid:
chlorides, PCI, and PC15 .
PCI 3 is formed when phos-
Phosphoric(V) acid is a weak acid and pH of the solution formed is o""'P-\ 'P"""'o phorous is reacted with
around 2. I P I //P"/ PC/5 (s)+4H 20(1)---> H3P0 4 (aq)+5HC/(aq) limited amount of chlorine
0/1/"0 0 0 while PCI, is formed when
0 Since the hydrochloric 1lCid formed is a strong acid, the pH of the resultant
(b) (i) 2Na 2 0 2 (s)+2C0 2 (g)--> 2Na 2C0 3 (s),·0 2 (g) phosphorous is reacted with
P4 0,o P,o, solution is around 1. excess chlorine.
(ii) Assuming room temperature and pressure conditions, PCI, reacts with water to
(b) Element: AI 0
P,O, is formed if white H fonm H3PO, and HCI. The
Volume of C0 2 exhaled by the eight submariners = 600 x 8 dm
3
= 4800 drn3 A,:
phosphorous is bu~ned in 27.0 16.0 1.0 resultant mixture has a low
No. of mol of C0 2 = 4800 + 24 = 200 limited supply of oxygen % composition by mass, %m : 45.0 pH (around 1) because HCI
and P,O, is fonmed rr white 53.3 1.7 which is a strong acid is
No. of mol of Na 2 0 2 needed to absorb C0 2 =no. of mol of C0 2 = 200 phosphorous is burned in molar ratio = %m .,. A, : 1.67 produced.
3.33 1.7
excess oxygen.
Molar mass of Na 20 2 = 23.0 x 2 + 16.0 x 2 g mol-' = 78 g mol""' dividing by smallest no. : 1 2 (b) Boehmite could be A/ 0 •
Sodium hydroxide is a 2 3
Mass of Na2 0 2 =200 x 78 g =15600 g = 15.6 kg strong base and dissoci· Hence, empirical formula of the boehmite is A!H0 :
H20. The empirical formula
ales fully. For a 0.1 mol 2 will thus be A/ H02.
3
dm"" of aq. NaOH, A/ +(aq)+30W(aq)---> AIH0 2 (s)+H2 0(1)
pOH = -log(0.1) = 1;
Question 7 pH= 14-1 = 13
(a) When heated in chlorine, aluminium and phosphorous form chlorides. Phosphoric(V) acid has a Questiou 8
K,, of7.1 x 10"" mol dm""at
(i) State the oxidation numbers of the elements in their chlorides, and 25 'C. For a 0.1 mol dm"" of (a) The melting points of some oxides of Group IV elements are given below.
write balanced equations tor their formation. aq. H3PO, fonmed,
(ii) Describe the reactions, if any, of the chlorides with water, suggesting 1 oxide melting point I 'C
the pH of the resulting solutions and writing equations where appro- [W] "'(7.1x10"' x0.1)l
priate. [7] C0 2 -78
= 0.0266 mol dm-'
(b) When aqueous ammonia is added to an aqueous solution of an aluminium which gives it a pH of 1.6"' 2. Si0 2 1610
salt, a precipitate of 'aluminium hydroxide' is formed as an amorphous
gelatinous mass. When dried, this precipitate forms a white crystalline Sn0 2 1630
compound called boehmite. ----

Boehmite has the following compositioins by mass: A/, 45.0%; 0, 53.3%; Describe th·e bonding in each oxide, and how it relates to its melting point.
H, 1.7%.
(i) co,
Calculate the empirical formula of boehmite, and write a balanced equation
(ii) Si02
for its formation from aluminium ions and hydroxide ions. [3]
[N02/P3/05 Or] ~~~ ~
(b) Writing balanced equations where appropriate, describe how the above
three oxides diller in their reactions with
(i) NaOH(aq),
(ii) HCI(aq). [4]
topic 9.1 The Periodic Table: Chemical Periodicity PageS topic 9.1 The Periodic Table: Chemical Periodicity Page9
~CORNER
(c) The last oxide in Group IV, PbO., reacts with concentrated hydrochloric acid ~CORNER
liberating chlorine gas. •
Use the Data Booklet to calculate the E ,!11 and to write a balanced equa-
[2] electrical
tion for this reaction. conductivity
[J03/P4/03]

Suggested Solution:
ON~~a~M~g--A7/~S7i~TP--TS--CT/~Ar
(a) (i) Strong double c~mvalent bonds between C and 0 atoms but weak Van
der Waals' forces between C0 2 molecules. Hence, co, has low melting Additional Information:
point. Down the Group, the
(ii) Strong single covalent bonds between Si and 0 atoms in a macromol- atomic size and first IE
ecule. Hence, Si02 has a high melting point. increase. Hence, there is ionic
radius
an increase in metallic
(iii) Strong ionic bonds between Sn" and O'· ions. Hence, SnO, has a high
character. In fact, Sn is
melting point. known to be a metal.
(b) (i) C0 and Si0 are acidic and they react with NaOH to form salts.
2 2 0
C0 2 + 2 NaOH ----> Na 2C0 3 + H20 .T-::-..--.---.---..-~
Na Mg A/ Si p S C/ Ar
Si0 2 + 2 NaOH ----> Na2 Si03 + H20 (ii) B.ne f_ly explain the shapes of each of your sketches.
SnO, is amphoteric and it also reacts with NaOH is a similar manner. melting p01nt, electrical conductivity, ionic radius . [6]
(b) (i)
Sn0 2 + 2 NaOH ----> Na 2Sn0 3 + H2 0 :;~~ an equation for the reaction of aluminium oxide with dilute sulphuric
(ii) w· ~~ equation for the reaction of each of the following oxides with
a;~t=
0
(ii) Both CO, and SiO, do not react with HCI.
SnO, is amphoteric and it reacts with HCI to form a salt.
sodium hydroxide.
Sn0 2 +4HCI ----> SnC/4 +2H 2 0
sulphuric dioxide,
aluminium oxide.
(c) Pb 4 • + 2e· E"=+1.69V
(~ii) Comment on the role of aluminium oxide in reactions (i) and (ii). [4]
C/2 +2e· E" = +1.36 V
(c) (1) :~ldtet aneqduation to~ the reaction of calcium hydroxide with ethanoic
Pb0 2 + 4HC/ ----> PbC/2 + 2Hp + C/2 Cl o pro uce calc1um ethanoate.

E:u = (+1.69)- (+1.36) = +0.33 V (ii) When calcium ethanoate is heated

C 62.1 %· H 1 3'¥<. o r "d
60, b a lqUI_ ketone A, of composition
· o, 0 • 27 · ' 0 Y mass w1th an M t 58 ·
empiri~al a~d id:n~:;~ced.
' ' '
Use these data to calculate the formula'

Question 9
Const~c~an equation for the thermal decomposition of calcium ethan~ate.
(iii) Descnbe tests which would confirm that A .1s a ketone. [4]
The use of the Data Booklet is revelent to this question.
(a) (i) Complete these sketches for elements of the third period to show each [N03/P2/Q1 j
property changes along the period.
Suggested Solution:
(a) (i)

melting
point melting
point

Na Mg AI Si P S C/ Ar 0

Si P S C/ Ar
Elements
 Page 10 tonic 9.1 The Periodic Table: Chemical Periodicit
topic 9.1 The Periodic Table: Chemical Periodicity Page 11
~CORNER (ii) c H 0 ~CORNER

"~"~'~~.
%mass 62.1 10.3 27.6 (c) (iii) lfAisaketone,rtwould
62.1 be propanone.
molar ratio 10.3 27.6
-
12 1 16 0
conduct;v1ty
~ 5.175 10.3 1.725
II
CH 3 -C-CH 3
5.175 10.3 1.725
--
'-C=O+ /N- ~
1.725 1.725 1.725 H, N',.-H
0
Na Mg A/ Si P
~~~
S C/ Ar 3 6 1 / H ~
Elements The empirical formula of A is C3 H 0. O,N NO,
6
Lei the molecular formula be C3nHsnOn.
0.25 ~
/H
n.[(3 X 12) + (6 X 1) + 16] ~58 )c=N-Nn • H,o
0.2 n=1
O,N NO,
~n~ 0.15 Hence, A is C3 H6 0.
rn~~
~m 0.1 (CH3 C00) 2 Ca --...:.... C 3 H6 0 (/) + CaC0 3 (s) Instead of Tollen's reagent,
Fehling solution, KMnO.f
0.05 . H,so, or K,Cr,o, / H,so,
(iii) Add 2, 4-dinilrophenylhydrazine. An orange precipitate will be formed if
0+--r-,.-~-r-,.-~- il is a carbonyl compound. could also be used where
Na Mg A/ Si P S C/ Ar no oxidation will take place.
Next, warm A with Tollen's reagent. No silver mirror will be formed if it is
Elements a ketone.

(ii) · The melting pain! increrases from Nato Mg to A/, due to increasing metallic !
bond strength, and peaks at Si which has a gaint molecular structure with Que.flion I Q
- strong covalent bonds. From P, to Ar, the non-metals exist as simple
molecules and hence their melting points are low due to the weak Van
The table below gives data on some oxides of elements in period 3 of the
der Waals' forces between the molecules. Periodic Table.
The electrical conductivity of the metals increases from Na to Mg to A/ due
tothe increasing number of valence electrons that contribute to the sea oxide Na 2 0 MgO A/2 0 3
of delocalised electrons. The rest of the elements are giant molecular (Si)
Si0 2 P4 0 6 so,
or simple molecular and they do not have delocalised charges to conduct melting point/ K 1193 3125 2345 1883 297 200
electricity. boiling point/ K 1548 3873 3253 2503 448 263
The ionic radius decreases from Na• to Mg'' to A/ 3' to Si 4' due to increas-
ing number of protons. pa-, S' and Ct· have higher ionic radii due to an (a) Write an equation for the reaction of phosphorous with oxygen to form
additional shell of electrons. The decreasing trend is due to the increasing phosphorous oxide, P,O,.
[1]
number of proton again.
(b) Drawing diagrams where appropriate, suggest, in terms of structure and
(b) (ii) WhenAI,O,reactswith
bonding, explanations for the following.
(b) (i) Al 20 3 (s)+3H 2S0 4 (aq)----'----> AI2 (S0 4 )s(aq)+3H 20(1) NaOH, an aluminate is
(i) the low boiling point of so,.
·formed. Aluminate can also
(ii) S0 2 (g)+2NaOH(aq)----> Na 2 S03 (aq)+H2 0(/) be represented as AIO,- (ii) the melting point of MgO is higher than that of Na,O. I

(instead of [AI (OH)J ). (iii) the melting point of Si02 is much higher than that of P,O,.
Alp 3 (s)+2NaOH(aq)+3Hp(i)----> 2Na[A/(OH) 4 ](aq)
AI20 3 (S)+2Na01-l(aq) -7 (c) By choosing a suitable example from the table, write an equation showing
(iii) A/20 3 is amphoteric. an oxide acting as a base.
2NaAI0 2 (aq) + H20(/) [1]
In (i), A/ 0 3 acts as a base. In (ii), A/2 0 3 acts as an acid. (b) When answering lhis
2 {N04/P2103]
question, candidates have
(c) (i) 2CH COOH(aq)+Ca(OH) 2 (aq)----> (CH 3C00) 2 Ca(aq)+2H 2 0(1) to correctly identify lhe lype
3 Suggested Solution: of particles present (e.g.
atoms, ions, molecules) and
(a) P4 (s)+30 2 (g) - - - t P4 0 6 (s) hence lhe type of bonding
present (e.g. metallic, ionic,
(b) (i) SO, exists as simple molecules with weak Van der Waals' forces between Van der Waals' covalent,
them. Hence, il has has a low boiling point. etc.). The physical proper-
(ii) Both MgO and Na,O are ionic. Mg'' has a higher charge than Na•. Hence, lies (e.g. mp, bp) can then
the ionic bond in MgO is stronger than that of Na,O and MgO has a higher be compared by comparing
melting point. the slrenglh of the different
bond types.
topic 9.1 The Periodic Table: Chemical Periodicity Page 12 topic 9.1 The Periodic Table: Chemical Periodicity Page l3
~CORNER
(iii) SiO, exists as a giant covalent compound with strong covalent bonds ~CORNER
joining Si and 0 atoms. P.O, is simple molecular With weak Van der (c) Other possible answers in- Question 12
Waals' forces between the molecules. Hence, SiO, has a higher melting clude Na,O and A/20 3. A
The melting points of the chlorides of th . .
point than that of P,0 10 • different acid e.g. H,SO,, given below, e elements from sod1um to silicon are
HNO, may also be used.
sodium magnesium aluminium silicon
Na 20 + 2HCI --> 2NaCI + H20 chloride chloride chloride chloride
MgO + H2S0 4 --> MgS0 4 + Hp
801 'C 701 'C 178 'C 70 'C

(a) State the formula. of each of these chlorides.

oostate Ihe type of chemical bonding in each of these chlorides.
~
[2]

(c) ~;~~~~~s :h:~:c~~~r~~~~i~. of each

11
of these chlorides with water. Write
(d) S I h · (3]
-up ur and chlonne react together to give a compound containing 31 o;. S
Question II (1) Calculate its empirical formula ' ·

The elements in Period 3 range from metals on the left of the Periodic Table (ii) ~~~~~t:eassh,.atspeempmca
of _its ml of lec~les, assuming its molecular formula is
ormula
to non-metab on the right.
(iii) Predict the pH of its solution in ~ater.
(a) Using one property of the element and one of its chloride, describe two [3]
pieces of evidence which support each of the following statements. {N04/P3/05 Or]
(i) Sodium is a metal.
(ii) Phosphorous is a non-metal. [4] Suggested Solution:
(b) The elements aluminium and silicon and their compounds have some (a) NaC/, MgC/2 , AIC/3 , SiC!,
properties characteristic of metals, and some of non-metals. Suggest an (a) The empirical formula of
example of each of the following. (b) ionic, ionic, covalent, covalent.
aluminium chloride is AICI
(i) a property of aluminium chloride that is typical of a non-metallic chloride, (c) SiCI, hydrolyses completely in water to give HC/. (not Af,CI,). It does not
(ii) a property of silicon that is characteristic of a metal. [2] exist as dimer in the soild
SiC!, +2H,O------> SiO, +4HC/ state.
(c) Aluminium hydroxide is amphoteric.
AICi, hydrolyses partially to give HC/. (c) [AI(H,O),]" can undergo
(i) Explain what the word in italics means,
further hydrolysis:
(ii) Describe two reactions which demonstrate the amphoteric behaviour of (Ai(H,OJst ~ (Ai(H2 0)5 (0H)j
2
' +H'
aluminium hydroxide. Write equations for these ractions and state which
MgCI, hydrolyses slightly to give HC/. [ AI(Hp)sOHt =='
reaction is typical of a metal and which is typical of a non-metal. [4]
[N04/P3/05 Either]
Mg'• + H,O ~ (Mg(OH)]' + H' J
[Ai(H 20) 4 (0H) 2 +W

Suggested Solution: (d) (i) s C/ (d) (iii) Being a chloride of a

(a) (i) Sodium conducts electricity in both soild and liquid states showing that it is 0
/o mass 31 69 non-metal, HC/ is formed
a metal which contains delocalised-electrons. It forms ionic Na•ct- which (a) Candidates should not refer when SCi, hydrolyses in
Ar 32 35.5
dissolves in water that conducts electricity due to presence of mobile ions. to the properties of metal/ waler.
non-metal to their ability to 31 69
(il) As a non-metal, phosphorous does not conduct electricity in the soild form basic/acidic oxides. molar ratio
state. It forms simple molecular PCI 3 and PCI 5 which have low melting 32 35.5
This would then be relying
poinis due to weak Van der Waal's forces. on the properties of the = 0.969 1.944
(b) (i) Aluminium chloride has a low boiling point. oxides instead of the ele- 2
ments.
(ii) Silicon is a semi-conductor and can conduct electricity. Empirical iormula : set,
(b) (i) AI C/ 3 is soluble in or-
(c) (i) It means both acid and basic properties. ganic solvent such as ben- (ii) Bent
(ii) A/(OH), shows basic property by reacting with an acid to form a salt. zene.

AI(OH) 3 + 3 HC/ ----> A/C/3 + 3 H20 (c) The 2nd equation could also ~s
·I·
This is typical of a metal.
be represented by ·;\
AI(OH), + NaOH--> C/ Cl
A/(OH) shows acid property by reacting with an alkali to form a salt.
3
A/(OH), +NaOH----> Na[A/(OH) 4 ] Na[A10 2 ]+2H 20 (iii) 1

This is typical of a non-metal.

 Page 14 tooic 9.1 The Periodic Table: Chemical Periodicit
top_ic 9.1 The Periodic Table: Chemical {Jeriodicity Pal!e 15
~CORNER
(c) n = 0.500 x
13 50
· = 6. 75 x 1o-a mol ~CORNER
H' 1000
Question 13
2H' + o 2 - ---. H2o
(b) Both magnesium and silicon react with chlorine to give their chlorides, which
differ iri their reaction with water. no•· =..!.n
2 H" =..!.x6.75x1o-
2
3
=3.375x10-3 mol
Describe these differences, and explain them in terms of the different struc-
tures and types of chemical bonding with the chlorides. [3] 0.1
·Hence, M, of M2 0 = - = 29.63

L·. [NOS!P3i05b Or]

2
1
A, oiM=-(29.63-16)=6.8
.
no2-

Suggested Solution: The element is Li.

,,,,, (b) MgC/ is an ionic compound which dissolves in water with minimum hydroly-
L 2
sis. The solution is weakly acidic. Question 15
' Mg 2 ' + H20 ~ Mg(OH)' + H'
SiC/, is simple molecular and contains Si - C/ covalent bonds. It readily This question concems the chlorides of the elements sodium to phosphorus of
the third period of the Periodic Table.
undergoes hydrolysis to give a strong acidic solution.
The melting points of these chlorides are given below.
SiC/4 +2H,0 ---> Si0 2 + 4HC/
d I sodium I I
magnesium aluminium silicon I phosphorus(V) I
~_!!!stion I; ~
compoun chloride chloride chloride tetrachloride chloride
\ melting
poinVK 1081 987 451' 203
\(a) Sodium, silicon and phosphorus form the oxides Na,O, SiO, and P,Q 10• 1 435
I (i). Explain why the oxides of sodium and silicon have these formulae. •sublimes at 451 K
. (ii) Describe the action of water on the oxides of sodium and phOsphorus, (a) Give the equation, with state symbols, for the reaction of phosphorus with
write equations tor any reactions that occur, and suggest the pH of
chlorine to form phosphorus(V) chloride, PC/ • [2]
each solution formed. [5] 5

(b) Suggest, in terms of the structure and bonding, explanations for the follow-
(b) Gallium, element number 31, is an important metal used in light emitting
ing. You should draw diagrams where you think they will help your answer.
diodes (LEDs). It is manufactured by electrolysis of a molten compound
formed by reaction of gallium oxide with sodium hydroxide. (i) the high melting point of sodium chloride
Suggest an equation for this reaction explaining your reasoning. [2] (ii) the low melting point of silicon tetrachloride
(4]
(c) A 0.100 g sample of a Group I oxide was dissolved in water and titrated (c) Write an equation for the reaction of silicon tetrachloride with water. (1]
with 0.500 mol dm.. hydrochloric acid. 13.50 em' of acid were needed to
(d) What is the pH of the solution formed when each of the following com-
reach the end-point. pounds is dissolved in water?
Calculate the M, of the oxide, and hence identify the Group I element it
contained. [3] NaG/ ......................................
[N06/P3!04]
PC/5 ••••••.•••••••••••••••••••••••••••••••• [2]

(e) When solid aluminium chloride is heated above 451 K, a vapour is formed
Suggested Solution: which has M, = 267.
. {a) (i) Sodium oxide exists as an ionic solid. The ions present are Na' and When this vapour is heated above 1100 K, the vapour has M, = 133.5.
O'·. To maintain electrical neutrality, for each 0'·, there would be
(i) What are the molecular formulae of these two forms of aluminium chlo-
2 Na•. Hence, the formula is Na,O. ride?
SiHcon dioxide is a giant covalent compound. Each Si atom is bonded to
4 0 atoms and each 0 atom is bonded to 2 Si atoms. Hence, its empirical at 460 K ........................................ at 1150 K ...................................... ..
formula is SiO,. (ii) Draw a 'dot-and-cross' diagram of tile form of aluminium chloride that
Hence, both have the same formula. exists at the higher temperature.

(iii) Draw a displayed formula of the form of aluminium chloride that exists
(ii) Na 0+H 20---> 2Na'(aq)+20H-(aq) pH=14 at the lower temperature. Indicate clearly the different types of bonds
2
P40 10 + 6H 20 ~ 4H3P04 present. (5]

H3P0 4 ~ H' + H2PO/- pH"'2 [N07/P2102]

(b) Ga 20 3 + 2NaOH ---> 2NaGa0 2 + H20

GaO is amphoteric. It reacts with a strong base e.g. NaOH to form a salt.
 Pa e 16 topic 9.1 The Periodic Table: Chemical Periodicity Page 17
to ic 9.1 The Periodic Table: Chemical Periodicit
~CORNER s
(d) The. reaction between 2C/2 an d water IS
. a redox reaction ~CORNER
Suggested Solution: Which product has been formed b y OXIdation
. . .
and which by. reduction?
.
(a) Affemative Answer:
(a) P (s) + 1OC/ 2 (g)---> 4PC/5 (s) 2P1,1+ 5C/2(g) ---> 2PC/ 51, 1 product formed by oxidation ·················· ····················
4

(b) (i) Na• & C/ - ions are held together with strong electrostatic force to make product formed by reduction
(b) (iij SiC/, is symmetrical, ······························ [2]
giant ionic lattice causing its melting point to be high.
non polar molecule. They [N07/P2103]
(ii) SiC/, is a covalent compound making simple molecular structure. These have only van der Waal's (a) Atomic number and num-
molecules have weak intermolecular forces i.e. (van der Waal's forces) forces among these ber of electrons in one atom
molecules.
Suggested Solution: of P, S & C/ are 15, 16, &
causing its melting point low.
17 respectively. There mol-
(c) Affemative Answer: (a) phosphorus: P, .
ecules are P,, s, &Cl, and
(c) SiC/4 + 2HP---> Si0 2 4HC/
• SiC/4 + 4H 20 -> Si(OH) 4 sulphur: s, their total number of elec-
+4HC/ chlorine: C/2 trons are 60, 128 & 34 re-
(d) NaC/: 7
spectively. As the total num-
PC/5 : between 1 - 4 • SiC/4 + 4H 20-> Si0 2.2H,O ber of electrons decrease in
(b) (i) S,' P,, Cl2.
at 1150 K: A/C/3 +4HC/ the orders, . P, , Cl, there-
(e) (i) at 460 K: Ai2Cf, (ii) Tolal number of electrons in S p , & fore order of melting point
(d) NaCI is made from a waal's forces decrease. '' • C/2 are decreasing, hence van der
XX IS the same.
(ii) strong acid and a strong
~ Cl ~ alkali, therefore pH of salt . (c) {iU) S,Gf, : s
X (c) (i) M,(S2Cf2) = (2x32.1) +(2x35.5) = 135 .2
solution will be 7. 1 : 1.5
AI PC/5 + 4H 20 ---> Hl4 + 5HC/ n(S2C/2) = _l:!__ = 0 0199- 0 02 or 2 :3
XX x• •X XX 135.2 . - .
~CI Cl~ As HC/ is produced, that {d) Oxidation no. of s in S,Gf,
XX XX is why solution will be (ii) n(S) = 0.96 = 0.03 IS Increased from +1 to 4 in

(iii)
strong acid and pH
would be 1 to 3.
32.1

moles of S produced by 1.0 mol of S 2C/2 = 0.03

H,so,.
s in s,ct, is reduced from
,
_ -- 1 .5 moles
(e) (ij At 460 K Ai,Gf, is 0 02 + 1 to 0 ih sulphur (free
present as a dimer as its (iii) 2S2C/2 + 3H20 -> 3S + H2S03 + 4HC/ state).
Mr i.e. 267 is twice the
Mr of A/C/3, i.e. 133.5
(d) product formed by oxidation.· H2 SO,
At 1150 K, dimer breaks
product formed by reduction: S
to give A/C/3 as shown
Question 16 from its Mr = 133.5.
The elements phosphorus, sulphur, and chlorine are regarded as having simple (iii) Lone pair from
neighbouring chlorine is Question 17
molecular structures.
(a) What are the molecular formulae of each of these three elements? mutually shared by
?opper and titanium are each used with . .
aluminium atoms making a light, strong and resistant to cerro . alummlum to make alloys which are
phosphorus .................... ,.......... .. dimer molecule i.e. PJ,Gf,. AI . . SIOn.
umlmum, AI, is in the third period of th . .
sulphur ......................................... are both transition elements. e Penodlc Table; copper and titanium
[3]
chlorine ...................................... . (a) Complete the electronic conf ·
number 22. lgurallon of aluminium and of titanium, proton
(b) (i) Place the three elements in order of tl)eir melting points with the high·

I~ I: :
est first.
(ii) Suggest an explanation for the order you have given in (i). [3]

(c) Sulphur and chlorine can be reacted together to form disulphur dichloride,
S 2C/2 • Aluminium reacts with chlorine. [1]
Disulphur dichloride, S C/ , is decomposed by water forming sulphur and (b) (i) Outl_ine how, starting from aluminium . .
2 2
a mixture of hydrochloric acid and sulphurous acid. carm~d- out in a school or college laborpowder,10
I~ IS reaction could be
alum1mum chloride. A diagr m . atory giVe a small sample of
When 2.7 g of S C/ is reacted with an excess of water, 0.96 g of sulphur, ii) a IS not necessary
2 2 (
S, is produced. ... 0 escribe what you would see d unng . . reaction
th1s ·
( Ill) At low temperatures, aluminium chlori .
(I) What is the amount, in moles, of S 2Ci2 present in 2.7 ·g?
Draw a 'dot-and-cross' diagram t ~e vapour has the formula AI2C/ .
(ii) What is the amount, in moles, of S produced from 1.0 mol of S 2C/2? Show outer electrons only. o s ow the bonding in AI2CI,. '
(iii) Construct a balanced equation for the reaction of S2C/2 with water. Represent the aluminium electrons by •.
[4)
 Page 18 topic 9.1 The Periodic Table: Chemical Periodicity_ Page 19
top_ic 9.1 The Periodic Table: Chemical Periodicity
~CORNER
Represent the chlorine electrons by x. (6]
Question 18
~CORNER
Copper forms two chlorides, CuC/ and CuC/2 •
Magnesium will react on heating with chlorine, or oxygen, or nitrogen to give
(c) When copper is reacted directly with chlorine, only CuC/2 is formed. the chloride, or oxide, or nitride respectively. Each of these compounds is ionic
Suggest an explanation for this observation. (1] and in them magnesium has :he same +2 oxidation state.
Titanium also reacts with chlorine. (a) (i) Write an equation, with state symbols, for the second ionisation energy
(d) When an excess of chlorine was reacted with 0.72 g of titanium~ 2.65 g of
of magnesium.

a chloride A was formed. (ii) Use the Data Booklet to calculate the enthalpy change that occurs
when o~·e mole of gaseous magnesium ions, Mg2<, is formed from one
(i) Calculate the amount, in moles, of titanium used.
mole of gaseous magnesium atoms.
(ii) Calculate the amount, in moles, of chlorine atoms that reacted, Include a sign in your answer.
(iii) Hence, determine the empirical formula of A.
enthalpy change =.......................... kJ mot-• [3]
(iv) Construct a balanced equation for the reaction between titanium and
chlorine. (4] (b) Separate samples of magnesium chloride and magnesium oxide are shaken
with water. In each case, describe what you would see when this is done,
(e) At room temperature, the chloride of titanium, A, is a liquid which does not
and state the approximate pH of the water after the solid has been shaken
conduct electricity. with it.
What does this information suggest about the bonding and structure in A? (2] (i) magnesium chloride
[J091P2101}
observation .........................................................................................................

Suggested Solution: approximate pH of the water ......................... ..

(ii) magnesium oxide
(a),--- 2 6 2 1 ]
AI 1s2 2s 2p 3s 3p
observation .........................................................................................................
6 2 6 2 2
Ti 1s2 2s 2 2p 3s 3p 3d 4s
approximate pH of the water ......................... .. [4]
By passing dry chlorine gas over heated aluminium powder. Vapours of (c) Magnesium burns in nitrogen to give magnesium nitride, a yellow solid
(b) (i) which has the formula Mg 3 N •
aluminium chloride are condensed in water cooled flask. 2

Magnesium nitride reacts with water to give ammonia and magnesium

(ii) Aluminium glows, yellow vapours are formed which condense to yellow
hydroxide.
solid. Yellowish green colour of chlorine fades away.
(i) Construct an equation for the reaction of magnesium nitride with water.
(iii) XX
(ii) Does a redox reaction occur when magnesium nitride reacts with water?
~ Cl ~
XX X• XX Use the oxidation numbers of nitrogen to explain your answer. [4]
~Cl ~A/~ Cl ~
XX • X X• XX [J09/P2/Q2}
~ Cl ~AI ~C/~
XX • X XX (b) (i) Salt of strong acid and
Suggested Solution:
~ Cl ~ weak base will show acidic
XX pH.
(a) (i) Mg•(g) -7 Mg 2•(g)+e-
(c) Chlorine being strong oxidising agent oxidises copper to its higher oxidation M MgO being slightly
state i.e. +2. (ii) tl.H1~ 151 + l'l.H1~ 2 ,d = +736+ 1450 =; 2186 kJ mor' soluble will show basic pH.

0 72 {b) (i) observation: dissolves in water

(d) (i) moles of titanium= · = 0.015 (c) (iO Oxidation numberofN
47.9 approximate pH of the water: pH6 to pH7 in Mg,N,:
2 65 0 72 (ii) observation: magnesium oxide is very slightly soluble in water. (2 x 3)+2N = 0 or N = -
(ii) moles of chlorine= · ·- · 0.06
35.5 3.
approximate pH of the water: pHS to pH11
Oxidation number of N in
(iii) Ti : C/ = 0.015 : 0.06 =1 : 4 NH,:
(c) (i) Mg 3N2 + 6H2 0 -7 3Mg(OH) 2 + 2NH3
empirical formula of A = TiC/,
N + 3 = 0 or N = - 3.
(ii) Oxidation number of nitrogen in Mg,N = -3
(iv) Ti + 2C/2 -4 TiC/4 2
Oxidation number of nitrogen NH, = -3
(e) As the compound A is liquid and does not conduct electricity, it has covalent
There is no change in oxidation number of nitrogen in two cornp, Jnd~.
bonds with simple molecular structure. Its liquid state shows, weak Van der therefore no redox reaction occurs.
Waal's forces between molecules.
topic 9.1 The Periodic Table: Chemical Periodicity Page20 topic 9.1 The Periodic Table: Chemical Periodicity Page 21
~CORNER
~CORNER
Question 19
The elements of the third period of the Periodic Table fomn chlorides of general
{d) {i) Suggest what type of bonding is present in sulfur dichloride
formula ECI, where E represents the element. These chlorides show a variation
(il)W'nte a balanced equation for the reaction between .~.
in oxidation number from sodium to sulfur.
silicon, SiC/,, and water. the chloride of
(a) (i) Use the information given to complete the table below. [2]
[N09/P2102]
formula of chloride NaC/ MgC/2 A/C/3 SiC/, PC/3 set,
Suggested Solution:
oxidation number of
element in the chloride (a) (i)

(ii) By considering the electron configurations of the elements, explain the formula of chloride NaC/ MgC/2 A/C/3 SiC/, PC/3 SC/2
variation in oxidation number in the chlorides from Na to AI and from
oxidation number of
~~& ~ +1 +2 +3 +4 +3
element in the chloride +2
Sodium hydride, NaH, is a colourless crystalline solid which melts at 800 •c
and has the same crystal structure as sodium chloride which has a melting (ii) Na to A/: These elements belong to group 1
11 111 Th 1
point of 808 •c. When molten sodium chloride is electrolysed using graphite valence electrons to give stable acta configur~tio~ of. Ne.ey oose their
electrodes, a shiny deposit, D, fomns on the cathode and a greenish-yellow gas
Si to S: These elements belong to grou IV VI v .
electrons to give stable acta configuratio~ of, A(.
is·evolved from the anode. When molten sodium hydride is electrolysed, under
. They gam or share
suitable conditions using graphite electrodes, the same shiny deposit D is fomned
on the cathode and a colourless gas, G, is evolved from the anode. {b) (i) Na:· and C/- ions are held with strong ionic bonds makin .
{b) (i) Describe with the aid of a diagram the bonding in a sodium chloride latttce. Na• ion is surrounded by six C/- . d g gtan~ tomc
rounded by six Na• ions. tons an each C/- ton ts sur-
crystal.
(ii) Suggest the type of bonding that is present in sodium hydride. cr
(iii) What is the oxidation number of hydrogen in sodium hydride?
(iv) Draw a 'dot-and-cross' diagram for sodium hydride. Show outer elec-
trons only.
(v) The metals magnesium and aluminium fomn hydrides with formulae
MgH and A/ H,. The non-metals phosphorus and sulfur form hydrides
2
with formulae PH, and H,S.
i3y considering their positions in the Periodic Table, suggest oxidation
numbers for these four elements in their hydrides.

compound MgH, A/H3 PH3 H,S

(il) Ionic
oxidation number of
element in the hydride (iii) -1
[8]

At room temperature, the chlorides of sodium, magnesium and aluminium are

all solids which dissolve in water. (iv) [=~~:f'· [:Hr
The hydrides of sodium, magnesium and aluminium are also solids which react
with water with the rapid evolution of the same colourless gas G in each case. {v)
compound MgH2 A11-f3 PH3 H,s
(c) (i) What is the pH of the solutions fomned when separate samples of sodium
chloride, magnesium chloride, and aluminium chloride are dissolved in oxidation number of
water? element in the hydride +2 +3 -3 -2

chloride sodium magnesium aluminium

(c) (i) (d) (i) Bond between non-
chloride sodium magnesium aluminium metallic atoms.
pH
pH 7 6.7 2 (iQ Affematively:
(ii) Suggest an equation for the reaction between sodium hydride and water.
(iii) Suggest a value for the pH of the solution fomned in (il). [4] (ii) NaH + H2 0 ~ NaOH + H,
, • . SiC/4 + 4H20 ~

,. Si0 2 .2H20+4HC/
{iii) 13
!
{d) (i) Covalent. SiC/4 + 2H20 ~
Si0 2 +4HC/
{il) SiC!, + 4H2 0 ~ Si(OH) 4 + 4 HC/
r Page 22 topic 9.1 The Periodic Table: Chemical Periodicity_
I
in
topic 9.1 The Periodic Table: Chemical Periodicity
~CORNER
(d) MgO: In molten form conducts electricity because free mobile ions are present.
Page23

~CORNER
i
and they carry current.
Question 20
SiO,: SiO, when molten does not conduct because it has no free ions present
The table below gives data. for some of the oxides of Period 3 elements. to conduct electricity.

MgO f.h03 Si02 P,Os S02

oxide Na20
2017 1607 24 -75 Question 21
melting point/"C 1275 2827
(a) Write a balanced equation for the reaction of each of the following chlorides
bonding with water.
structure phosphorusM chloride ................................................................................................

(a) Complete the table by filfing in silicon(IV) chloride................................................................................................. [2]

(i) the 'bonding' row by using only the words 'ionic' or 'covalent', (b) When sulfur is heated under pressure with ch!orine, the major product is
[2] SCI, (C/-S-C/).
(ii) the 'structure' row by using only the words 'simple' or 'giant'.
S,(g) + 8CI,(g) --> BSC!,(g)
(b) From ·the table of oxides above, suggest the formula of one oxide that is
[1] Use data from the Data Booklet to calculate the enthalpy change, !J.H, for
completely insoluble. in water.
this reaction.
(c) Separate samples of Na,O and SO, were added to water. The eight sulfur atoms in the S, molecule are all joined in a single ring by
(i) For each oxide, write a balanced equation for its reaction with water single bonds. (2]
and suggest a numerical value for the pH of the resulting solution.
(c) Under suitable conditions, SCI, reacts with water to produce a yellow pre-
(ii). Construct a balanced equation for the reaction that occurs when a cipitate of sulfur and a solution A. Solution A contains a mixture of SO,(aq)
solution of Na,O in water reacts with a solution of so, in water. [5] and compound a.
(d) Separate samples of the oxides MgO and SiO, are melted: (i) What is the oxidation number of sulfur in SCI,?
Each molten sample is then tested to see whether or not it conducts elec- (ii) Work out how the oxidation number of sulfur changes during the
tricity. reaction of SCI, with water.

Suggest what would be the results in eacb case. Explain your answers. (iii) Suggest the identity of compound B.
[4] I
(iv) Construct an equation for the reaction between SCI, and water.
[J10/P2/03]
(v) What would you observe when each of the following reagents is added
to separate samples of solution A?

Suggested Solution:
~
AgNO,(aq) ...........................................::::::::::::::::::::::::::::::::::::·.:·.·.:·.·.·.·.·.·.-.·.·.·.·.·.·.·.-.-.......
(a , ,.,,. , t<,Cr,O,(aq)........................................... [N10/P4101)

Na20 MgO AI203 Si~ p,Os so, (a) Na 20, MgO and A/20 3 have
oxide giant ionic lattice structure
2017 1607 24 -75 while SiO, is macro-molec-
melting point/"C 1275 2827 Suggested Solution:
ular lattice.
Ionic/ covalent covalent covalent
bonding Ionic tonic (a) phosphorus(V) chloride: PC/5 + 4H20--> H3P0 + 5HC/
covalent 4

giant simple simple silicon(IV) chloride: SiC/4 + 2 H,O --> Si02 + 4 HC/
structure giant giant glanf

(b) S 8 (g)+ BC/2 --> BSC/2

(o) AI,O, or SiO, . Bond breaking __, Bond making
(c) (i) On dissolving Na,O,
(c) (i) Na,o strong alkali is formed, 8 X B.E.(S-S) + 8 X B.E.(C/-G/) ..... 6 X B.E.(S-GI)
equation: Na 20 + H 20 ----t 2NaOH hence high pH of the 8x 264+ ex 244 ..... 16 X 250
pH: 12 - 14 (a strong alkali is formed in the solution). solution.
tJ.H"' = Bond breaking- Bond making
(iQ SO, dissolves to form
so, H,so,, hence tow pH (2-5). = (8 X 264) + (8 X 244)- {16 X 250) = 64 kJ mOl-l
equation: S0 2 +H 20 ----t H2S0 3
(c) (i) +2
pH: 2 - 5 (resulting solution is acidic in nature).
(il) sulfur is reduced from +2 oxidation state to 0.
(ii) NaOH + H2S0 3 ----t ·NaHS0 3 + H,O sulfur is oxidised from +2 oxidation state to +4.
 . 9•1 The Periodic Table : Chemical Periodicity
top1c

(iii) HCI solution.

Page 24
~CORNER 7opic 9.2
(c) (v) SolutionAhaschloride
(iv) 2SC/2 + 2H20-> S(s)+ S02(g) + 4HC/ ions, it reacts with AgNO, to
(v) AgNO,(aq): White precipitates.
form white ppt. of AgCI.
so is a reducing agent, it
9roup gg
K,Cr,0 7 (aq): O range solution of K,Cr,O; will change to green solution. red~ces acidified dichro-
matesolutionfromorange to
green.
Content
Similarities and trends in the properties of the Group II metals magnesium to barium and
their compounds
2 Some uses of Group II compounds

Learning Outcomes
Candidates should be able to:
(a) describe the reactions of the elements with oxygen and water.
(b) describe the behaviour of the oxides with water.
(c) describe the thermal decomposition of the nitrates and carbonates.
(d) interpret, and make predictions from, the trends in physical and chemical properties of
the elements and their compounds.
(e) explain the use of magnesium oxide as a refractory lining material and calcium carbonate
as a building material.
(f) describe the use of lime in agriculture.
(g) interpret and explain qualitatively the trend in the therma.l.stability of the nitrates and
carbonates in terms of the charge density of the cation and the polarisability of the
large anion.
(h) interpret and explain qualitatively the variation in solubility of the sulfates in terms
of relative magnitudes of the enthalpy change of hydration and the corresponding
lattice energy.

Note: The additional learning outcomes to be studied by A2 candidates are shown in bold type. The A2
components will assess all learning outcomes and will not be limited to those in bold type.
topic 9.2 Group II
Page I topic 9.2 GrOUQ II
Page2
~CORNER
(d) On heating a Group II carbonate, the corresponding oxide and carbon dioxide
is formed:
~CORNER
MC0 3 (s) ----> MO(s) + C0 2 {g)
q?(j]) rN fl ;jJ Evolution of C0 2 results in loss of mass.
1.1 \!j/lf U \!;;J qpening ....... . No. of mol of C0 2 =
1 34
· · = 0.03045
12.0 + 16.0 X 2
No. of mol of MO : No. of mol of C0 2 = 0.03045
Question 1
M 4.50
(a) Describe and explain the variation down the group of the ease of thermal M, of co3 = _ = 147.8
0 03045
decomposition of the Grcup II mc;tal nitrates. Write an equation for the
reaction thai takes place. [4] A, of MC0 3 =147.8-12.0-16.0x 3 =87.8
(b) When water is a:Jded to the solid remaining after barium nitrate has been Hence, M is Sr.
heated, an alkaline solution is produced. The addition of sulphuric acid to
this solution produces a white precipitate.
Identify the products of these two reactions, and write equations for them. [3] Question 2
(c) When the procedure described in {b) is repeated using the soild remaining Strontium, Sr, is an element in Group II of thePeriodic Table.
after magnesium nitrate has been heated, several differences are observed.
(a) State the full electronic configuration of an atom of strontium. [1]
Describe clearly what these differences are, and explain why they occur. [3]
(b) (i) Write a balanced equation for the action of heat on strontium nitrate.
(d) A 4.50 g sample of a carbonate of a Group II metal {known to be either
(ii) Magnesium nitrate decomposes at a lower temperature than strontium
calcium or strontium) lost 1.34 g in mass when heated strongly. Identify t.he
nitrate. Explarn why these two nitrates decompose at different tempera-
metal, showing clearly your working. [2]
tures. [4]
{NOO/P1/Q5]
(c) Name a magnesium compound and state its commercial use. [1]
(d) Strontium metal can be obtained by the electrolysis of molten strontium
Suggested Solution: bromide, SrBr,, using the apparatus shown in the diagram.
(a) The ease of thermal decomposition of Group II metal nitrate decreases down
the group. This is because. the cationic size of Group II metal ions increases
down .the group as consecutive members have one more filled inner principle
quantum shell. Since Group II metal ions have the same charge of +2, the
charge density decreases down the group as ionic size increases. The
polarising power of the cation decreases as the charge density decreases so
that the electron cloud on the nitrate ion is less distorted down the group.
Hence it becomes more difficult for the Group II nitrate to decompose on heating
down the group. "-
Equation for the reaction : molten
strontium
2M(N0 3 h{s) ~ 2MO{s)+2N0 2 (g)+0 2 (g) bromide
where M is Mg, Ca, Sr or Ba.
of the reaction between the residue (SaO) and water is barium
{b)
t
heat
BaO(s)+H.0(l) ~ Ba(OH) 2 (aq) (i) Write the equations, including state symbols, for the electrode reac-
of the reaction between the solution and dilute sulphuric acid is lions,
at the anode,
sulphate :
at the cathode.
Ba(OH)2 (aq)+H2 S0 4 (&q) ~ BaS0 4 {s)+2H20(1) (c) For Group II ionic com-
pounds, the trend of solubiltty (ii) Explain why an atmosphere of argon is used around the cathode.
obtained by heating magnesium nitrate does not dissolve in water · . depends on the size of the (iii) A current of 5.0 A was passed through molten strontium bromide for 60 min.
solution is formed. On addition of dilute sulphuric acid to anions. For small anion
Calculate
the residue dissolved to give a colourless solution. such as hydroxide and ftuo-
how many coulombs were passed,
ride, solubility increases
is magnesium oxide which has very exothermic lattice energy the mass of strontium metal formed.
down Group II. For large
the high charges and small sizes of Mg'' and 0'-. It does not react with (iv) Explain why aqueous strontium bromide cannot be used to extract
anions such as carbonate
to give Mg(OH), unlike BaO which reacts with water to give aq. Ba(OH),. strontium by electrolysis.
and sulphate, solubility [7]
a basic oxide, MgO reacts with dilute sulphuric acid to give MgSO, decreases down the group. {J01/P2/Q3]
is soluble, unlike BaSO, which is insoluble.
 Page3 topic 9.2 Group II
topic 9.2 Group II Page4
~CORNER
Suggested Solution: (a) Explain why the add~ion of carbonate ions in Step 1 has to be controlled. [2J ~CORNER
The numerical values of the relevent solubility products are given below, (b) (iJ MgO is a base and
(a} 1s' 2s' 2p' 3s' 3p' 3d'• 4s' 5s' (d) (iv) Metals with standard
reduction potential greater reacts with an acid to give
magnesium carbonate 1.0x10'5
(b) (i) 2Sr(NOJ)2(s) ----> 2Sr0(s}+4N02(g)+02(g) . than zero, such as copper a salt. Since Jhe salt re·
. . r uantum shells than stront1um, mag- calcium carbonate 5.0x10'9 quired is achloride, the acid
(E .. = +0.34V) and silver
(ii) Having less number of fllle~ lnnde.. tqhan strontium ion The charge density used is dilute hydrochloric
· h a smaller iomc ra n · 1 ·sation (E • = +O.BOV), may be (b) (i) Write an equation for Step 3. acid:
nesium 1on as . f Sr'' and Mg'' has greater po an
of Mg'• is thus higher than that ~ d of a nitrate ion is distorted by Mg'' obtained by eleclrolysis of (ii) Suggest a reagent for step 4. MgO(s) + 2HC/(aq) ~
power than Sr''. The elect~n(~~u) decomposes at a lower temperature an aqueous solution con· (iii) Suggest how Step 5 could be carried out. MgC12(aq)+H20(/)
to a greater extent so that g 3 ' taining their ions. This is
than Sr(N0 3),. • because their ions are (iv) Write an equation for Step 5. Chlorides such as aqueous
[4]
(c) One magnesium compound is magnesium . oxide and it is used as a refractory more easily reduced com- sodium chloride cannot be
(c) State a use for magnesium or magnesium oxide. State which substance
material, e.g. in lining a furnace. pared to H· which is also you choose. [1] used since no reaction
present due to se~·ionisation occurs between MgO and
(d) (i) • At the anode:2Br-(/) ----> Br2(g)+ 2 e· of water. (d) (i) Write an expression for the solubility product of magnesium carbonate. NaC/.
• Atthecathode:Sr 2'(1}+2e·----> Sr(l} . Metals with not too neg a· (ii) Calculate the concentration, in mol dm"", of each of the two cations in (iii) In using electrolysis to
live standard reduction po· saturated solutions of the following. obtain magnesium, the
. d reacts readily with oxygen in the air to
(ii) Strontium is a rea~tlve metal .an t the hi h temperature used in the tential, such as chromium magnesium carbonate, magnesium chloride used
form strontium OXide, especially a. ed ~o ensure an inert atmosphere (E .. = -0.74V) and lead calcium carbonate. · must be in the mellen form
electroylsis. An atmosphe~e of a~gon ~~ u~ with air and remains unoxidised. (E .. = -0.13V), may still
[3] and not aqueous form. If
so that molten strontium IS not In con ac (e) The soild calcium carbonate produced by this process can be decomposed aqueous magnesium chlo-
be obtained by electrolySIS by heating.
. secon ds)-50x60x60=18000
(iii} No. of coulombs= current (in amp) x time (In - . . ride is used, hydrogen gas
of an aqueous solution
containing their ions pro· from water instead of mag.
no. of coulombs _ 18000 =0.1865 (i) Write an equation for the themnal decomposition of calcium carbonate,
· nesium will be produced.
No. of mol of electrons = F - 96500 vided that the concentra·
(ii) Calcium carbonate decomposes at a lower temperature than barium The displacement by addi-
tions are high enough. carbonate. Explain why this is so. [3]
- ~xO
1 tion of a more reactive
N0.0f mol of Sr deposited= -xno.
2 of mo 10 f e-- 2 ·1865 = 0.09326 Even though their ions are
metal to aqueous magne·
harder to be reduced com· (f) Explain why lime is used in agriculture.
[1] sium chloride cannot be
Mass of strontium formed =0.09326 x A' of Sr = 0.09326x 87.6g = 8.17g . pared to H' ions which are
used because the metal
also present, their ions are [N01/P2/Q3}
. . nnot be used because aqueous solution used (e.g. calcium or so·
(iv) Aqueous strontium. bromide t~a If-ionisation of water. Since H+ is much present in greater concen·
contains hydrogen IOns fromSr'e
more easily reduced than ', y r
s:
d ogen is discharged at the cathode
even if strontium metal is dis-
!ration than the H' ions from
the sen-ionisation of water.
Suggested Solution: dium) reacts with water
instead. However, if solid
magnesium chloride is
instead of strontium metal. Furthe~ore~etal will react with water present The greater concentration (a) The purpose of Step 1 is to precipitate out most of the calcium ions as calcium
charged strontium being a very reac IVe heated with more reactive
of their ions favours the carbonate but to leave magnesium ions in solution. For the same concentra-
to give ~trontium hydroxide and hydrogen gas. discharge of these metals. tion, calcium ions are most likely to be precipitated out as calcium carbonate
metal such as calcium,
magnesium is likely to be
Metals with very negative than magnesium as magnesium carbonate since the former has a lower
obtained. This method is not
solubility product. However, if too much carbonate is added, magnesium ions
standard reduction pcten· viable since the more reac-
Question 3 may also be precipitated out as magnesium carbonate and magnesium oxide
tial, such as aluminium tive metal is likely to be more
will not be obtained after Step 2 and 3.
The four most abundant salts in sea-water are as follows. (E .. = -1.66V) and SO· expensive and. rarer than
salt tonnes km-3 dium (E .. = -2.71V), can· (b) (i) Mg(OH)2(s) ~ MgO(s)+H20(g) magnesium.
not be obatined by elec· (iv) A half equation is re-·
sodium chloride 27 500 000 (ii) Dilute hydrochloric acid.
trolysis of an aqueous quired to show the electro·
magnesium chloride 6 750 000 (iii) Electrolysis of molten magnesium chloride. lytic process. ·
solution containing their
magnesium sulphate 5 625 000 ions. This is because their (iv) Mg 2'(1)+2e- ~ Mg(/) (c) Magnesium oxide is also
1 800 000 ions are much harder to be used to make some toilet
calcium sulphate
reduced compared to H' (c) Substance : magnesium oxide, preparations aild tooth
. . . ions from water. Despite paste. If substance chosen
MagneSIUm OXide IS 0 bt a1·ned from sea-water by the following steps.

B the higher concentration of Use : Refractor}' material used to line furnace. is magnesium, magnesium
Step 2 is used to make into light
their ions, it is still easier for
Step 1 addition f. ,1 (d) (i) Ksp of MgC0 3 = [Mg 2• (aq)][Co~- (aq)]
~ controlled addition~ filtrate ~ IMg(OH),(~1 H' to be reduced than their alloys (especially wilh alu-
minium) for construction of
~ of co~- (aq); filter of OH (aq) ions. Hence, instead of 2
these metals being dis- (ii) • [Mg •(aq)] in a saturated solution of MgC0 aircraft and automobile.

'"~'
3
charged at the cathode, Magnesium is also used as
hydrogen gas is produced =JKsp of MgC0 3 =)1.0 x 1a-s =3.16 x 10-3 mol dm-3 a s3crilicial anode to inhibit
instead. corrosion of steel.
2
[Ca ' (aq)] in a saturated solution of CaC0

~~8~8
3 Common Error
=JKsp of CaC0 3 =J5.0 x 1o- 9 =7.07 x 1a-s mol dm·3 (b) (ii) Giving answers like
HCl is not acceptable.
 PageS topic 9.2 Group)/
topic 9.2 Group II Page6
~CORNER
Question 5
~CORNER
(e) (i) CaC0 3 (s) ~ Ca0(s)+C0 2 (g)
(ii) A calcium ion is smaller than a barium ion since it has less filled inner (a) Describe and explain the trend in the thermal stabilities of the nitrates of
quantum shells but the same charge. Hence, Ca'• has a higher charge the Group II elements from Mg to Sa. Write a general equation for the
density and a greater polarising power. Ca'• distorts the electron cloud reaction that occurs on heating. [3]
of the carbonate ion to a greater extent than Sa'• so that calcium carbon-
ate decomposes mere readily and at a lower temperature. {b) Describe the reactions that occur when limestone, CaCO,, is heated strongly,
and.then a small amount of water added, followed by an excess of water.
(f) Plants need an optimal pH to grow well. Due to pollution, rain becomes acidic, Write equations where appropriate. [4]
causing soil to be too acidic for good plant growth. Lime, which is calcium
oxide, is basic in natL!re and is used to increase and hence control the pH (c) Calcium sulphate occurs naturally as the dihydrate gypsum, CaS0,.2H,O.
of soil affected by acid rain by neutralising excess acid in soil. When healed to 160 oc, gypsum loses some of its water to give plaster of
Paris, which is used for making fine plaster casts and for setting broken limbs.
During the process, 100 g of gypsum loses 15.7 g of water. Calculate the
formula of plaster of Paris. [3]
Question 4
[N02/P3/04]
(a) Write an equation to represent the thermal decomposition of calcium ni-
trate, Ca(NO,),. [1] Suggested Solution:
{b) Describe and explain how the thermal stabilities of the Group II nitrates vary
down the group. [3] (a) Thermal stability of nitrates of Group II elements from Mg to Sa increase down
(a) Nitrates of Group II ele·
the group. From Mg'• to Sa'•, ionic radius increases and since the ions are
(c) When a molten nitrate of a Group I metal is heated strongly, it evolves ments are decomposed to
of the same charge, the charge density decreases. Polarising power of the
I oxygen and leaves the metal nitrite, MNO, (M = Na, K, Rb orCs).
ions thus decreases down the group and the electron cloud of the nitrate ion
the oxide. nitrogen dioxide
and oxygen. The driving
(i) Write a balanced equation for this reaction. is distorted less by ions dovvn Group II. Since nitrate ions are progressively
force for the decomposition
(ii) When a particular Group I metal nitrate was heated in this way until no less distorted down Group II. temperature needed to decompose the nitrate
is the much more exother-
further change occurred, it lost 10.85 % of its mass. Calculate the A,. ions increases down Group II and thermal stability increases.
mic lattice energy of the
of the metal and hence identify it. [3] General equation for the thermal decomposition of Group II nitrates: oxide since the oxide is a
{J02/P4!03] much smaller ion than
(c) When Group I nitrates are 2M(N0 3 )2 (s)----> 2MO(s)+4N02 (g)+0 (g)
2 nitrate and has a higher
heated, the products are where M = Mg, Ca, Sr or Sa. charge.
nitrates and oxygen while
Suggested Solution: The temperature for
group II nitrates give ox· {b) When limestone is heated strongly, it decomposes to calcium oxide and carbon
(a) 2Ca(N0 3 ) 2 (s) ~ 2Ca0(s)+4N0 2 (g)+0 2 (g) ides, oxygen and nitrogen dioxide: decomposition of the nitrate
dioxides on heating. Group is dependent on how dis·
(b) Thermal stability of Group II nitrates increases down the group. Down Group I ions have a lower charge CaC0 3 (s) ----> CaO (s) + C0 2 (g) torted the electron cloud of
II, the cationic size increases but charge of the ion remains the same. The density and hence lower the nitrate is. The more
charge density and thus the polarising power of the cation decreases down When a small amount of water is added, much heat is given out and calcium distorted the electron
polarising power than
Group II. As the electron cloud of the nitrate ion is less distorted by the cation oxide is converted to calcium hydroxide: cloud, the greater the ease
group II ions since group I
down Group II, it is more difficult to decompose the nitrate and hence thermal ions have a charge of +1 and hence the lower the
CaO (s) + H2 0 (/) ----> Ca (OH) 2 (s)
stability of the nitrate increases down Group II. and group II ions have a temperaturefordecomposi·
charge of +2. Hence nitrate On addition of an excess of water, calcium hydroxide dissolves: lion. Metal ions with higher
(c) (i) 2MN0 3 (s) ~ 2MN0 2 (s)+0 2 (g) ions are polarised to a charge density distorts the
smaller extent by group I Ca (OH) 2 (s) + aq ----> Ca (OH) 2 (aq) electron cloud of the nitrate
(ii) Let the A, of the M be q. ion to a greater extent so
ions and decomposed to
M, of MN0 3 = q + i4.0+16.0x3 = q+ 62.0 nitrate rather than oxide. (c) M, of gypsum, CaS0 4 .2H20 = 40.1 + 32.1+ 16.0x4+2(1.0x2+16.0) = 172.2 that a Group II ion with
smaller ionic radius distorts
However, UNO, on heating
M, of MN0 2 = q +14.0+16.0x 2 ~ q +46.0 No. of mol of gypsum used=~= 0.5807 the electron cloud of nitrate
gives Li 20, N0 2 and O,
172.2 more. Thus, temperature
lv1, of MN0 2 100-10.85 (which is similar to group II
needed for decomposition
nitrates) even though Li • is 15 7
M, of MN0 3 100 No. of mol of water lost= · = 0.8722 of the nitrate increases
a group I ion. This is be· 18.0 down Group II and so does
q+46.0 89.15 cause Li - has a very high
=> ---=-- thermal stability.
q+62.0 100
charge density and thus No. of mol of water lost per mol of gypsum= 0 ·8722 = 1.5
great polarising power due 0.5807
=> 100(q+46.0)=89.15(q+62.0) to its very small ionic radius. Thus, 1 mol of gypsum, CaS0 4 .2H2 0, loses 1.5 mol of H2 0 to become Plaster
Thus it distorts the electron
i OOq- 89.15q = 5527.3 -4600 of Paris.
=> cloud of nitrate sufficiently
enough to cause it to break
=> = 5527.3-4600 = ~ = 85.5 Formula of Plaster of Paris= caso, . .."1.H2 0 or 2CaS0 4 .H 0
down to lithium oxide on 2
q 100-89.15 10.85 2
heating.
Hence M is rubidium, Rb.
 topic 9.2 Group 11 Pa e8

Page 7
Suggested Solution:
~CORNER
topic 9.2 Group II ~CORNER
(a) 2 M(N03)2 ~ 2M0+2N0 2 +0,
The ease of thermal decomposition decrea .
Question 6 position is facilitated by the polan·s t' f ses down the Group. The decom-
(b) Alternatively, the process G . a 1on o the NO - anion by M" 0
roup, cat1on size increases char e d . own the
decreases. There is less poiarisat~n ~nt~lty decreases and polarising power
3 •
Cement is manufactured by heating an excess of limestone (a form of calcium cculd be solved by using
carbonate) with clay in a kiln at a temperature well over 1000 oc.
One of the mass ratio. N- 0 bond is reduced. Hence it bee~ e amon and the weakening of the
reactions in the kiln breaks the clay down to give Si0 2• The kiln process results the Group. ' mes more difficult to decompose down
1 mole of CaSi,O, is pro-
in the !ormation of calcium silicates, CaSi0 3 and CaSi,O,. duced from 1 mol of caco,.
(a). Write two equations for the formation of the calcium silicates in the kiln.[2] (c) (i)
=> 176.3g of CaSi 20 5 is Ba 0
(b) Calculate the mass ofcalcium carbonate necessary to form 44 tonnes of produced from 100.1g of %mass: 81.1 18.9
CaSi,O,. [2] caco, 81.1 18.9
molar ratio:
(c) When used to produce the hard material we call 'concrete', water is added => 1g of CaSi 20 5 is pro- 137 16
to the powdered cement and well mixed. The mixture becomes hot. =0.59 1.18
Suggest why the action of the water on cement is exothermic. duced from ~
176.3
g of
= 1 2
Suggest which gas is absorbed from the air as the wet concrete loses
caco, The formula is Bao 2.
moisture and hardnes. [2]
[N04/P2!04] => 44 tonnes of CaSi,O,
(ii) BaO, + 2 H,O ----+ Ba(OH), + H,O,
is produced from
BaO, reacts with water to give H2 0 ,.
~x44 !annes of
Suggested Solution: 176.3 H,0 2 + 21· +2H' ----+ 12 + 2 H,O

(a) (i) CaC0 3 + Si0 2 ~ CaSi03 + C0 2 CaCO, H,O, oxidises f· in acidic medium to give I ,.
= 25tonnes
(ii) CaC0 3 + 2 Si0 2 ~ CaSip 5 + C0 2
Question 8
(b) M, of CaSi 0 = 40.1 +28.1x2+ 16.0x 5 = 176.3 Extra information
2 5
(c) Quick lime, CaO. is hygro- This
sium question is about the elem en1s .m Group II of the Periodic Table, magne-
to barium.
6
44x 10 5 scopic. It readily accepts
nc 8 s;,o, =~ =2.50x10 mol
moisture in the air to form (c) Samples of magnesium and calci
Ca(OH), (s). The process of and left for some time In each um ar: placed separately in cold water
adding water to quick lime write a balanced equaiion for eacahse, e_scribe what you would see and
c react1on.
(Ca(OH),) is highly exother-
M, of CaC0 3 = 40.1 +12.0+16.0x3 = 100.1 (i) magnesium
mic.
mcaco =2.50 x 105 x 100.1 =2.50 x 107 g =25 tonnes Ca(OH),. being alkaline.
observation:
3 equation:
readily absorbes acidic
(c) The excess heated limestone becomes GaO, and this reacts exothermically gases such as co,. (il) calcium
with water to give Ca(OH),.
Ca(OH), + C0 2 --t observation:
!l.H<O
GaO+ H20 ~ Ca(OHh equation:· [6]
CaC0 3 +H 20
CO, is absorbed. (d) (i)
Strontium nitrate, Sr(NO3 )' un dergoes thermal decomposition.
ii) St~te one observation you would make during this reaction.
( Wnte a balanced equation for this reaction. [4]
Question 7
[J07/P2/Q3(c,d)J
(a) The nitrates of the Group II elements are unstable to heat.
Describe and explain the trend in the thermal decomposition of the nitrates
of the Group II elements Mg to Ba, writing an equation for any reaction that Suggested Solution:
occurs. [3] (c) (i) obse~ation: very slow reaction. Few bubbles of colourless gas
(c) When barium metal is burned in air, an oxide is formed which contains equation: Mg + H,O --t MgO + H,
(d) (i) NO, gas is produced
81.1% of barium by mass. which is brown in colour.
(ii) observation: faster reaction than with magne .
(i) Calculate the formula of the oxide, colourless gas. White suspension is formed. Slum. Steady evolution of (iO Nitrates of 2nd group
(ii) When this oxide of barium is added to water, barium hydroxide and metal decompose on heat-
another compound are formed. When the solution is acidified, and added equation: Ca+2H,O --t Ca(OH), +H, ing to produce metal oxide
to potassium iodide solution, iodine is formed. nitrogen dioxide and oxy:
(d) (i) brown gas is evolved
Suggest an explanation for these observations and write equations for gen.
the reactions occuring. [4] (ii) 2 Sr(N03)2 --t SrO + 4 N0 2 + o 2
[N05/P3!05{a,c) Or]
 topic 9.2 Group II Page 10
Page9
top_ic 9.2 Group II
~CORNER Suggested Solution: ~ CQRNER
(a) Solubility decreases, as the cationic size increases and lattice energy
Questio11 9 decreases. The hydration energy of cation also decreases. The decrease in (a) 6H.,.,,, = !'.H,.""''"''" +
(a) Write an equation showing the reaction that occurs when calcium nitrate, hydration energy is more than the lattice energy therefore 6H solution
becomes more endothermic. !l.HHyrh~on
Ca(NO,),, is heated. [1]
(b) Describe and explain the trend in thermal stability of the nitrates of the (b) identity of A: MgC 20 4 (aq) If 6HLE > 6HHyd•ation , the
Group II elements. [3] change will be endothermic
identity of B: CaC 20,(s) and not feasible.
(c) Gently heating ammonium nitrate, NH,N0 3 , in a test tube produces a mix-
ture ot two gases A and B. No residue remains in the tube. equations: Mg(OH) 2(s) + H2 C20 4 (aq) -->·MgC 20 4 (aq) + 2H2 0(s) (c) (i) Oxidation number in-
The mass spectru1J1 of gas A contains peaks at mle (mass number) values creases from -1 (in HC~
of 16, 17 and 18, whereas that of gas B has peaks at mle values of 14, MgC 20 4 (aq) + Ca(N0 3 ),{aq)--> Mg(N0 3 ) 2 (aq) +CaC 20 4 (s)
to +2 (in KCrCIO,).
16, 26, 30 and 44.
(i) Identify the peaks in the mass spectra, and suggest the molecular
(c) (i) K5P = [ Mg 2• ][OW r mol 3 dm- 9 (iO Cr,o;- mustactasan
formulae of the gases A and B. oxidising agent oxidising Cl-
(ii) Let the concentration of Mg(OH), = x mol dm-3 to C/2, therefore equation for
(ii) Hence suggest an equation ·for the tl1ermal decomposition of ammo-
2 oxidation will be
nium nitrate. [5] [ Mg •] = x, [ OH-] = 2x,
(J07/P4!02] 2C/---> C/2 + 2e- f• = -1.36

Suggested Solution:
Ksp = [ Mg •] [OW
2
J Combining the two equa-
(a) 2nd group metal nitrates tions resu Its in
decompose on heating to ~ 2.0x 1o- 11 = x(2x) 2
(a) 2Ca(N0 3 h --> 2Ca0 + 4N0 2 + 0 2 give metal oxide, nitrogen
cr,o;- + 6CI- + 14W -->
11
2.0x10- =4x 3 => x=1.71x1o-• mol dm-3
(b) Thermal stability increases down the group as the cationic size increases, dioxide & oxygen. 2Cr 3 • + 3CI2 + 7H20
· ionic charge density decreases .and its polarising power decreases. (iii) Less soluble, because common ion effect will shift the equilibrium
(b) As cationic size increases.
E,~ for the reaction
bond become more ionic Mg(OH) 2 (s) ===' Mg 2• + 20W to the left.
(c) (i) A 16= [o]' B 14=[NJ', 30={NOJ'
and difficult lo break. = + 1.33- 1.36 =- 0.03

17={0HJ' 16=[0]', 44=[Np]' (c) (i) Positive charge must As the E:, value is nega-
be shown on every fragment Questio11 Jl tive, the reaction will not be
18=(H2 0]' zs = [N2r. feasible.
shown.
(a) (i) Describe and explain the trend observed in the thermal stability of the
A=HP B=N20 carbonates of the Group If elements.

(ii) NH,N0 3 --> N20 + 2H 20 (ii) By quoting suitable data from the Data Booklet suggest how the thermal
stabilities of
• zinc carbonate and
Questio11 10 • lead carbonate
(a) Describe and explain the trend in the solubilities of the sulphates of the might compare to that of calcium carbonate. [6]
Group II elements. [4]
(b) Malachite is an ore of copper. It contains the following percentages by
(b) . The salts formed by the Group If elements with other divalent anions show mass.
a similar trend in their solubilities, whereas most of their salts with monova-
copper 57.7%
lent anions are very soluble. oxygen 36.2%
Use this information to predict the identities of compounds A and B in ttie carbon 5.4%
following description of some reactions of Group If compounds, and write hydrogen 0.9%
balanced equations for the reactions.
Magnesium hydroxide, Mg(OH),, is almost insoluble in water. Stirring a Malachite reacts with dilute H,SO, producing a gas B that turns limewater
milky and leaving a blue solution C.
mixture of magnesium hydroxide and aqueous ethanedioic acid, H 2C 20 4 ,
produces a clear colourless solution containing A. When a solution of When heated in the absence of air, malachite produces gas B and steam,
calcium nitrate, Ca(N0 ) , is added, a white precipitate of B is formed. [3] and leaves a black solid D. D reacts with dilute H,SO, to produce the same
3 2
blue solution C.
(c) . :~~-~o~u~~i~ .product, Ksp' of magnesium hydroxide has a numerical value Adding iron filings to C produces a pink solid E and a pale green solution
F.
(i) Write an expression for the K of magnesium hydroxide, stating its
(i) Calculate the empirical formula of malachite.
units. sp
(ii) Use the value of Ksp given to calculate th·e concentration of Mg(OH), (ii) Suggest the formula of the ion responsible for the blue colour of so-
lution C.
1n a saturated sofut1on.
(iii) Explain whether magnesium hydroxide would be more or less soluble
in 0.1 mol dm-a MgSO,(aq) than in water. [5]
[N07/P4102]
 Page 11 topic 9.2 Group II
topic 9.2 Group II . Page 12
~CORNER
. nd calculate the mass of D that could be
(iii) Identify the black_ solid D ~f malachite. Question 12
~CORNER
10
obtained by healing g . . t'fy the pink solid E and the
(a) Describe and explain how the solubilities of the sulfates of the Group II
(iv) Use data from the Data Bookletr'onl1~;t~e reaction producing them.
solution F, and suggest an equa lo d E and F? elements vary down the group.
(3]
. . the reaction that pro uces . (b) The following table lists some enthalpy changes for magnesium and stron-
(v) What type of reaction IS ld see happen when dilute NH,(aq)
tium compounds.
(vi) Describe and explain wha~ ~ou w~uuntil it is in an excess. (13]
is added slowly to the so u 10n {NOBIP4!03]
value for value for
enthalpy change magnesium strontium
I kJ mol-1
(a)
2
(i) Structure of C0j ion is lattice enthalpy of M (OH)2
. -2993
I kJ mol-1
Suggested Solution: the group so high temperature is -2467
. e more stable down d the
(a) (i) Carbonates b ecom ron M'' radius increases own o- enthalpy change of hydration of M 2+ (g) -1890 -1414
required to decompose ~ecau,s~~a ~ecreases and co,-• suffers less
group and charge dens1ty o o=c /"-o- enthalpy change of hydration of OH'" (g) -550 -550
polarisation.

(ii) Ionic radii of cu•2' zn•2 and Pb'2 are: When a cation with high (i) Use the above data to calculate values of tiH,~utlon for Mg(OH), and
charge density is present, for Sr(OH),.
' 0099 nm Zn'• = 0.074 nm, Pb'' = 0.120 nm it polarises the Amon (ii) Use your results in (i) to suggest whether Sr(OH) is more or less soluble
Ca • = · ' . z co is less
·~y' I Zn'• is more and Pb'' IS less. So n ' ·more and thermal stability 2
Thus chadrgePbdCeOnsl is omore stable than CaCO,. decreases. in water than is Mg(OH),. State any assumptions you make.
stable an ,
0 (iii) Suggest whether Sr(OH), would be more or less soluble in hot water
c H than in cold. Explain your reasoning.
(b) (i) Cu 0
5.4 0.9
M'' o-'=c( (5]

57.7 36.2 0 {J70/P4/Q2 a,b]

63.5 16 12 As a result MO + CO, is
= 0.90 Suggested Solution:
= 0.91 =2.26 =0.45 formed.
0.45 0.90 (a) Solubilities of group (II) sulphates decreases down the group.
0.91 2.26
0.45 0.45 BeS04 - MgS0 4 highly soluble
0.45 0.45
2 caso. sparingly soluble
2 5
SrS0 4 - BaS04 insoluble
empirical formula: Cu, 0 5 CH,
Hydration energy and lattice energy both decrease down the group but H.E.
2+ greatly decreases, as a result tiH,!,uuon becomes more endothermic down the
(ii) Cu2•(aq) OR [Cu(Hp)6 ] group.

(Iii) D: GuO (Copper(ll) Oxide) (b) (i) Mg(OH),: t1H:',;1ulion = H.E.- L.E

cup 5 c~ 4 2Cu0 + C02 + Hp = (-1890+2(-550))-(-2993) = +3 kJmol- 1

221 ---+159 Sr(OH),: tiH!,utlon = H.E. - L.E

10 ---+ ~x10=7.19(g) = (-1414+2(-550))-(-2467) = -47 kJmor 1

221
(li) Sr(OH), should be more soluble in water than Mg(OH), as t;.H:',; uuon for
1
(iv) E is copper, F is Feso. Sr(OH), is more exothermic.

Fe+cu2• 4 Fe2• +Cu (iii) Sr(OH), should be less soluble in hot water because tiH,!,ulion is exother-
mic and· all exothermic reactions are favorable at low temperature.
(v) Redox reaction.
H ) 1
·s added to solution C.lf excess
(vi) Blue Precipitate is formed when. N ,(aq d d rk blue solution is formed.
NH3(aq) is added, precipitate dissolve an a
 topic ,,,j Group IV

9.3
Page 1

:Jopic ~CORNER

9roup 9V ~fr}) IN !141

" ~ t.r u \!;;;J qpening ....... .
Question 1
The element~ carbon to lead as a group in which the physical and chemical properties of
(a) The melting points of some oxides of Group IV elements are given below
the elements change with increase in proton number from non-metals through metalloids to
metals and their compounds. oxide melting
point /'C
C02 -78
Content Si02 1610
The variation in melting points and electrical conductivities of the elements.
Sn02 1630
2 The bonding, molecular shape, volatility and hydrolysis of the tetrachlorides.
Describe the bonding in each oxide, and how it relates to its melting point.
3 The bonding, acid/base nature and thermal stability of the oxides of oxidation states
(i) co,
II and IV. (ii) SiO,
4 The relative stability of higher and lower oxidation states for the elements in their oxides
~~~ ~
and aqueous cations.
(b) Writing balanced equations where appropriate, describe how the above
three oxides differ in their reactions with
(i) NaOH(aq)
Learning Outcomes
(ii) HC/(aq) [4]
Candidates should be able to:
(a) outline the variation in melting point and in electrical conductivity of the elements and (c) The last oxide in Group IV, Pb02 , reacts with concentrated hydrochloric acid
liberating chlorine gas.
interpret them in terms of structure and bonding.
Use the Data Booklet to calculate the Ec:n and to write a balanced equa-
(b) describe and explain the bonding in, molecular shape and volatility of the tetrachlo- tion for this reaction. [2]
rides.
[J03/P4/Q3]
(c) describe and explain the reactions ofthe tetrachlorides with water in terms of struc-
ture and bonding. Suggested Solution:
(d) describe and explain the bonding, acid-base nature and thermal stability of the oxides
(a) (i) C0 2 : co, is a simple molecular covalent compound with weak van der
of oxidation states II and IV. · waal's forces of attraction between the molecules. Hence it has low melting
point.
(e) describe and explain the relative stability of higher and lower oxidation states of the
elements in their oxides and aqueous cations including, where relevant, E"' values. (ii) Si02 : Si02 is a macromolecular covalent compound with large number of
interatomic continued covalent bonds which are very difficult to break-
(/) recognise the properties and uses of ceramics based on silicon(IV) oxide. down hence very high melting point.
(iii) Sn02 : SnO, is a macromolecular covalent with some ionic character hence
high melting point.
(b) ~) SiO, reacts with con-
(b) (i) NaOH(a·q): 2Na0H+C0 2 ~ Na C0 +H 0 centrated alkali to form sili·
2 3 2 cates.
Sn0 2 +2NaOH ~ Na 2 Sn0 3 +~0

(ii) HCI(aq): Si02 and C02 will not react with HC/ as both are acidic oxides.
SnO, is amphoteric it reacts with both acid and alkali.
Sn0 2 + 4HCI ~ SnC/4 + 2H20

Note: The additional learning outcomes to be studied by A2 candidates an;! shown in bold type. The A2
components will assess all learning outcomes and will not be limited to those in bold type.
,,
Page2
topic 9.3 Group IV topic 9.3 Group IV
~CORNER Page3

(c) Pb0 2 +4HC/----> PbC/2 +2Hp+C/2 (d) SiC/, is used to make high-purity silicon for the semiconductor industry. ~CORNER
Alter it has been purified by several fractional distillations, it is reduced to
EC:n ;: :; Er:duction hall - E;idalion hall silicon by heating with pure zinc ,
=1.47-1.36 (i) Suggest an equation for the reduction of SiC/, by zinc.
=+0.11V>0 (ii) Use your equation to calculate what mass of zinc is needed to produce
,I 250 g of pure silicon by this method. · [3]
As E" is positive reaction is energetically feasible.
{J04/P4/Q2}

Question 2 Suggested Solutir;m:

All the Group IV elements form chlorides with the formula MCI,. (a) (i) bonding: Covalent bonding with simple molecular structure
(a) Describe the bonding in, and the shape of, these chlorides. (ii) shape: Tetrahedral

(i) bonding
(2] (b) (i) 150°C +----+----+---+-----f

/
/
i' _L
,, /
chloride b.p.fOC
SiC/• 58 L
1oooc -+-----t----t--/-,L,L--+-----+
GeCt. 83
/
SnC/• 114

h following axes and extrapolate your graph to L

(b) (i) ~;~~i~~~a~~~= ~~iii~; point of PbCI, would be if it did not decompose.
150°C -+----+--+--1-=J
50°C +-~LL...t------,r-----t---+
Si Ge Sn Pb

(ii) All tetrachlorides of group IV are simple molecular covalent molecules

with weak van der waal's forces of attraction. As size of molecules
increases, number of electrons increases. Hence, strength of van der waal's
forces increases and thus b.p. increases.
100°C -1----+--.,--t-~1---::I
l!i (c) (i) In CC/4 empty d-orbitals are not available for temporary bonding with water
molecules, hence hydrolysis does not occur.
(c) d-orbitals are absent in
i!i' carbon as d-orbitals are
(ii) SiC/4 +2H2 0--->Si(OH)4 +4HC/ present in 3rd period to
or SiC/4 + 2H20----> Si02 + 4HC/ onwards. These empty
d-orbitals available in Si to
;t; 50°C 1===t===t===+===:!- (iii) Yes, as Ge also have empty d-orbitals available for temporary bonding
with water.
onwards help to form tem-
porary bond.
f'• Si Ge Sn Pb
rj
' ., (ii) Suggest why the boiling points vary in this way. [4]
(d) (i) SiC/4 (/)+2Zn(s) ----> Si(s)+2ZnC/2

(ii) 28.1 g of pure silicon is produced by 2 x 65.4 g of Zn

;-,:,: (c) SiC/ reacts vigorously with water whereas CCI, is inert.
H' (i) ~uggest a reason for this difference in reactivity. 250g of pure silicon will be produced by
2 6
x S.4 x250=1163.7,1164g
.\'• , (ii) Write an equation for the reaction between SiC!, and water. . 28.1
,;;' (Iii) Suggest, with a reason, whet her you wou ld expect GeCI• to react w1th
131

~-----wate_r·------------------~-----------------------
 Page4 topic 9.3 Group IV PageS
top_ic 9~Group IV
~CORNER
(b) (i) CO acts as a reducing agent and oxidises to form CO,. ~CORNER
Question 3 C0+.2_0 2 -----> C0 2
2
(a) (i) Use the following sets of axes to sketch graphs of the variations in the
melting points and the electrical conductivities of the Group IV elements. (ii) Pb02 decomposes on heating and changes to PbO.

2Pb0 2 (s) heating

· electric conductivity 2Pb0(S)+02(g)
melting point
(c) It is used as Pottery, because of its high melting point and hardness.
high high (d) (i) Amphoteric

(ii) SnO + 2 HCI -----> SnC/2 + H20

medium Sn0+2NaOH-----> Na 2Sn02 +H20

medium

Question 4
low low
(a) Describe and explain how the boiling points of the tetrachlorides of the
C Si Ge Sn Pb C Si Ge Sn Pb Group IV elements vary down the group. [3]
(b) The tetrachlorides are all covalent co'!lpounds. Draw a diagram showing
(ii) Explain how the variation in conductivity is related to the structure and the shape of a molecule of silicon tetrachloride, including values for bond
bonding in the elements. [6] angles. [2]
(b) Going down Group IV there is a variation in the relative stabilities of the (c) The noble gas xenon forms a tetrafluoride, XeF,. Only four of xenon's outer
higher and lower oxidation states of the elements in their oxides. shell electrons are used in bonding to the fluorine atoms.
Illustrating your answers with balanced chemical equations, in each of the (i) Draw a dot-and-cross diagram showing how the outer-shell electrons
following cases suggest one piece of chemical evidence to show that are arranged in XeF,.
(i) CO is less stable than C0 2, (ii) Predict the shape and the bond angles in XeF,. [4]
[3]
(ii) PbO is more stable than Pb02 • (d) Describe and explain how the reactions of CCI, and SiC I, with water differ.
(c) Name one ceramic based on silicon(IV) oxide, and explain what properties Write an equation for any reaction that occurs. [3]
of the oxide make it suitable for this use. [1] (a) Carbon has allotropes (e) Many tonnes of lead tetrachloride used to be produced to make the anti-
graphite and diamond, knock petrol additive tetraethyl-lead, Pb(C 2 H5),, by the following reaction.
(d) Tin(ll) oxide reacts with both acids and alkalis. their conductivities are d~­
(i) What name is given to this property of an oxide? ferent. Diamond is a poor PbCI, + ............ Na + ............ C2H5C/ ... Pb(C 2H5), + ............ NaC/
conductor while graphite is
(ii) Write suitable equations to show these two reactions of tin(ll) oxide. a very good conductor of Balance this equation and use it to calculate the mass of sodium needed
[N05/P4/03] to produce 1.0 kg of tetraethyl-lead. [3] ,
electricity with water mol-
ecules which facilitate hy- [N06/P4/01] I
drolysis.
Suggested Solution: Suggested Solution:

(a) (i) (a) Boiling Points of group IV tetrachlorides increases down the group. As size
melting point electric conductivity of molecule increases, number of electrons increases. Strength of Van dar
waal's forces increases hence boiling point increases.
high
high ~b) Cl

medium medium Ci •" )~ 1095'

Ci C!
low low
(c) (i) XX XX
C Si Ge Sn Pb
C Si Ge Sn Pb ~Fx X F~
XX o • XX
(ii) Tin, lead and graphite has free delocalized electrons hence have high
conductivity, while Diamond, silicon and germanium have no free XX
..
Xe
XX
~ F X XF~
electrons.
XX XX
 topic 9.3 Group IV Page 7
Page6
1
topic 9.3 Group IV ~CORNER (ii) Pb30,--+3Pbo+..!.o
2 2 "LAM.~M,
..._,~ CORNER
(ii) Shape of XeF, is square planner, bond angle is 90'.

(d) CCI, does not react with water as the carbon atom in CCI, does not have (iii) Pb 304 +4HN03--'> 2Pb(N03)2 +Pb02 +2H20
empty d-orbitals which are required for temporary bonding with water mol-
ecules. However SiC/, reacts with water according to the following reaction. (ill) PbO reacts with HNO to reduce
HNO,, which shows that :bo . Pb(NO,!, and PbO, do not react with
IS more bas1c than PbO,.
SiCI (/)+4H 20(1) -----> Si(OH) 4 +4HCI
4

(e) PbCI, + ..1! ... Na + .. ~ .. C,H,CI ~... Pb(C,H,), + . .!L NaG/

M, of Pb(C 2H 5 ) 4 = 207 + 4 x 29 = 323

323g of Pb(C 2H5 ) 4 needs 8x23 =184g of Na
Question 6

184 (a) By choosing the chlorides of two of the G

1000 g of Pb(C 2H 5 ) 4 needs x 1000 = 569 g of Na. describe the trend in the reactions of th rou~l I~ elements as examples,
323
an explanation for any differences and eset c onde.s With water. Suggest
that occur. ' wn e equations for any reactions
131
Question 5 (b) The standard enthalpy changes of for .
chloride are given in the followin t mbaltlon of lead(ll) chloride and lead(IV)
Carbon forms two stable oxides, CO and CO,. Lead forms three oxides: yellow g a e.
PbO, black PbO, and red Pb,O,. compound t.H~ I kJ mol·'
(a) Carbon monoxide burns readily in air. Heating black lead oxide produces
oxygen gas, leaving a yellow residue. PbCk(s) -359
(i) Suggest a balanced equation for each reaction. PbC/4(1) -329
(ii) Explain how these two reactions illustrate the relative stabilities of the
Use these data, and also bond en r
+2 and +4 oxidation states down Group IV. [3] calculate the enthalpy changes for th gyf dllata. from the Data Booklet, to
e o OWing two reactions
(b) Red lead oxide contains lead atoms in two different oxidation states.
(i) CC/2(g)+CI2(g)--'> CC/4 (g) .
(i) Suggest what these oxidation states are, and calculate the ratio in which
they occur in red lead oxide. (ii) PbC/2(s) + Ct2(g) __, PbCI,(I)
(ii) Predict the equation for the action of heat on red lead oxide. (iii) Make use of your answers to art (") ..
stabilities of the two oxidati! ~ t and (u) to suggest how the relative
1
When red lead oxide is heated with dilute nitric acid, HNO,, a solution s a es vary down the Group. 131
of lead(ll) nitrate is formed and a black solid is left.
[N07/P4/Q4}
(iii) Suggest an equation for this reaction:
(iv) Explain how this reaction illustrates the relative basicities of the two
Suggested Solution:
oxidation states of lead. [5]
(a) CCI, is unreactive due to non av .1 bT .
(c) Both tin(ll) oxide and tin(IV) oxide are amphoteric. rides react with increasing vigour~' a ' fly of d·Orbilals. Other group IV chic-
Write a balanced equation for the reaction between tin(ll) oxide and aque·
(a) Oxygen in water offers lone
ous sodium hydroxide. [1] SiC/, + 2H20 --" Si02 + 4HC/ pair to available d-orbital
[J07/P4/Q3]
making reaction possible.
(b) (i) BE(C/2) = 244 This facility is not available
Suggested Solution: 2BE(C- C/) = 2 X 340 = 680 in carbon atom, therefore
CCI, do not react with
(a) (i) 2CO + 0 2 --'> 2C02 tf.H" = +244- 680 = -436 kJ mol·'
water.
2Pb0 2 --'> 2Pb0 + 0 2 (ii) t.HRB = t.H,(products)- t.Hf(reactants) (b) (i) One mole of CI-C/
(a) (iO In stable C0 2 only
(ii) +2 state becomes more stable down the group. = (-329)-(-359) = +30 bond breaks and two C-CI
oxidation state is +4,
bonds are formed.
(b) (i) Pb'" and Pb'"
whereas going down the :. H" = 30 kJ mor' + 244- 2 X 34Q: -436 kJ
group +4 oxidation state
In red lead i.e. Pb,O,. (iii) Since reaction in part (ii) is end . mol·'.
becomes less stable and +2 stable than +2 oxidation state. othermlc, the +4 oxidation state is less
let number of Pb(ll) atoms = x, and oxidation state becomes
(ii)
more stable as in the case
let number of Pb(IV) atoms = 3 -. x
of Pb, that is why Pb(IV) ~HReaction = tlHiormationolprndud
x(2)+ (3- x)4 -8 = 0 oxide decomposes into
-ll.Hiorrnationofreactants
2x+12-4x-8=0 Pb(ll) oxide on heating.
2x =4

Pb 2•: Pb4 • = 2: 1
 PageS topic 9.3 Grou12_ IV
togic 9.3 Group IV Page 9
~CORNER

Question 7
(ii) Use the Data Booklet to predict the products formed, and write equa-
lions for the reactions occurring, when
I ~ CORNER

(c) All the oxides of the elements in Group IV in their +4 oxidation state are I • an equimolar mixture of Sn'"(aq) and Sn'•(aq) is added to l (aq),
2
high melting point solids except co,. an equimolar mixture of Pb'•(aq) and Pb'•(aq) is added to SO,(aq).
(i) Explain this observation by describing the bonding in CO,, Si0 2 and [4]
Sn02 • (d) (i) The Sn- C/ bond energy is +315 kJmol-1 • Use this and other values
(ii) State the difference in the thermal stabilities of Sn02 and Pb02 • Illus- from the Data Booklet to calculate ·t.H• for the reaction
trate your answer with an equation.
MC/2 (g) + Cl,(g) -> MCI,(g)
C0 dissolves in water to fomn a weakly acidic solution containing the
2 for the folloWing cases.
hydrogen carbonate ion.
M= Si
(iii) Write an equation for the reaction of C0 2 with water, and write an ex-
pression for the equilibrium constant, K,.
M = Sn
(iv) Explain the role of the hydrogen carbonate ion in controlling the pH of (ii) Do your results agree with the trend in relative stabilities of the +2 and
blood, illustrating your answer with relevant equations. [7] +4 oxidation states in (c)? Explain your answer. [3]
[JOB!P4!02(c)]
{JOB/P4/Q3}

Suggested Solution:
Suaaested Solution:
{c) {i) All the elements of
C0 : Simple covalent molecules and weak intermolecular forces. group IV exhibit +2 and
(a) C/ All bond angles are 109°, shape is tetrahedral.
2 (a) All tetrachlorides of
Si0 : Giant covalent molecules and covalent bonding. +4 oxidation state. The I group IV have simple
/~
2 stability of +4 compounds molecular struclure.
SnO,: Ionic bonding decreases with increasing C/ pw·ct As each central atom is
atomic number. C!
SnO, is stable, PbO, is not stable. surrounded by four
(iQ lnSn{Tin)compounds bonding pairs of electrons,
PbO, ~Pb0+0 2 +4 is only slightly more (b) Volatility of group IV chloride, decreases down the group due to greater Vander the molecular shape
stable than +2. In Pb waals forces. (Number of electrons increases down the group). of XCI, is tetrahedral
C02 + HP ~ H' +HC03 {lead) +2 is more stable x=c, Si, Ge. Sn, Pb.
4 22
than +4. (c) (i) Pb +/Pb • E" = + 1.69 V Sn4• /Sn 2• E" = + 0.15 V
Kc = [H'][HC0 3 r j[Hp][C0 2]
Sn'• can easily oxidise because Sn'• is more stable than Sn'•, Pb<+ is (b) Simple molecules are
easily reduced because Pb'• is more stable than Pb'•. held by Vander waal
HC0 0+ H' ~ H 2C0 3
forces. As a result, the
+ 12 ~ Sn'' + 21·
2
II HC03 +OH- ~co~- +HP (ii) • Sn '
XCI, are volatile liquid at
HCo; can control the pH according to reaction I and II. Pb'· + S0 2 + 2H2 0 .... 2H' +so!- + Pb 2' room temperature. They
have low boiling point.
It can react both with H• ions and oH- ions, hence can keep the pH
constant. (d) (i) • M = Si: t.H" = 244- 2(359) = -474 kj /mor- 1

M = Sn: t.H" = 244-2(315) = -386 kj/mol- 1

8 (ii) Yes, the +4 state becomes less stable, the t.H is less exc:h&rmic down
the group.
elements of Group IV all form tetrachlorides with the general formula MC/4 •

Draw a diagram of a molecule of SiC/, stating bond angles. [2]

Describe and explain how the volatilities of the Group IV chlorides vary
down the group. [2]

The relative stabilities of the M '"(aq) and M ''{aq) ions also vary down
Group IV.
(i) Use the Data Booklet to illustrate this observation when M = Sn and
M = Pb.
 topic 9.3 Group IV Page 11
Page 10
topic 9.3 Group IV
~CORNER Suggested Solution: ~CORNER
(a) SiF, is with perfect tetrahedral geometry and equal and opposite dipoles cancel
Question 9 b 1 out the effect of each other while SF, has lone pairs of Cs and is polar.
. than both silicon and sulfur, u
(a) Fluorine is much more electronegative rail dipole that of SiF' has none. (b)
whereas the molecule of SF, has an ove ' [1] compound molecule has an molecule does not have
eason for this difference. overall dipole an overall dipole
1
Sugges a r . I cules will have an overall dipole. BC/3 ,/
(b) P diet whether or not the following moe
P~:ce a tick in the appropriate column. PC/3 ,/
,,I
·molecule has an molecule does not have cct. ,/
compound overall dipole an overall dipole
SFs ,/

BC/s
(c) (i) Si and B have empty orbitals available for temporary bonding with water
PC/3
molecules while in CCI, no empty orbitals are available.
CCI•
(ii) BC/3 + 3H20--> H380 3 + 3HCI
SFs [2] SiCI4 +2H2 0--> Si0 2 +4HCI
d' entlo carbon in the periodic table.
(c) Boron and silicon are two elements a JaC SCI and SiC/ do react. (d) (i) M, of compound is 396
CCI, does not react with water, whereas . ' . . '
Molecular formula is Si,Ct,o,
. est a reason for this difference In reactiVIty. .
(1) Sugg . . action of these two chlorides Wllh (ii)
(ii) Construct equat1ons showmg the re [3] mass number structure
an excess of water. 'd
tit of water SiC! produces an oxychlon e
(d) When reacted with a small quan Y ' ak~ at mass numbers of 133, 133 C/3Si
X Si Cl 0 . The mass spectrum of X shows pe that the species responsible
149.'247)63 and 396. (You sh,~~d~~:s~~7 and the '"Si isotopes only.)
for all these peaks contain the ' 247 CI3Si-O-SiC/2
h d Ia to deduce the molecular formula of X.
(i) Use I ese a k 1 the
,. of the fragments responsible for the pea s a
(ii) Suggest the structures
following mass numbers. 263 C/3 - Si-OSiC/2 - 0

mass number structure

(iii) cz /0""- /0""- ?

133 Si Si Si
I \ I \ I \
Cl Cl Ct Cl Cl Cl
247

Question 10
263
The most typical oxides of tin and lead are SnO, SnO,, PbO and PbO,.
[5]
(iii) Hence suggest the displayed formula of X. The following two generalisations can be made about the oxides of the ele·
[J10/P4/03] ments in Group IV.

As the metallic character of the elements increases down the Group, the
oxides become more basic.
The oxides of the elements in their higher oxidation states are more acidic
than the oxides of the elements in their lower oxidation states.
(a) Use these generalisations to suggest which of the above oxides of tin or
lead is most likely to react with each of the following reagents. In each
case write a balanced equation for the reaction.
topic 9.3 Group IV Page 12

(i) with NaOH(aq)

formula of oxide ............................................................................................... ..
~CORNER
::Iapre 9.4
equation .............................................................................................................. .
(ii) with HC/(aq)
formula of oxide ................................................................................................ . 9roup vgg
equation .......................................................................................................... [4]
(b) 'Red lead' is used as a pigment, and as a metal primer paint to prevent the
corrosion of steel. It is aR oxide of lead that contains 9.30% oxygen by mass.
Calculate to 3 significant figures the number of moles of oxygen and lead The similarities and trends in the physical and chemical properties of chlorine, bromine and
iodine.
contained in a 100.0 g sample of red lead. Hence calculate its empirical
formula. [2]
(N10/P4104 a,b]
Content
Characteristic physical properties.
Suggested Solution:
2 The relative reactivity of the elements as oxidising agents.
(a) (i) with NaOH(aq):
3 Some reactions of the halide ions.
formula of oxide: SnO,
4 The manufacture of chlorine.
equation: 2 NaOH + Sn0 2 -+ Na 2Sn0 3 + H20

(ii) with HC/(aq): 5 The reactions of chlorine with aqueous sodium hydroxide.

formula of oxide: PbO 6 The important uses of the halogens and of halogen compounds (see also Section 10.3).
equation: PbO + 2 HC/ -+ PbC/2 + Hp
Learning Outcomes
93
(b) Moles of oxygen; · ; 0.581 mol
16 Candidates should be able to:

Moles of lead;
90 7
· ; 0.438 mol (a) describ~ the trends in volatility and colour of chlorine, bromine and iodine.
207
(b) interpret the volatility of the elements in terms of van der Waals' forces.
Pb : 0
0.438 : 0.581 (c) describe and deduce from £" values the relative reactivity of the elements as oxidising
agents.
0.438 0.581
0.438 0.438 (d) describe and explain the reactions· of the elements with hydrogen.
: 1.33 (e) (i) describe and explain the relative thermal stabilities of the hydrides.
multiply by 3
(ii) ·-interpret these relative stabilities in terms of bond energies.
3 4
(f) describe and explain the reactions of halide ions with
empirical formula: Pbp 4
(i) aqueous silver ions followed by aqueous ammonia.
(ii) concentrated sulfuric acid.

(g) outline a method for the manufacture of chlorine from brine by a diaphragm cell (see
also Section 6).

(h) describe and interpret in terms of changes of oxidation number the reaction of chlorine
with cold, and with hot, aqueous sodium hydroxide.
(i) explain the use of chlorine in water purification.

OJ recognise the industrial importance and environmental significance of the halogens and
their compounds (e.g. for bleaches, PVC, halogenated hydrocarbons as solvents, refrig-
erants and in aerosols) (see also Section 10.3).
:1 Page 1 topic 9.4 Group VII Page 2
I topic 9.4 Group VII
I ~CORNER ~CORNER
(ii) The diagram below shows part of the structure of ordinary ice.
rf
f
l
qpening ....... . 0 oxygen

• hydrogen
1111 hydrogen bond
Question I
(a) (i) State three different substances in everyday or industrial use which
contain chlorine.
(ii) For each substance, state one use and explain how the use depen~~
on a revelent property of the substance.
(b) Comment on any problems which arise from the disposal of materials whif
contain chlorine.
2
1
1 Explain why the bond angles in ice are 109°.
(b) When a sample of methane hydrate was brought to room temperature and
[2]

pressure 160 em' of methane and 1 000 g of water were produced.

Quality of Language [4]
(i) How many moles of methane are contained in 160 em'?
[NOO/P21Q5]
(ii) How many moles of water are contained in 1000 g?
(iii) How many moles of water are associated with each mole of methane
in methane hydrate? [3]
Suggested Solution:
(a) Other possible chlorine-ron· (c) Suggest two of the difficulties that could be anticipated in the commercial
(a) (i) first substance : poly(chloroethene) taining substances: exploitation of methane ice. [2]
second substance : sodium chlorate(l)
1. chlorine which is used [N01/P2/Q2}
third substance : tetrachloromethane
as a disinfectant due to tts
(ii) Poly(chloroethene) is used to make pipes because it is relatively inert, ability to kill germs.
durable and strong and can be easily moulded. . Suggested Solution:
2. CCI,F, dichlorine
Sodium chlorate(l) is used as a bleach as it oxidises coloured sta1ns to (a) (i)
colourless products.
Tetrachloromethane is used as a solvent as it is inert and not flammable.
difluoromethane which is
used as a refrigerant fluid
due to its low melting point
./. (a) (i) Alonepairofelectrons
is attracted by one nucleus,
~
0 unlike a bond pair which is
and inertness. \')IIH •. . ·denotes lone pair of electrons
attracted by two nuclei.
If materials containing chlorine are buried, the _material m~y be n?n·biode· [ 150°
(b) gradable so that they remain around for a long t1me occupy1ng prec1ou~
land H Hence, lone pairs are
closer to nucleus and exert
space If they are biodegradable_, !he chlorine may be converted by m1cr~or· Oxygen in water has two lone pairs of electrons which exert greater greater repulsion than
anis~s into organochlorine compounds which may be harmful. Malena s electronic repulsion than the bond pairs. The H - 0 - H bond angle is
~ontaining chlorine on incineration produces tox1? gass~s such as hydroJe~ thus 105°, smaller than the tetrahedral angle of 109.5°.
bond pairs.
chloride and may also form the very toxic diox1ns wh1ch are suspecte o Common Error
(il) In ice, the H2 0 molecules are held in fixed positions. The lone pair of elec-
causing cancer in humans. DO NOT forget to include
trons on oxygen are attracted by the hydrogen nuclei of other H 0
2 the lone pair of electrons in
molecules in ice. Being attracted by two nuclei instead of just one, each lone
the diagram.
pair of electrons is further from the oxygen nucleus in ice compared to that
Question 2 in water so that they exert less repulsion. The repulsion exerted by the fbne
pair of electrons of oxygen in ice is similar to that of bond pairs so that the
A newly discovered source of frozen fuel is 'methane ice', also called 'metha~e
bond angles in ice are 109°, close to the tetrahedral angle.
hydrate' This is methane trapped in ice about 500 m to 2000 m be~ow I ~
ocean ~urface. Deposits have been detected off Norway, North Carohna an (b) (I) Amount of methane in 160 em' at room temperature and pressure
in the Pacific Ocean off Japan, Indonesia and New Zealand.
The ice in methane hydrate has a more open structure than ordinary ice and = ~ = 6.67 x 1 o-3 mol (to 3 s.f.)
24000
contains spaces large enough to contain methane molecules.
. 1000
(a) (I) Draw a diagram of a water molecule and explain why its bond an~~ (ii) Amount of water 1n 1000 g = _ + x _ = 55.6 mol (to 3 s.f.)
16 0 2 1 0
is about 105o.
(ill) Amount of water associated with each mole of methane

55.6 I(
_ x _ = 8.33x 103 mo to 3 s.f.)
6 67 10 3
 topic 9.4 Grou12. VII
Page3 Page4
top_ic 9.4 Group VII
~CORNER ~CORNER
(c) One difficulty is mining the methane ice from the depth of the ocean whereby Question 4
specialised equipment and personnel are required. (c) Another difficulty is to keep
the frozen fuel in its frozen
(Another difficulty is to separate the methane which is the fuel from the large In 1819, the element fluorine was known to exist but had not been isolated. The
form when it is taken to the
amount of water in methane ice. 1000 g of methane ice yields only about mineral flurospar, which contained calcium fluoride, CaF , had many properties
surface.lnthegreatdepth of similar to those of other calcium halides.
2
16.0 x 6.67 x 10"' = 0.107 g of methane.)
the ocean when the pressure
is high and temperature is (a) What type of bonding is present in calcium fluoride? [1]
low. the fuel is kept frozen.
Once brought to surface
{b) When calcium fluoride reacts with concentrated sulphuric acid, gaseous
Question 3
hydrogen fluoride is produced. A similar reaction occurs with calcium chlo-
where temperature is higher
Chlorofluorocarbons, CFCs. are small alkane molecules in which some of the ride but with calcium bromide, bromine is formed.
and pressure is lower, the
hydrogen atoms have been replaced by atoms of chlorine and fluorine. (i) Write an equation for the reaction of calcium fluoride with concentrated
fuel melts and the methane
will escape as methane gas. sulphuric acid.
(a) (i) State two uses of CFCs.
(ii) What property of CFCs causes them to be useful? [2] Common Error (ii) Why, when reacted with concentrated sulphuric acid, does calcium
bromide form bromine whereas calcium forms hydrogen chloride?
It is not acceptable to talk
(b) A typical CFC is CHF,CHC/F.
about the general hazards (iii) Suggest a possible reaction product of the concentrated sulphuric acid
(i) Which covalent bond in this CFC is the weakest? associated with CH, e.g. in the raction (ii) above. [3]
(ii) Why does this CFC present an environmental concem? [3] combustibility, greenhouse
effect, etc. (c) Many of the early attempts to produce fluorine involved the electrolysis of
(c) Another CFC contains the following elements by mass. The value of its M, aqueous solutions of metallic fluorides. In every case, oxygen was pro-
duced at the anode.
is 135.
C, 17.8%; H, 1.5%; Cl, 52.6%; F, 28.1% (i) When NaF(aq) is electrolysed, hydrogen is produced at the cathode
Use these data to determine the molecular formula of the CFC. [3] and oxygen at the anode. Give the half equation for each electrode
reaction.

(ii) By considering appropriate E" values, suggest a reason why fluorine (b) The reaction between con·
Suggested Solution: is not produced in the electrolysis of NaF(aq). [4] centrated sulphuric acid
(a) (i) Propellant in spray can and refrigerant and air-conditioner gases. (d) In 1886, Henri Moissan succeeded in obtaining fluorine by the electrolysis and the soild halide salts to
of molten potassium hydrogendifluoride, KHF,, which is an ionic compound form hydrogen halides is
(ii) CFC are chemically inert. favoured by the higher vola-
containing one calion and one anion.
(b) The C - H, C - F and tility of the hydrogen
(b) (i) The C - C/ bond is the weakest. C - Cl bond enthalpies (i) Write the formulae of the ions present in KHF,. halides compared to cone
(ii) In the stratosphere, chlorine radicals are generated by the cleavage of the are 413, 485 and 339 kJ sulphuric acid:
(ii) Suggest a structure for the anion and state what types of bonding occurs
C - C/ bond by uv light. Cl radical reacts with ozone to form chlorine mol-' respectively. The within it. [3]
oxide and oxygen: C - Cl bond is cleaved MX(s) + H2S0 4 (aq)
C/ (g)+ 0 3 (g) -----> C/0 (g)+ 0 2 (g) homolytically by uv radiation (e) Fluoride ions are ofte·n present in riatural waters. They may be added .io
in the stratosphere but not domestic water supplies because they help to prevent tooth decay. They ==MHS04 (s)+HX(g)
Chlorine oxide reacts to· regenerate chlorine radicals: the stronger C - H and strengthen tooth enamel by converting the hydroxyapatite,
C- F bonds. Thus a com- Ca,(PO,),.Ca(OH),, present in tooth enamel, into fluoroapatite, [X= F, Cl, Br or IJ
2C/O(g)-----> 0 2 (g)+2CI(g)
pound that contains only Ca,(P04) 2 .CaF2 • The gaseous HX escaped
Hence one chlorine radical can destroy many ozone molecules. Since C- H and C- F bonds, from the system thus driv-
Suggest why hydroxyapatite is soluble in the acids present in food whereas
ozone molecules in the stratosphere are important in shielding off harmful e.g. CH,F 2 is more 'ozone ing the position of equilibrium
fluoroapatite is not. [2]
uv radiations from earth, destruction of ozone by CFC presents an envi- friendly' than one which to the right.
ronmental concern. contains C- C/ bond, e.g. [N021P2103] Both hydrogen bromide
CH CI F, since the tatter and hydrogen iodide are
2
(c) Element: c H C/ F generates chlorine radicals further oxidised by concen-
52.6% 28.1% in the stratosphere which Suggested Solution:
Percentage: 17.8% 1.5% trated sulphuric acid to
19.0 destroys ozone. (a) Ionic bonding. bromine and iodine resp-
35.5
A,: 12.0 1.0
ectively. Concentrated
1.483 1.500 1.482 1.479
Percentage.,. A, : (b) (i) CaF2 (s)+2H2 S0 4 (aq) ~ Ca(HS0 4 h(s)+2HF(g) sulphuric acid is it self
1.67 1.00 1.01 1.00 1.00 cone. reduced to SO,, S or H,S :
.,. by smallest value :
(ii) Br- is more easily oxidised than Cl- as the valence electron is more easily e.g .. 2HBr+H,so, ~
Empirical formula is CHCIF. lost in Br- since it is shielded by more inner filled quantum shells. Con- Br2 + S02 + 2H20
Let the molecular formula of the CFC be (CHCIF)n· centrated sulphu[ic acid is strong enough an oxidising agent to oxide HBr
produced to Br, whereas concentrated sulphuric acid is too weak an Concentrated sulphuric acid
(12.0 +1.0+ 35.5 +19.0)n = 135 oxidising agent to oxidise HCI produced to chlorine. is not strong enough an
oxidising agent to oxidise
67.5n=135 ~ n=~=2
67.5
(iii) sulphur dioxide.
hydrogen fluoride or hydro-
gen chloride.
Hence, molecular formula of the CFC is C 2H2CI2F2 •
 Page 5 topic 9.4 Group VII Page6
topic 9.4 Group VII
~CORNER ~CORNER
Suggested Solution:
(c) (i) cathode: 2H'(aq)+2e- ---> H2(g)
anode: 40W(aq) ---> 0 2(g)+2H 20(/)+4e-
(a) (i) Anode: cr ____, ic 12 +e· (a) (i) An anode is an elec-
trode where oxidation
(ii) An aqueous solution of NaF contais both F- and OH- (from self-ionisation Cathode: H' + e· ----> ..!.H takes place while a
2 2
of water) ions. The standard reduction potential, E e- values for reduction cathode is an electrode
of F, to F- and 0 to OH· are + 2.87 V and -0.40 V respectively. (ii) Th e diaphragm prevents the mixing of C/, and NaOH that are pro duced. where reduction takes
2 place.
Thus, the standard oxidation potential for oxidation of F- to F, and OH· 2 NaOH + C/2 ----> NaC/0 + NaC/ + H20
to 0 are - 2.87 V and + 0.40 V respectively.
2 (iii) OH-
Since the standard oxidation potential of oH· is greater than F·, it is eaiser
for OH· to be oxidised than F- so that fluorine is not produced. 02 + 2H20 + 4 e- <==== 40H" E" = +OAO y

(d) (i) cation: K•

C/2 + 2e- <==== 2Cr E" =+1.36 V
anion: HF; By ~o-mparing theE", OW is more easily oxidised. However CJ- exists
:n h•gh concentration. This shifts the equilibrium to the left ~nd '! .
(ii) F - H ----- F. anger under standard condition. C/- is more readily oxidised. I IS no
t t
covalent bond hydrogen bond (b) 6Na0H+3C/2----> NaC/03+5NaC/+3H20
(b) In hot NaOH, CIO,· is
(e) Hydroxyapatite, Ca,(P0,) 2 .Ca(OH) 2 , contains oH· which reacts with H• in food. formed instead of CJO-.
(c) (i) I 2 +2Sp~- ____, 2 I-+ sp~- C/O· is formed if cold
Thus, it is soluble in acid in food.
40 0 NaOH is used. CJO· readily
However, fluoroapatite, Ca,(PO,),.CaF 2 , does not contain OH· ions which react ns,o;- = 010
· x · ~ 0.00400 mol disproportionates to give
with H+ and the CaF, has a very exothermic lattice energy due to the small 1000
Ct and Cto,· when heated.
F·.
n,, =..!.ns,o;- = 0.00200 mol
2

(ii) I-+ IC/n ----> 12 (unbalanced)

Question 5
(a) Chlorine is manufactured from brine by electrolysis. Chlorine gas is evolved n 1c,, = 0.0010 mol
at the anode. The anode and cathode compartments are separated by a n,, = 0.0020 mol
diaphragm or membrane.
In 0.0020 mol of I there are o0040
(i) Write ionic equations for the reactions occuring at the anode and at the ICI,, the balance ~i 0. 0030 mol has ~~~eo:r~·ms~~-ce 0.0010 mol is from
cathode.
(ii) Explain the purpose of the diaphragm. Suggest what the products might I-----> .!.I +e·
2 2
be if the diaphragm were removed, by writing an equation for any reac-
tion that occurs. There is a transfer of 0.003 mol of e·.
(iii) What other anion does the solution of brine contain? By reference to Hence, each
the Data Booklet explain why it might be expected that this ion is more - mol of ICI" gain 0.003 = 3 mol of e·. The oxidation state of
0 001
likely that chloride ion to be discharged. Suggest a reason why chlo~ I in IC/, is +3. Therefore, n = 3.·
ride ions are in fact dicharged preferentially. [6]
(iii) 3C/2 + 12 ----> 21 C/3
(b) Write a balanced equation for the reaction between chlorine and hot
NaOH(aq). [1]
(c) Iodine and chlorine react together to form compound X (ICIJ Question 6
When 0.0010 mol of X was reacted with an excess of KI(aq), all of its iodine (a) De~cribe and explain how the thermal stability of th
was converted into I • The iodine liberated required 40.0 em' of 0.10 mol vanes down Group VII. e hydrogen halides
2
dm_, sodium thiosulphate, Na,s,o,, for complete reaction. (b) Desc 'b h t (3]
(i) Calculate the amount (in moles) of iodine produced. [1] brom;~e~ ~r~e Y~~ =~~~~i~:~~~ ~~~rrineeacw,.ater
1on.
is added to aqueous sodium
121
[ 12 + 2 sp~- ----) 21· + sp~- J (c) When chlorine is bubbled throu h .
hydroxide and sodium bromide g bran -~queous solut•~n. containing sodium
containing oxyanion. Careful additioom I e IOns are_ oxldl~ed to a bromine-
(ii) Hence calculate the value of n in IC/,. [1] ing solution precipitates 4_31 g of AgnC~f ~~ueo~~- Sllvermtrate _to the result-
(iii) Write a balanced equation for the reaction between C/2 and I,. [1] and more silver nitrate solution added .1 18en f IS precipitate IS filtered off,
{N03/P3!05 Either] The solid had the following composT '
20.3%.
b
g o a cream solid is produced.
' IOn y mass: Ag, 45.8%; Br,33.9%; 0,
 topic 9.4 Group VII
Page 7 PageS
topic 9.4 Group VII
~CORNER (i) Calculate the formula of the salt. ~CORNER
(i) Calculate the formula of the cream soild.
[2]
(ii) Calculate the number of moles of cream solid and of silver chloride (c) (iii) To construct a bal· (ii) Calculate the change in oxidation number of bromine during this
reaction.
anced equation:
formed.
[2] (iii) Construct an equation for the reaction.
First write down the [4]
(iii) Construct a balanced equation for the reaction between chlorine, so- reactants and products.
[N05/P3/Q5 Either]
dium bromide and sodium hydroxide. [1] C/2 + Br- +OW --> Cr + BrOj
[N03/P3/05 Or]
Next, fromthecalcula· Suggested Solution:
lion in (ii), (a) KC/: white fumes of HC/.
Suggested Solution: nAgC, 3.00x10-2 6
- - =----3-=- CI-+H2 S0 4 ~ HC/+HSO;j
n.. e.o, 5.00x10 1
(a) 2HX ----t H2 + X 2
KBr: white fumes of HBr and some brown solution of Br,.
The thermal decomposition of HX depends on the strength of H- X. Down C/2 + Br- +OW --> 6Cr + BrO)
the Group, X becomes larger and its orbital used for bonding becomes more
The 3rd step is to bal- Br- +H2 S0 4 ~ HBr+HSO;j
diffuse. Hence, the overlap of orbitals beiween H and X becomes less effec-
ance Cl and Br. 2Br-+H2 S04 +2W ~ Br2 +S02 +2H 0
tive and the H - X bond becomes weaker. The thermal decomposition be- 2
comes easier down the Group. 3C/2 + Br- +OW
Kl: dark brown soild of 12 and little white fumes of HI.
__, 6Cr + sra;
(b) CI2 +2Br- ----t 2CI-+Br2 61-+H2 S0 4 +6W ~ 312 +S+4H2 0
lnthe4thstep, balance
The solution would tum orange due to the formation of Br,.
the charge by adding a The reducing property increases from Ct- to 1- down the Group. The size of
coefficient to OH ·. the anion increases from Cl- to 1- and the valence electron become more
(c) (i) Element: Ar Br 0 easily lost. While KCI is not oxidised, some Br is oxidised to Br,, while most
3C/ 2 + Br- + 60W
33.9 20.3 1- is oxidised to 12 by the concentrated H,SO,.
%mass: 45.8
--> 6CI- + BrO)
A,: 108 79.9 16.0 (b) (i) Na Br 0
The last step is to
45.8 33.9 20.3 %mass: 15.2
balance H and 0 by adding 53.0 31.8
molar ratio 16.0
108 79.9 H20. 15.2 53.0 31.8
~ 0.424 : 0.424 : 1.27
molar ratio :
3CI2 +Br- +60W 23 79.9 16
0.424 0.424 1.27 0.66 0.66 1.99
--> 6C/- + BrO) + 3H20
~ 0.424: 0.424 : 0.424
1 3
~1 1 3 OR
lnthe4thstep, balance The formula is NaBr03
Hence, empirical formula of the cream solid is AgBr0 3 .
0 by adding a coefficient (ii) From 0 to + 5.
(ii) M,(AgBr0 3 ) ~ 108 + 79.9 + 3 x 16.0 ~ 235.9 to OH·.
3C/2 + Br- + 30W (iii) 3Br2 +60W ~ BrO:J +5Br-+3H2 0
1.18 -3
nAgsra, ~ _ ~ 5.00 x 10 mol --> 6Cr + BrOj
235 9
Mr(AgCI) ~ 108 + 35.5 ~ 143.5 Then add H' to bal· Question 8
ance H.
(a) (i)
nAgCI ~ 4 31
" ~ 3.00 x 1o-2 mol 3C/2 + Br- + 30W
Describe what you would see when aqueous silver nitrate is added to
143.5 separate tubes containing aqueous sodium chloride, aqueous sodium
--> 6Cr + sra; + 3W bromide and aqueous sodium iodide.
(iii) 3C/ +Br-+60W ----t 6Cr+Br0:J+3H 2 0
2
Finally, add 3 oH- to (ii) Describe and explain the effect of adding aqueous ammonia to each
both sides so as to of the resulting mixtures. [4]
neutralise the H'. [N06/P3/Q5(a) Either]
Question 7
3CI2 +Br-+60W
(a) The halide ions C/-, Br-and I- differ in their reactions with concentrated
--> 6CI- + BrOj" + 3H20 Suggested Solution:
sulphuric acid.
Describe what you would see if concentrated sulphuric acid is added to
(a) (i)
separate samples of the solids KC/, KBr and Kl. Suggest an explanation AgN03 NH3
for the differences in reaction, and write equations illustrating the types of NaC/ white precipitate precipitate dissolves
reaction undergone. [6]
NaBr pale yellow precipitate precipitate dissolves slightly
(b) When chlorine gas is passed through a strongly alkaline solution of sodium
Nal yellow precipitate precipitate insoluble
bromide, a salt is produced which has the following composition by mass: I
Na, 15.2%; Br, 53.0%; 0, 31.8%.
 Page 9 topic 9.4 Group VII Page 10
topic 9.4 Group VII ~CORNER I 11 L,. ~-: ~-"
...._.,.,.~
(iii) CIO, can be made in the laborato .
(ii) For NaCI, the precipitate AgCI react with NH 3 to fonn the soluble complex !rated H,So,. Other products are KrySOby rKeCact1ng KC/0, with concen- CORNER
, ,. 10, and H2 0
ion [Ag(NH,J,]'. Construct a balanced equation for thi · •..
Ag• + cr ~ AgCI of oxidation numbers helpful. s reaction. You may f1nd the use
[5]
AgCI+2NH 3 ~ [Ag(NH3),r +Cr
(b) Sulphur dioxide is an atmospheric pollutant.
For AgBr, its solubility product is much lower than that of Ag_CI. Hence,
(i) State two sources of atmospheric SO that . f
it is only slightly soluble, to form [Ag(NH,),]•. (ii) . ' anse rom human activity.
Explain why so, is a pollutant, and state an
Agl solubility product is too small for it to be soluble in NH,. quence of this pollution. environmental conse-
[3]
[J08/P4!02(a,b)J

Question 9
Suggested Solution:
(a) (i) Write an equation for the reaction between chlorine and hydrogen.
(ii) Describe and explain the trend observed in the reactions of the ele- (a) (i) !1H = (4x278)-(244)-(2x496)= -124 kJmol·'
ments chlorine, bromine and iodine with hydrogen. [5]
(ii) -;::?C!~
(b) An industrial use of hydrogen chloride is to make chlorine dioxide, which e~:~:n~s bent due to one lone pair and one unpaired
0 0
is manufactured on a massive scale for the bleaching of wood pulp and
purification of water supplies. The equation for the reaction is as follows:
(iii) 3KCIO,+H,SO, ->K,SO,+KC10,+H,0+2CIO,
NaC/0 + 2HCI ~ C/0 2 + )':; C/2 +NaG/+ H20
3
(b) (i) Coal fired power stations car exh
Discuss the changes in oxidation number of chlorine that occur during this phide ores etc. ' austs, contact process, roasting of sul-
reaction. [2]
[N06/P3105(a,b) Or] (ii) Causes acid rains - which lower H
aquatic animals and plants and : of lakes •. l~aches AI from soil, kills
amages bwld1ngs.

Suggested Solution:
Question 11
(a) (i) H2 (g)+CI2 (g) ~ 2HCI(g)
The gaseous hydrogen halides HC/ HB
(ii) H2 + X2 ~ 2HX the corresponding sodium salt w'th ~ ~nd HI, may be prepared by reacting
The reaction becomes less vigorous from C/2 to I 2 • For I,, a catalyst is When the sodium halide NaX w~s u:~:
;ous pho~phoric(V)
acid, H,PO,.
required and the reaction is incomplete. This is due to the decrease in a sample of gaseous HX was collect d '. he follo~lng reaction occurred and
e 1n a gas Jar.
reactivity (oxidising power) of C/2 to I 2 • The ability to accept electrons to
form compound decreases from C/2 to I,, due to the increasing molecular
NaX + H3PO4 -> NaH,PO4 + HX
size of the halogen.
A hot glass rod was placed in the sam I .
colour was observed. P e of HX and Immediately a red/orange
(b) From +5 in NaC/0 3 to +4 in C/0 2•
From -1 in HCI to 0 in C/2 • (a) What is the'identity of NaX?
111
(b) What gas, other than HX would be .
were used with NaX inst~ad
h f~rrn_ed If concentrated sulfuric acid
of
P osp onc(V) acid? 111
Question 10
(c) Suggest why phosphoric(V) acid rather
This question is about the properties and reactions of the oxides of some el- used to make samples ot HX from h than conce.ntrated sulfuric acid is
Expla' n t e corresponding sodium salt
ements in their +4 oxidation state. 1 your answer. ·
[1]
(a) Chlorine dioxide, C/0 , is an important industrial. chemical, used to bleach [N10/P2/Q5}
2
wood pulp for making paper, and to kill bacteria in water supplies.
However, it is unstable and decomposes into its elements as follows. Suggested Solution:
2CIO,(g) -> Cl,(g) + 20 2 (g)
(a) NaBr
(i) The chlorine atom is in the middle of the C/02 molecule. Using the (b) Concentrated H,so, is a
chlorine-oxygen bond energy as 278 kJmol-', and other values from (b) so, gas. Sulfuric acid will get reduced by HB r t0 f onn SO, and Br, vapours. stronger oxidising agent
than H,PO, hence can
the Data Booklet, calculate t1H lor the above reaction. (c) Concentrated sulphuric acid is an oxidising agent and ..
(ii) Assuming the C/-0 bonds in chlorine dioxide are double bonds, predict
while pho h · .
sp one ac1d can not oxidise HX.
can ox1d1se HX -> x2 oxidise, 2HX-> x; or

the shape of the C/0 2 molecule. Explain your answer. 2Br- ->Br2
II,.
tooic 9.5 An Introduction to the Chemistrv of Transition Elements

9.5
Page 1

7opic ~CORNER
q?fi}) fP) (} //}
7/n gnlroduclion lo /he C.hemislry of I.J \!!/ t.r IJ \!;;;l qpening ....... .
7ranstfion 0femenls Question I

(a) State the electroni~ configuration of the chromium atom, and predict two of
Content the likely oxidation states of chromium. (2]
General physical and characteristic chemical properties of the first set of transition (b) Use the Data Booklet to predict the outcome of mixing acidified aqueous
potassium dichromate(VI) with
elements, titanium to copper.
(i) aqueous iron(ll) sulphate,
2 Colour of complexes.
(ii) aqueous potassium iodide.

Learning Outcomes In each case, calculate the E~ 1 for the reaction and write a balanced equa-
Candidates should be able to: ~ ~
(a) explain what is meant by a transition element, in terms of d-block elements forming
(c) When an iron sheet is made tha anode during the electrolysis of very
one or more stable ions with incomplete d orbitals.
concentrated aqueous potassium hydroxide, an anion containing iron in
(b) *state the electronic configuration of a first row transition element and of its ions. a high oxidation state is formed in solution. The addition of an excess of
(c) state that the atomic radii, ionic radii and first ionisation energies of the transition barium nitrate to this solution precipitates a red solid having the following
composition by mass:
elements are relatively invariant. Ba, 53.3 %; Fe, 21.7 %; 0, 24.9 %.
(d) *contrast, qualitatively, the melting point, density, atomic radius, ionic radius, first
ionisation energy and conductivity of the transition elements with those of calcium as (i) Calculate the empirical formula of the red solid and the oxidation
number of the iron in it.
a typical s-b\ock element.
(e) describe the tendency of transition elements to have variable oxidation states. (ii) After a current has been passed through the solution for some time, the
addition of barium nitrate produces 1.00 g of the red solid. Calculate
(f) predict from a given electronic configuration, the likely oxidation states of a transition
how many moles of red solid are formed, and hence calculate how
element. many coulombs of electricity were needed. (6]
(g) describe and explain the use ofFe>+fFe'+, Mn04-/Mn,. and Cr,o,•-tcr>+ as examples
[JOOIP1/04)
of redox systems (see also Section 6).
(h) predict, using E" values, the likelihood of redox reactions. Suggested Solution:
(i) *explain the reactions of transition elements with ligands to form complexes, includ-
ing the complexes of copper(II) ions with water, hydroxide and ammonia. (a) Electronic configu!ation of chromium is 1s' 2s' 2p' 3s 2 3p' 3d' 4s'.
Likely oxidation states of chromium : +6 and +3
OJ explain qualitatively that ligand exchange may occur, including the complexes of
copper(Il) ions with water, hydroxide and ammonia. (b) (i) For the reaction beteen Fe'• and acidified aq. Cr'o,•-.
(k) describe the shape and symmetry of the d orbitals, and the splitting of degenerated
E;_ 11 = +1.33-0.77 = +0.56 V > 0 V ::::> reaction is energetically feasible.
orbitals into two energy levels in octahedral complexes using the complexes of copper(Il)
ions with water and ammonia as examples. Fe•• is oxidised to Fe"' while Cr,O,>- is reduced to Cr"'.
(l) explain the origin of colour in transition element complexes resulting from the ab- Equation:
sorption of light energy as an electron moves between two non-degenerated orbitals.
Cr2 0 7 -(aq) + 6Fe •(aq) + 14W(aq) - > 2Cr 3•(aq) + 6Fe 3•(aq) + 7~0(/)
2 2

(m) describe, in qualitative terms, the effects of different ligands on absorption, and hence
colour, using the complexes of copper(II) ions with water, hydroxide and ammonia as (ii) For the reaction between 1- and acidified aq. Cr,o,>-,

examples. E.;;,11 = +1.33-0.54 = +0. 79 V > 0 V ::::> reaction is energetically feasible.

(n) state examples of catalysis by transition metals and/or their compounds, including iron
1- is oxidised to 12 while Cr,O, ,_ is reduced to Cr"'.
in the Haber process and vanadium in the Contact process.
Equation:
Note: The additional learning outcomes to be studied by />2. candidates are shown in bold type. The />2.
components will assess all learning outcomes and will not be limited to those in bold type. Cr2o/-(aq)+6-(aq)+14W(aq)-> 2Cr 3 •(aq)+312 (aq)+ 7H 0(/)
2
 topic 9.5 An Introduction to the Chemistry of Transition Elements Page3
. 9•5 An Introduction to the Chemistry of Transition Elements Page 2
topic
~CORNER (ii) The E" values for the reduction of Cr'+, Fe"' and Co•· to their respective
~CORNER
Element Ba Fe 0 +2 ions are -0.41 V, +0.77 V and + 1.80 V respectively. The decreasing
(c) (i)
% age Composition 53.3 21.7 24.9 Extra Information E" value from Cr'+ to Fe'• to Co"' indicates that the oxidising ability of the
16.0 (c) Half equation at the anode: +3 ion increases from Cr'+ to Fe"' to Co". Hence of the three ions, Co"'
A 137 55.8
is the strongest oxidising agent while Cr"• is the weakest oxidising agent.
0.3891 0.3889 1.556 Fe(s)+80W(aq) ;===
%age+ Ar
(c) (i) No reaction occurs when aqueous solutions of Fe"' and Ct are mixed.
0.3891 0.3889 1.556 FeO, 2-(aq) + 4Hp(l) + 6e-
stoichiometric Ratio 0.3889 . 0.3889 0.3889 (ii) Co'• oxidises Br to Br' while itself is reduced to Co'•:
1: 1: 4 6 electrons are needed for 3
the formation of one FeO t · 2Co •(aq)+2Br-(aq)-----> 2Co 2 '(aq)+Br2 (aq)
The common oxidation
Empirical fonmula of the red solid is BaFeO,.
states of iron are +2 and E:, = E: -Et = 1.80 = 1.09 = +0.71 V
11

Let oxidation state of Fe be x. +3. The +6 oxidation state

(iii) I, oxidises Cr'• to Cr"• while itself is reduced to 1- :
in which iron exists as
+2 + X + 4( -2) = 0 => X = 8- 2= 6 FeO ,. is rather uncommon.
2Cr'•(aq) + 12 (aq) -----> 2Cr 3 '(aq) + 2r(aq)
Hence, oxidation state of Fe in the red solid is +6. FeO•,_ is a strong oxidising
age~t and is formed by E,~ 11 = E:- E~ = 0.54- (-0.41) = +0.95 V
(ii) M of the solid= 137 + 55.8 + 16.0 x 4 = 256.8 treating a freshly made
' of mol of the solid formed = 1.00 ~
· 256. 8 = 3894x10"" suspension of iron(ll)
No. · .
hydroxide in concentrated
1 Question 3
To oxr.d.rse Fe to FeO-
, • 6 mol of electrons is equired for the fonmation o potassium/ sodium hydrox·
1 mol of Feo,-. ide with chlorine o r ozone.
Chromium is used extensively in steel alloys. It is extracted from its ore chromite,
Hence, no. of mol of e- required = 6 x 3 ·894 X 10-"- - 0 ·02336. FeCr,O,, which contains chromium in the ·+3 oxidation state.

Coulombs of electricity needed= no. of mol of e-x F (a) Give the electron configuration of the elements iron and chromium (after the
argon configuration).
= o.o2 336 X 9.65 X 10 C
4

iron [Ar]
= 2255 C (to 4 S.F.)
chromium [Ar]
[1]
(b) What is the oxidation state of iron in chromite? [1]
Question 2 Chromium is produced in two forms - ferrochrome and pure chromium metal.
(a) Complete the electronic configuration of the Fe"' ion. (c) To produce ferrochrome, chromite is reduced with carbon at a high tem-
[1] perature.
1s' 2s' 2p' 3s' 3p'
FeCr2 0 4 +4C-----> Fe+2Cr+4CO
B uotin suitable data from the Data Boo kl. ~-'t exp lain how E" values can ferrochrome
(b) b~ ~sed ~o show the relative oxidising abrlrtres of
(i) Suggest how environmental problems posed by the carbon monoxide
(i) the halogens Cl,, Br,, 1,. [ ] produced in the process can be minimised.
· cr'+ • Fe"' • co•· · 3
(ii) the transition metal 1ons (ii) Calculate the volume of CO, measured at room temperature and pres-
sure, that is produced when 2.24 kg of chromite is reduced.
.
h ther a reaction will occur when the
(c) Use these E" values to pre~~~~ w ere mixed If a reaction occurs, write (iii) Ferrochrome is used to make stainless steel. Suggest one property
following pairs of aqueous so u Ions a .
chromium brings to the iron to make it useful as cutlery. [4]
a balanced equation and calculate the E:,n · {d) Several steps are needed to produce pure chromium from chromite as
(I) Fe 3 '(aq) and cnaq) shown below.
(ii) c 0 3•(aq) and Br-(aq) FeCr2 0 4 -----> Na 2 Cr04 -----> Na 2 Cr20 7 -----> Cr2 0 ~Cr
3
[4] chromite
(ii) cr''(aq) and l,(aq)
[J02/P4/04]
(i) Complete this table, which asks for the oxidation states of chromium
in some. of these compounds, and also their colours.
(b) (i) For the redox reaction
Suggested Solution: between Cl- and Fe,., compound oxidation state of Cr colour
Na,cro, yellow
E:n=E;-E~
00~ ... Na,cr,o,
. I hlorine bromine and IOdine to their =0.77 -1.36
(b) (i) TheE" values fo~ the reduction~ c 1 07 V
and +0.54 V respectively. A cr,o,
respective halide ~ons are + 1.36 t~;ea.se of reduction and hence greater
=-0.59 V<O

greater E" value Indicates a gr_~~ . g ability decreases from chlorine to => the reaction is not (ii) Write an equation for the last step, the action of aluminium on Cr,O,. [3]
oxidising ability. Thus, the OXI ISin energetically feasible dnder
bromine to iodine. standard conditions. {N02/P2102]
topic 9.5 An Introduction to the Chemistry of Transition Elements Page4 topic 9.5 An Introduction to the Chemistry of Transition Elements PageS
~CORNER
Suggested Solution:
cyuestion"J ~CORNER
(a) Theelectronicconfiguration
(a) iron [Ar]3d' 4s' (a) Explain why so many transition element complexes are coloured. [3]
of Cr is [Ar]3d' 4s' and not
chromium [Ar]3d' 4s' [Ar]3d' 4s'. This is because (b) Anhydrous copper(ll) sulphate, CuSO,(s), is a white powder which readily
(b) Oxidation state of iron in chromite is +2. the energy of 4s-orbital and dissolves in water.
3d-orbital of Cr are similar.
(c) (i) Oxidise CO to C0 2 for example, by burning CO in air/oxygen and utilise Describe and explain what is seen when CuSO,(s) is stirred with water,
To minimise repulsion, the
the heat evolved. followed by the addition of NH,(aq) until in excess. [3]
six outenmost electrons in Cr
(ii) M, of FeCr,O, = 55.8 + 52.0 x 2 + 16.0 x 4 = 223.8 occupy the five 3d-orMals (c) 'Blueprints', the detailed plans for architectural or engineering projects, were
3
and one 4s-orbital singly made in the 19th century by forming the insoluble complex "Prussian Blue"
. 2.24x10 instead of occurring as apair
No. of mol of FeCr2 0 4 = 223:s-
= 1O.D1 mol on sensitised paper. Prussian Blue is the name given to the deep blue pre-
in the 4s-orbital where they cipitate formed by adding a solution of Fe"'(aq) to a solution of [Fe(CN),r (aq).
would face electronic repul-
No. of mol of CO= 4 x no. of mol of Fe,Cr,o, = 4 x-10.01 = 40.04 mol (i) Construct a balanced equation for this reaction. [1]
sion.
Volume of CO = 40.04 x 24 dm' = 961 dm' (to 3 s.f.) (ii) Suggest a reason for the difference between the following redox po-
tentials.
(iii) Corrosion resistance 3
[Fe(H2 0) 6 ] ' + e· ====" [Fe(H,0)6 ] 2 ' E" =+0.77 V
(d) (i) compound oxidation state of Cr colour [Fe(CN) 6 ] 3
- + e· ====" [Fe(CN) 6 ] 4 - E" =+0.36 V
Na2 cro, +6 yellow
[2]
Na,cr,o7 +6 orange (d) (iij AI is a more reactive (iii) Suggest why the red colour of a solution of [Fe(SCN)(H,O),]'' ions is
green metal than Cr. It reduces destroyed by adding F·(aq) ions. [1]
Cr,Os +3
- Cr,o, to Cr and itself is
[N03/P3/Q4]
oxidised to AI,O,.
(ii) 2AI(s)+Cr20 3 (s) ----7 Al 20 3 (s)+2Cr(s)
Suggested Solution:

(a) In transition element complexes, the central metal (ion) has partially filled d
Question 4 subshell. This allows d-d transition. When an electron in a lower d-subshell
(a) Titanium is an important transition metal. The metal itself is a component is excited, it absorbs wavelength in the visible spectrum. Hence, colour comple-
of many highstrength low-weight alloys, and its oxide is used as an opaque mentary to these wavelengths absorbed is observed.
agent in many paints and pigments.
(b) The white powder first turns into blue crystals (CuSO, . 5H 0).
2
(i) Write out the electronic configuration of the titanium atom. (b)
CuS0 4 (s)+5H2 0(1) _____. CuS0 4 • 5H 0(1)
2
(ii) Titanium forms two chlorides. Suggest possible formulae for them.[2] Cu
2
' + 20H"-.===: Cu(OH),
it then dissolves in water to give a blue solution.
(b) Anhydrous copper sulphate, CuSO,(s), is a white powder that readily dis-
2
Cu ' + 4NH 3 -.===: [Cu(NH 3 ) 4 J''
solves in water. CuS04 • 5~0(s) ~ Cu 2 '(aq) + s~-(aq)+5H2 0(1)
blue The above 2 equilibria are
(i) Describe and explain what is seen when CuSO,(s) is stirred with water. established when NH,(aq)
When aqueous NH, is added, blue precipitate of eu(OH), is formed, which
is added. The OH· is formed
(ii) Describe and explain the final colour change seen when an excess of then dissolves in excess NH, to give a deep blue solution containing
[Cu(NH,),]''· by the reaction of NH, with
NH,(aq) is added to CuSO,(aq). [4] H,O.
[J03/P4/Q6} Cu''(aq)+20H-(aq) _____. eu(OH)2 (s)
NH 3 +H 20 == NH.' +OH"
eu(OH) 2 (s) + 4NH3 (aq) ----7 [eu(NH3 ll' (aq)+ 20H"(aq) When excess NH, is added,
Suggested Solution: the 2nd equilibirum shifts
(a) (i) 1s' 2s' 2p' 3s' 3p' 3d' 4s'
(b) (ij
(c) (i)
3
4Fe '(aq) +3[Fe(CN) 6 t (aq) ----7 Fe 4 [Fe(eN) ] (s)
6 3
to the right, thus reducing
[Cu,.] This in turns causes
(ii) TiC/2 , TiC/, (ii) eH- is a strong ligand and it stabilises Fe(lll) with respect to Fe(ll). Hence, the 1st equilibrium to shift to
CuSO 4 ( s) + 5H 20(/) the left. Hence, Cu(OH)2
it makes [Fe(eN),],_ more difficult to be reduced to the Fe(ll) state com-
(b) (i) The white solid first turns blue where CuSO, . 5H,O is first. It then dis- ~ CuS0 4 . 5H 20(s) dissolves.
solves in water to give a blue solution. pared to [ Fe(H,O), ]''. Therefore, theE" value for [ Fe(eN),],_ is lower.
(ii) A blue precipitate is first formed due to the formation of Cu(OH),. CuS0 4 -5H 20(s)
(iii) F- is a stronger ligand than SeN-. When it is added to the complex, it
~ CuS0 4 (aq)+5H20(1) displaces SeN-. The product formed is colourless. (c) (iii) F· oould further dis-
Cu2'(aq)+20W(aq)- Cu(OH),(s) place the H, 0 ligands in
The precipitate then dissolves in excess ammonia to give a deep blue [Fe (SeN)(H2 0) 5 f' + F- ----7 [FeF(H20)5 ]2' +SeN- [FeF(H,O)J'' and eventu-
solution. A soluble complex ion is formed. red colourless ally FeF," could be formed.
These F-containing com-
Cu(OH),(s)+4NH 3 ( a q ) - [Cu(NH 3 ) 4 f (aq)+20H"(aq) plex ions are all colourless.
lCD
 topic 9.5 An Introduction to the Chemistry of Transition Elements Page 7
Page 6
to ic 9.5 An Introduction to the Chemistry_of Transition Elements
~CORNER ~CORNER
Question 7
Question 6 (a) What do you understand by the term transition elemenn [1]
(a) Describe two physical properties of transition metals in which they differ (b) State the electronic configurations of
from a typical s-block metal such as calcium. [2]
(i) an atom of chromium,
(b) Vanadium and its compounds find many uses in technology, industrial
chemistry and medicine. One of its oxides is a useful catalyst in the Contact (ii) the Cr"' ion. [2]
process for manufacturing sulphuric acid, and other compounds show useful [N05/P3/04(a,b)}
anti-tumour activity. The metal itself is often a component of steels used to
make springs and sp~nners.
(i) Apart from the use of vanadium oxide mentioned above, name another
Suggested Solution:
transition metal (or one of its compounds) used as catalyst, and state (a) filled
A transition element is a metal th at forms .Ions or compounds with incompletely
d-subshell.
the reaction it catalyses.
(ii) Give the electronic configuration of the vanadium atom. (b) (i) Cr : 1s' 2s' 2p' 3s' 3p' 3d' 4s'
(iii) Predict the likely oxidation states of vanadium. (ii) Cr 3' : 1s' 2s' 2p' 3s' 3p' 3d'
(iv) Vanadium forms many coloured complexes. For example, the ion
[V(H,O),]"' is blue-green. Explain why this colour arises.
(v) The sea worm Ascidia nigra accumulates vanadium from seawater to Question 8
an enormous extent. The concentration of vanadium in its blood cells
is 14 g dm"" and each animal has about 3 ml of blood. One litre of (b) Cryolite contains one species of cation and a complex anion.
seawater contains 7.1 )Jg of vanadium. Assuming that Ascidia nigra (i) What is meant by the term complex ion?
extracts 100% of the vanadium, calculate how many lit res of sea water
each animal has to process to achieve this concentration in their blood. (ii) s uggest the formula of the complex anion present in cryolite. [3]
[1 )Jg = 1 X 10.. g). [8) [N06/P210 1(b)}
[N041P2104}

Suggested Solution:

Suggested Solution: (a} Metals are also better elec- (b) (i) ~~~ea~dZ~d;here a central metal (ion) is bonded (dative bonds) to 2 or
(a) They form coloured compounds e.g. Cu'' is blue, Fe'' is green. trical conductors. Note that
They have extremely high melting points (e.g. > 2000 •c) compared to s-b\ock catalytic properties and abil·
ity to show variable oxida·
(ii) [AIF6 t
metals (e.g. < 1000 •c).
tion states are not physical
(b) (i) Iron: Haber Process.
3~ +N2
2
== 2NH 3
properties.
(b) (i} Otherexample include:
s,o,'· +21- ... 2so;· +12
f!!!estion 9

:he following passage is taken from an A level Chemistry text book

(ii) 1s' 2s' 2p' 3s' 3p' 3d' 4s
catalyst : Fe'' or Fe" . In an ISOlated atom~ ·the five d-orbitals have the sam .
(iii) 2+, 3+, 4+, 5+ iOn, however, the presence of the ligands splits thee fienergy: In an oclahedral complex
CH 2 = CH2 +H, -> CH 3CH 3 and a group of two Th tw . ve orbilals Into a group of three
(iv) [V(H 0),]"' has partially filled d-subshe\1. . ese o groups have slightly different energies."
2
The d-subshell is split into different energy levels.
catalyst : Ni or PI
(a) Use the following sets of axes to draw th
of the two groups mentioned above.
h 1 · .
e s ape o one d-orb1tal m each
I
An electron at a lower level absorbs energy from the visibile light and is
excited to a higher energy level. Hence, colour complimentary to those
absorbed is observed.
,,,,,,,,,,, ,,,,

/<:.
In this case, red-orange lights are absorbed and the complex appears lift,,,,, ,,,,,,,,,,

;:>~
blue-green.
3
(v) Mass of vanadium in blood= 14 g dm- x 3 mL
=14x3x10-3

=4.2x 10"2 g
4 2
= 4.2x 10 )Jg (b) Explain how the presence of the six li ·10 . [ ]
orbitals into two groups of different ene~ands, ~· [FeL,]'' splits the 3d
4 2 104 orbital group or the three-orb"! gy, an e_xplam whether the two-
' a1 group has the h1gher energy. [3]
Volume of sea water= · x
7.1
=5915 L
topic 9.5 An Introduction to the Chemistry of Transition Elements PageS topic 9.5 An Introduction to the Chemistry of Transition Elements Page9
~CORNER
(c) The following table lists the colours and energies of photons of light of
(c) (i) solution C: red solution 0: blue ~CORNER
certain wavelengths (ii) Complex C, because absorption is at lower wavelength or higher fre-
energy of colour of quency.
wavelength
/nm photon photon

400 high violet

Question 10
450 J, blue
The following account describes the preparation of Peligot's salt, named after
500 lower green the 19th century French chemist who first made it.

600 J, yellow Place 6.0 g of potassium dichromate(¥!) in a 100 em' beaker and add 8.0 g of concentrated
hydrochloric acid and I .0 em' water. Warm the mixture gently; if carefully done the
650 low red
-
dichromate(¥!) will dissolve without the evolution of chlorine. On cooling the beaker in
an ice bath the solution will deposit long orange-red crystals of Peligot's salt.
The visible spectra of solutions of two transition metal complexes C and 0
are shown in the diagram below. An analysis of Peligot's salt showed that it contained the following percentages
by mass:
1.4~---------~
K, 22.4%; Cr, 29.8%; Cl, 20.3%; 0, 27.5%.
1.2
(a) Calculate the empirical formula of Peligot's s·au.
1.0 [2]
Ql
g 0.8 (b) Suggest a balanced equation for the formation of Peligot's salt. [1]
"'
~ 0.6 (c) The instructions suggest that strong heating might cause chlorine to be
evolved.
.g"'
(i) What type of reaction would produce chlorine in this system?

(ii) Use the Data Booklet to identify relevant half equations and E 0 values
400 for the production of chlorine from the reaction between K,Cr,O, and
wavelength I nm HCI.
Use these equations to write the overall full ionic equation for this
(i) A list of possible colours for these complexes is as follows. reaction.
yellow red green blue
{Iii) The use of dilute HCI (aq) does not result in the production of chlorine.
Choose one of these words to describe the observed colour of each Suggest why this is so.
solution. (iv) Use the Data Booklet to suggest a reason why it is not possible to
solution C ............................................ solution 0 ................................................ prepare the bromine analogue of Pe\igot's salt by using HBr(aq)
instead of HCI (aq). [6]
(ii) In which complex, C or 0, will the energy gap between the two groups
of orbitals be the larger? Explain your answer. [3] [N07/P4/03] I

[J07/P4/04]
Suggested Solution:
Suggested Solution: (a) K : Cr CJ : 0
percentage = 22.4 29.8 20.3 27.5
(a)
Ar 39.1 52.0 35.5 16.0
mole ratio 0.573 0.573 0.572 1.719
simple ratio 1 1 1 3
.. emperica\ formula = KCrC\0 3

(b) K2 Cr2 0 7 + 2HCI--> 2KCrC.03 + H2 0

(c) (i) Oxidation

(b) When six ligands, approach along the axis, octahedral complex is formed. The
energy of those d-orbitals which are lying on the axis i.e. dx"- y" and dz2, wi\1
increase relative to other 3d-orbitals. Therefore two orbital groups will form.
One group having two orbitals at high energy and the other group having
three orbitals at lower energy.
 Page 10 topic 9.5 An Introduction to the Chemistry of Transition Elements
topic 9.5 An Introduction to the Chemistry of Transition Elements Page 11
~CORNER
£ 9 = 1.33 v
~CORNER
(ii), CrzO~' + 14H' + 6e' ______., 2Cr,. + 7H20 Question 12
E = 1.36 v (c) (jij
6x( C/2 + 2e---> 2Cr] (a) Complete the electronic structures of the C"""
,- an d Mn' • 1ons.
.
cr,o;-lcr'' E" = +1.33
Cr'· 1s'2s'2p' .................. .
Overall ionic reaction:
and CI 2 /CI- E8 = + 1.36
crp~- + 6Cr + 14H' ______., 2Cr3' + 3C/2 + 7Hz0 Mn'' 1s'2s'2p' .................. .
Gr,o;- will not be able
(iii) In dilute HC/ £ 8 value for Cr2 o~- I Cr 3' will be lowered or less positive
(b) (i) Describe what observations o ld
is added slowly and with shay u wou m~~~ when dilute KMn04(aq)
(2]
to oxidise Cf· to C/2.
shifting equilibrium to the left hand side. until the KMnO is ·In I kmg to an acidified solution of FeSO 4(aq)
(iii) Decrease in 4 a arge excess.
(iv) £ 8 Br I Br- = +1.07 so Cr o~- will oxidise Br to Br2 , therefore Peligot's
2 2 concentration of Cf· or H'
will shift equilibrium to left
(ii) construct ah ionic equation for the reaction that occurs. [4]
salt using HBr cannot be prepared.
side therefore chlorine will (c) By selecting relevant £"" data fro 1 ·
not be produced. solutions of Fe'' (aq) are relativelm s~=b~a:~ Bo?kl~t explain why acidified
freshly prepared precipitate of Fe(6H) . OXIdation by air, whereas a
alkaline conditions. ' IS readily oxldlsed to Fe(OH), under
Question 11 [4]
[1]
(a) Explain what is meant by the term transition element. {J10/P4!04 a,b,c]

(b) Complete the electronic configuration of

1s'2s22p' ........................................... . Suggested Solution:
(i) the vanadium atom,
1s'2s'2p' ............................................ [2] (a) Cr'• 1s 22s'2p' .~!!.~~P.~.~~~-
(ii) the Cu'• ion.
[1] Mn'• 1s'2s'2p' .~!!.~~P.~.~~:.
(c) List the four most likely oxidation states of vanadium.
(b) (i) Acidified FeS04 is pale green soluti .
(d) Describe what you would see, and explain what happens, when dilute 11, solution initially changes to c °~· Whe~ dilute KMn0 4 is added to
obtained at neutralisation. On fuort~~~ es~d~_ntll
1
aqueous ammonia is added to a solution containing Cu'' ions, until the permanent pink colour is
1110
purple solution is formed. a n of KMn04 solution, deep
ammonia is in an excess. [5]

(e) Copper powder dissolves in an acidified solution of sodium vanadate(V), (ii) MNO;; (aq.) + 8H' (aq.) + 5Fe2• (aq.) ----> Mn2'(aq.) + 4H20 (I)+ 5Fe3• (aq.)
NaVO,, to produce a blue solution containing VO'' and cu•· ions.
By using suitable half-equations from the Data Booklet, construct a bal-
anced equation for this reaction. [2]
(c) In acidic condition: o2 + 4H+ 4e---> 2H,O £"" = +1. 23 V
{J09/P4!03] Fe3• + e· --> Fe2•
E""
cell -E""
- red- E""
oxi =1.23-0.77 =+0.46 V.
Suggested Solution: In alkaline condition: o2 + 2H2o + 4e. --> 40 H" £"" = +0.40V
(a) An element from d-block of periodic table with partially tilled d-orbitals. Fe3• + e· --> Fe2• E"" =-0.56 V
(b) (i) the vanadium atom, 1s22s'2p'3s'3p'3d 4s'
3
E!u = 0.40- (~0.56) = +0.96 v.
(ii) the Cu'' ion. 1s22s 22p'3s'3p'3d'
Explanation: More positive £""
cell means more likelihood of reaction to occur

(c) +2, +3, +4, +5 As £""cen ·In a lk arme condition is greater than in a "d" .. . ·
(d) NH, being stronger ligand oxidise to F " . . Cl IC condition hence· Fe'• will
(d) When aqueous ammonia is added to pale blue solution of Cu'' ions, blue will replace H20 from e more rapidly In alkaline condition.
precipitate of Cu(OH), is seen. On addition of excess of aqueous ammonia, (Cu(H, 0) 6]'" complex ion.
Cu(OH), precipitate dissolves to give deep blue solution containing
[Cu(NH ) (H 0),]'' complex ion. This is obtained by ligand replacement.
3 4 2

(Cu(H 0) 6 j" + 4NH 3 --> (Cu(NH 3 ) 4 (H20)2] + 4H20

2

(e) 2 x ( vo; + 4W + e· --> vo 2- + 2H20 J

2
+ Cu --> Cu ' + 2e-
2 2
2V03 + sH• + Cu--> 2V0 - + 4H 20 + Cu '
 topic 9.5 An Introduction to the Chemistry of Transition Elements Page 13
Page 12
tooic 9.5 An Introduction to the Chemistrv of Transition Elements
~CORNER Suggested Solution: ~CORNER
(a) (i) Ligand is a neutral molecule or anion with at least one lone pair of elec-
Question 13
trons which can form dative covalent bond with Transition element.
(a) (i) What is meant by the term ligand in the context of transition element
(ii (a) (iQ NH 3 reacts with H+ to
chemistry? species can be a ligand cannot be a ligand form NH;. As NH; ion
(ii) Decide which of the following species could be a ligand, and which OH- ,{ hasnolonepairof electrons
could not be. hence cannot be a ligand.
Place a tick ( .t') in the appropriate column. NH,• ,{

CH30H ,{
can be a ligand cannot be a ligand
species
CH3NH2 ,{
OH-

NH; (b) (i) solution C: [Cu(NH 3 J 6 tso~­

CH30H solid 0: CuO (black solid)

CH3NH2 [3] solution E: Na 2 S0 4

white precipitate F: BaS0 4 (White insoluble solid)
(b) Read the following description of some reactions of copper(\\) sulfate, and
(ii) Acid-base neutralisation.
answer the questions that follow.
When 0.1 mol of white anhydrous CuSO, is dissolved in liquid ammo- (c) (i) Brown fumes of NO, are formed leaving behind black residue of CuO.
niaat -33 oc,
a deep blue solution C results.
When 0.2 rno! of solid NaOH is added to solution C, and the ammonia (ii) 2Cu(N0 3)2 (s) ~ 2CuO(s)+4N0 2 (g)+0 2 (g)
solvent allowed to evaporate, a solid residue is obtained.
Heating this residue to 200 oc
produces a dark coloured mixture of two
solids.
When water is added to this mixture, a black.solid 0 and a colourless
solution E are formed. Neither 0 nor E contains nitrogen.
Adding BaCI,(aq) to solution E produces a white precipitate F.
Solid 0 dissolves in HNO,(aq) on warming,_ without evolution of gas,
to give a pale blue solution containing Cu(NO,),(aq).
(i) Suggest the formula of the compound contained in each of the following.
solution C .............................................................................................................

solid 0 .................................................................................................................. .
solution E .............................................................................................................

white precipitate F ..............................................................................................

(ii) Name the type of reaction that is occurring when 0 reacts with HNO,(aq).
[5]

(c) (i) Describe what you would observe when a solid sample of anhydrous
Cu(N0,) is strongly heated.
2 [2]
(ii) Write an equation for this reaction.
[N10/P4102]
 topic 9.6 Nitrogen and sulfur
Pagel

7opic 9.6 ~CORNER

Xilroyen and du/fur 0?)Jenmg

' ....... .

Question 1

A car ~an be considered to run on octane, C,H,..

Content (a) Wnte an equation for the complete combustion of octane 1
Nitrogen The_ composition of the exhau · [1
engine is given below. st gases (fumes) from a petrol (gasoline)
(i) Its unreactivity
(ii) Ammonia, the ammonium ion, nitric acid and fertilisers. Percentage
Gas
(iii) The environmental impact of nitrogen oxides and nitrates. byvotume

2 Sulfur carbon dioxide 9

(i) The formation of atmospheric sulfur dioxide, its role in acid rain formation, the use water vapour 8
of sulfur dioxide in food preservation. oxygen 4
hydrogen 2
(ii) Sulfuric acid.
carbon monoxide 3-6
hydrocarbons 0.2
Learning Outcomes nitrogen oxides 0.4 0.05

Candidates should be able to: (b) (i) What gas, omitted from the table m
the exhaust fumes? ' akes up most of the remainder of
(a) explain the lack of reactivity of nitrogen.
(ii) Explain why there is always water vapour in the exhaust fumes. [2)
(b) describe:
(c) (i) State two gases in the exhaust fumes whi .
(i) the formation and structure of the ammonium ion. Also state briefly for each the rr ch are po1sonous to humans.
(ii) Th pa ICU 1ar effect on humans.
(ii) the displacement of ammonia from its salts. e two gases you have given in (c)(')
(c) describe the Haber process for the manufacture of ammonia from its elements, giving a platinised catalytic converter Th I dcan be removed by reaction in
~erter are not hazardous. For ~ache ~ro ucts of th~ reaction in the con-
essential operating conditions, and interpret these conditions (qualitatively) in terms of lion which shows how it is remo d /o,u' gases In (c)(i) give an equa-
the principles of kinetics and equilibria (see also Sections 7 and 8). (iii) Suggest one reason wh th ve o onn less hannful substances.
c t ly1. Y e exhaust fumes fro .
(d) understand the industrial intportance of ammonia and nitrogen compounds derived from a a IC converter are still haza d m a car f1tled with a
. r ous 1o human health to some degree.
ammonia. [5)
(e) understand the environmental consequences of the uncontrolled use of nitrate fertilisers. [N03/P2/Q2]
(j) understand and explain the occurrence, and catalytic removal, of oxides of nitrogen.
Suggested Solution:
(g) explain why atmospheric oxides of nitrogen are pollutants, including their catalytic role
(b) (iQ Major part of exhaust
in the oxidation of atmospheric sulfur dioxide. (a) CaH,a+12.!o
2 2 ~ 6CO 2 +9H2 0 fumes is air which contains
(h) describe the formation of atmospheric sulfur dioxide from the combustion of sulfur 79% Nitrogen gas.
{b) (i) Nitrogen gas.
contaminated carbonaceous fuels. (c) (i) It react with hae-
(ii) Exhaust fumes are made by bum·
(i) state the role of sulfur dioxide in the formation of acid rain and describe the main hydrocarbons bums to fonn wat lng o1 hydrocarbons, and hydrogen in moglobin in red blood cells
er. and decreases oxygen car_
environmental consequences of acid rain.
(c) (i) gas 1: carbon monoxide. ry1ng ability of red blood cells.
(j) state the main details of the Contact process for sulfuric acid production.
effect: reduces oxygen absorption by. red blood celts. • Acid rain causes
(k) understand the industrial importance of sulfuric acid. gas II: mtrogen oxides NO, NO, poisoning of water by dis-
(/) describe the use of sulfur dioxide in food preservation. solving heavy metal salts in
effect: form photochemical smog which . water like mercury com-
diseases. causes respiratory problems, skin
pounds, lead compounds.
topic 9.6 Nitrogen and sulfur Page2 toQic 9.6_Nitromm. and sulfur
~CORNER Page3

(ii) CO+NO-----> C0 2 +_!N2

2
or
1
CO + 2" 0 2 -----> C0 2
Suggested Solution:
~CORNER
(a) CO(NH2 ) 2 +H2 0 - - - t 2NH +C0
3 2
NO + HC-----> C0 2 + H20 + N2 (a) It is hydrolysis of urea.
(b) (i) N2 (g)+3H2 (g) =:= 2NH (g)
3
(iii) Catalytic converter will remove toxic fumes only when it gets heated up,
hence not effective for short joumeys. (ii) Temperature: 400-500'C
CO, is not removed which causes global warming. Pressure: 200-250 atm.
Catalyst: Iron based· iron powder of iron (Ill) oxide.
(iii) 1. Main use of ammonia is in the form ot fertilisers.
Question 2
Ammonia, NH,, is a colourless, pungent-smelling gas which has been known 2. Ammonia is used for nitric acid formation which is further used for
making explosives.
to man from the beginning of recorded time. It is given off from urine such as
that on a wet nappy from a baby.
(c) (i) No. moles of NH , n = Volume of gas
The nitrogen-containing substance in urine is urea, CO(NH,),, and this decom· 3
Molar volume of gas
poses by hydrolysis into ammonia and another colourless gas.
(a) Construct an equation for the hydrolysis ot aqueous urea. [2] = .!.:3.
24
= 0.05 moles
Ammonia was named after the shrine ot Jupiter Ammon which was near
the Egyptian-Libyan border. In ancient times ammonia was obtained by (ii) 2NH3 + H2 S04 - - - t (NH4 ) 2 S0
4
distilling camel dung.
(b) Now ammonia is synthesised from its elements in the Haber Process. (iii) Moles of H2 S04 , n = o.os = 0.025
2
(i) Write an equation for this process.
n=CV
(ii) State the three usual operating conditions ot the Haber Process.
(iii) State two modern commercial uses of ammonia. [4] Vol. of H2S04 = ~
c
(c) 1.20dm' of ammonia gas were dissolved in water to form 200 em' of aqueous 0.025
alkali at room temperature and pressure. 0.5
(i) Use the Data Booklet to calculate how many moles of NH,(g} were = 0.05dm 3 =50 cm 3
dissolved.

[ .r~,,J
(ii) Write the equation for the neutralisation of aqueous ammonia by dilute (d)
sulphuric acid.
(iii) Calculate the volume of 0.50 moldm-" sulphuric acid that is required to e
neutralise the 200 em' of aqueous ammonia.
(d) In the boxes below, draw diagrams to show the shapes of an ammonia mole-
[3]
H"'j~ H'"j ~
cule and an ammonium ion. Clearly show the bond angles on your diagrams. H 107' H
H H

ammonia ammonium ion

(e) (i) ...4.. NH,(g) + .. ~ .. 0 2 (g) ....?.... N2 (g) + ..!i... H,O(g)

(ii) Oxidation state of nitrogen in Ammonia is -3, ft changes to 0 in N • Hence

2
ammonium ion nitrogen is oxidized. Oxygen changes from 0 to -2. Hence it is reduced.
ammonia
[4]
Question 3
(e) Ammonia does not burn in air but will bum in pure oxygen.
(i) Balance the equation for this reaction: Nitrogen, which makes up about 80% of the Earth's atmosphere, is very un-
reactive.
...... NH,(g) + ...... O,(g) -----> ...... N2(g) + ...... H20(g)
(a) (i) Explain the lack of reactivity of nitrogen.
(ii) Use oxidation numbers to explain why this is a redox reaction. [3]
(ii) Nitrogen does, however, undergo some reactions. Write an equation for
[J04/P2/Q3]
one reaction of nitrogen, stating the conditions under which it occurs.
(iii) Suggest why nitrogen does react in the example you have chosen.
[6]
 topic 9.6 Nitrogen and sulfur PageS
Page4
topic 9.6 Nitrogen and sulfur
~CORNER Hydrogen sulphide burns with bl ·
~CORNER
sulphur dioxide and water. a ue flame in an excess of oxygen to form
Ammonium nitrate, NH,NO,, is a commercially important compound of nitrogen.
(d) (i) Write a balanced equation for the complete combustion of H S
(b) (i) State one large-scale use of ammonium nitrate.
(ii) Wh at is the change in the oxidation number of sulphur in this reaction?
'·
(ii) What are the environmental consequences of the uncontrolled use of
ammonium nitrate? [4] from ....................................................... to
When solid ammonium nitrate is heated with solid sodium hydroxide in a test- (iii) What v~lurne of oxygen, measured at··;~~~··;~~ .. ·~;~;-~;~..~~~··················
tube, three products are fonned. A colourless alkaline gas, Y, is given off, and IS required for the complete combustion of 8.6~ g of H S? ~ressure,
a colourless liquid can be seen on the cooler parts of the test-tube. A white answer to two decimal places . · , · 1ve your[5]
solid remains in the tube.
[J05/P2102 (a,b,d)]
(c) (i) Identify gas Y.
(il) Write an equation, with state symbols, for the reaction of ammonium
nitrate with sodium hydroxide. [3] Suggested Solution:
(d) In order to produce gas Y in a pure state in the laboratory, it must be (a) 1 S(s}+02 ---7 so2 (g)
passed through a drying agent.
Why is concentrated sulphuric acid not suitable for drying gas Y? [1] 2 2S02(g}+02(g) == 2S0 3(g)
[N05/P2103]
3 S0 3 (g}+H2SO,(I} == H2S20 7 (01eum}

(b) Vanadium(v) oxide (V,O,)

Suggested Solution:
(a) (i) In nitrogen molecule N = N is present. High activation energy is required (d) (i) 2H2$+302 ---7 2H20(g}+2S02(g}
to break this bond, hence N, reacts only at very high temperature
(il) from ..................... ::-..~............................. to .............................:!"..~ ......................... .
(ii) equation: N2(g)+3H 2(g) ~ 2NH3 (g}
(iii) 68.2g of H S reacts with= 3 x 24dm3 of
2 02
conditions: • high temperature 300 - 500 'C
~~~ 4 x 8.65 = 9 _13 dm3
high pressure 200 - 250 atm
Catalyst Iron (II} oxide
8.65g of H2S reacts with=
2
(iii) Activation energy of reaction is decreased by catalyst. Activation energy
is also overcome by high temperature. Question 5

(b) (i) Fertiliser ~a~t~s a~~~~~~: ~~:7 ;~~~~ ~;;,~~~~:e solid which is soluble in water. Mohr's
(ii) Excessive ammonium nitrate used in fann land is wasted into water sources
which leads to excessive growth of algae and fungi in water. Oxygen two cations, one of which is Fe'',
content of water decreases which causes death of aquatic life. This
process is known as eutrophication. one anion which is so~· ,
and water of crystallisation.
(c) (i) Ammonia gas.
(il) NH N0 (s} + NaOH(s)--?NH3(g)+ NaN0 3(s) +H,O(I) (a) The. identity of the seco nd ca1·IOn· was determined by the following test
4 3
Sohd Mohr's salt was heated with solid d" . ·
(d) Concentrated sulphuric acid reacts with ammonia gas to form ammonium gas was evolved. The . . so IUm. hydroxide and a colourless
solution; gas readily dissolved m water giving an alkaline
sulphate.
(i) What is the gas?
... Wh at is the formula of the second cation identified by this test?
(ii)
Question 4
(111) In this test, a grey/green solid residue was also fonned .
Sulphur and its compounds are found in volcanoes, in organic matter and in
~uggest a name or formula for this solid. · [3]
minerals.
(b) The 1dent11y of the anion present in Mohr' .
dilute hydrochloric acid followed by aqueo~ss~t ~as c~~fl~ed
Sulphuric acid, an important industrial chemical, is manufactured from sulphur
by adding
~f f~r~~~~
by the Contact process. There are three consecutive reactions in the Contact
ous solution Mohr's salt. A white precipitatea:: to an aque-
process which are essential.
:i appropriate) for each of these Suggest the 1dent1ty of the white precipitate. [1]
(a) Write a balanced equation (using where [4]
reactions in the correct sequence.
[1]
(b) What catalyst is used?
topic 9.6 Nitrogen and sulfur Page6 topic 9.6 Nitrog.en and sulfur
Page7
~CORNER
(c) When a double salt such as Mohr's salt is made, the two individual salts
are mixed together in a 1:1 molar ratio, dissolved in water and the solution Question 7
~CORNER
crystallised.
Nitrogen makes up about 79% of the Earth's atmosphere. As a constituent
(i) Give the formula of each of the two salts that would be mixed to make
element of proteins, it is present in living organisms.
the double salt, Mohr's salt.
Atmospheric nitrogen is used in the Haber process for the manufacture of
(ii) Calculate the relative formula mass of each of the salts present in ammonia.
Mohr's salt.
(a) Write an equation for the formation of ammonia in the Haber process.[!]
salt 1
relative formula mass of salt 1 ................................. . {b) The Haber process is usually carried out at a high pressure of between 60
and 200 atmospheres (between 60 x 105 Pa and 200 x 105 Pa).
salt 2 State two further important operating conditions that are used in the Haber
relative formula mass of salt 2 ................................. . process.
(iii) The crystals of the. double salt contain water of crystallisation. For each of your conditions, explain why it is used. [4]
The relative formula mass of Mohr's salt is 392. Use your answers to (c) State one large-scale use for ammonia, other than in the production of
(ii) to calculate the number of moles of water of crystallisation present nitrogenous fertilisers. [1]
in one mole of Mohr's salt. [6] (d) The uncontrolled use of nitrogenous fertilisers can cause environmental
(J06/P2101]
damage to lakes and streams. This is known as 'eutrophication'.
What are the processes that occur when excessive amounts of nitrogenous
Suggested Solution: fertilisers get into lakes and streams? [2]
(a) (i) Ammonia gas is evolved In many countries, new cars have to comply with regulations which are intended
to reduce the pollutants coming from their internal combustion engines.
(ii) NH;
Two pollutants that may be formed in an internal combustion engine are caribon
(a) Ammonia is an alkaline gas
(iii) Iron (II) hydroxide or Fe(OH), monoxide, CO, and nitrogen monoxide, NO.
always formed on reaction
(b) Barium sulphate or BaSO, forms white precipitate. with alklies. (e) (i) Outline how each of these pollutants may be formed in an internal
combustion engine.
(c) (i) salt 1 : FeSO, salt 2 : (NH,) 2 SO,
(ii) State the main hazard associated with each of these pollutants. [4]
(ii) salt t: (M,) of FeS0 4 =55.8+32.1+(4x16)=151.9 Pollutants such as CO and NO are removed from the exhaust gases of internal
combustion engines by catalytic converters which are placed in the exhaust
salt 2: (M,) of (NH 4 ) 2 S0 4 = 2(14+4)+32.1+ (4x16) = 132.1 system of a car.

(iii) FeS0 4 ·(NH4 hS0 4 ·xH20 = 392 (f) (i) What metal is most commonly used as the catalyst in a catalytic con-
verter?
151.9+132.1+ x(18) = 392
x(18) = 392-(132.1+151.9) (ii) Construct one balanced equation for the reaction in which both CO
and NO are removed from the exhaust gases by a catalytic converter.
X=t08= 6 [2]
18
Hence one mole of Mohr's salt has six moles of water of crystallization. {N10/P2!02]

Suggested Solution: (b) As ammonia formation is

Question 6 an exothermic reaction,
hence it is favoured at
This question is about the elements of Group VII, the halogens. (a) N2 +3H2 ;o==: 2NH3
low temperature. But in
(c) When dilute nitric acid and aqueous silver nitrate are added to a solution industrial process at low
of a magnesium halide, MgX 2 , a pale cream precipitate is formed. (b) condition 1: Temperature 400 • 450 ·c. temperature, rate of reaction
This precipitate is soluble in concentrated aqueous ammonia but not soluble reason: at high temperature equilibrium shifts backward direction but rate of will be very low and catal·
reaction increases. yst would not work and
in dilute aqueous ammonia.
over all process will be un-
(i) What is the identity of the precipitate? condition 2: catalyst.
economical. Therefore high
(ii) Give an equation, with state symbols, for the reaction of the precipitate reason: increases rate of reaction by decreasing activation energy. temperature is used to in-
with concentrated aqueous ammonia. [3] crease the rate.
(J06/P2103 (c)] (c) Ammonia is used for manufacture of nitric acid which is further used for making
explosives. (c) • Ammonia can also be
(c) (i) Ag· form complex with used as coolent.
Suggested Solution: (d) When excessive amounts of nitrogenous fertilisers get into water systems, it
amenia by dative covalent causes a problem of eutrophication. Excessive growth of algae and fungi use • Aqueous ammonia is an
(c) (i) AgBr or Silver bromide. bond [Ag(NH 3) 2]'. oxygen from water and causes oxygen depletion due to which aquatic life die. important lab reagent
(ii) AgBr(s) + 2NH 3 (aq) ----t [Ag(NH3 hr (aq) + Br-(aq) for identification of cations.
topic 9.6 Nitrogen and sulfur

(e) (i) CO: It is formed by incomplete' combustion of fossil fuel. .

Page 8

.
~CORNER r:loprc 10.1 Or.i_anr"c G.£emr"slry
. I N and 0 from air at high temperature m car engine.
NO: By reacI1on o 2 2 . • •

CO is a poisonous gas and causes breathing difficultieS. It IS IQXIC

(ii) CO:
and reduces oxygen carrying ability of red blood cells. gnlroduclory 7opics
Toxic, fomnation of acid rain. (~ (i) Rh. Pd. are rare
NO:
metals. These can also be
used as a catalyst in cata-
(f) (i) Platinum.
lytic converter.
(ii) 2C0+2N0~2C02+N2 Content
Molecular, structural and empirical formulae.
2 Functional groups and the naming of organic compounds.
3 Characteristic organic reactions.
4 Shapes of organic molecules; cr and 1t bonds.
5 Isomerism: structural; cistrans; optical

Learning Outcomes
Candidates should be able to:
(a) *interpret, and use the nomenclature, general formulae and displayed formulae of the
following classes of compound:
(i) alkanes, alkenes and arenes.
(ii) halogenoalkanes and halogenoarenes.
(iii) alcohols (including primary, secondary and tertiary) and phenols.
(iv) aldehydes and ketones.
(v) carboxylic acids, esters and acyl chlorides.
(vi) amines (primary only), nitriles, am ides and amino acids.
[Candidates will be expected to recognise the shape of the benzene ring when it is
present in organic compounds. Knowledge of benzene or its compounds is not required
for AS.]
(b) interpret, and use the following terminology associated with organic reactions:
(i) functional group.
(ii) homolytic and heterolytic fission.
(iii) free radical, initiation, propagation, termination.
(iv) nucleophile, electrophile.
· (v) addition, substitution, elimination, hydrolysis.
(vi) oxidation and reduction.

[in equations for organic redox reactions, the symbols [OJ and [H] are acceptable]
(c) (i) *describe the shapes of the ethane, ethene and benzene molecules.
(ii) *predict the shapes of other related molecules.
(d) *explain the shapes of the ethane, ethene and benzene molecules in terms of cr and n
carbon-carbon bonds.
 topic 10.1/ntroductorvtopics Page 1

~CORNER
(e) describe structural isomerism, and stereoisomerism (cis-trans and optical).

(f) describe cis-trans isomerism in alkenes, and explain its origin in terms of restricted
rotation due to the presence of n bonds.

(g) *explain what is meant by a chiral centre and that such a centre gives rise to optical c;;;?(j}) rN (} /JJ
isomerism.
deduce the possible isomers for an organic molecule of known molecular formula.
t-1 ~t.r IJ ~ qpening ....... .
(h)
(i) identify chiral centres and/or cis-trans isomerism in a molecule of given structural formula.
Question I

Some perfumes and scents of flowers and fruit contain compounds which are
structural isomers. Two such examples are citronellol and geraniol.

OH H H H H CH3 H H H
I I I I I
H-e-e-c-c-e cH
I I I I
3
CH-C-C-C-C
3 H
I I I I 1\ I IH HI HI HI\C=CI
H H CH 3 H H C=C
.. I \ I \
H CH3 CH 3 CHpH
citronellol geraniol

(a) Confirm that citronellol and geraniol are isomers by calculating their
molecular formula and their relative molecular mass, M,.
(i) Molecular formula,
00~ ~
(b) Name two functional groups present in both molecules. [3]
Citronellol and geraniol also show stereo isomerism.
(c) On the diagram of the structure of citronellol above, draw a circle around
a chiral carbon atom. (1]
{d) (I) Draw the other cis-trans isomer of geraniol. [In parts (d) and (f) use
R - to represent a part of the molecule.]
(li) Explain why geraniol has no optical isomers. [2]
(e) State what you would expect to see if citronellol was reacted with aqueous
bromine. (1]

[N04/P2!04]

Suggested Solution:
(a} (i} Molecular formula: C, 0 H,.0
(ii} M, = (12 X 10) + (1 X 20} + 16 = 156

(b) (i} Primary alcohol.

(ii) Alkene.

(c) Carbon atom number 6 circled.

(c) Chiral carbon atom is an
OH H H H H unsymmetrical carbon

H-~-~4~-~
attached with four different
CH groups.
I
H
I
H
'f
CH 3 H
I I\
H C=C
I
3

I \
H CH3

citronellol
 Page 2 topic 10.1 Introductory topics Page3
topic 10.11ntroductory topics
~CORNER ~CORNER
(d) (i) R ".. /CH,OH (c) 2Fe 2 • + H2 0 2 + 2W ---> 2Fe 3 • + 2H 20 E,".11 = 1.77-0.77 = 1.00 V > 0
(d) (i). It is a cis isomer.
C=C 2Fe 3 • + H20 2 ---> 2Fe 2 • + 0 2 + 2W E:., 11 = 0. 77 = 0.68 = +0.09 V > o
HC/ "'.H
J
The 2 steps in the pathway have positive E,;:, 11
and hence are energetically
(ii) Geraniol does not have any chiral carbon atom. feasible.
(e) Aqueous bromine is decolourised.

Question 3

Question 2 Ibuprofen is one of the most commonly used non-steroidal anti-inflammatory

drugs, used to treat chronic arthritic pain caused by inflammation of the joints.
(a) Use the concept of activation energy, together with an appropriate sketch
of the Boltzmann distribution, to explain why the addition of a suitable catalyst CH 3
speeds up a chemical reaction. [4] I
(b) Use appropriate bond energy values from the Data Booklet to suggest which IH3 rnrc~c~o
of the following three reactions has the lowest activation energy and which
has the highest activation energy. Explain your reasoning. /C~).V I
CH 3 CH 2 OH
. CH4 ---> "CH3 + H"
"CH 3 + C/" ---> CH3CI II
ibuprofen
C/2 ---> 2C/" Ill [3]
(a) (i) Draw a circle around any chiral centre(s) in the above structure.
(c) The decomposition of solutions of hydrogen peroxide is catalysed by cer- (ii) Write down the molecular formula of ibuprofen.
tain transition element ions.
(iii) Calculate the M, of ibuprofen and use it to calculate how many grams
2H2 0 2 (aq)-------> 2H 20(1)+0 2 (g) are needed to make 100 em' of a
0.15 mol dm"' solution.
The relevant half-equations are {N06/P4/Q2 (a)}
H20 2 ---> 0 2 + 2H• + 2e·

H2 0 2 + 2W + 2e· ---> 2H 2 0 Suggested Solution:

Referring to relevant E" data from the Data Booklet, suggest a mechanism (a) (i)
for the catalyst of this reaction by Fe'• ions. [3]
{N06/P3/03 Or]

Suggested Solution: (a) E, is activation energy for

traction of particles uncatalysed reaction while
(a) A catalyst provides an alternative with energy E
pathway with a lower activation en- E', is for catalysed reaction.
ergy lor a reaction to take place. As E, decreases rate of
(ii) C,H,O,
reaction increases.
With a lower E~ , there will be more
particles with energy greater than (iii) M, value of Ibuprofen = (12 x 13) + (1 x 18) + (16 x 2) = 206
this new but lower E~ . Hence, No. of moles = cone. x vol
there will be more effective colli-
sion between particles and the =0.15x~=0.015
reaction rate increases. 1000
= 1.5 x 10-2 moles
Mass of Ibuprofen= no. of moles X M,
= 1.5 X 10'2 X 206
(b) (I) Involves breaking of C - H bond !lH =BE= 410 kJ mol''
=3.09.,3.1 g
(II) Involves forming a C- C/ bond !lH =-BE= -340 kJ mol·'
(Ill) Involves forming a Cl- Cl bond !lH =-BE= -244 kJ mar'
Hence, (II) is the most feasible and it has the lowest activation energy. (I) has
the highest activation energy since this step is endothermic.
 Page4
topic lO.ltntroducto!Y..JQQics Page 5
topic lO.llntroductorytopics
~CORNER Suggested Solution: ~CORNER
Question 4 (a) C,H,O,
(a) Empirical formula
An organic ester, B, has the empirical formula C 2 H,O. An experiment by a (b)
student in a college gave a value of 87.5 for M, of B. mass =(12x 2)+(1x4)+ 16
=24+4+16=44
(a) What is the molecular formula of B? (1]
n M,
(b) In the boxes below, draw the structural formulae of four isomers of B that are
Empirical formula mass
esters.
= 87.5 "'2
HC02 CH(CH 3 )2 44
HC02CH2 CH2 CH 3
So 2(C2H40) = C4H80 2

(b) Alcohols and carboxylic

acids react to give esters.
Esterification takes place
much faster in the
w X presence of a catalyst,
such as hydrogen chloride
or concentrated sulphuric
acid. Esterification is a
condensation reaction i.e.
w X (Addition and Elimination)

CH 3 C02 CH2 CH 3 (c) Hydrolysis is the reverse

CH 3CH 2 C02 CH3
of esterification. On acid
hydrolysis, the products
are respective acid and
;:,! alcohol.
:~:! Primary alcohol on
y
z oxidation give aldehyde
'1:! and secondary alcohol
,~:!
1< on oxidation give ketones.
(c) (i) Presence of Carbonyl group "-. (d) If a carbon atom is bonded
/C=O
y z to four different groups,

II
'~~~~~
(4]
(ii) - CHO group (Aldehyde) is absent OR
(iii) Alcohol C is (CH,),CHOH
ketone is present. it is called chiral carbon.

~'•~'.1· The student hydrolysed his sample of B by heating with aqueous mineral acid
and then separating the alcohol, C, that was formed. He heated the alcohol C (iv) W
~~ under reflux with acidified dichromate(VI) ions and collected the product D.
l~il A sample of D gave an orange precipitate with 2,4-dinitrophenylhydrazine
(d) None. No chiral centres are present in any of the four esters.
1:.'1
r::l reagent. A second sample of D gave no reaction with Tollens' reagent.
;.::
1:1· (c) (i) What group does the reaction with 2,4-dinitrophenylhydrazine reagent
H show to be present in D?
\:.
!.': (ii) What does the result of the test with Tollens' reagent show about D?
h
H
t'
(iii) What is the structural formula of the alcohol C?

!: (iv) Which of your esters, W, X, Y, or Z has the same structure as that of

the ester B? [4]
r..: (d) Which, if any of your esters, W, X, Y, or Z is chiral? Explain your answer.
[1]
;I
[N08/P2/Q5]
 (g) suggest how 'cracking' can be used to obtain more useful alkanes and alkenes oflower

'Jopic 10.2 (h)

M, from larger hydrocarbon molecules.

~e~cribe and explain how the combustion reactions·of alkanes lead to their use as fuels
m mdustry, m the home and in transport.

J(yrfrocarbons (i) recognise the environmental consequences of:

(i) ~arbon monoxid:, oxides of nitrogen and unbumt hydrocarbons arising from the
mtemal combustiOn engme and of their catalytic removal.
(ii) gases that contribute to the enhanced greenhouse effect.

Content ·
OJ describe the chemistry of arenes as exemplified by the following reactions of benzene
and methylbenzene:
Alkanes (exemplified by ethane).
(i) *substitution reactions with chlorine and with bromine.
(i) Free-radical reactions.
(ii) nitration.
(h) Crude oil and 'cracking'.
(iii) oxidation of the side-chain to give a carboxylic acid.
2 Alkenes (exemplified by ethene).
(i) Addition and oxidation reactions.
(k) m *~esc~ibe the mechanism of electrophilic substitution in arenes, using the mono-
mtratton of benzene as an example.
(ii) Industrial importance.
1• ~
/jjl descn'b e the effect of the delocalisation of electrons in arenes in such reactions.
3 Arenes (exemplified by benzene and methylbenzene).
(I) predict _whether halogenation will occur in the side-chain or aromatic nucleus in aren
(i) Influence of delocalised 1t electrons on structure and properties.
dependmg on reaction conditions. es
(h) Substitution reactions with electrophiles.
(m) apply the knowledge of positions of substitution in the electrophilic substitution of
(iii) Oxidation of side-chain.
arenes.
4 Hydrocarbons as fuels.

Learning Outcomes
Candidates should be able to:
(a) show awareness of the general unreactivity of alkanes, including towards polar reagents.
(b) describe the chemistry of alkanes as exemplified by the following reactions of ethane:

(i) combustion.
(ii) substitution by chlorine and by bromine.
(c) *describe the mechanism of free-radical substitution at methyl groups with particular
reference to the initiation, propagation and termination reactions.
(d) describe the chemistry of alkenes as exemplified, where relevant, by the following
reactions of ethene:
(i) *addition of hydrogen, steam, hydrogen halides and halogens.
(ii) *oxidation by cold, dilute, acidified manganate(VII) ions to form the diol.
(iii) oxidation by hot, concentrated, acidified manganate(VII) ions leading to the
rupture of the carbon-to-carbon double bond in order to determine the position of
alkene linkages in larger molecules.
(iv) polymerisation (see also Section I 0.8).
(e) *describe the mechanism of electrophilic addition in alkenes, using bromine/ethene as
an example. Note: The additional learning outcomes to be studied by A2. candidates are shown in bold ty Th A2.
(f) explain the use of crude oil as a source of both aliphatic and aromatic hydrocarbons. components will assess all learning outcomes and will not be lim~ed to those in bold type.pe. e
I

I topic 10.2 Hydrocarbons

Page 1 topic 10.2 Hydrocarbons Page 2

I ~CORNER
(b) Type of reaction: Electrophilic addition ~CORNER
l qjl(j}) rN (J ;jJ
Condition: Room temperature
Mechanism:

{1) CH,CH,CHc=CHCH,CH,--+- CH,CH,CH-CHCH,CH, + Br·

IJ \!!/ t.r IJ ~ qpening ....... . Br IH-
1
<il 8: slow
rl carbocat1on 1
•srO-
Question 1
~-
Hex-3-ene occurs in two isomeric forms but cyclohexene occurs in only one
(2) CH,CH,CH-CHCH,CH,--+- CH,CH,CH-CHCH,CH, fast
form. <tl I I I
(a) Draw the displayed formulae of the two isomers of hex-3-ene and explain Br Br Br
why such isomerism is not possible with cyclohexene. [3] The electron rich C=C polarises as bromine molecule and causes the bromine
molecule to cleave heteroly1ically forming the carbocation I and bromide ion
(b) Describe the mechanism of the reaction between hex-3-ene and bromine.
in the slow rate determining step as shown in step (1 ).
Your account should A bromide ion then attacks the carbocation I to form 3,4-dibromohexane as
• name the type of reaction undergone, shown in step (2).
state the conditions of the reaction,
show the movement of electrons during the reaction, (c) The reaction of HBr with both trans- and cis-hex-3-ene results in the formation
• include the formulae of the product and any intermediates. [4] of the same product, 3-bromohexane, CH,CH,C'HBrCH CH CH,. Since car-
2 2
(c) Explain why the reaction of either isomer of hex-3-ene with hydrogen bro- bon-3 is chiral, the product exhibits optical isomerism. In the reaction, H• is
mide gives the same equimolar (1:1) mbcture of two isomers of the product. first added to the carbon-4 to form a carbocation. The "+" charge is on carbon-
(c) Both cis-hex-3-ene and
[2] 3 which has a sp' hybridisation and the molecular geometry about this carbon
trans-hex-3-ene react with
is thus trigonal planar. Subsequent attack by Br can be from above or below
hydrogen bromide to fonn
(d) The compound hex-3-en-1-ol, A, has a strong 'leafy' smell of newly cut the plane resulting in both optical isomers of 3-bromohexane being formed.
3-bromohexane. Carbon-3
i!"i grass and is used in perfumery. Since there is equal likelihood of carbon-3 being attacked from both above
is chiral so that 3-
and below, equimolar amount of the isomers of the product is formed.
CH 3CH2CH = CHCH 2CHpH bromohexane exhibits
{d) CH,CH,COOH and HOOCCH,COOH. optical isomerism and
A exists as 2 optical isomers
Suggest the structural formulae of the compounds produced when A is as shown below:
rr treated with an excess of hot concentrated KMnO, in acid solution. [3] (a) The structures of three CH,CH,
I yH,CH,
[JOOIP1/Q6] cycloalkenes are shown
Br"f'cH,CH,CH, CH,CH,CH;'C\""Br

cxH aH
below: H
Isomer I
Suggested Solution: c( H H H
lsomer/1 H
In the reaction of HBr with cis-hex-3-ene, H· is first added to
(a) cis-hex-3-ene to fonn carbocation I as shown.
H
I
H
I
H
I
H
I 77 H The configuration about each
CH,CH, CH,CH, CH,CH, CH,CH,
H-C-C
I I'
HH'c=C
/1
C-C-H

HH
I
H-c-c,
I I 'c=C
/
H H
double bond is clearly cis.
Transoonfigurationforthese
H
>==<H + HBr---+
H
XH
H
+ Br·

/ "' HH/ "'-t-b-H three cycloalkenes are not

favoured because of great
carbocahon I
H H H I I Attack of Br from below of the plane at carbon-3 resulls in isomer
H H angle strains.
cis-hex-3-ime trans-hex-3-ene
0: (LH
I while attack of Br from the above results in isomer II. Since there
is equal likelihood of carbon-3 being attacked from the above or
below, an equimolar mixture of the two isomers of the product is

/ra~ene
Such isomerism is not possible for cyclohexene because in a 6-membered obtained.
ring, only the cis-form is possible: cis-cyclooclene
Similarly in the reaction of HBrwith trans-hex-3-ene, W is first added

ex: %
However, as ring size to trans-hex-3-ene to fonn carbocation II as shown below:
increases, angle strain be-
H CH,CH, H CH,CH,
oomes less severe so that
trans-fonn of cyclooctene
>==<H
CH,CH,
+ HBr---+
CH,CH,
~H
H
+ Br'

and bigger cycloalakenes, carbocation II

cis-form trans-form are possible. The consider-
Attack of Br from below the plane at carbon-3 results in isomer II
able angle strain still
As can be seen from the diagram above, the trans-form results in distorted ring while attack of Br from above results in isomer I. Since there is
existing in the trans-fonn
with great angle strain and is not formed. equal likelihood of carbon-3 being attacked from above or below,
causes the cis-form to be
an equimolar mixture of the two isomers of the product is again
more stable. obtained.
 topic 10.2 Hydrocarbons Page4
Page3
topic 10.2 Hydrocarbons
~CORNER (ii) Explain how the composition of 100 em' of this gas mixture Gould be
~CORNER
determined in this apparatus.
Question 2 (iii) Write an equation for how A reacts with one of the gases in the mixture.
Crude oil is largely a mixture of alkanes. [3]

(a) Describe how crude oil is used as a source of aliphatic and aroma~~ [NOO/P2/03(a)]

hydrocarbons.
(b) Discuss how 'cracking' can be used to obtain more useful alkanes and Suggested Solution:
alkenes of lower M, from larger hydrocarbon molecules. (a) (i) Aqueous bromine (a) Alternatively, liquid A can be
Illustrate your answers in (a) and (b) with suitable examples. [2] cold aqueous KMnO,.C,H,
(ii) Ethene reacts with aqueous bromine to give 2-bromoethanol which dis-
Quality of Language [4] reacts to give a diol which
solves in water. Hence C,H, is removed by reaction with aqueous bro- is soluble in the aqueous
[JOO/P2/Q6] mine while ethane is not (the reaction should be performed in the dark
solution while ethane is
so that Br, will not react with ethane). Hence the volume of the remaining insoluble and remains in the
gas is due to that of ethane and this is found by reading the volume of gaseous form. Equation for
gas syringe 2.
Suggested Solution: the reaction:
Crude oil is a complex mixture of both aliphatic and aromatic h~drocarbons. % composition by volume of ethane ~~~v~ol~u~m_e~o_f~e~th~a~n~e~~-x 1 00% C2H4(g)+ H20(/) +[OJ
(a) ue to differences in the ranges of boiling points, different fr~ctlons are ob- total volume of gaseous mixture
fained from crude oil using fractional distillat_ion. Th~ fractions ~nclu~~ na~~~:
etrol kerosene, diesel oil, lubrication 011 and b1tumen res1_ ue. eP (b) Cracking is believed to take (iii) C2H4 (g)+Br2(aq)+H2 0(1) ~ CH2 0HCH28r(aq)+H8r(aq)
fi.!~ii~n co~tains a high amount .of useful aliphatic and aromat1c hy;tocabons place via a radical mecha-
and may be further refined. Fractions that contam larger hydroca d o~_s hm~y nism. The first step involves
be cracked to obtain the more useful smaller_ hydrocarbons an a 1p a IC a homolytic cleavage be-
hydrocarbons may be reformed to give aromatic hydrocarbons. tween two carbons: Question 4

~~-~c-·~ Poly(propene) is a polymer used for making rigid containers and carpets. It is
obtained industrially by polymerising propene, CH,=CHCH,.
Sincethecleavagecanoccur (a) (i) By what type of polymerisation is poly(propene) made?
Cracking is the process in which shorter chain and more useful hydrocarbon anywhere within the chain,
(b) molecules are obtained from longer chain molecules. The larger _hydrocarbon (ii) Draw a section of the poly(propene) chain containing two monomer
a variety of products are
molecules are passed over a catalyst of aluminium oxide at a h1gh tempera- repeat units. [2]
obtained. Besides alkanes
ture. Many different products may be obtained even from the same hydrocar- and alkenes, a significant (b) Propene is obtained industrially by the cracking of longer chain hydrocar-
bon molecule eg. proportion of small molecules bons such as decane, C 10 H22 •
such as hydrogen, methane
C,sH34 ----t C,oH22 +CsH12 or C,sHs, ----t CaH,s +2C2H, +C,Ha (i) What conditions are required for a cracking reaction?
and ethene are also formed.
The shorter chain hydrocarbons may be used as petrol and the alkenes (ii) Write a balanced equation showing the production of propene (along
obtained may be polymerised, eg. ethene polymerised to form poly(ethene). with other products) from decane. [2]
The products from cracking may. be purified by using fractional distillation. (c) Propene can be made in the laboratory from propane by the following
route.

CH3 CH2 CH3 ~ CH3 H7 8, ~ CH2 = CHCH3

Question 3 A
The ases iven off during the eruption of a volcano include hydrocarbons (i) Suggest suitable reagents and conditions for reactions I and 11.
such gas eth~ne and ethene, also ~ulph~r-containing molecules such as hydro-
(ii) Name and describe the steps in the mechanism of reaction I. [6]
gen sulphide, H,S, and carbon d1sulph1de, CS,.
(a) The composition of a gaseous mixture containing only ethane and ethene (d) Substance A is a mixture of two structural isomers. Draw their structural
can be detemnined by using the apparatus below. fomnulae and explain why both will give propene under the conditions of
reaction II. [2]
gas syringe 1 gas syringe 2
[J01/P1/06]

Suggested Solution:
(a) (i) Addition polymerisation.

H CH,H CH,
I I I I Structure of poly(propene) containing
(ii) -c-c-c-c- two monomer repeat units
1 I I I
(i) Suggest an appropriate liquid A. H H H H
 topic 10.2 Hydrocarbons PageS topic 10.2 Hvdrocarbons
Page6
~CORNER ~CORNER
(b) (i) Conditions required for a cracking reaction are high temperature and (iii) The oxidation of propene with cold, acidified potassium manganate(VII).
pressure and the use of a catalyst such as aluminium oxide on silica. (iv) The reaction of cyclohexene with hydrogen bromide.
(b) (iij Other answers are
possible, as long as the total (v) The reaction of cyclohexene with hot acidified potassium
(ii) C10H22 ----'> C3Hs + C2H, + C5H12
manganate(VII). [5]
number of C is 10 and total
(c) (i) Reaction I : Reagent used is bromine and conditions are room no. of H is 22. One of the (b) Write equations for the following reactions.
temperature and ultraviolet light. product is usually an alkane (i) The complete combustion of ethane.
Reaction II : Reagent used is ethanolic potassium hydroxide and and the others alkenes. Other
condition is reflux. acceptable answers: (ii) The action of steam on propene in the presence of a catalyst.
(iii) The reaction of cyclohexene with hydrogen in the presence of a cata-
(ii) Reaction I proceeds via a free radical substitution mechanism. C10H22 ->C 3H6 +C 4H6 +C 3H6
Firstly, the initiation step occurs whereby a bromine molecule cleaves ~ ~
Or
(c) The process of cracking produces useful substances from oil.
homolytically to give two bromine radicals: Br2 ----'> 2Br •
C10H22 -> C3H, + C5H10 + C2H6 (i) Explain why cracking is useful.
Propagation then occurs whereby a bromine radical is used up to
(ii) Suggest an equation for the cracking of C10H34 into at least three fragments.
generate a propyl radical. The propyl radical then reacts with a bromine
molecule to give bromopropane and a bromine radical: [3]
{J02/P2/05]
Br· + C3H8 -----> C3H7 • + HBr
C3H7 • + Br2 ----'> C 3H7Br + Br•
Suggested Solution:
The two steps above occur repeatedly resulting in a chain reaction. Many
bromopropane molecules are produced by the generation of just a few (a) (i) CH,CH 2 Br
bromine radicals.

?H, ~r
1
Termination occurs when two radicals combine: (ii)
Br • + Br • -----> Br2 c-c
I I
C3H; • + Br• ----'> C3 H 7Br
H H n
C 3H; • + C3H7 • -----> C6H14
(iii) CH 3CH(OH)CH 20H
(d) Isomers of substance A:
H H H H H H (iv) Br
I I I

0
I I I
H-C-C-C-H H-C-C-C-H
I I I I I I
H H Br H Br H
Isomer I Isomer II
(v) HOOCCH,CH 2 CH 2CH 2COOH
},' In the elimination of HBr from a bromoalkane, the bromine atom and a hydro· (b) (iij Propan-2-ol is the
~i gen atom attached to an adjacent carbon are removed. (b) (i) 2C 2 H6 + 70 2 -----> 4C0 2 + 6H2 0 major product rather than
i:
r For isomer I, the bromine atom on carbon-1 and a hydrogen atom on carbon- propan-1-ol (predicted by
~ 2 are eliminated resulting in the formation of propene. (ii) CH3CH = CH2 + H2 0 ~CH 3 CH(OH)CH
3
Markovnikov;s Rule).

0 0
\" For isomer II, the bromine atom on carbon-2 and a hydrogen atom on carbon- The electrophilic H' adds to
1 or carbon-3 are eliminated, also resulting in the formation of propene.
the first carbon (to form the
(iii) + H, catalyst more stable secondary
carbocation) while the nu-
Question 5 cleophilic OH- adds to the
second carbon so that
Crude oil is the principal source of hydrocarbons. The following are examples (c) (i) From fractional distillation of oil, the proportion of the more useful hydro- porpan-2-ol is obtained.
of such hydrocarbons. carbons with a chain length of six to eight carbon produced is limited by
what is naturally present in the sample of oil. Since cracking breaks down (c) (1~ Other possible an-
H H swers include:

0
H bigger hydrocarbons into smaller hydrocarbons, the proportion of the

>=<
H
I I
H-C-C-H
smaller, more useful hydrocarbons may be increased by cracking the bigger
C15H34 -+ ~H,. + C7H14 + C2H4
hydrocarbon molecules.
I I
H H
H CH 3
Also cracking produces alkenes which are useful reactive intermediates.
C, 6H34 -> C6H12 + C8H16 + C2H6
etc.
ethane propene cyclohexene (ii) C16 H34 -----> C6 H14 + C8 H16 + C 2H4
Answers are acceptable W
(a) Give the structural formulae of the organic products in the following reactions. the total number of C and H
(i) The reaction of ethane with bromine in the presence of u.v. light. in the products adds up to
16 and 34 respectively.
(ii) The polymerisation of propene.
 Page7 topic 10.2 Hydrocarbons Page 8
topic 10.2 Hydrocarbons
~CORNER Suggested Solution: ~CORNER
Question 6 (a) (I) To produce A from methylbenzene, methylbenzene is reacted.with chlo- {a) {i) A is formed by elec-
rine in the presence of aluminium chloride. trophilic substitution of chlorine
Methylbenzene reacts with chlorine under two different sets of conditions to To produce B from methylbenzene, methylbenzene is reacted with chlo- intobenzenering. Thus, a halogen
give compound A or compound B. rine in the presence of ultraviolet radiation. carrier such as aluminium

9 0'
chloride is used to generate
(il) The compound is first warmed with aqueous sodium hydroxide. The mixture the electrophile, Cl'. 8 is
is cooled and excess dilute nitric acid followed by aqueous silver nitrate formed by free radical substi-
is then added. A gives no white precipitate of silver chloride but B gives tution of the methyl group so
a white precipitate of silver chloride, that uv light is need to gen-
erate the chlorine radical, Cl·.

0 ¢ ¢
(b) (i) COOH {iij Cl in A is directly attached
Cl concHNO, aq KMnO, to the benzene ring. A lone
cone H,SO~ diiH,SO, pair of electrons in a p-orbttal
A B in Cl delocalises into the ben-
warm warm
zene ring so that the C-CI
(a) (i) Describe the conditions used to produce A and B respectively.
bond has partial double bond
(ii) Describe a reaction by which you could distinguish between A and B. NO, NO, character and is not easily
state the reagents and the observations with each compound. [4) cleaved. Thus, on heating Awilh

6
aq NaOH, no Cl- is formed an
(b) During aromatic substitution, the position of the incoming group, th~ new (ii) COOH no ppt of AgCI is observed on

0
COOH
substituent, is determined by the nature of the group already present In the
ring. For example, the following reactions produce the bromo-compounds =HNO, aq KMnO,
diiH,SO, concH,SO,
addition of Ag·.
Cl in 8 is attached to the
methyl group. The C-CI
shown:
QNO
warm warm
,
cleaves on warming wilh aq.

0 ¢
NaOH so that Cl· is formed. A
ppt. of AgCI is observed on
(c) Reagents and conditions for step C : tin and concentrated hydrochloric acid, addition of Ag• to 8 which has
bromination ~ reflux. been warmed with aq. NaOH
and acidified with dil. HN01.
Reagents and conditions for step D : ethanol, concentrated sulphuric acid as Acidification with dil. HNO, rs
catalyst, reflux. necessary to neutralise any
Br excess OH-. Otherwise, OH·

6,,
reacts with Ag· to form brown
CO,H
insoluble Ag,O which will mask
Question 7

6 bromination ~

Use this knowledge to devise two-step syntheses, starting with

methylbenzene, of
(a) Chlorine reacts with both propane and propene, but under different con-
ditions.
Write equations, giving the structural formulae of the organic products, and
state the conditions for the reaction of chlorine.
the AgCI even ff it is formed.
{b) {i) Reagents and con-
ditions for nttration into the ben-
zene ring is warming the arene
with cone. HNO, and HJSO,.
The cone. H,so, is neeoed to
(i) with propane, generate the electrophile NO;
(l) 4-nitrobenzoic acid, from· HNO,.
equation
Reagents and conditions for
(ii) 3-nitrobenzoic acid. conditions oxidation of methylbenzene
Identify the reagents at each step, and draw the structural formulae of the (ii) with propene, into benzoic acid is warming
intermediates. [4) the arene with acidified
equation KMnO . Dilute sulphuric acid
(c) Benzocaine, a local anaesthetic, can be synthesised from 4-nitrobenzoic rather /han dil. hydrochloric acid
conditions [4)
acid in two stages. is used as the latter contains
(b) (i) Draw a section of poly(propene), giving three repeat units. Cl which can be oxidised by

9.c~
MnO,·.
(il) To which homologous series does poly(propene) belong? -CH, group is 2,4-directing
while -COOH group is
(iii) Accidents or ruptures (hemias) can cause damae to muscles. When a
3-direcling.
surgeon repairs a wound in a muscle, a mesh can be inserted below
Thus, {i) to form 4-nffrobenzoic
the muscle tissue so that on healing the wound. is less likely to re-open
acid from methylbenzene,
NH, and the repair is stronger. methylbenzene is first nitrated
Poly(propene) is the recommended material for the mesh. before the product is oxidized.
Suggest reagents and conditions for steps C and D. [2) Suggest two reasons why poly(propene) is used rather than a natural {b) {ii) To form 3-nttroben-
[N021P3!06] fibre like cotton or a synthetic one such as a polyester, a polyamide zoic acid from methylbenzene,
or Lycra. (4) methylbenzene is first nttrated
before the product is nitrated.
[N03/P2/Q5]
topic 10.2 Hydrocarbons Page9 topic 10.2 Hydrocarbons Page 10
~CORNER ~CORNER
Suggested Solution: H, /H
(a) (ij The reaction is a free H, /H c·
(a) (I) CH 3CH 2CH3 + Cl 2 - - 4 CH 3 - 9H- CH 3 + HCI
Cl
radical substitution. In the
equation, any of the hydro-
gen atoms can be substi-
c
~----- Br""
H/ 'H
v(" ~
I
H-C-Br + Br-
1
H
Conditions : uv radiation
tuted
(ii) CH3CH = C~ + Cl 2 CH3 yH- fH2 H, /H H
--4 CH 3CH 2CH 3 +CI 2 c· I
Cl Cl -> CH 3CH 2CHP+ HCI I~ H-C-Br
. I
H-C-Br + Br- ~
Conditions : room temperature, dark. In addition, more than 1 H-C-Br
I
hydrogen atoms may be H I
(b) (I) CH, CH, CH, substitution. H
I· I I (ii) The reaction is elec- (ii) Benzene undergoes electrophilic substitution with Br, in the presence of
- C...,-CH,- C- CH,- C-: CH,-
I ,.. I I trophilic addition. No special a halogen carrier as catalyst e.g. FeBr,.
H H H conditions (e.g. light, heat,
Br
catalyst) are required for the
(ii) Alkane
(Iii) Poly(propene) is a non-polar and saturated hydrocarbon. It is therefore
inert and is not readily hydrolysed unlike cotton, polyester or polyamide. (b~H,(i)H
I I
reaction to proceed.

+CH, Ht
I I
0 +Br,
FeBr,

6 + HBr

nC=C - c-c The Br, molecule is polarised by the electron-deficient FeBr,.

I I I I
H H H H n .5+ t5-
Question 8 Br-Br+FeBr3 --4 Br ...... Br ...... FeBr3
(iij When propene
(a) Describe and contrast the conditions used for, and the mechanisms of, the polymerised, it becomes
Similar to alkene, the benzene ring, being electron rich, attacks the Br"
saturated. The polymer is
reactions of bromine with and a C - Br bond is formed.
thus an alkane and NOT an
(i) ethene,

~Br ~
alkene anymore.
[8]
(li) benzene.
(iii) Being inert is a critical .. cfr.... f'eBr, Q < : r + FeBr,-
(b) Predict the products of the following reactions. criterion for use. Otherwise,
the material will readily de·
However, unlike alkene, a H• is then ejected from the intermediate and

0
compose and deteriorate
and maycausefurthercom· bromobenzene is formed to restore the resonance stability.
plications in our body.
(i) HNO,+H,SO, (cone)
~H
~Br~ 0
~Br
+H"

Q
H" +FeBr4- --4 HBr+FeBr3

Br,(aq) Both reactions can occur in the dark. However, for the electrophilic sub-
(II} stitution of benzene, a catalyst such as FeBr, is required.
(b) (i) Depending on the con-

Suggested Solution:
NH, [2]
{N03/P3/QB (Either)]
(b) (I)

&NO, Md Q CH,
dftions, methylbenzene can
be polysubstituted. When
heated, the following prod-
ucts could be obtained.
CH,
qNO, O,N'O'NO, O,N*NO,
CH,

NO,
(a) (i) Ethene undergoes electrophilic addition with Br,.
(ii) NO, NO, .

~~.,
H H
H, /H I I (iij NH2 is an activating
C=C + Br, ~ H-C-C-H
group and ftmakes benzene
H/ 'H I I ring more susceptible to
Br Br
The electron-rich double bond polarises a nearby Br, molecule. The Br- electrophilic substitution.
Both the 2-posftions with
Br bond gradually breaks as a Br atom gradually forms a bond with the NH,
carbon atom. A bromonium ion is formed and it readily combines with the respect to NH, will be
subsituted.
Br formed to form 1,2-dibromoethane.
topic 10.2 Hydrocarbons
Page ll topic 10.2 Hydrocarbons Page 12
~CORNER ~CORNER
Question 9 Question 10
(a) Some of the larger hydrocarbons in crude oil are subjected to the process (a) (i) State the conditions used for the reaction between ethane ·and bro-
of cracking. mine.
(i) What do you understand by the term cracking? C2H6 + Br2 ---> C2H5Br + HBr
(ii) What conditions are used for this reaction? (ii) Why is this described as a free-radical substitution reaction?
(Iii) Construct a balanced equation to show one possible way i(l which a (iii) Explain why this reaction is an example of homogeneous catalysis. (4]
molecule of decane, C 10H22 , can be cracked.
(iv) Briefly explain why cracking ·is a commercially important process. (5] (b) An alkane B is a component of petrol. When treated with bromine under
free radical conditions it produces a mixture of brominated compounds,
(b) Name and describe the mechanism of the reaction between ethene and including C, C,H,Br,. Dehydrobromination of C produces D, C,H 10 • When
bromine. [3] Dis oxidised by hot concentrated KMnO,, three compounds, C0 2 , CH3C0 2 H
and CH3COCO,H, are formed in equimolar amounts.
(c) Predict the product of each of the following reactions.
(i) Suggest reagents and conditions for the conversion of C to D.
(i) CH 3 " /CH 3 (ii) Suggest a structure for compound D, and hence deduce the structure
C=C H,O + H"

CH 3 / "' CH 3
of compound B.
(iii) There are four possible isomers of C,H,Br, that could give D on
dehydrobromination. Draw the structures of two of them.

hot concentrated acidified KMnO, • (2] (iv) Suggest, with a reason, the number of stereoisomers of compound D. (6]
(ii)o
. [N06/P3/Q(j}
[NOSIP3/08 Either]

Suggested Solution:
Suggested Solution: (a) (i) uv light.
(a) (i) Cracking is a process whereby a large molecule is broken down into (ii) The reaction goes via a free-radical pathway, and the overall reaction is
smaller molecules. a substitution (where a H in C,H, is replaced by a Br).
(ii) Heat and/or with a catalyst. (iii) The reaction is catalysed by the uv light and both C,H, and Br2 are both
in the gaseous phase (hence homogeneous).
(iii) C10H22 ---> C 5H10 +CsH,2
(b) (i) NaOH, ethanol solvent, heat.
(iv) It allows the formation of useful smaller molecules from the larger but less
useful molecules.
H H CH, H
I II I
(b) Electrophillic addition (ii) D =H-C=C-C=C-CH,
CH,
I
B =CH,- CH,- CH - CH,CH3

H
I
H
I
CH H
I 'I ~ ~ yH, ~
The electron rich double polarises the Br2 molecule. The Br- Br bond un- (iii) H-C-C-C-C-CH3 H-C-C-C-C-CH3
dergoes heterolytic cleavage and a bromonium ion is formed. The Br then I I I I I I I I
Br H Br H H Br Br H
attacks the bromonium ion to form 1 ,2-dibromoethane.
(iv) 2
(c) (i) CH CH3 Only the C = C bond at C - 2 and C - 3 can show cis-trans isomerism
3
since 2 different groups are bonded to each of these 2 carbon atoms.
I I
CH3 - C - C-CH3
I I
H OH

(ii) HOOC - (CH,), - COOH

topic 10.2 Hydrocarbons Page 13 topic 10.2 Hydrocarbons Page 14

~CORNER (iii)
~CORNER

~cr A
Question 11
Methylbenzene is a useful starting material for the synthesis of many interme· ~
diates used to make pharmaceuticals, dyes and agrochemicals.
(a) Suggest the reagents and conditions needed for each of the reactions I, II,
Ill and IV in the following scheme. [4]
><I
0'"
CH,yll ¢J c~ 6 9
[FeCI,r /J H Cl
~

Cl ·
+ FeCI, + HCI

molh-'ooo 6~ m C/ COC/ Question 12

'Z.O"
The following scheme shows some reactions of methylbenzene.

6
0 6C/
9 6
N K
II

(b) Describe and explain the relative ease of hydrolysis of the chloro com-
pounds K, J and K. [3]

(c) The electrophile in reaction II is the C/' cation.

Cl
~Ill F

E
(i) Explain the meaning of the term electrophile.

OH 6'
(li) Suggest how C/' is ·formed from the reagents for reaction II that you
mentioned in part (a).
(iii) Suggest the mechanism of the reaction of the electrophile with IV
methylbenzene. [3]
[N06/P3/QB Either]
G

Suggested Solution: (a) Suggest reagents and conditions for reactions I to IV. [4]
(b) What type of reaction is each of the following?
(a) I : Limited Cl,, uv light
reaction I, reaction Ill. (2]
II : Limited Cl,, FeCI, catalyst
(c) Compound F can be converted into 2·phenylethylamine in a two-stage
Ill : KMnO ,, dilute H,SO,, heat process. Suggest a structure for the intermediate, H, in the box below, and
IV: PCI 5 suggest reagents and conditions for the steps V and VI.

(b) Ease of hydrolysis: K > H > J

J is difficult to be hydrolysed because there is partial double bond character
between C and C/. The C/ p-orbital can overlap with the 11:-orbitals of benzene
ring.
K is hydrolysed readily because the presence of 2 highly electronegative 0
and C/ makes the carbon atom in -COC/ highly electron deficient, and hence
oc·_v VI
6c~~

readily attacked by water nucleopile.

(c) (I) An _electrophile is an electron deficient species that readily accepts an elec-
tron pair. F H

(ii) FeCI 3 +CI2 - - - t (FeCI,r +CI' reagents and conditions for step V ......................................................... .

FeCI, is a lewis acid and it readily accepts an electron pair from Cl,. reagents and conditions for step VI ......................................................... [4]
Cl undergoes heterolytic fission, thus generating a Cl•.
2
 topic 10.2 Hvdrocarbons Page 16
topic 10.2 Hvdrocarbons Page 15
~CORNER (d)
~CORNER
reagent
(d) The compounds E, F and G react at different rates with nucleophilic reagents. compound
Draw structures for the products of each compound with the following reagents. cold water hot NaOH(aq)
If no reaction occurs, write •no reaction" in the box.

reage.nt
compound
coldwater hot NaOH(aq)
E no reaction no reaction

F no reaction
60H
F
COOH COO-Na'

G
G

6 6 r.

Question 13
The molecular formula of a compound states the number of atoms of each
[6] element that are present in one molecule. It contains no information about the
(J07/P4/Q5] structure of the molecule. Hydrocarbons with the molecular formula C5 H10 may
be branched chain, straight chain or cyclic.
(a) Draw a displayed formula of C,H, 0 as a branched chain hydrocarbon.[1]
Suggested Solution:
Pent-2-ene is one straight chain hydrocarbon with formuia C5 H10 •
(a) Reagents Conditions
(b) Pent·2·ene exhibits cis-trans isomerism. Draw and label the structural for-
C/2 / A/C/3 heat mulae of the two cis-trans isomers of pent-2-ene. (2]
II. C/2 uv (c) In the spaces be_low draw the structural formulae of two alcohols which
Ill. KMn0 4 H'(dil. acid) would each produce pent-2-ene on dehydration.

)V. SOC/2 room temperature

(b) reaction 1: electrophilic substitution

reaction Ill: oxidation

(c)
[2]

VI (d) One of these alcohols exhibits optical isomerism. Draw the structural for-
mulae of the two isomers of this alcohol. Your structures should clearly
indicate the three-dimensional nature of the structures. [2]
(e) Pent-2-ene decolourises aqueous bromine. Suggest the structural formula
of an isomer of C,H, 0 which does not decolourise aqueous bromine. (1]
(f) Pent-2-ene can be polymerised. Draw a section of the polymer chain pro-
F H
duced showing two repeat units. (1]
reagents and conditions for step V: KCN I ethanol heat [N07/P2/Q4}
reagents and conditions for step VI: LiA/ H, dry ether
topic 10.2 Hydrocarbons Page 17 topic 10.2 Hydrocarbons Page 18
~CORNER
Suggested Solution: ~CORNER
(a) 2uestion IJ
H H H
(a) Alternative structure:
I II H H H
The nitration of benzene occurs in the following steps.
H-C=C-C-C-H

0 • ~ ~r~ 6 •
I I I I I
H-C=C-C-C-H
I H H
H-C-H
I H-C-H
I~ NOi W

H I (a) What reagents and conditions are needed for this reaction? [2]
H
(b) or (b) Write an equation showing how the electrophile NO~ is formed from the
H3 C'-.... /C 2 H5 H'-... /C 2 H5
re!lgents. [1]
C=C C=C H H H
H/ '-...H CH( "-H I I I (c) The nitration of methylbenzene produces mainly 2-nitromethylbenzene,
H-C-C=C-C-H whereas the nitration of benzoic acid produces mainly 3-nitrobenzoic acid.
cis trans
I
H HI I
(c)

OH
I
OH
I
-
H-C-H

must be shown.
I
Note: All hydrogen atoms
o·~
2-nitromethylbenzene
600
3-nitrobenzoic acid
2

CH 3 - CH - CH 2Cli 2CH 3 CH 3CH 2 - CH - CH?- CH 3 (c) Pent-2-ol will produce pent-

1-ene & pent 2-€ne. Use this information to suggest suitable intermediates G and H in the following
Pent-3-ol will produce two 2-stage syntheses of chlorobenzoic acids, and suggest suitable reagents
for reactions I to IV.
pent-2-eneonly.

o~D - ore•
(d) CH 3
r3 II

I
c c
~~OH

"·~· D
""-cH 2CH2CH3 CH3CH 2 C2H / !:

6c,
HO
. / J
i i

(e)
H

CH 2
H

(e)
d~olourise aqueoou~s bnot
Isomer which d

mme should not h ro-

- IV

/~

0
double bond and !hate a
po 'bl . IS only
SSI e In cyclopentane.
or c\ ;H2 reaction 1........... .. reaction II
·················
CH 2- C H 2 reaction Ill ..................................... reaction IV ......................................... [4]
[N07/P4107]

(f)
CH 3 C2H5 CH3 C2H5
Suggested Solution:
I I. I I
-c-c-c-c- (a) Cone HN0 3 +Cone H2S0 4 at 50-60 oc
1 I I I
H H H H (b) 2H2S04 +HN0 3 -t 2HS04 +H30+ +NO~

f JiFJM¥7
 Page 19 topic 10.2 Hydrocarbons Page 20
topic 10.2 Hydrocarbons
~CORNER Suggested Solution: ~CORNER
(c)

@] Oc'
(a) (i)

-
H H H Br
II I I I I
CH 3 y Br-C-C-Br
I I
H-C-C-Br
I I

6~
H H H H
D

@]
E

IV

Oc, (ii)

Br
" C=C/
"
Br Br
"C=C/
"
H
(a) (i~ Cis trans isomerism
arises when rotation
about a bond is restricted.
It is common in
H/ H H/ Br
" C=C /
reaction 1: C/2 & A/C/3 reaction II: KMno,JH+ cis trans / "
Cis and trans isomers
reaction Ill: KMn0 4 1H' reaction IV: C/2 & A/C/3 occur in pairs. Cis isomer
(b) (i) Hydrogen
has the two groups on the
Nickel catalyst.
same side of the double
(ii) Isomer formed is: 1 > 2 d.ibromoethane (D) above. bond while trans isomer
Question 15 has the two groups on the
reason: Cis isomer has one Br atom on each carbon atom on the same
Two types of isomerism found in organic compounds are structural isomerism side of the double bond. opposite sides of the double
bond.
and cis-trans isomerism.
(a) Draw displayed formulae for
(i) two structural isomers of C,H,Br,, Question 16

Both ethene and benzene react with bromine, but the mechanisms and the
types of products of the two reactions are different.
reaction I
no heat, no light, no catalyst needed

D E

(ii) the cis· and the trans- isomers of C,H,Br,.

0 reaction II
heat and catalyst needed

(a) State the type of reaction undergone in each of reactions I and II. [2]
(b) tn each of reactions I and II, the intermediate is a bromine-containing cation.
In each of the following boxes, draw the intermediate and use curly arrows
to show how it is convened into the product.

cis trans [4]

(b) (i) The cis- isomer of C H Br can be converted into one of the structural
reaction I
isomers of C,H,Br,. St;te the reagent(s) and conditions you would use ----7
to do this. - product

(ii) Which of your structural isomers, D or E, would be formed? Explain

your answer. [3]
intermediate
{J08/P2104]
 10.2 Hydrocarbons Page 21 topic 10.2 Hydrocarbons
II' topic
Page 22
~CORNER
The following table lists some electron-withdrawing and electron-releasing ~CORNER
substituents.

reaction II electron-withdrawing groups electron-releasing groups

~ ~ product
-N02 -CHa
-COGH3 -CH2Br
I -CO;,H
1~!: intermediate -NH2 I
[4) Use the above information to draw relevant structural formulae in the boxes in
the schemes below.
(c) Why do ethene and benzene differ in their reaction with bromine? [1)

6
{J08/P4/05]

Suggested Solution: (I) KMnO, + OH"

(a) reaction 1: Electrophillic addition. '>•'"" (II) W

reaction II: Electrophillic substitution.

(b) I
1st Step

e
2nd Step

e
j (I) KMn04 + OH"
(li) w
A B

reaction I CH,-CH, CH,-CH)

~
I I e ~ product
Br Br Br (I) Sn+ HCI
HN03+H2S04 (II) OH"

intermediate

1st Step 2nd Step

c D E I

-
[5]
reaction II

[G)' loss of H' ~ product

Suggested Solution:
{JOB/P4/06]

intermediate
COOH

Q
Electron releasing groups are
(c) Delocalised ring of electrons (in benzene) is stable so reformed in the 2nd step.

Question 17

The substituted benzene compound 6 y

can be further substituted.
6j Br2+AICI3

(i) <Mn0 4
(ii) i '
+0~ Br
A
Q) KMn04 + OH"
(II) H'

¢ Br
B I
ortho or para (2 & 4) direct-
ing. In the fonnation of B,
oxidation of

OCH~
takes place.
OCOOH
In the fonnation of E, reduc-
tion of -N02 group to -
COOH COOH NH 2 occurs.
If Y is an electron-withdrawing group, the next substitution will be in position 3.
If Y is an electron-releasing group, the next substitution will be mostly in po-
sition 4.

0 HNO., + H,SO,

(}~
(I) Sn +HCI
(IQ OH"

c.~
-COOH group is elec-
tron, withdrawing the next
substitution will be in position

6x ¢
3.

if Y is electron-withdrawing

+X 6 if Y is electron-releasing

+X

X
c D E

-·-·-·---·----. -·--.
 Page23 topic I 0.2 Hydrocarbons Page24
topic 10.2 Hydrocarbons
~CORNER (ii) ldentily the molecular formula (including isotopic composition where
~CORNER
relevant) of these 6 peaks.
Question 18
(a) Natural bromine consists of the two isotopes "Br and "Br in roughly equal mass number molecular formula
proportions. 31
The mass spectrum of bromine consists of 5 peaks.
106
(i) Suggest the mass numbers for the 5 peaks and the identities of the
species responsible for them. 108
(ii) Suggest the ratios ?f the relative abundances of 185
the three lines with the highest mass numbers,
187
the two lines with the lowest mass numbers. [4]
189
Esters of 2,3-dibromopropan-1-ol with phosphoric acid are useful flame
retardants used in plastics and fibres. [5]
2,3-dibromopropan-1-ol can be made from propenal by the following two- [N08/P4/Q1}

stage process.
Suggested Solution:
(a) (I)

propenal
- I
- (ii) •
79 81

158, 160, 162

1 : 2 : 1
160 162

2,3-dibromopropan-1-ol
A
79: 81

(b) (i) Draw the structure of the intermediate A in the box opposite. 1 : 1

(ii) Suggest reagents and conditions for (b) (i)

reaction I,
reaction II. [3] H
(c) The mass spectrum of 2,3-dibromopropan-1-ol includes the following peaks.

mass number

31
relative abundance

100
propenal
- I CH,- C -CHO
I
Br
I
I
Br
-
II

2,3-dibromopropan-1-ol
A
106 44

45 (ii) • reaction 1: Br, in CCI,

108
reaction II: Li A/ H,/ Ether or (NaBH,)
185 0.3
(c) (i) 218, 220, 216
187 0.6
(ii) mass number molecular formula
189 0.3
31 CH30+
(i) At what mass number would you expect the molecular ion to occur? 106 C2H3 7•sr•

108 C2 H3 Br61 +

185 C2H3 79 Br;

187 C2H3 7"Br 61

Br•
61
189 C2H3 Br Br6 1+
 topic 10.2 Hydrocarbons Page26
Page 25
topic 10.2 Hydrocarbons
~CORNER ~CORNER
(b) • step II: C/2 +light.
Question 19 • step Ill: KCN (in ethanol)+ heat. Temperature"' 7s•c.
(4-aminophenyl)ethanoic acid (4-APEA) and its derivatives are being investi-
gated as possible drugs to treat chronic inflammation of the intestines. • step V: Sn+HC/+heat. (NaOH is used to separate Amine].
The synthesis of 4-APEA from methylbenzene is shown in the following scheme.

Question 20
CH2CI

6
Phenol and chlorobenzene are less reactive towards certain reagents than

HN03 + H2S04 ¢ N02

similar non-aromatic compounds.
Thus hexan-1-ol can· be converted into hexylamine by the following two reac-
tions,

I II
CH 3 (CH 2) 50H ~ CH 3 (CH 2 )5CI ~ CH3 (CH 2)5 NH 2
G I hexan-1-ol 1-chlorohexane hexylamine

whereas neither of the following two reactions takes place.

!"'
CH2C02H
CH2CN

>< ©rCl >< ~NH

2

¢ "~¢
0
©rOH 0

(a) (i) Suggest reagents and conditions for

N02
NH2 reaction I,
I reaction II.
4-APEA H
(ii) What type of reaction is reaction II?
(a) Draw the structures of the compounds G and H in the boxes above. [2]
(iii) Suggest a reason why chlorobenzene is much less reactive than
(b) Suggest reagents and conditions tor the following steps. 1-chlorohexane. [4]
• step II, • step Ill, • step V (3]
(N08/P4/05] (b) Phenylamine can be made from benzene by the following two reactions.

Ill rAT
~ NO
2
~NH
2
Suggested Solution:
(a) © IV

¢'
(i) Suggest. reagents and conditions for

6 HN03 + H2S04
¢ NO, N02
In Step I, Nttration reaction
takes place. Nitrating mix-
ture is required and
reaction Ill,
reaction IV.
(il) State the type of reaction for
reaction Ill,
temperature is about 30"C reaction IV. (5]
G because ring activating
group is attached. (c) Suggest a reagent that could be used to distinguish phenylamine from
hexylamine.
In Step IV, reduction of

COOH
l"' - NO 2 group takes place. reagent and conditions

¢
Sn and HC/ is used as observation with phenylamine

¢~ ¢
reducing agent.
observation with hexylamine [2]
IV
v
H3 o•
N02 N02
NH2
H
4-APEA
 Page27 topic 10.2 Hydrocarbons Page28
topic 10.2 Hydrocarbons
~CORNER ~CORNER
(d) Phenylamine is used to make azo dyes. In the following boxes draw the
(c) reagent and conditions: Bromine water, room temperature.
structural formula of the intermediate D and of the azo dye E. observation with phenylamine: Colour of bromine (aq) turns brown to
colourless and· white precipitate is produced.
observation with hexylamine: No change.

NH 2 (d)
rAY' NaN02 + HCI
1-- ci-i,
~
~OH
T<5°C . +-
NH 2
NaN02 + HCI ~N=NC/
lVlcH, T <·soc
- CH 3

in NaOH(aq) ©roo CH3

D

in NaOH(aq)

:'

;&~
~N=N CH
3
.

E
[2]
[J09/P4/06]

E
Suggested Solution:
(a) (I) reaction 1: reagent: PC/5 Question 21
condition: dry ether.
(a) All the carbon atoms in benzene lie in the same plane. This means that
reaction 11: reagent: NH, they are coplanar, but this is not the case with cyclohexane.
condition: concentrated ammonia under pressure.

(ii) Nucleophilic substitution

(iii) Delocalisation of lone pair on chlorine over benzene ring produces a
stronger C - Cl bond. benzene cyclohexane

(b) (i) reaction Ill: reagents: Cone. HNO, and cone. H,so, By rotating the molecule around its several C - C bonds, all the carbon
at 55- 60 oc. atoms in butane can be made to lie in the same plane, but this is not the
condition:
case with methylpropane.
reaction IV: reagents: Sn and cone. HC/
condition: heat under reflux.

(ii) reaction Ill: Electrophilic substitution

reaction IV: Reduction
butane methylpropane
 topic 10.2 Hydrocarbons Page 29 topic 10.2 Hydrocarbons Page30

By considering the 3·dimensional geometry of the following five molecules,

~CORNER ~CORNER
and allowing rotations around C-C bonds, decide whether or not the carbon
atoms in each molecule can be arranged in a coplanar fashion. Then
place a tick in the appropriate column in the table below.

6 IV

6boo H3C '

H3C
/0~ /CH 3

,,,,...... c~ /c ........,
O CH 3 I H

~ v

I
A B

H2N~M C
c

/N02
6" y
OOH
CH3CH(OH)CO2H II
0
c~
I CH3
H
0
t VI

D E
II

compound
all carbon atoms
can be coplanar
not all carbon atoms
can be coplanar
Q("/1()
A benzyl benzoate

B (i) Draw the structural formula of the intermediate H in the box above.

,~ I
c (ii) Suggest reagents and conditions for each reaction.
reaction Ill
D
reaction V
q E reaction VI
- ---
li[ (3] (iii) State the type of reaction occurring during
,:ij reaction Ill,
(b) Methylbenzene can react with chlorine under different conditions to give
.'iii the monochloro derivatives F and G. reaction V. [6]
1:;:

0'
1;: {N09/P4/05]

6 6
lit
jl
I II
\!
'i: Suggested Solution:
{
,, (a)
ii Cl compound all carbon atoms
can be coplanar
not all carbon atoms (a) A: All carbons are sp'
,n':I
can be coplanar hybridised.
F G
A ./ B: Caribons in benzene are
,,·I! Suggest reagents and conditions for each reaction. coplaner but carbons in
"
:r.
reaction I
B ./
cyclohexane are sp'
reaction II (2] c ./ hybridised, therefore not in
a plane.
(c) Benzyl benzoate is a constituent of many perfumery products, and has also D ./
been used in the treatment of the skin condition known as scabies. II can C: Six carbons in a plane
be made from methylbenzene by the following route, which uses one of the E ./ and oxygen atoms above
L___

chlorination reactions from (b). and below the carbon .

plane.
(b) reaction 1: reagent: C/2 & AIC/3 • condition: warm under reflux.
D: All carbons in a plane.
reaction II: reagent C/2 • condition: heat or light.

,/
I
' I - ~::5'_?.-G.~~~-·.;..-~>~.'~e "'::"'-~!-.. ..
topic 10.2 Hydrocarbons Page31 topic 10.2 Hydrocarbons Page32
~CORNER ~CORNER
(c) (I)
Question 22

IV {d) Predicl the organic products of the following reactions and draw their struc-
tures in the boxes below. You may use structural or skeletal formulae as
you wish.

H
hot cone.
MnO;;+W

hot cone.
'---------~r------~ MnO;j+H'

t VI

benzyl benzoate
y(}OH hot
Cr2 0~+ H'

condilion: heat OH
{li) reaction Ill: reagent KMnO,/ OH-.
reaction V: reagent NaOH aqueous. condition: heat [4]
condition: heat (e) KMnO, and K,Cr,o, are the reagents that can be used to carry out the
reaction VI: reagent Cone. H,so,.
following transformation.

(iii) reaction Ill: Oxidation

reaction V: Nucleophilic substitution

y _ _ _1_1- . - x C H O

OH

(i) Draw the structure of intermediate E in the box above.

(ii) Suggest reagents and conditions for the following.
reaction 1 •••••••••••••••••••••••••••••••••••••••••••

reaction 11 ........................................... [3]

[J10/P4104 d,e]
topic l 0.2 Hydrocarbons Page33
topic 10.2 Hydrocarbons
Page34
~CORNER
Suggested Solution:
(i) Give the conditions for two different processes by which long chain · ~CORNER
(d) molecules may be cracked.

u
(ii) Undecane, C11 H24 , can be cracked to form pentane, C H , and an alkene.
5 12
hot cone. 0 Construct a balanced equation for this reaction. (3]

CY Mn04+ H'
+ CH,COOH
Pentane, C 5 H 12 , exhibits structural isomerism.

(c) (i) Draw the three structural isomers of pentane.

hot cone.
ffCOOH
yV Mn04+ W

I
HOOC
isomerS isomerC isomer D

hot
CH,'-. ffCHO (ii) The three isomers of pentane have different boiling points.
Which of your isomers has the highest boiling point?

~OH
Cr,Of+W Suggest an explanation for your answer. [6]
c ..
The unsaturated hydrocarbon, E, is obtainE>d by cracking hexane and is impor-
II tant in the chemical indus:ry.
OH 0
The standard enthalpy change of combustion of E is -2059 kJ mot·'.

(d) Define the term standard enthalpy change of combustion. [2]

(e) (I) When 0.47 g of E was completely bumt in air, the heat produced raised the
temperature of 200 g of water by 27.5 •c. Assume no heat losses occurred
during this experiment.

XCH,OH (e) (i) Use relevant data from the Data Booklet to calculate the amount of heat

y I

I OH
II XCHO

OH
released in this experiment.
(ii) Use the data above and your answer to (i) to calculate the relative
molecular mass, M,, of E. [4]
(f) Deduce the molecular formula of E. [1]
E
{N10/P2/Q3}

(ii) reaction 1: cold, dilute KMnO,, mild condition. Suggested Solution:

reaction II: acidified K,Cr,O,, distill the vapours. (a) (i) hydrocarbon: A compound which is made up only of carbon and hydro-
(a) (iO • Fractional distillation
gen is known as hydrocarbon.
is separation of miscible
(ii) fractional distillation: It is a separation technique in which separation of liquids.
Question 23 compounds is according to difference in their boiling points.
• Separation is based on
Crude oil is a naturally occurring flammable liquid which consists of a complex (b) (i) process 1: high temperature and high pressure. difference in boiling points.
mixture of hydrocarbons. In order to separate the hydrocarbons the crude oil process 2:· high temperature in the presence of catalyst (AI 0 ).
Lowest boiling point fraction
2 3 is separated first.
is subjected to fractional distillation.
(ii) c,2H24 ~ CsHt2 + CsHt2 (b) (0 Veryhightemperature
(a) Explain what is meant by the following terms.
of about 1000 ·cis used.
(i) hydrocarbon This is called thermal
(ii) fractional distillation [2] cracking while if catalyst
is used temperature is·
(b) Undecane, C11 H24 , is a long chain hydrocarbon which is present in crude oil. reduced to 450 ·c.
Such long chain hydrocarbons are 'cracked' to produce alkanes and alk·
enes which have smaller molecules.
 topic 10.2 Hydrocarbons Page35 topic 10.2 Hydrocarbons Page36
~CORNER ~CORNER
(c) (i)

CH3
I
CH 3CH 2CH 2CH2CH 0 CH3 CH 2CHCH 3 CH 3 -C-CH 3
me nth one menthol
I I
CH 3 CH3 -~p2

isomerB isomerC isomerD

(ii) isomer: B
explanation: Straight chain or unbranched molecule has greater area of
contact hence greater strength of intermolecular forces of attractions and +
high boiling points.

{d) It is the enthalpy change when 1 mol of a substance is completely burned in

oxygen at standard condition of temperature and pressure.
L M
(e) (i) Heat evolved= mcll T
(i) Suggest reagents for
= 200 X 4.18 X 27.5
step 1 .................................. ._ ........................................_ ......................................
= 22990 J or 23.0 kJ
step 2 ·····················································--·--·························································
(ii) 23.0kJ produced from 0.47g of E
(ii) Suggest structures for L and M and draw them in the boxes above. [4]
0.47•x2059
2059kJ produced from= 42.08 g of E (c) When heated with concentrated, acidified KMnO,(aq), one of the two alk-
23.0
anes L or M produces the dicarboxylic acid N.

(f) M, of C3H6 = 42
hence E is C 3H6 .
~
N
Question 24 (I) Give the Jetter of the alkene that produced N by this ·reaction.
Menthane, C 10 H,.O, is !'I cyclic ketone that occurs in oil of peppermint. (ii) Suggest the structure of the product, P, of the reaction between the
other alkene you have drawn and hot concentrated acidified KMnO,.

menthane
(a) Use asterisks (•) on the formula above to identify any chiral centres in the
molecule of menthane. [2]
p
(b) Menthane can be reduced to menthol, which can be dehydrated to a mixture
of two alkanes, L and M. (Iii) Suggest one chemical test that would enable you to distinguish
between N and P.

reagent(s) .............................................................................................................
observation .................................................................................................... [3]
(d) Chlorocyclohexane can be prepared by bubbling HC/(g) through a solution
of cyclohexene.

(YCI
0 v +HC/-

···························--------------------l-----------------~~- -~- ~-~-i i i ~ - -~ - -~-~--~~-~- - -~ - - - - - ~-~- -,- - ·,; · - ; ;·; ;· ~;.;,;;;;..;..;.;;..;;;;;,;;;;,;,;;;;;:;;.~~-i:~~~~-'";::::7:-~r;;,ff~?..(~-~

topic 10.2 Hydrocarbons Page37
~CORNER
Suggest the mechanism of this 2-stage reaction by means of a diagram.
Include all whole or partial charges, and represent the movements of elec·
Iron pairs by curly arrows. [3]
7oprc 10.3
{N10/P4/06]

Jfaloyen :Deriualiues

,., >-b-
Suggested Solution:

Content
Halogenoalkanes and halogenoarenes.
menthone (i) Nucleophilic substitution.
(b) (i) step 1: LiAiH, dissolved in ethanol. (ii) Hydrolysis.
step 2: Cone. H,so, at 130°C or hot A/,03 at 350"C. (iii) Formation ofnitriles, primary amines.

(ii) (iv) Elimination.

HO

>--b- ~>-b-
2 Relative strength of the C-Hal bond.

Learning Outcomes
menthone menthol Candidates should be able to:

~p2 (a) recall the chemistry of halogenoalkanes as exemplified by

(i) the following nucleophilic substitution reactions of bromo ethane: hydrolysis,
formation of nitriles, formation of primary amines by reaction with ammonia.
(i i) the elimination of hydrogen bromide from 2-bromopropane.
(b) *describe the mechanism of nucleophilic substitution (by both SNl and SN2 mecha-

>-0- +
>-0- (c)
nisms) in halogenoalkanes.
interpret the different reactivities of halogenoalkanes e.g. CFCs, anaesthetics, flame
retardants, plastics and chlorobenzene (with particular reference to hydrolysis and to
the relative strengths of the C-Hal bonds).
L M
(d) explain the uses of fluoroalkanes and fluorohalogenoalkanes in terms of their relative
(c) (i) M chemical inertness.
(ii) (e) recognise the concern about the effect of chlorofluoroalkanes on the ozone layer.

~=e
0
p

(iii) reagent(s): 2, 4-Dinitrophenyl hydrazine.

observation: Orange precipitates are formed.

(d) (YH
~f-1----CCI- ~CBJcr-
CCH
C/
 Page 1 topic 10.3 Halogen Derivatives Page2
topic 10.3 Halogen Derivatives
~CORNER ~CORNER
Question 2
Methylbenzene can react with chlorine in two ways, depending on the condi-
Cf?fii) IN fl !lJ tions of the reaction.

1.1 ~ tr U \!;;I qpening ....... . CH 2 CI

Question 1
The volatile liquid F/uothane, CF,CHBrC/, is commonly used as an anaesthetic
0 Cl
-
Ci:!

reaction I 0- Ci:!

reaction II 0
A 8
. in hospitals. It has the advantage that it does not readily react with sodalime
(which contains NaOH), used in closed anaesthetic systems to remove the CO, (a) State the condition needed for
breathed out by patients. (i) reaction I,
(a) Write an equation for the absorption of co, by NaOH. [1] (ii) reaction II. [2]
When Fluothane, was being developed, it was tested to ensure it did not (b) On.e of the two compounds A and 8 react~ with NaOH(aq), but the other
react with NaOH. If it had reacted, bromide ions would have been produced.
1s mart. \
(b) (i) Write an equation for a bromoalkane, e.g. RBr, reacting with aqueous (i) Which one (A or B) does not react? Gi~e a reason for your answer.
NaOH.
(ii) Write an equation for the reaction with NaOH(aq) that does occur. (2]
(ii) What type of reaction is this? [2]
(J021P2/Q6J (a) Forelectrophilicsubstitution
(c) In an attempt to hydrolyse Fluothane, a mixture of Fluothane and sodalime
of Cl into benzene ring, a
was stirred for an hour. It was then acidified and tested with the following
Suggested Solution: halogen carrier such as
reagents.
FeCI, or AICI 3 is required.
Describe what you would expect to observe if bromide ions had been (a) (i) FeCI, I A/C/3 as catalyst This is because the Jt-elec-
produced, and write an equation in each case. trons in the benzene ring
(ii) ultra-violet light
(i) aqueous silver nitrate are delocalised and not
(b) (i) A does not react. This is because Cl is directly attached to the benzene polarising enough to gener-
observation
ring. Due to the delocalisation of a lone-pair of electrons on C/ into the ate the Cl' electrophile, un-
equation benzene ring, the C - Cl bond has partial double bond character and like in alkenes where halo-
(ii) aqueous chlorine does not cleave easily. gencarriersarenotrequired.
observation For substitution of Cl, at the
(II) alkyl side-chain, uv light is
equation (4]
needed to convert Cl, to the
(d) The attempted hydrolysis failed to break the C- Br bond in Fluothane. It reactive Cl radical to propa-
may be confidently assumed, therefore, that the other two types of C- Hal gate the reaction by free
bond in Fluothane also remain intact when hydrolysis is attempted. radical sllbstttution.
Give a reason for the confidence of this assumption. [1]
(JOOIP2/Q4I
Question 3

(a) 1-Bromobutane can be obtained either from butane or from butan-1-ol.

Suggested Solution:
(I) t?escribe the reagents and conditions needed for each of these reac-
(d) Bond enthalpies(in kJ mol-') tions. (2]
(a) C0 2 (g) + 2NaOH(s) ---4 Na 2C0 3 (s) + H20(/) of C- F, C- Cl and
C- Br are 485, 340 and (ii) Give the name of, and describe, the mechanism of the reaction fomning
(b) (i) RBr+NaOH ---4 ROH+NaBr 280 respectively. The bond 1-bromobutane from butane. [4]
enthalpies decrease from (Iii) 1-Bromobutane reacts with sodium hydroxide to re-fomn butan-1-ol. Give
(ii) Nucleophilic substitution
C- F to C- Br because the name of, and describe, the mechanism of this reaction. [2]
(c) (i) Cream precipitate formed: overlap between orbitals of
C and the halogen atoms is (b) Identify S and T, the products of the following reactions.
Ag•(aq)+Br-(aq) ---4 AgBr(s) less effective as size of
[0] HCN
halogen atom increases, CH 3CH2 CH2CH2 0H ------> C4H80 ~ T
(ii) Orange solution formed: also the difference in elec· 5
q(aq)+2Br-(aq) ---4 2CI-(aq)+Br2 (aq) tronegativitydecreasesfrom [2]
F to Br so that the bond
(N03/P3/Q8 Or]
(d) C - Br bond is weaker and hence more easily broken than C - F and has less ionic character from
C- F to C- Br.
C- Cl bonds.
 topic 10.3 Halogen Derivatives Page3 topic 10.3 Halogen Derivatives Page4

Suggested Solution:
~CORNER ~CORNER
Question 4
(a) (i) CH,CH,CH,CH,
(a) (i) CH,CH,CH,CH,:
Reagent: Br, (limited) This question is concerned with organochlorine compounds.
limited amount of Br2 has to
Conditions: uv be used to minimise (a) State the conditions needed to produce the two compounds A and B.
'
ii
CH,CH 2CH 2CH,OH
poly substitution.
I'

I
9 6 0
CH,CH 2CH 2CH,OH al·
Reagent: HBr tematively, amixture of solid
Conditions: heat NaBr and concentrated C/2 C/2
[ H,SO, could be used.
(ii) Mechanism: Free radical substitution reaction I reaction II

I Initiation: In the presence of uv light, Br, undergoes homolytic

cleavage. Cl

A B
t s';lrsr ~ 2Br.
(i) conditions for reaction
Propagation: The Br. radical formed abstracts a H atom from butane
(ii) conditions for reaction II [2]
to form HBr, and a butyl radical is formed.

CH 3CH 2CH2CH3 + Br • ~ CH3CH 2CH 2CH 2 • + HBr (b) State the reagent needed to carry out the following reaction.
I C02 H

6 ~""""' 6
The butyl radical then abstracts a Br atom from another COC/
Br, molecule to form 1·bromobutane and another Br
radical.

' Termination:
CH 3CH2CH 2CH2 • +Br2 ~ CH3 CH,CH,CH2 Br +Br·

The reactions repeat and more 1·bromobutane

molecules are formed.
In the process of the reaction, any 2 radicals may
combine and a molecule is formed. Hence, the reaction
reagent for reaction Ill:
c
[1]
ceases to proceed. (c) The three chloro-compounds A, B and C vary in their ease of hydrolysis.
Br· + Br• ~ Br2 (i) Place a tick in the box corresponding to the correct relative rates of
hydrolysis. [the symbol '>' means 1aster than']
CH 3CH,CH2CH 2 • + Br· ~ CH 3CH,CH2CH2Br

CH 3CH2 CH2 CH2 • + CH3CH2CH2CH2 • ~ CH3 - (CH2 ) 6 -CH3 place one

tick only in
this column
(iii) Mechanism: Nucleophilic substitution
A>B>C
oH-, being electron rich, is a nucleophile, and it readily
attacks the electron deficient C at the C - Br bond. A>C>B
B>A>C

. £1-c~:oH· ~ Br" +
H

H/1
'c-OH
B>C>A
C>B>A
I 'cH,cH,cH,
H CH,CH,CH, C>A>B
The C - Br bond cleaves and a C- 0 bond is formed.
(ii) Suggest an explanation for these differences in reactivity. [3]
1·Butanol is obtained.
[N04/P4!05 (a,b,c)]

0
II (b) Under controlled oxidation, Suggested Solution:
(b) S = CH,CH,CH,C- H the 1" alcohol is oxidised to (a) (I) AICI, + heat
an aldehyde (S). The alde-
OH hyde then under goes nu- (ii) u.v. light.
I cleophilic addition with HCN
T = CH 3CH 2CH 2 - CI - CN in the presence of a base to (b) PC/5 or SOC/2 •
form the cyanohydrin (T).
H
 topic 10.3 Halogen Derivatives Page 5 topic 10.3 Halogen Derivatives Pa e6

(c) (i)
~CORNER ~CORNER
place one
tick only in Question 6
this column
(b) Describe the mechanism of the reaction between bromoethane and sodium
A>B>C cy~~ ~
A>C>B (c) Identify the compounds J - M in the following reactions
B>A>C
(i) hot KOH in ethanol
B>C>A (CH 3 ) 2CHCH 2Br J
C>B>A -/
KCN heat with f-i:!S04 (aq)
C>A>B (ii) (CH3 ) 2 CH8r K L
(in ethanol) followed by ethanol,
S-
O) conc.H2 S04 and heat
ll.. f'o S-
(ii) Acyl chloride is most reactive because R-C-C/ carbonyl carbon atom (iii) BrCH2CH2Br + CH CH NH,
3 2 M [4]
t:Nu (in ethanol)
(in an excess)
is very electropositive and easily attacked by nucleophile.
{N05/P3/Q8(b,c) Or]
CH,

~ is least reactive because the benzene ring electrons are delocalised

Suggested Solution:

C/ (b) Nucleophilic substitution

over the ring causing the C- C/ bond to become stronger. H
I
CH,-C-CN
I
Question 5 H

Compound G, in which R- represents ihe rest of the molecule, was made lor CN· acts as a nucleophile and attacks the electron deficient carbon atom C.
use as a tear gas in World War 2. C- CN bond is formed, while C - Br bond cleaves heterolytically.
H
(c) (i) J = (CH3 ) 2 C = CH2
R-C-CN
I
(ii) K = (CH,),CHCN
I
Br
L = (CH,),CHCO,CH,CH 3

compoundG
Compound G was made by the following sequence of reactions.

stage I stage II stage Ill R--GHBrCN

R--GH _ ____,,.. R--GH CI R--GH CN _...:....___
3 2 2

(a) (i) For stage I and lor stage II, state the rea!lent(s) and condition(s) used
to carry out each change. Question 7
(ii) Suggest the reagent(s) and condition(s) necessary to carry out
Halogenoalkanes are readily hydrolysed by OH· ions to form alcohols.
stage Ill. [6]
Primary halogenoalkanes and tertiary halogenoalkanes are hydrolysed by
[J05/P2/Q4 (a)] different mechanisms.

(a) Describe the mechanism of the hydrolysis of CH,CH,Br.

Suggested Solution:
In your answer show any relevant charges, dipoles or lone pairs of elec-
(a) (i) stage I reagent(s): C/2 gas trons you consider to be important in this mechanism. [3]
condition(s): u.v. light (b) 3-bromopropene, CH,=CHCH,Br, can be hydrolysed by NaOH(aq) to form
stage II reagent(s): KCN CH,=CHCH,OH. Results of an investigation into the kinetics of this reaction
are given below.
condition(s): heat in ethanol.

(II) reagent(s): Br, (a) (iO It is true radical substi-

tution. hence U.V. light is
condition(s): U.V. light needed.
topic 10.3 Halogen Derivatives Page 7 topic 10.3 Halogen Derivatives t'age o

~CORNER ~CORNER
experiment [CH2=CHCH2Br] [NaOH] relative initial Question 8
number /mol dm-3 /mol dm-3 rate
1 0.10 0.20 1.00 Ethylbenzene is an important starting material for making polystyrene

6'CH:o00oU 6c
(poly(phenylethene}}.
2 0.20 0.10 2.00
3 0.30 0.20 3.00 CH 2 CH 3
2

(i)
4 0.60 0.40 6.00

Use the data in the table to deduce the order of reaction with respect
to CH, = CHCH,Br and with respect to NaOH.
order with respect to CH, = CHCH,Br
6
ethyloenzene
reaction!

+ C!2

B phenylethene
--H
polystyrene

order with respect to NaOH

(il} Write an overall rate equation for the reaction between CH, = CHCH,Br (a) (i) State the conditions needed to carry out reaction I in the laboratory.
and NaOH. [3] (ii) State the reagent and conditions needed lor reaction 11.
(c) (i) Is the mechanism of this hydrolysis the same as or different from the (Iii) Draw the structure of the repeat unit of polystyrene.
one you have described in (a)? Explain your answer.
(iv} There are several polymers that consist of phenylethene co-polymerised
(ii) Suggest the structure of the intermediate formed in the hydrolysis of with other monomers. The following formula shows part of the chain of
CH, = CHCH 2Br. l2l one such co-polymer.
(d) The bromine atom in CH, = CHCH,Br is very reactive.
-CH -CH-CH -CH-CH -CH-CH-
2 I 2 2 I 2

60
The bromine atom in CH, = CHBr is unreactive.
Suggest an explanation for the unreactivity of the bromine atom in CH,=CHBr. CN CN
[2]
[N06/P2103}
Deduce the structural formula of the other monomer. [5]
Suggested Solution: i I {N06/P4!04(a)}

(a)
HO-:~C-Br
H....._;;;+ Go- 1
~
S- ~ S-] ,..--H
----.,) Ho-q_,CH, + :B( Suggested Solution:
HI [HO ..·-~:;C,::::~~: Br H
CH 3 (a) (i) U.V. light. (a) (0 It is free radical sub-
stitute, hence requires U. V.
(ii) Alcohlic KOH and heat. light to generate free radi-
The C-Br bond is polar due to the electronegative Br. The negatively charged
cals.
nucleophile, OH-, attacks the electron deficient C in C-Br. The C-0 bond

''"f6~cH,1
is formed while the C-Br bond is cleaved at the same time, going through
a pentavalent transition state which is unstable and breaks to form the prod-
(iO It is elimination this
ucts.
copolymer is formed by
(b) (i) order with respect to CH, =CHCH,Br: addition polymerisation.
order with respect to NaOH: 0
(iv) CH,=CH
(ii) CH2 =. CHCH2Br + NaOH ----+ CH2 = CHCHpH + NaBr
I
CN
(c) (i) No. This reaction has a first order kinetics. In 3(a), the reaction has a
second order kinetics.

(ii) H H
'/ C=C /
'" H
H 'c...--
/
H
(d) The p-orbital of Br can intetact with the 11-orbital in the C=C bond. This strength-
ens the C - Br where it has partial double bond character.
 topic 10.3 Halogen Derivatives Page9 topic 10.3 Halogen Derivatives Page 10
~CORNER ~CORNER
Question 9 (c) Moles of C4H9 0H = ~ = 0.208
74
One method of making 1-bromobutane in the laboratory is described below. Moles of C4 H9 Br expected= 0.208 (c) From answer to part (a),
stage II,
22 5
Stage 1 Place 35 g of powdered sodium bromide, Actual yield of C4 H9 Br = · = 0.164 moles
137 C4H90H: C4H9Br :: 1: 1
30 em' of water,
and 25 em' (20 g) of butan-1-ol, 0 164
percentage yield= · x 100 = 78.8%
0.208
in a 250 em' two necked flask fitted with a tap funnel and reflux
condenser.
(d) inorganic by-product : Bromine.
Stage 2 Concentrated sulfuric acid (25 em') is then placed in the tap
role of cone. H,SO, : 'Acts as an oxidising agent.
funnel and added drop by drop to the reagents in the flask,
keeping the contents well shaken and cooled occasionally in organic by-product : but-1-ene.
an ice-water bath. role of cone. H,SO, : Acts as a dehydrating agent.

(a) The overall reaction may be considered to take place in two stages. In the
first stage the inorganic reagents react together to form HBr. In the second Question 10
stage, the organic reagent reacts with the HBr that is formed in the first stage.
Wriie an equation for each of these stages. [2] (a) Complete the following reaction scheme which starts with 1·bromobutane.
In each empty box, write the structural formula of the organic compound
(b) Jn this preparation, by using the amounts given above, one of the reagents, that would be formed.
sodium. bromide or butan-1-ol, will be present in an excess.
Use your equations in (a) and the data above to determine, by calculation,
which reagent is in an excess. (2]
CH 3 CH 2CH2CH 2Br
(c) In a laboratory preparation of 1-bromobutane, when 15.4 g of butan-1-ol
was used, 22.5 g of 1-bromobutane was obtained after purification.

N'O~'""'"
""""~·--
· Calculate the yield of 1-bromobutane as a percentage of the theoretical
maximum yield. (2]
reflux reflux
(d) When the concentrated sulfuric acid is added to the reaction mixture (stage
2), unless the temperature is controlled carefully, the acid may react with
either of the original reactants (sodium bromide or butan-1-ol) to give at
least two by-products, one of which is inorganic and the other organic.
What inorganic and organic by-products may be formed?
In each case, identify one by-product and state the role of the concentrated
sulfuric acid in the formation of this by-product. (4]
w X ..

[N09/P2/Q3} K2Cr20 7/W

heat under
cone. KMnO,fH+ ~ 1/':

~~~ I
heatunde
reflux reflux [,I!.l
Suggested Solution:

(a) stage 1: NaBr +H2 SO 4 ~ NaHSO4 + HBr (a) A/temativefy:

. I''
,: I
•I'
stage II:. Cii9 0H + HBr ~ C4 H9Br + H2 0
2NaBr+H 2S0 4 ~
Na 2SO 4 + 2HBr
~ i

(b) Moles of NaBr = ~ = 0.34

y z
103
(4]
::::. moles of HBr = 0.34
(b) One of the compounds W, X, Y or Z can be polymerised.
20
Moles of C4 H9 0H = = 0.27
74 (i) Identify this compound by its letter.

0.27 moles of C4 H,OH will react with 0.27 moles of NaBr, (ii) Draw a section of the polymer chain formed by this compound.

NaBr is in excess Show two repeat units. [2]

[N09/P2/Q4}
 topic 10.3 Halogen Derivatives Page 11
topic 10.3 Halogen Derivatives Page 12
~CORNER
Suggested Solution:
{b) When 1-iodobutane, CH 3CH,CH,CH 2 1, is reacted under the same condi- ~CORNER
(a) tions as those used in reaction 1, butan-1-ol is fomned.
What difference, if any, would there be in the rate of this reaction compared
CHsCH 2CH 2CH 2Br to the reaction of 1-bromobutane?
Use appropriate data from the Data Booklet to explain your answer. [3]
(a) (i) nucleophilie substitu-
tion. Dichlorodifluoromethane, CCI,F,, is an example of a chlorofluorocar\oon (CFC)
~at u t und that was formerly used as an aerosol propellant. In September 2007, at the
(ii) oxidation. Montreal summit, approximately 200 countries agreed to phase out the use of
refl1 lflux
CFCs by 2020.
.~
(iii) elimination.
(iv) oxidation. (c) State two properties of CFCs that made them suitable as aerosol propel-
lants. [2]
CH 3CH 2CH 2CH20H CH 3 CH 2CH = CH2 (d) When CFCs are present in the upper atmosphere, homolytic fission takes
place in the presence of ultraviolet light.
w X
(i) What is meant by the term homolytic fission?

K2Cr201/H+ cone. KMnO ,JH+ (ii) Suggest an equation for the homolytic fission of CCI,F,. [2]
heat under heat und1 (e) The most common replacements for CFCs as aerosol propellants are
reflux reflux hydrocar\oons such as propane and butane.
Suggest one disadvantage of these compounds as aerosol propellants.
[1]
CH 3CH 2CH 2C0 2H CH 3CH 2C0 2H [N10/P2104)

'
y z Suggested Solution:

{b) (i) X (a) reaction 1 reagent: NaOH or KOH (a) Reaction 1 is nucleophillic
solvent: H,O substitution, if dilute
(ii) C2H5 H C2Hs H aqueous alkali is used it is
reaction 2 reagent: NH,fammonia
I I I I solvent: Alcohol or ethanol
nucleophillic substitution,
-c-c-c-c- while if alcohlic alkali is
used elimination occurs
1 I I I reaction 3 reagent: NaOH or KOH
and alkene is fonmed.
H H H H solvent: Ethanol

{b) The rate of reaction with iodobutane will be faster than with bromobutane
because C - I bond is weaker than C - Br bond. (b) As covalent bond length
Question 11 increases, bond strength
B.E for C - I bond is 240 kJ/mol decreases. hence C-1
Halogenoatkanes have many chemical uses, particularly as intermediates in B.E for C -Br bond is 280 kJ/mol bond is longer and weaker
organic reactions. as compared to C-Br
Hence C - I bond is easier to break. CH,CH 2 CH,CH,I reacts faster than
Three reactions of 1-bromobutane, CH,CH,CH,CH,Br, are shown below. bond.
CH 3CH,CH 2CH 2 Br.

CH 3CH2CH2CH20H ~ / CH3 CH2CH2CH2NH2 (c) 1. Nontoxic or inertness.

2. Easy to vaporise or volatile compound.
reaction 1~ /reaction 2
{d) (i) It is a type of bond breaking in which each atom takes its electron and
forms free rat!ical in the presence of u.v. light.
CH 3 CH2CH2CH2Br
(ii) CCI2F2 --t CCIF2 +CI
reaction 3
(e) These compounds are highly flammable and can easily catch fire.

CH 3CH 2CH=CH 2

(a) For each reaction, state the reagent and solvent used. [6]
 topic 10.4 Hydroxy Compounds Page I

~CORNER
:Jopic 10.4
q?(i)) IN fJ 4J
Jfydroxy Compounds tJ \.!!/ t.r IJ \!;;I q;:;ening ....... .

Question 1

Content Eugenol is an important compound in many spices, e.g. cinnamon and cloves.
CH,O
Alcohols (exemplified by ethanol)
(i) Formation of halogenoalkanes.
HO-b-CH,CH=CH,
(ii) Reaction with sodium; oxidation; dehydration; esterification; acylation.
(iii) The tri-iodomethane test. [The CH,O group is inert and can be disregarded in this question.]

2 Phenol (a) Explain why eugenol is more soluble in aqueous sodium hydroxide than in
water. [2]
(i) Its acidity; reaction with sodium.
(b) Draw the structures of the organic products when eugenol reacts with each
(ii) Nitration of, and bromination of, the aromatic ring.
of the following reagents.

(i) cold. dilute manganate{VII) ions (II) hot, concentrated manganate(VII) ions
Learning Outcomes
Candidates should be able to: (a) In general. an organic com-
(a) recall the chemistry of alcohols, exemplified by ethanol: pound with abenzene ring is
insoluble in water unless it is
(i) combustion. charged. Henoebenzoic acid
and phenylamine are in-
(ii} substitution to give halogenoalkanes. soluble in water. However
(iii) ethanoyl chloride (tv) aqueous bromine
(iii) reaction with sodium. sodium benzoate (which
contains the anion of benzoic
(iv) oxidation to carbonyl compounds and ·carboxylic acids. acid) and phenyl ammonium
chloride (which contains the
(v) dehydration to alkenes. cation of phenylamine) are
(vi) ester formation. soluble in water. Hence ben·
zoic acid and phenylamine
(b) (i) classify hydroxy compounds into primary, secondary and tertiary alcohols. can be made to dissolve in
[5] water by adding an alkali
(ii) suggest characteristic distinguishing reactions, e.g. mild oxidation.
(c) Eugenol can polymerise. {eg. NaOH) or an acid (eg.
(c) deduce the presence of a CH,CH(OH)- group in an alcohol from its reaction with (i) What kind of polymerisation can occur with eugenol? dil. HCI) respectively.
alkaline aqueous iodine to form tri-iodomethane. (ii) Draw one repeat unit for the polymer of eugenol. [2] Eugenol reacts with aq.
NaOH to form its sodium
(d) recall the chemistry of phenol, as exemplified by the following reactions: [JOO/P2105]
salt:
(i) with bases. CH,O
Suggested Solution:
(ii) with sodium.
(iii) nitration of, and bromination of, the aromatic ring.
(a) Due to the hydrophobic benzene ring, eugenol is not very
soluble in water despite the presence of the phenolic OH group
HO~CH,CH=CH, + NaOH

which enables eugenol molecules to form hydrogen bonds

(e) explain the relative acidities of water, phenol and ethanol. CH,O
with water molecules.
The phenolic OH group is acidic and loses a H• when reacted
with aq. NaOH so that the sodium salt of eugenol is formed.
~ Na··o~CH,CH=CH, + H,O

Being ionic, the attraction between this salt and water is ion- The greater interaction of
dipole interaction which is stronger than hydrogen bonds. the charged salt with water
Hence eugenol is more soluble in aq NaOH than water. causes it to be more soluble
Note: The additional teaming outcomes to be studied by A2 candidates· are shown in bold type. The A2
than the netural eugenol.
components will assess all learning outcomes and will not be limited to those in bold type.
'I
 topic 10.4 Hydroxy Compounds Page2 topic 10.4 Hydroxy Compounds Page3

(b)
~ COI!NER -~CORNER
(b) (i) 0 eH,
(I) cold, dilute manganate(Vil) ions (il) hot, concentrated manganate(VII) ions II I
eH,- e- 0 - eH,eH,eHeH,
CH,O CH,O
(ii) 3-methylbutan-1-ol is warmed with glacial ethanoic acid using concen-

HO-b-CH,,H-~H, HO-b-COOH
(iii)
trated sulphuric acid as a catalyst.

OH OH eH, eH,

(Iii) ethanoyl chloride (iv) aqueous bromine

I
eH,- eH,- eH,- eH,- eH,OH eH,- eH,- e·- eH,OH eH,-
I
r-
I
eH,OH
(c) ToundergotheiJi.iOOomethane
reaction, the compound
needed to have either of the
H eH,
CH,O CH,O structures shown:
(c) A primary alcohol has two hydrogen atoms attached to the same carbon to

"o*c,,<><-c~
H
which the hydroxyl functional group is attached. To undergo tri-iodomethane I
CH,-u-0-b-CH,CH=CH, reaction, the alcohol has a methyl and a hydrogen atom on the carbon atom CH -C-R CH,-fr-R
I I - to which the hydroxyl functional group is attached. Hence for a primary alcohol ' I
0 Br OH Br OH 0
to give a positive tri-iodomethane test, the alkyl group which is attached to the
carbon with the OH group attached has to be a methyl group. This explains why where R is either H, alkyl
ethanol is the only primary alcohol to undergo the tri-iodomethane reaction. or aryl group.
H H
(c) (i) Addition polymerisation (iil I -e
-e I- Question 3
l I

C,,O~"
(a) (i) Describe all the reaction conditions necessary to produce ethanol by
fermentation.
(ii) Suggest a suitable raw material for this process.
(iii) Why does fermentation stop when about 15% ethanol has been formed?
OH (iv) What further processing is used to obtain a product richer in ethanol?
(v) Why is this process preferred to the catalytic hydration of ethane to
(a) Primary alcohols are first make alcoholic beverages? [6]
Question 2 oxidised to aldehyde which
(b) Reaction of an alkene H with hot concentrated potassium manganate(VII)
is further oxidised to car-
produced the two acids CH3CO,H(J) and eH.eH,eO,H(K) in equimolar
(a) Explain how primary, secondary and tertiary alcohols can be distinguished boxylic acid. An alternative amounts.
on the basis of their oxidation products. [3] method from the one sug-
gested is to warm the (i) Suggest the structural formula of alkene H.
(b) The ester formed between 3-methylbutan-1-ol and ethanoic acid contrib-
alcohols with acidified potas- Acids J and K can be made from ethanol by the following routes.
utes to the flavour of ripe pears.
sium dichromate(VI) and to
(i) Draw the structural formula of the ester. I
collect the organic product e,H,OH ~ eH,eO,H
(ii) What conditions and reagents would you use in the laboratory to make by immediate distillation. J
the ester from the acid and the alcohol named above?
(iii) Draw the structural formulae of three primary alcohols that are isomers
Both primary and secondary
alcohols tum acidified potas·
Ju
of 3-methylbutan-1-ol, labelling with an asterisk any chiral carbon atom sium dichromate(VI) from Ill IV
orangetogreenwhiletertiary L ~ eH,eH,eN ~ eH,eH,eO,H
they contain. · [6] K
alcohols have no reaction.lf
(c) Explain why ethanol is thl1 only primary alcohol that undergoes the tri- aprimary alcohol is present, (ii) Suggest suitable reagents and conditions for reaction I.
iodomethane (iodoform) reaction. [3] the distillate obtained is an (iii) Suggest a structure for L, and hence suggest suitable reagents and
[NOOIP1/Q7} aldehyde which can be conditions for reaction II.
identified by reaction with (iv) Suggest suitable reagents and conditions for reactions Ill and IV. [6] (a) Yeast contains enzymes,
blue Fehling's solution which in the absence of air,
Suggested Solution: [J01/P1/QB}
yielding a brick red precipi· causeglucosetobreakdown
(a) Primary alcohols are oxidised to carboxylic acid, secondary alcohols are tate of Cu,O or reaction with to ethanol and CO,. The
oxidised to ketones while tertiary alcohol~ do not undergo oxidation. Tollen's reagent to give a Suggested Solution: reaction produces enegy
To distinguish between the classes of alcohols, acidified potassium silver mirror. Secondary which can be used by yeast
alcohols are oxidised to (a) (i) Reaction conditions necessary to produce ethanol by fermentation is to for growth and other func-
manganate(VII) solution is added to the alcohol and the mixture is warmed.
ketone which does not react react a substrate containing sugar with yeast in the absence of oxygen. tions. In the presence of air,
Decolourisation is observed for primary and secondary alcohols but not for
with Fehling's solution or The temperature of fermentation should be below 40 oe or the yeast may the usual products of respi-
tertiary alcohols. 2,4-dinitrophenylhydrazine is then added to the resultant
Tallen's reagent but gives an be killed. ration such as co,and H,O
mixture. An orange precipitate of 2,4-dinitrophenylhydrazone is observed if
the alcohol is a secondary alcohol but no orange precipitate is observed if the orange precipitate with 2,4- (ii) A suitable raw material is barley (or other starchy foods such as potato, are produced instead of
alcohol is a primary alcohol. dinitrophenylhydrazine. rice etc.). ethanol.
 topic 10.4 Hydroxy Compounds Page 4 topic 10.4 Hydroxy Compounds PageS

(iii) The yeast that catalyses the reaction is killed by the high concentration
~CORNER ~CORNER
of ethanol. (iii) NH,-Q-o-
(iv) Fractional distillation.
(v) The flavour and smell of the alcoholic beverage is conferred by the sub-
(c) (i) Ethanoyl chloride, CH,COCI
strate used and the other products formed by the reaction of yeast with
the substrate. Hence alcoholic beverages formed from the fermentation of (ii) PCI,fPCI,fSOCI,
grape juice taste and smell different from that obtained from the fermen-
tation of barley. The ethanol produced by the catalytic hydration of ethene
does not have the unique flavour and smell desired in alcoholic beverages.
Question 5
(b) (i) H H
I I (a) There are four structural isomers of C,H,OH. The structure of one isomer,
CH,- C = C- CH,CH, 2-methylpropan-2-ol, is shown below.
(ii) Reagents for reaction I is potassium manganate(VII) solution acidified with
dilute sulphuric acid and the condition is warming the reaction mixture. CH,
I
(iii) L is CH,CH,Br (or CH,CH 2 CI). Suitable reagent is PBr, (or PCI,) and CH -C-CH
condition is room temperature. ' I '
(iv) Reagents for reaction Ill is ethanolic potassium cyanide and the condition OH
is reflux.
tertiary
Reagents for reaction IV is dilute sulphuric acid (or dilute hydrochloric
acid) and the condition is reflux.
(i) Draw the structures of the other three isomers of C ,H,OH and classify
each as either primary, secondary or tertiary.
Question 4

The common analgesic drug paracetamol has the following structure.

isomer
CH3CONHOOH

(a) Name the two functional groups in the paracetamol molecule

.............................................................. and ........................................................... [2] classification
(b) Draw the structural formulae of the molecules or ions formed when
paracetamol reacts with (ii) State how 2-methylpropan-2-ol could be distinguished by a simple
chemical test from any one of the other three isomers. State which
(i) Br,(aq), (b) Due to the phenolic-OH isomer you choose.
(ii) NaOH(aq) in the cold, group, the benzene ring is
activated towards electro- isomer
(iii) NaOH(aq) under reflux. [3]
philic substitution so that test
(c) Paracetamol can be synthesised by reacting 4-aminophenol with compound two Br atoms are added to
X. results [4]
the 2- and 6- position with
H2 N O O H +X ~ paracetamol respect to the -OH group. (b) 2-bromobutane reacts with aqueous hydroxide ions to give bulan-2-ol.
'·
Phenolic-OH is acidic (i) Write an equation for this reaction.
(i) Suggest a possible identity of X. enough to react with aq
NaOH so that the satt is (ii) State what type of reaction this is.
(ii) What reagent would you use to convert ethanoic acid, CH,CO,H, into formed on addition with cold
~ ~ (iii) Describe and explain in detail the mechanism of this reaction.
aq NaOH. The C- N bond
[J02/P4/Q5] in the amide group is not (iv) When chiral (optically active) 2-bromobutane reacts with aqueous hy-
broken at room temperature droxide ions, the optical isomerism of the product is reversed. Suggest
Suggested Solution: and requires refluxing to and explain with the aid of displayed formulae, why the optical isom-
break when reacted with erism is reversed.
(a) Phenolic-hydroxyl and amide aq. NaOH. In your answer, mark the chiral centre with an asterisk('). [7]
(b) (i) Br (c) Due to delocalisation ofione
(c) Write the displayed formula of the product when 2-methylpropan-2-ol is
pair of electrons on 0 of
heated with an excess of concentrated sulphuric acid. [1]
CH,CONH-QOH -OH group into benzene
ring, phenolic-OH does not [N02/P2/Q5]
Br react with carboxylic acid.
Hence to convert phenol to
(ii) CH,CONH - Q - o - phenolic ester, acid chloride
needed to be used.
topic 10.4 Hydroxy Compounds Page6 topic 10.4 Hydroxy Compounds Page 7

Suggested Solution:
~CORNER ~CORNER
Question 6
(a) (i)
(a) State the reagents and conditions needed to convert ethanol into
CH, (i) bromoethane,
CH,-CH,-CH,-CH, CH,-CH,-CH -CH, I
isomer CH,-CH-CH, (ii) ethanal,
I I I (a) (i~ Acidified potassium
OH OH OH (iii) ethene. [3]
manganate(VII) may also be
I II Ill used to distinguish 2-methyl- [N05/P3/08(a) Or]
propan-2-ol from the other
classification primary secondary primary two isomers. This is because Suggested Solution:
alltheotherisomersareeither
(ii) isomer: I primary or secondary (a) (i) PBr,
test: Warm the· alcohol with a few drops of aqueous potassium alcohols which can be (ii) K,Cr,o,, dilute H,so,, heat with immediate distillation.
manganate(VII} acidified by dilute sulphuric acid. oxidised by KMnO, into
carboxylic acids or ketones (iii) Concentrated H,SO,; heat.
results: 2-methylpropan-2-ol does not decolourise potassium
manganate(VII) but isomer I decolourises purple acidified potassium and KMnO, is reduced to
manganate(VII). colourless Mn'•. However,
2-methylpropan-2-ol is ater- Question 7
tiary alcohol and cannot be
(b) (i) CH 3 CHBrCH 2CH 3 +OW ~ CH 3 CH(OH)CH2 CH 3 + Br- oxidised by KMnO, so that Ethanoic acid, CH,CO,H, is fomned as vinegar by the bacterial oxidation of
no decolourisation is ob- ethanol present in wine and other solutions.
(ii) Nucleophilic substitution
served when this alcohol
(iii) In 2-bromobutane, carbon-2 at which the partially negative bromine is is warmed with acidified CH 3CH 20H + 2[0] ~ CH3 C0 2 H+ H,O
attached to is partially positive and is susceptible to attack by the KMnO,.
Ethanoic acid can also be formed in the laboratory by the oxidation of ethanol.
nucleophililic OH-. The OH- attacks from the side furthest away from bro- Altematively,K,Cr,O,,acidi-
mine, forming a pentavalent transition state as C - OH bond is being fiedwith H,So, may also be (a) (i) What oxidising agent is used for this laboratory reaction?
fomned while C- Br bond is being broken. The subsequent loss of bro- used. The 1' and 2' alcohols
mide ion results in the fomnation of butan-2-ol. (ii) What colour change would be observed?
will reduce it to green Cr".

J- from ................................................... to ·········-········-··-·······-·-··········-········· [2]

~
The triiodomethanetest can
H_,. CH, .::- ::-
CH,._:.Ii+ &-- slow &-- ' _-- H &-- H
.::;_.;CH, be used to distinguish 2-
_ C-Br- HO----C---Br - H O - C +8( methylpropan-2-ol from iso- When ethanoic acid is prepared in this way in the laboratory, the reagents are
OH'-.__....)f/
CH,CH,
I
CH,CH,
". CH,CH, mer II. isomer II, having the heated under reflux for some time before the ethanoic acid is separated.
-C(CH,)HOH group, reacts (b) (i) Why is the reaction carried out by heating under reflux?
with alkaline aqueous
rear side attack pentavalent transition state butan-2-ol iodine to give a yellow pre- (ii) What would be the main organic compound fomned if, instead of heat-
cipitate oftriiodomethane but ing under reflux, the reagents were heated together and the products
(iv) The attack of the OH- is from the side furthest away from bromine, as immediately distilled off? (2]
not2-methylpropan-2-ol.
shown in the diagram in (b)(iii). Subsequent loss of Br results in a product
which has configuration reversed to that of the original reactant. (b) (iv} The question asks for (c) Ethanoic acid is manufactured from methanol, CH,OH, by reacting it with
carbon monoxide in the presence of a catalyst containing rihodium metal
the displayed formula of
H and iodide ions.
the product so that all bonds
HH H I in the product need to be CH,OH +CO ~ CH3 C0 2H
I ,, = C-H
H-e-.:-·
I C-Br
·'/1 shown. The reaction proceeds in a number of stages.
H-0-C"H/H
H
H-C
I c
(c) Heating alcohol with excess
of concentrated sulphuric
(I) One stage in this process is the reaction of methanol with hydrogen
iodide.
I 'H / 'c-H acid resutts in dehydration,
H-C H / ' What organic compound is formed in this reaction?
I 'H H H with the fomnation of an alk-
ene. 2-Methylpropan-2-ol de- (ii) A later stage involves the conversion of an intemnediate compound.
H
hydrates to form 2-
2-bromobutane butan-2-ol CH 3C=O ~ CH 3C=0
methylpropene:
CH, H CH, I I
(c) H I cone H,SO, I I OH
I CH-C-CH
I ~ H-C=C-CH 3 +HO What type of reaction is this?
3 1 2 [2]
H-C-H
H
I
I H
I
OH Note that the question asks
for the displayed formula
(d) Methanol can be converted into ethanoic acid in the laboratory in a three-
stage process.
H-C=C-C-H of the product so that all
I bonds in the product need to step I step II step Ill
CH 3 0H - - - CH 3 I - CH 3C N - CH 3C02 H
H be shown.
topic 10.4 Hydroxy Compounds Page 8 topic 10.4 Hydroxy Compounds Page9
~CORNER ~CORNER
What reagent{s) and conditions are used in each step of the conversion? (b) Suggest reagents and conditions for converting 1-naphthol into each of tl)e
following compounds.
step I reagent(s)

a¢'&
conditions (i) OH

step II reagent(s)
conditions

step Ill reagent(s)

(6] Br
conditions
{N07/P2/Q5]
(ii) OH

Suggested Solution:
(a) (i) acidified potassium dichromate
(ii) from orange to green

{b) (i) To avoid escape of low boiling reactants and to ensure complete oxida-
o¢ N02

tion of alcohol. (2]

(li) ethanol (c) Compound Dis an isomer of 4-nitro-1-naphthol. Dis formed as a by-product
during the reaction in b(ii). It can be converted into 2-amino-1-naphthol, E.
(c) (i) lodomethane
(ii) Nucleophilic substitution

{d) step I reagent(s): red phosophorus and iodine

conditions: heat

step II reagent(s): KCN in aqueous ethanol D E

conditions: heat under reflux
(i) Suggest the structural formula of the isomer D.
step Ill reagent(s): aqueous mineral acid
(ii) Suggest reagents needed for reaction I.
conditions: heat
(iii) Suggest the structural formula of the compound formed when
compound E reacts with an excess of CH3 COC/. (3]

Question 8 (d) When an alkaline solution of compound E is added to a solution containing

Cu'•(aq) ions, a pale green-blue precipitate F forms. Analysis of F shows
The phenol 1-naphthol is a starting point for the manufacture of carbaryl, an that its formula is Cu(C,H,NO),(H,O),.
insecticide and a plant groW1h inhibitor.
(i) Complete the following structural formula of F.

o6 .~oH OH

1-naphthol c carbaryl
When an excess of concentrated NH3(aq) is added to F, the precipitate
dissolves to form a deep blue solution.
(a) (i) Suggest a structure for the intermediate C and draw it in the box above.
(li) State the formula of the ion responsible for the deep blue colour.
(ii) Name the functional groups in carbaryl.
(iii) What type of reaction is occurring here? [3]
(iii) Suggest structures for the three products formed when carbaryl is
{N07/P4/Q6]
hydrolysed.
(iv) What reagents and conditions would you use for this hydrolysis? [7]
 topic 10.4 Hydroxy Compounds Page 11
10.4 Hydroxy Compounds Page 10
~CORNER
topic
~CORNER
Suggested Solution: Question 9
(a) (i) (a) In the following boxes draw the structural formulae of three alcohois having
CH 3NH-C=O

oo·
straight (i.e. unbranched) chains, with the molecular formula C,H,O.
I
0
OH

o6 1-naphthol
+NaOH

c
+CH 3 NHCOC!

o6carbaryl

(a) (i) Do not show A B c

[2]
(ii) amide, ester covalent bond between '0'
and 'Na', i.e. 0--Na Use the letters A, B or C as appropriate when answering the following
OH
questions. Each letter may be used once, more than once or not at all.

(iii) C02, CH 3 NH2,

00
(iv) dilute HC/, heat at about 80 'C
(a) (iii)

CH3-NH+~=O
0
(b) Which of the alcohols are chiral?
(c) (i) Which of these alcohols react with alkaline aqueous iodine?
(ii) Describe the observation you would make during this reaction.
(iii) Draw the structural formulae of the products of this reaction.
(1]

(4]

(b) (i) aqueous bromine 00 (d) Draw the structural formula of the product obtained when each of the alcohols
A, B and C is heated with an excess of acidified K,Cr,O,(aq).

ro•o,
(ii) dilute nitric acid Amide & ester groups are
hydrolysed as shown india-

I I
A---..
gram.
OH OH

W""'
(o) (l) I

D E
I I
c-
I
(ii) Tin & dilute hydrochloric acid

(iii) I (3]

o5c:~cocH, (e) One of the many suggestions for converting biomass into liquid fuel for
motor transport is the pyrolysis (i.e. heating in the absence of air) of cellulose
waste, followed by the synthesis of alkanes.
(i) In the first reaction, cellulose, (C,H 100 5),. is converted into a mix1ure of
carbon monoxide and hydrogen. Some carbon is also produced.
Complete and balance the equation for this reaction.

a H2~ ~2xo
(d) (i)
(CsH,oOsln ·_. + +------

u>r<o ~d
(ii) The second reaction involves the combination of CO and H, to produce
alkanes such as heptane.
7CO + 15H2 -+ C7H16 + 7Hp
heptane
2
H OH2 Using the value of 1080 kJ mol·' as the value for the C = 0 bond energy
(d) (iQ (Cu(HN 3 )4 (H20hf in CO, and other relevant bond energies from the Data Booklet, cal-
is also a correct answer culate the t.H lor this reaction. (5]
(ii) (Cu(NH 3 ),j"
2 {J09/P4/05]
but not (Cu(NH 3 ),] '.
(iii) Ligand exchange reaction

- ~
·topic 10.4 Hydroxy Compounds Page 12 topic 10.4 Hydroxy Compounds Page 13
~CORNER
Suggested Solution: (c) Draw the following formulae. ~CORNER
(a) (i) the structural formula of pentan-1-ol
(ii) the displayed formula of pentan-2-ol
(iii) the skeletal formula of pentan-3-ol
OH OH OH (3]
I I I When one of the three pentanols in (c) is dehydrated, alkenes with two different
structural formulae are formed.
CH 3CH 2CH 2CH 2CH2 CH 3CH 2CH 2CH CH3 CH3CH 2CH CH2CH3
(d) Identify this alcohol and give the structural formula of each alkene.

A B c
(b) B

(c) (i) B (c) ~) Alcohols having

(ii) Yellow precipitate OH
(iii) CHI 3 (1odoform) and CH 3CH2 CH2C0 2Na
-
I
C- CH, group
(d)
will give iodoform test.
alkene 1 alkene 2
A-----<~ CH3CH2CH 2CH 2C02H [3]

(d) Primary alcohol will oxidise A number of alcohols wit~ molecular formula C,H,O are branched chain com-
to carboxylic acid and sec- p_ounds ~nd may be considered as derivatives of butanol or propanol with alkyl
ondary alcohols will oxidise Side cha1ns.

B to ketones.
-----<~ CH 3CH 2CH2COCH 3 (e) (i) Draw the structural formula of the derivative of propanol that has the
molecular formula c,H, 20.

(ii) Draw the stru~tur~l formula of the organic compound that will be present
when th~ den~~t~ve of propanol you have given in (i) is heated under
reflux With ac1d1f1ed potassium dichromate(VI). [2]
c CH 3CH 2COCH 2CH3
[N09/P2/Q5)

Suggested Solution:
5n H, 5n CO nC
(e) (I) (CsH,oOsln--> - - - - - + ------- + ------- (a) reagent(s): 2,4-dinnrophenylhydrazine.
observation: yellow precipitate.
(ii) !!.H =7(C = 0)+15(H-H)-6(C-C)-16(C-H)-14(H-O) (e) (ii) t.H = bonds broken -
bonds formed.
!!.H = 7(1 080) + 15(436)- 6{350) -16(410) -14(460) (b) observation: S~dium will dissolve and colourless gas will be given.
=7560+6540-2100-6560-6440 = -1000 kJ mor' equation: C4H9 0H+Na--> C4 HgONa+~~

Question 10
The fermentation of starch or molasses using the bacterium Clostridium (ii) HHHOHH
acetobutylicum, produces a mixture of propanone and butan-1-ol. I I I I I
H-c~c-C-C-C-H
(a) Give the reagent(s) and state what would be observed when one test is
carried out to confirm the presence of propanone in a mixture of propanone I I I .I I
and butan-1-ol. (2] H H H H H

(b) What will be observed when a small piece of sodium metal is dropped into
(iii) OH
a dry sample of bulan -1-ol? Write an equation for the reaction that takes
place.

The molecular formula C,H,p represents a number of alcohols.

Three alcohols with molecular formula C,H,p are straight chain pentanols.
(2]
Vv
 topic 10.4 Hydroxy Compounds Page 14
topic 10.4 Hydroxy Compounds
~-CORNER Page 15
(d) name of alcohol: pentan-2-ol
(iii) The material labelled X can be broken crockery, broken brick or pumice. ~CORNER
(d) Pentan-2-ol will produce Give the chemical formula of a compound that is present in one of
these materials.
two different alkanes i.e.
pent-1-ene and (iv) State another reagent that could be used to produce propene from an
pent-2-ene.
CH 3CH 2CH 2CH = CH 2 CH3 CH 2CH = CHCH3 alcohol. [5]
(c) Give the structural formula of the organic product formed when propene
reacts separately with each of the following substances.
(i) bromine

alkene 1 alkene 2 (ii) cold, dilute manganate(VII) ions

(iii) hot, concentrated manganate(VII) ions
[3]
(d) Propene may be polymerised.
(e) (i) CH,
(i) What is the essential condition for such a polymerisation?
I (ii) The disposal of waste poly(propene) is very difficult.
H,C - C- CH 20H
I Give one important reason for this. [2]
CH,
{J10/P2/Q5}

(ii) CH 3
Suggested Solution:
I
H C - C-C0 H
3 2 (a) (i) Propane-1-ol or Propane-2-o\.
I OH
CH,
(ii) /'....._ OH or A
(iii) Elimination or dehydration of alcohol.
Question II
(b) (i) Carbon black soot is produced by decomposition of alcohol on strong
Alkanes such as propene can be readily prepared from alcohols in a school heating.
or college laboratory by using the apparatus below.
(ii) Delivery tube is removed immediately to avoid sucking back of water into
the hot tube.
propene (iii) Sio, (b) (iii) X is a catalyst which
is made of Si02 or Al 20 3
(iv) Hot cone. H,so, or compounds called
_-_-.!fl___ _ Aluminosilicates.
--.0.-
(c) (i) CH,CHBrCH,Br
(ii) CH,CH(OH)C_H,OH
mineral wool
soaked with (iii) CH,COOH
the alcohol
(d) (i) Very high pressure or Ziegler-Natta catalyst.

(ii) Poly propene is non-biodegradable. Hence it is not naturally decomposed

and produces poisonous fumes on combustion.
(a) (i) Give the name of an alcohol that can be used in this apparatus to
prepare propene.
(ii) Draw the skeletal formula of the alcohol you have named in (i).
(iii) What type of reaction occurs in this case? [3]
(b) (i) During the reaction, the material X becomes black in colour.
Suggest the identity of the black substance and -.suggest how it is
produceQ during the reaction.
(ii) At the en'd of the experiment, when no more propene is being pro-
duced, the delivery tube is removed from the water before the appa-
ratus is allowed to cool.
Suggest why this done.

;,.,_~;ot:_.:: ::!{,:; .~ ()
~~1~~---
 topic 10.5 Carbonyl Compounds
Pagel

~CORNER
7opic 10.5
q?fii) !N f1 /JJ
Carbonyl Compounds IJ \!!/ t.r I.J \!.ol q;:;ening ....... .

Question I

The timescale that collects in kettles in. hard water areas is mostly cal .
Content carbonate. I~ can be removed fairly harmlessly by a warm solution of vin Clum
~ht·lch conta1~s ethanoic acid. The timescale dissolves with fizzing and :gs~:
Aldehydes (exemplified by ethanal) 1
u 1on o calc1um ethanoate remains.
(Q Oxidation to carboxylic acids. (a) Write a balanced equation for the
(ii) Reaction with hydrogen cyanide. calcium carbonate.

(iii) Characteristic tests for aldehydes.

2 Ketones (exemplified by propanone and phenylethanone)
(Q Reaction with hydrogen cyanide.
(ii) Characteristic tests for ketones. (b) ~he~ 0.10 g of G was injected into a gas syringe at a temperature of 383
an a pressure of 1.0 x 10' Pa (1 atm), 55 em' of vapour were produced
Calculate the relative molecular mass of G ·
. [2]
Learning Outcomes (c) Compound G is neutral and water-soluble. G does not react with sod·
Candidates should be able to: ~e!al nor with Fehling's solution but it does react with alkaline aque~u~
IOdine. Suggest a structural formula for G. Justify your answer b I
(a) describe to these properties of G Y re erence
. [5]
(i) the formation of aldehydes and ketones from primary and secondary alcohols (d) Constru_ct a balanced equation for the formation of G by the action of heat
on calc1um ethanoate.
respectively using Cr20,'-tH•. [1]
(e) Suggest a ~imple one-step test you could carry out to confirm the identi
(ii) the reduction of aldehydes and ketones e.g. using NaBH4 •
obi the fu~chonal
group present in G. You should give the reagent and th~
(b) *describe the mechanism of the nucleophilic addition reactions of hydrogen cyanide o servat1on you would make
. [2]
with aldehydes and ketones. (f) S~g~est the structural formula of the organic product you might expect when
ca Clum propanaote ' (CH,CH,CO,),Ca, is heated strongly. [1]
(c) describe the use of 2,4-dinitrophenylhydrazine (2,4-DNPH) reagent to detect the pres-
ence of carbonyl compounds. [JOOIP1/Q8}

(d) deduce the nature (aldehyde or ketone) of an unknown carbonyl compound from the Suggested Solution:
results of simple tests (i.e. Fehling's and Tollens' reagents; ease of oxidation).
(a) 2CH3COOH(aq) + CaCOa(s) ------+ (CHaC00)2Ca(aq) + C02(g) + ~0(/)
(e) describe the reaction of CH, CO- compounds with alkaline aqueous iodine to give tri-
iooomethane. (b) Assuming ideal behaviour, pV = nRT.
5
.. n= pV = 1.0x10 x55x10-6
1.728 X j 0-3
RT 8.31x383

M, ofG=~=57.9
n
(c) Compound G is propanone: CH,COCH,

CH,COCH, is neutral and water soluble and does not react with sodium
hydroxyl group) nor with Fehling's solution (not an aldehyde) Ha · t(hno
-GH C - 0 group prop . · v1ng e
, - • anone reac1s w1th alkaline aq. 12 to give triiodomethane:

Note: The additional learning outcomes to be studied by A2 candidates are shown in bold type. The A2
components will assess all learning outcomes and will not be limited to those in bold type.
~-~m~ 1
CH3COCH3 + 31 2 +40W ------+ CH3coo- +CHJ + 3!- + 3 ~ 0
3

CH ,CO~H, has a relative molecular mass of 58 which agrees with that cal
-
topic 10.5 Carbonyl Compounds Page2 topic 10-5 Carbonyl Compounds Page 5
~CORNER
{d) {CH3COOJ,Ca{s) ~ CH 3COCH 3 {g)+CaC0 3 {s) (ii) R can be distinguished from a
using sodium. Effervescence of hydrogen ~CORNER
is observed when sodium is added to R while no H, is evolved when
(e) The functional group is the carbonyl group. To test for its presence, a few sodium is added to a.
drops of 2,4-dinitrophenylhydrazine is added to G. Formation of orange crys- (d) CH,
tals of 2,4-dinitrophenylhydrazone confirms the presence of the carbonyl group. (Q I
(f) CH CH COCH,CH 3 (CH 3CH 2COO),Ca(s) ~
_....c,
3 2 CH, \H CH,
CH 3CH 2COCH 2CH 3 (g) + CaC0 3 (s) I I
CH,....._ COOH
CH,
Question 2 I
(a) (~ Phenol reacts with _....CH....._
The compound 4-ethylphenol, E, ·and chlorinated products derived from it have aqueous chlorine to give a CH, CH,
useful antiseptic properties. polychlorinated phenol with
Cl substituted into 2-,4- and
CH,CH,-Q-OH 6-position. Eis aphenol with Question 4
an alkyl group at the 4-po-
E sition so that the product (a) Draw the structures of a secondary alcohol and a tertiary alcohol of your
fonnBd by E has Cl substi- choice. Describe a simple one-step reaction you could carry out to distin-
Depending on the conditions of the reactions, compound E can react with
tuted into the 2- and 6-posi- guish between a secondary and a tertiary alcohol. You should state re-
chlorine in two different ways, giving the two isomers F -and G. In these reac- agents, conditions and observations with ·each alcohol. [3]
tions. Hydroxyl group is a
tions chlorine reacts in a similar manner to bromine. stronger director than ethyl
(b) Ester B (M,, 116) is used in synthetic fruit flavours. When B is subjected {a) Other secondary alcohols or

I
C8H8CI20
group so that the Cl is sub-
C8H8C/20 E to hydrolysis, an acid C and an alcohol D are produced. tertiary alcohols can also be
C/2 (aq) stituted into the 2- and 6-
When 1.00 g of the monoprotic acid Cis titrated with 0.500 mol dm"" sodium used. A secondary alcohol
F G positions relative to the hy-
hydroxide, 33.0 em' of hydroxide are needed for neutralisation. Alcohol D has two alkyl groups at-
droxyl group {and not the 2-
(a) (i) Suggest a structural formula for compound F. reacts with alkaline aqueous iodine giving a precipitate E. D exists as a tached to the carbon to
position relative to the ethyl

I
(ii) Explain whether you would expect F to be more or less acidic than pair of isomers, both of which are oxidised to ketone F. This ketone also which the -OH is attached
group).
phenol. [3] reacts with alkaline aqueous iodine, giving the same precipitate E and a while a tertiary alcohol has
{i~ Cliselectron-withdraw- solution containing a sodium salt G. three alkyl groups attached
{b) Compounf G reacts with NaOH{aq) to give H, C,H,p,, which immediately ing and increases the acidity to the carbon to which the
losses water to give J, C,H,O,. Compound J is insoluble in water but it of F with respect to phenol. (i) Suggest suitable reagents and conditions for the hydrolysis of B. -OH is attached. Besides
dissolves in NaOH{aq). It reacts with 2,4-dinitrophenylhydrazine and with The presence of the ethyl (ii) Calculate the M, of acid C, and hence identify it. potassium manganate(VII),
alkaline aqueous iodine, but not with Fehling's solution. group, which is electron- potassium dichromate(VI)
(iii) Explain and illustrate the type of isomerism shown by D.
(i) Identify and draw the structural formulae of compounds G, H and J. donating, decreases the ecid- may also be used.
Explain the reactions describe and write equations where appropriate. ity of F with respect to phe- (iv) Describe and explain the reactions of D and of F with alkaline aqueous Note that even though for
nol. However the Cl present iodine, identifying E and G.
(ii) Suggest suitable conditions for reaction II. [9] the two alcohols shown,
are found in the 2- and 6- (v) Suggest the structural formulae of· D and F. alkaline iodine can be used
[NOOIP1/08) positions and has astronger to distinguish the second-
effect than the ethyl group in (vi) Hence identify the original ester B and write a balanced equation for
ary alcohol from the tertiary
the4-postlion so that overall, its hydrolysis. [9]
alcohol, alkaline iodine is not
Suggested Solution: the acidity of F is expected {J01/P1/Q7) generally accepted as the
(a) (i) The structural formula of F is tobehigherthanthatofphenol. answer. This is because
{b) 0) The fact that G reacts not all secondary alcohols
Suggested Solut(on:

CH,CH,*OH with aq. NaOH shows that

the two Clare attached to the
alkyl group rather than the
(a) The structures of a secondary alcohol and tertiary alcohol are shown below:
H H
react with alkaline iodine to
give CHI, but only those
with the CH,CH(OH)-struc-
ture react with alkaline io-
ber.zene ring. The spontane- CH,
Cl
ous loss of water from H secon dary
I I
CH -C-C-CH I tertiary dine. Hence ~ the sec-
alcohol ' 1 1 ' CH-C-CH ondary alcohol chosen is
(ii) The chlorine atoms found in the 2- and 6-positions are electrons-withdraw- gives the information that the ' I ' alcohol
ing so that they stabilise the anion formed by enhancing the dispersal of OH groups must be attached H OH OH CH,CH,CH(OH)CH,CH,,
the negative charge into the benzene ring. Since the anion formed by the to the same Cand hence the alkaline iodine will not be
The secondary alcohol may be differentiated from the tertiary alcohol by able to differentiate tl from
dissociation of F is more stabilised than that formed by phenol, F dissociates two Cl in G must be on the warming the alcohols with potassium manganate(VII) solution acidified with
to a greater extent than phenol and is thus a stronger acid than phenol. same C. Thefactthat J does the tertiary alcohol shown.
dilute sulphuric acid.
not react with Fehling's so- However, the difference in
(b) (I) The structural formulae of G, H and J are shown below: With the secondary alcohol, purple acidified potassium manganate(VII) solu- reaction with an oxidising
lution shows that J is not an
tion is decolourised to Mn'' as the secondary alcohol is oxidised to a ketone. agent such as KMnO,JH• is
C/ OH aldehyde so that the two Cl
With the tertiary alcohol, purple acidified potassium manganate(VII) solution always observed between
CH,-~~-Q-oH
atoms must be attached to
the carbon attached to the is not decolourised as tertiary alcohols are not oxidised. a secondary alcohol and a
CH,-t-Q-OH CH,-f-Q-oH tertiary alcohol and should
benzene ring rather than the (b) (i) The reagent used for the hydrolysis of B is dilute sulphuric (or hydrochlo-
C{ OH OH carbon further away. thus be used as a distin-
H J ric) acid and the condition is refluxing.
G guishing test.
 topic 10.5 Carbonyl Compounds Page 7
Page6
topic 10.5 Carbonyl Compounds
~CORNER ~CORNER
33 0 Questio11 5
(ii) No. of mol of OW = · x 0.500 = 0.0165
1000
(a) The four compounds below may be distinguished by simple chemical tests.
No. of mol of the monoprotic acid C = no. of mol of OH- = O.o165
CH3CH2CH2CH20H CH3CH2C~CHO CHaCH2CH = CH CH CH COCH
1 00 A 2 3 2 3
M ' oI ac<"dC = 0.0165
·
=
606
. B C D
For each of the compounds A 1 0
Let C have a molecular formula of RCOOH. from the other three and descri~e t~=:~sae reatgent whhich distinguishes it (a) (i) A is an alcohol which
. rva <ens t at would be made is the only compound
For 1 mol of C, mass of R = 60.6- (mass of COOH in 1 mol)
(i) A Reagent · amongst the four that con-
. =60.6-(12.0+16.0x2+1.0)=15.6 tains a H acidic enough to
Observation
R is likely to be CH, which has a mass of 15.0 per mol of C. react with sodium. Sodium
(ii) B Reagent hydroxide or sodium car.
Hence C is ethanoic acid, CH,COOH. Observation bonate cannot be used as
(iii) Isomerism shown by D is optical isomerism. This type of isomerism arises the alcoholic-OH group is
from the tact that D contains a chiral carbon whereby the four groups. (iii) C Reagent not acidic enough to react
attached to this carbon are different. The isomers are mirror images that Observation with these bases.
cannot be superimposed on each other and each isomer rotates plane- PCI, may also be used as
polarised light in an equal but opposite direction from each other. (iv) D Reagent A will react with PCI to give
Observation white fumes of Hd. How-
CH 3 [8] ever since PCI, fumes with
I
_.)~··.,, {b) ~:~:~~und A can be converted into compound D by the reaction sequence moisture in the air, white
fumes may also be observed
C,H, H OH
with the rest due to
C s~p1 moisture in the air. Acidified
As can oe seen later, D is CH,CH(OH)C,H,, and the optical isomerism H3CH,CH,CH,OH _ _.:..__.., CH,CH,CH =CH,
KMnO, cannot be used as
shown by it is illustrated above.
A, B and C will decolourise
A lstep 2
(iv) D is first oxidised by alkaline aqueous iodine to form a methylketone. The hot acidified KMnO,.
methylketone reacts with alkaline aqueous iodine to give the yellow pre- C step 3
H,CH,COCH, CH 3CH,CH(OH)CH, (iO Alternatively, Totten's
cipitate of triiodomethane (E) and a sodium carboxylate salt (G).
D reagent may be used. on
F, is a methylketone which is oxidised from the alcohol D. It is a warming B with Tollen's
methylketone and reacts with alkaline aqueous iodine to give the yellow ~tate the reagents and the conditions in each of the three steps. reagent, a silver mirror is
precipitate of triiodomethane (E) and a sodium carboxylate salt (G). (1) Step 1 observed. B being an alde-
E is triiodomethane, CHI, while G is sodium propanoate, (ii) Step 2 hyde is easily oxidised so
that it is the only compound
CH,CH,COO-Na'. (iii) Step 3 that reacts with mild
[3]
(v) Let B have the molecular formula of CH,COOC,H 1,,11" oxidising agents such as
{J01/P2/Q4]
Fehling'ssolutionandTollen's
12.0+ 1.0x 3 + 12.0+ 16.0 x 2 + 12.0x z + (2z + 1) x 1.0 = 116 reagent
::::> 12Z+2Z+ 1 = 116-(12.0+1.0x 3+12.0+ 16.0x2) =57 Suggested Solution: 2,4-dinitrophenylhydrazine

(a) {I) A Reagent: sodium metal

cannot be used as both e
::::> z= 57-1 = 4 and D will react with nto
14 Observation: On addition of sodium to A, bubbles of colourless and form orange precipitate.
Hence B is CH,COOC,H, and D is C,H,OH. odourtess hydrogen gas which 'pops' with a lighted splinter
are observed. (ifi) The reaction needed
From the informaton given, D contains one chiral carbon since it is op- to take place in the dark
tically active and contains a CH,CH(OH)- group since it reacts with alka- (li) B Reagent: Fehling's solution since with uv light, bromine
line aqueous iodine to give CHI,. Hence D is butan-2-ol and correspond- Observation: On ~~rmin~ B with the blue Fehling's solution brick-red water may be decolourised
ingly, F is butanone: prec1p1tate IS formed. ' by the other three com-
pounds due to free radical
H H H (iii) C Reagent: bromine water
substitution since the other
I I I Observ. alien: .On add"<ng b. rom<~e
· water to C in the dark, the bromine water compounds contain c-H
D CH-C-C-CH CH-C-C-CH F
3 I I ' 3 I II ' IS decolounsed Immediately. bonds.
H OH H 0
(iv) D Reage.nt: aqueous iodine and aqueous sodium hydroxide (iv) Dis the only compound
(vi) B is CH,COOCH(CH,)CH,CH,. ·o
Observation·· On warming . WI·th a m1>cture of aqueous iodine and
outofthefourwhichcontains
the-CH,C = 0 group which
a9ueous sodium hydroxide, a yellow precipitate of
CH COOCH(CH )CH 2CH 3 + Hp ----> CH3COOH + CH 3CH2CH(OH)CH3 reacts with aqueous alkaline
3 3 tmodomethane is observed.
iodine to give triiodo-meth-
ane.

-w'"-'·"""""'""'" __,.__ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ __
 PageS
topic 10.5 Carbonyl Compounds
~CORNER topic 10.5 Carbonyl Compounds Page9
{b) (i) Step 1
Reagents: concentrated sulphuric acid
(b) (i) Nucleophilic addition. ~CORNER
Conditions: Excess concentrated sulphuric acid and reaction at a Conditions: room temperature with a little amount of aq sodium hydroxide (b) Cyanide ions are produced
temperature of 170 •c. added as catalyst. The solvent used is water. at the fast step so then only
a small amount of OH·
(ii) Sodium hydroxide reacts with HCN to produce the nucleophile CN- : needed to be used to gener-
(ii) Step 2
ate CN· needed in the slow
Reagents: concentrated sulphuric acid followed by water OH" + HCN ---4 H20 + CN" step.
Conditions: The alkene is mixed with cone H,SO, at room temperature. In the fast step, besides
CN· then attacks the li + carbonyi·C of propanone to produce an anionic
Water is then added and the mixture is warmed. intermediate: HCN, H" may also be ex-
tracted from H,O which is
(iii) Step 3 used as a solvent:
(os- o· o·
Reagents: potassium manganate(VII) solution and dilute sulphuric acid
Conditions: Warming the mixture of alcohol and acidified KMnO,(aq).
gs. ~
I
c d\.....H0aH ~ CH,...-dI'CH,
OH
+OH
CH: j'CH, CH:I'cH, CH,...-I'CH, •• ,_
CN anionic CN CN
CN- intermediate The OH· formed may react
Question 6 The anionic intermediate then extracts a proton from HCN to form a with HCN to form more
cyanohydrin as a product: CN·.
(a) For each of the following compounds, describe one simple chemical test
by which you could distinguish it from propanone, CH,COCH,.
(a) (i) Since propanone is a
o· OH Besides using sodium
I\ (! I hydroxide, acatalytic amount
(i) methyl ethanoate, CH,C02CH 3 ketone, it reactswith
2,4-dinitrophenylhydrazine
C~H-CN ~
CH: I'CH, 6 • o- cH;Y'c + cN· of sodium cyanide may be
(ii) propanal, CH,CH,CHO to form 2.4· CN H, used instead to provide
CN
For each test state th.e reagents you would use, and the observations you dinitrophenylhydrazone CN· needed for the initial
would make witt) each compound undergoing the test. [4] which appears as an orange cyanohydrin nuclecphilic attack.
ppt. Methyl ethanoate is an
(b) (i) What type of reaction is undergone when propanone reacts with hy- ester and does not react with (c) The carbonyl compound E is a ketone with the structural formula of: 0
drogen cyanide, and what conditions are necessary for the reaction to 2.4-{Jinitrophenylhydrazineso II
that no orange ppt. is formed. 0 a....-c, b c
take place?
Alternatively, thetriiodoform
II CH, CH,-CH,
(ii) Briefly describe the steps in the mechanism of this reaction. [4] test may be used to distin-
. . . c, (c) Assignment of peaks:
CH, CH,-CH,
(c) Compound E is carbonyl compound with the molecular formula C,H.O- Fig .. guish methyl ethanoate from H• gives rise to the singlet
propanone. The two com- E is not an aldehyde since no proton corresponding to the chemcial shift (no H on neighbouring C)
7.1 shows its nmr spectrum. Suggest a structure for E, based on your
pounds are warmed with (around 10) of an aldehydic H is observed. with li = 2.
predictions of the number of protons in each group of the spectrum, and aqueous iodine and sodium
the number of protons adjacent to them. [2] hydroxide. Having the The 3 : 2 : 3 ratio of the H with different chemical shifts show that two -CH, H' gives rise to the quartet
-CH, C=O group, propanone groups and one -CH, group present. The fact that the peak at li = 2 is a singlet (3 Hon neighbouring C) with
3 li = 2.2.
t
absorbance
reacts with l,fOH· to give
CHI, which is observed as
a yellow ppt. No yellow ppt.
indicates that one methyl group has no H attached to an adjacent atom.
Thus the ketone is butanone. H' gives rise to the triplet (2
H on neighbouring C) with
of CHI, is formed with methyl li = 0.9.
3
ethanoate. li values of H' and Hb are
"?,DO Question 7
(iij Since propanal is an

~
higher than H' since they are
aldehyde which is more
easily oxidised than Chloroacetophenone (compound D, below) was formerly the most widely used more deshielded being next
propanone which is a ke- tear gas, under the codename CN. It was used in warfare and in riot control. to the carbonyl group.
tone, mild oxidising agents It can be synthesised from ethylbenzene, A, by the following route.
10 9 8 7 6 5 4 3 2 1 0
such as Fehling's solution .,
chemical shifl/li ~ '!
and Tollen's reagent may be -! I II Ill IV
Fig. 7.1 used to distinguish the two. Q-cH2 CH 3 - Q-cHCICH 3 - Q-cH(OH)CH3 - Q-coCH 3 - Q-coCH2 CI
[N02!P3107] n Tollen's reagent is used
instead of Fehling's solution, a A B c
silver mirror is formed for .l D
propanal but not for j {a) Suggest reagents and conditions for step I. [1]
propanooe. J
Suggested Solution: Attematively, thetriiodoform
1 {b) Suggest reagents and conditions for converting. ethylbenzene into com-
1
(a) (i) To distinguish methyl ethanoate from propanone, 2,4- test may be used to distin- 1 pound E, an isomer of B.
dinitrophenylhydrazine is added to the two compounds separately. An guish propanal from
orange precipitate of 2,4-dinitrophenylhydrazone is observed for propanone. Propanone re·
acts with l,fOH·to give CHI, 1 Cl-o-CH 2CH3

I
propanone, but not for methyl ethanoate. which is observed as a
yellow ppt. No yellow ppt. E
(ii) To distinguish propanal from propanone, the two compounds are warmed [1]
of CHI is formed with
separately with Fehling's solution. A brick red precipitate of Cu,O is ob- 1
propana1. (c) Draw the structure of the product obtained by heating ethylbenzene with
served for propanal but not for propanone.
KMnO,. [1]
i
 Page 10 topic 10.5 Carbonyl Compounds
topic 10.5 Carbonyl Compounds Page l1
~CORNER ~CORNER
(d) Describe a test (reagents and observations) that would distinguish com·
Question 8
pound C from compound F.
Lactic acid (2-hydroxypropanoic acid), J, occurs in soured milk. It can be
synthesised from ethanol by the following series of reactions.
I II Ill
[2] C,H,OH - G H - CH,CH(OH)CO,H
HCN + trace NaCN J
(e) The efficiency of a tear gas is expressed by its 'intolerable conce~ra;io~··
1c. The J.C. of the tear gas CN has been measured as 0.030 _gm o air. Compounds G and H both react with alkaline aqueous iodine. Compound G
How many moles of chloroacetophenone need to b~ sprayed 1nto a roo~ reacts with 2,4-dinitrophenylhydrazine and also with Fehling's solution. Com-
pound H reacts with sodium metal.
of volume 60m' in order to achieve this concentratiOn? [ 1
(a) (i) Identify G and H, explaining how the identities you suggest fit in with
(f) Residues of CN can be destroyed by hydrolysis with an aqueous alkali. the test reactions described above.
(ii) Suggest reagents and conditions for reactions I and Ill.
Q-cocH2ct + oH- - Q-coCH20H + cr- [7]
(b) On heating in the absence of air, lactic acid loses water to give a single
o compound K, C,H,O,. K is a neutral compound that does not react with
(a) This is a free radical sub- sodium or with 2.4-dinitrophenylhydrazine. Its NMR spectrum consists of a
Compounds G and H are isomers of compound D.
stitution reaction and u.v. o o
6-proton doublet at 1 .2 and a 2-proton quartet at 5.2. Suggest the identity
of K and explain the splitting pattem in its spectrum. [3]
light is required to intitiate
ct-Q-cocH3 the reaction. [N04/P3/QB Either}
H Q-cH,CH, + Cl,
(a) I:
Suggested Solution:
· (i) Arrange the three isomers D, G and H in order of increasing ease of
hydrolysis. ~ Q-cHC.CH, + HC/ (a) (i) G is CH,CHO. CH3CH20H + [0] '"'""' CH3CHO + H20

(ii) Explain the reasoning behind your choice. [3] H is CH3 CHOH. II:
With excess Cl2, multiple
[J03/P4/Q4} substitution will take place.
I CH3CHO + CN" -n"'uo~oop,...,.t""mc-ad"'diti""·on--J) CH3 -TH -OH
CN
(b) FeCI, or AICI, catalyst is CN
Suggested Solution: required to effect the electro- H Ill:
philic substitution reaction. I
(a) Limited amount of Cl, and u.v. light. j
G contains CH3 -C-OH group and H contains CH,CH-0H+2HP+W hydro~•· CH3CHOH+NH:
Q-cH,CH, + Cl, t
I 0 I I
(b) Cl 2 and FeCI, catalyst. j CN C02H
II
(c)
~ C/-o-CH,CH, + HC/ CH3 - C - group. Both give positive triiodomethane
test on heating with l,fNaOH to give CHI,.
(c) Alkylbenzenes are oxidised CH,CHO being a carbonyl, undergoes condensation with 2,4-
when heated with acidified dinitrophenylhydrazine.
KMnO to form benzoic acid
(white precipitate). H H
(d) reagents : 1,
2
aqueous NaOH, heat Q-cH,CH, + 6[0]
CH,-~~o 'H,N-~-p-NO,
observation with C : yellow precipitate
~ Q-co,H +CO,+ 2H,O
observation with F : no yellow precipitate NO,
C is a methylketone and
(e) Mass of CN =. 0.030 g m-3 x 60 m3 = 1.8 g As an aldehyde, CH,CHO reduces Fehling's solution to give red precipi-
it gives a positive tri-
tate of Cu,O. ·
M, of CN (C 6 H5 COCH2 CI) = 154.5 iodomethane test.

nCN
=~=0.01165
154.5
mol o- COCH, + 31, + 40H-
The hydroxy group in H functions as an acid and gives H, on reacting with
Na.

----7 Q-co,· +CHI,! +31"+ 3H,O CH3CH- OH+Na---> CH3CH- o-Na• +_!H
(f) (i) H, D, G 2
I I 2
(il) G is an acid chloride and undergoes hydrolysis readily in water. CN CN
o undergoes hydrolysis only when heated with aqueous NaOH.
(ii) I : K,Cr,o,, dilute H,SO,; heat with immediate distillation.
H does not undergo hydrolysis even when heated with aqueous _NaOH.
The c_ Cl bond has partial double bond character and 1s d1ff1cult to II : dilute H,SO,; heat under reflux.
cleave.
 Page 12 topic 10.5 Carbonyl Compounds
topic 10._5 Carbonyl Compounds Page 13
~CORNER
(b) K is CH, 0
1
(iii) 212+e- -----t 1- e =+0.54 v ~CORNER
' CH-C~
0/ '0 For the reaction,

' C-CH/
2 3
Fe '(aq) + _:1_1 2 (s) -----t Fe '(aq) + 1-(aq) Ec:n = 0.54-0.77 = -0.23 V<O
0~ ' CH,
2
Hence, it is energetically not feasible.
The 2 CH, groups are identical and are in the same chemical environment.
The 6 protons thus show a signal and it is split by the adjacent proton into (c) (I) ls' 2s' 2p' 3s' 3p' 3d 10
a doublet. The 2 single protons are also identical and are in a same chemical
environment. The 2 protoris thus show a signal and it is split by the adjacent (ii) In A, Cu(l) has a fully filled d-subshell. The d-d electronic transition is not
possible. Hence, it is white. In CuSO,, Cu(ll) has a 3d' configuration. The
3 protons into a quartet.
partially filled 3d·subshell allows d-d transition and hence, it is coloured.

(d) (I) cu'• + c- ~ Cu' E" = +0.15 V

Question 9
_:1_12 +e-~r E" =+0.54 V
Iron and copper are both transition elements. 2
[1]
(a) Explain what is meant by the tenm transition element. Ec:n = (0.15)- (0.54) = -0.39 V < 0
(b) Aqueous solutions of chlorine and iodine are added separately to two test·
tubes each containing Fe'• ions. Aqueous sodium hydroxide is then added (ii) The Cu• formed is removed from the aqueous solution as Cui precipitate.
to each tube. Results are given in the table below. This causes the equilibrium to shift to the right. Hence, the reaction pro-
ceeds.
I Cl2(aq) added \ 12(aq) added
green solution turns no observable
Fe2 ' (aq)
yellow change l}.uestion 10
after addition
of NaOH(aq) 1 brown precipitate / green precipitate Ethanedial (glyoxal) is used in the production of fabrics which have penmanent
creases.

(i) What does the colur change when Cl,(aq) is added to Fe'•(aq) indicate? O=C-C=O
(ii) Use E" values from the Data Booklet to explain you answr to (i). I I
H H
(iii) Use E" values to explain why there is no change when l,(aq) is added
~~~~- ~ ethanedial
Ethanedial undergoes many of the reactions of aldehydes.
(c) The atomic number of copper is 29.
(i) What is the electronic configuration of copper in the white solid A? (a) Ethanedial reacts with Tollens' reagent.
(ii) Explain why A is white whereas aqueous copper(ll) sulphate is coloured. (i) What would you see if you carried out this reaction?
[4]
(ii) What is the structural fonmula of the organic compound fonmed? [2]

(d) Standard redox potentials may be used to predict the feasibility of a reaction. (b) Ethanedial reacts with hydrogen cyanide, HCN, to give compound F.
(i) What is ·the structural fonmula of F?
(i) Use E" values from the Data Booklet to show that the reaction be·
tween aqueous copper(ll) sulphate and aqueous potassium iodide is (ii) What type of reaction is this?
unlikely to occur. (iii) What is the structural fonmula of the compound fonmed when F is heated
(ii) By using your answers to (c)(iii) and (c)(iv), suggest one reason why with an aqueous mineral acid such as dilute sulphuric acid? [3]
this reaction does, in fact, occur. [3] (c) Ethanedial can be oxidised and reduced.
[N06/P2102}
(i) What is the structural fonmula of the organic compound fonmed when
ethanedial is heated under reflux with an excess of acidified potassium
dichrotnate(VI)?
Suggested Solution:
(ii) What is the structural formula of the compound fonmed when ethanedial
(a) A transition element is a metal that has partially filled 3d·subshell. is reduced?
(b) (i) Cl, is a strong oxidising agent. It oxidises Fe(ll) to Fe(lll). (iii) What reagent would be used for this reduction? [3]

(ii) Fe 3' +e- ~Fe'' e =o.nv (d) When ethanedial is reacted with NaOH and the product treated with a mineral
acid such as dilute sulphuric acid, the following reaction sequence takes ,
_:1_CI 2 +e- ~cr E" =1.36 V place.
2
I CHOCHO + NaOH -+ HOCH,CO,Na
Fe2 '(aq)+_:1_CI (g)----> Fe3 '(aq)+Cqaq) E:, = 1.36-0.77 = +0.59 V > 0
2
2 HOCH,CO,Na + H• -+ HOCH,C02 H + Na•
Hence, the reaction is energetically feasible.
 topic 10.5 Carbonyl Compounds Pa e 15

topic 10.5 Carbonyl Compounds

Page 14
~CORNER (ii) Use your equation to calculate the volume of C02 , in dm 3, measured
~CORNER
[1] at room temperature and pressure, which will be formed when .3.5g of
(a) U) Structure of Ketene is
What type of reaction is the overall change? ketene are burned in an excess of air.
with sodium metal to give Give your answer to two significant figures. [4] H
(e) An isomer of ethanedial exists which reacts ""-c=C=O
{NOBIP2/02(a,b)] H/(j) ®
hydrogen. [2]
Suggest the displayed formula of this isomer.
(JOBIP2105] Carbon number 1 has
Suggested Solution: three pairs of electrons
(a) (i) H-C-H: 120' C=C=O: 180' around the cenlral atom.
(double bond is assumed
Suggested Solution: (ii) Molecule contains both ketone and alkene.
(a) Tollen's reagent is a as to occupy the position
colourless solution of of one electron pair in a
(a) (i) Silver or black ppt. (b) (i) C2H2 0 + 20 2 --> 2C0 2 + H2 0
[Ag(NH 3) 2f. It is mild single bond). So angle is
(ii) o = c - c = o oxidising agent which can (ii) From equation 42 g C2H2 0 gives C0 2 = 48 g 120'.
I I oxidise only aldehyde. Carbon number 2 has
HO OH Ketone have no reaction 48 3 5 3 two double bonds around,
3.5g C2 Hpgives= x · =4.0dm
with Tollen's reagent. 42 so it shows a linear
(b) (i) CN CN arrangement. Therefore
I I Question 12
C=C=C, angle is
180'.
Ho-c-c-OH
I I (b) (i~ Reaction starts by Organic chemistry is the chemistry of carbon compounds. The types of organic
H H the attack of Nucleophile reactions that you have studied are listed below.
(ii) Nucleophilic addition. but overall reaction is the addition elimination hydrolysis
addition of HCN across the
oxidation reduction substitution
(iii) HO,C CO,H double bond.
I I Addition and substitution reactions are further described as follows.
Ho-c-c-oH electrophilic nucleophilic free radical
I I Complete the table below.
H H
Fill in the central column by using only the types of reaction given in the lists
(c) (iii) Metal hydrides
(c) (i) HOOC - COOH above. Use both lists where appropriate.
UA/ H, or NaBH 4 are
(ii) H H reducing agents, they are In the right hand column give the name(s) or formula(e) of the reagent(s) you
would use to carry out the reaction given.
I I used in ethoxylthane which
must be dry because
HO-C-C -OH reagent(s)
organic reaction type of reaction
I I hydride reacts with water.
H H (d) When same species
partially oxidised and CH3CHO-.
(iii) NaSH, or LiAIH,
partially reduced it is called CH3 CH(OH)CN
(d) Both oxidation and reduction (Disproportionation). disproportionation react1on.

or C,H,02
(e) HO-C== C -OH
CH 3CH2CH2CH3 ->
CH3 CH2 CHBrCH3
Question 11
. . class of unsaturated organic compou~ds that
.Ketene, C,H,O, IS a member ~!
is widely used m pharmaceu 1c
:1
research for the synthesis of organic com-
CH3 CH(OH)CH3 -.
pounds. CH3 CH=CH2
CH, =C= 0
ketene

for the
H-C-H and C = c = o bond angles in ketene.
(a) (i) suggest va Iues CH3 CH=CH2 ->

I
C=C=O ................................... .
H-C-H ........................ .. CH3 CH(OH)CH,OH
(ii) By considering the structure of the molecule' suggest why the na~~
ketene is used. {N08/P2/Q4]
. . t f m car!Jon dioxide and water.
(b) Ketene burns completely m air o or .
(i) Write a balanced equation for thiS react1on. l
I
I

~~=~-~~--------------------~--------------
 topic 10.5 Carbon vi Compounds Pa2e 17
Page 16 ~CORNER
toQic 10.5 CarbQllY/ Com.eounds ~CORNER
Question 13

s ted Solution· Shifting of ~ electrons (a) Complete the following reaction scheme which starts with e!hanal.
reagent(s) towards more electro-neg a· In each empty box, write the structural formula of the organic compound
type of reaction tive atom is called mesom·
organic reaction that would be formed.
eric effect. So Carbonyl
HCN and CN- carbon becomes electron
Nucleophillic Tollens'
CH 3 CHO~ ' deficient. I
addition HCN reagent
CH 3CH(OH)CN "'-c<li-o_, CH 3 CHO
/ -
i
Reaction starts by the ··~
Br2 in CCI. B E I
attack of Nucleophile but
CH 3CH2CH2CH 3 ~
Free radical
substitution
(Organic solvent) over all reaction is the
addition of HCN across
1 dilute H2S04
CH3CH2CHBrCH 3 reduction
the double bond. !! heat
H -~
cw + )c"' o-)•
CH 3CH(OH)CH 3 ~ Cone. H,so. CH,
Elimination
CH 3CH=CH2
H CN
""-c/ o· + H"
D
OW/kMnO•
CH3CH=CH2 ~ Oxidation (Mild oxidation) cH( \ )
cone. H2S04 ·
CH 3CH(OH)CH 20H
heat
CH-C-CN
, I
OH

CH 2=CHC02H

cold dilute
Mno:;JH•

Cr20~"/H"
heat under reflux

c
[6]
b) Write the structural formula for the organic compound fomned when, under
suitable conditions,
(i) compound C reacts with compound D,
(ii) compound C reacts with compound E. [2]

(c) Compound B _is chiral. Draw displayed fomnulae of the two optical isomers
of compound B, indicating with an asterisk (*) the chiral carbon atom. [3]
[J09/P2/Q4]
 topic 10.5 Carbonvt Compounds Page 19
Page 18 ~CORNER
topic 10.5 Carbonyl Compounds ~CORNER (c)

Suggested Solution:
c· c·
(a) Toll ens'
reagent //~ /\~
HCN CH 3C02H H / OH OH \. H
CH 3CHO C~N C=N
CH3 CH(OH)CN ~
E
B Question 14

reduction Propanone, CH,COCH,, an important industrial solvent, can be converted into

dilute H2 SO,
another industrially important solvent, MIBK, by the following sequence.
heat
step I step II
2 CH3C ; Q - C6 H12 0 2 - CH 3 - C;O
I
CH
F I
CH;C(CH3 ) 2
3
CH 3CH,OH
CH 3CH(OH)CO,H
G (C6 H10 0)

cone. H,so,
heat
0

l"'""'
CH 3C;Q
I
CH2CH(CH3 ),
MIBK

(a) When F is formed in step I no other compound is produced.

Suggest a structural formula for F, which contains one -OH group. [1)
(b) Compound G has two functional groups.
Name one functional group present in G and show how you would identify
it. Put your answers in the table.
cold dilute
Mno;tr~•
functional group in G reagent used in test what would be seen

cr,o~·tw HO,CCOCO,H
HOCH,CH(OH)CO,Hl-----he_a...:t::.u!.:n~de~r:__r-:ef;;:lu-::"x~--~
[3)
(c) G is formed from F in step II.
c Use your answers to (a) and (b) to suggest
(i) what type of reaction occurs in step II,
(ii) a reagent for step II. (2)
(b) (i) OH 0
(d) The production of MIBK from G in step Ill involves the hydrogenation of the
I II >C;C< group and is carried out catalytically. A mixture of compounds is
HO-CH,-'-C- C - 0-C,Hs
formed because the >C;O group is also reduced.
I What reagent(s) and solvent are normally used in a laboratory to reduce
H
a >C;O group without reducing a >C;C< group present in the same
0 molecule? [2)
(li)
II G has a number of structural isomers.
H,C-0-C -CH,
(e) Draw the displayed formulae of a pair of structural isomers of G which
I
H c - o - c -cH,
contain the CH,CQ- group and which exhibit cis-trans isomerism.

o=c-oH
I II
o
I Label each structure cis or trans and give your reasoning. [3]
{J09/P2/Q5)

l
top_ic 10.5 Carbonyl Compounds

Suggested Solution:
Page20
~CORNER r:fopic 10.6
(a) 0 OH
II I Carboxylic 7/cids and 7Jeriualiues
CH 3- C - CH 2 - C - (CH3),

(b) reagent used in test what would be seen

functional group in G
Br2 (aq) reddish brown colour Content
Alkene
decolorised
or Carboxylic acids (exemplified by ethanoic acid and benzoic acid)
KMnO.(aq) purple colour
decolorised CO Formation from primary alcohols and nitriles.

yellow I orange ppt

(ii) Salt, ester and acyl chloride formation.
or Carbonyl DNPH
2 Acyl chlorides (exemplified by ethanoyl chloride)
CO Ease of hydrolysis compared with alkyl and aryl chlorides.
(c) (i) dehydration I elimination
(i0 Reaction with alcohols, phenols and primary amines.
(ii) Cone. H,so,.
3 Esters (exemplified by ethyl ethanoate and phenyl benzoate)
(d) NaSH, in water .. CO Formation from carboxylic acids and from acyl chlorides.
(ii) Hydrolysis (under acidic and under basic conditions).
CH3CO CH 3
(e) CH 3CO
" C=C/
H
" C=C/
(iii) Uses of esters.

CH3/ "
CH3
CH( "-H
Learning Outcomes
cis
trans Candidates should be able to:
(a) describe the formation of carboxylic acids from alcohols, aldehydes and nitriles.
(b) describe the reactions of carboxylic acids in the formation of,
(l) salts.
(ii) esters.
(iii) acyl chlorides.

(c) explain the acidity of carboxylic acids and of chlorinesubstituted ethanoic acids in
terms of their structures.
(d) describe the hydrolysis of acyl chlorides.
(e) describe the reactions of acyl chlorides with alcohols, phenols and primary a mines.
(/) explain the relative ease of hydrolysis of acyl chlorides, alkyl chlorides and aryl chlo-
~- .

(g) describe the formation of esters from carboxylic acids or acyl chlorides, using ethyl
ethanoate and phenyl benzoate as examples.
(h) *describe the acid and base hydrolysis of esters.
(i) describe the formation of polyesters (see also Section 10.8).
OJ state the major commercial uses of esters e.g. solvents, perfumes, flavourings.

Note: The additional learning outcomes to be studied by A2 candidates are shown in bold type. The A2
components will assess all learning outcomes and will not be limited to those in bold type.
 topic 10.6 Carboxylic Acids & Derivatives Pa e 1 topic 10.6 Carboxylic Acids & Derivatives Page2
~CORNER
Since hydrochlo~c acid is a strong acid, the pH of D is expected to be the ~CORNER
lowest (for solut1ons of the same concentration). .

B con:ains a chlori.~e atom which is electron-withdrawing. The anion that B

r;;;?/ii) fP) (} 4J forms IS more stab11Jsed than that formed from A since the negative charge
IJ ~If U ~ qpening ....... . of the am_on of B _(CH,CH?ICO.o-) IS more greatly dispersed by the electron-
WJth-drawJn~ chlonne. B dissociates to a greater extent than A and the pH of
1ts solution Js lower than that of A for solutions of the same concentration.
Hence, A has the highest pH of 3.0 while D has the lowest pH of 0.5 while
Question 1 B has a pH or 3.0. '
Three chlorine-compoonds can be made from ethanoic acid (A) by the follow- The white precipitate is silver chloride and is formed in the solution formed
ing routes: by D and wa:er. Only in the solution formed by adding D to water are there
I free chlonde ~ens. Insoluble silver chloride is precipitated out when aqueous
CH,CO,H ~ CH,CiCO,H ~ CHCi,CO,H Sliver mtrate 1s added to this solution:
A B C
Ag•(aq)+Cr(aq)----+ AgCI(s)
tn
CH,COC/ (d) C has one more electron:withdrawing chlorine atom than B and hence its pH
IS lower than that of B. Smce B has one more chlorine than A and has a pH
D
~;.0.5 lower than that of A, C is expected to have a pH of 2.0 (0.5 lower than
(a) Suggest reagents and conditions for reactions I and II. [2]
(b) When D reacts with ethanol, steamy fumes are evolved and a fruity-smell-
ing liquid is produced.
Question 2
Write a balanced equation for this reaction, drawing the structural formula
of the organic product. Name the functional group that it contains. (31
(a) The synthetic path~ays below show reactions using 4-methylbenzoic acid
(c) When compounds A, B and D (not necessarily in that order) are added to as a start1ng matenal.
separate portions of water, solutions are formed with pH values of 0.5, 2.5
and 3.0. When aqueous silver nitrate is added to these three solutions, two
show no reaction but the third one produces a thick white precipitate.
Suggest, with explanations, which pH value is associated with each of A,
B and D. Explain the formation of the white precipitate. (5]
(d) Predict, with a reason, the likely pH value of an aqueous solution of com-
pound C. [2]
[N01/P1/Q6] A
PC/,
0 CO,H
4-methyl
benzoic acid
C,H,OH
cone H,SO,

D
(a) The substitution of a hydro-
gen atom by ahalogen atom
lNH, Cl, 11
uv radiation
cone HNO,
cone H,SO,
Suggested Solution: at the a-carbon (carbon to
(a) For reaction I : Reagent : chlorine gas which the -COOH group is
Condition : presence of a small amount of phosphorous attached) of the carboxylic
acid in reaction I is called a-
For reaction 11 : Reagent : phosphorous(lll) chloride/phosphorous(V) halogenafion. The phospho-
chloride/thionyl chloride rous is needed to cause
Condition : warming halogenafiontooocurspecifi-
cally at the a-carbon.
(b) CH3COCI(I)+CH3 CH2 0H(/) ~ CH3 COOCH2CH3 (/)+HCI(g) (c) Even though 8 has a chlo-
B c E

H 0 H H
rine atom, this chlorine atom, (i) ~rite a structural formula for each of the organic products B, c and o
I II I I unlike that in D, is not at- 1n t~e boxes.
Structural formula of organic product : H-C-C-0-C-C-H tached to acarbonyl carbon
I I I and does not hydrolyse in (li) Sug~est a structural formula for compound E and write it in the box
H H H prOVIded. ( )
water. Thus, no free chloride 5
Functional group : ester ions are present in asolution (b) (i) Explain why 4-methylbenzoic acid is insoluble in cold water.
formed by the addition of 8
(c) pH associated with A, B and D are 3.0, 2.5 and 0.5 respectively. to water and no white pre- (ii) ~xplain, with the aid of an equation, why 4-methylbenzoic acid is soluble
D is an acyl chloride which hydrolyses in water to give a carboxylic acid and cipitate of silver chloride is 1n aqueous sodium hydroxide. [3)
hydrochloric acid: observed when aqueous
[N01/P2/Q5]
silver nitrate is added to a
CH 3COCI(I) + H20(/) ~ CH 3COOH(aq) + HCI(aq)
solution of 8 in water.

Ji
'i
~
 top_ic 10.6 Carboxylic Acids & Derivatives Page3
topic 10.6 CarboxyjkAcids & Derivatives Page4

Suggested Solution:
~ CORNER
Suggested Solution: ~CORNER
(a) (i), (ii) (a) Poly-substrtuted poducts for
Compound F, G and H are:
C and E are acceptable

Q Q
0

Q ~
answers.
C:
OH II OH ~
c,
¢' &e'eN, Br*OH
&e'o"
C=O
PC/,

CO,H
C,H,OH
cone H,sO:
CO,C,H,
¢CI,
:j.,
F
0 G
CH,

H
I 4-methyl CO,H CO,H
Br ·
C/ A benzoic acid D E: CH CH, J
1
~ The reaction between phenyl
\l J, a phenolic ester, hydrolyses in aq NaOH to give the corresponding phenoxide

~
co O,NqNO, ¢'NO, ~ and carboxylate salt: ethanoate and aluminium chloride
NH, Cl, nl
adiation ~
is called the Fries rearrangement.
"
CO,H CO,H ~ o· The phenolic ester undergoes a

qNO, k~ 'oeN, .,ow----+ 0

k~ 'o~
OH O 0

Q Q'
rearrangement reaction where
(b) The solubility of a solute in
a solvent depends on the "
g
~~
'
llJI . heat + CH,OH + H,O the -CH,C=O group migrates
from the phenolic 0 to a 2- or 4-
interaction between the ';!
position, for example:
solute and solvent com- -~
pared to that within the
;:;(
0
CO,H .l II
C=O CO,H
solute and within the sol- :!'i Acidification causes H to be produced: 0-C-CH, OH ~
I
NH, B c E vent. Strong interactions R 0
II 6 ~ o~'CH,
--a>,
between the solule and sol- j OH
0
(b) (I) 'Like dissolves like'. 4-Methyltienzoic acid has a big hydrophobic group
CH,C,H, -which hinders its ·solubility in polar water. Despite the fact that
vent favours its solubility in
water. Water has relatively
strong hydrogen bonding
,, &e'o~.,. OH II
The -OH and -CH,C=O groups
it has a hydrophilic -COOH group which can form hydrogen bonding with ~ in Fare 1,2· to each other and not
water, 4-methylbenzoic acid is not soluble in cold water. between water molecules. ~
~~
1,4- because H is 2-
4-Methylbenzoic acid is -~ hydroxybenzoic acid and not 4-
(ii) CH,-o-COOH(s) + NaOH(aq) ~ CH,-Q- COO"Na"(aq) + H,O(I) insoluble in water despite ~~
[l
Thus H is 2-hydroxybenzoic acid. hydroxybenzoic acid. Since H is
the fact that it can form
On reaction with aqueous sodium hydroxide, 4-methylbenzoic acid forms hydrogen bonding with -~ H is also obtained from the reaction of F with aqueous alkaline iodine. The re-
actions involves an oxidative cleavage of -CH'CO group with the formation of -
derived from F, the -OH and
-CH,C=O groups in F must be
the ionic 4-methylbenzoate which forms ion-dipole interaction with water. water due to the -COOH ~
~ coo- and triiodomethane, CHI,: 1,2; to each other.
group present. That is be-
ion-dipole interactions are stronger attractive forces than hydrogen bonding
j 0

Lt,
and make 4-methylbenzoic acid soluble in aqueous sodium hydroxide. cause4-methylbenzoic acid 0
has a relatively large hydro- OH II
phobic -CH,C,H, group
which takes up much space u F CH, +31,+40H" ----+ &e'o~ •eNr, •sr •SN,o
Question 3
This question is about compound F, C,Hp,, which is formed when phenyl
and does not interact well
with water. There is greater
interaction between water
t The carboxylate salt on acidification yields H:
ethanoate, CH,CO,C,H,, is warmed with aluminium chloride.
Compound F is insoluble in water, but dissolves in NaOH(aq).
II reacts with 2,4-dinitrophenylhydrazine, 2,4-DNPH, but not with Fehling's
molecules within water
than between water and
4-methylbenzoic acid
I
H
. OH

6-e'o~ •w----+
0
II
OH w
ae~ON
molecules. Hence. 4-
solution.
With bromine water, F gives G, C,H,O,Br2 •
With alkaline aqueous iodine followed by acidification, F gives H, C,H,O,.
Methylbenzoic acid is
insoluble in cold water.
4-Methylbenzoate ions I
I
Compound H dissolves in both NaOH(aq) and Na,CO,(aq). Compound H can form ion-dipole interactions F is likely to contain a hydrophobic benzene ring since it is insoluble in water.
also be obtained by reacting oil of wintergreen, J with hot NaOH(aq), followed with water molecules so
F reacts with aq NaOH to give the phenoxide. Being ionic, the phenoxide has
by H,SO,(aq). that interactions between
stronger intera·ction with water so that F dissolves in aq NaOH:
the ions and water are

o::,CH,
J
relatively strong, aiding its
solubility. i Lg,
u F CH, + O H . - + 0~g, OCH,+H,O
Deduce the structures of compounds F, G and H. Explain the chemistry of the
reactions described, writing equations where appropriate. [There is no need to Since F is a ketone, it reacts with 2,4-DNPH but not with Fehling's solution:
comment on the chemistry of the formation of F from phenyl ethanoate.] [10]
[N02/P3!06 Either]

''·
-~
topic 10.6 Carboxylic Acids & Derivatives PageS topic 10.6 Carboxvtic Acids & Derivatives Pa e 6
~CORNER
{b) H H ~CORNER

o OH
0
II
Fc "-cH,+H,NNH yo
O,N
NO,
CH
___..RC-
Q--oH
'"- -N-N
H
ly-

O,N
NO,+H,O
B is

Cis
CH,-C=C-CH,CH,

CH,-C=C-CH,
I

~
I

yH,
(b), (c) Since D and E each
has 2 oxygen atoms. they
are carboxylic acids (since
alkenes are oxidised by hot
(c) (i) D Mno,- to co,. ketone or
. . . h lic-OH reacts with bromine water to give carboxylic acids}. f is a
F• containing the highly actlva~lngbp eno b;tituted at the 4- and 6- positions. 1•1 (b) ~0
a dibrominated product, G, With romlne su CH,-CH,-C"\ ketone since nhas only one
OH oxygen atom. Hence, 0
0 0 is CH,CH,CO,H, E is

Br~OOH
(o)
OH II

a>~ + 2Br, ___.. y GM"-cH, + 2HBr

1
The 3 protons· (a) signal is split by the 2 protons (b) into a triplet. The 2
protons {b) signal is split by the 3 protons (a) into a quartet. Proton (c) is
remote from the rest and its signal is not split. Thus it shows up as a singlet.
CH,C0 2H and f is

II
0
CH3CCH3.
(ii) Signal at o 9.8 would disappear due to proton ·exchange at -GOOH.
(c) (iQ Compoundswithacidic
Br
CH3 CH2 COOH + D2 0 ~ CH3 CH2 COOD + HOD Hreadily undergoes deute-
rium exchange 020. Hence,
its signal in an NMR disap-
Question 4
Question 5 pears when D,O is added to
(<I) Illustrate the various_ types of lsoml en~m
. ·
that can be shown by alkanes,
C H as examoles. Include
n.
using compounds w1th the molecu ar omnu 1a ~ •• dh e Suggest methods by which the following compounds could be distinguished
the structural fomnulae of all the pos~ible isomers 1n your answ. '1", an enfs] from each other by chemical tests. The distinguishing of some of these pairs
state the total number of alkanes with this formula. may rely on a preliminal)' breaking-up of the compounds, and subsequent
f 1 c H were oxidised by hot concan- testing of the reaction products. Do not use spectroscopic techniques.
Two alkanes with the moleculoar Co~~ a and
!rated KMnO,. Alkene B gave • , , ,. C
EH •
C H 0 as oxidation products,
(a) CH,CH=CHCH,OH
whereas alkene C gave E, C,H,O,. and F, , , ·
2'
0 and CH,-CH,
I I
{b) Suggest structures for the two alkanes B an d c. [2! CH,-CH-OH
[2]
(c) The NMR spectrum of one of the products (0, E or F) consists ~ 3;p;o~o; o: {b) CH,-CH,-CH,
o
triplet at 0 1 .O, a 2-proton quartet a 2.5, and a 1-p.roton. s1ng e a ~c: and CH,CH- CH,-CH,
{") Suggest which of the three oxidation products gives nse to thiS sp
I I I I
1 CH,CH-0-CO CH,-0-CO
trum and explain the splitting pattem observed.
(ii) Wha; would be the effect on the NMR spectrum of adding D,O to ~~~ [3]
sample? Explain your answer.
[N04/P3/Q6}
(c) C/-o--CHO and Q-coc! When candidates answer such
[2] questions, they should give the
Suggested Solution: test reagents and conditions, ob-
servations for both compounds,
(a) Structural isomers: {d) o-CONHCH, and CH,CONH-o and any relevant equations for
H CH,
H
I
~ /CH, I I (a) Cyclic alkanes such as
[3]
the reactions taking place.

H-C=CHCH,CH,CH, H-C=CH-CH H-C=C-CH,CH, cyclopentane and methyl (a) Both are alcohols and hence
"cH, cyclobutane are not alkenes [N04/P3/Q7} general OH tests e.g. PC/5
(2) (3)
(1) a~hough they have the same would not work. The test
molecular formula. These Suggested Solution: should rely on the c = c
H H H CH, are not aoceptable answers.
double bond. Note that cold
I I I I {a) Add Bromine. Only CH3CH = CHCH20H would decolourise Br,. alkaline KMnO, where only
CH,-C=C-CH, CH,-C=C-CH,
the alkene decolourises the
(5} CH3CH=CHCH2 0H+Br2 ---.... CH3 CH -CHCH 0H
(4} 2 KMnO, and gives a brown
I I precipitate may be used but
(4) shows cis-trans isomerism. Br Br
not hot KMnO, (both could
H /H H /CH,CH, {b) Heat with aqueous NaOH and 1,. Only the first ester would give a yellow be oxidised).
'c=c 'c=c precipitate of CHI,.
/ '-. / '-. (b) Both are esters and they
CH, CH,CH, CH, H
CH2 - CH2 -CH2 OH have to be first hydrolysed.
trans (4b} Subsequent tesls may then
cis (4a} I I I rely either on the alcohols or
CH 3 - CH - 0 - CO+ OH" ~ CH3 - CH- CH2 CH2 CH C02
Altogether, there are 6 isomers. 2 the acids.

<
 topic 10.6 Carboxylic Acids & Derivatives

OH
Page7
~CORNER I I
~
topic 10.6 Carboxylic Acids & Derivatives

Suggested Solution:
0
PageS

~CORNER

L"o-~-0-CH,-Q
I
~
CH - CH - CH2 CH2CH 2C02 + 412 + 60W (a) (i)
3
~ CH1 + -o2C- CH 2CH2CH2
3
- C02 +51- + 5Hp ~
~
o-~-0-o-CH,
(c) Alternative ways include

I
(c) Add aqueous AgN0 . Only C6H 5COCI gives a white precipitate of AgCI.
3 adding 2,4-DNPH. Only the
aldehyde gives an orange
~· P =
Q - c o c l + H,O ~ Q - c o , H + HCI precipttate.
'
HCI(aq) + AgN0 3 (aq) ~ AgCI(s) + HN0 3 (aq)
C/-o-CHO + H,N-NH-p-No;
NO,
' (il) o - C O , H + PCI, ~ o - C O C I + POCI, + HCI

(d) Heat with aqueous NaOH. Cool and add dilute HCI followed by aqueous Br,.
~ C/-o-C=N-NH-p-NO,+H,O
NO,
Or add aqueous Na,CO,.
I
Il!i o- COCI + HO-o-CH, NaOH) P + HCt

Only CH,CONH -Q decolourises Br, and gives a white precipitate.

Only Q- COCI gives
I
'ill (iii) KMnO,, H,SO, heat

o-
effervescence of CO,.
;1'!

-o
(b) (i) Acidity : N > a > M
Q-coC.'+H,O 'H
H·~

~ heat - HA~H'+A-
-~
CH,CONH + OH 9H,CO, + NH,
~ Q-co,H + HCI The more stable the A- fomned, the greater is the tendency for HA to
dissociate; and hence the greater the acidity of HA.
2HCI + Na 2C0 3 • :;?,
o-NH, • 38,, a,-QNH, • 3HB'
ii<.
;.'?
--> -> 2NaCI +CO,+ H20
c\. e

I
.

o-
(d) Both are amides and they o-
Br have to be first hydrolysed. 0
l
Subsequent tests may then <
.
rely either on the acids or the The co,- is greatly resonance stabilised over the 2 C- 0 bonds.
,
Question 6 amines.

o-
Hence, N is the strongest acid.
Compound L is used medicinally as an anti-spasmodic agent. Hydrolysis of L
produces equimolar amounts of phenylmettianol, M, and benzoic acid, N.
In o·, there is also delocalisation of electrons from - o- into

L + H,O
Q-cH,OH

M
+

Compound P is an isomer of L, and is used in perfumes. Hydrolysis of P

Q-co,H

N the benzene ring. However, this is not as extensive as in

Hence a is less acidic than N.

o- co;.

produces 4-methylphenol, a, and benzoic acid, N.

In M, the negative charge on o- is intensified by the Q - c H , group
CH,-Q-OH + Q-co,H
P + H,O
Q N by inductive effect and hence the Q-cH,o· is the least stable.

(a) (i) Suggest structures for L and P.

Therefore, M is the weakest acid.
(ii) Suggest a route for the synthesis of compound P from compounds a
and N. (il) M does not react at all.
(iii) Suggest reagents and conditions for the conversion of compound M
into compound N. [6]
a is acidic enough to react with NaOH only.

(b) (i) Describe and explain how the acidities of compounds M, N and
compare with each other.
a CH,-o-OH + NaOH ~ CH,-o-0-Na' + H,O

(ii) How would each of these compounds react with t: NaOH(aq),

ll: Na,CO,(aq)? [4]
[N06/P3/0B Or]

~ ---------
 topic 10.6 Carboxylic Acids & Derivatives Page9 topic 10.6 Carboxylic Acids & Derivatives
~CORNER Page 10

~CORNER
N reacts with both NaOH and Na,CO,. (ii) Tollens' reagent
compound:
Q - c o , H + NaOH - Q-co,-Na' + H,O observation:

2 o- CO,H + Na,CO, - 2 o- CO;Na' + H,O + CO,

(e) One of the three compounds X y 0 Z
.
0 raw displayed, ' ' ' r • shows stereoisomerism
labelled structures of the sten . .
eo1somers of this compound.
[4]

[2]
[J07/P2/Q4)

Question 7 Suggested Solution:

Commercial paint and varnish removers contain a mixture of dichloromethane, (a) (i) observation: white precipitate
CH,C/2 , and methanol, CH,OH. product responsible: silver chloride (a) (i) CH,Cf, reacts with
(a) What would be observed when the following reactions are carried out? NaOH lo substitute Ct ion
In each case, give the name or formula of the reaction product which is (ii) observation: white misty fumes which reacts with Ag· ion to
responsible for the observation you have made. product responsible: hydrogen chloride produce white AgC/ precipi-
tate.
(i) CH,C/2 is reacted with NaOH(aq) and AgNO,(aq) and the mixture left (iii) observation: colourless gas evolved
to stand. (i~ CH,OH + PC/5 ~
product responsible: hydrogen gas
observation: CH,CI + POC/3 + HC/
product responsible: (b) (iii) CH,OH + Na ~
c H 0
(ii) CH,OH is mixed with PC/5 • percentage CH30- Na• +~H
Ar
40 6.7 53.3 2
observation: 12 16
product responsible: mole ratio 3.33 6.7 3.33
(iii) CH,OH is reacted with sodium. simple ratio
2
observation:
:. emperical formula of w = C,H,o, = CH,O
product responsible: [6]
(b) When CH2 C/2 is heated under reflux with an excess of NaOH(aq), a com- (c)
pound W is formed. H
(c) alternative answer for Y:
W has the following composition by mass: C, 40.0%; H, 6.7%; 0, 53.3%. I H"-. /H
H
Use this information and the Data Booklet to show that the empirical for- H-C-C=O C=C I H-O H
mula of W is CH 2 0. [2] I I H-o/ "-o-H H-0-C-H "c=c/
H 0-H I w/ "'-o-H
(c) Compounds with the empirical formula CH 20 can have the molecular for- H-C=O
X either Cis or trans isomer is
mula c,H.o,. y
Two possible structural formulae for compounds with molecular formula z to be shown.
C2 H4 0 2 are HCO,CH, and H2C=C(OH) 2_ (d) (i) SOlid NaHC0
3
In the boxes below, draw displayed formulae for three further structural
compound: X
isomers with the molecular formula C,Hp,. (d) (~ Xis an carboxylic acid,
Do not attempt to draw any structures containing rings or 0 - 0 bonds. observation: Carbon dioxide gas evolved with eff thereforegivesCO gaswnh
.l) ervescence. NaHCO,.
2
(l Tollens' reagent
compound: z (i~ Z being an aldehyde,
produces silver mirror or
observation: silver mirror or
black precipitate black precipitate with tollen's
(e) reagent
X y z [3]

(d) Identify which of your compounds, X, Y, or Z, will react with the following
reagents.
H-o/
H'c=c/H
"--o-H
H-O

H
'
/c=c/
H

"--o-H
(e) Two carbon atoms bonded
with double bond and each
cai!Jonacrossthedoublebond
Cis is bonded with two different
In each case, state what you would observe. trans
groups i.e. H & OH.
(i) solid NaHC03
compound:
observation:

~1.
topic 10.6 Carboxylic Acids & Derivatives Page ll
topic 10.6 Carboxylic Acids & Derivatives
~CORNER Pa,g_e 12

Question 8
(iii) NaOH(aq) ~CORNER

o£P
Chemists use skeletal or partial-skeletal formulae to represent larger structures.
For example the structure
CH OH
3
I
/CH 2 "'-.. _.......-C('
I H
HC C "-
21 I CH2 (iv) CH,COC/

I
~£f)
H 2 C~ /
CH
--._ CH
CH 2

may also be represented as follows.

~~-

c6" (v) hot acidified K2Cr,0 7

mammals.
H
Oestradiol is one of the hormones that controls the reproductive ·cycle in female

Suggested Solution:
o£P [J07/P4/Q6]
[7]

(a) (i)
HO

~
.H
HO
oestradiol

(a) (i) On the above structure of oestradiol, circle one chiral centre.
(ii) What is the total number of chiral centres in the oestradiol molecule? HO
[2]
oestradiol
(b) Complete the following part-structures (which have the -OH groups removed) (ii) 5
to show the products obtained when oestradiol (above) is reacted with the (b) (i)
stated reagents. (ii)
~a

(i) sodium metal

H

~{j) Br

QCJ~ Na+O-
HO
I
Br

(iii)
(ii) Br,(aq) (iv)

~{j)
QCJ~
CH 3COO
 topic 10.6 Carboxylic Acids & Derivatives Page 14
Page 13
topic 10.6 Carboxylic Acids & Derivatives
~CORNER CORNER

(v)
+

a triglyceride, M, =890 glycerol

HO

Question 9 . . biodiesel, M, = 298

(c) A good way of making synthetic amino acids uses chloro-acidS as Interme-
(a) Name the functional group present in triglycerides. [1]
diates.
(b) Suggest reactants and conditions for
NH 3(excess)
c~ + trace of p CH3 CH(NH 2)C02H
CH CH CO H CH 3 CHC!C02H reaction I,
3 2 2 I alanine
reaction II. (4]
(i) Suggest the role that the trace of phosp~orus plays in reaction I. (c) Suggest the structural formula of the compound formed when glycerol is
(ii) Write a fully balanced equation for reaction I. . reacted with

(...
111) State the type of mechanism of react1on II. . (i) an excess of HBr(aq),
d · th · 2 stage synthesis a
(iv) When 1 0.0 g of propanoic acid wa~ use In IS - • (ii) an excess of hot acidified K2 Cr,O,(aq). (2]
yield of 9.5 g of alanine was obta1_ned.
151 (d) Calculate the mass of biodiesel that can be produced from 1000 kg of dried
Calculate the overall percentage yield.
algae, assuming that 50% of the algal mass is triglycerides. (2]
• lanine exists as a zwitterion.
(d) In the solid state and in aqueous so 1u~1on~, a .
121 (e) (i) Construct an equation for the complete combustion of biodiesel.
Draw th·e structural formula of this zwlttenon.
[N07/P4/Q1(c,d)] (ii) Use your equation to calculate the mass of CO, produced when 10 kg
of biodiesel is burned. (3]
(f) The production of biodiesel is at present an expensive process.
Suggested Solution: Suggest a reason why the development of biodiesel as an alternative to
(c) (i) Catalyst fossil fuels is important. [1]
[JOBIP4/Q4]
(ii) CH3CH2C02H + Cl2 --> CH2CHCIC02H + HCI

(iii) Nucleophilic substitution Suggested Solution:

M,(CH 2 CH(N~)C02H =89 (a) Ester
89
. w1ll
:. 10g of propanoic ac1d · produce alamne-
' - X 10 = 12.03 g (b) reaction 1: W(aq) (HC/ or H2 S0 4 ), heat or reflux Temperature > 80 oc (b) Hydrolysis is lhe reverse
74
of esterification. Esters
reaction II: MethanolfCH3 0H (heat with cone. H,SO,)
are readily hydrolysed
Percentage yield = ~ x 100 = 79 %
12.03 by refiuxing with acid or
(c) (i) CH,- CH - CH,Br
base. (Esters are much
I I more resistant to
Br Br hydrolysis under neutral
(d)
(ii) HOOC - CO - COOH condttions).
(c) (iQ In
(d) 890 g of triglycerid produces (3)(298) = 894 g of biodiesel.
CH 2-CH-CH2
Therefore 500g produces 500 x ~~ri = 502 kg biodie'sel.
I I I
OH OH OH
Question 10 . . (e) (i) C17 H35 C02 CH3 +27.50 2 -->19C0 2 + 19Hp
. th production of the fuel biOdlesef there are two primary
Recently much interest has been sho~nt~n d~ed algae is composed of lipids, alcohols which are
from algae. Up to 55% of the mass o e (ii) 10x44xd/s- = 28.05Kg.
oxidised to carboxylic acid
the majority of which are triglycerides. .
(f) 1. we can save diminishing resources. and one secondary
To convert triglycerides into biodiesel, the following processes are earned out. alcohol which is oxidised
2. It is renewable. to Ketone.
3. Oil will become increasingly more expensive as it runs out.
topic 10.6 Carboxylic Acids & Derivatives Page 15 l topic 10.6 Carboxylic Acids & Derivatives
~
~CORNER
Page 16
j
(d) (I) Name the functional group that is common to compounds J and K. ~CORNER
Question 11
Compounds J and K are isomers with the molecular formula C,H,NO, and they
contain the same functional group.
i (ii) Name the functional group that is common to compounds N and P. [2)

{N09/P4!06]
They may both be obtained from ethanol by the following routes.
Suggested Solution:
CH 3CHpH
(a)
CH 3CH 2 0H
HBr~hea/ ~r207 +H 2 S04 +heat
HBr+hea/ ~Cr2 07 +H2 S04 +heat

CH3CH 2Br CH3C02H

L II M
L M
NH3 (excesy ~ NH3 (excesy ~
CH3CH2 CN
CH2 CN

N (C 2H 7N)

1\ v
CH3 COCI
CH3CH2 NH2

N (C2 H7 N)

\ CH3 COC/

CH 3CH 2C02H CH3CH 2CH 2NH2

a
JI
p
a p
+v
CH 3CH 2COCI

J
L .,
CH3 CH2 COCI
tv
I
lvJ VII
i VI VII

CH3 CH2CONHCH2CH3 CH3CONHCH2CH2CH3

J K J K

(a) Draw the structural formulae of the lettered compounds J 10 a in the boxes {b) reaction 1:
~~- m reaction II:
reagent: KCN.
reagent: PC/5 •
condition; heat.

(b) Suggest reagents and conditions for the following. condition: dry, no moisture.
reaction IV: reagent: LiAIH,. condition: dry ether.
reaction I
reaction II (c) reaction IV: Reduction.
reaction IV [3)
reaction VI: Nucleophilic substitution.
(c) What type of reaction is occurring in
{d) (i) Amide
reaction IV,
reaction VI? [2) (ii) Amine
 topic 10.6 Carboxylic Acids & Derivatives Page 17 topic 10.6 Carboxylic Acids & Derivatives Page 18
~CORNER ~CORNER
(b) (i) pV= mRT
Question 12
M,
An organic compound, E, has the following composition by mass: => M = mRT = 0.13x8.31x400 = 74 _5 mol-'
C, 48.7%; H, 8.1%; 0, 43.2%. ' pV 1.00x105 x58.0x10-6 g

(a) Calculate the empirical formula of E. [2] (ii) Emperical formula mass(C3H60 2 ) =36 + 6 + 32 =74
(b) When vaporised in a suitable apparatus, 0.130 g of E occupied a volume
n = Molecular Formula Mass 74.5.,
of 58.0 em' at 127 oc
and 1.00 x 10 5 N m-2 . 1
Emperical Formula Mass 74
(i) Use the expression pV = mRT to calculate M, of E, Hence Molecular Formula is C3H.02
M,
where m is the mass of E. (c)

(il) Hence calculate the molecular formula of E. [4]

(c) Compound F, is an ester with the molecular formula C,Hp2 •
F is one of four isomers, S, T, U, and V, that are all esters. HC02 CH(CH3 ) 2 HC02CH 2CH2CH3 CH3 C02CH2 CH3 CH 3CH2 C02CH 3
In the boxes below, the· structural formula of S is given.
Draw the structural formulae of the other three isomers of F that are esters.
s T u v
(d) (i) Dilute aqueous acid or dilute aqueous alkali.
(ii) Carboxylic acid or salt of carboxylic acid.

(e) (i) Aldehyde

s T u v (ii) G is a primary alcohol because primary alcohol oxidises to aldehyde.

(iii) CH,OH or CH3CH 20H or CH,CH2CH,QH.
(3]
(d) When the ester F is hydrolysed, an alcohol G is produced. (f) (I) S (Q (i) Ester S is made
from propane-2-ol which
(i) What reagent can be used to hydrolyse an .ester to an alcohol? (ii) On hydrolysis of S, secondary alcohol propane-2-ol is produced. oxidises to ketone, hence
(II) What other type of organic compound is produced at the same time? it cannot be ester F.
[2]
Question 13
(e) On mild oxidation, the alcohol G gives a compound H which forms a silver
mirror with Tollens' reagent. (a) Compound G can be synthesised from benzene by the route shown below.
(i) What functional group does the reaction with Tollens' reagent show to
be present in compound H? Give the name of this group.

~6
(ii) What type of alcohol is G?
HN03 +
n~
(iii) What could be the.structural formula of the alcohol G? [3]
(f) (i) Which of the four isomers, S, T, U, or V, could not be F?
(ii) Explain your answer. [2]
v 55°C

{J10/P2/Q4]

H step 3!
Suggested Solution:
0
(a) c H 0

Divided by Ar value
48.7 8.1 43.2 A OH

~6
12 1 16
No.. of Moles

Simplest whole no. ratios

= 4.06
1.5
3
8.1
3
6
2.70

2
- 6-
step 5 step 4

.. Emperical formula = C 3H60 2 G

.1·
 topic 10.6 Carboxylic Acids & Derivatives Page 20
topic 10.6 Carboxylic Acids & Derivatives Page 19
~CORNER Suggested Solution: ~CORNER
(I) Name the functional group formed in step 5.
(a) (I) Ester
(II) Draw the struclures of the intermediates H and J in lhe boxes above.
(ii)
(iii) Suggest reagents and conditions for the following.
step 2 ...................................................................................................................
step 3 .................................................................................................................. . NH2
HN03 +

o~
6 ~6
slep 4 ...................................................................................................................
slep 5 ........................................................................................................... [7) 55"C
(b) in a reaction discovered just over t 00 years ago by the German chemist
Karl Fries, compound G is converted inlo compound K when it is heated
with A/C/3 •
Compound K is a structural isomer of G. H I step 3l
0
0

Ao
6 CH3~0 OH N'==Ncr

6=6~ 6
CH,
A/C/3

G K (C 8 H80 2)
G I
J (C6 H5 N2 CI)
Compound K is a 1,4-disubstituted benzene derivalive. It is insoluble in
water, but dissolves in NaOH(aq). It gives a white precipitate with Br,(aq), (iii) step 2: Sn and concentrated HCI.
and a yellow precipitate with alkaline aqueous iodine.
step 3: HN02 (NaN0 2 + HC/), temperature 0 - 10 "C.
(i) What is meant by lhe term structural isomerism?
step 4: Heat the solulion above 10 "C.
(ii) Use the information given above to name two lunctional groups in
CO!lJPOUnd K. step 5: Ethanoyl chloride or CH,COC/.
(iii) Suggest the structural formula of K, and draw it in the box above. (b) (i) It is phenomenon by which different chemical compounds have same
(iv) Suggest structures for the aromatic producls of lhe following reaclions. molecular formulae but different structural formulae.

l, , ,
K (ii) Phenol and Ketone.

NaOH(aq) (iii) ~

c~o AIC/3

H,C-C-0
¢
G K (C 8 H8 0 2 )

(7]
[N10/P4/Q5]
 topic 10.6 Carboxylic Acids & Derivatives
Page 21
~CORNER 7opic 10.7
(iv)

Xi/roy en Compounds

¢
Content

¢coo- "'*"' COCH, COCH,

2
Primary amines (exemplified by ethylamine and phenylamine)
(i) Formation.
(Ii) Salt formation.
(iii) Other reactions of phenylamine.
Amides (exemplified by ethanamide)

I
(i) Formation from acyl chlorides.
(u) Hydrolysis.
3 Amino acids (exemplified by aminoethanoic acid)
(i) Acid and base properties.

~
(ii) Zwitterion formation.
4 Proteins
(i) Structure, based on the peptide linkage.
(ii) Hydrolysis of proteins.

Learning Outcomes
Candidates should be able to:
(a) describe the formation of ethylamine (by nitrile reduction -see also Section I 0.3) and
of phenylamine (by the reduction of nitrobenzene).
(b) explain the basicity of a mines.
(c) explain the relative basicities of ammonia, ethylamine and phenylamine in terms of
their structures.
(d) describe the reaction of phenylamine with:
(i) aqueous bromine.
(ii) nitrous acid to give the diazonium salt and phenol.
(e) describe the coupling of benzenediazonium chloride and phenol and the use of similar
reactions in the formation of dyestuff.
(/) describe the formation of amides from the reaction between RNH, and R'COCL
(g) describe amide hydrolysis on treatment with aqueous alkali or acid.
(h) describe the acid/base properties of amino acids and the formation of zwitterions.
(i) describe the formation of peptide bonds between amino acids and, hence, explain pro-
tein formation.
OJ describe the hydrolysis of proteins.
(k) describe the formation of polyamides (see also Section 10.8).

Note: The additional learning outcomes to be studied by A2 candidates are shown in bold type. The A2
components will assess all learning outcomes and will not be limited to those in bold type.

~' '"'·" "'-

topic 10.7 Nitrogen Compounds Page 1 topic 10.7 Nitrogen Compounds
~CORNER
Page2

(e) Compound C is an diacyl chloride with an electronegative oxygen and chlo- ~CORNER
rine attached to carbon-1 and carbon-4. The carbonyl carbons are thus much
more partially positive than the corresponding Carbon·1 and carbon-4 in 1,4-
~(j}) fP) fi4J dichlorobutane at which chlorine atoms are attached. Carbons 1 and 4 in

fJ \.!!/ t.r u~ qpening ....... . compound C are so partially positive that they are attacked by even a weak
nucleophile such as water. Also carbons 1 and 4 in compound C are sP'
hybridised (compound to those 1,4·dichlorobutane which are sp' hybridised)
so that they are less sterically hindered and more easily attacked by nucleo-
Question 1 philes. Hence, compound C reacts with water much more vigorously than 1,4·
dichlorobutane.
The compound butane-1,'1-diamine, E, can be synthesised by the following route. Organic product from C is butanedioic acid (HOCCH,CH,COOH).
I II (f) (i) Dehydration/Condensation (Q · F is an acidic anhydride and
HO,CCH,CH,CO,H -~ C.COCH,CH,COC/ --+ C,H,N,O, reacts with ethanol with the
(ii) HOOC - CH 2CH, - COOC,H
8 c D 5 following mechanism:

(a) Suggest reagents for steps I and II.

lm
NH,CH,CH,CH,CH,NH,
E
[2)
~
~--7ri--?r1o
(V· ~-
C,H,--o,__
/~
0

C,H, 'tJ H ) C,H,

0

+
- r-{_3"-
}?'o
1 5
CH
CH,-0-H

CH/
2 5
s: 0

+C H 0H
H C,H,-0 C,H,-0-H 2 5
(b) Name the functional group present in D and suggest its structural formula [2)
"'H 'H
(c) What type of reaction occurs in step III? [1)
(d) E can react with C to form a polymer. Question 2
(i) What type of polymerisation is this?
(ii) Draw the displayed formula of one rspeat un~ of the polymer formed. [3) When dissolved in water, ethylamine, C,H,NH2 , produces an alkaline solution, (b) (i) In general, alkylamines
whereas ethanoic acid, CH,CO,H, forms an acidic solution. are stronger bases than
(e) Compound C reacts with water much more vigorously than 1,4-
(a) Write equations to explain the chemical behaviour shown in these reac- ammonia. This is because
dichlorobutane does.
tions. · [2] alkyl groups are electron-
Suggest ari explanation of this arid identify the organic product from C. [2)
donating so that they make
(f) When heated strongly, 8 produces compound F. (b) Describe and explain the lone-pair of electrons on
(i) why the basicity of ethylamine differs from those of ammonia and N more available for bond-
0
1/ phenylamine; ing. The basicity of
CH,-C, alkylamines increases with
I o (ii) why the acidity of ethanoic acid differs from that of chloroethanoic acid, the number of alkyl groups
CH - C / CH,C/CO,H. [5)
2 ~ attached to N so that
0 (c) Ethylamine ·and ethanoic acid react together at room temperature to pro- (CH,) 2 NH is a stronger
F duce compound A (C,H,O,N). Suggest a structure lor compound A, and base than CH,CH,NH2.
(i) What type of reaction has occurred in the formation of F? describe the type of reaction undergone. [2) Generally, arylamines are
weaker bases than ammo-
(ii) F slowly reacts with water, giving 8 again. Suggest the structural for- (d) Suggest the structural formulae for compounds 8 and C in the following
scheme: nia. This is because the lone-
mula of the compound that might be produced if F were to react with
pair of electrons on N
ethanol rather than water. · [2)
PC is C2NsNH2 delocalises into the ben-
[JOO!Pt/07] CH3 C02H or SOC/2 B c zene ring. Electron-with
drawing groups such as
[2)
bromineandNO,onthering
Suggested Solution: (e) Suggest reagents and conditions needed to re-form ethylamine and ethanoic enhances the delocalisation
(a) Reagent for step I : PCI, acid from C. . [1] of the lone-pair of electrons
Reagent for step II : concentrated ammonia into the benzene ring so that
[NOO/P1/06]
their presence decreases
(b) Amide, 0 0 the basicity ofthe ary/amine.
II II Suggested Solution: On the other hand, electron-
H,N-C-CH,CH,-C-NH,
(a) donating groups such as
(c) Reduction CH3 NH2 + H20 ~ CH 3NH3++OW alkyl and OH decreases the
delocalisation of the lone-pair
(d) (i) Condensation polymerisation CH3 COOH + H2 0 ~ CH 3 Coo- + Hp• of electrons into the benzene
0 0 H H (b) (i) The basicity of ethylamine is higher than that of ammonia which is higher ring so that their presence
. II II I I than that of phenylamine. increases the basicity of the
(il) -C-CH,CH,-C-N-CH,CH,CH,CH,-N- arylamine.
 topic 10.7 Nitrogen Compounds
Page3 Page4

~
topicl0.7 Nitrogen Compounds
~CORNER
CORNER

Lone pair of electrons is donated by a base to water so that the basicity In general, acidity of an
(b) (iij Question 4
of a base depends on the availability of the lone pair for donation. The acid is enhanced by the
presence of electron-with- (a) Suggest reagents and conditions for each . . .
of the amino acid alanine and identit th s~ep rn th_e following synthesis
ethyl group in ethylamine is electron donating so that it causes the lone
pair of electrons on N to be more available for donation compared to that drawing groups and de-
' Y e rntemnedrate E
creased by the presence of
in ammonia so that ethylamine is a stronger base than NH,.
For phenylamine, due to the overlap of the p-orbital of N with the n-elec-
electron-donating groups. CH 3CHC/CN ___t__. E ~ CH3CH(NH2 )C0 2H
.
(c) Ethanoic acid is weak acid alanine
[4]
tron cloud of the benzene ring, the lone pair of electrons on N is delocalised while ethylamine is a weak
into the ring. It is thus less available tor donation so that phenylamine is (b) Draw the structural formulae of the compounds formed
base. When they are mixed when glycine,
a weaker base than ammonia and hence a weaker base than ethylamine. NH,CH,CO,H, reacts with
at room temperature. they
react to give ammonium (i) aqueous NaOH
(ii) The acidicity of an acid is dependent on its degree of dissociation which
elhanoate: (ii) aqueous HCI. '
is dependent on the stability of its anion formed by the dissociation of the
acid. Due to its electronegativity, chlorine is electron-withdrawing and CH 3COOH + CH 3CH 1NH 1 (c) Proteins are polymers fomned b . . . [2]
disperses the negative charge on the chloroethanote ion. Charge dis- (I) Give the name and the d" I Y Jornrng together many amino acids.
~ CH 3COO"CH 3CH 1NH 3•
persal results in stability so that chloroethanote is more stable than acids in proteins. rsp ayed formula of the linkage between amino
ethanoate. Hence chloroethanoic acid dissociates to a greater extent than (d) An acid chloride is formed
(ii) State which reagents and conditions can be used to h d I
ethanoic acid and so ethanoic acid is a weaker acid than chloroethanoic when an acid reacts with Ieins. Y royse pro-
PCI, or soq, e.g. : 3
acid. (d) Partial hydrolysis of a tetra e tid . . [ ]
(c) A is CH,COO-CH,CH,NH,•. The type of reaction is neutralisation. CH 3C00H+PCI 5 pr?duces the following thre~ ~ipe~t~ontarnrng four amino acid residues)
acrds. 1 es, as well as the individual amino
~ CH 3COCI + HCI + POCI,
(d) B is CH,COCI while C is CH,CONHC,H,.
(e) To re-form ethylamine and eth.anoic acid from C, C is hydrolysed by heating
with aqueous sodium hydroxide (or dilute sulphuric acid).
An acid chloride readily
reacts with an amine to form I
~
NH,CH,CONHCH(CH3)CO,H NH,CH,CONHCH,CO,H
Deduce the order in which the a . . NH,CH(CH,)CONHCH(CH3)CO,H
tetrapeptide. explaining your reasomnr~o acrds are bonded together in the
~
an amide and water: rng. [3]
CH 3COCI + C1H5NH 1 {N01/P1/Q7]
~ CH 3CONHC 1H5 +HCI
Question 3
Suggested Solution:
(e) Amides can either by hy·
drolysed by heating it with a (a) For reaction 1: R eage_nt : Dilute hydrochloric/sulphuric acid
dilute acid or a base. How-
(a) For each of the compounds shown, suggest the approximate pH values of Condrtron : reflux -
ever the products of the
the solutions formed when each dissolves in water. hydrolysis is not a carboxy· For reaction 11: R eag_ent : concentrated aqueous ammonia
lie acid and an amine but a Condrtron ·· w amnrng
· · a sealed tube
E: ................................ ,F: ................................... , G: ..................................... [2] carboxylic acid and the rn
amine salt in acid hydroly-
(b) Apart from their pH values in aqueous solution, describe one typical chemi- 0
sis and the carboxylate salt
cal reaction tor each, including the relevant equation. [6] and the amine in base
II
(b) (i) H,N-CH, -C-O"Na· (b) OH- removes H' from
[J011P2105} hydrolysis: NH,CH,CO,H to give
CH 3CONHC 1H5 + H,O + W H 0 NH,CH,CO,· and water.
Suggested Solution: ~ CH 3COOH+C 1H5NH,• (ii) crH-W-CH,-C-OH
I II NH,CH 2C02H(aq) + OH·
I . (<KJ)
(a) E Approximate pH ; 10 CH 3CONHC 1H5 + OH' H
-> NH,CH,CO,-(aq) +
F Approximate pH ; 6
~ CH 3COO- + C1H5NH 1 0 H,O(I)
G Approximate pH ; 4 II
To obtain carboxylic acid and (c) (i) amide linkage : H· protonates
(b) E is an amine and reacts with an acid to form a salt, e.g. with dilute hydro- -C-N-
an amine after base hydroly- NH,CH 2CO,H.
chloric acid, ethylammonium chloride is formed : 1
sis, the mixture containing H
CH,coo· and c,H,NH, is NH,CH,C02H(aq) + H'(aq)
C H NH (aq) + HCI(aq) --> C 2H5NH;cqaq) (ii) Reagents :
2 5 2 fraclionally distittea to obtain dilute acid such as dilut h d . .
ethylamine. The resultant such as aqueous sod_e yhrochl~nc acrd or dilute alkali -> 'NH,CH2CO,H(aq)
F is an amino acid containing the -NH, group and reacts with nitrous acid to
mixture is then acidified to Condition : reflux rum ydroxrde.
give nitrogen gas: obtain carboxylic acid.
H NCH C0 H(aq) + HN0 2 (aq) --> HOCH2 C0 2H(aq) + N2 (g)+ H,O(!) (d) From the structures of the two di .
2 2 2 NH,(CH(CH,)CONHCH(CH )CO H ·t peptrdes NH2CH2CONHCH2CO H and
G is a carboxylic acid and reacts with sodium carbonate solution to give carbon molecules of NH CH CO H' 2 1.' r can be seen that in the tetrapeptide two
' ' 2 are rnked conse r 1 •
dioxide gas : molecules of NH CH(CH )CO H . cu rve Y to each other and two
2CH CH C0 H(aq) + Na C0 (aq) --> 2CH 3CH 2 CO;Na•(aq) + C0 2 (g) + H2 0(/) respectively. 2 ' 2 are lrnked consecutively to each other
3
3 2 2 2
,.

,>

til~.. . ~.~
(r( .......

topic 10.7 Nitrogen Compounds Page6

PageS
toQicl0.7 fl}itrog_en CQ!flQ.ounds ~CORNER (iii) The lone-pair of electrons on N in phenylamine delocalises into the ~CORNER
benzene ring and is thus less easily available for donation. Since a base
From the structure of the dipeptide NH,CH,CONHCH(CH,)CO,H, it can be is a lone-pair donor, and the lone-pair in phenylamine is less ·available
seen that starting from the -NH, end, NH,CH,CO,H appears before than that of ammonia, phenylamine is a weaker base.
NH,CH(CH,)CO,H. (c) {i) Sodium nitrite, dilute hydrochloric acid, 0 - 5 oc.
From this information, it can be deduced that starting with the -NH, end, the
order in which the four amino acids are bonded in the tetrapeptide is
NH CH C0 H, NH,CHCO,H, NH,CH(CH,)C02H and NH,CH(CH,)CO,H.
2 2 2 (iii)o-
. N=N
-o-
(ii) Aqueous sodium hydroxide

~ OH
(c) Diazonium ion and azo dye
formation are no! required in
the revised syllabus .

Question 5 CH,
Phenylamine is an important intermediate compound for the production of dyes.

ONH2 Question 6

phenyl amine This question is about compound K, C,H,ON, which is formed when
phenylhydroxylamine, C,H,NHOH, is warmed with dilute sulphuric acid.
(a) Phenylamine can be synthesised from benzene in two steps. Draw the
structural formula of the intermediate Y in the scheme below, and suggest Compound K is not very soluble in water, but dissolves in HC/(aq).
reagents and conditions for steps 1 and ll. II also dissolves in NaOH(aq), but not in Na,CO,(aq).
On reaction with 1 mol of ethanoyl chloride,CH3COC/, K forms compound
L, C,H,02 N.

0 - y
- II
o-~H2 L is no longer soluble in HC/(aq), but is still soluble in NaOH(aq). On reaction
with Br,(aq), L produces compound M, C,H,O,NBr,. When K is reacted with 2
mol of ethanoyl chloride, it produces compound N, C, 0 H,O,N, which is not
soluble in either HCI(aq) or NaOH(aq).

reagent + conditions for step 1 Compound K can be synthesised by treating phenol with dilute nitric acid,
[4] followed by reaction with zinc metal and hydrochloric acid.
reagent + conditions for step 11
Deduce the structures of compounds K, L, M and N. Explain the chemistry of
(b) Phenylamine is a weak base. the reactions described, writing equations where appropriate. [There is no need
(i) Write an equation showing phenylamine acting as a base .. to comment on the chemistry of the formation of K from phenylhydroxylamine.]
(ii) How would you expect its basicity to compare with that of ammonia? [10]
(iii) Explain the reasoning for your answer in (ii). [3] {N02/P31QB Or]
(c) Dyes can be made from phenylamine by first converting it into
benzenediazonium chloride, and then coupling this with a phenol.
IV Suggested Solution:

O NH
lll -dye
ON2+c!- Structure of K, L, M and N :
2 - +a phenol
H H H
(i) Stale the reagents and condition needed for step lll. I I I
(ii) What reagent is the phenol dissolved in for step IV to be effective? r;ryNH, aN-A-CH, BruN-A-CH, aN-~-CH,

H~ L HO~ M
(iii) Suggest the structural formula of the dye formed when
benzenediazonium chloride is coupled with 2-methylphenol. [4] HO)Vl K CH -C-0)\)l N
(J021P4!07]
Br ' M
K contains a benzene ring and is not ionic so it does not dissolve in water. However,
Suggested Solution: the presence of a basic -NH, group makes it soluble in dilute HCI as the ionic
(a) reagent + conditions for step l : concentrated nitric acid, concentrated sulphuric amine salt is formed on acidification:

acid, 60 oc. ~NH,

reagent + conditions for step ll : tin and concentrated hydrochloric acid, reflux.
(a) The concentrated sulphuric
acid is needed to generate
the NO( electrophile from
HO)Vl K + H• ----->HOC""·
(b) (i) o - N H , + H,O .- --" o - NH; + OH- nitric ac1d:
H2SO, +HN0 3 --tHSO; +H 2NO;
(ii) Its basicity is lower than that of ammonia.
H2NO; --tH,O+NOi

'',
-' ,,
'
I'
 Pa e3
Page 7 topic 10.5 Carbonyl Compounds
topicl0.7 Nitrogen Compounds
~CORNER ~CORNER.
On reaction with aq. NaOH, nucleophilic substitution occurs:
K also contains an acidic phenolic-OH group and reacts with aq NaOH to give
Cl OH .
the ionic phenoxide:

NH, - ONH, C H , - t - o - O H + 20H. ~ C H , - t - o - O H + 2Ci"

+OH ~ + H,O OH
Cl H
G
HO K -o Since the two hydroxyl groups are on the same carbon. H immediately
K is not a carboxylic acid since it does not react with aq Na,CO,. loses water to give J:
Ionic organic compounds are more soluble than the corresponding non-ionic OH
compound as the former forms stronger ion-dipole interactions with water mol-
ecules than the latter which can form only hydrogen bonding with water molecules CH,-t-Q-oH
or interact with water molecules with van der Waals forces.
OH H
On reaction of K with 1 mol of ethanoyl chloride, an amide L is formed: (iQ Chlorination of the alkyl
J is a ketone with a carbonyl functional group and reacts with 2,4-
IN-n dinitrophenylhydrazine to give an orange precipitate of 2,4-
group of an alkyl benzene

o.
occurs via a free radical
0 -CH, dinitrophenylhydrazone: substitution mechanism.
~NH, II
+
0 + HC/ NO, Substitution occurs at the C

HO)VK
CH,-C-C/
HO L

An amide is neutral since the lone pair of electrons on N is much less available
for donation due to the withdrawing effect of the carbonyl group so that L is not
c",-i-Q-o" •
0
".N'" -b
~
---> c><.-i-0-o" •
N
.;,o
attached to the benzene ring
because the radical formed
is stabilised by resonance.

I CH,-~H-o-OH

'0'0'0,
soluble in dil HC/. However, the presence of the phenolic-OH group in L enables NO,
NH
it to dissolve in aq NaOH: Hence G is formed rather
than the following isomers:
H
I

HOo. L
N-TIO-CH,
+ OH

On reaction of L with bromine water, dibromination occurs at the 2- and 6- position

due to the highly activating phenolic-OH group to form M :
J has the CH C = 0 functional group and reacts with alkaline aqueous iodine

to give CHI,:
3
I
CH,C/-?H -Q-oH
C/

CHC/,- CH, -Q-oH

H
H CH,-c-Q-OH + 31, + 40H-
11
~ · o -IIc - Q - O H +CHI, + 3H,0 + 31-
I I
N-OTI-CH, + BruN-~-CH, + 0 0
2HBr J is not an aldehyde and thus has no reaction with Fehling's solution.
2Br, ~

HO L HO~M (ii) G is reacted with chlorine at room temperature in the presence of u.v. light.
Br

On reaction of K with 2 mol of ethanoyl chloride, an amide and ester N is formed:

Question 3
H
I The three formulae P, Q and R shown below are of compou~ds which are
N-C-CH important flavours in citrus fruits. These compounds are much used in the food
II ,
0 and perfume industries.
~NH,+ II CH - C - 0 N O + 2HC/ CH, CH, CH,
I I
2CH,-C-C/ , II I /CH...._
/c, /CH...._
HO)VK 0 CH, ...,CH CH, CH, CH, CH,
I I I I I I
CH, CHO CH, CHO CH, CH,OH
Since neither of the amide or ester group is basic or acidic, N does not react with ......
...... 'cH
aq. NaOH or dil HCI to form ionic salts so that N is not soluble in aq. NaOH or ?H, ?H,
I '
HC/. c c c
On treating phenol with dilute nitric acid, 4-nitrophenol is formed : CH;' """cH, CH;' """cH, cH;' """cH,

~
p Q R

HO~
ONO,+
+ HNO, 2H,O (a) State the type of isomerism which occurs in Q but not in P and draw two
HO structures which illustrate this isomerism in Q.
 Page 7
topic 10.7 Nitrogen Compounds Page 8
topicl0.7 Nitrogen Compounds
~CORNER Reaction of 4-nitrophenol with zinc and hydrochloric acid causes -N0 group to ~CORNER
K also contains an acidic phenolic-OH group and reacts with aq NaOH to give be reduced to -NH, group forming K : 2

the ionic phenoxide:

O
NO, JO:NH,
~NH, rnrNH,
+ 6[H] ----7 K + 2H,O
HO}VJK + OH
~ ·o)VJ + H,O
HO HO

K is not a carboxylic acid since it does not react with aq Na,CO,.

Ionic organic compounds are more soluble than the corresponding non-ionic Questio11 7
compound as the forrr]er forms stronger ion-dipole interactions with water mol- Caffeine is a stimulant found in coffee and tea.
ecules than the latter which can form only hydrogen bonding with water molecules It is also added to cola drinks.
or interact with water molecules with van der Waals forces.
The structure of caffeine is given below.
On reaction of K with 1 mol of ethanoyl chloride, an amide L is formed:
0 CH3

I
N-C-CH
CH, II
"N ,.....--c "c ,.....--N"
I
II ,
C
rnrNH, 0

HOJV K + CH 3-~-C/ ~
HO O
+ HCI

0~
I
N
II #C-H
#c"- ,.....--c"-N~
An amide is neutral since the lone pair of electrons on N is much less available I
CH3
for donation due to the withdrawing effect of the carbonyl group so that L is not
soluble in dil HC/. However, the presence of the phenolic-OH group in L enables (a) (i) On the structure above, label (with a ') a carbon atom with bond angles
of 109•.
it to dissolve in aq NaOH:
H (ii) Also on the structure above, draw a circle round an amide group. [2]

I I {b) Decaffeinated coffee and lea are made by extracting the caffeine from solid
N-C-CH
II • OH---> _OoN-g-CH, coffee or tea using a solvent

HO C 0
3

On reaction of L with bromine water, dibromination occurs at the 2- and 6- position

+ H,O Suggest, with two reasons, which of the following industrial solvents would
be the most suitable.
benzene
a hydrocarbon, such as cyclohexane
due to the highly activating phenolic-OH group to form M :
Cl liquid carbon dioxide
H

I
N-C-CH BruN-~-CH3
I
+ {c) {i)
solvent chosen
State the molecular formula of caffeine.
[3]

II
C
3
2HBr (ii) Calculate the relative molecular mass of caffeine.
HO 0 + 2Br, ~
HO~M (iii) A can of cola contains 50 mg of extracted caffeine in a volume of 330
em'. Calculate the concentration of caffeine in mol dm""'. [4]
Br
[N03/P2/Q4}
~ On reaction of K with 2 mol of ethanoyl chloride, an amide and ester N is formed:
H Suggested Solution: (a) (i) Theremaining5carbon
Tl
in: I
N-C-CH
(a) (i) (ii) ,. - . atoms have trigonal planar
ar II , • :0\ "" structure.

~NH,+
2CH,-C-CI
0
II ~ CH,-C-O II JO: 0 + 2HCI
CH3 }
-x<,....c~
',_N __ / c/N
_.-{---- II
I
II : CH3

"
(iQ Only one carbon atom
needs to be labelled and one
amide group needs to be
HO}VI< 0 ('df' '-.. N'yC "-N,f'C- H circled (not all 3).

(b) A suitable solvent should be

Since neither of the amide or ester group is basic or acidic, N does not react with ---------( one that dissolves caffeine
aq. NaOH or dil HCI to form ionic salts so that N is not soluble in aq. NaOH or 'CH3
readily. At the same time,
HC/. {b) Liquid carbon dioxide after extraction, it should be
On treating phenol with dilute nitric acid, 4-nitrophenol is formed : easily removed from the
Reason 1: Caffeine contains polar amide and amine groups and hence is
coffee/tea to minimise con-

~
soluble in liquid carbon dioxide which is also polar.
{a) tamination. Liquid CO, has
+ HNO, a N O , + 2H,O Reason 2: both properties. In addition, it
Alter extraction, carbon dioxide can be easily removed since it
HO)Vl is very volatile. is also non-toxic.
HOA)
 Page9 topic 10.7 Nitrogen Compounds Page 10
topic 10.7 Nitrogen Compounds
~CORNER ~CORNER
(iii) Describe the different conditions needed to make A and B from
(c) (i) C,H,N,O, 2-bromopropane. [1]
(ii) M, = 8 X 12 + 10 X 1 + 4 + 14 + 2 X 16 = 194
(b) (i) Identify the lettered compounds C - F in the following scheme of
3 reactions.
SOx 10- I
(iii) n = mo
194 C ~ CH 3 CHBrCH 3
NaCN
~ D
50x10-3
Concentration = 194
~=

1000
7 ·81 x 10--4 mol dm-3
1 heat with H30+

(CH,),CHCONHCH(CH 3 ) 2 PCI5
F ~ E [4]
G

Question 8 (il) Name the functional group present in compound G. [1]

. . 1 · anic synthesis. It can be made
2-Bromopropane is a useful dmtermd edlae: ~::~ely of reactions, some of which [N03/P2/06]
industrially from propene, an un ergo (a) AfurthersludyofspectrumA;
are mentioned below. . The 3 protons at li = 1.7
d 'th d'um
1 hydroxide under d11ferent Suggested Solution: ppm is adjacent to a C -
(a) When 2-bromop~opane is treated w~ (~~ ) and 8 (C H OH), are formed.
conditions, two different compoun s, 3 , 3 ' H group since the. signal is
Their nmr spectra are shown below. H H H aduplet.
(a) (i) I I I
3H A H-C-C=C-H H H
I I I
H i.e. H-C-C
The dulpet at '6 = 1. 7 ppm corresponds to the CH 3 group. The quartet at
I
H
li = 5.0 ppm corresponds to the = CH 2 group. The multiplet at '6 = 5.8 ppm
corresponds to the C - H group. The 2protons at li =5.8 ppm
are not identical (due to the
H H H restriction in rotation at the
I I I doublebond), thequadruplet
B : H-C-C-C-H
is a double splitting pattern,
I I I one bigger than the other
H OH H
one.
The duple! at li = 1 ppm corresponds to the 2 identical CH 3 groups. The
c~ =
singlet at li 2 ppm corresponds to the OH group. The multiplet at li = H..,_ /H
4 ppm corresponds to the C - H group. C=C
I I
3.0 2.5
I I
2.0 1.5
/ '-H
5.0 4.5 4.0 3.5 (ii) There is no effect to A.
chemical shift '61 ppm The 2 sets of splitting is
A The singlet at li =2 ppm will disappear. caused by an adjacent
(iii) A : Ethanol solvent, heat. C - Hgroup and the other
(6H) one by the close neighbour
B : Water solvent, heat. C - Hat the double bond.
(b) (i) C: CH -CH-CH Afurtherstudyofspectrum B:
3 I 3
The 6 protons at li = 1ppm
NH,
is adjacent to aC- Hgroup
D: CH 3 -yH-CH 3 since the signal is a duplet.
(1H) H H H
CN
I I I
E: CH 3 -yH-CH3 H-C-C-C-H
I I
(1~) CO,H H H
F: CH 3 -CH-CH
I , The single proton is sextet
li = 4 ppm is due to the 2
9 8 7 6 5 4 3 2 0 COCJ
11 10 adjacent groups of CH,.
B chemical shift OJ ppm (ii) Amide The proton in the 0 - H is
remote from the rest. Hence,
(i)
. .
Use the spectra to 1dentlfy compoun_ s
d A and B and draw their struc-
• [ ] n appears as a singlet at
(a) 3 li = 2ppm i.e. the signal is
tural formulae. Explain your reasomng.
not split.
(ii) Predict the effect on their nmr spectra (if any) of adding D,O to separj\j
samples of A and B.
 topic 10.7 Nitrogen Compounds Page 11 topicl0.7 Nitrogen Compounds Page 12
~CORNER
(ii) Construct a balanced equation for this reduction. Use [H] to represent ~CORNER
Question 9 the reducing agent. (2]
The thyroid gland concentrates iodine and uses it to produce thyroxine, which (c) Lycra is a polyamide which is made from a diamine produced by a similar
is a hormone that controls the metabolic rate. reduction.

(i) There are six structural isomers of diaminomethylbenzene,

HO-P-'o0-P-'oLL/
CH,C,H,(NH,),. Draw the structures of three of the six isomers.

I I "-oH
H NH,
[. l

thyroxine
[The - 0 - group is inert and for the purpose of this question is to be con-
sidered as not affecting the adjacent benzene rings.]
The manufacture of Lycra involves one of these six isomers. A small
(a) (i) Draw a circle around the chiral centre on the formula of thyroxine printed
section of Lycra is shown below.
above.
(ii) Thyroxine can undergo self-polymerisation. State what type of H H
polymerisation thyroxine can undergo. o~ I I .f'o
(iii) Draw the displayed formula of the linkage formed when thyroxine polymerises. .......-c-N'QN-c, _
(3] 0
(b) In the space below write the formula of the organic product when thyroxine CH,
reacts with cold aqueous sodium hydroxide. [2] ~~
[N031P3!06] !I! (ii) Draw the structure of the isomer of diaminomethylbenzene used in the
manufacture of Lycra. (You may or you may not have included this
isomer in the ones you have drawn in (c)(i).) [4]

I o*I HH O
Suggested Solution: [N04/P2/05]

0 ?+c(
Suggested Solution:

(a) (i) HO (a) 2H2 S04 +HN03 ;===: N02 ' +2HSo,- +H3 0'
Cf- (a) Thyroxine is an amino acid
H NH OH

*
and it undergoes condensa-
I I ' CH, CH,
tion polymerisation and
(ii) Condensation polymerisation amide bonds are formed.

Qvto: ~ ~~
t
(b) (iQ To balance the equa-
0 H
H
I
~
HHOt
I I II
N-~-C
tion, first balance all atoms
(other than 0 and H) :
...>
(111 -e-N-
II I H,N-y-CO,H + H,O

9~9
9
R
~:

0~
I l
Th

N<t-o-P-o-P-b-b-c~
0 NO, NH,
im1
an< (b)
I NHI "-o-N •
H
l I '
a
(b) The phenolic group and car-
boxylic acid group react with
OH-to form salts (phenoxide H NO,
NO,
•HM, Next. balance 0
adding H20:
by

Q~Q.,~
and carboxylate).
The reaction between concentrated H,SO, and HNO, produces the electrophile,
NO,+. The Nb,+ acts as an electrophile and attacks the electron rich benzene
Question 10 ring, followed by the release of H• to form the product.
NO, NH,
Methylbenzene (toluene) is an important industrial chemical. One of its uses is (b) (I) Sn + concentrated HC/
Lastly, balance H by
in the production of fibres such as Lycra. adding [H] :

9
(a) The first stage of the manufacture involves the nitration of methylbenzene.
CH, CH,

"''9 ¢ ¢
Describe the mechanism of the nitration of methylbenzene to form
(a) + 6(H] ~ + 2H,O
4-nitromethylbenzene. [3] + 6[H] --7 + 2H,O
(b) 4-nitromethylbenzene can be reduced to 4-aminomethylbenzene.
NO, NH, NO, NH,
(i) Suggest a suitable reducing agent for this reaction.

i~

~ -.
I I :I
j I
 Page 13 topicl0.7 Nitrogen Compounds Page 14
topic 10.7 Nitrogen Compounds
~CORNER ~CORNER
(c) (i)

q
CH, NH, H,N~NH,
v
6
HN)UlNH,
Question 12

Compound B is an intermediate in the production of a drug which is being

developed to reduce the effects of the HIV virus.
OH
2
I
NH, CH,CHCHCO,H
(c) (i)

CH,
Theother3isomersare

CH,
(Y I
NH,
CH,
6cNH, bNH,
~NH,
compound B

NH, H,N
NH,
(a) Name three functional groups, other than phenyl, which are present in B. [3)
(b) How many chiral centres are present in a molecule of B? [1)
(iQ Fromtheslructure,we (c) At pH 7, B exists as a zwitterion.
can see that the 2 N atoms (i) Explain the meaning of the term zwitterion.
are bonded to the benzene
(ii) Draw the structural formula of the zwitterionic form of compound B. [3)
ring at the 2 and 4-positions
c w.r.t. CH,. Hence, the mono- B can be synthesised from the naturally occurring amino acid phenylala-
Question 11
mer should be 2,4- nine by the following route.
2-phenylethylamine, M, is the 'feel-good' factor in chocolate. II can be synthesised diaminomethytbenzene.
from methyl benzene in a 3-stage process as follows._ ·

____.!__, C H CH C/ ~ L ~ C6H5 CH2CH2NH2 compound C

l
H CH 3
C 65 65 2 M

(a) (i) Suggest reagents and conditions for reaction I. phenylalanine sttip Ill

(ii) use equations to describe the mechanism of this reaction. [5)

OH
(b) (i) Suggest an identity for compound L. I

CH,
(c) (i)
(ii) Suggest a reagent for reaction II.
(iii) What type of reaction is this?
Suggest reagents and conditions for reaction Ill.
(ii) What type of reaction is this?
[3)

[2)
or CH,CHCHCO,H
I .
NH,

compound B

(d) (i). ·suggest what type of reaction is step 1.

{N04/P3/03 Or]
(ii) Draw the structure of the intermediate compound, C.
(iii) What is the significance of step II in this synthesis? [3)
Suggested Solution: (e) Step Ill is a hydrolysis reaction. Draw the structural formula of the product
(a) (i) Limtted amount of Cl,
formed when C is hydrolysed by
(a) (I) Limited amount of C/2 ; uv light. is necessary to reduce
polychlorination of the CH, (i) an excess of hydrochloric acid;
(it) Free radical substitution : group. (ii) an axcess of aqueous sodium hydroxide. [2)
Initiation: C/2 ~2C/· (f) The anti-HIV drug is made by combining B, which is an amino acid, with
the amino acid glycine, H2 NCH,C02 H.
Propagation : C/· + C 6H5 CH 3 ---> CaHsC;H2 + HC/
OH
C 6H5CH2 + C/2 ---> C6 H5CH 2Ci + Cl · I
~CH,,HCHCO,H
Termination : 2C 6 H5 CH 2 ---> C 5H5 CH2 - CH2 - C5Hs
(b) (i) From C,H,CH,C/ to
C,H,CH 2CH2NH2, there is
v NH,
(b) (I) C,H,CH,CN
an increase in the number of compound B
(ii) Alcoholic NaCN Catom(by 1). The pathway, (i) What type of linkage wil be formed between B and glycine?
therefore, is likely to involve
(iii) Nucleophilic substitution (ii) Draw the structures of two different compounds that could be formed
(a) the use of a cyanide.
when one molecule of B reacts with one molecule of glycine. [3)
(c) (i) H2 , PI
[N06/P2104]
(ii) Reduction
 Page IS topic I 0. 7 Nitrogen Compounds
top_ic 10.7 Nitrogen Compounds Page 16
~CORNER
Suggested Solution: Questio11 13
~CORNER
(a) 1. amino (- NH 2 )
Suggest a test or simple reaction you could carry out on each of the following
2. alcohol (- OH)
pairs of compounds to enable them to be distinguished.
3. carboxylic acid (- COOH)
(a) CH,COCH 2CH 2CH 3 CH3CH 2 COCH 2CH
(b) 2 3
J K
(c) (i) It is a dipolar ion when the amino acid exists as a cation (NH, ') and anion
(i) description of test or reaction
(Co,-) at the same time.
(ii) observation with compound J
(ii) OH (iii) observation ·with compound K
[2]
I
~CH,,HCH-CO,- (b)

v •NH, o-NH2 o-NH2

L M
(d) (i) Reduction
c (i) description of test or reaction
(ii) OH
I (ii) observation with compound L
~CH,,H- CHCN (iii) observation with compound M
[2]

v NH, (c) CH3CH 2COC/

N
CH3 CH 2 CH 2 C/
p
(iii) Increase the number of carbon by 1.
(i) description of test or reaction
(ii) observation with compound N
(e) (i) OH
(iii) observation with compound P
I [2]
~CH,,HCHCO,H
CH, v •NH,
(d) CH3 CH,CONH

a
2 CH,CH,CH,NH,
A
(i) description of test or reaction

(ii) OH (ii) observation with compound Q

I (iii) observation with compound A
[2] (a) Only Carbonyl compound
~CH,,HCHCO,-
with CH 3-CO bond

Qu, v NH,
S!lggested Solution:
{N08/P4/Q6}
group gives yellow
crystals of CHt 3 when
warmed with alkaline
The (a) (i) Alkaline aqueous Iodine. aqueous Iodine. K have
imp• (f) (i) Amide
(ii) J gives yellow precipitate. no CH3-CO- group.
and
(ii) (iii) K gives no reaction. (b) Arylamine undergo
OH
OHO H
I II I I (b) (i) Add aqueous Bromine.
electrophillic substitution

a
with aqueous Bromine at
I
CH,CHCHC- N- CH ,CO,H ~CH,,HCHCO,H (ii) No change.

NH, v N-H
I
(iii) White precipitate formed.

(c) (i) Add few drops of water.

room temperature and
form tribromination
product. It is a white
precip~ate.
C=O
(ii) Fizzing takes place and gives off steamy fumes.
I (iii) P has no reaction.
(c) Acyl chlorides are readily
CH, hydrolysed by water at
I {d) (i) Universal indicator solution or litmus.
room temperature to
carboxylic acids. Heat and
NH,
(a) S (ii) Q shows no change. fumes of HCI are evolved.
51
{iii) A will turn solution blue. (d) Amines are basic in
nature.
 topic 10.7 Nitrogen Compounds Page 18

topic 10.7 Nitrogen Compounds

Page 17
~CORNER (b) ~CORNER
halide observation when observation when observation when
AgNOa(aq) dilute NH3(aq) concentr.ated
is added is added NH3(aq) is added
Question 14
chloride white ppt dissolves dissolves
(a) Describe and explain how the basicities of ammonia, ethylamine and
bromide cream ppt slightly dissolves dissolves
phenylamine differ.

6
iodide yellowppt insoluble no reaction

NH 3 CHpH2NH 2

[3)
(c) (i) Ksp =[Ag'J[ Br- J
ethylamine phenylamine
ammonia
as J
[ Ag' =[Br- J
(b) Describe how the use of aqueous silver nitrate and aqueous ammonia can
distinguish between aqueous solutions containing chloride, bromide or ~ Ksp = [ Ag' ][ Ag' J
iodide ions by filling in the following table.
observation when ~ [ Ag' J = ,JK;, = Js x 1 o-'3 = 7.07 x 1o-7 mol dm-3
observation when observation when
halide concentrated
AgNOa(aq) dilute NH3(aq)
NH 3(aq) is added (li) A gB r will be less soluble in KBr solutio 11 · d .
is added is added of Br ion on the right hand side n. . IS ue ~o common ion effect (c) (ii) Le Chatelie(s principle.
to the left-side. of the equation making equilibrium to shift
Cl chloride
bromide
iodide [3)
units: mol-' dm'

(c) Silver bromide is sparingly soluble in water.

3 6
AgBr(s)-.==== Ag'(aq)+Br-(aq) Ksp =5x10-' mol' dm- (II) (c)(i)),
Assuming thenthat most of the Ag'(aq) ' has gone to the complex
· (from part

(I) Calculate [Ag•(aq)] in a saturated aqueous solution of AgBr.

[ Ag'(aq)J = 7.1 x 1o-7 moldm-a,
(ii) State and explain whether AgBr will be less or more soluble in
Q.1 mol dm-o KBr than it is in pure water. [2]
[ Ag(NH3 )~]
(d) Silver ions form complexes with ammonia and with amines. [ Ag'][NHl
CH,
Ag'(aq)+2RNH2 (aq) -.:=== [Ag(RNH 2 ) 2 )'(aq) [ Ag(NH 3 )~] 0.1
(i) Write an expression for the K, lor this react!on, and state its units.
7
K, x[ Ag' J (1.7x107)( 7 .1 x 1o-7) =0.091 moldm-3
K, has the numerical value of 1.7 x 10 when R = H.
(ii) Using your expression tor K, calculate the [NH,(aq)] needed to change (Iii) When H is replaced by c H K · .
the [Ag•(aq)] in a 0.10 mol dm"" solution of silver nitrate to the value group will make the lone pai~· of 'e::c~~ely to ~e greater, since the alkyl
making it more basic. on on mtrogen be more available,
~-
that you calculated in (c)(i).
(iii) Explain whether you would expect the K, lor the reaction where
Th~ R = c,H, to be greater or less than that tor the reaction where R H. =[5)
imp1
and [N09/P4!02]
B~efly explain why the benzene molecule is planar.
Bnefly length.
same· explain why all the carb on-carbon bonds in benzene are the
2
Suggested Solution:
(a) Basicities are ethylamine > ammonia > phenylamine. In ethylamine, the ethyl Benzene can be nitrated by wamn· ·11 . . [ )
and nitric acids. mg With a m1>cture of concentrated sulfuric
group releases electrons towards nitrogen, making lone pair on nitrogen more
available, and in phenylamine, the lone pair is delocalised over the ring, so
(I) ~y ~~:~::c~~~-n equation, illustrate the initial role of the sulfuric acid
is less available.
(il) Name the type of reaction and des 'b .
reaction, including curly arrows s~n ~ thet~echamsm for the nitration
and all charges. owmg e movement of electrons
(a) s [4)
st
 topic 10.7 Nitrogen Compounds
Page 19 topic 10.7 Nitrogen Compounds
~CORNER
Page20

~CORNER
6
(c) State the reagents and conditions needed to convert benzene into chlo· (ii) type of reaction: Electrophilic substitution.
robenzene. (1]
.

6
NO~ l)~
N~
(d) Nitrobenzene undergoes further substitution considerably more slowly than
chlorobenzene. In nitrobenzene the incoming group joins to the benzene mooMm•m•
ring in the 3-position, whereas in chlorobenzene the incoming group joins
to the benzene ring in the 4-position. + H'
(i) Use these ideas to suggest the structures of the i;,termediate com-
pounds Y and Z in the following synthesis of 4-chlorophenylamine.
(c) Cl, + anhydrous AIC/ •
3

~o
(d) (i)

0- I ___!!_.

CH,-
y z
(ii) Suggest the reagents and conditions needed for reaction Ill in the above
. synthesis.
(iii) Suggest the structural formulae of the products A, B, C and D of the
following reactions. If no reaction occurs write "no reaction" in the
Cl

Q_c_/ ~~
(ii) Sn and concentrated HC/.
9 ~o
Ct
z Ct

relevant box.
(iii)

¢'
NH 2

~o~
~*'' -o~ o
NH
Br (aq) ¢NHCOCH,
2

~
A CI I B I
Ct

/Jet~
CH-(
, I q) NaN02 A
~----------~~ +HCir-~------------~ C/B
~t1(aq
(
NaNO
+Hct'
(ii)'

r---
·~.
The thrE
importari
and perf
c D

[J10/P4/05]
[8]
no reaction

c
I

I I
I
QCt
D

Suggested Solution:
(a) (i) Because all carbon atoms are bonded at an angle of 120° and sp'
hybridised.
(ii) Each carbon atom forms n-bond and n-e· cloud is evenly distributed
through out the molecule.

(b) (i) HN0 3 +2H 2 S0 4 ->N0~+H,0.+2HS04

t) State !I
structur
 topic 10.8 Po/ymerisation Page 1

7opic 10.8 ~CORNER

?ofymerisafion
on ' ....... .
-:.renmg

Question 1

Contellt Lycra is a P?lyur~thane fibre wide!

to produce tight-fitting and elastic Jo~~=~
of these two monomers.
.
T
fash~on
.
and sportswear. It is used
· ycra IS made by the polymerisation
Addition polymerisation.
2 Condensation polymerisation. O=C=N-(CH)
. 2.- N = C =0 and H-0-(CH)
2 r -0 -H

[x and Y are usually between 3 and 8]

Learning Outcomes One repeat unit of the polymer has the structure below.
CH,·
Candidates should be able to:
O-CO-NH-(CH2)x -NH-CO-O-(CH2)y-
(a) describe the characteristics of addition polymerisation as exemplified by poly(ethene)
(a) (i)
···) Deduce
. the type of po1ymensation
. in the formation of L
and PVC.
(b) *recognise the difficulty of the disposal of poly(alkene)s, i.e. nonbiodegradability and (I Explain your answer. ycra.
(b) The standard enthalpy chan h [2]

(c)
harmful combustion products.
describe the characteristics of condensation po!ymerisation
~~ng~~~ ~~r':n~~ c~~c~~~~~!iii~~o~~~e~:~~~to~~~ i~of~:~~o~~:a~~
(i) State the bonds involved .
(i) in polyesters as exemplified by Terylene.
(ii) in polyamides as exemplified by peptides, proteins, nylon 6 and nylon 6,6. I bonds broken I bonds formed
(d) predict the type of polymerisation reaction for a given monomer or pair of monomers.

CH,-1 (e) deduce the repeat unit of a polymer obtained from a given monomer or pair of mono-

J. mers. (ii) Use the Data Booklet to calcul

(j) deduce the type of polymerisation reaction which produces a given section of a polymer ~ne ~epeat unit is formed. Stat~t~~e~hsta~~ard enthalpy change when
erm1c or exothermic. er e overall process is endot-
(il) molecule.
(g) identify the monomer(s) present in a given section of a polymer molecule. bond energy of bonds broken
bond energy of bonds formed
llH of polymerisation
Queslif1.
(c) Make drawings ·to show th [6]
of the following e shapes, and give the bond angles , for each
The thn
importar (I)
and pert ..) the - NCO group of the monomer
(11 the- NHCOO - group of the polymer
(d) !he polymer is hydrolysed when it i . [5]
ide. Suggest a structure for the nit~o~~~~~don~·t_h.
a•mngaqueous sodium
molecule hydrox-
produced.
[1]
{N02/P2/04]
(a) Lycra is a common
commerical condensation
Suggested Solution: polymer. 11 is an unusual
(a) (i) Condensation polymerisation condensation polymer al·
though there is no elimi·
(ii) The diol is saturated an d thus not undergo addT
1•on polymerisation. nation of small molecules
a) State t during polymerisation and
structu the polymer has the same
Note: The additional learning outcomes to be studied by A2. candidates are shown in bold type. The A2. composition as the mono-
components will assess all learning outcomes and will not be limited to those in bold type. mers.

1\,

n:t
 topic 10.8 Polymerisation Page2 topic 10.8 Polvmerisation Page3
~CORNER
(b) (i) bonds formed
(iii) Draw the structural formulae of products J and K in the boxes above. ~CORNER
bonds broken
[4]
N=C 0-C
(b) The diacid L occurs naturally and is used as a food additive to enhance
0-H N-H the acidic flavour in some fruit drinks.
N-C
H0 2 CCH2 CH2 C0 2H
(b) The form one -NHCOO- L
(ii) Bond energy of bonds broken ; 2[E(N :::C)+ E(O- H)]
Iinkage. one 'H - 0' and When the diacyl chloride of L is reacted with HOCH,CH,OH, a polymer is
;2(610+460);2140 kJ one 'N - C' bonds are formed.
broken and one 'H - N'
Bond energy of bonds formed ; 2[E(O- C)+ E(N- H)+ E(N- C)] and one' C- 0' bonds are (i) What type of polymerisation is occurring here?
;2(360+390+305);2110 kJ broken.lnthe polymeristion, (ii) Write an equation showing the reaction between one mole of the diacyl
2!! mols of - chloride of L and two moles of HOCH,CH,OH. [3]
AH of polymerisation = 2140 - 2110 = 30 kJ mol-' NHCOO- are formed for n
Hence, the overall process is endothermic. mol of each monomer used: (c) The following formula represents a section of another polymer.

CH,- (c) (i) the -NCO group of the monomer nO =C = N -(CH 2), -N =C =O+nH-0-(CH 2),-0-H -CO -Q-coNHCH 2 CH 2 CH 2 CH2 NH-
180' ---t n-[OCNH-(CH 2),-NHCOO-(CH 2),-Q]-
(i) What type of polymer is this?
.. f:\
/~=C=O (ii) Draw the structural formula of each of the monomers that make up this
(d) On hydrolysis. the
120' -NHCOO-Iinkage (called polymer. [3]
the urethane linkage) is
(ii) the -NHCOO- group of the polymer {J03/P4/Q5]
cleaved to form -NH,, -
120' OH and C0 2 ·
>LC)-~ RNHCOOR' + H20 Suggested Solution:
fJ c 105' -> RNH, + CO, + R'OH
H1 ~ Thus the polymer on hy·
(a) (i) PC/5 or SOC/2 • (a) (i) PC/5 or SOC/2 used
has to be anhydrous.
109.5' drolysis will yield Otherwise, they would be
H2N - (CH,),- NH 2, (ii) NaOH + o-OH ---7 o - o " N a • + H,O readily hydrolysed.
CH-( (d) H,N - (CH,), - NH,
HO - (CH,), - OH and
, I co,. PC/5 +4H 20-> H,PO, +5HCI
(
0 SOC/2 + H20-> S0 2 + 2HC/
Question 2
(ii) (a) Acyi chlorides are useful intermediates for making various acid derivatives.
(iii) J = c H , - M - o - Q
(iO Q-o- is a
The following reaction scheme shows some of the reactions of ethanoyl better nucleophile than

I
0

Questio .
chloride.
K = CH,-C-NH,
II Q- OH due to the
presence of acomplete nega-
The thn tive charge. This facilitates
importar· (b) (i) Condensation polymerisation the formation of ester since
step I CH COCI Q-oH + NaOH(aq)
and pe~ the reaction involves a nu·
CH 3C02 H 3 (ii)
step II cleophilic attack of the elec-

step Ill l NH 3 J
0
II
CI-C-CH,CH,-C-C/ + 2 HO-CH,CH,-OH
0
II
tron deficient C in -COC/.

0 0

~
II
HO-CH,CH,-0-C-CH,CH,-C-0-CH,CH,-OH + 2HC/
II (c) (iO Instead of the dicar-
boxylic acid, the following
may also be used.
(c) (i) Condensation polymer
·a) State· 0 0
K II n.__ll
structu 0 0 CI-C""'"'U'C-CI
(i) Suggest a reagent for step I.
(il) H o - M - Q - M - o H and H,N-CH,CH,CH,CH,-NH, 0 0
(ii) Write an equation showing the reaction between phenol and NaOH(aq), 11~11
CI-C ""'"'U'C- OH
the reagents in step II.
 topic 10.8 Potvmerisation PageS
Page4
10.8 Potvmerisation
~CORNER
topic
~CORNER
Question 4
Question 3 (a) Draw the structure of the repeat unit of a typical polyester. (1)
Animal fibres such as wool are made of protein. The synthetic polymer nylon
{b) The following two formulae represent sections of two polymers, A and B.
66 is used to blend with wool in clothes. This question is about the chemical
nature of protein and nylon 66.
(a) Name the functional group common to both protein and nylon 66. [1) -CO 0 CONHCH 2 CH2 CH,NHCO 0 CO-

{b) Draw two repeat units of Section of A

(i) a protein, using a general formula lor the amino acid residues,
(4) - CH(CH,)CH,CH,CH,CHCICH,-
(ii) nylon 66.
(c) Amino acids exist as zwitterions under n'eutral conditions.
Section of B
(i) Draw the structure of a zwitterion
For each of the two polymers A and 8
CH,-
inv~lved
(ii) Explain how this zwitterion is formed.
(I) state the type of polymerisation
(iii) Crystals of the simplest amino acid, glycine, NH,CH,CO,H, melt be-
tween 230 and 235 •c. Suggest why the melting point of glycine is Oil suggest the structures of the monomers from wh·IC h th ey are formed.
higher than that of hydroxyethanoic acid, HOCH,CO,H (m.p. 75 - 80 [6)
~- ~ (c) ~loyme_rs diller in the following properties, among others,
(d) Protein and nylon are polymers which have some similarities and some their hydrophillic or hydrophobia nature,
differences. Suggest two differences between a protein such as wool and
their ease of biodegradability.
nylon 66.
You may use material from your studies or observations from everyday life. Suggest, with reasons how the two 01
[2) each other with respe~t to each of thp ymers A. and B might diller from
ese properties. 131
[N04/P2106]
{N05/P3/06]

·H,-c-· Suggested Solution:

Suggested Solution:
0
II (a) Peptide linkage is also an
(a) Amide acceptable answer. 0 0
J II II
(a) -0-R-0-C-R'-C-
H R 0 H R 0
(ii) G
I I
-N-C-C-N-C-C-
II I I II (b) (I) A : condensation polymerisation
(b) (i)
1 I B : addition polymerisation
H H
1e three (ii)
iportantl
H HO OH HO 0
ld perfur
I I II II I I II II
-N-(CH,),-N-C-(CH,),-C-N-(CH,),-N-C-(CH,),-C-
B: CH,-C=CH CH 2 =CH 2 CH,=CHCI
c R I '
I H
c H,N
•-c-eo,
I -
(c) (i)
(c) A is more hydrophilic · ·t
I H-bonds with water. smce I contains polar amide linkages which can form
H
Cf B is less biodegrable since it is a haloalkane.
(li) The zwitterion is formed when the acid -GO,H group loses a H• while
the basic -NH 2 group accepts a H•.
(c) (iii) Due to presence of
State the (iii) In hydroxyethanoic acid, intermolecular hydrogen bond exists. However,
the zwitterion, the dipolar
structure! the ionic attraction between the complete charges present in the zwitte-
form, the particles exhibit
rion ion in glycine is much stronger than the hydrogen bond.
exceptionally high attractive
(d) Nylon 66 is formed from 2 monomers (1, 6-diaminohexane and hexane- forces compared to the
1,6-dioic acid) while a protein can be formed from many amino acids. H-bond.
II: Nylon 66 is synthetic while a protein is a natural product.
 ~·

topic 10.8 Potvmerisation Page 7

Page6
topic 10.8 Polymerisation ~CORNER Suggested Solution: ~CORNER
CH,
Question 5 polymer addition or
condensation? formulae of monomers
Each of the following structures is an B·atom segment of the chain of a com-
mercial polymer. ~0 0
For each structure, Ill
[ H
II
!I
• decide whether it is part of a condensation or an addition polymer, and
• draw the structural formulae of the monomer(s) from which the polymer
{c\ /c\ /c\/ HOOC-COOH

l
/N\ Condensation
is made. ·
NH 2 - CH2 CH2 - NH2
~ CH2~ ~
-

addition or formulae of monomers

polymer condensation?

\o o
0 0
i II H i\
CH-C· !I II
' II }\ /\ /\/\,II il CH2 C CH2 I;
0

I~ CH, II ~ I \/\/\!\_~
CH 0 CH 0 Condensation
HO-CH 2 -CH(C2 H5 )-COOH

HO- CH2 - CH(CH 3) - COOH

'· 0 I I
CH2 CH3

J
0 0 i \ CH3
i
%\/\;\/\ ~~
\\ !\
to

CH-C-
' II
0
J i::
(ii) G i::.·
CH

\
C\

CH3
0 CH

\
CH3
0

l \ CH3

I
CH2
rf
I
~p\ /c\ /c\ /c\;
CH2 CH2
CONH2

CH~
addition
CH,= CH -CH,

CH, = CH -

CH2 = CH -
CONH,

C8H5

ION~
Question '' '
The three.
important II
and perfun·
1"' \'""'" Question 6

c
I
c
yc\ /c\ /c\ /c\
CH2 CH2 CH2
I
CH21
(a) The viscosity of engine oil can be improved by the addition of certain medium
chainlen'gth polymers.
A portion of the chain of one such polymer is shown below.

-CH,CH(CH 2 CH 2CH,)CH 2 CH(CH 2 CH,CH,)CH 2 -

Cl
[B] I 0n average, the molecules of the medium-chain polymer contain 40 carbon
[JOBIP4!07] J atoms.

(a) State the (i) Suggest the structure of the monomer.

structure. (ii) How many monomer units are incorporated into the average molecule
~~~~~ ~
 topic 10.8 Polymerisation Pa e 9

~CORNER
PageS
topic 10.8 Polymerisation
~CORNER Suggested Solution:
(b) Used car engine oil can be recycled for use as a fuel by the processes of (a) Protein is a polymer of amino acids · Amt'no ac1'ds are monomers.
CH,
distillation and cracking.
(i) Assuming a typical molecule of engine oil has the formula C,0 H82 , suggest (b)
an equation for a cracking reaction that could produce diesel fuel with H 0 H 0 H 0 H
the formula C H34 and other hydrocarbons only.
16
I II I II I II I
H,N-C-C-OH + H,N-C-C-OH H,N-C-C-N -C-COOH + H,O
(ii) What conditions are needed for this cracking reaction?
(Iii) Considering only the bonds broken and the bonds formed during the
I I I I I
H H H H CH,
reaction, use the Data Booklet to calculate the enthalpy change for the
reaction you ·wrote in (b)(i). Peptide bonds are formed by the loss of H,O molecule.
(iv) Comment on how the conditions you described in (b)(ii) relate to the 0 0
enthalpy change you calculated in (b)(iii). [4]
[N08/P4!04] H,N- CH + R )- II
C -~-CH + II
R' ) - C -~-CH + R")-COOH

H H
Suggested Solution:
:H,-C (a) (i) This is addition (c) W 1heat > 90 •c or NaOH, temperature > 90 •c
(a) (i) CH2 = CH- CH2 CH2 CH3
I polymmisation so Mono-
(d) (iO There is a bss of six
0 (it) 8 mer is alkene. (d) (i) Six
water molecules, so their
Mr is deducted.
(b) (i) C40 H82 ~ C16 H34 + 2C 12 H24 (ii) Mr = (3x 75) + (2 x 89) + (2x 165)-(6x 18) = 625

(il) Cracking is done at high temperature i.e. above 5oo•c and use SiO,
or A/20 3 as catalyst.

(Iii) bond broken: 4(C- C) = 4 x 350 = 1400 kj/mol

J
bond formed: 2(C=C) = 2x 610 = 1220 kj/mor'
tc. t.H = +180 kj/mol-
1

1,-c- (iv) Endothermic reaction. t.H is greater than zero.

11
0
J Question 7
(ii) G [1]
(a) Explain briefly what is meant by the word protein.
(b) Describe how peptide bonds are formed between amino acids during the
---,. formation of a tripeptide. Include diagrams and displayed formulae in your
~uestion'' ~~ ~
he three·· (c) Describe how proteins can be broken down into amino acids in the labo-
nportant ratory without the aid of enzymes. [2]
nd perfu i
(d) When a small polypeptide S was broken down in this way, three different

-
amino acids were produced according to the following reaction.

2 NH2CHC02H + 2NH2CHC02H
3 NH2CH2C02H +
s I I
CH 3 CH2

) State t
M,=75 M,=89
6M,= 165

structu1 (i) Hoi!J many peptide bonds were broken during this reaction?
[3]
(il) Calculate the M, of the polypeptide S.
[N08/P4!07]
pic lt
OJ discuss the genetic basis of disease (for example, sickle cell anaemia) in terms of

7opr"c 11.1 7/ppfz"ca/z"on of C.hemr"slry

(k)
altered protein structure and function.
explain how modification to protein/enzyme primary structure can result in new struc-
ture and/or function. ·
CH,-
7he Chemislry of Bi{e (I) outline, in terms of the hydrolysis of ATP to ADP + P;, the provision of energy for
the cell.
(m) understand why some metals are essential to life and, given information and with
reference to the chemistry of the core syllabus, be able to explain the chemistry involved
(for example, iron in haemoglobin (section 9.5 (g) and ll.l(e) and (j)), sodium and
Content potassium in transmission of nerve impulses (section 3, ion solvation and section 5,
Protein chemistry. energetics), zinc as an enzyme cofactor (section 10.1, nucleophilic attack, li.I(e)).
(n) recognise that some metals are toxic and discuss, in chemical terms, the problems
2 Genetic information.
associated with heavy metals in the environment entering the food chain, for example
3 Energy. mercury (development of methods to detect and address these problems will be dis-
4 Metals in biological systems. cussed in 11.2(i) and 11.3(1)).

CH,-C Learning Outcomes

II
c Candidates should be able to:
(a) recall that proteins are condensation polymers formed from amino acid monomers and
recognise and describe the generalised structure of amino acids (link to core syllabus,
sections 10.7 and 10.8).
(b) explain the importance of amino acid sequence (primary structure) in determining the
properties of proteins.
(c) distinguish between the primary, secondary and tertiary structure of proteins and
explain the stabilisation of secondary and tertiary structure using the chemistry learnt
in the core syllabus, sections 3 and 10.7.
CH-C (d) describe and explain the characteristics of enzyme catalysis, including
, II
c (i) specificity (using a simple lock and key model) and the idea of competitive
inhibition.
(ii) structural integrity in relation to denaturation and noncompetitive inhibition.
given information, use core chemistry to explain bow small molecules interact with
(e)
proteins and how they can modify the structure and function of biological systems (for
Questio. example, as enzyme inhibitors or co factors, disrupting protein-protein interactions,
The th blocking ion channels) (link to 11.3 (a)).
import~'
and pe describe the double helical structure of DNA in terms of a sugar-phosphate backbone
(j)
and attached bases (Candidates will be expected to know the general structure in terms
of a block diagram but will not be expected to recall the detailed structures of the
components involved. Where these are required they will be given in the question
paper.).
(g) explain the significance of hydrogen-bonding in the pairing of bases in DNA in rela-
tion to the replication of genetic information.
(h) explain in outline how DNA encodes for the amino acid sequence of proteins with
reference to mRNA, tRNA and the ribosome in translation and transcription. Note: The additional learning outcomes to be studied ·uy ""
·- candidates are shown in bold type. The A2
components will assess all learning outcomes and will not be limited to those in bold type.
(a) Sta (i) explain the chemistry of DNA mutation from provided data.
stn
 Pagel topic 11.1 The Chemistry of Life Pa e2
topic 11.1 The Chemistry of Life
~CORNER
(c) The table below shows the 3-base codes used by RNA. ~CORNER
uuu phe ucu ser UAU tyr UGU cys
CH,-
uuc phe ucc ser UAC tyr UGC cys
r;;(jlfi)) rN f1 ;1J UUA leu UCA ser UAA stop UGA stop
IJ ~ r.r !J ~ qpening ....... .
UUG leu UCG ser UAG stop UGG trp

cuu leu ccu pro CAU his CGU arg

cue leu CCC pro CAC his CGC arg
CUA leu CCA pro CAA gin CGA arg
Question I CUG leu CCG (a) 0) Addition polymer is
pro CAG gin CGG arg made from alkenes, its
c . . . ·ned together by a process called
(a) (I) In a prote!n, amino ~cldl~ ar~J~:tion potymerisation is used in some AUU ile · ACU thr AAU asn AGU ser
empirical formula remain
condensatton polymensa ton. AUG ile same as thai of monomer,
ACC thr AAC asn AGC ser
synthetic polymers, such as poly(propene). . I" AUA ile and there is no loss of mass
ACA thr AAA lys AGA arg
State two important differences between condensation potymensa ton AUG met/ ACG thr AAG lys AGG from reactant to product.
arg
and addition polymerisation. . . start
Condensation polymer is
. . . and alanine shown, draw the dls_Piayed made from a compound
(li) Using the ammo _acid~ glycine I rly labelling the peptide link. GUU val GCU ala GAU asp GGU gly
fomnula of the dipeptide ala-gty, c ea having two functional group
GUC val GCC ala GAC asp GGC gly which could react to give a
H GUA val GCA ala GAA glu GGA gly
~H,-~ H small molecule e.g. H20 &
I I
H N-C-C02H
GUG val GCG ala GAG glu GGG gly HCI, therefore there is loss
0 H N-C-C02H
2 I 2 I (i) What amino acid sequence would the following base code produce? ofmassfromreactanlto prod-
uct.
CH3
H (You may use abbreviations in your answer.)
(ii) Alanine should be
alanine
glycine -AUGUCUAGAGACGGGUAA- shown on left side &glycine
(4] on the right. Carboxylic
(ii) What would be the effect on the amino acid sequence ff a mutation
group of alanine reacts with
(b) The diagram below shows a section of DNA. caused the base G at position 13 in the sequence to be replaced by U?
amino group of glycine.
Identify the blocks labelled X, Y and Z. [3]
(d) (i) (b) As it is a DNA molecule so
Name a disease which results from a genetic defect.
Xis not a ribose, il must be
(ii) Explain how the genetic defect can bring about your named disease. deoxyribose. Adenine and
[3] thymine are complementary
CH-C basessoZmustbethymine.
, II [J07/P4/Q7}
0· (c) Q) UAA is stop condon
and it does not code for any
Suggested Solution: amino acid, so only a
(a) (i) Addition polymer requires a double bond in the monomer {alkene). sequence of five amino
':.: acids is produced rather
,·· Condensation polymer produces a small molecule e.g. H 0 or HC/ along than six amino acids.
2
;1:·,· with polymer.
Questil:' , (ii) (ii) GGG codes for gly-
peptide link cine but UGG oodes fortryp-

H~-HL~cH, -co,H
The thl''i::
tophan, so the mutation
import~.', : causes change in amino
and pe'.: acid sequence, which may
in tum affect 3 - D
CH3 H
structure of protein.
X ................................. y ································· z .......................... ...... [3] (b) X: deoxyribose Y: phosphate Z: thymine (d) 0) Allemative answers:
Huntigton's, cystic fibrosis,
(c) (i) (met) - ser - arg - asp - gly sickle cell axaemia, thalas-
semia, muscular dystroply
(ii) The amino acid gly (GGG) would be replaced by amino acid trp (UGG). etc.

(d) (i) haemophilia (iO In this disease blood

clotting factor VII or VIII is
(ii) Due to mutation a different amino acid sequence . results information of absent, so in case of injury,
(a) Sic incorrect protein or there is a change in 3 - D structure of protein. If it blood does not clot and
stri' is an enzyme, its active site is lost so it is not able to function. person dies due to loss of
blood.
~1u.:
topic 11.1 The Chemistry of Life Page3 topic 11.1 1ne c..:nemistry of Life
Page4
~CORNER
(c) Give two examples of how interchanging the positions of two amino acids
could affect the bonding in, and hence the overall structure of, the protein.
~CORNER
Question 2
CH,- [4]
(a) DNA carries the genetic code in living organisms and consists of a double
helix. [J08/P4/QB)

(i) Describe what is meant by a double helix.

(ii) How are the strands of the double helix held together? [2] Suggested Solution:
(a) (i) Thissortofcharacteris
(a) primary: Covalent bond (Peptide)
(b) In replicating the genetic code two RNA molecules, mANA and tRNA, are shown specifically in double
used to perform functions called transcription and translation. helix of DNA. 0 0
Cl Describe the role of the RNA molecules in these two functions. [4]
(iQ Adenine makes two II II
(c) When an egg is boiled, the protein changes from a viscous liquid to a solid. hydrogen bonds with thym- - HN - CH - ( R)- C - N - CH - ( R')- C - N - CH - ( R")- COOH

(i) Suggest what causes this change as the protein is heated.

ine andguaniine makes three I I
hydrogen bond with cytosine. H H
(ii) Why is there. no change to the primary structure of the protein under
these conditions? [2] (b) transcription·
In synthesis of mRNA, ad- secondary: Hydrogen bonds
[3]
(d) Describe in outline how energy is provided in animal cells. enine binds with uracil and c-
[N07/P4/Q8] while guanine binds with
1
CH-C cytocine. The reaction is c
, II caialysed by RNA +O -s
N - 0 - C = o ....... H - N /
0 polymerise.
Suggested Solution: / '\.
/c-o
H-N
(a) (i) Two strands·of DNA (intertwined (woven) around each other. translation: -
mRNA acts as genetic code "-c
(ii) By hydrogen bonds between complementary bases i.e. A= T, G =C which is decoded by tRNA
in the form of a polypeptide
(b) transcription: DNA unwinds and one of the strands acts as a template upon
chain which folds to make tertiary:
which mANA synthesis by addition of complementary bases of RNA to the
final protein structure.
bases of DNA strand. 1. Hydrogen bonds.
N ~0 /N'\.
(c) (Q As the temperature 2. Electrostatic (ionic) attraction. H/ '\.C:/" 0= C H
translation: mANA is released from nucleus of cell and binds to ribosome in
increases, hydrogen bonds
the cytoplasm. tRNA translates the codons by mANA by binding to it with the
in secondary structure breaks
3. Vander waals forces. I I
help of anticodon and carrying amino acids to the ribosomes which make a 4. Covalent (disulphide bridges). C-CH,-S- S-CH - C - H
& later tertiary and quater-
CH-C
polypeptide chain. nary structure is also dis- I ' I
, I rupted by breakage of ionic, 0 N N 0
(
(c) (i) Heat causes disruption of tertiary structure of protein by breaking hydro-
disulphide and non-polar in-
~/'\. /'\.1'
gen, ionic & disulphide bonds. C H H C
teractions, finally:)..-0 protein
(ii) Primary structure contains only peptide bonds which are strong covalent structure is denatured.
(ii) bond and can not be broken easily. (b) met-ala-gly-ala-gly-arg-val-lys
(d) The energy released by
(d) Energy is provided by hydrolysis of adenine triphosphate (ATP). hydrogen of ATP is actually
(c) Potential effects on tertiary structure by amino acids side chains.
ATP~ADP+Pi+energy the binding energy of inor-
Ques~ ganic phosphate group. One 1. Disruption of hydrogen bonding.
when glucose undergoes respiration during Kreb ATP is synthesised by ATP molecule contains 31 2. Disruption of disulphide bridges.
The ti' :
import,: phosphorilation of ADP i.e. ADP +Pi ~ ATP kJ mol-' energy. 3. Disruption of ionic attraction.
and p. 4. Disruption of Vander waals forces.

Effects on Proteins:
Question 3
Changing the active sites.
(a) State and show, using suitable diagrams, the types of bonding that occur
in the primary, secondary and tertiary: structures of a protein.· [6] Proteins become less soluble (e.g. sickle cell)
Unfolding of tertiary structure.
(b) Analysis of a polypeptide A showed that the amino-(N-)terminal end is
methionine (met) and that the carboxyi-(C-)terminal end is lysine (lys).
Enzymic hydrolysis of the polypeptide produced the following tripeptides,
with the amino acid residue on the left having the free amino group.
met-ala-gly gly-arg-val ala-gly-arg arg-val-lys ala-gly-ala gly-ala-gly
(a) S
s Work out the sequence of amino acids in A. using the 3-letter abbrevia-
tions. Use each tripeptide once only. [2]
 I
PageS 11.1
topic 11.1 The Chemistry of Life topic The Chemistry of Life Page6
~CORNER
Suggested Solution: ~CORNER
Question 4
(a) (i)
CH,- (a) Enzymes play a vital role in all living organisms, helping chemical reactions
to take place at body temperature.
(i) The diagram below shows the reaction pathway of an enzyme-catalysed
reaction without an enzyme present. On the diagram sketch the path- energy
way if the enzyme was present.

products

reaction pathway
energy
(ii) Proteins or Polypeptides.
reactants
(iii) They are denatured and lose their secondary or tertiary structure because
Hydrogen bonds and vander waals forces are broken.
products
(b) (i) Competitive inhibitors resemble the substrate and competes for the active
CH,- reaction pathway site of the enzyme. Non competitive inhibitors can bind to different site on
the enzyme or form covalent bonds permanently with the enzyme.
(ii) What type of molecule are most enzymes?
(iii) Why do many enzymes lose their catalytic effectiveness above 40 ·c? (ii)
(3]

(b) (i) Explain the difference between competitive and non-competitive inhi-
bition of an enzyme.
(ii) The graph below shows how the rate of an enzyme-catalys.ed r~action
varies with substrate concentration in the absence of an inhibitor.
For a given amount of enzyme, Vm~ represents the rate when all of the
active sites on the enzyme are being used.

CH,-,
substrate concentration

(c) (i) - S- H group OR Cysteine residue.

(li (ii) This reduces the enzyme activity. The bonding disrupts the 3-dimensional
structure of the enzyme.

Que"-'·
=· ,. Question 5
The::
impc substrate concentration Metals play a vital part in biochemical systems. In this question you need to
and, Sketch on the diagram curves to show the effect on the rate of reaction consider why some metals are essential to life, whilst others are toxic.
of: (a) For each of the metals, state where it might be found in a living organism,
and what its chemical role is.
a competitive inhibitor;
II a non-competitive inhibitor. iron location in organism ..............................................................................
Clearly label your curves. [4]
role ..........................................................................................................
(c) Heavy metal ions like Hg'• can bind irreversibly to enzymes and this can sodium location in organism ..............................................................................
result in poisoning.
role ..........................................................................................................
(i) Suggest to what atom or group Hg'• ions bind.
(ii) Explain how this affects enzyme activity. (3] zinc location in organism ..............................................................................
(a)
[NOBIP4/Q8)
role ......................................................................................................... (6]

,:
•nm. ~-c·--:-:c::·:_-·· c•··--------
iclO topic 11.1 The Chemist!Y_ of Life
top_ic 11.1_The Chemistry of Life Page7 PageS
~CORNER Suggested Solution: ~CORNER
(b) Heavy metals such as mercury are toxic, and it is important that these do
not enter the food chain. (a) primary structure
CH,- (i) Give a possible source of mercury in the environment.
HO-C=O
(ii) Describe and explain two reasons why mercury is toxic, using
diagrams and/or equations to help your explanation. [4]
I
H H 0 CH 2 H H 0 H 0
[J09/P4/Q7] II II I I I II I II
·N-C-C-N-C-C-N~C-C-N-C-C
I I I II I I I
Suggested Solution: CH 3 H H 0 C H H
(a) iron, location in organism: Red blood cells (haemoglobin) I
CH 2
role: To transfer oxygen to cells and take CO, away from cells
I
sodium, location in organism: In nerve cells OH
role: Regulation of nerve impulses Primary structure of a protein shows the sequence of amino acids in a chain
joined with covalent bond, through peptide linkage.
zinc, location in organism: In blood
role: As an enzyme co-factor secondary structure
CH,-·
(b) (i) In the manufacture of sodium hydroxide. H 0 H 0
(ii) 1. Mercury breaks disulphide bond and unites with S-H group. I II I II
- N - CH2 -C-N-CH2 -C-N-CH 2 -C -N -CH 2 -C - - - ,
2
(-CH 2 -S-S-CH 2 -)+4Hg• ---+ 2-CH 2 -S-Hg+2Hg • I II I II \
H 0 H 0 '.
2. It bonds to carboxyl side chains in amino acids. '
''
-C0 2H+Hg• ---+ -C0 2 Hg+W 0 H 0 H ,''
II ·1 II I /
- C- CH 2 - N - C - CH 2 - N - C -CH2 - N - C - CH ....,...- N ---'
2

Question 6
II I II I
0 H 0 H
(a) Explain, using diagrams where appropriate, the types of interaction respon-
CH,-:· sible for the primary, secondary and tertiary structure of a protein. [6] Secondary structure of a protein is the shape of the protein molecules caused
by the hydrogen bonding between - C = 0 and -N-N groups within the chain
.:·r (b) Enzymes are particular types of protein molecule. Explain briefly how
enzymes are able to help to break down molecules in the body. [2]
,,[:.: tertiary structure
(c) The graph below shows the effect of inhibition on an enzyme-catalysed
reaction. (a) Hydrogen bond.

reaction 0 represents protein molecule

0-N--"-H··········O=C-0
Qui',:: rateV
~.::!
(b) Disulphide bond
Th(: Vmax
im~'~: 0-CH,-S··········S-CH,-0
an~':
(c) ionic bond
0 0
- II • - II
0-CH,-C-NH,··········O-C-CH,-CH,-0

substrate concentration [S]

State the type of inhibition shown, giving a reason to support your answer.
(a [2]
[N091P4/Q7]
 topic 11.1 The Chemistry of Life Page 9 topic 11.1 The Chemistry of Life
~CORNER
Page 10
(d) van der Waal's force. Suggested Solution:
~CORNER
CH,-
(a)
~~~~a~ st~~~ure:_ Sho~s sequence of amino acids, it is a linear polypeptide
D-cH,-Q-oH w 1c am1no ac1ds are linked by covalent bonds.
tertiary structure: It is 3 o· .
- 1mens1onal final functional form of proteins.
(b) (i) disulfide cross link between two cystein residues.
CH,"-CH-0
CH,/ s------s
I I
c Tertiary structure is the folding and bending of the protein molecule caused
CH,
I
CH
I '
by hydrogen bonding, dipole-dipole interaction, covalent disulphide links and H,N-C-COOH H,N-C-COOH
ionic interaction. I I
H H
{b) The molecules in the body (substrate) binds to the active site of the enzyme.
This lowers the activation energy and causes specific bond to be weakened (ii) Dehydrogenation or oxidation.
helping molecule to break.
(iii) ~ertiary stru~tur~
of protein is stabilised by hydrogen bond between polar
(c) type of inhibition: Non-competitive inhibition group, IOnic linkages between ionised A-groups, van der waal's forces
between non polar A-groups.
reason: Rate never reaches Vm.,
(c) (i) Hydrogen bonds.
(ii) R H 0 R H 0
QueJtion 7 I I II I I II
c
Human hair and silk both consist of proteins. Proteins are described as having
three major levels of structure: primary, secondary and tertiary.
' N/
1.,
" CH
C/
II._
N
'\._/'\._/
CH
I
N
CH
"c " /
N c
/ '
CH
H 0
1., II._ I
R !::! Q R
(a) Outline what is meant by the terms primary structure and tertiary structure
of a protein. [2]
0'-
=
H" 0'- H"
(b) In hair, the secondary structure consists of a-helices which are cross-linked
by disulfide bonds. The amino acid responsible lor this cross-linking is
II
c
II II II
N c N

CH,-,
:·
cysteine, H2 NCH(CH,SH)C0 2 H.
(i) Show by means of a diagram how the disulfide cross-links are formed.
(ii) What type of reaction is this?
"I CH

R
/
"I CH

R
/

(iii) State three other interactions that stabilise the tertiary structure of
Hydrogen bonds between two polypeptide chains.
proteins. [4]
(c) The ~-pleated sheet is a different form of secondary structure found. in pro- (d) Ther~ are strong, rigid dissulfide bridges in ~-keratin while only weak v d
waals forces between the layers of silk. an er
teins, such as those in silk.
(i) What type of bonding is responsible for stabilising the ~-pleated sheet
Qu~:~·· in silk?
Question 8
The ~;. (ii) On the diagram below, draw a second polypeptide strand and show
1
imp1.i!•.'
and:,:.:·
how bonds would be formed that stabilise this ~-pleated sheet.
:~il~te s~;~~::~;ts of some metal ions are vital in the human body, others
R H 0 R H 0
I I II I I II (a)
CH N C CH N C ~g; i~n~ are toxic f~r a. number of reasons. Hg>• ions can react with the
,/'\._/'\._/'\._/'\._/'\._/' - - - group, wh1ch IS found in proteins.
N C CH N C CH
I II I I II I R-S-S-R + 2Hg'• + H, ~ 2 R-8-Hg• + 2H•
reaction 1
H 0 R H 0 R (i) Wh at is the name of the R-S-S-R group in proteins?
[3]
(ii) Wh. h
(d) The cysteine-containing protein in hair is called a-keratin. A similar ... IC level of protein structure will be affected by reaction 1?
sequence of amino acids can produce ~-keratin proteins found in the scales, (Ill) Why will this affect the activity of an enzyme?
claws and shells of reptiles such as tortoises. In ~-keratin the secondary . . ~

structure of the protein is in the form of a ~-pleated sheet. (b) Ag~ Ions ~an c~mbin~ with free -GOOH groups in the side chains of th
Suggest what makes the ~-pleated sheet in ~-keratin so much less flexible
~:~.o acid residues In proteins to form partially covalent silver carboxy~
(a)
than the ~-pleated sheet in silk. [1]
RCOOH + Ag• ~ RCOOAg + H• reaction 2
[J10/P4/06]
(i) Wh
at type of behaviour is the -GOOH group showing in reaction 2?
- ~·-

0.5
Or
tog_ic 11.1 The Chemistry of Life
Pag_e 11

(ii) What types of R group interactions will be affected by reaction 2? Explain

~CORNER r:lopL'c 11.2
your answer. [4]
(c) By contrast, iron is an extremely important metal used in haemoglobin to
-l,-(
transport oxygen molecules from the lungs to muscle cells and to carry 7/pphca/ions of 7/na/yiLcal Ch'emislry
carbon dioxide in the reverse direction.
One haemoglobin molecule contains four haem groups, each of which
s contains one iron atom. In the haem group four nitrogen atoms are in the
lc
same plane as the iron atom. The oxygen molecule is attached above this
plane, and the iron atom is joined to a protein chain below this plane. Content

cr CHz cH Methods of detection and analysis.

3

~~
H 2 Applications in chemistry and society.
H3C ~C
{ ( Learning Outcomes

~
HC1 ) F e J\H
:t;/
(a)
Candidates should be able to:

describe simply the process of electrophoresis and the effect of pH, using pep tides and
N N ~
;H-C 3 amino acids as examples (link to ll.I (a)).
, I' H3C .,__ CH
( ~c (b) explain, in simple terms, the technique of DNA fingerprinting and its applications in
H forensic science, archaeology and medicine.
HOOC COOH (c) describe the importance to modern medicine, and the challenges, of separating and
haem characterising the proteins in cells (link to 11.1).
(i) How many oxygen atoms could one haemoglobin molecule transport? (d) outline in simple terms the principles of nuclear magnetic resonance in 1H and be able
(ii) By what type of bonding is the oxygen molecule likely to be held to the to interpret simple NMR spectra.
iron atom in haem? (e) show awareness of the use of NMR and X-ray crystallography in determining the
, (iii) What is the geometry of bonding around the iron atom? [3]
structure of macromolecules and in understanding their function (link to ll.l (c) and
[N10/P4!07] 11.2 (c)).
CH,- (f) state what is meant by partition coefficient and calculate a partition coefficient for a
Suggested Solution: system in which the solute is in the same molecular state in the two solvents.

(a) (i) Disulfide bridge. (g) understand qualitatively paper, high performance liquid, thin layer and gas/liquid chro-
matography in terms of adsorption and/or partition and be able to interpret data from
li (il) Tertiary structure of protein.
. these techniques.
(iii) Shape of active site of an enzyme is changed, thus its catalytic activity will
be affected by breaking of bonds in protein. (h) explain the concept of mass spectroscopy, deduce the number of carbon atoms in a
Qu• compound using theM+ 1 peak and the presence of bromine and chlorine atoms using
(b) (i) It acts as a proton donor.
The the M+2 peak and suggest the identity of molecules formed by simple fragmentation
(il) Ability of -COOH to form hydrogen bonds and ionic linkages is affected
im~
because of this reaction, and a stronger salt linkage of -eoo-
Ag• is in a given mass spectrum (see also core syllabus, section I (c) and (d)).
am
formed. (i) draw conclusions given appropriate information and data from environmental monitor-
(c) (i) 8 oxygen atom can attach with one molecule of haemoglobin. ing (for example, PCBs in the atmosphere, isotopic ratios in ice cores).
(ii) By dative covalent bond.
(Iii) Octahedral.

Note: The additional learning outcomes to be studied by A2 candidates are shown in bold type. The A2
(t components will assess allleaming outcomes and will not be limited to those in bold type.
 topic 11.2 Applications of Analytical Chemistry Page l topic 11.2 Applications of Analytical Chemistry
On Pa e2
~CORNER
~CORNER
c F is CH3 CH(COCI),.
I
,-cI CH3CH(C02H)2 + 2SOCI2 --> CH3CH(COCI)2 + 2S02 + 2HCI

c q?fi)) fP) fl@ G is cHgcH•rco 2 cH~J _

2
Sir IJ ~ t.r IJ ~ qpening ....... . CH3CH(COCI)2 +2CH30H--> CH3CH(C02CH3)2 +2HCI
los
In the NMR spectrum, the signals at 12 3o
protons d, e and f respectively. Proton dis. n·e~ t .1 and <i 3.8 c_orrespond to
Question I a doublet. Proton e is next to a CH hen .
0
a CH, hence 1! appears as
CH,
Compound C, C,H,.O,, is an important intermediate used to make a variety of f remains as a singlet and is not sp'i·t . ce I! appears as a quartet. Proton
' smce there are no adjacent
pharmaceutical drugs. Hydrolysis of C produces two compounds D and E. None of these protons are liabl H , . pro1ons.
addition of D,O. H is a cyclic :~id:_nce, the spectrum IS not affected by the
J The mass spectrum of D shows peaks at mass numbers 17, 29 and 46.
di
dil The NMR spectrum of E consists of a doublet at 15 1.2, a quartet at o 3.1 and
a singlet at 15 11 .5. The integrated areas of these three peaks are in the ratio
3:1:2 respectively. On shaking the sample with D2 0, the 2-proton peak at 15 11.5 CH,CH(COCI), + H,N-CH,CH 2 -NH, --7
-c- disappears. Titration of a 0.0500 g sample of E requires 8.45 em' of 0.100 mol + 2HCI
' II dm-" NaOH for neutralisation.
0 When E is reacted with SOC/2 , fumes are evolved and compound F is formed.
Reacting F with an excess of methanol produces compound G. The NMR
spectrum of G consists of a doublet at 8 1.2, a quartet at 8 3.1 and a singlet
at o 3.8. The integrated areas of these three peaks are in the ratio 3:1 :6 re-
spectively. None of these peaks is affected by the addition of D2 0.
The reaction between F and 1 ,2-diaminoethane produces the neutral compound
H, C,H 10 N20 2 • Question 2
J
Identify compounds C- H, and explain the above observations. [10]
(a) In an NMR spectrum explain wh roton . .
!I [N05/P3/Q7) ments absorb at different freque~cies. s m different chemical environ-
(b) The amide E C H NO b [3]
l-C· The NMR sp~ct;a ~~f F' acnadn Ge hydr?lysed to an amine F and an acid G
, II Suggested Solution: are g1ven below. ·
0 D is CH,CH,OH;
F
,, The peaks in the mass spectrum correspond to OH• (m/e = 17), CH,CH,•
(mle = 29), CH,CH,OH' (m/e = 46). relative peak __.
(ii) f 2 2 6
areas
E is CH3CK' -COi-f
--~·,,·

!ueslit,: ',. :
I
GOlf
·he thl :. ,
In the NMR spectrum, the signals at 0 1.2, 0 3.1 and 0 11.5 corresponds to
,porta':,
md pe' protons a, b and c respectively. Proton a is next to a CH, hence it appears
as a doublet. Proton b is next to a CH,, hence it appears as a quartet. Proton
c is labile .and it readily undergoes rapid exchange with D,O. Signal 0 11.5
disappears when D,O is added. 8 7 6 5 4 3 0
For the titration, chemical shift, 0
0.0500
4.237 x 1o-4 mol
n add = 4(12) + 6(1) + 4(16)

8.45 -4
nNaOH = 0.1 OOx iOOO = 8.45 x 10 mol

Hence, nacld: n NaOH = 1: 2, i.e. Eisa dibasic acid.

(a) St
st C is an ester, CH 3CH(C02 CH 2CH 3) 2 • It undergoes hydrolysis to give D and E.

CH3CH(C0 2CH 2CH3 h + 2H20 ----4 CH 3CH(C0 2Hh + 2CH 3CH20H

 topic 11.2 Applications of Analytical Chemistry Pa~

~CORNER
Pa!!e3
~ ~CORNER
]~
I

Jn r<
Cl G
before
+[ •
relative peak 3
I 2

• ••
-c- .__ areas _.
1
Cl disappears
after +[ • ]-
with D 2 0 p a R s
Sine•
lose! + (i) Which amino acid existed mainly as a zwitterion in the buffer solution?

CH,-
}-..-
12 11
I
10
I
9
Explain your answer.
(ii) Assuming amino acids R and S carry the same charge when in this
I
buffer solution, which is likely to be the larger molecule? Explain your
I I
0
--~ ~
I I 1
I
.!. I
5 4 3 2
8 7 6
J is chemical shift, & (c) Amino acids may also be separated by using two-dimensional paper chro-
dini matography. This involves putting a spot of the mixture on the comer of a
dinil (i) Suggest reagents and conditions for the hydrolysis of .E. piece of chromatography paper and allowing a solvent to soak up the pape~
(ii) Interpret the spectra above to suggest structures for F and G, explain- The paper is then dried, tumed through 90° and placed in a second sol-
vent. This method gives better separation than a one solvent method.
ing your reasoning. [7].
[N06!P3!07]
-c--< ·
(i) Paper chromatography relies on partition between the solvent. applied
and another phase.
II
0 What is this second phase?
Suggestf!d Solution:
(a} Different chemical environments create different magnetic field at the nucleus (ii) The table below shows the R, values for some amino acids in two
ar:d hence opposes the external applied field to different extent. The nucleus different solvents.
is thus shielded to different extent and hence resonate at different frequencies.
amino acid R, solvent 1 R, solvent2
(b) (i) Dilute HCI, heat. A 0.1 0.2
H CH, B 0.0 0.4

to (ii} F =•
H,N- CH,-C~- CH,
" I , c 0.3 0.0
=
The signals at 8 0.8, 1.3, 1.8 and 2:6 correspond to protons a, b, c and D 0.8 0.9
~-C- d respectively. The presence of proton c next to protons d and a accounts
, II for the doublets. Proton b is labile. Hence, the signal disappears upon E 0.6 0.5
0 addition of D,O- The presence of 2 proton d and 6 proton a accounts for
J the multiplets for the signal corresponding to proton c. Use the grid on next page to plot the positions of the amino acids after
two-dimensional paper chromatography using solvent 1 followed by
(ii} G e I g
=
G CH,-CH,-CO,H
solvent 2.
=
The signals at & 1. '\, 2.2 and 11.8 correspond to protons e, f and g
(iii) Which amino acid travelled fastest in both solvents?.
respectively. Proton g is labile. Hence, .the signal disappears upon ad-
Question (iv) Which amino acid did not move at all in solvent 2? (5]
=--- dition of D,O. Proton e is next to a CH, group. Hence, the signal appears
The thre as a triplet. Proton f is next to a CH, group. Hence, it appears as a quartet.
importan,
and peri

Question 3
(a} Electrophoresis can be used to separate amino acids which are produced '
by the hydrolysis of a polypeptide.
Using glycine as an example, explain why the result of electrophoresis
depends on pH. [3]
(b) The diagram below shows the results of electrophoresis in neutral solution.
At the start of the experiment a spot of a solution containing a mixture of
amino acids P, a, RandS was placed in the middle of the plate. Following
electrophoresis the amino acids had moved to the positions shown in the
(a} Sta
strl lower diagram.
 topic 11.2 Applications of Analytical Chemistry PageS
on~ topic 11.2 Applications of Analvfical Chemistry
Cl
~CORNER Page6
I
,_.c-
, I
front Question 4 ~CORNER
(a)
Cl Explain with reference to energy states how 'H NMR can supply information (c) (iii) D has Rf values 0.8
about the structure of molecules. in diagram (1) and 0.8 in
(b) [3] diagram (2).
Nuclear magnetic resonance is used in magnetic resonance imaging scan-
ners. These scanners are increasingly used in hospitals to detect tumours.
Suggest why magnetic resonance techniques are better than X-rays.
(c) [2]
The NMR spectrum shown below was obtained from a simple organic
solvent 1 molecule, G, C,H,O,. When a sample ofG was placed in a mass spectrom-
eter, the ratio of the M : M+ 1 peaks for the molecule was 14.5 : 0.66.

J iS
3
din it
dinitr

-C~•
I
absorbance 3
spot applied
II here solvent2-
0
solvent 2
front
[J07/P4/QB]
(a) Allow pH lone pair of elec·
1 lu
11 10 9 8
!ron at nitrogen bonds with H· 7 6 5 4 3 2 1 0
Suggested Solution: NH • a cation which moves towards ion producing -NH,· and at
(a) At low pH -NH, is protonated to ~ose~ 'proton to' produce -coo-, an high pH -CO,H loses
- - chemical shift, a
cathode. At high pH -co,H group (i)
proton to produce -COO·· Calculate how many carbon atoms there are in the molecule.
anion, which moves toward anode. . (ii)
tO g. a Use
(b) (i) As a remains at midway indicates no charge upon it and rs present as
(b) (i) being zwitterion is of G. the NMR spectrum and the Data Booklet to work out the structure
present having both groups
[5]
--{ s as -NH,· and -COO·
-If
0
(ii) zwitterion.
R is expected to be larger since R moves slower than
(c) (i) Water
moves.
on the same molecule, does
not move either to positive or Suggested Solution:
[N071P4!09}

J iS\.] negative side.

(ii) (a)
G i~,\:, front
(c) (iij Insolvent 1amino acids
A, B, c, D& Eare expected ,,--------~against field
D to move like (diagram1)
_ , ""
-,
i~o(1)
I'
I '
E
1 '~------ +~with field
Ic
A no field
solvent 1 field applied
. 8
Spinning proton has a magnetic moment. In the absence of an eX1emal field,
after turning the sheet to
the spin states of a given proton are of equal energy, however, in an eX1emal
90'C·Ieft and working with
magnetic field, two spin states occupy two different energy levels in the radio
solvent 2, amino acids will
frequency range. The difference of energy level is related to the chemical
move as shown in diagram environment of the 'H.
2, separating components
A more effectively. NMR imaging do not damage tissue where as X-rays are harmful and can
affect skin, blood and the genitals. NMR is not obscured by bones or skeleton.

[}'r
B
spot applied M 100
here solvent2-
solvent
M+1 =un
=1.1 x MM+ 1 =1100.1 x ~
14.5 =~
front 100
15.95 =3. 76 "' 4 carbon atoms.
(iii) D n
(iv) C c
 r'

rbt
Page 7 topic 11.2 Applications of Analytical Chemistry
top_ic 11.2 Applications pf Analytical Chemistry PageS
~CORNER
}aC
(ii) Singlet at B2 suggest methyl adjacent to C=O group. Quartet at M
(c) (i) Peak at mle 79 and 81 and at m/e 94 and 96. ~CORNER
suggests a -CH, group adjacent to a methyl group. Triplet at B1.2 sug-

~
(iij In chlorine the M and M + 2 peaks are in the ratio 3:1 where as in bromine
gests a methyl group adjacent to a - CH 2 - . they are approximately 1:1.

0
;e tl II Question 6
~s v.. G is ethyl acetate CH 3 -C-O-CH 2CH 3
The technology of DNA fingerprinting has enormously advanced scientific iden-
01
tification techniques in medicine, crime detection and archaeology in recent years.
I
-c Question 5 (a) (i) In order to prepare a DNA sample for analysis, the DNA is treated with
I Much of the preparation of evidence to solve crimes now relies on instrumental
restriction enzymes. What do restriction enzymes do?
0
analysis. This question deals with some of tlie techniques used. (ii) What is the next stage in DNA analysis, after the treatment with restric-
is a tion enzymes?
(a) Electrophoresis can be used to separate amino acids produced by hydrol-
initrc (iii) How are the DNA fragments made visible? [3]
ysing proteins. The amino acids are placed in a buffered solution in an
initro
electric field. In a solution of given pH, what two factors affect the movement (b) NMR and X-ray crystallography have made significant contributions to our
of a given amino acid? [2] knowledge of the structure of proteins and, in the pharmaceutical industry,
how drugs react with target proteins.
--(· (b) Nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry
are also used in the detection of certain molecules, particularly those
containing hydrogen atoms.
(i) Suggest an advantage of each technique in helping to determine protein
structure.

(i) Explain how and why the NMR spectrum of propanol, CH,CH,CHO, (ii) MRI scanning is a medical technique based on NMR spectroscopy. It
would be different from that ol propanone, CH,COCH,, which contains is particularly useful for looking for tumours in healthy tissue.
the same atoms. Suggest how this technique can distinguish tumour tissue from healthy
tissue. [3]
(ii) Explain how and why the mass spectrum of the two compounds in (i)
would be different. [4] (c) A saturated molecule of formula C,H,NO was subjected to analysis by mass
spectrometry and NMR spectroscopy. In the mass spectrum of the com-
(c) At one time, bromomethane, CH,Br, was widely used to control insect pests
J hal pound, the M peak was at mle 73 and the ratio of the heights of the
in agricultural crops and timber. It is now known to break down in the M : M + 1 peak was 48 : 1.7.
stratosphere and contribute to the destruction of the ozone layer.
to gi (i) Using the data from the mass spectrum, determine the values of x and
Samples can be screened for traces of bromomethane by subjecting them y in the formula of the compound.
to mass spectrometry.
-C~
(ii) Use the data from (i) together with the NMR spectrum below to deduce
(i) Which peak(s) would show the presence of bromine in the compound? a structure for the compound, explaining how you arrive at your
II
0
answer.
(ii) How could you tell by studying the M and M+2 peaks that the com-
J is pound contained bromine rather than chlorine? [3]
[JOB!P4!09)
(ii) G i!

Suggested Solution:
-
uestion .·
he three
nportant
(a) (i) Molecular size I M, I shape.
(ii) Voltage size.
•nd·pertu (b) (i) CH,- CO - CH, would show a single peak, no spin - spin coupling
because all the Protons(H) are in the same chemical environment and [4]
peak at 8 : 2.1 is due to CH,CO group. CH,- CH,CHO would show 3 II
peaks, since there are 3 different protons environment.
11 10 9 8 7 6 5 4 3 2 0
There would be a peak at 8 = 9.5- 100 due to CHO group.
- chemical shift, Blppm
Peak at 8 = 0.9 due to CH,.
[N08/P4/Q9)
Peak at 8: 1.3 due to CH 2 •

(ii) Different fragments:

CH COCH, would form fewer fragments CH,CO• at mle 43.
(a) Stat 3
CH,CH,CHO would form fragment of CH,CH 2CO+ at mle 57.
stru
CH 3CH 2' at mle 29.
 topic 11.2 Applications of Analytical Chemistry
Page9 ~-----~--------lP~a~ge~JO~-,----------------
11.2 Applications of Analytical Chemistry
~- ~
topic
~CORNER
{),Je<
{c) The diagram shows the result of two-way paper ch roma tography. /1 -L" ._ ,
....._v~ CORNER
CJ

Cfl~--\
Suggested Solution:
{a) {i) Restriction enzymes cut DNA into fragments called minisatellites.
I
CJ

Since
~
{ii) It is placed on agarose gel (undergo electrophoresis).
(iii) Radioactive phosphorus/ P32 or darken photographic film. r •
(b) (i) NMR can be done in solution shows the position of dif:erent kinds of solvent
• •
Cf\-1
proton.
X-ray crystallography shows the positions of most atoms in their molecular
structure, their bond length and bond angles.
2
•
Jis ·
(ii) Different types of tissue have protons in different chemical environment.
• •
din ill'
din~n' (c) (i) M:M+1;48:1.7
(c) Number of carbon atoms
in a compound can be
determined by the
starting point _.)...-- X •
x;~=3.2 following formula
1.1x48
i,-c l Hence there are 3 carbon atoms in the compound. Since the compound X= tOO X AM+1
solvent!-

II~' has m/e of 73 and contains 3 carbon atoms, 1 Nitrogen atom and 1 Oxygen 1.1 AM (i) H~w many spots were there after the first solvent had b
0 atom, y;73-(36+14+16);7. So (C 3 H,NO).
A..., =Abundance of (ii) Circle the spot that moved ve r . een used?
distance in solvent 1. ry Jttle 10 solvent 2, but moved a greater
(ii) The NMR spectrum shows a triplet at 16 value indicates its neighbour M+1 peak
has two protons and quartet indicates its neighbour has four protons. So (iii) Draw a square around the spot that c d
AM =The abundance of by using only solvent .
1
oul be separated from the rest
CH - - CH • The other broad peak is due to N-- H Protons structure CH 3 [3]
3 2 molecular ion, Mpeak.
CH, CO NH,. [J09/P4/QB]

J h1 Suggested Solution:
Question 7 (a) (i) Partition coefficient is an e Tb .
to 1.· A large number of organic compounds are soluble in both water and non- of a solute between two i~%'is~~~ csoo~~~~~~-representing the distribution
aqueous solvents such as hexane. If such a compound is shaken with a mixture
-c--< of water and the non-aqueous solvent, it will dissolve in both solvents depend-
(ii) If 0.4 g has been extracted
' o•1 g rema·In .1n aqueous layer.

I
0
ing on the solubility in each.
the concentration in the hexane layer= ~-: = 0.02 gcm-3
(a) {i) State what is meant by the term partition coefficient.
J i:. :·:J : (ii) When 100 cm3 of an aqueous solution containing 0.50 g of an organic the concentration in the aqueous layer;~_- 0.001 gem-3
{ii) a,:i · compound X was shaken with 20 cm3 of hexane, it was found that 0.40 100
: 1: g of X was extracted into the hexane. Kc Concentration in hexane 0.02
---;.• Calculate the partition coefficient of X between hexane and water. 2
Con_centration in water = 0.00! = 0
3
estioti: :·•· ·:
~··i:
(iii) If two 10 cm 3 portions of hexane were used instead of a single 20 cm (Iii) 1st extracti~n:
portion, calculate the total amount of X extracted and compare this with
~ thre~' ';:; 3
>ortani. the amount extracted using one 20 cm portion. [5] If x be the amount dissolved in hexane
j perf
then amount in water = o. 50 -x. '
(b) PCBs are highly toxic compounds released into the atmosphere when some
plastics are burned at insufficiently high temperatures. In recent years PCB Concentration in hexane;.!_ gcm_3
residues have been found in the breast milk of Inuit mothers in northern 10
Canada. Foods, such as oily fish, seal and whale meat, which are high in
Concentration in water ; 0.50- x
fat, form an important part of the Inuit diet. 100
(i) Suggest why berries and drinking water are not contaminated by PCBs X.
in the same way that oily fish, seal and whale meat are. K - 10
pc- 0.5-x
(ii) Based on the information provided, what can you say about the par- 100
tition coefficient between fat and water for PCB residues? [3] X.
=> 20 = __1_0_
0.5-x
.!_; 20 (0.5- X)
10 100
100
Sta
=> X=l-2x => X =J
1 = 0.33 g
stn
Amount of solute left in water = 0.50 - 0.33 = 0.17 g

'
i i ..•
 Garb
topic 11.2 Applications of Analytical Chemistry Page 11 topic 11.2 Applications of Analytical Chemistry Page 12
1 rea<
~CORNER
;I 2nd extraction: ~CORNER
6~
\
Let y be the amount dissolved in hexane.
Question 8

The residues from organohalogen pesticides are known to be a major cause

Cl
Concentration in hexane = l'.. gcm-3 of the decline in numbers of different birds of prey in many countries. These
10 residues are concentrated in birds at the top of food chains.
)ince ·
0 17
oses 1 Concentration in water= · - Y gcm-3 (a) Analysis of the bodies of birds of prey show that the pesticide residues
100
c y accumulate in the fatty tissues of the birds. This is because of the high

,H,-C
I K =___.IQ__
partition coefficient between the fat in !be tissues and water found in blood.
pc 0.17-y Explain what is meant by the term partition coefficient.
I 11)0 [2]
( (b) A particular pesticide has a partition coefficient of 8.0 between the solvent
y
20 = ___.IQ__ hexane and water. If a 25 em' sample of water containing 0.0050 g of the
J is :,
0.17-y pesticide is shaken with a 25 em' sample of hexane, caiculate the mass
dinitr' 100 of pesticide that will dissolve in the hexane layer. [2]
dinitr<'
1'..=20(0.17-y) (c) Compounds used as pesticides may contain bromine or chlorine.
10 100 (i) What would be the difference in the ratio of the M: M+2 peaks if the

-~~~', Y=0.34-2y ::::> y=0.11g

Total extracted amount = 0.33 + 0.11 = 0.44 g
pesticide contained one chlorine rather than one bromine atom?
(ii) If a given pesticide contains two chlorine atoms per molecule, deduce
0 the relative heights of the M, M+2 and M+4 peaks. [3]
Difference = 0.44-0.40 = 0.04 g
(d) The following graph shows the occurrence of pesticide residues in the eggs
0 04 of fish-eating birds of prey upstream and downstream of a paper mill at
%= · x100 = 10%
0.4 Castlegar on the Columbia River in Canada.

(b) (i) Berries have aqueous media and PCBs are insoluble in water, therefore, Columbia River Basin
berries will not be contaminated with PCBs.
120~-------------
J h',
(ii) Partition coefficient of PCBs in fat & water is PCB = ~ . As PCB is 1ooi__ _ _ _ _ _ _ _ _ _ _ ____
[Water] c
to g
more soluble in fat, therefore partition coefficient will be greater than one.
~ ~ PCBs
(c) (i) Four
Iiic. llli'!ll Other Dioxins/Furans
(/)
1: ~ Dioxin 237BTCDD
(ii), (iii)
"'c.
(/) 40 • Furan 237BTCDF
aw
(ii)

-----1~!1: ~~; >

Questi~!'',
l
solvent
• ••
[!]
1- 20

C') ..,. l() CD ,... C') ..,. l() CD ,._

"'"' "'"' "'"' "'"' "'"' "' S!?"' "'m

"' (J)
2 ~ "
~ ' (J)
~ ~
The thr/',':
importa(,' upstream of Castlegar downstream of Castlegar
and pef,,:,
!•
• @• PCBs, the dioxin 2378TCDD, and the luran
chemicals containing chlorine.
2~78TCDF all come from I
:
(i) Suggest which compounds are present directly as a result of the paper
mill.
- (ii) By studying the data for 1994, suggest which chemical(s) come from
solvent1- sources other than the paper mill.
(iii) Compare the downstream data for 1994 with that for 1997. Suggest
what might be responsible for the change.
(iv) A molecule of 2378TCDD contains four chlorine atoms. How many
molecular ion peaks would this compound show in its mass spectrum?
(a) s [4]
sl, ,
[N09/P4/08]
 topic 11.2 Applications of Analytical Chemistry · Page 14
Pa e 13
~CORNER ~CORNER
eact
Suggested Solution:
.
(a) Ratio of the concentration o
f a solute in two immiscible solvents.
eJ • A
•s/ • c
Je
mixture placed here
(b) Let amount of pesticide in hexane= x
~ amount of peslicide in waler = 0.005- x amino acid relative size charge

tee t [pesticide in hexane] A

;es v Kpc = [pesticide in water]
B
d X= 0.00444 g
X ~ x=0.04-8X ~
\'.'. ~ 8=~ c
_c, [3]
, I
( (d) The sequence of amino acids in a polypeptide may be determined by partial
.c
(c) (i) Ratio is 3 : 1 hydrolysis of the chain into smaller pieces, often tripeptides .
1 ·ts ''' 35C/ 37C/ 37C/ 37C/
35C/ 35C/ (i) Following such a partial hydrolysis, the following tnpeptides were ob-
din itt',~ . (ii)
1 1 tained from a given polypeptide.
(~x~)x2
d"tnitPr 3 3 -x-
-x- 4 4 ala-gly-asp gly-ala-gly lys-val-ser ser-ala-gly val-ser-ala
4 4
Given that the N-tenminal amino acid is lysine (lys) suggest the amino

"-4,·:, 9
16
6
16 16
acid sequence of the shortest polypeptide that would give the above
tripeptides. ·
0 M+2 (72) M+4 (74) The structural formulae of the amino acids in the polypeptide are given below.
M (70)
9 6 abbreviation amino acid structural formula

Dioxin and furans ala alanine H2NCH(CH3)CO,H

(d) (i)
(ii) PCBS asp aspartic acid H,NCH(CH,CO,H)CO,H
(iii) Removal of dioxins and turans. gly glycine H,NCH,C02 H
(iv) Five lys lysine H,NCH(CH,CH,CH,CH,NH2)CO,H
td•
ser serine H,NCH(CH,OH)CO,H
Question 9 . val valine H,NCH(CH(CH3)2)CO,H
. . be separated using electrophoresis. A typical
A mixture of am1no ac1ds may .
· h in the diagram. (ii) Which of the tripeptides in (i) has the lowest M,?
'·-t'.il.t.· practical set-up IS s own
d.c. power supply
(iii) Select one amino acid from those listed In the table which contains
.an ionic side-chain at pH 8. (4]
l\\) ::!ir;~,r· ~ [J10/P4/Q7]

~·,:,':~;',.
QueSII;i, . io) ·.•.
~:<:~.{
The 1''''•,;. Amino acids at their isoelectric point are in the fonm of zwillerion and do not

i:~oii;:,j:,.
show any movement in electric field.

H,NCH,coo-, (at pH 10) (b) At high pH amino acids

exists in lhe fonm of anion.
amino add relative size charge

A smallest negative
amino acid mixture placed here
. . d on some amino acids may not move, 8 largest negative
( a) When the power supply IS swltct he xp'lanation for this observation. [2)
. r ry sugges an e c average size positive
but remam sta IOna . . ula H NCH CO,H. Identify the species
(b) The amino acid glyctne ha~f thle f_ormmove~ to the left (positive) end of the
fonmed on the filter paper I g yclne . [1) (I) lys-val-ser-ala-gly-ala-gly-asp.
filter paper. . from another electrophoresis. What ca_n (ii) gly-ala-gly.
(a]. (c) The following result was obt_alne~ f and charges on, the amino acid (iii) aspartic acid.
be deduced about the relative Sizes o ,
species A, B and C?
~· Page IS topic II .2 Applications of Analytical Chemist!]I_
topic 11.2 Applications of Analytical Chemistry Pagel6 _ __
~CORNER
~
, reac Suggested Solutton:
. CORNER
(a) NMR: Protons.
;I Question 10

b-4
I
(a) NMR spectroscopy and X-ray crystallography are two techniques that use
electromagnetic radiation to look af the structures of large molecules.
In NMR, energy is absorbed due to the spin of protons as they absorb
radiations from radio frequency region and acquire lwo different energy
states.
Cl For each technique state the sub-atomic particle involved, and explain how
X-ray: Electrons.
this particle interacts with the radiation. [4]
Since X·rays are diffracted because of regions of high electron density.
(b) The two NMR spectra 1 and 2 were obtained before and after an alcohol,
loses
Y, was oxidised to give compound Z. The numbers of hydrogen atoms respon· (b) (i) spectrum 1
sible for each P!Jak have not been shown. All t'le peaks have been shown.
reason: In alcohol, hydrogen atoms are present in different chemical
cH,- environment, hence there should be more than one peaks which are present
only in spectrum 1.

(ii) Spectrum 2 shows only one peak hence it must be a ketone. It means it
J i~ must be a secondary alcohol.
din·,',,,
din Number of carbon atoms = ~ = 3
17.6x1.1

~
Hence spectrum 1 is of alcohol Y which is propan-2-ol.
Spectrum 2 is of compound Z which is propanone.
-c- (iii)
' II
0 6 5 4 3 2 1 0
11 10 9 8 7 OH
5/ppm
1 I
Y is /
, I
CH-C-CH
,
H

(iv) All the protons in Z are same chemical environment hence single peak
is obtained.

7 6 5 4 3 2 0
10 9 B
o/ppm
2
(i) State which spectrum, 1 or 2, was produced by the alcohol, giving a
reason for your answer.
(ii) The mass spectrum of Y showed an M: M + 1 peak ratio of 17.6:0.6.
Use this and other information in the question to suggest the identities
of both Y and Z.
(iii) Draw a displayed formula for Y in the box provided

Vis

(iv) Explain why the NMR spectrum of Z only shows one peak. [7]
[N10JP4/QB]
 topic 11.3 Design and Materials Page 1

r:loptc 11.3 ~CORNER

7Jesign and !Jl(alerials q?li/) fP) fi;?J

IJ ~ t.r IJ \!;;I qpening ....... .

Question 1

Content (a) Graphite and buckminsterfullerene

referring to diagrams of their stru I are two structural forms of carbon. By
Medicinal chemistry and drug delivery. properties.._ c ures, suggest three differences in their

2 Properties of polymers.
3
4
NanotechnologY:
Environment and energy. ~
Learning Outcomes
Candidates should be able to use the concepts and knowledge from the core syllabus and
sections I 1.1 and 11.2 to:
~
(a) discuss the challenges of drug design and explain in simple terms how molecules may graphite buckminsterfullerene
be identified and developed to overcome these problems. 3
(b) Nano-sized 'test-tubes' can be 1 d f [ 1
(b) discuss the challenges of drug delivery and explain in simple terms how materials may What is the relationship between orme rom carbon structures.
structural forms of carbon sh thebparts of these 'test tubes' and the two
be developed to overcome these problems. own a ove?. [3],
(c) discuss the properties and structure of polymers based on their methods of formation (c) Many modern sunscreens contain n · .
This substance does not absorb tat no:~ Jzed part~cles of titanium dioxide.
(addition or condensation, link to core syllabus, section 10.8). 1
u rav1o et rad1at1on
Suggest how these nano-particl es are able to protect· skin from ultraviolet
radiation.
(d) discuss how the presence of side-chains and intermolecular forces affect the proper-
[1]
ties of polymeric materials (for example, spider silk).
{J07/P4/Q9}
(e) show awareness of nanotechnology and, given information and data, be able to discuss
the chemistry involved with reference to the core syllabus Suggested Solution:
(f) discuss how a knowledge of chemistry can be used to overcome environmental prob-
graphite conducts electricity
(a) Altemative Answers:
. terns (for example, ground water contamination, oil spillage, CFCs). • graphite has higher
layers in graphite slide over one another
(g) discuss how a knowledge of chemistry can be used to extend the life of existing re- density
graphite has higher m.p than buckminsterfullerene
sources, to identify alternative resources and to improve the efficiency of energy pro- • graphite has lower
The walls of nano-sized test tub ·
duction and use.
of the tube is caped by half cueps cfobnsJskts ?I
rolled graphite sheets and side
o uc mmsterfullerene.
solubility
• buckminsterfullerene
(c) Particles are similar in size to the wav I .
radiation instead of absorbing it. e ength of UV light and reflect the harmful cage can trap atoms,
molecules within them-
selves.

Question 2

Read the following article about the use of b . . . .

the questions that follow it. actena In mJmng, and then answer

The discovery that bacteria could 'mine' metals for us wa . .

mme, m the southwest corner of Spain a . . 11 s made m Spam. The Rio Tinto
some 2,000 years ago. In 1752 so ' w ~ ongma y mmed for copper by the Romans
it could possibly be re-opened Th me mmdmg engmeers looked over the mine to see if
.Note: The additional learning outcomes to be studied by />2 candidates are shown in bold type. The 1>2 . · ey notice streams of a blu 1. .
spoi heaps of the processed rock that I d e-green Jqu•d running from
ra 1 . . ay aroun the mine When th" bl
components will assess all learning outcomes and will not be limited to those in bold type. n over Iron, II coated the iron with a b fit . •s ue-green liquid
rown I m. The brown film was metallic copper.
 topic 11.3 Desig_!J_and Materials
Page2 Page3
top_ic 11.3 Design and Materials
~CORNER
There was still some copper left in the spoil heaps. At the time, everybody thought that
Question 3 1 ~ CORNER
the copper was being dissolved in the liquid through a simple chemical reaction. But in
1947, US scientists discovered that the copper was being 'mined' by a bacterium called (a) A number of drugs, such as insulin for diabetics, are delivered by injection
rather than by mouth (oral delivery). Suggest two reasons why this might
Thiobacillus ferrooxidans.
be necessary. [2]
The bacterium Thiobacillus ferrooxidans lives off the chemical energy trapped in metal
sulphides. In the ore, the copper exists as copper sulphide. The bacteria gain energy by (b) M<my patients prefer oral delivery to injection, and a number of methods
converting the copper sulphide to copper sulphate, which is then excreted. At the same for overcoming the problems of oral delivery are being investigated. Several
time, they absorb the difference in energy in the chemical bonds. These bacteria can also of these use nanotechnology.
obtain energy in similar reactions with ores of zinc: lead ·and uranium. Study the passage and diagram and then answer the questions that follow.

(a) Use the Data Booklet to explain why the blue-green liquid coated the iron At a 2004 meeting, engineers from the University of Texas described their
with copper. Write an equation for the reaction. (2] research into nanospheres for oral drug delivery. Nanospheres can trans-
port a drug safely through the hostile environment of the stomach.
(b) Suggest two reasons why this method of extracting copper might be useful
The nanospheres are created from hydrogels which are stable, organic
tor ore containing only a small percentage of copper. [2]
materials formed from a network of polymer chains. Hydrogels have a variety
(c) Suggest one disadvantage of using bacteria rather than traditional mining of uses including disposable nappies, soft contact lenses, dressings for
and smelling methods. [1] burns and, more recently, drug delivery. The drug is contained in the hydrogel
nanosphere as shown in the diagram below. Hydrogels absorb water and
(d) In conventional copper mining, the ore will typically contain 0.5 - 2.0%
swell at a rate dependent on the pH of their environment. As the hydrogel ,
copper, which gives an idea of what a valuable resource copper is. swells, the drug is released. I
(i) The ore from a particular mine contains 0.75% copper, and 150 000
tonnes of ore are mined each year. From this ore about 60% of the hydrogel
copper is extracted, and the remainder is left in the 'spoil heaps' of coal
processed ore.
What mass of copper is extracted each year?
(ii) If the use of bacteria can recover a further 17% of copper from the spoil
heaps, what is the extra mass of copper produced? [2]
(e) Suggest why bacteria are unlikely to be used in the extraction of aluminium.
(1] drug
nanosphere
(f) Metals like copper and zinc from abandoned mines can contaminate ground·
water. Suggest one way of removing these contaminants. (1] (i) What is a nanosphere?
[N071P4/010] (ii) Suggest why the stomach might be a particularly hostile environment
for drugs.
(iii) Suggest two ways in which the nanosphere shown in the diagram can
Suggested Solution: be modified to change the rate of drug release. [4]
(a) Iron being higher in reactivity series displaces copper from its soluble salt.
(c) Hydrogels may be fomned as homopolymers (using a single monomer), or
2 heteropolymers (using two or more different monomers).
Cu 2•(aq) + Fe(s)---+ Fe •(aq)+ Cu(s)
By using the monomers below, you are to draw sections of both a
(b) (i) It does not require large investment in machinery & work force.
homopolymer and a heteropolymer. Each of your drawings should show a
(ii) It does not require use of large amount of energy. three-monomer section of the polymer.

(c) The process is very slow and takes a long time to complete. HOCH;CH,OH HO,CCHRNH, HO,CCH(OH)CH,C0 H
2

[3]
(d) (i) . mass <if copper in ore=~
100
x 150000 = 1125 tonnes
[JOB/P4/Q 1OJ

I
'I copper extracted = 60 x 1125 = 675 tonnes
100
Suggested Solution:

(ii) copper left in spoil heap= 1125-675 = 450 (a) (i) To speed delivery of the drug to target organ. (Faster response)
(ii) To avoid the drug being hydrolysed.
copper recovered by bacteria = 450 x .!2..
100
= 76.5 tonnes
(b) (i) Sphere with a diameter of the order of nanometres between 10 - 500nm.
(e) A/ is a reactive metal. Fe being less reactive can not displace it from its aqueous (ii) It is highly acidic/low pH.
solution. (iii) Use hydrogels of different (wall) thickness to release drug over lime.
(f) Ions of Zn'• & Cu'• can be precipitated as there carbonates by adding sodium
carbonate solutions.
 Page 4 topic 11.3 Design and Materials PageS
topic 11.3 Design and Materials
~CORNER ~CORNER
Suggested Solution:
(c) homopolymer:
(a) (i) Silkworm: Hydrogen bonds.
0 0 0 Ordinary silk produced by

-~-CHR-~- ~-CHR-~-~-CHR-
Spider: Vander waals OR hydrogen bonds. silk moth has a P·pleated
sheet structure, held
NH- (ii) 1. Spider silk is more elastic than silkworm silk, it has a lower density
together by hydrogen
and less rigid.
bonds.
H H 2. Silkworm silk absorb water more easily.
The elasticity of spider silk
(iii) This increases the elasticity of the silk. comes from regions that
heteropolymer: are rich in glycine. In these
R (b) (i) A polymer formed with the elemination of small molecule e.g. H 0 or HC/. regions sequence of fine
0
I H 0 C (ii) A polyethene is formed.
2
amino acids is repeated .
R IIc-cI/ " c /I"N/ (iii) Addition polymers have a limited range of monomers. Addition polymers After each sequence
are non polar. a 180' turn occurs
I
e-N
/ I II H I Condensation polymers/proteins have a range of combinations of amino producing a spiral.
/1 I CH, 0 H
acids which give a wide range of properties.
-cII H H
" CO,H Condensation polymers/proteins have more functional groups/side chains
0 and different sequences of amino acids result in different secondary or
tertiary structure.

Question 4 Question 5
(a) Silk from silkworms, us~d as a fabric shows a different secondary structure
(a) Spider silk is a natural polymer which has an exceptional strength for its
to that produced by spiders.
weight. Kevlar is a man-made polymer designed to have similar properties.
It has a wide variety of uses from sporting equipment to bullet-proof vests.

Cl

silkworm silk highly ordered

~sheets
Kevlar
(i) What sort of bonding would you expect to occur between adjacent
parts of the protein chains in each form of Silk? (i) In Kevlar, the polymer strands line up to form strong sheets with bonds
between the strands.
silkworm, spider.
On the diagram above, draw part of a second polymer chain showing
(ii) Suggest two differences in properties that these forms of silk could how bonds could be formed between the chains.
have. Explain your answer.
(il) Suggest what type of bonds these are.
(iii) Spider dragline silk contains larg~ amounts ~f ~e amino acid glyci~;j
How does this affect the propertieS of the Silk. (iii) Draw two possible monomer molecules for making the polymer Kevlar.
[5]
(b) Both forms of silk are condensation polymers. (b) The transport of oil by sea has resulted in a number of oil spills in recent
(i) Explain what is meant by a condensation polymer. years. As well as a waste of a valuable resource, these have caused major
(ii) Another type of polymer is called an add TI lon p
clymer . Name an ex- environmental problems. Traditional sorbent materials absorb water and
ample of an addition polymer. . sink. Researchers have developed new sorbent materials to help collect
(I the spilled oil. The sorbent consists of a material called 'hydrophobic
. 1
(iii) Suggest why condensation po_vmers
such as proteins show a Wider
[ ]
5 aerogels'. This is a network of silicon(IV) oxide with some of the silicon
range of properties than additiOn polymers. atoms attached to fluorine-containing groups.
[NOBIP4/Q10]
!2.lili·.
Page6 topic 11.3 Design and Materials
topic 11.3 Design and Materials Page 7
~CORNER
The introduction of these fluorine-containing groups allows the oil to be Question 6
~CORNER
c absorbed but not the water. Tests show that these materials can absorb
more than 200 times their mass of oil without sinking. (a) Put the following items in order of increasing size. Use the number 1 to
(i) Suggest what the word hydrophobic means. indicate the smallest and 3 to indicate the largest.

(ii) Suggest why the fluorine-containing groups allow oil to pass through
but not water molecules.
(iii) Suggest another important fluorine-containing polymer that repels water-
contain in~ materials. [4]
[J09/P4!09]

Suggested Solution:
H

M~
(a) (i) ;._~.t ·. length of DNA molecule nanosphere diameter
Q ---e/ in a chromosome
cell diameter

eH,~. HI Me 011

--....N 011

~e MN--....e 11
Q ~•
(b) Nanotechnology has an increasing range of uses across a number of fields
[2]

including sport. For example, golf clubs are now being made using
--....N 0 nanomaterials.

---cII
0 M ~
:
!
:
!:
~: r(YC--.... 0
II

. 0 r(YN--.... )-VJ
7 M~--....N~ b
0II MN--.... C I
H

/C--.... N 0II cross-section of normal cross-section of golf club

golf club shaft shaft with nanomaterial fill
I
H
Use the diagrams above and your knowledge of nanomaterials to suggest
two properties of the new shafts. Explain your answers. [2]

(c) A miXture of nano-sized particles of tungsten and vanadium(IV) oxide can

(ii) Hydrogen bond be applied to the surface of windows and reflects heat whilst letting all light
in the visible range through.
0 0
11~11 Suggest how this variable reflective property is possible using nano-sized
CI-C-o C-CI particles. [2]
(iii) H 2N - o - N H2
(d) Although silver is well-known as a precious metal, its medicinal properties
have been used for hundreds of years. In ancient Greece silver was used
(b) (i) Water repelling or water resistant. to purity water and until the development of antibiotics, silver was important
(ii) Sorbents containing fluorine absorbs oil through van der waal bonds. As in the treatment of large wounds.
they cannot make hydrogen bond with water, therefore it is not possible
(i) What property of silver makes it useful for jewellery?
for sorbents to absorb water.
(ii) Suggest the property of silver that makes it useful in the treatment of
(iii) polytetraf\uoroethylene or teflon. large wounds.

(iii) Suggest why nano-sized silver particles are more useful in treating
( wounds. [3]

[N09/P4/Q9}
 II""'''
£!'

topic 11.3 Design and Materials PageS

topic 11.3 Design and Materials
Suggested Solution:
~CORNER Page9

~CORNER
CH, (i) Suggest a material for the electrodes.
a)
(ii) Use your knowledge of hydrogen to suggest a disadvantage of these
length of DNA molecule nanosphere diameter cell diameter fuel cells in powering vehicles. [2]
in a chromosome
(e) Many of the world's countries are developing ways of recycling materials
3 1 2 which are valuable or which require large amounts of energy to produce.
For each of the following recyclable materials, state whether recycling of
this material is important in saving energy or in saving resources. Use your
(b) 1. The gaps .1n the structure of shaft
lureare· much smaller mak.lng I., more flex- knowledge of chemistry to explain eacli choice.
ible hence less chance 1o 1rae . glass, steel & plastics.
2. Co~posites and carbon nanotube~ ~~i ~~~!r dense than metal of compa-
rable strength making golf club s a g .
[3]
[J10/P4/QB}

(c) As the wavelength of infrared ener~y

.s longer than that of light, the gaps
1 Suggested Solution:
through but reflects infrared
between nano-sized particles allow light to pass '
energy. '(a) Reaction (II), as electrons are used up here. Electrons move from negative to
positive electrode.
(d) (i) .
Resistance to corrosion, retams I·1s shine for longer. time.
.
(ii) Silver is able to kill
. bactena
· a nd prevents its mu1t1ply1ng. . Ee- = -0.13 V
(iii) Very much large surface area mean s that they dissolve more easily.

(c) (i) +3
Question 7 . earch area in
The des1gn
. an d development of batteries has been a maJOr res
(iij They are lighter than lead acid batteries and less polluting to environment
as cone. H,so, is not used in these batteries.
recent years. d of a number of recharge-
cal Lead-acid batteries, used in ca~s. adre mlap:d ~~ 1860 They have the dis- (d) (i) Platinum or graphite.
store d. ouring
0
able ·cells .m sene
· s • and were f1rst eve ·
. ared to the energy
advantage of a relatively high ~ass ~o~: ells of these batteries are as (ii) Hydrogen is highly flammable, hence is difficult to store the fuel cells.
discharge, the electrode reactions In e c
follows.
(e) glass: Saves energy. Few materials for glass formation are easily available.
Pb+ so~- --7 PbS0 4 +2e- (e) Plastics are made from
steel: Saves energy. Extraction of iron needs energy and mining the ore
is also energy intensive. alkenes · which are
ll Pb02 + 4W +so~-+ 2e- --7 Pbso. + 2~0 obtained by cracking of
plastics: Saves resources. Petroleum is a non renewabre longer petroleum fractions
State which of these reactions o~c~rs at th e positive electrode in a lead-
[1] source and recycling of plastics will save the resource. recycling of plastics can
acid cell during discharge, explalmng your answer. th save resources.

(b) Use the Data Booklet and the ·~qu~l under standard conditions.
lions I and II above to calculate e Question 8
(2]
voltage produced by a lea~-aCI : developed in the 1980s and have
(c) Nickel-metal hy.dride battenes ;~c~larly for small devices such as mo?ile A possible source of energy for the road vehicles of the future is hydrogen. One
become increasingly common P d ar-constant sources of electncal. of the problems still to be solved is the storage of the hydrogen in the vehicle.
phones and digital camera.s that ne~ dr~~ide (NiO(OH)) as one electrode A conventional tank holding liquid hydrogen would have to be pressurised and
energy. These cells us~ mckel oxo ~ LiNi as the other electrod~. refrigerated. In a crash, this type of tank could break resulting in the rapid
,, . and a hydrogen-absorbing alloy sue as ' release of hydrogen and an explosion.
One reaction that takes place in these batteries is One alternative. is to use a fuel tank packed with carbon nanotubes. The hy-

NiO(OH)+~O+e- == Ni(OHh +OH-

drogen in the tank would be absorbed onto the surface of the nanotubes at a
pressure of no more than a few atmospheres.

(i) (a) (I) What is the approximate width of a carbon nanotube?

State the oxidation state of nickel in NiO(OH) ....................:. 'd
(ii) In what structural form is the carbon in a nanotube?
(ii) Suggest a likely advantage of these ba11 enes
· compared w1th lead-ac1(2]
(! ;
batteries. · (Iii) What forces could be responsible for holding the hydrogen on the surface
of the nanotubes? Explain your answer. (4]
(d) Hydrogen fuel cells hav~ been sugge fuel cells hydrogen is oxidized to
sted as the next major advance m
electrically powere.d v:h~~~=iy!~ ~~~s~ert electrodes. (b) The hydrogen atoms in a fuel tank packed with nanotubes are closer
produce water, usmg together than in liquid hydrogen. Suggest one advantage of this. [1]
 1~
AL Chemistry !une 2011 Paper 2 o Page I
Page 10
topic 11.3 Design and Materials
~CORNER ~CORNER
(c) When a nanotube-packed fuel tank is full of hydrogen there is a steady June 2011 Paper 2
H; pressure of hydrogen in the tank. While hydrogen gas is being removed
from the fuel tank to power the car, the pressure in the fuel tank drops very
Answer all questions.
little for some time. State Le Chate\ier's principle, and suggest how it explains
this observation. [4]
[N1 OIP4/09}
Question I

Ethanoic acid can be reacted with alcohols to form esters, an equilibrium mixture
Suggested 5o/utic;m: being formed.
(approximately 1/50,000th of the width of a human
(a) (i) A few nanometers
CH3C0 2H + ROH ~ CH3C02R + H20
hair).
(ii) Graphite. The reaction is usually carried out in the presence of an acid catalyst.
(iii) There are Vander waal's forces of attractions between carbon atoms in (a) Write an expression for the equilibrium constant, K,, for this reaction, clearly
nanotubes and hydrogen gas as both are simple moleculer covalent com- stating· the units. [2]
pounds with weak Vander waal's forces of attraction.
In an experiment to determine K, a student placed together in a conical flask
~- (b) More volume of hydrogen can be carried in the same space. 0.10 mol of ethanoic acid, 0.10 mol of an alcohol ROH, and 0.005 mol of hydro-
' gen chloride catalyst.

(c) Hz(absorbed) === H2(gaseous)

The flask was sealed and kept at 25 'C for seven days.
After this time, the student titrated all of the contents of the flask with 2.00 mol
As hydrogen is used up to power the car, the equilibrium will shift in forward dm-3 NaOH using phenolphthalein indicator. ·
direction to release more hydrogen gas. At the end-point, 22.5cm' of NaOH had been used.
Hence according to equilibrium taw i! a system at equilibrium is disturbed, it
will shift so as to cancel out the affect of that disturbance. When H, is removed, (b) (i) Calculate the amount, in moles, of NaOH used in the titration.
pressure drops and equilibrium will shift in forward direction. (ii) What amount, in moles, of this NaOH reacted with the hydrogen
chloride?
(iii) Write a balanced equation for the reaction between ethanoic acid and
NaOH.
(iv) Hence calculate the amount, in moles, of NaOH that reacted with the
CH 3 - ethanoic acid. [4]
(c) (i) Use your results from (b) to calculate the amount, 'in moles, of ethanoic
acid present at equilibrium. Hence complete the table below.

(li):'' CH3C02H ROH CH3C02R H20

initial
0.10 0.10 0 0
~: amount/ mol
Ques'
equilibrium
The;·' amount/mol
impol ·
and 1 (ii) Use your results to calculate a value for K, for this reaction. [3]
(d) Esters are hydrolysed by sodium hydroxide. During the titration, sodium
hydroxide reacts with ethanoic acid and the hydrogen chloride, but not with
the ester.
Suggest a reason for this. [1]
(e) What would be the effect, if any, on the amount of ester present if all of the
water were removed from the flask and the flask kept for a further week at
25'C?
Explain your answer. [2]
[Total: 12}

(a)
 c AL Chemistry
June 2011 Paper 2 o Page 2 AL Chemistry June 2011 Paper2 o Page 3
~CORNER ~CORNER
Suggested Solution: (b) Another halogenoalkane which was used as a refrigerant, and also as an
aerosol propellant, is dichlorodifluoromethane, CC/,F •
(a) 2

(CH 3C0 2R][Hp] Stale two reasons why compounds such as CH,CH,F and CC/ F have
no units been used as aerosol propellants and refrigerants.
2 2
[2]
(a) K, = (CH C0 Rl[ROHJ' (CH3C0 2Rl[H 20]
s 3 2
K, (CH3 C0 2R](ROH] CCI,F, is one of many chlorofluorocarbon compounds responsible for damage
lc
Moles of NaOH =Cone. of NaOH x Volume of NaOH (in dm3) to the ozone layer in the stratosphere.
(b) (i)
22 5
3
. [ mol/dm moVdm J[ 3
J
= 2 OOx · = 0.045 moles umls: [ mol/dm ][mol/dm']
3 (c) By using relevant data from the Data Booklet, and your answer to (a)
Cf- . 1000 suggest why CCI2 F2 is responsible for damage to the ozone layer in the
=1 stratosphere whereas CH,CH,F is not. (2]
(ii) NaOH is a monoacidic base. HCI is a monobasic acid.
Hence, therefore no units. Both CH,CH 2 F and CCI2 F2 are greenhouse gases.
moles of NaOH reacted with HCI =moles of HCI = 0.005 moles. The 'enhanced greenhouse effect' is of great concern to the inlernational
c community.
c
(iii) CH 3COOH + NaOH ---> CH 3COONa + H20
(d) (i) What is meant by the term enhanced greenhouse effect?
(iv) Moles of NaOH that reacted with ethonoic acid (ii) Water vapour is the most abundant greenhouse gas.
=Moles of NaOH used in titration- Moles of NaOH that reacted with HCI What is the second most abundant greenhouse gas? [3]
-C·
II '
o·
= 0.045 - 0.005 = 0.04 moles A greenhouse gas which is present in very small amounts in the atmosphere
is sulfur hexafluoride, SF,, which is used in high voltage electrical switchgear.
(c) (i) From equation in part (b)(iii),
(c) (i) Moles of ROH (where (e) What shape is the SF, molecule? (1]
NaOH and ethanoic acid are reacting in ratio 1 : 1 R is Na in this case) and
CH 3C0 2H al equilibrium are [Total: 12]
Therefore, using the answer from part (b)(iv), we have,
0.04. Therefore moles of
CH3C02H ROH CH3C02R H20 CH 3C0 2R and H20 are Suggested Solution:
0.1-0.04 =0.06 mol.
initial 0
(a) Bonds broken Bonds formed
0.10 0.10 0
amount/ mol 4 C-H 5 C-H
equilibrium 0.06 0.06 C=C C-F
0.04 0.04
amount/ mol HF c-c
-c'
II
o:· [ CH 3C02R l[Hp] 0.06 X 0.06 = _25
Let bond energy of C-F bond be x.
2
(CH3C0 2Rl[ROH] 0.04x 0.04 .. Energy required to break bonds= (4 x 41 0) + (1 x 61 0) + (1 x 562) = 2812

il) ,c:. (d) The activation energy required for the reaction between NaOH and an ester
Energy required to form bonds= (5 x 41 0) + (1 x x) + (1 x 350) = 2400 + x

is high. Thus NaOH does not react with the ester. !lH,!action =2812-(2400+x)
(e) According to Le Chatelie~s principle, to restore system to equilibrium, that side -73 = 2812-2400-x
estil;
-~",/·,··
~: •-·. of the reaction would be favoured which produces mor~- amount of water. X= 281_2- 2400 + 73
~ thif.~; ,' Hence the equilibrium will shift towards the right hand s1de and more ester = +485 kJmol- 1
10rt~·J: would be produced.
I P~))l- (b) 1. They are non-flammable.
(b) Aftemative reasons:
2. They are non-toxic. These compounds are
Question 2 - unreactive
(c) CCI,F, contains C-GI bonds which have a bond energy of 340 kJ/mol.
- volalile
Halooenoalkanes have been widely used as aerosol propellants, refrigerants From part (a), the bond energy of C-F bond is 485 kJ/mol. Hence, C-F bond
- easily liquified.
and ;olvents for many years. is stronger than the C-GI bond. The C-H bond, having a bond energy of
Fluor6ethane, CH,CH,F, has been used as a refrigerant. It may be made by 410 kJ/mol, is also stronger than the C-G/ bond.
reacting ethane with hydrogen fluoride. Therefore C-G/ bonds are broken by uv light, producing Ct free radicals,
which are responsible for damaging the ozone.
You are to calculate a value for the C-F bond energy in fluoroethane.
(a) Use relevant bond energies from the Data Booklet, and the equation below (d) (i) The term enhanced greenhouse effect refers to the trapping of reflected
heat from the earth in the lower atmosphere, which contributes to global
to calculate a value for the bond energy of the C-F bond. warming.
St;
str CH2 = CH 2(g) + HF(g) ---> CH3CH2F(g) !lH" = -73kJmol- 1 (ii) Carbon dioxide.
[4]
(e) Octahedral
).Sr'' '
AL Chemistry
June 2011 Pap_er 2 o Pag_e 4 June 2011 Paper 2 o Page 5
01 AL Chemistry
~CORNER
Suggested Solution: ~CORNER
-(
Question 3 (a) R: BaO S: BaC/2
Barium, proton number 56, is a Group II element which occurs in nature as the T: Ba(OH}, U: Baso,
carbonate or sulfate. V: Baco,
s The element was first isolated by Sir Humphry Davy in 1808.
W: Ba(NO,},
Ia Some reactions of barium and its compounds are shown in the reaction scheme (b) (i) compound T to compound W:
below. Ba(OH} 2 + 2HN0 3 ----> Ba(N0 3 }i+ 2H2 0
CH
the roasting of V in air:
heat gently
Ba(s) R(s)
BaC0 3 ----> SaO+ C0 2
in oxygen
J (ii) reagent: Carbon dioxide.
d
d H,O(i) equation: Ba(OH} 2 + C0 2 ----> BaC0 3 + H2 0

(c) Na,so,
(c) Any soluble sulfale can be
dilute H,SO, (d) (i} used for reaction 1.
-c-. dilute HCI U(s) Percentage of Ba in X= 100-18.9 = 81.1%
II I S(aq) T(aq)
0 Element Ba 0
Percentage 81.1 18.9
Na 2C0 3(aq) dilute HN0 3
Ar 137 16
reaction 1 81.1
No. of moles 18.9
137 16
V(s) W(aq)
0.592 1.181

0.592 1.181
simple ratio
0.592 0.592
(a) State the formula of each of the barium compounds R to W. [6]
2
H-C (b) (i) Write balanced equations for the following reactions.
, II Empirical formula of X = Ba02
0 compound T to compound W,
(ii) Baso,
the roasting of V in air.
(ii) Suggest a gaseous reagent for the conversion of T into V and write a (iii) Baa, + H,SO, ----> saso, + H2 0 2
(li)
balanced equation for the reaction. [4]

--~· (c) Suggest the formula of an aqueous reagent, other than an acid, for reaction 1.
[1]
Queg1:~j;i~ Question 4

The tt"c·~:i'
When barium is heated strongly in oxygen, an oxide X is formed.
Chlorine is manufactured by electrolysis from brine, concentrated aqueous
The oxide X contains 18.9% of oxygen by mass. sodium chloride.
import;,:·;
and pt::t1 The oxide X reacts with dilute sulfuric acid in a 1:1 ratio.
(a) (i) Describe, with the aid of a fully labelled diagram, the industrial elec-
Two products, one insoluble and one soluble, are formed.
trolysis of brine in a diaphragm ceiL State what each electrode is made
of and show clearly the inlet for the brine and the outlets for the products.

~- ·,
Ba(s)
heat strongly
in oxygen
X(s)
+dilute H,so,

L:JB (ii) Write a half-equation, with state symbols, for the reaction at each
electrode.
anode:
cathode:
(d) (i) Calculate the empirical formula of X.
(ii) Suggest the identity of the solid Y. (iii) Name the chemical that is produced in solution in this electrolytic
process. [7]
(iii) Use your answers to (i) and (ii) to .construct an equation for the reaction
of X with H,so,. [4] [Total: 7]
(a) q [Total: 15}
St'.
 AL Chemistry June 2011 Paper 2 o Page 7
June 2011 Paper 2 o Page 6
re
~CORNER
1 AL Chemistry
~CORNER Oleic acid is the cis isomer and elaidic acid the trans isomer of
;J
l Suggested Solution: CH,(CH,),CH = CH(CH,),CO,H.
I:;J (a) (i) The diaphragm cell consists of a titanium anode and a steel cathode. An
asbestos diaphragm is placed between the electrodes.
(c) By using this form Ia d
showing the stereo~h~m~:t%.the structural formula of elaidic acid, clearly

ince
Purified brine solution, consisting of Na•, W, cr and OW ions, is pumped 01 '
e1c and elaidic acids are exa 1 f
~]
into the anode compartment and the level is kept above that of the
!SeS Many vegetable oils contain este~po~s ~ umono-unsaturated acids.
cathode compartment. This allows brine solution to seep through the porous
often hydrogenated to form esters c p t Y. nsaturated fatty acids. Such oils are
asbestos diaphram into cathode side, and also prevents hydroxide ions fatty acids. on a1n1ng saturated or mono-unsaturated
migrating to the anode. Thus sodium hydroxide solution is formed in the
cathode compartment. The cr ions are oxidized at the anode and the H+
(d) (i) Suggest the meaning of the term polyunsaturated fatty acid.
ions are reduced at the cathode to form chlorine and hydrogen gas
respectively. The asbestos diaphragm also prevents sodium hydroxide (ii) What reagent and condition(s) are
unsaturated fatty acid? used for the hydrogenation of an
from making contact with the chlorine, thereby preventing the .formation
co.okin~, unsaturated fats are often oxidised to give aldehydes or keton~:l
J is::·
dinif.. of sodium chlorate(l). ':
dinir''I_:''
brine ( ) (1) Give the structural formulae of the t .
oxidation of the unsaturated fat b ~o aldehydes formed by the partial
In th t t eow.
e s rue ure, X, represents the rest of the fat molecule.
r<·,;·
J '
CH3(CH,)7C1 = CH(CH,hX
NaC/(aq) D<J.---+-- diaphragm
steel cathode
graphite --'f-------1- (ii) Name the reagent you would use t
anode either an aldehyde or a keton Woh show that the product contained
... e. at change would be seen?
(m) What reagent would you use . ·
What change would be seen!~ confirm the presence of an aldehyde?
J h, A"
mmal fats and vegetable oils can b .
~
+ rancid fat or oil has an unpleasant secolml e rancid because of oxidation. The
to •. me and taste.
(ii) anode: 2Cr(aq) -----> C/2 (g)+2e- ~ntioxid~nt~ are used to prevent the spoilage of many foodstuffs by oxidation
cathode: 2W(aq)+2e- -----> H2 (g) ne antiOXIdant that is widely used is vitamin C, ascorbic acid. .

(iii) Sodium Hydroxide. HO

Question 5
HO~o
Although there are many different types of food eaten around the world, animal
fats and/or vegetable oils are commonly used in cooking. HO OH
Animal fats and vegetable oils are usually glyceryl esters, that is esters of glycerol, ascorbic acid
propane-1 ,2,3-triol. (f) (i) How many chiral carbon atoms .
CHpH acid? If none, write 'none'. are present In one molecule of ascorbic
I (ii) Th e ascorbic acid molecule contains three functional groups
CHOH
I Two of these are alcoh 1 ( ·
Wh t . h o pnmary and secondary) and alkene •
CHpH
a IS t e name of the third functional group? . [2]
Many animal fats contain esters of stearic acid, CH,(CH 2) 16C0 2H.
[Total: 14]
Vegetable oils often contain esters of oleic acid, CH,(CH,),CH = CH(CH,),CO,H.
(a) Draw the structural formula of the glyce,YI ester formed when one molecule
of glycerol is completely esterified with stearic acid. [1]
(b) What reagent(s) would you use, in a school or college laboratory, to obtain
Sta a small sample of oleic acid, C 17 H33 C0 2 H, from the glyceryl ester present
stn...
in a vegetable oil? [1]
lEi June 2011 Pa_per 2 o Page 8
June 2011 Paper 4 o Page 1

ea
AL Chemistry
~CORNER ~CORNER
Suggested Solution:
June 2011 Paper 4
--4 (a) CH 20CO{CH 2 ), 6CH3 Section A
1
CHOCO(CH 2 ) 16CH 3 Answer all questions.
~e
1
35' CH,OCO{CH2 ) 16 CH 3
c Question 1
(b) Dilute Hydrochloric acid.
1 (a) Hydrogen fluoride, HF, behaves as a weak acid in water, with
-s (c) CH 3 (CH2),"'- >H
K,; 5.6 X 10-< mol dm-<l.
C=C Calculate the pH of a 0.050 mol dm-{3 solution of HF. [2]

is i
nitr.
H/ "
(CH2) 7CO,H (b) Gaseous ammonia and hydrogen fluoride react together to give solid ionic
ammonium fluoride.
nilr<: (d) (i) Fatty acids that contain more than one C=C bond are known as
NH3 {g)+HF(g) ~ NH4F(s) !'.H; -147kJmol-'
polyunsaturated latty acids.
(i) What type of reaction is this?
(ii) reagent: Hydrogen
-(; condition(s): Nickel (ii) Draw dot-and-cross diagrams (outer shells only) describing the
bonding in the three compounds involved in this reaction.
(e) (i) CH 3(CH 2hCH0 + OHC(CH,),CX
(ii) reagent: 2,4-dinitrophenylhydrazine.
observation: orange precipitate. (e) (iii) Tollens reagent could
also have been used, in
(iii) reagent: Fehling's solution
which case, a silver mirror
observation: Brick red precipitate. would have been observed.

J hE NH 3 HF NH 4 F
(f) (i) two
(ii) Ester (iii) There are three types of bonding in NH,F.
to ~ ·
Give the names of each of the three types, and 'slate where in the
compound each type occurs.
(iv) The reaction between NH, and HF is reversible. What conditions of
temperature and pressure would favour the reverse reaction, i.e. the
dissociation of NH,F?
Explain your answer. [9]
(c) Many commercial copper and brass polishes contain ammonia. The tarnish
that forms on _the surface of copper is often copper sulfide, CuS. In the
presence of 0 2 from the air, NH, can combine with this copper sulfide to
~?r~. produce the soluble cuprammonium sulfate, [Cu(NH 3 ) 4]S04 •
1 thre1:i;~ (i) Construct an equation for this reaction .

~o~:~;<~\ .(ii) State. the colour of cuprammonium sulfate solution.

(iii) Describe what you would see if a solution of cuprammonium sulfate
:/! was diluted with water. Explain your answer. [3]
".~ .
(d) When sulfun·c acid is added to Cu'•(aq), no colour change occurs, but when
concentrated hydrochloric acid is added to Cu'•(aq), the solution turns yellow-
green. The solution reverts to its original colour when it is diluted with
water.
Suggest the type of reaction occurring with HC/(aq), suggest what is formed
during the reaction, and write an equation for the change. [3]
{Total: 17}

a) Sta
stn.
 l'·i;
AL Chemistry June 2011 Paper 4 o Page 3
June 2011 Paper 4 o Page 2
AL Chemistry
~CORNER CORNER
C, , high I f I I_______J_ -~ high ; 1r-----t--:--
Suggested Solution:
c: i I I I I :u
~ I I I i
"6

ftH!;-+
:::l
"0
(a) HF==H• +F- ~medium
[H.][F-]
c 8medium ~--;--+
~
~_!j_LJ i I I I
"iii
K•=(HF] u
E
low ·u low+-+'- - ; -
1
-.l---+-'- I

J
Ql
HF behaves as a weak acid in water, a;

[F-]=[W],
I I I I ! i1
I I I
c C Si Ge Sn Pb C Si Ge Sn Pb
I [H.][H+l
K.=(HF]
=c) [H•]2 = [HF]K.
(ii) Suggest explanations of these trends in terms of the structure and
·C'
~ bonding of the Group IV elements.
<i. (H+j 2 = 5.6 X 10-4 X 0.05
melting point
[WJ = ,)5 _6 x 1o_. x o.o5 = o.oo529 electrical conductivity [6]

pH= -log 10 [W] (b) Choose one reaction to illustrate each of the following statements. Write an
equation for each of your chosen reactions, and describe what you would
= -log 10 (0.00529) = 2.277 "2.3 see as the reaction is carried out.
(b) (i) Neutralisation reaction. (i) PbO is more stable than Pb02 •
(ii) ~-------, (ii) CO is easily oxidised to C02 •
(iii) Aqueous SnC/2 is a useful reducing agent. [4]
H:N:H
H
.. [Total: 10}

Suggested Solution:
HF (a) (i)
L_H_h-as covalent bonding. HF has covalent bonding. NH,F has ionic,
N high I I i
~
I :
high ,--~-~~-1--
co:alent and dative bonding. I
c: :u 1 I I i
(Iii) Covalent bonding occurs between N & H.
"6 :::l
"0 I I ___L!
! j_I ___ .l__
Dative bonding occurs between N & H.
~medium
~
gmedium I
i
l
T I I I

Ionic bonding occurs between NH~ & F-·

a;
E
~
·;::
I
I I I I !
low ~ low J ! I :
(iv) High temperature: lncreasi_ng the temperature would favour the reverse a; -T I I i
reaction as it is endothermic. . ;i I
I
I
!
1
!
Low pressure: Lowering the pressure would favour the reverse reaction C Si Ge Sn Pb C Si Ge Sn Pb
which would cause an increase in the number of gaseous molecules.
(ii) melting point: Melting point decreases as the bonding of elements
(c) (I) 4NH3 +CuS+20 2 ~[Cu(NH3 ).JSO• changes from giant macromolecular, e.g. Diamond, to relatively weaker
metallic bonding, e.g. Tin.
(ii) Deep blue. . .
... Dee blue colour would change to light blue. ThiS IS because of the electrical conductivity: Tin and lead have free delocalized electrons
(In) fon!tion of the [Cu(H,O,)]'• ion due to ligand exchange of NH 3 by 1-J,O. and hence have high electrical conductivity, whereas diamond, silicon
and germanium have no free electrons.
(d) Type of reaction: Ligand exchange reaction.
What is formed: [CuCI,]'- anion. (b) (i) PbO, decomposes on heating and changes to PbO.
Equation: [Cu(H 20) 6 ] 2 + + 4Cr ~ [CuC/4 f- + 6H20 2PbO, heating ) 2Pb0 + 02

(ii) Burning CO in air produces co,

Question 2 C0+~0 2 ------> C0 2
(a) (i) On the lollowing grids, plot points showing ~he variation in the named (iii) SnC/2 will tum KMnO, from purple to colourless.
ro ert of the Group IV elements. Your points should ~~ow _fo~ ~ac~
a)
~le~e~, whether the melting point/electrical conductiVIty IS_ high, 5Sn • + 2Mno; + 16W ------> 5Sn4 • + 2Mn2• + 8H 0
2
2
'medium' or 'low'. The point for silicon has already been plotted 1n each
.I case.
,'. ~

.\
li.lli\Jll..
3rb' AL Chemistry June2011 Paper4 c Page4 AL Chemistry
June 2011 Paper 4 c Page 5
~CORNER
reac
Question 3
Amount of charge passed, Q = It ~CORNER
= 0.5x(30x60) = 900 C
--4· (a) State the relationship between the Faraday constant, F, the charge on the
electron, e, and the Avogadro number, L [1] Q 900
Number of electrons passed=-= - - -- = 5.625 x 10 21
(b) If the charge on the electron, the A, and the valency of copper are known, e 1.6x10-19
ICC the value of the Avogadro number can be determined experimentally. This L = number of electrons passed
;es • is done by passing a known current for a known time through a copper
moles of electrons required
electrolysis cell, and weighing the mass of copper deposited onto the
c cathode. 5.625x1021 = 5.97x1023 mol-'
!
,-( (i) Draw a dia§ram of suitable apparatus for carrying out this experiment. 9.42x10 3
Label the following: power supply_ (with+ and- terminals); anode;
{c)
cathode; and ammeter. compound product at anode product at cathode
State the composition of the electrolyte.
is. AgF o.
linit: ., · The following are the results obtain'ed from one such experiment. Ag
linitr: «· current passed through the cell = 0.500 A Feso. a. H2
time current was passe~ through cell = 30.0 min MgBr2 Br2 H•
initial mass of copper cathode = 52.243 g
. ~+
.. ~- '; final mass of copper cathode = 52.542 g
\···
(ii) Use these data and relevant infor~ation from the Data Booklet to
calculate a value of L to 3 significant figures. [9] Question 4
(c) Use relevant information from the Data ·aook/et to identify the substances
formed at the anode and at the ca~hode when aqueous solutions of the {a) Polyvinyl acetate, PVA, is a useful adhesive for gluing together articles
following compounds are electrolysed .. made from wood, paper or cardboard. The monomer of PVA is ethenyl
ethanoate, B.
compound product at anode product at cathode 0

J(
AgF
CH3 Ao~
Feso.
B
to: MgBr2
PVA is formed from B by the process of addition polymerisation.
[5j 1
[rota/: 15] ; (i) Draw a section of the PVA molecule containing at least 2 monomer
-C-'
II:.;.:' molecules, and identify clearly the repeat unit.
The ester B can be hydrolysed in the usual way, according to the
Suggested Solution: following equation.

(a) F= Le
0 0

CH3Ao~
(b) (i)
+ H2o - - CH3AOH +
B
C{C2 H40)
(ii) Use this information to suggest a possible structure for C and draw it
in the box above.
; ·~ ~ -. r

,J! When substance C is extracted from the product mixture, it is found that it
does not decolourise Br2 (aq), but it does form a pale yellow precipitate with
!·!i, ·h, alkaline aqueous iodine.
(iii) Suggest a structure for C that fits this new information.

final mass -initial mass (iv) Suggest a confirmatory test for the functional group in the structure you
(ii) Moles of copper deposited have drawn in (iii). Your answer should include the reagent you would
i.:·. A,ofCu
use and the observation you would make. [6]
52.542-52.243 = 0 _0047087 " 4.71 x 1o-3 mol
63.5 .
since, cJ• + 2e---> Cu
3
moles of electrons required= 4.71 x 1o-3 x 2 = 9.42 x 1o- mol
 June 2011 6 June

CORNER
(iv) Add 2,4-Dinitrophenylhydrazine reagent to substance ·c.
(b) The following diagram represents a section of another polymer.
tio; Observation: Orange precipitate.

\hi'· D
(i) On the above formula draw brackets, [ ], around the atoms that make
01-'.· D
up the repeat unit of this polymer.
I: (ii) Ester.
·C'· (ii) Name the functional group in polymer D.
I 1 (iii) Suggest and draw the structure of the monomer, E, that could form this
o:~ .:' H H H 0
'. polymer.
(iv) What type of polymerisation is involved in making polymer D from its
I I I II
H-C-C-C-C-OH
monomer? I HI OH
H
I
(v) What is the relationship between the repeat unit of polymer D and the
repeat unit of PVA? [5] (lv) Condensation polymerisation.
(c) Monomer E exists as two stereoisomers. Heating either isomer with AI,O, (v) Both are esters and have same molecular formula, i.e. c,H,O, .
gives a mixture of two unsaturated carboxylic acids F and G, which are
stereoisomers of each other. (i) Optical isomerism.
(i) Name the type of stereoisomerism shown by compound E.
(ii) Suggest structures for F and G, and name the type of stereoisomerism
they show.
(ii) E A/203 ~CO,H CO,H
~
+ "==/

E".!!!.; + F G

F G type of isomerism: Geometrical isomerism.

[4]
type of isomerism.
[Total: 15]

(a) Describe and explain how the acidities of ethanol and phenol compare to
Suggested Solution:
~~-~ ~
(a) (i) (b) Complete the foiiowing equations showing all the products of each of these
OCOCH, OCOCH,
reactions of phenol. Include reaction conditions where appropriate in the
boxes over the arrows. If no reaction occurs write no reaction in the
products box.

.~DL--_1-
(li)
H H
I I
C=C
I OH
H
I
C(C2 H40)

D
6 ·~"
(iii) H 0 0,
I I
H-C-C-H
I
H
I
~----------------~
 AL Chemistry June 2011 Paper 4 o Page 8 AL Chemistry
!X June 2011 Paper 4 0 Pag_e 9
~CORNER
or;.

-·
::::
OHD
6 ·C~~" I I
Suggested Solution:

(a) Ethanol is relatively less acidic than water. This is because the C,H,- group
on ethanol, is electron donating and intensifies the electron density in the
0-H bond. This causes the 0-H bond to become more stronger and less
easier to break.
~CORNER

Phenol is relatively more acidic than water. When phenol loses an H• ion, the Note that:

0
hE
phenoxide ion is stabilised due to the delocalization of anionic charge over The more stable an ion is,
~a:
OH the whole ring. If a water molecule loses an H• ion, the hydroxide ion formed the more likely it is to form
)\·1· 17 will not stabilize like the phenoxide ion.
L~ '
n 6 ·"· (b)

6 ... c:=Ji
1 I

6~,; ."·
OF
OH
[5]
a·f··:··;:r,:
~:~: <·: :
(c) The analgesic drug paracetamol can be synthesised from phenol by the
following route.
Suggest reagents and conditions for the each of three steps, and suggest the
structure of the intermediate H. Write your answers in the boxes provided.
".:1. ;).;
' , OH
{.
''.

6 6 •N,ON8 6'. i + H,O

I

!I
~---------------

"'P'
vA +CH3C02HDl ,_,00 I
H
OH Br, must be aqueous

·~'II OH
!
6 + Br2

' *" Br

¢ NH 2

~'JI.--
OH
-1
¢ NHCOCH 3
paracetamol [4]
[Total: 13]
 AL Chemistry June 2011 Paper 4 o Page II
June 2011 Paper 4 o Page 10
AL Chemistry ~CORNER Section B
~CORNER
Answer all the questions.
I' {c) OH

6
',•
Question 6

Enzymes are protein molecules that are highly efficient in catalysing specific

l
"'" 1

OH
Dilute HNO,
Heat
chemical reactions in living organisms.
(a) To work in tissues, enzyme molecules generally need to be water-soluble.
What does this tell you about the nature of the side-chains on the exterior
of the molecules? [1]

¢
(b) Enzymes function by a substrate molecule interacting with a particular part
of the enzyme known as the 'active site'. The substrate is converted into
I
l· products that are then released, to be replaced by another substrate mol-
-~~ .1 •
ecule.
NO,
(i) Describe briefly the primary, secondary and tertiary structures of an
H
enzyme .

CH,::·
:\;.
..,'\ OH
Sn + Cone. HC/
Heat under reflux
(ii) The activity of an enzyme depends upon the tertiary structure of the
protein molecule. Explain how the tertiary structure produces an effec-
tive active site.
(iii) Give two conditions that can reduce the activity of an enzyme, explain-
[6]

¢
ing the reason in each case.
(c) An individual enzyme operates best at a specific pH. Different enzymes
operate best under conditions of different pH. Three enzymes involved in
the digestion of food are amylase, pepsin and trypsin.
NH2 Amylase, found in saliva, hydrolyses starch to a mixture of glucose and
maltose under approximately neutral conditions.
CH3COC/ Pepsin hydrolyses proteins to peptides in the acid conditions of the

'"' \ OH
Heat stomach.
Trypsin continues the hydrolysis of peptides to amino acids in the mildly
alkaline conditions of the small intestine.

¢
The graph below shows the activity of two of the three enzymes mentioned
above.

activity
NHCOCH3
paracetamol

0 2 7 10
pH

(i) Label each peak shown with the name of the enzyme responsible,
either amylase, pepsin or trypsin.
(ii) On the axes above, sketch the graph that the third enzyme would
produce, and label it with the name of that enzyme. [3]

[Total: 10]
~D AL Chemistry June 2011 Paper 4 o Page 12 AL Chemistry
June 2011 Paper 4 o Page 13
~CORNER ~CORNER
Suggested Solution: (c) The following DNA fingerprints were taken from a family of mother, father
and four children.
(a) The side-chains on the exterior of the molecules are hydrophilic.
i;' mother
cH . (b) (i) The primary structure is the sequence of amino acids. The secondary child 21father child 4
!"
structure constitutes of polypeptide bonds that may form a-helix or cT11_ __LeT3j_
-- -
p-pleated sheets. The tertiary structure gives the overall 3D shape due to
hydrogen bondings, disulphide bridges, Van der Waal's forces and ionic
interactions.

j; :H
(ii) The tertiary structure of the enzyme provides a complementary shape to
that of the substrate.
(iii) 1. Increased temperature can cause the 3D structure of the enzyme to
change, thereby causing the enzyme to denature. ~
---
2.

(c) (i) & (ii)

Addition of inhibitors, competitive or non-competitive, will cause the
active sites of the enzymes to be occupied by these inhibitors,
thereby reducing enzyme activity.

(i)
- 2 3 4
-G~·.i·

5 6
Are all of the children related to the mother? State the evidence for your
activity answer.
(ii) Which child is unlikely to be related to the father? State the evidence
for your answer. [2]
(d) DNA fingerprinting has been successfully used in archaeological
investigations.

(i) Ancient writings were often made on goatskins. Over the centuries these
have often become broken into fragments, making reconstruction of the
writings almost impossible.
Suggest how the use of DNA fingerprinting might be able to identify
which fragments came from a particular skin.
(ii) Apart from the examples of human remains and goatskins, state one
0 2 7 10 other material that could be investigated using this technique. [3]
pH
[Total: 10]

Suggested Solution:
Question 7
(a)
The technique of DNA fingerprinting has been one of the most important stages process correct sequence
developments in biochemical analysis in recent times. It has enabled enormous _{numbers)
advances to be made in forensic science, medicine and archaeology. A place samples on agarose gel 4
(a) The table shows different stages in the production of a genetic fingerprint. B use polymerase chain reaction 3
Use the numbers 1 to 6 to put the stages in the correct sequence in the
c label with radioactive isotope 6
blank column.
D extract DNA 1
correct sequence
stages process (numbers) E use restriction enzyme 2 i
A place samples on agarose gel F carry out electrophoresis 5
I
B use polymerase chain reaction
(b) (i) Phosphorous
c label with radioactive isotope
extract DNA (ii) This isotope causes the DNA bonds to become visible, which then helps
D
in identifying the DNA bonds.
E use restriction enzyme
(c) (i) Yes, as all 4 children share at least one band with the mother's DNA.
F carry out electrophoresis
[3] (ii) Child 2, as he/she shares none of the bands of the father's DNA.

(b) One of the stages above uses a radioactive isotope. (d) (i) DNA fingerprints for each fragment would be compared and DNA patterns
(i) What isotope is used? matched to determine which fragment came from which skin.
(ii) Why is this isotope chosen?
[2] (ii) Wool
 AL Chemistry June 2011 Paper 4 o Page 15
June 2011 Paper 4 o Page 14
AL Chemistry ~CORNER Suggested Solution:
~CORNER
··:· (a)
Question 8
.·H'I,, Nanotechnology is a fast-developing area of science based on the ability to
manipulate materials of very small dimensions.
(a) On the scale shown in metres, mark the upper and lower limits of the range (b) of
Allotropes
atoms. are different forms of the same element w"th
1 d"ff
I erent arrangement

of sizes for nanoparticles.

(c) Drugs can be enclosed within nanop rt' 1 T .
to~
11 12
10 into the cells through the cell membrana IC eth· hese nanopartlcles can pass
to-7 to-a 10-9 10- to- 10-
-~~----~~~----~~----~,~--~r,----~~~--~1 [2]
. e as ey are smaller than animal cells.

(d) (i) Reduction.

(b) One of the most commonly recognised nanoparticles is the 'buckyball', a
spherical form of carbon containing 60 carbon atoms. It has been referred
(ii) M, of chalcopyrite =63.5 +56+ 64 =183_5
to as the third allotrope of carbon. A, of copper = 63.5

Percentage of copper in chalcopyrite = 63.5_ x 100 -_ 34.6 oYo

183 5

(iii) 1 tonne of ore contains 2% of chalcopyrite by mass

mass of chalcopyrite =~
100 x 1000 =20 kg.
ii:: from (d)(ii), 34.6% of chalcopyrite is copper,
·' ~
34
mass of copper in 1 tonne ore = 100·6 x 20 -_ 6.92 "' 6.9 kg.

(iv) A reactive metal such as A/ can b .

Diamond and graphite are two other allotropes of carbon. Suggest what is copper(ll) sulfate thereby recoverin~ ~~~~et~ i~~~~~~~icc~~;:~ from
meant by the term allotrope. [2]
(c) Nanoparticles are used to deliver drugs within cells. Suggest what property
of nanoparticles enables them to be used in this way. Explain your answer.
[2]

(d) Copper is an important metal that has been used for thousands of years.
The problem today is that most of the ores rich in copper compounds have
been used up. A century ago ores containing >2% of copper by mass
would have been worked; today's mines have to operate at much lower
percentages, down to 0.5% of copper by mass.
(i) By what type of reaction is the copper present in the ore converted to
copper metal?
One of the main ores of copper contains the mineral chalcopyrite, CuFeS,.
(ii) Calculate the percentage of copper by mass in chalcopyrite.
(iii) If the ore contains 2% of chalcopyrite by mass, calculate the mass of
copper which can be produced from each tonne of ore.
(lv) Certain bacteria are able to extract copper from the 'spoil' heaps of
previously mined copper ore. These bacteria are sprayed onto the spoil
heaps in an aqueous solution and the resulting solution containing
iron(ll) sulfate and cppper(ll) sulfate is collected in tanks.
Suggest how the copper could be recovered as metal. [4]
[Total: 10]
~!
AL Chemistry November 20 II Paper 2 o Page 2
November 2011 Paper 2 0 Page I
!, AL Chemistry

::l
~CORNER suggested Solution: ~CORNER
November 2011 Paper 2 (a) (i) Mass of carbon present in 0.352 g of C0
2
molecular mass of carbon in C0 2 ( f CO
Answer all questions. = x mass o 2 collected)
M, of C0 2
I
I.
I 1: 12
: [, 12 + (16 X 2) X 0.352 = 0.096 g
! t \• ~(
Question I
Compound A is an organic compound which contains carbon, hydrogen and moles of carbon present in A = mass of carbon in A
oxygen. A, of carbon
When 0.240 g of the vapour of A is slowly passed over a large quantity of 0.096
= ~ = 0.008 moles
heated copper(ll) oxide, GuO, the organic compound A is completely oxidised
to carbon dioxide and water. Copper is the only other product of the reaction.
The products are collected and it is found that 0.352 g of CO, and 0.144 g of (ii) Mass of hydrogen present in 0.144 g of H2 0

H,O are formed. molecular mass of hydrogen in H2 0 fH t d

= x mass o 2 0 co 11 ec e
M, of H2 0
(a) In this section, give your answers to three decimal places.
_ 2x 1
(i) Calculate the mass of carbon present in 0.352 g of C0 2 • - (1x2)+16 x0. 144 = 0.016 g
Use this value to calculate the amount, in moles, of carbon atoms present
in 0.240 g of A. moles of hydrogen present in A= mass of hydrogen in A
(ii) Calculate the mass of hydrogen present in 0.144 g of H 20. A, of hydrcgen
:i Use this value to calculate the amount, in moles, of hydrogen atoms
~
0.016
- - = 0.016 moles
present in 0.240 g of A. 1
(iii) Use your answers to calculate the mass of oxygen present in 0.240 g
(iii) Mass of A = mass of oxygen in A +mass of hydrogen in A
. -~
of A.
,·p Use this value to calculate the amount, in moles, of oxygen atoms +mass of carbon in A
present in 0.240 g of A. [6) => 0.240 =mass of oxygen in A+ 0.016 + 0.096
(b) Use your answers to (a) to calculate the empirical formula of A. [1) => mass of oxygen in A= 0.240-0.016-0.096
=0.128g
(c) When a 0.148 g sample of A was vapourised at 60 oc, the vapour occupied
a volume of 67.7 em' at a pressure of 101 kPa.
moles of oxygen present in A = mass of oxygen in A
(i) Use the general gas equation pV = nRT to calculate M, of A. A, of oxygen
[3] 0 128
(ii) Hence calculate the molecular formula of A. = · = 0.008 moles
16
(d) Compound A is a liquid which does not react with 2,4-dinitrophenylhydrazine
reagent or with aqueous bromine. (b) Consider the number of moles of carbon, hydrogen, and oxygen present
Suggest two structural formulae for A. in A

Element c H 0
No. of moles 0.008 0.016 0.008
[2 0.008 0.016 0.008
simple ratio
0.008 0.008 0.008
1 2 1
Empirical formula of A = CH2 0
(e) Compound A contains only carbon, hydrogen and oxygen.
Explain how the information on the opposite page about the reaction of A (c) (i) pV = nRT
with CuO confirms this statement. [1]
[Total: 13] => pV=(..'!!..)RT (since n = ..'!!..)
M, M,
=> M = mRT
r pV
- (0.148)(8.31){273+ 60)
- (101x10 3 ){67.7x10-6 )
= 59.896" 59.9
 AL Chemistry
November 2011 Paper 2 ° Page 3 AL Chemistry November 20 II Paper 2 o Page 4
~CORNER
molar mass (d) (i) Complete the 'conductivity' row by using only the words 'high', ~CORNER
(ii) n = empirical formula mass 'moderate' or 'low'. ·

59.896 (ii) Complete the 'melting point' row by using only the words 'high' or 'low'.
---- [5]
c -12+2+16
When Mendeleev published his first Periodic Table, he left gaps for elements
- 59.896 = 1.996"' 2
- 30 that had yet to be discovered. He also predicted some of the physical and
chemical properties of these undiscovered elements.
Molecular formula of A= CnH2nOn
For one element, E, he correctly predicted 1he following properties.
=C2H402
melting point of the element high
{d) melting point of the oxide high
H 0 0 H boiling point of the chloride low
I II II I
H-C-C-OH H-C-0-C-H The element E was in the fourth Period and was one of the elements from
I I gallium, proton number 31, to bromine, proton number 35.
H
H
(e) By considering the properties of the third Period elements aluminium to
chlorine, suggest the identity of the fourth Period element E. [1]
d two oxides H 0 and CO,.
(e) The only products of the r~actiont area~~~e~;;rogen and o~yg~n. (c) (i) ,At: 1S1, 2S 1, 2P6,
Hence compound A contams on Y c • [Total: 15]
351, 3P'

Suggested Solution: 11
Mg: 1S1, 2S 1, 2P6, 3S 1
Question 2 (a) S(g)--> s+(g)+1e· Despite having a higher
. derived directly from that proposed in effective nuclear charge
The Periodic Table we currently use dis It ms in the physical and chemical (b) This is because the nuclear charge across the period increases as a proton than Mg, A/ has a lower 1st
1869 by Mendeleev who had notiCe pa e IE. This is because the elec-
is added to the nucleus but shielding remains approximately constant since
ro erties of the elements he had studied. .
~h: f~rst the electron is added to the same valence shell. Effective nuclear charge tron to be removed from A/
diagram below shows the first ionisation energies of the 18 elements is a higher energy p-elect-
increases across the period resulting in a general increase in first ionisation
of the Periodic Table. energies across the period from sodium to argon. ron, which is further away
from the nucleus as com-
2500 pared to the lower energy s-
(c) (i) In A/, outermost electron is in 3P whereas, in Mg outermost electron is in
38. The 3P electron is at higher energy, so it is further away from Nucleus. electron in Mg, which is
2000
nearer to the nucleus.
first (ii) For phosphorus, 3P subshell is singly filled whereas, for sulfur, one 3P
ionisation Ar
1500 orbital has paired electrons. Paired electrons repel. (ii) 3P subshell:
energy
/kJ mol-1 1000
(d) (i)&(ii)

element Na Mg AI Si p s
p
11 11 11 I
500
Li Na
conductivity high high high moderate low low
s
11~ 11 11 I
ol-~2~3-.4-5.-6~7~8-9~1~0711~1~2~1~3~14~15~1~6~t771ts
0
melting point low high high high low low Despite having a higher
proton number effective nuclear charge
(a) Give the equation, including state symbols, for the iirst ionisation energy[~; (e) Geumanium. than P, S has a lower 1st
IE. This is because the elec-
sulfur. · oss tron to be removed from S
. e in first ionisation energ1es acr
(b) Explain why there is a genera I mcreas [ ] comes from a p-orbital with
3
the Period from sodium to argon. . . ater than Question 3 a pair of electrons and is
(c) (i) Explain why the first ionisation energy of magnesium IS gre aided by repulsion while the
For some chemical reactions, such as the thermal decomposition of potassium electron to be removed from
that of aluminium.
hydrogencarbonate, KHCO,, the enthalpy change of reaction cannot be mea- P comes from a singly oc-
. . phosphorus is greater than
(ii) Explain why the first iomsat1on energy o1 [ ] sured directly. cupied orbital, not aided by
4
that of sulfur. . . . sulfur and In such cases, the use of Hess' Law enables the enthalpy change of reaction repulsion.
The table below refers to the elements of the third Penod sod•um to to be calculated from the enthalpy changes of other reactions.
is incomplete. (a) State Hess' Law. [2]
Na Mg AI Si p s
element In order to determine the enthalpy change for the thermal decomposition of
conductivity high potassium hydrogencarbonate, two separate experiments were carried out.
melting point high
 l!)l'l
i'•l·•
AL Chemistry November 2011 Paper 2 o Page 6
di: November 2011 Paper 2 o Page 5
AL Chemistry
~CORNER (iii) Heat produced by 0.02 moles of K2 C03 = 652.08 J ~ CORNER

;,· experiment 1 . 652.08

heat produced by 1 mole of K2 C0 3 = - -
30.0 em' of 2.00 mol dm""" hydrochloric acid (an excess) was placed in a conical 0.02 (b) (iii) Negative sign
flask and the temperature recorded as 21.0 oc. = 32604 J"' 32.60 kJ indicates that reaclion is
When 0.0200 mol of potassium carbonate, K,CO,, was added to the acid and exolhermic and heal is
the mixture stirred with a thermometer, the maximum temperature recorded was enthalpy change per mole of K2C0 3 = -32.60 kJ/mol
;. ~ : released inlo the environ-
•\ '·' 2~2°~ . (iv) This is done to ensure that all of the K,CO, is completely neutralised.
ment.
(b) (i) Construct a balanced equation for this reaction.
(ii) Calculate the ·quantity of heat produced in experiment 1, stating your (c) (i) KHC0 3 + HC/ --t KC/ + H2 0 + C0 2

units. (ii) VHCI = 30.0 emil

Use relevant data from the Data Bookiet and assume that all solutions
have the same specific heat capacity as water. Heat absorbed, Q = m c tJ. T

(iii) Use your answer to (ii) to calculate the enthalpy change per mole of = 30x4.18x(21-17.3)
K,co,. =30x4.18x3.7
Give your answer in kJ mol·' and include a sign in your answer.
= 463.98 J per 0.0200 moles of KHC03 (c) (iii) Positive sign
(iv) Explain why the hydrochloric acid must be in an excess. [4] indicates that reaclion is
(iii) 0.02 moles of KHC0 3 cause the absorption of 463.98 J of heat endothermic and heat is
experiment 2 1 absorbed during lhe
Heat absorbed per mole of KHC0 3 = - - x 463.98
The experiment was repeated with 0.0200 mol of potassium hydrogencarbonate, 0.02 reaction.
KHCO,. = 23199J"' 23.20 kJ
All other conditions were the same.
In the second experiment, the temperature fell from 21.0 oc to 17.3 oc. Enthalpy change per mole of KHC0 3 = +23.20kJ/mol
(c) (i) Construct a balanced equation for this reaction.
L\Hreaclion
(ii) Calculate the quantity of heat absorbed in experiment 2. (d) 2KHCO, K,CO, + CO,+ H,O

~
(iii) Use your answer to (ii) to calculate the enthalpy change per mole of
KHCO,.
Give your answer in kJ mol·' and include a sign in your answer.
[3] KC/ + H,O + CO,
/e
(d) When KHCO, is heated, it decomposes into K,CO,, CO, and H,O. Using Hess's law, tJ.Hreact;on + tJ.H8 = tJ.HA
2KHC0 3 --t K2 C0 3 + C0 2 + H2 0
::;, llH,eaction = llHA - llHs
Use Hess' Law and your answers to (b)(iii) and (c)(iii) to calculate the = (2 X +23,20)- (-32.60)
enthalpy change for this reaction. = 46.40 + 32.60
Give your answer in kJ mol·' and include a sign in your answer. [2]
[Total: 11] = +79.00 kJ/mol

· Suggested Solution:
(a) The overall enthalpy change for a reaction is independent of the number of
steps that are involved in the reaction, provided that the initial and final con-
ditions are kept the same.

(b) (i) K2C0 3 + 2HC/ --t 2KC/ + H20 + C0 2

3
(ii) VHcl = 30.0 cm
:. Heat produced, Q = m c tJ. T
=30x 4.18 x (26.2- 21)
=652.08 J per 0.0200 moles of K2C0 3
~~
~I: 1 \ ! AL Chemistry
'i.l November 2011 Paper 2 c Page 7 November 20\ I Paper 2 c Page 8
(i ~I Al Chemistry
;.lj
~CORNER Suggested Solution: ~CORNER
'~ 1 : : (a)

Question 4 d in the petrochemical

But-1-ene, CH,CH,CH=CH,, is an important compoun
industry.
f b t 1 ene are given below. H2 0( g)
(a) Some reactions o u - - f of the organic compound Mn04 -/W
In each empty box, draw the structural ormu 1a H3P04 catalyst hot, concentrated
formed.
Mno4-/W
cold, dilute

Mn04/W
hot, concentrated CH3 CH,CH(OH)CH3 CH3 CH2 C02 H

T
u

CH3CH2CH(OH)CH 20H

v
T
u
Cr2 0l-/H+

j heat under reflux

v
CH,CH,COCO,H

l
Cr 20/-iW
heat under reflux w
H H
I I //0
(b) H-C-C-C
I I I H H H
H H 0'- I I I
C-C-C-H
I I
H"(;I H H
w
[5] I '-H
H
(b) Compound T reacts with compound U. . t"on [2]
· product of this reac I ·
Draw the displayed formula of the orgamc Question 5
[Total: 7]
Astronomers using modern telescopes of various types have found many
molecules in the dust clouds in space. Many of these molecules are those of
organic compounds and astronomers constantly look for evidence that amino
acids such as aminoethanoic acid, H,NCH,CO,H, are present.
One molecule that has been found in the dust clouds is hydroxyethanal,
HOCH,CHO.
(a) Hydroxyethanal contains two functional groups.
(i) Name, as fully as you can, each of the functional groups present in
hydroxyethanal.
(ii) For each functional group, identify a reagent that will react with this
group and not react with the other functional group present.
In each case, describe what would be observed when this reaction is
carried out.
 .ML ._,llt:'IIII~Uy

November 2011 Paper 2 o Page 9

~CORNER
2!£::; AL Chemistry
~CORNER
functional group 1 reagent ...................................................... . November 2011 Paper 4
(•,!'
observation ................................................. .

I' functional group 2 reagent ...................................................... . Section A

~ r
[7]
observation ................................................... Answer all questions.

: ! l ~ (b) Give the skeletal formulae of the organic compounds formed when
.:: ..
hydroxyethanal is reacted separately with the following .
,! Question I
(i) NaBH,
(a) The halogens chlorine and bromine react readily with hydrogen.
(ii) cr,o;- I H' .under reflux conditions [2]
In a school or college laboratory, it is possible to convert a sample of X:;(g)+H2 (g)--> 2HX(g) [X =CI orBr]
i:[! ! hydroxyethanal into aminoethanoic acid in a three-step process.
(i) Describe how you could carry out this reaction using chlorine.
HOCH 2 CHO~ X~ Y ~H 2 NCH 2 C0 2 H (ii) Describe two observations you would make if this reaction was carried
By considering the possible reactions of the functional groups present in out with bromine.
hydroxyethanal, you are to deduce a possible route for this conversion.
(iii) Use bond energy data from the Data Booklet to calculate the tJ.H"" for
(c) (i) In the boxes below, draw the structural formulae of your suggested this reaction when
intermediates X and Y. X= Cl,
X= Br.

(iv) What is the major reason for the difference in these two tJ.H"" values?
[8]
(b) Some halogens also react readily with methane.

y CH4 (g) +X 2 (g)--> CH3 X(g) + HX(g)

X
(i) What conditions are needed to carry out this reaction when X is
(ii) State the reagents for each of the three steps you have chosen. [5] bromine, Br?
[Total: 14] (ii) Use bond energy data from the Data Booklet to calculate the tJ.H"" of
this reaction for the situation where X is iodine, 1.
(iii) Hence suggest why it is not possible to make iodomethane, CH,J, by
Suggested Solution: this reaction. [4]
(a) (i) 1. Primary Alcohol, 2. Aldehyde
(c) Halogenoalkanes can undergo homolytic fission in the upper atmosphere.
(ii) functional group 1 (a) (ii) Some other tests for (i) Explain the term homolytic fission.
observation: white misty fumes of HCI Primary alcohol are: (ii) Suggest the most likely organic radical that would be formed by the
reagent: PC/5
homolytic fission of bromochloromethane, CH 2 BrC/. Explain your
reagent observation
functional group 2 answer. [3]
observation: brick-red precipitate Na Eftervescence
reagent: Fehling's Reagent (d) The reaction between propane and chlorine produces a mixture of many
RC02H Fruity smell compounds, four of which are structural isomers with the molecular formula
C3 H6 C/2 •
(b) (i) OH/'VOH (ii) 0
Other tests for Aldehyde are:
OH~OH
Draw the structural or skeletal formulae of these isomers, and indicate any
observatio; chiral atoms with an asterisk ('). [3]
reagent
0 1 {Total: 18}
Tollens Black
reagent precipitate
(c) (i)
H 0 H 0 2, 4- Orange
I II I II dinitropheny\- precipitate
C/-C-C-H C/-C-C-OH hydrazine
I I
H H

y
X

step 2: KMnO, I H• step 3: NH 3

(ii) step 1: PC/5
 AL Chemistry November 20 II Paper 4 c Page 3
November 2011 Pa'Ep~er:_:4~0'_:P':'a~g~e!:.2_
1_ _- - ; - - - - - - ~CORNER
AL Chemistry
~ CORNER

suggested Solution: Questio11 2

(a) (i) By shining UV light on the gaseous mixture of hydrogen and chlorine. Acetals are compounds formed when aldehydes are reacted with an alcohol
and an acid catalyst. The reaction between ethanal and methanol was studied
,I_ I (ii) White misty fumes would be produced and reddish-brown colour of
in the inert solvent dioxan.
bromine would disappear.
(iii) X= C/: CH 3CHO + 2CHpH CH 3CH(OCH 3 )2 + H20
Ct-CI = 244, H-C/ = 431 ethanal methanol acetal A
Bond energies, H-H = 436,
llH<> =(436+244)-(431x2) (a) When the initial rate of this reaction was measured at various starting
= -182 kJ/mol concentrations of the three reactants, the following results were obtained.

X= Br: experiment [CH3CHOJ [CH30Hh [H•]

Br-Br = 193, H-Br = 366 relative rate
Bond energies, H-H = 436, number I moldm- /moldm- /mol dm- 3

llH" = (436+193)-(366x2) 0.20 0.10 0.05 1.00

= -1 03 kJ/mol 2 0.25 0.10 0.05 1.25
(iv) H- C/ bond is stronger than H- Br bond. 3 0.25 0.16 0.05 2.00

(b) (i) Ultraviolet light 4 0.20 0.16 0.10 3.20

(ii) Bondenergies: C-H=410, 1-1=151, H-1=299, C-1=240
(i) Use the data in the table to determine the order with respect to each
energy gained for breaking bonds = (41 0 x 4) + 151 = 1791 J reactant.
energy lost in forming bonds = (41 0 x 3) + 240 + 299 = 1769 J order with respect to [CH,CHO] ................................. .
order with respect to [CH,OH] ................................. .
llH" = 1791-1769 = +22 kJ/mol
order with respect to [H•] ................................. .
(iii) CH,I cannot be made as the overall reaction is endothermic.
(ii) Use your results from part (i) to write the rate equation for the reaction.
(c) (i) Homolytic fission is the breaking of a bond to form two radicals. (iii) State the units of the rate constant in the rate equation
(iv) Calculate the relative rate of reaction for a mixture in which the starting
(ii) -CH,C/.
concentrations of all three reactants are 0.20 mol dm--'. [6]
c _ Br bond with Bond energy of 280 kJ/mol is the weakest bond as
compared to c _ c and c - C/ bonds with bond energ1es of 41 0 kJ/~ol (b) The concentration of the acetal product was measured when experiment
and 340 kJ/mol respectively. Hence C- Br bond will break most eas1ly. number 1 was allowed to reach equilibrium. The result is included in the
following table.

(d) Cl [CH3CH~
Cl~ [CH30H] [H'] [acetal A! [H20]

Cl~ /moldm /mol dm-3 /moldm-3 /mol dm- /moldm-3

Cl at start 0.20 0.10 0.05 0.00 0.00

at equilibrium (0.20-x) X

., at equilibrium 0.025
Cl Cl
Ct~CI /(_ (i) Complete the second row of the table in terms of x, the concentration
of acetal A at equilibrium. You may wish to consult the chemical equa-
tion opposite.
(ii) Using the (acetal A] as given, 0.025 mol dm--', calculate the equilibrium
concentrations of the other reactants and products and write them in
the third row of the table.
(iii) Write the expression for the equilibrium constant for this reaction, Kc,
stating its units.
(iv) Use your values in the third row of the table to calculate the value of
~ ~
[Total: 15]
mr AL Chemistry November 2011 Paper 4 o Page 5

~·.M
.•;•\
AL Chemistry ~CORNER
(i) Draw an orbital energy diagram to show this, indicating the number of ~CORNER
'·' Suggested Solution: orbitals in each group.
idl·
l•r ·
p;: (a) (i) order with respect to [CH 3CHO] = 1
·,,;

~ :ii. i
'•;I j order with respect to [CH 30H] = 1
order with respect to [H'] = 1
[.ii\ :: (ii) Rate equation: k[CH,CHO][CH,OH][H']
energy
l'\i\:i
\)i. i (iii) Units: mol-' dm' s-•
;)\':! i ~
~.; :~ t.~l
0 20 0 20
(iv) Rate of reaction= · x · x
0.20 0.1 0.05
~ {il) Use your diagram as an aid in explaining the following.
!d
iil1
l': 1

i I
= 2 x 4 = B times as fast as reaction 1.
Transition element complexes are often coloured.
~! h . I

Hence relative rate of reaction= B. The colour of a complex of a given transition element often changes
,,.,
iHj'. '
when the ligands around it are changed. [7]
HLl1··
l:W1:·
~~:l·h -~
I

:
(b) liJ Ol \II}

[CH3CHOJ [CH30H1
/moldm-
[H']
/moldm-
3
[acetal A1
/moldm-
[H20] 3
/moldm-
I Heating a solution containing potassium ethanedioate, iron(ll) ethanedioate
and hydrogen peroxide produces the light green complex K 3Fe(C 20 4)a, which
;r-1:~ /moldm-
0.00 0.00 I contains the ion [Fe(C2 0 4)a]>-.
0.05
ll\:1 at start 0.20 0.10 The structure of the ethanedioate ion is as follows.
cJ~il
fi-U at equilibrium (0.20-x) (0.10-2X) 0.05 X X
-o o-
;·r.:L: 0.05 0.05 0.025 0.025 \ I
,~ '·: at equilibrium 0.175 c-c
II ~
0 0
(iii) K [CH3CH(OCH3),][H20] (i) Calculate the oxidation number of carbon in this ion.
2
c [CH 3CHO][CH30H]
(ii) Calculate the oxidation number of iron in [Fe(C2 0 4 )a]>-.
3 (iii) The iron atom in the [Fe(C2 0 4 )a]>- ion is surrounded octahedrally by six
units= mol-' dm
oxygen atoms. Complete the following displayed formula of this ion.
(iv) K = [CH3CH(OCH3),][Hp] 3-
2
c [CH3CHO][CH,0H] 0
0 ·025 x 0 ·025
0.175 X (0.05)
2
1.4286 = 1.43 mol-' dm
3
0,,, I ·"
''"·······.. Fe ..~···"'"

o/J~
Question 3
(a) On the following diagram draw a clear labelled sketch to describe the shape
(iv) In sunlight the complex decomposes into potassium ethanedioate,
and symmetry of a typical d-orbital. [2] iron(ll) ethanedioate and carbon dioxide.
Use oxidation numbers to help you balance the following equation for
this decomposition.

K3Fe(Cp4 Js-+ ......... .K 2C2 0 4 + ......FeC 20 4 + ......C0 2

[5]
[Total: 14]

(b) Although the five d-orbitals are at the same energy in an isolated atom,
when a transition element ion is in an octahedral complex the orbitals are
split into two groups. ·
 November 2011 Paper 4 c Page 6 AL Chemistry
AL Chemistry November 2011 Paper 4 c Page 7
~CORNER
Suggested Solution: (iii) ~CORNER
3-
(a)
i
~·

(b) (i)
Question 4

(a) (i) Write the equation for a reaction in which ethylamine, C2 H NH , acts
5 2
energy as a Bf121nsted-Lowry base.
(ii) Ammonia, ethylamine and phenylamine, C6 H5 NH 2 , are three nitrogen-
containing bases.
Place these three compounds in order of basicity, with the most basic
first.
(ii) • In trans1·t·1on element complexes ' the central metal (ion) has· partially
1
filled d subshell. This allows d-d transition. When an electron m a ower most basic least basic
d-subshell is excited, it absorbs wavelength in the VISible spe~trum.
Hence colour complementary to these wavelengths absorbed IS
observed.
(iii) Explain why you have placed the three compounds in this order. [4]
The size of !:I.E i.e. change in energy between higher and lower energy
(b) (i) Write an equation for a reaction in which phenol, C6 H5 0H, acts as a
d-orbitals, depends upon the ligand. If the ligand changes, !:I.E also
Bf121nsted-Lowry acid.
changes and so does the f in E ~hi ' thereby changing the colour of
The pK. values for phenol, 4-nitrophenol and the phenylammonium ion
the complex. are given in the table.

(c) (i) Let the oxidation number of carbon be x, compound pKa

(-2x4)+ (2x X)~ -2
-8+2X ~-2 orOH
10.0
2x=6
x~ +3

oxidation number of carbon ~ + 3

JVOH
7.2
(ii) Let the oxidation number of iron be y, 02N
(-2x12)+(+3x 6)+ Y ~ -3
-24+18+ y ~ -3 +
-6+y~-3 orNHa 4.6
y ~+3

oxidation number of iron ~ + 3

(ii) Suggest an explanation for the difference in the pK. values of phenol
and nitrophenol.
(iii) Using the information in the table opposite, predict which of the follow-
ing pK. values is the most likely for the 4-nitrophenylammonium ion.
+
3
JOrNH

0 2N
~·!pi
~)\·I:! AL Chemistry
November 2011 Paper 4 o Page 8
~CORNER
AL Chemistry November 2011 Paper 4 o Page 9

1< I.
i;jlj\.
Place a tick (/) in the box beside the value you have chosen. (iv) The Nitro group, which is an electron withdrawing group, will increase the ~CORNER
l"l'illt acidity of the 4-nitrophenylammonium ion, due to which the value of K,
1'\i! II pK, will increase. Increasing the K, value will decrease the pK, ·value.
cJ :. :11 ·
lil ~ 1i 1.0 (c) (i)
1 \ !_ ~
•i\l 4.5
tl.~)"' j"

o~
OH OH

6'
l; 7.0

~6~¢
j

10.0
l.il.·.\i'
:~ ~ , I 1\ (iv) Explain your" answer to part (iii).
[5]
(i• 1: (c) Phenylamine can be converted to 4-nitrophenol by the following steps.
!lt!l\
ll,l!:.t
OH OH
B
N02

m·~u-

6~ ~6~¢
(ii)
,,.J
,fl l' ·l reagent(s) conditions
~T
!rl L' step 1
L
HNO, temperature< 1 O'C
4H step 2 H,o heat at temperature> 1O'C
jfJii. B
N02
step 3 HN03 dilute
C!il!l\1
]!J!!! (i) Suggest the identity of intermediate B by drawing its structure in the
',';. \rl
•,'\.\:f ·I
box above. Question 5
j:.¥-fl'' (ii) Suggest reagents and conditions for the three steps in the above
scheme Compound C has the molecular formula C 7 H14 0. Treating C with hot concen-

1n
J1!i r
b.Ht~.l~
w;~!! ':!.i ·,
1 step 1
step 2
reagent(s) conditions
trated acidified KMn0 4 (aq) produces two compounds, D, C4 H8 0, and E, C3H4 0 3 •
The results of four tests carried out on these three compounds are shown in
the following table.

result of test with

(~!& j,':\ step 3 [5] test reagent
compound C compound D compound E
{Total: 14]
Br2(aq) decolourises no reaction no reaction
Na(s) fizzes no reaction fizzes
Suggested Solution:
i2(aq) + OW(aq) yellow yellow
no reaction
precipitate precipitate I
(a) (i)

(ii)
C2H5NH2 + HA --> C 2H5NH; +A-

most basic
least basic
2,4-
dinitrophenylhydrazine
no reaction
orange
precipitate
orange
precipitate
J
Ammonia Phenylamine
Ethylamine (a) State the functional groups which the above four reagents test for.
(i) Br2 (aq)
(iii) Ethylamine is more basic than Ammonia due to the electron donating
ethyl group. Phenylamine is less basic than Ammonia due to delocalisation (ii) Na(s)
of lone pair of nitrogen over ring. (iii) 12 (aq) + OH-(aq)
(iv) 2,4-dinitrophenylhydrazine [4]
(b) (i) C6H50H +OW --> C 6H50- + H.O
(ii) pK, of nitrophenol is smaller than phenol as nitrophenol is a stronger acid {b) Based upon the results of the above \('sts, suggest structures for compounds
and dissociates more than phenol. This is because the anionic charge is
D and E.
spread out more over the NO, group.

(iii} pK, l D, C4 H80 E, C3H 4 03 [2]

1.0 / I
(c) Compound C exists as two stereoisomers.
4.5 Draw the structural formula of each of the two isomers, and state the type
of stereoisomerism involved. [3]
7.0
[Total.· 9]
10.0
--
 W"
~~-- AL Chemistry November 2011 Paper 4 o Page II
November 2011 Paper 4 0 Page 10
AL Chemistry
~CORNER The nature of the gro~p ~ affects which bonds are formed as the secondary ~CORNER
Suggested Solution: structure of the protein 1s further folded to give the tertiary structure.
Complete .'he table in?icatin~ the type of tertiary bonding that each pair
(a) (i) Br,(aq): C=C double bonds. of the am1no ac1d res1dues 1s likely to produce.
(ii) Na(s}: -OH groups.
residue 1 residue 2 type of tertiary
(iii) l,(aq) + OH-(aq): CH,CO- and CH,CH(OH)- groups.
bonding
0
II -HNCH(CH2CH2CH2CH2NH2)CO-- -HNCH(CH2CH2C02H)CO--
(iv) 2,4-dinitrophenylhydrazine: Carbonyl groups (-c-)

-HNCH(CH 3 )GO-- -HNGH(CH3)CO-

{b) H H 0 H H 0 0
I I II I I I II
H-C-C-C-OH -HNCH(GH2SH)CO-- -HNGH(CH2SH)CO--
H-c-c-c-c-H
I HI I I
H H H -HNGH(GH?OH)GO-- -HNGH(CH2G02H)GO--

E, C3H,03
o. c,H.O [4]
[Total: 10}

(c) H,C-H,C" /CH,-OH H3C-H2C" /CH3

Suggested Solution:
c=C C=C
H c/ "-cH, H,C/ "CH,..-OH (a) (i) 2H,NGH2G0 2H-+ H2NGH2 GONHGH2G0 2H + H20
3
(ii)
cis trans

type of stereoisomerism: cis-trans.

Section B
Answer all the questions.
(b) (i) 1. a-Helix
2. p-pleated sheets
Question 6
(ii) a-Helix
Proteins exist in an enormous variety of sizes and structures in living organ-
isms. They have a wide range of functions· which are dependent upon their
structures. The structure and properties of an individual protein are a result of
the primary structure -the sequence of amino acids that form the protein.
(a) Proteins are described as condensation polymers.
(i) Write a balanced equation for the condensation reaction between two
glycine molecules, H2NCH2C02H.
(ii) Draw the skeletal formula for the organic product. [2]

{b) x-ray analysis has shown that in many proteins there are regions with a
regular arrangement within the polypeptide chain. This is called the sec-
ondary structure and exists in two main forms.
(i) State the two forms of secondary structure found in proteins.
(ii) Draw a diagram to illustrate one form of secondary structure. [4]
(c) There are around 20 different common amino acids found in humans most
of which have the same general structure.
R
I
H2N-C-C02 H
I a-Helix
H
 fl'!H
~'1:1·, November 2011 ~er 4 o Page 12 AL Chemistry
November 2011 Paper 4 o Page 13
:;!\: ALChemist!}'_
~CORNER
~CORNER
.!·;
Ill{:,
(c) (i) Hydrogen atoms have only one electron, hence they do not produce images
(c') . ' type of tertia!)'
i\11\ residue 2 bonding using X-ray crystallography. -
l '\); i' residue 1
c"~ ~ 'IJL Ionic bonding (ii) Sulphur would show up most clearly as it has the greatest atomic number.
1 -HNCH{CH,CH,CH,CH,NH,)C0- -HNCH{CH,CH,CO,H)C0-
:·:'1: -HNCH{CH,)C0- Van der Waal's
-HNCH{CH,)C0-
Question 8
I•· -HNCH{CH,SH)C0- Disulfide bonds
-HNCH(CH,SH)C0-
In today's world we make use of a wide range of different polymers. These
-HNCH(CH,CO,H)C0- Hydrogen bonds polymers are often substitutes for traditional materials, but may have more useful
--HNCH(CH,OH)C0-
properties.
(a) Complete the table identifying one traditional material that has been
replaced by each polymer.
Question 7
traditional material modern polymer and its use
One of the key areas of investigation in understanding the structures of polypep-
tides and proteins is the sequence of amino acids that make up the polypeptide
PVC in packaging
chains.
(a) One of the methods used to determine the amino acids present in a Terylene in fabrics
polypeptide chain is electrophoresis.
Sketch and label the apparatus used to carl)' out electrophoresis. [4] polycarbonate bottle
- [2]
(b) In electrophoresis, different amino acids move in different directions and at (b) Throwing away articles made from polymers after use is a major environ-
.different speeds. mental concern for two main reasons. Identify each of these reasons and
(i) What factors determine the direction of travel of an amino acid? suggest a strategy that has been adopted to try to overcome each of these.
(li) What factors determine the speed of movement of an amino acid? [3]
[3]
(c) One suggestion for the disposal of polymers is to use them as a fuel to
(c) Another important technique used to examine the structure of proteins is provide energy for small-scale power stations or district heating schemes.
X-ray crystallography. In this technique the position of individual atoms can Identify one polymer which would be unsuitable for this use, explaining the
be determined, and the. distances between them measured. reason behind this. [2]

(I) Hydrogen atoms never produce images using X-ray crystallography. (d) Polymers can be either thermoplastic or thermosetting.
Explain why this is the case. Name a thermoplastic polymer.
(ii) Suggest and explain which one of the atoms in a molecule of cysteine, State which type of polymerisation produces thermoplastic polymers,
H NCH(CH SH)C0 H, would show up most clearly using X-ray crystal- explaining your answer in terms of the structure of the polymer. [3]
2 2 2
lography. [3]
{Total: 10} [Total: 10]

Suggested Solution:
Suggested Solution:
traditional material modern polymer and its use
(a) d.c. power supply
Cardboard PVC in packaging

Cotton Tery/ene in fabrics

Glass polycarbonate bottle

reasons: Ploymers pollute the environment for a long time as they do not
decompose. Also, they produce toxic gases on burning.
strategy 1: Biodegradablo polymers are being developed.
strategy 2: Polymer waste is being recycled.

filter paper soaked in buffer solution ploymer: PVC

amino acid mixture placed here
reason: It's combustion would produce pollutants such as dioxins and HC/.
(b) (i) The pH of the buffer and the charge on the amino acid species
Name: Polythene.
determines the direction of travel of an amino acid.
Type: Addition Polymerisation.
(ii) The magnitude of charge of the amino acid species, the size of the amino
The polymer consists of chains that do not have strong bonds
acid species, the voltage applied, and the temperature determine the speed
between them, hence they are easy to melt.
of movement of the amino acid.
 AL Chemistry June 2012 Paper 2 o Page 2
June 2012 Paper 2 o Page I
AL Chemistry
~CORNER Suggested Solution:
~CORNER
June 2012 Paper 2 (a) (i) Phosphorous. (a) m Silicon, found in the
3rd period of the periodic
(ii) Sulfur
table, also forms a chloride
Answer all questions. (iii) A white solid is formed and chlorine gas decolourises. which is liquid at room tem-
'i; (iv) 2A/(s) + 3C/2 (g) ------> 2A/C/3 (s) perature.

(v) Argon's ionization energy is too high and it's valence shell of electrons (iii) Aluminium is also
Questio11 I is full. Hence, no chloride of argon· has ever been produced. seen to glow during the
reaction.
The elements of the third period of the Periodic Table, sodium to sulfur, all form (b) (i)
chlorides by direct combination. Does the chloride approximate pH of
element·
dissolve or react? the resulting solution
(a) (i) Sulfur forms a number of chlorides which are liquid at room tempera-
Na dissolve 7 (b) ro The chloride of SO·
ture. · ·d dium is neutral and thus
Which other element of the third period forms a chloride which is 1iqu1 A1 react 2 gives a pH of 7. However,
at room temperature? Si react 2.5 the chlorides of aluminium
(ii) Name one element of the third period which burns in chlorine with a and silicon are acidic caus-
coloured flame. (ii) Hydrolysis ing the pH to decre9se.
(iii) Aluminium chloride may be produced by passing a stream of chlorine
(c) (i) nitrogen atom: One lone pair
over heated aluminium powder in a long hard-glass tube. ·
State two observations you could make during this reaction. sulfur atom: Two lone pairs (c) ro Nitrogen hes 5 outer
shell electrons and sulfur
(iv) Write a balanced equation, with state symbols, for this reaction of alu- (ii) Angle 'a' will be smaller. This is because two· lone pairs repel more than
a single lone pair due to the fact that lone pair-lone pair repulsions are has 6 outer shell electrons.
minium with chlorine. Two electrons are used in
stronger than bond pair-lone pair repulsions.
(v) No chloride of argon has ever been produced. bounding from each atom.
Suggest a reason for this. [7] Hence, Nitrogen is left with
3 electrons and sulfur is left
(b) When chlorides of the elements of the third period are added to water, Questio11 2 with 4 electrons.
some simply dissolve while others can be seen to react with the water.
Alcohols such. as methanol, CH,OH, are considered to be possible replace-
(i) Complete the table below, stating how the chlorides of Na, A/, and Si
ments for foss1l fuels because they can be used in car engines.
behave when mixed with water. In the first column use only the terms
'dissolve' or 'react'. (a) Define, with the aid of an equation which includes state symbols, the stan-
approximate pH of dard enthalpy change of combustion, tJ.H':, for methanol at 298 K. [3]
Does the chloride
element dissolve or react? the resulting solution
Methanol may be synthesised from carbon monoxide and hydrogen. Relevant
Na tJ.H': values for this reaction are given in the table below.
A/
compound t.H~ /KJ mol·1
Si
CO( g) -283
(ii) What type of reaction takes place between a chloride and water? [7]
H2(g) -286
(c) Sulfur forms the compound S,N, with nitrogen. The structure of S,N, is
CH30H(g) -726
shown below.
Assume all bonds shown are single bonds.
(b) Use these values to calculate Mi"reactioo for the synthesis of methanol, using
the following equation. Include a sign in your answer.

CO(g)+2H2 (g)------> CHpH(g) (3]

(c) The operating conditions for this reaction are as follows.

pressure 200 atmospheres (2 x 107 Pa)

temperature 600 K
(i) Determine the number of lone pairs of electrons around a nitrogen atom catalyst oxides of Cr, Cu, and Zn
and a sulfur atom i.n S,N,.
Explain how each of these conditions affects the rate of formation of
(ii) Which bond angle, a or b, in the S,N, molecule will be smaller? Explain methanol. [6]
your answer. [2]
{Total: 16] [Total: 12]
 June20l2 Paper 2 o Page 3 AL Chemistry June 2012 Paper 2 o Page 4
AL Chemistry
~CORNER ~CORNER
Suggested Solution: H02CCH 2CH(OH)C02 H
heat with heat with
CH 30H/W CH 3C02H/H'
(a) equation: CHpH(I)+ ~0 2 (g) ~ C0 2 (g)+2H 2 0(/)

I
2
definition: Standard enthalpy change of combustion of a substance is the heat

~~·-·1
evolved when 1 mole of a substance, at its standard state, is completely burned
in oxygen under standard conditions of 1 atm and 298 K.
H,so,

(b) CO(g) + 2H,(g)

/j.H!aclion
CH,OH(g) I A I B

~ CO,( g) + H,O(~
/ (c) Pressure: Increasing lhe
pressure will increase the
concentration of the reac·
tants i.e. there would be
t.H;:,a<tion + (-726) = (-283) + (-286 x 2) more moles of reactant par·
c
ticles per unil volume. hot concentrated
t.H;:,action =-283- 572 + 726 Mn04-IH',
steam/H,PO,
Temperature: Increasing
=-129 kJ/mol the temperature would

(c) pressure: Increasing the pressure will increase the rate of fonnation of
cause the reactant mol·
ecules to have more energy.
I cold dilute
Mno,-tH·
methanol, due to the fact that the frequency of collisions will increase, thereby
leading to more fruitful collisions.
temperature: Increasing the temperature will increase methanol's rate of
formation as more molecules would have energy greater than the activation
The molecules having En·
ergy greater than E, could
then take part in the reac·
lion.
I D
I E

energy, and thus more successful collisions will take place. Catalyst: A catalyst always
catalyst: The use of a catalyst would increase the rate of fonnation of methanol lowers the E, by providing
by providing an alternative route of lower activation energy to the reaction an alternate chemical path·
pathway. way.
F
[6]
(b) What type of reaction is each of the following conversions?
Question 3
Food additives are substances added to food to preserve the flavour or to malic acid into C ..................................................

improve its taste and appearance. CintoD ..................................................................

European Union legislation requires most additives used in foods to be
labelled clearly in the list of ingredients, either by name or by an 'E number'. C into E.................................................................. [3]
E296 is malic acid which occurs in unripe fruit. (c) Suggest one major commercial use of compounds such as A or B. [1]
Malic acid has the structural fonnula HO,CCH,CH(OH)CO,H.
(d) (i) Malic acid is chiral.
· (a) Some reactions of malic acid are shown below. Draw fully displayed formulae of the two optical isomers of malic acid.
In the boxes below, give the structural fonnulae of organic compounds A Indicate with an asterisk (*) the chiral carbon atom.
~~ .
(ii) Compound C also shows stereoisomerism.
Draw the skeletal formulae of each of the stereoisomers of C. label
each isomer. [6]
(e) The food additive E330 is another organic compound which occurs natu-
rally in fruit.
E330 has the following composition by mass: C, 37.5%; H, 4.17%; 0, 58.3%.
Calculate the empirical formula of E330. [3]
[Total: 19}
 AL Chemistry June 2012 Paper 2 o Page 6
June 2012 Paper 2 0 Page 5
AL Chemistry
~CORNER ~CORNER
(e) element c H 0
Suggested Solution: % 37.5 4.17 58.3
(a)

heal with
H0 2CCH2CH(OH)CO,H l heat with
"\H 3C0 2H/W
Ar

no. of moles ;
37 5
·
12 1
4.17
16
58.3

CH,OH/~ 12 1 16
; 3.125 4.17 3.644
0 H H 0 3.125 4.17 3.644
H 0 H H 0 H II I I II simple ratio
I II I I II I concentrated Ho-c-c-c-C-OH H 3.125 3.125 3.125
H -c-o-c-c-c-c-o-c-H H,so.
1
H
"- I
o-c-c-H 1 1.33 1.166
I I I . I
H H OH H II I
0 H 6 8 7
B
A
empirical formula ; C6 H80 7

0 H H 0
II I I II
HO-C-C=C-C-OH Question 4
c Oxygen-containing organic compounds may contain a number of different func-
hot concentrated . / tional groups including alcohol, aldehyde, carboxylic acid, ester or ketone func-
Mno.-JH'/ tional groups. These functional groups may be identified by their reactions with
0 H OH 0 specific reagents.
0 0 II I I II
cold dilute HO-C-C-C-C-OH (a) On treating compounds containing each of these functional groups with the
II II I I reagents below, only five reactions occur. Complete the table by placing
HO-C-C=OH Mn04/H'
H H a tick ( ,/) in each box where you believe a reaction will occur. You should
E place no more than five ticks in the table.
D

reagent alcohol aldehyde carboxylic ketone

0 H H 0 R2CHOH RCHO acid RC02H RCOR'
II I I II
HO-C-·C-C-C-OH
I I (a) C to F is oxidation.
OHOH Na
cold dilute
F \ I KMnO.(aq) I I
c=c ~-e-e-
l \ I I [5]
(b) malic acid into C: Dehydration OH OH
C into D: Oxidation The conversion of malic acid Compound G has the empirical formula CH,O and M, of 90.
C into E: Hydration into A and B is an example An aqueous solution of G is neutral. There is no reaction when G is treated with
of esterification. NaHCO,.
(c) Such compounds may be used in perfumes.
When 0.30 g of pure G is reacted with ·an excess of Na, 80 em' of H,, measured
0-H at room temperature and pressure, is produced.
(d) (i) 0-H
I I (d) (i) For a carbon atom to be
chiral, it should have 4 dif· (b) (i) What functional group do these two reactions show to be present in G?
C=O
C=O
I I
H-C-H
ferent groups attached to (ii) Use the data to calculate the amount, in moles, of hydrogen atoms
H-C-H it. produced from 0.30 g of G.

H-.6•~0-H ·6-H
A···~
(iii) Hence, show that each molecule of G contains two of the functional
groups you have given in (i). [4]
O=C<f. H-0<1 J=O
(c) Treatment of G with 2,4-dinitrophenylhydrazine reagent produces an
I 0-H orange solid.
0-H
When G is warmed with Fehling's reagent, no reaction occurs.
(i) What functional group do these reactions show to be present in G?
(ii)

o=()-OH HO,
I(
0
~1~ "'oH
Draw the displayed formula of this functional group.
(ii) Use your answers to (b)(i) and (c)(i) to deduce the structural formula
of G. 2]

cis trans
 AL Chemistry June 2012 Paper 4 o Page I
AL Chemistry June 2012 Pa~r 2 o Page 7

~CORNER ~CORNER
(d) Compound G can be both oxidised and reduced.
June 2012 Paper 4
(i) When G is heated under reflux with acidified K,Cr2 0 7, compound H is
formed.
Give the structural formula of compound H. Section A
(ii) When G is reacted with NaSH, under suitable conditions, compound Answer all questions.
J is formed.
Give the structural formula of compound J. [2]
{Total: 73} Question 1

(a) (i) What is meant by the term enthalpy change of hydration, I!.H:;;d?
Suggested Solution:
(ii) Write an equation that represents the t.f1i!d of the Mg'' ion.
(a) aldehyde carboxylic ester ketone (a) Cr,O,'"" is an oxidizing agent
reagent alcohol
RCHO acid RC02H RC02R' RCOR' and is able to oxidize (iii) Suggest a reason why !!.H:;;d of the Mg'' ion is greater than t.H:;;d of
R2CHOH
the Ca'' ion.
./' R,CHOH and RCHO .
NaHC03 (iv) Suggest why it is impossible to determine the enthalpy change of
Also. all carboxylic acids re· hydration of the oxide ion, 0'-. [5]
Na ./' ./'
act with metals and metal
Cr20, 2-/H+ ./' ./' hydrogen-carbonates. (b) The enthalpy change of solution for MgC/2 , t.H:'c;, (MgCI2 (s)), is represented
by the following equation.

(b) (i) Alcohol MgC/2(s) + aq ---> Mg 2'(aq) + 2Cr{aq)

Number of moles of H2 = ~ = 3.3 x 1o- mol

3 Describe the simple apparatus you could use, and the measurements you
(ii)
24000 would make, in order to determine a value for t.H:'c;, (MgC/ (s)) in the labo-
2
3
ratory. [4]
Number of moles of H atoms= 2x 3.3x10- = 6.6x 10-3 mol
(c) The table below lists data relevant to the formation of MgC/ (aq).
2

(iii) NumberofmolesofG=
90
?· 30
=3.3x10- mol
3
enthalpy change value I kJ mor'

number of moles of G : number of moles of H atoms t.Hf (MgC/2(s)) -641

3.3x10-3 : 6.6x10-3
t.Hf (MgC/2(aq)) -801
1: 2
Each -OH group produces 1 H atom. thus, each molecule of G contains
two - OH groups.
lattice energy of MgC/2(s) -2526
I
(c) (i) functional group: Ketone,
!!.H::d (Mg2+(g)) -1890
J
By constructing relevant thermochemical cycles, use the above data to cal-
displayed formula: '-c =0
/ culate a value for

(i) I'.H:'c;, (MgC/2 (s)),

(ii) Compound G: H 0 H
(ii) t.H:;;d (Cf·(g)).
H-o-c-c-c-o-H
I II I [3]
Describe and explain how the solubility of magnesium sulfate compares to
I
H
I
H
that of barium sulfate. [4]

[Total: 16)
(d) (i) This is an example of
(d) (i) Compound H: o 0 0
oxidation of compound G.
II II II
H-O-C-C-C-0-H
The enthalpy change when 1 mol of gaseous ions dissolve in sufficient (a) (iii) Although the charge
(ii) This is an example of water to give an infinitely dilute solution. on the Mg" and Ca'' ion is
(ii) Compound J: H reduction of compound G the same, Mg'' has a
(ii) Mg 2'(g)+aq---> Mg 2+(aq) smaller ionic radius than
I (iii) Mg'' has greater charge density than Ca2' .
Ca''. Hence, Mg'• has a
H 0 H greater charge denstty than
I I I
H-o-c-c-c-o-H
(iv) This is because the oxide ion reacts with water to give OH-. Ca".
o 2- +H2o ___, 2ow
I I HI
H H
AL Chemistry June 2012 Paper 4 o Page 2 AL Chemistry June 2012 Paper 4 o Page 3

~CORNER
(c) Carbon monoxide reacts with a ruthenium(ll) chloride complex according
~CORNER
(b) Apparatus: Insulated Calorimeter, Water, Thermometer.
Pour a known volume of water into the calorimeter. Record the temperature to the equation
of the water. Add a known mass of MgC/2 into the water, and record the [Ru(H20) 2 C/4 ]2 " +CO --> [Ru(H2 0)(CO)C/.)'· + H2 0.
highest temperature change of the solution. These measurements would be
(i) Describe the type of reaction that is occurring here.
sufficient for determining a value for 6H,::;, (MgC/2 (s)).
(ii) During the reaction, the colour of the solution changes from deep blue
t,H':o, (MgC/,(s)) to green.
(c) (i) MgC/,(s) + aq Mg'" (aq) + 2Cr(aq) Explain the origin of colour in transitiol) element complexes, and why
different complexes often have different colours.

t,H1°(MgC1,~ ~:(MgCI,(aq)) The following table _shows how the initial rate of this reaction varies with
different concentrations of reactants.
Mg(s) + C/,(g)
([Ru(H,O),Ct.)2l I mol dm-a [CO)/ mol dm-a rate/mol dm-3 s-1
6Ht(MgC/2 (s)) + t,H:O, (MgC12 (s)); 6Ht (MgC/2 (aq)) 1.6x10-7
1.1 X 10-2 1.7x 10-a
-641+ f>.H:O, (MgC/2 (s)); -801 1.6x 10-2 3.6x 10-a 2.3x10-7
t,H:O, (MgC/2 (s)); -801 + 641 2.2x 10-2 2.7x 10-3 3.2x10-7
; -160 kJ/mol
(iii) Use these data to determine the order of reaction with respect to each
reagent, and write the rate equation for the reaction.
(ii) 6H:." (Mg2 •(g)) + 26H:-,d (Cr(g)); 6H:0, (MgC/2 (s)) + LE of MgC/2 (s)
There are three possible mechanisms for this reaction, which are described
-1 890 + 26H:-,d (Cr(g)) ; -160- 2526 below.
26H"~" (Cr(g)) ; -160- 2526 + 1890 mechanism 1 [Ru(H,0),C1 ]2- + CO ~ [Ru(H 0)(CO)C1J 2- + H,O
4 2

2f>.H:-,d(Cr(g)); -796
mechanism 2 [Ru(H 20)2C1J 2- ~ (Ru(H2 0)C1J 2- + H,O
t,H:," (Cr(g)) ; - 796
2
[Ru(H 20)C1J'- + CO ~ [Ru(H 20)(CO)C1J 2-
; -398 kJ/mol

(d) Magnesium sulfate is more soluble than barium sulfate because 6H, 01 is more mechanism 3 [Ru(H 20),C1,) 2- +CO ~ [Ru(H 2 0)2(CO)C1 4]2-
exothermic for magnesium sulfate than barium sulfate. Increasing the ionic
radius, leads to a smaller lattice and hydration enthalpy. Therefore, as Ba•' [Ru(H20),(CO)C14)2- ~ [Ru(H 20)(CO)C1 4)2- + H,O
has a larger ionic radius, the lattice enthalpy of b.arium sulfate is smaller than
(iv) Deduce which of these three mechanisms is consistent with the rate
magnesium sulfate and the hydration enthalpy of Ba•' is lesser than Mg•'.
equation you suggested in part (iii). Explain your answer. (1 OJ
However, the change in hydration enthalpy is more dominant and hydration
enthalpy decreases more than LE, causing magnesium sulfate to be more [Total: 15]
soluble than barium sulfate.
Suggested Solution:
(a) (i)

88
Question 2
Carbon monoxide, CO, occurs in the exhaust gases of internal combustion 0
engines. •
(a) (i) Suggest a dot-and-cross diagram for CO.
(ii) Suggest one reason why CO is produced in addition to CO, in some (ii) This is due to the incomplete combustion of hydrocarbon fuels.
internal combustion engines.
(iii) Carbon monoxide can be removed from the exhaust gases by a cata- (iii) CO+NO--> iN,+C02
lytic converter.
Write an equation for a reaction that occurs in a catalytic converter that (b) C(s) + CO,(g) ------7- 2CO(g)
removes CO. (3) ~ /
(b) The standard enthalpy change of formation, t.H't, of CO is -111 kJ mol·', C(s) + O,(g)
and that of co, is -394 kJ mol·'. Let enthalpy change of the reaction be x.
Calculate the standard enthalpy change of the following reaction.
•• X +(-394); (-111)x2
C(s)+C0 2 (g) --> 2CO(g) [2) X; -222+394
;+172 kJ/mol
 AL Chemist!l.. June 2012 Paper 4 o Page 5
AL Chemistry June 2012 Paper 4 o Page 4

'!I ~CORNER (iii) When 20.0 em• of a solution of compound A was acidified and titrated ~CORNER
il (c) (I) Ligand exchange reaction.
with 0.0500 mol dm"' K,Cr,O,, 7.50 em• of the K,Cr,O, solution was
i
i (ii) In transition element complexes, the central metal (ion) has a partially needed to reach the end-point.
i
filled d-subshell. The d-subshell is split into different energy levels and the Calculate [A] in the solution. [5]
I!II'!I
Iil ! energy gap ( llE) between these levels depends upon the ligands (c) When lawsone is reacted with NaOH(aq), compound B is produced.
!ii surrounding the central metal ion.
An electron at a lower energy level absorbs energy from the visibile light
and is excited to a higher energy level. Hence, colour observed is the

o¢r
jn
compliment of the color absorbed.
o o-Na•
li NaOH
If the ligand changes, llE also changes. As E = hf, the value of f also lawsone--+- --+-
changes for different values of E. Thus a different frequency is absorbed
for different energy gaps, thereby changing the colour of the complex. (c) (iii) From rows 1 and 3:
Ratio of concentrations of 0
(iii) From Rows 1 and 3, it can be clearly seen that doubling the concentration
c
[Ru(H,OhC/4 ] 2- B
of [Ru (H,O),Ct,f· doubles the rate of the reaction. Thus the concentration
of [Ru (H,O),CI,f- and the rate of the reation are proportional to one =2.2x1o-' =2 Reacting B with ethanoyl chloride, CH 3 COC/, produces compound C, with
another. Increasing or decreasing ·the concentration of carbon monoxide 1.1xto-' the molecular formula C,H,O,.
does not affect the rate of reaction. Hence, order of reaction with respect
ratio of rates of reaction: (i) Suggest the identity of compound C, and draw its structure in the box
to [ [Ru (H,O),Ci.f·] = 1 and order of reaction with respect to [CO] = 0.
7 above.
= 3.2x10- =
:. rate equation= k[[Ru(H2 0) 2 Ct,]'·] 2
1..6x10-7 • Another compound, 0, in addition to C, is produced in the above reaction.
(iv) Mechanism 2, since it is the only mechanism that does not involve carbon D is an isomer of C which contains the same functional groups as C, but
Therefore. the concentration
monoxide in the rate detennining step (i.e the slow reaction). · in different positions.
of [Ru(H 20) 2CI,]'· and the
rate of reaction are propor. (ii) Suggest a possible structure for D.
tiona! to one another.

Questio11 3
Lawsone is the dye that is extracted from the henna plant, Lawsonia inermis.
Although its natural colour is yellow, lawsone reacts with the proteins in hair
and skin to produce the characteristic brown henna colour.
Lawsone can readily be reduced to 1,2,4-trihydroxynaphthalene, compound A. D

~OH
vy oqOH (Iii) Suggest a mechanism for the formation of D from B and ethanoyl
chloride by drawing relevant structures and curly arrows in the follow-
ing scheme.

l
+ 2W + 2e- '<"" E" = +0.36V

(a) (i)
lawsone
0 OH
1 ,2,4-trihydroxynaphthalene, A

Name three functional groups in lawsone.

ocl~· ]-
(ii) Describe a reaction (reagent with conditions) that you could use to +
distinguish lawsone from compound A.
B o~c/cz D
Describe the observations you would make with both compounds. I
CH 3
(iii) Suggest a reagent that could be used to convert lawsone into com-
pound A in the laboratory. [3]1
[Total: 14]
(iv) Draw the structural fonnula of the compound fonned when lawsone is
·reacted with Br,(aq). [5] (a) (i) Other functional groups
. · Suggested Solution:
(b) Compound A can be oxidised to lawsone by acidified K,Cr,o,. present are: Arene, aryl,
(a) (i) Ketone, Alcohol, Alkene benzene, phenyl.
(i) Use the Data Booklet to calculate the E.;';, 11 for this reaction.
(ii) Add 2,4-Dinitrophenylhydrazine (DNPH) to both compound A and lawsone (iiQ Other suitable reagents
(ii) Construct an equation for this reaction. Use the molecular formulae of and heat. Lawsone will give an orange/red precipitate whereas no reac- could be: LiAIH, , Snct, ,
lawsone, C,H,03 , and compound A, C 10 H8 0 3 , in your equation. tion will be observed with compound A. Na + Ethanol, SO 2 .

(iii) NaBH,
AL Chemistry
June2012 Paper 4 o Page 6

~CORNER
AL Chemistry .June 2012 Paper 4 o Page 7

~CORNER
,
(iv) Bromine would not Question 4
substitute in the aryl ring
(a) Describe and explain the trend in the volatilities of the halogens C/ , Br
as no activating group is 2 2

present. ~~ ~
(b) For each of the following pairs of compounds, predict which compound has
the higher boiling point, and explain the reasons behind your choice.
Use diagrams in your answers where appropriate.
(b) (0 From Data booklet.
(b) (i) Ece 11 =1.33-0.36=(+)97V

(ii) Crp~- + BH' + SC 10H8 0 3 ---> 2Cr 3 • + 7H2 0 + 3C, 0 H60J

Cr,O/- + 14W + 6e-
2Cr 3• + 7H,O F" =+1.33
== (i) H,O and H2S
(ii) CH,-CH 2 -CH 3 and CH,-0-CH, [4]
(c) Briefly explain the shape of the SF, molecule, drawing a diagram to
illustrate your answer. [2]
(iii) Moles of K 2Cr20 7 = 7.50 x 0.05 =3.75 x 10-4 moI [rota/: 9]
1000
K 2Cr2 0 7 : A :: 1: 3
Suggested Solution:
moles of A= 3.75x10-4 x 3
= 1.125x10-3 mol (a) Volatility: Cl2 > Br2 > 12
(a) The number of electrons in·
Reason: Down the group, the number of electrons increases causing the van
concentration of A= [A] creases down the group as
der waal's forces of attraction to increase. Therefore the volatility of the
1.125 X1 o-J the halogens have a bigger
1000
X halogens decreases down the group.
cloud of electrons down the
20
2 2 3 (b) (i) H,O has a higher boiling point due to H-bonding in Hp. However, there group.
= 5.625 x 10- "5.63x 1o- mol/ dm
is no H-bonding in H2 S.

(c) (i)

N~~o
I o-Na· __ (ii) CH,- 0 -
CH 3 - 0 -
CH 3 has a higher boiling point than C~,- CH 2 -
CH 3 is polar, and CH 3 - CH 2 - CH, IS not.
CH since
3
lawsone ~vy

(c) SF, has 6 bonding pairs and no lone pairs.

0
The shape is octahedral.
B
F
(ii)
F"- 1/F
s
F/1'----F
F

Question 5
(iii) (a) Describe and explain how the acidities of CHC/2C02 H and CH 2C/CO H

'*"'' lolol -
0 compare to _each other, and to the acidity of ethanoic acid. [3]

otc~
(b) For each of the following pairs of compounds, suggest one chemical test
{!) (reagents and conditions) that would distinguish between them. .
State the observations you would make with each compound, writing 'none'
if appropriate.

0~
B + o}~
""'c
0~
I
CH 3
AL Chemistry June 2012 Paper 4 o Page 8
AL Chemistry
~CORNER
June 20 12' Paper 4 o Page 9

first second test observation with observation with (b) ~CORNER

compound compound (reagents and conditions) first compound second compound
first second test observation with
compound compound observation with
(reagents and conditions) first compound
second compound
O N H , o - N H2
O N H , o - N H2 Br2 (aa) None White ppt formed
CH3CH,COC/ CH3COCH,C/
CH3CH,COC/ CH3COCH,Ci 2, 4-DNPH None Orange ppt formed
CH3CH,CHO CH3COCH3
CH3CH,CHO CH3COCH3 To lien's Reagent+ warm Silver/Black ppt None
[7]
(c) The following diagram shows a section (not a repeat unit) of a polymer, G,
that can be made from the two monomers E and F. (c) (i) Condensation

(ii) , - - - - - - - - - - - - ,

~lj
(c) (i) ff there is a condensation
E + F-- HO~ ·:.1
HO~OH
polymer,

~OH
0
II
polymerG R,-C-0-R,,
0 0 -
E then it's monomers would
(i) What type of po/ymerisation made this polymer? F
IJ:e:
(ii) Draw the structures of the two monomers E and F. 0
(iii) Convert F into a diacyl chloride and add it to a solution of aqueous sodium II
hydroxide and E. R,-C-OH + HO-R,

(iv) Monomer to be changed: F

(iv) Other possibilities could
HO,C"Q have been:

HO,C

E F ~CO,H 0 CO,H
(iii) Suggest the conditions needed to make polymer G from E and F in the
laboratory. HO,C -CH,-CH, -CO,H
(iv) One of the monomers, E or F, could be changed to make a more rigid
polymer of a similar chemical type to G. H H
I I
Suggest which of your two monomers could be changed, and suggest Section B HO,C-C=C-CO,H
a structure for the new monomer. [6]
Answer all the questions.
{Total: 16] •"'' !~·

Question 6
Suggested Solution:
(a) The table shows the structures of four amino acids found in proteins in the
human body.
(a) Acidities: CHC/2 C0 2 H > CH 2 C/C0 2 H > CH 3C0 2 H.
(a) The electronegative chlorine Complete the table by indicating the type of tertiary interaction each side-
CHC/2C0 2 H and CH 2C/C0 2 H have chlorine atoms which are more electron
atoms weaken the 0-H chain is most likely to have when its amino acid is present in a protein
withdrawing than H. The anions formed by CHC/2 C0 2 H and CH,C/C0 2 H are chain.
bond and hence stabilise
more stabilized than that formed from CH 3C0 2 H, since the negative charge of the resulting anion.
the anions of CHC/2 C0 2 H and CH,C/CO,H is more greatly dispersed by the amino acid structure type of interaction
electron withdrawing chlorine atoms. Since CHC/2CO,H has two chlorine atoms alanine H2 NCH(CH 3)C02H
as compared to CH 2C/C02 H, the charge on CHC/2CO,- is more greatly
cysteine H,NCH(CH 2 SH)CO,H
dispersed than on CH 2 C/COO-. Hence, CHC/2 C0 2 H dissociates to a greater
extent than CH,C/CO,H which in tum dissociates more than CH,CO,H. lysine H2 NCH((CH 2 ) 4 NH 2 )C02 H
serine H,NCH(CH,OH)CO,H
I [3]
 AL Chemistry June 2012 Paper 4 o Page II
June 2012 Paper 4 o Page 10
AL Chemistry
~CORNER ~CORNER
(b) Metal ions play an important role in the biochemistry of the human body. Question 7
For each of the following metal ions, outline one of the places in the body
NMR and X-ray crystallography are two important a~alytical techniques which
it can be found and its main role there.
can be used to study the structure and function of molecules.
iron,
(a) Nuclear magnetic resonance, NMR, arises because protons possess spin
potassium, wh1ch gen~rates a small magnetic moment. When an external magnetic fi
zinc. [3] eld IS. applied the protons can align with or against the external field. If they
(c) Many chemical reactions at a cellular level require energy in order to take are ,g1ven a s~all amount .of energy in the radio frequency range each can
place. This energy is largely provided by the breakdown of one particular be promoted so that the1r magnetic moment opposes the external field.
compound. Two ;actors can infll_lence the energy required for this promotion. What are
(i) Write an equation showing the breakdown of this compound. ~~. ~
(II) What type of chemical reaction is this? [2] (b) A compound, J, has the formula C,H,p. The NMR spectrum of J is shown.
(d) Cystic fibrosis is a genetic disease caused by a mutation in the DNA
sequence resulting in the production of a faulty version of an important
protein which acts as an ion pump in the cell membrane. This pump con- 9
trols the flow of ions into and out of cells.
People with the faulty protein show two major symptoms.
water is retained in cells in the lungs resulting in the formation of a
thick, sticky mucous outside the cells;
their sweat is very salty.
Based on the information given for people with cystic fibrosis,
(i) suggest which ions are involved in the ion flow, 1
(ii) suggest and explain what type of bonding might result in thick or sticky I
mucous. [2]
(Total: 10}
10 9 8 7 6 5 4 3 2 '0
0/ppm
Suggested Solution:
(i) Indicate the groups responsible for each peak and hence deduce the
(a) type of interaction structure of J.
amino acid structure
peak at 1 .26 B .•••••••..•...•••••••.•••••.••••• peak at 2.0 B ...••.....•.....•....•..••....•..
H2NCH(CHa)CChH van der waals'
alanine structure of J:
H2NCH(CH2SH)C02H disulfide bonds
cysteine (ii) Th ere are three other isomers of J containing the same functional group
H2NCH((CH2)4NH2)C02H hydrogen bonds as J.
lysine
Draw t~e structures of two of these three isomers and indicate how
H2NCH(CH20H)C02H hydrogen bonds
. serine many different chemical shifts each would show in its NMR spectrum.
isomer 1 isomer 2
(b) Iron: Location: Red Blood cells (Haemoglobin)
main role: To transfer Oxygen to cells and take CO, away from cells.

potassium: Location: In cell membranes.

main role: Controlling the llow of ions and water molecules into or out of cells.

Zinc: Location: In Blood number of groups of peaks ........... number of groups of peaks ........ ..
main role: As an enzyme cofactor. [6]
X-ray crystallography can be useful in gathering Information about the
(c) (I) ATP+H2 0----+ ADP+Pi structure of large organic molecules, such .as nucleic acids.
(ii) Nucleophilic substitution. (I) Which ele~ent will show up most strongly in the X-ray crystallography
of a nucleiC acid? Explain your answer.
(d) (i) Sodium is involved due to salty sweat.
Potassium is involved due to water retention in cells. (ii) X
. -ray crystallography will not detect hydrogen atoms. Explain why this
IS SO. [2)
(ii) type of bonding: Hydrogen bonding
[Total: 10]
explanation: Hydrogen bonding may develop between the water
molecules and the mucous molecules leading to the formation of thick or
sticky mucous.
 11: AL Chemistry June2012 Paper4 o Page 12 AL Chemistry June 2012 Paper 4 o Page t3

Suggested Solution:
~CORNER (ii) For one of the areas, A, B or C, suggest why this would not be an
~CORNER
I (a) 1. The strength of the applied magnetic field.
appropriate place to carry either molecule. [3]
I
I 2. The electronegativity of the atom on which the proton is attached. (b) When liposomes are used to carry drugs, their main purpose is to prevent
the drug molecules from being broken down on passage through the di-
i
i!IJI
(b) (i) peak at 1.26 o: Methyl peak at 2.0 o: Alcohol gestive system.
(i) Name a functional group present in drug molecules that might be broken
Structure of J: down by acid in the stomach.
ii:,'l
CH,
i!i CH-C-OH
I (ii) Name the type of reaction that would cause such a breakdown.
, I (iii) The drug Siro/imus is used to suppress possible rejection by the body
after kidney transplants.
CH,
OH

iJi (ii) isomer 1 isomer 2 (b) (ii) Another isomer could

H have been:
H H H H
I I I I I H
I
H-C-C-C-C-OH
H-c-H H-C-H
I
H
I
H H
I I
H H I H H H
I I
I H,c
I I
H-C-C-C-OH
H-C-C-C-OH
I I I
H H H
I HI HI
H 5 groups of peaks.

number of groups of peaks: 5 number of groups of peaks: 4

(c) (i) Phosphorous, since it has a high electron density

(ii) H atoms do not have enough electron density to be detected by X-Ray
crystallography. ~H,
Sirolimus

Circle two bonds, each in a different functional group that could be

Question 8 broken down in the digestive system. [4]
The developments in nanotechnology and drug delivery over the past 20 years (c) Sirolimus is not very soluble in water, greatly reducing its effectiveness
have been wide-ranging. when given by mouth or by injection. To increase its effectiveness when
(a) One of the most widespread developments for delivering a range of phar- taken by mouth nano-sized crystals of the drug combined with poly(ethylene
maceutical products has been the use of liposomes. These are artificially glycol) or PEG (shown below) are produced.
created spheres made from phospholipids which have an ionic phosphate
'head' and two hydrocarbon 1ails'. HO- (CH,- CH 2 - O)n- H
(i) Suggest what is meant by the term nano-sized.
(ii) Suggest where on the molecule of PEG the drug would be attached.

~
(iii) Why would bonding the drug to a PEG molecule improve its solubility
A in water? [3]
[Total: 10]

Suggested Solution:
(a) (I) a hydrophilic moisturiser: C
phospholipid liposome a fat-soluble vitamin: B
Liposomes have also been used to carr)i pharmaceuticals such as vitamins (ii) Area A
and moisturisers used in cosmetic anti-ageing creams. Otherwise these reason: In area A, the molecule could be exposed to air (oxidation),
phanmaceuticals may I:;Je oxidised or dehydrated if exposed to air. water molecules (hydrolysis) or enzymatic attack.
(i) State in which area of the liposome, A, B or C, each of the following (b) (I) Peptide.
types of molecule would be carried.
(ii) Hydrolysis
a hydrophilic mol stu riser ..............................
a fat-soluble vitamin ............................. .
 June 2012 Paper 4 o Page 14 AL Chemistl}' November 2012 Paper 2 o Page I
AL Chemlstl}'

~CORNER ~CORNER
(iii) OH
November 2012 Paper 2

~ 0
Question I
Answer all questions.

H3C Zinc is an essential trace element which is nElcessary for the healthy growth
of animals and plants. Zinc deficiency in humans can be easily treated by using
zinc salts as dietary supplements.
(a) One salt which is used as a dietary supplement is a hydrated zinc sulfate,
ZnSO,.xH,O, which is a colourless crystalline solid.
Crystals of zinc sulfate may be prepared in a school or college laboratory
by reacting dilute sulfuric acid with a suitable compound of zinc.
Give the formulae of two simple compounds of zinc that could each react
with dilute sulfuric acid to produce zinc sulfate. (2]
(b) A simple experiment to determine the value of x in the formula ZnSO,.xH2 0
is to heat it carefully to drive off the water.

(c) (i) An object is considered to be nano-sized if it can be measured in ZnS0 4 .xH20(s) ..... ZnS0 4 (s) + ~O(g)
nanometers (nm) i.e. between 10-s and 10"" m. A student placed a sample of the hydrated zinc sulfate in a weighed boiling
(ii) On one of the -OH groups. tube and reweighed it. He then heated the tube for a short time, cooled it
and reweighed it when cool. This process was repeated four times. The
(iii) As PEG contains many oxygen atoms, it can H:bond with water and final results are shown below.
therefore improve the solubility of the drug it is attached to.
', \
mass of mass of tube + mass of tube + salt
empty tube I g hydrated salt I g after fourth heating I g
74.25 77.97 76.34

(i) Why was the boiling tube heated, cooled and reweighed four times?
(ii) Calculate the amount, in moles, of the anhydrous salt produced.
(iii) Calculate the amount, In moles, of water driven off by heating.
(iv) Use your results to (ii) and (ill) to calculate the value of x in ZnSO,.xH,O.
(7]
(c) For many people, an intake of approximately 15 mg per day of zinc will be
sufficient to prevent deficiencies.
Zinc ethanoate crystals, (CH,C02 ) 2 Zn.2H,O, may be used in this way.
(i) What mass of pure crystalline zinc ethanoate (M, = 219.4) will need to
be taken to obtain a dose of 15 mg of zinc?
(ii) li this dose is taken in solution as 5 em' of aqueous zinc ethanoate,
what would be the concentration of the solution used?
Give your answer in mol dm--'. (4]
{Total: 13]
(a) Zn(N0,)2, ZnO and other
Suggested Solution: compounds of Zn which re-
act with su~uric acid could
(a) Znco, and Zn(OH),
also have been used.
(b) (i) This was done to ensure that all of the water of crystallization was driven
(b) (i) If the boiling tube had
off and a constant mass of the tube and salt was obtained.
been heated only once, !here
(ii) Mass of ZnS0 4 = 76.34-74.25 = 2.09g could have been the pos-
sibility that not all of the H,O
M, ofZnS04 =65.4+32.1+(4x16.0)=161.5
was driven off from the hy-
2 09 drated zinc suWate. Hence lhe
number of moles of anhydrous ZnS04 = ·
161.5 experiment would have pro-
duced wrong resulls.
=0.01294 = 1.29 x 10-2 moles.
 AL Chemistry November 2012 Paper 2 o Page 2 AL Chemistry November 2012 Paper 2 o Page 3

~CORNER Suggested Solution: ~CORNER

(iii) Mass of HzO driven off = 77_97- 76,34 = 1,63 g
M, of H20=(1x2)+16=16 (a) (i) The thermal stability decreases from HC/ to HI.
1 63
,, number of moles of H20 driven off = - (ii) 2HX ----t Hz + X2
i;l 16 (a) (iij X can be chlorine, bro-
i!! = 0,09055"' 9,1 x1 o-2 mol.
The thermal decomposition of HX depends on the strength of the H- X mine or iodine_
1
;,I
,1 bond. Down the Group, the atomic size of X increases and its orbital, used
1~1 for bonding, becomes more diffuse. Hence, orbital overlap between H and
(iv) In 1.29 x 1o-2 mol of ZnS04, number of mol of H20 driven off = 9.1 x 1o-2
I
X becomes smaller and less effective causing the H- X bond to become
;;I 9.1 x 1o-2 weaker. Therefore thermal stability of these hydrides decreases down the
In 1 mol of ZnS0 4 , number of mol of HzO driven off Group_
1.29 X 10"2
I! = 7.054"' ?mol
(b) K - [Hl]2 (b) Unit of [HI], [H 2 ] and [I 2 ]
Thus, the value of x = 7. No units.
,-[H2]x[l2]' =mole/dm3
0 015 For unit of K,,
(c) (i) Number of moles of zinc in 15 mg of zinc= · (c) (i) As the number of moles on the right hand side and left hand side of the
65.4
= 2.294 x 1o_. " 2.29 x 10_. mol.
equation are same, increasing the pressure will have no effect on the
equilibrium position.
K=~
' [H 2 J[I 2 )
As the number of moles of zinc =-number of moles of zinc ethanoate, (ii) Decreasing the temperature would favour that side of the reaction which [mol/dm'f
hence, the mass of pure crystalline zinc ethanoate required produces more heat. As the forward reaction is exothermic, the equilib-
[mol/dm3 ] [mol/dm3 ]
= 2,29 X 1o·• X 219.4 rium will move to the right hand side of the reaction.
3
= [mol/dm f =
= 0.05024 g (d) 1
H2(g) + [mol/dm3 ] 2
" 0_05 g = 50 mg I2(g) ..-- 2HI(g)
Initial moles .-_ K, has no units
3 0.02 0,02 0
(ii) Volume of aqueous zinc ehanoate = 5 cm 3 = 0.005 dm
moles at equillibrium 0.02-x 0.02-x 2x (c) (ii) Increasing the tempera-
2 29 10 concentration (in mol/dm 3 ) ture would favour that side of
concentration of solution = · x _.
0,005 0.02-x 0.02-x 2x the reaction which loses
at equillibrium
heat. As K, decreases with
= 0.0456 = 4.56 x 1o-2 mol 1dm 3 1 1 1
increasing temperature, this
[Hif shows that [HI]' decreases
K, = [Hz] X [II] with respect to [H,] x [I,) Le_
Question 2
the concentration of products
Each of the Group VII elements chlorine, bromine and iodine forms a hydride. (2x) 2 is less as compared to the
59
(0.02- x)(0.02- x) concentration of the reactants,
(a) (i) Outline how the relative thermal stabilities of these hydrides change
Hence, by increasing the
from HC/ to HI.
59=~2 temperature, the LHS of the
(ii) Explain the variation you have outlined in (i). [3] (0.02-x) reaction is favoured. This
shows the forward reaction to
Hydrogen iodide can be made by heating together hydrogen gas and iodine
vapour. The reaction is incomplete.
.J59=~ be exothermic and the re-
0.02-x
verse reaction to be endot-
H2 (g) + I 2(g) <=== 2HI (g) o.o2.J59- .J59 x = 2x hennic_
(b) Write an expression for K, and state the units. [2] 2X+ .J59 X = 0.02.,[59
(c) For this equilibrium, the numerical value of the equilibrium constant K, is 0.02.,[59
140 at 500 K and 59 at 650 K. X= 2+.J59
Use this information to state and explain the effect of the following changes = 0.01567"' 0.016
on the equilibrium position.
(i) increasing the pressure applied to the equilibrium .. at equillibrium,
(ii) decreasing the temperature of the equilibrium [4] moles of HI = 2 x 0.01567
(d) A mixture of Q_02 mol of hydrogen and 0.02 mol of iodine was placed in = 0.03174" 0.032 mol
a 1 dm3 flask and allowed to come to equilibrium at 650 K.
moles of H2 =moles of I 2 = 0.02-0.01567
Calculate the amount, in moles, of each substance present in the equilib-
= 0.00413"' 0.004 mol
rium mixture at 650 K.
H2(g) + I2(g) ..--
~
2HI(g)

initial moles 0,02 0.02 0 [4]

[Total: 13]
 November 2012 Paper 2 0 Page 4 AL Chemistry November 2012 Paper2 o Page 5
AL Chemistry
~CORNER
(b) (i) NH,CI and Ca(OH) 2
~CORNER
Question 3 (ii) 2NH4 C/ + Ca(OHh ----+ CaC/2 + 2NH3 + 2H 20
Ammonia is an important industrial chemical which is manufactured on a large (iii) Calcium oxide would be used.
scale by using the Haber process. Calcium oxide is basic in nature and will not react with ammonia.
(a) (i) Write a balanced equation, with state symbols, for the reaction However, both, phosphorus(V) oxide and sulfuric acid are acidic and
occurring in the Haber process. will react with ammonia.
(ii) Give three essential operating conditions that are used in the Haber
(c) NH 3 + W ----+ NH;
process.
(iii) State one large scale use of ammonia. (5] Ammonia fomns a. dative bond with H' to form an ammonium ion.

(b) Ammonia may be prepared in a school or college laboratory by using the

apparatus below.

ammonium chloride
and calcium hydroxide Question 4
Many organic compounds, including alcohols, carbonyl compounds, carboxylic
ac1ds and esters, contain oxygen.
(a) The table below lists some oxygen-containing organic compounds and some
heat common laboratory reagents.
tower
(i) Complete the table as fully as you can.
If you think no reaction occurs, write 'no reaction' in the box for the
structural fomnula(e).

The reaction involves the displacement of ammonia from one of its organic structural formula( e) of
reaction reagent
compounds. compound organic product(s)
(i) Give the formulae of the two reactants that are heated together to Cr20, 2-/W
produce ammonia. A (CH3)JCOH
heat under reflux
(ii) Construct a balanced equation for the reaction between your two
Fehling's reagent
reagents. s CH3CH2CHO
warm
(iii) Common drying agents include calcium oxide, concentrated sulfuric
acid and phosphorus(V) oxide. NaOH(aq)
Which one of these would be used in the drying tower in this experi- c HC02CH(CH3)2
warm
ment? Explain your answer. · (5]
(c) Ammonia is a weak base which fomns salts containing the ammonium ion. D CH2 =CHCHO NaSH4
Describe, with the aid of an equation, the fomnation and structure of the
ammonium ion. E (CH3)JCOH NaSH,
You should use displayed fomnulae in your answer. (3]
[Total: 13] Mno,-/W
(a) (ii) The temperature range F CH3CH2COCH3
heat under reflux
for the Haber process can
Suggested Solution: range from 300-550'C <lid the
(ii) During some of the reactions in (i) a colour change occurs.
pressure can range from 60-
Complet~ the table below for any such reactions, stating the letter of
(a) (i) ~(g)+ 3~(g) ~ 2NH3(g) 250 atm.
the react1on and what the colour change is.
(iii) Other uses of ammonia
(ii) 1. A pressure of 200 atm.
include: colour at the beginning colour at the end
2. A temperature of 350'C. reaction
• manufacture of HNO,. of the reaction of the reaction
3. An iron catalyst.
• as a cleaning agent.
(iii) Manufacture of fertilisers. • as a refrigerant.
• manufacture of explosives.
[10]
 November 2012 Paper 2 0 Page 6 AL Chemistry November 2012 Paper 2 0 Page 7
AL Chemistry

(b) Some oxygen-containing compounds react with 2,4-dinitrophenylhydrazine.

~CORNER ~CORNER
Question 5
o,N
Compound X has the molecular formula C,H,O,.

H 2NNH-O-N02 (a) (i) Treatment of X with sodium metal produces a colourless flammable
gas.
What does this result tell you about the functional groups that could be
2,4-dinitrophenylhydrazine present in X?
(i) Draw the structural formula of the organic compound formed when (ii) There is no reaction when X is treated with sodium hydrogencarbonate,
HOCH,CH 2 CHO reacts with 2,4-dinitrophenylhydrazine reagent. NaHC0 3 •
What does this result tell you about the functional groups that could be
(ii) Suggest the colour of the organic product. (2]
present in X?
[Total: 12]
(iii) When X is shaken with aqueous bromine the orange colour disap-
pears.
Suggested Solution: What does this result tell you about the functional groups that could be
present in X? (3]
(a) (i)
(b) The molecule of X has the following features.
organic structural formula(e) of
reaction reagent
compound organic product(s) The carbon chain is unbranched and the molecule is not cyclic.
2
Cr,o, -tH• No oxygen atom is attached to any carbon atom which is involved
A (CH,)3COH no reaction in " bonding.
heat under reflux
(a) (i) Reaction B is an example
No carbon atom has more than one oxygen atom joined to it.
Fehling's reagent of oxiuation.
B CH,CH,CHO CH,CH,CO,H There are five possible isomers of X which fit these data. Four of these
warm Reaction C is an example of
hydrolysis. isomers exist as two pairs of stereoisomers.
NaOH(aq) HCO,Na and
c HCO,CH(CH,), Reaction D is an example of (i) Draw displayed formulae of each of these two pairs.
warm (CH,) 2 CHOH reduction.

D CH 2 =CHCHO NaBH, CH 2 =CHCH 2 0H

E (CH,)3COH NaBH 4 no reaction

pair 1
Mno, -,H.
F CH 3 CH,COCH, no reaction
heat under reflux

(ii) colour at the beginning colour at the end

reaction
of the reaction of the reaction

B blue brick red

pair 2
-----

(b) (i) ON

HOCH,CH,CH•NNH ~NO, (ii) These four isomers of X show two types of stereoisomerism.
State which type of isomerism each pair shows. [6]
(ii) Red [Total: 9]
 AL Chemistry
AL Chemistry November 2012 Paper 2 o Page 8 November 2012 Paper 4 o Page 1

~CORNER
Suggested Solution: November 2012 Paper 4
~CORNER
(a) (i) . acl'd gr0 up and/or an alcohol group.
X contains a carboxylic
I! I
·1
(a) (ii) If a carboxylic acid group
was present in X, a reaclion
> (ii) Only the alcohol group is present in X. Section A
would have occurred be.
(iii) x contains an alkene group. tween Xand NaHCO,. caus- Answer all questions.
ing effervescence and col-
(b) (i) ourless C0 2 to be released.
Question 1
(iii) Bromine water always
decolorises in the presence
H (a) Write down what you would see, and write equations for the reactions that
of a 'c=C/ group. occur, when silicon(IV) chloride and phosphorus(V) chloride are separately

pair 1
H-o-t"
~ C=C H
/H ·/ ' mixed with water. [4)
(b) lron(lll) chloride, FeCI3 , is used to dissolve unwanted copper from printed
circuit boards (PCBs) by the following reaction.
H/ "6-o-H

~ 2FeC13 (aq) + Cu(s) ~ 2FeCI2 (aq) + CuCI (aq)

2
A solution in which [Fe 3•(aq)] was originally equal to 1.50 mol dm"" was
re-used. several times to dissolve copper from the PCBs, and was then
titrated as follows.
H H 3
A 2.50 cm sample of the partially-used-up solution was acidified and
I I .titrated with 0.0200 mol dm"" KMnO,.
0 0
I I This oxidised any FeCI, in the solution back to FeCI •
3
H-C-H H-C-H It was found that 15.0 cm 3 of KMnO,(aq) was required to reach the end
pair 2
H t I
~~,
H
I
point.

6=c.('i "o-H H-o"'.=. C=C

H I I
(i) Construct an ionic equation for the reaction between Fe'• and MnO;
in acid solution.
I I H
H H
H H (ii) State here the Fe'•: MnO; ratio from your equation in (i).
(iii) Calculate the number of moles of MnO; used in the titration.
(iv) Calculate the number of moles of Fe'• in 2.50 cm 3 of the partially-used-
up solution.
(ii) Pair 1: cis-trans isomerism.
(v) Calculate the [Fe'•] in the partially-used-up solution.
Pair 2: optical isomerism.
(vi) Calculate the mass of copper that could still be dissolved by 100 cm 3
of the partially-used-up solution. [6)
(c) When SiCI, vapour is passed over Si at red heat, Si,CI, is formed. Si CI,
contains a Si-Si bond. 2

The reaction of Si2 CI, and Cl, re-forms SiCI,.

Si2 CI6 (g)+CI2 (g) ~ 2SiC14 (g)

Use bond energy data from the Data Booklet to calculate tJ.H<T for this
reaction. [2)

(d) Calcium forms three calcium silicides, Ca2 Si, CaSi and CaSi • The first of
these reacts with water as follows . 2

........ Ca 2 Si + ........ Hp ~ ....... Ca(OH)2. + ...... Si0 + ..... H

2 2
(i) Balance this equation. You may find the use of oxidation numbers
helpful.
(ii) During this reaction, state
which element(s) have been oxidised,
which element(s) have been reduced.
[2)
[Total: 14]
 November 2012 Paper 4 c Page 2 AL Chemistry
AL Chemistry November 2012 Paper 4 c Pag_e 3
~CORNER
Suggested Solution:
Question 2 ~CORNER
(a) SiC/4 + 2Hz0 ---> Si0 2 + 4HCI
(a) The diagram below shows an incomplete experimental set-up needed to
observation: White I steamy fumes of HCI are produced.
measure the Ece 11 of a cell composed of the standard Cu'•ICu electrode and
an Ag•l Ag electrode.
PCI5 + 4H 20 ---> l-l,P04 + 5HCI
observation: Fizzing occurs and white I steamy fumes are produced.

5Fe 2 • + MnO~ + ~W ---> Mn

2 3
(b) (i) • + 4H 20 + 5Fe •

(ii) 5: I

(iii) Moles of MnO~ = 0.02 x ~ = 3 x 1o-4 mol.

copper
electrode electrode B
1000
3
(lv) Number of moles of Fe 2 • = 5 (3 x 1o-•) = 1.5 x 1o- mol. saturated
3 solution A solution
v IFe .z . . I d I . 1.5x10- solidAgCI ofAgCI
() 1tn parttal y use up so utlon = - -2.5
- x 1000
(i) State the chemical composition of
=0.6 molldm 3
solution A,
100 electrode B.
(vi) Moles of Fe 3 • in original solution of 100cm
3
=1.50x 1000 =0.15 moles
(ii) Complete the diagram to show the whole experimental set-up. (4]
100
moles of Fe 2 ' in partially used solution= 0.6 x = 0.06 moles (b) The above cell is not under standard conditions, because the [Ag•] in a
1000
saturated solution of AgCI is much less than 1.0 mol dm"". The E, ectrode is
remaining moles of Fe 3• = 0.15-0.06 = 0.09 moles related to (Ag'] by the following equation. 1

since, Fe3• Cu : : 2 : 1, equation 1

Eelectrode = E~ectrode +0.06\og(Ag+]
:

0 09
0.09 moles of Fe 3 ' can react with · = 0.045 moles of Cu
2
3 -~i: (i) Use the Data Booklet to calculate the E~ 1 cell if the cell was operating
mass of copper that could still be dissolved in 100 cm of partially used up under standard conditions.
solution = 0.045 x 63.5
(c) The structure of Si,CI, is In the above experiment, the E0 , 11 was measured at +0.17V.
: 2.8575"' 2.86 g
Ci Cl (ii) Calculate the value of E,1eclrode for the Ag• I Ag electrode in this experi-
(c) Bond energy of Si-Si Bond= 222 kJimol I I ment.
CI-Si-Si-C/
Bond energy of Si··CI Bond= 359 kJimol I I (iii) Use equation 1 to calculate (Ag•] in the saturated solution. [3]
Ci Cl
Bond energy of CI-CI Bond= 244 kJimol
From here it can be seen (c) (i) Write an expression for K,P of silver sulfate, Ag,SO,, including units.
bonds broken= (Si-Si) + 6(Si-CI) + (C/-CI) that 1 Si-Si and 6 Si-C/
bonds are broken. Using a similar experimental set-up to that illustrated opposite, it is found
: 222 + 6(359) + 244
that [Ag'] in a saturated solution of Ag 2 SO, is 1.6 x 10·• mol dm"".
=2620
(ii) Calculate the value of K,P of silver sulfate. (3]
(d) Let oxidation state of Si in
bonds formed= 2 x (4 x Si-C/)
Ca,Sibe X (d) Describe how the colours of the silver halides, and their relative solubilities
=8 (Si-C/)
:. 2(+2)+x=O in NH,(aq), can be used to distinguish between solutions of the halide ions
=2672 Ct·, Br· and J·. (4]
:. X=- 4
tl.H~ = 2620-2872 Let oxidation state of Si in (e) Describe and explain the trend in the solubilities of the sulfates of the
= -252 kJimol Si02 bey elements in Group II. (4]
:. y + 2(- 2) = 0
[Total: 18]
(d) (i) Ca 2 Si + 6H2 0 ---> 2Ca(OH) 2 + Si0 2 + 4H2 :. y = + 4
Hence Si is oxidized. Simi·
(ii) Silicon is oxidized
!any, oxidation state of H in
Hydrogen has been reduced H, 0 = + 1 and oxidation
state of H in H, =0. Hence
Hydrogen is reduced.
 November 2012 Paper 4 ° Page 4 AL Chemistry
AL Chemistry
~CORNER November 2012 Paper 4 o Page 5

Suggested Solution: ~-CORNER

Questio11 3
(a) (i) Solution A: CuSO,
Electrode B: Silver (a) Catalysts can be described as homogeneous or heterogeneous.

(ii) (i) What is meant by the terms homogeneous and heterogeneous?

(ii) By using iron and its compounds as examples, outline the different
modes of action of homogeneous and heterogeneous catalysis.
Choose one example of each type,- and for each example you should
state what the catalyst is, and whether it is acting as a homoge-
neous or a heterogeneous catalyst,
electrode B
copper write a balanced equation for the reaction,
electrode
outline how the catalyst you have chosen works to decrease the
saturated activation energy. [8].
solution
ofAgCI (b) The reaction between SO,, NO, and 0 occurs in two steps.
2

so2 ~ NO + so3
(b) (i) Ag• +e- === Ag Ea = +0.80 V
N02 +
~ N02
t.Hf = -88 kJ mol-1

Cu2• + 2e- === Cu Ea = +0.34 V

NO+i02 t.Hf =-57 kJ mol-1

E!n = 0.80- 0.34 The activation energy of the first reaction, E , is higher than that of the
81
=+0.46V second reaction, E ,
82
( 1••1) Ecell-_ 0 · 17 v' standard E!11 = 0. 46 V
Use the axes below to construct a fully-labelled reaction pathway diagram
a -Ecell = 0.46-0.17
Ecell =0.29 V for this reaction, labelling E , E ,
81 82
t.H'; and t.Hf.
.. EAg electrode =0.80-0.29 =0.51 v

(·,·,·,) Eelectrode -- Ea d +0.06log[Ag•1

electro e
0.51 = 0.80 + 0.06 log [Ag•1
0 51-0.80
log [Ag+1- . 0.06

log [Ag+1 = -4.8333

[Ag• 1= 1o-4.6333 N02 +S02
3
= 1.47 x 10·5 mol/ dm
3 energy
units: mol /dm"

(ii) Ag2S04 === 2Ag• +So:t (d) White precipitate of AgCI

dissolves in both dilute
[S0421 : [Ag•1 = 1: 2
and concentrated NH,.
cream precipitate of AgBr
=:> [S0
4
- 2] = [A~+] is insoluble in dilute NH,
2 but dissolves in concen-
1.6 X 10" ) _2 2 X
.. Ksp = (1.6x10 ) ( trated NH,. Yellow precipi-
2
9 tate of Agl is insoluble m
_ 2 048 x 10-s "'2.05x 10-6 md/dm both dilute and concentr-
. . ~ . (a ) decreases down the grou~. ~lso, A~CI ated NH,.
(d) Solubility of stlver Halides tn NH3 q A I is ellow in colour. Thts tnformatton extent of reaction
is white, AgBr has acre~m colour, andol~ion: of the halide ions Cl-, sr- and (e) 1\Hsotution =1\HtaOceonorgy+
can be used to distingUish between s [2]
6.Hhydration .
I-. as the cationic size increases and lattice [rota/: 10}
(e) Solubility decreases down the group, f the cation also decreases. The If t.HLE > 1\Hhyd;~on • the
Th hydratton energy o f
energy decreases. e . th n the lattice energy there ore change will be endothermic.
decrease in hydration energy ts more a

Ht.Hsolution beco mes more endothermic.

 AL Chemistry
November 2012 Pap_er 4 o Page 6 November 2012 Paper 4 o Page 7
AL Chemistry
~CORNER ~CORNER
Suggested Solution: Question 4
(a) (i) If a catalyst is present in the same phase as the reactants, it is known as The compound responsible for the hot taste of chilli peppers is capsaicin. Its
homogeneous catalyst. molecular structure can be deduced by the following reaction scheme.
If the phase of the catalyst is different from the phase of the reactants,
it is known as heierogeneous catalyst.

(ii) For homogenous catalysis:

2
homogeneous cfjtalyst: Fe •
capsaicin, C18 H27 N03
equation: 2Sp~- + 21- ~ 2SO~- + 12
how catalyst works: S 20 8 + 2Fe
2
• ~ 2SO~- + 2Fe
3
•
reaction 1 I
boil with H,O'

2Fe3+ + 21- ~ 2Fe

2
• + 12
~ ~
For heterogeneous catalysis:
heterogeneous catalyst: V2 0 5 (vanadium (V) oxide).
''~
HO A;J'"'
OCH 3
+
equation: 2 2 ~so 3
so 2 +.!.o
C, C10H18 0 2
how catalyst works: S0 2 + V20 5 ~ S0 3 + V20 4 t" 1heat with concentrated
reac ton 2 acidified KMn0
1 4
V2 0 4 +"20 2 ~ V,0 5
!
(b)

+
D, C6H100 4 E,C 4 H8 0 2
reaction 5 f
reaction 3

NO,+ SO, (CH 3),CHCH,OH

F,C 6H8N2

energy
i!>Ht
reaction 4 1 heat with KCN
Br(CH 2 ) 4 Br

Compounds C, D and E all react with Na,CO,(aq).

Answer tha following questions.
NO,+ SO,
(a) Suggest reagents and conditions tor reaction 3.
, [1]
(b) What type of reaction is reaction 4? [1]
(c) Suggest reagents and conditions tor reaction 5. [1]
(d) Name the functional group in C lila! has reacted with hot concentrated
acidified KMnO,. [1]
extent of -reaction
(e) Suggest the name of the functional group in capsaicin that has reacted in
reaction, 1. [1]
{f) Work out structures for compounds C-F and capsaicin, and draw their struc-
!ural formulae in the boxes opposite. [5]
[Total: 10]
 AL Chemistry
November 2012 Paper 4 o Page 8 November 2012 Paper 4 o Page 9
AL Chemistry
~CORNER ~CORNER
(b) Complete the following table with information about the reactions of the
Suggested Solution: three stated reagents with compound G.
(a) K,Cr,O, 1 H' + heat under reflux.
reagent observation structure of organic product type of reaction
(b) Nucleophilic substitution
(c) Heat under reflux+ aqueous HCI
sodium
(d) Alkene
metal
(e) Amide
(f)
OH

H,C~
co~ OCH,
aqueous
bromine

CH, capsaicin, C18H27 N0 3

reaction 1 I
boil with H30'
aqueous
alkaline

f ! iodine

L..__---.J_ _ ____,_ _ _ _ _ _ _- - - ' - - - - - - . J [B)

HO
~'"' +
H,C~CO,H

CH 3
(c) The dye H can be made from compound G by the route shown below.

OCH 3
C, C10H180,

reaction 2
I heat with concentrated
acidified KMn04
J
-step 1

! :~ I step 2
CH,
To
HO,C~
+ H,C~CO,H
~~
CO,H

D. C6H, 0 0• E. c.H.o,

reaction 51 reaction 3
S03 H
dye H
NC~CN
(CH 3 )2CHCH 20H (i) Draw the structures of the amine J and the intermediate K in the boxes
above.
F, C6H8N2

reaction 4 l heat with KCN

(ii) Suggest reagents and conditions for
step 1,
step 2.
Br(CH 2) 4Br [5)
(d) Suggest a reaction scheme by which compound G and propanoic acid
could be converted into compound L.
Question 5 0

0~
Compound G is a naturally occurring aromatic compound that is present in
raspberries.

~o)U
0

HOC
(a) Identify the functional groups present in compound G. [2)
compound L [3)
[Total: 18)
 AL Chemistry November 2012 Paper 4 o Page 11
November 2012 Pl!J?.er 4 o Page 10
~CORNER ~CORNER
AL Chemisi!X_
Section B
Suggested Solution: Answer all the questions.
(a) Phenol and Ketone
Question 6
structure of organic product type of reaction
(b) reagent observation
Proteins are complex molecules made up from long chains that are folded to
I give a three-dimensional structure.
0

0~
(a) Study the table which describes aspects of bonding in proteins. For each
sodium effervescence redox
description of a bonding type, indicate whether it contributes to the primary,
metal occurs secondary or tertiary structure of a protein.

bonding type structure involved

,,~
disulfide bonds between parts of the chain
aqueous aqueous electrophilic hydrogen bonds in a p-pleated sheet
bromine bromine substitution
ionic bonds between parts of the chain
decolourises
HO peptide links between amino acids
Br [3]
,'~'.'
(b) Explain, with the use of diagrams as appropriate, the difference between
~: competitive and non-competitive inhibition of enzymes. [4)
Aqueous yellow ~CO,Na oxidation (c) The diagram shows one strand of DNA. Draw a matching strand showing
alkaline precipitate is
clearly, with labels, the bonds holding the two strands together.
iodine produced
HO Name the bases in your strand, indicating clearly which base bonds to
each base in the strand shown.

o (c) (i)
.-------~

H,~so,H -
step 1
N;--Q-so,H
compound G [3)
[Total: 10]
J

Suggested Solution:
0 (a)
bonding type structure involved

HOz~,O,H
·disulfide bonds between parts of the chain tertiary
hydrogen bonds in a p-pleated sheet secondary
ionic bonds between parts of the chain tertiary
peptide links between amino acids primary

dye H (b) Competitive inhibitors resemble the substrate and are able to bind to the active
site of the enzyme. Thus, they compete for the active site of the enzyme and
(ii) Step 1: reagents: NaN0 2 + HCI prevent ttie substrate from binding.
condition: at a temperature lesser than 10 "C

~w c:[j)

e
Step 2: reagents: K and G
conditions: aqueous NaOH

(d)

CH,CH,CO,H PCI, +Heat >CH,CH,COCI Add to G in NaOH(aq) >

Jo~ compound L
c:O
Key: E : enzyme, S : substrate, I : inhibitor.
 AL Chemistry November 2012 Paper 4 o Page 13

~CORNER
~CORNER
N
AL Chemistry Q) Q)
c c
Non-competitive inhibitors can bind to a different site (other than the active 0 ~ ~ ~
site) on the enzyme. This causes the shape of the active site to change. They ~ ~ QJE "'E
may also form permanent covalent bonds with the enzyme. :::l
rn 5rn ·5 ·5
""" ._,., ..-~ """" """ -start point

~
~inhibitor
inhibitor Q
(c) Names of bases= Adenine and cytosine.

(i) Indicate with an X on the diagram wh· h r

suspect 2 cannot distinguish whi~h o;cth~~es from suspe~t 1 and from
ii) was present 1n the house

you expect this to be? Expla·,npeyco was arre~ted. Which suspect would
( Based on this evidence one sus 1 ·
· ur reasomng. [2]
T G
analysed using mass' spectrometry a~~ ~~~cene of the crime and was
(c) A sample of a liquid p was found h
II~H-bonds~lll
c The mass s ectrum h . spectroscopy.
A M peak at ~/e = 88. as M and M+ 1 peaks m the ratio of 5.1 : 0.22 with the

The NMR spectrum is shown

Question 7
DNA fingerprinting has become an important analytical technique, largely due

1~1
to its use in 'screening' crime suspects. It also has a range of applications in
modem analysis Including determining family links, medicine and archaeology.
II
(a) (i) DNA fingerprinting uses an analytical technique you have studied. What
T
is the name of that technique? 11 10 9 8 7 6 5 4 3 2 0
(ii) In order to carry out DNA fingerprinting, the DNA must first be broken o/ppm
down into shorter lengths of polynucleotides. How is this accomplished?
Use the data to suggest a structure for p' explaining your answer. [5]
(iii) What part of the DNA fragments enables them to move in an electric
~~ ~ [Total: 10]

(b) The DNA fingerprints shown were obtained from a crime scene. DNA
samples were recovered from two rooms in the house where the crime took Suggested Solution:
place. The victim's DNA and that of two possible suspects were included (a) (i) Electrophoresis.
in the analysis. (ii) By using a restriction enzyme.
(iii) The phosphate group.
AL Chemistry November 2012 Paper 4 0 Page 14 AL Chemistry November2012 Paper4 0 Page 15

(b) (i)
~CORNER (b) Lactic acid exists in two stereoisomeric forms. Draw the other form in the ~CORNER
N
Q) Q) box.
c c
N Q) Q)
0 0
t) t)
E
Q) Q)
c.
"'
Q) "'
Q)
c.
t5 E E
"':::> :::>
<I)

·:;: -c -c
0 0

....,
"' "'
...,. """' c:oo ..,..!-start point

[1]
(c) One of the reasons PLA has attracted so much attention is that it is
biodegradeable. This does, however, restrict some potential uses. The simple
polymer has a melting point of around 175 •c, but softens between
60-80 •c. However, its thermoplastic properties enable it to have a range
of uses in fibres and in food packaging.
(i) Explain why PLA would not be a suitable packaging material for foods
pickled in vinegar.
..!. (ii) PLA containers are not used for hot drinks. Suggest why. [2]
(ii) Suspect 2. The DNA fingerprint of suspect 2 matches crime scene 1 . (d) Lactic acid can also be co-polymerised with glycolic acid.
H 0
(c) P is CH,C02 CH2 CH, I II
There are 3 different proton environments. HO-C-C-OH
100 0 22 I
Total number of carbons= x · = 3.922"' 4 carbon atoms. H
5.1x1.1 glycolic acid
The NMR spectrum shows a total of 2 + 3 + 3 = 8 hydrogen atoms.
(i) Draw a section of the co-polymer showing one repeat unit.
:. mass units remaining= 88- (8 + 12 x 4) = 32
(ii) Suggest what type(s) of bonding will occur between chains of this
which is equivalent to the mass units of 2 oxygen atoms. co-polymer, indicating the groups involved.
thus, molecular formula= C 4H80 2 (iii} Suggest one property in which the co-polymer differs from PLA. [5]
4 peaks (Ou<:rtet) at 4.1 shows an adjacent CH,. 3 peaks (triplet) at 1.3 shows {Total: 10]
an adjacent CH, .
Hence P = CH,CO,CH,CH 3 Suggested Solution:
structure of P: (a} (i} High acidity could denature the en~yme and alter it's tertiary structure and
H 0 H H active site.
I II I I
H-C-C-0-C-C-H (ii} Condensation
I I I {b)
H H H
CO,H
I
Questio11 8
H\''i'--oH
The increasing awareness of the diminishing supply of crude oil has resulted H3 C
in a number of initiatives to replace oil-based polymers with those derived from

t
natural products. One such polymer, 'polylactide' or PLA, is produced from com
starch and has a range of applications. (c) (i} The acid present in vinegar would hydrolyse the ester linkage.
(ii} Hot water would cause the PLA container to soften.
(a) The raw material for the polymer, lactic acid (2-hydroxypropanoic acid), is
formed by the fermentation of com starch using enzymes from bacteria.
(i) Calcium hydroxide is added to the fermentation tanks to prevent the
(d) (i)
- I
H
0-C-C-0-C-C
0
II
CH,
I
Ot
II
production of lactic acid from slowing down.
Why might high acidity reduce the effectiveness of the enzymes? I I
(ii) The structure of lactic acid is shown.
H H
C02H (ii} Type of bonding : Van der waals'
I Groups involved : Methyl/ CH 3 group

Ho/\"""'H Type of bonding : Permanent dipole-dipole interaction

CH, Groups Involved : Ester Group

What type of reaction takes place in this polymerisation? [2] (iii} The co-polymer has a different melting point as compared to PLA.
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