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Edexcel IAL Chemistry Unit 4 Jan19-Jan24

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0% found this document useful (0 votes)

532 views405 pages

Edexcel IAL Chemistry Unit 4 Jan19-Jan24

Compilation of Past Papers published by Edexcel online

Uploaded by

Ahsan Habib

We take content rights seriously. If you suspect this is your content, claim it here.

Available Formats

Download as PDF, TXT or read online on Scribd

You are on page 1/ 405

Please check the examination details below before entering your candidate information

Candidate surname Other names

Pearson Edexcel Centre Number Candidate Number

International
Advanced Level

Thursday 10 January 2019

Afternoon (Time: 1 hour 40 minutes) Paper Reference WCH04/01

Chemistry
Advanced
Unit 4: General Principles of Chemistry I – Rates, Equilibria and
Further Organic Chemistry (including synoptic assessment)
Candidates must have: Scientific calculator Total Marks
Data Booklet

Instructions
• Use black ink or black ball-point pen.
• centre
Fill in the boxes at the top of this page with your name,
number and candidate number.
• Answer allthequestions.
Answer
• – there may bequestions in the spaces provided
more space than you need.

Information
• The total mark for this paper is 90.
• – usemarks
The for each question are shown in brackets
this as a guide as to how much time to spend on each question.
• written
Questions labelled with an asterisk (*) are ones where the quality of your
communication will be assessed
– you should take particular care with your spelling, punctuation and grammar, as
well as the clarity of expression, on these questions.
• A Periodic Table is printed on the back cover of this paper.

Advice
• Read each question carefully before you start to answer it.
• Show all your working in calculations and include units where appropriate.
• Check your answers if you have time at the end.
Turn over

*P54560A0128*
P54560A
©2019 Pearson Education Ltd.

2/1/1/1/1/1/
SECTION A

Answer ALL the questions in this section. You should aim to spend no more than 20 minutes on

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this section. For each question, select one answer from A to D and put a cross in the box .
If you change your mind, put a line through the box and then mark your new answer with
a cross .

1 Propanone reacts with iodine in acidic solution according to the equation

CH3COCH3(aq) + I2(aq) → CH3COCH2I(aq) + H+(aq) + I–(aq)

Which method would not be suitable for obtaining the rate of this reaction?

A Colorimetry.
B Measuring the increase in pH of the solution.
C Measuring the increase in the infrared absorption for the C–I bond.
D Quenching followed by titrating with sodium thiosulfate.

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(Total for Question 1 = 1 mark)

2 For the reaction

2HgCl2(aq) + C2O42–(aq) → 2Cl–(aq) + 2CO2(g) + Hg2Cl2(s)
the rate equation is
rate = k[HgCl2(aq)][C2O2–
4 (aq)]
2

The concentrations of both HgCl2 and C2O42– are increased by a factor of three.
The rate of reaction increases by a factor of
A 3
B 9
C 12
D 27
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(Total for Question 2 = 1 mark)

2
*P54560A0228*
3 To determine the activation energy, Ea , for a reaction, a graph was
plotted of ln k against 1/T, where k is the rate constant.
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The Arrhenius equation is

Ea
ln k = − + constant
RT
The gradient of the graph is equal to
A −Ea
E
B − a
R
Ea
C −
T
Ea
D −
RT
(Total for Question 3 = 1 mark)

4 Which is correct for standard molar entropy?

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Highest entropy Medium entropy Lowest entropy

A Hydrogen Nitrogen Iron
B Nitrogen Iron Hydrogen
C Nitrogen Hydrogen Iron
D Iron Nitrogen Hydrogen

(Total for Question 4 = 1 mark)

5 The Haber process is used to make ammonia from nitrogen and hydrogen at 450°C.

N2(g) + 3H2(g)  2NH3(g) ∆H = −92 kJ mol−1

When the temperature of the system is increased,

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A Kp decreases.
B Kp increases.
C Kp stays the same.
D Kp increases and then decreases.

(Total for Question 5 = 1 mark)

3
*P54560A0328* Turn over
6 When magnesium hydroxide dissolves in water, the following equilibrium is established.
Mg(OH)2(s)  Mg2+(aq) + 2OH−(aq)

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The expression for the equilibrium constant, Kc , is
A [Mg2+(aq)] × 2[OH–(aq)]
B [Mg2+(aq)] × [OH–(aq)]2

[Mg2 + (aq)] × 2[OH− (aq)]

C
[Mg(OH)2 (s)]

[Mg2 + (aq)] × [OH− (aq)]2

D
[Mg(OH)2 (s)]
(Total for Question 6 = 1 mark)

7 Energy is given out when one mole of gaseous magnesium ions is hydrated.
Mg2+(g) + aq → Mg2+(aq)

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This is more exothermic than the corresponding value for barium ions, Ba2+,
because the
A ionic radius of Mg2+ is less than that of Ba2+.
B ionisation energy of magnesium is greater than that of barium.
C lattice energy of magnesium oxide is more exothermic than that of barium oxide.
D solubility of magnesium hydroxide in water is less than that of barium hydroxide.

(Total for Question 7 = 1 mark)

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4
*P54560A0428*
8 The graph shows the yield of product in a gaseous equilibrium at different temperatures
and pressures.
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400 atm

200 atm
Yield of
product at
equilibrium

Temperature

The forward reaction is

A exothermic, and there are more moles of gas on the right-hand side.
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B endothermic, and there are more moles of gas on the right-hand side.
C exothermic, and there are fewer moles of gas on the right-hand side.
D endothermic, and there are fewer moles of gas on the right-hand side.

(Total for Question 8 = 1 mark)

9 An aqueous solution contains 4.0 g of sodium hydroxide in 250 cm3 of solution.

[Kw = 1.00 × 10−14 mol2 dm−6 Molar mass of NaOH = 40 g mol–1]

The pH of the solution is
A 13.0
B 13.4
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C 13.6
D 13.9

(Total for Question 9 = 1 mark)

5
*P54560A0528* Turn over
10 A solution containing HCN and KCN is a buffer. When a small amount of acid is added, the
solution acts as a buffer because

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A hydrogen ions in the acid combine with cyanide ions to make HCN.
B hydrogen ions in the acid combine with HCN to make H2CN+.
C HCN dissociates to make more CN− ions.
D the hydrogen ions in the acid prevent dissociation of the HCN.

(Total for Question 10 = 1 mark)

11 When 0.1 mol of hydrogen and 0.1 mol of iodine were allowed to react according to
the equation
H2(g) + I2(g)  2HI(g)
30% of the hydrogen was found to have been converted at equilibrium.
The number of moles of each gas present at equilibrium is

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Hydrogen Iodine Hydrogen iodide
A 0.03 0.03 0.07
B 0.03 0.03 0.14
C 0.07 0.07 0.03
D 0.07 0.07 0.06

(Total for Question 11 = 1 mark)

12 Which compound can show both geometric and optical isomerism?

A (CH3)2C CHCH(CH3)CH2CH3
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C (CH3)2C C(CH2CH3)2
D CH3CH2CH CHCH2CH(CH3)2

(Total for Question 12 = 1 mark)

6
*P54560A0628*
13 Which set of reagents is not suitable for the step indicated?

OH
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Step 1 Step 2
CH3COCH3 CH3 C CN CH2 C CN
CH3 CH3

Step 3

Step 4
CH2 C COOCH3 CH2 C COOH

CH3 CH3

A Step 1: HCN and KCN

B Step 2: hot ethanolic KOH
C Step 3: warm aqueous H2SO4
D Step 4: CH3OH with an acid catalyst
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(Total for Question 13 = 1 mark)

14 The molecule shown has three functional groups labelled x, y and z.

x z
Br O

Which of the functional groups can undergo nucleophilic attack?

A x, y and z
B x and z only
C x only
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D z only

(Total for Question 14 = 1 mark)

7
*P54560A0728* Turn over
15 What is the formula of the pale yellow solid formed when propanone reacts with
iodine in the presence of sodium hydroxide?

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A NaI
B CH3COCH2I
C CH3I
D CHI3

(Total for Question 15 = 1 mark)

16 Butanone can be distinguished from butanoic acid by the addition of

A Fehling’s solution and warming.
B Tollens’ reagent and warming.
C 2,4-dinitrophenylhydrazine solution.
D acidified potassium dichromate(VI) solution and refluxing.

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(Total for Question 16 = 1 mark)

17 Which could be used to make CH3CONHCH3?

A CH3COOCH3 and NH3
B CH3CONH2 and CH3NH2
C CH3COO−Na+ and CH3NH2
D CH3COCl and CH3NH2

(Total for Question 17 = 1 mark)

18 Which reaction may be used to make a carboxylic acid in a single step?

A Hydrolysis of an ester with hydrochloric acid. DO NOT WRITE IN THIS AREA

B Hydrolysis of an ester with sodium hydroxide.

C Reaction of acidified potassium manganate(VII) with an alkene.
D Reaction of an acyl chloride with ammonia.

(Total for Question 18 = 1 mark)

8
*P54560A0828*
19 The mass spectrum of ethanoyl chloride would not be expected to have a peak at the
m / e value of
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A 35.5
B 37
C 43
D 78

(Total for Question 19 = 1 mark)

20 A ketone which would not be expected to have a peak in its mass spectrum at m / e = 57 is
A butanone, CH3CH2COCH3
B 3-methylbutanone, (CH3)2CHCOCH3
C pentan-3-one, CH3CH2COCH2CH3
D hexan-3-one, CH3CH2CH2COCH2CH3
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(Total for Question 20 = 1 mark)

TOTAL FOR SECTION A = 20 MARKS

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9
*P54560A0928* Turn over
SECTION B

Answer ALL the questions. Write your answers in the spaces provided.

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21 Methanol has been proposed as a carbon-neutral fuel because it can be synthesised
from carbon dioxide, as shown in the equation
CO2(g) + 3H2(g) → CH3OH(g) + H2O(g)
(a) Standard enthalpy change of formation and standard molar entropy data for the
reactants and products are shown in the table.

CO2(g) H2(g) CH3OH(g) H2O(g)

ΔH fd / kJ mol−1 −394 0 −201 −242
d
S / J K–1 mol−1 214 131 238 189

(i) Calculate the standard enthalpy change for this reaction.

(2)

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(ii) Calculate the standard entropy change in the system, ΔSsystem , for this reaction.
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10
*P54560A01028*
(iii) Calculate the total entropy change, ΔStotal , for this reaction at 298K.
(3)
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(iv) Calculate the highest temperature at which the reaction is feasible.

(2)
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(v) State why the industrial process is carried out at a higher temperature than
you have calculated.
(1)

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11
*P54560A01128* Turn over
(b) (i) Write the equation for the complete combustion of methanol in the gas phase.
State symbols are not required.
(1)

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*(ii) Suggest why this combustion reaction in the gas phase is likely to be
thermodynamically feasible at all temperatures.
Calculations are not required.
(3)

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. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

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(c) Give two reasons why methanol, synthesised from carbon dioxide and hydrogen,
may not be a completely carbon-neutral fuel.
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. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(Total for Question 21 = 16 marks)

12
*P54560A01228*
22 This question is about three colourless liquids butanal, pentane and propenoic acid.
The bottles have lost their labels.
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(a) Propenoic acid is the simplest carboxylic acid containing a carbon to carbon
double bond.
(i) Draw the displayed formula of propenoic acid showing all the bonds.
(1)

(ii) Propenoic acid reacts with methanol at a temperature of 100 °C in the

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presence of an acid catalyst.

Name the product of this reaction and draw its skeletal formula.
(2)

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(iii) Under appropriate conditions, propenoic acid will react with

lithium tetrahydridoaluminate(III) (LiAlH4).
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Identify the conditions necessary for this reaction and give the structural formula
of the expected product.
(2)

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13
*P54560A01328* Turn over
(iv) The polymerisation of propenoic acid forms poly(propenoic acid), which is
used in the manufacture of superabsorbents.

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Draw the structure of poly(propenoic acid) showing two repeat units.
(1)

(b) The three liquids can be identified by their boiling temperatures.

(i) Complete the table with the boiling temperatures of butanal and pentane in °C and
the number of electrons in propenoic acid. Use the Data Booklet where necessary.
(2)

butanal pentane propenoic acid

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Boiling temperature / °C 141

Number of electrons 40 42

*(ii) Explain the differences in boiling temperature of these three compounds

using the information in the table and their structures.
A detailed explanation of the forces involved is not required.
(3)

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. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

14
*P54560A01428*
(c) Chemical tests can also be used to identify two of the liquids, and hence, by
elimination, the third.
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Give two chemical tests and the expected positive results.

The use of indicators will not be accepted as a chemical test.
(4)

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. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

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15
*P54560A01528* Turn over
(d) The three liquids can also be identified using infrared spectroscopy.
(i) Spectrum A contains very few peaks.

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Identify which of the three liquids gives this spectrum and explain why it has
fewer peaks than the other spectra.
(2)
0.8

0.6
Relative
transmittance
0.4

0.2

3000 2000 1000

–1
Wavenumber / cm
Spectrum A

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16
*P54560A01628*
(ii) Spectra B and C are the infrared spectra of the other two liquids.
Using information from the Data Booklet, identify the bonds responsible for
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the peaks labelled P, Q and R.

Hence state which spectrum is given by which liquid.
(3)

Spectrum B
0.8

Relative 0.6
transmittance
P
0.4

0.2 Q

3000 2000 1000

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–1
Wavenumber / cm

Spectrum C

0.8

0.6
Relative
transmittance
0.4 R

0.2

3000 2000 1000

–1
Wavenumber / cm
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P .. . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

Q . . . . . ...................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

R . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

Spectrum B . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................................... . . . . . . . . . . . . . . . . . . . .

Spectrum C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(Total for Question 22 = 20 marks)

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*P54560A01728* Turn over
23 Compound X can be formed by a dimerisation reaction where two molecules of
ethanal link together, as shown in the equation.

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2CH3CHO → CH3CH(OH)CH2CHO
Compound X
(a) Give the name of compound X.
(1)

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(b) The following three-step mechanism has been suggested for this reaction.
Steps 2 and 3 of this mechanism have some similarities to the reaction of aldehydes
with hydrogen cyanide in the presence of potassium cyanide.

Step 1

: OH–

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H O H O
−
H C C :C C + H2O

H H H H

Step 2
−
:

H O H O H O H O
H C C : C− C H C C C C

H H H H H H H H

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O
H H
H
−
:

H O H O H O H O
H C C C C H C C C C + :OH–

H H H H H H H H

18
*P54560A01828*
(i) Deduce the role of ethanal in Step 1.
(1)
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(ii) Complete Step 2 of the mechanism showing the relevant curly arrows.
(2)

Step 2
−

:
H O H O H O H O
H C C : C− C H C C C C

H H H H H H H H

(iii) Deduce the type and mechanism of the overall reaction.

(2)
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(iv) State the overall role of the hydroxide ion, OH–, in the suggested mechanism.
Justify your answer.
(2)

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19
*P54560A01928* Turn over
(v) Explain why the sample of X produced by the reaction in (b) does not rotate
the plane of plane-polarised light.
(2)

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rate = k[CH3CHO][OH–]
When the concentration of ethanal was 0.20 mol dm−3 and the concentration of

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sodium hydroxide was 0.040 mol dm−3, the rate of the reaction at 298 K was
8.8 × 10−3 mol dm−3 s−1.
(i) Calculate a value for the rate constant at this temperature.
Include units in your answer.
(2)

(ii) Give a reason why the rate equation suggests that Step 1 is the
rate-determining step for this reaction.
(1)
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(Total for Question 23 = 13 marks)

TOTAL FOR SECTION B = 49 MARKS

20
*P54560A02028*
SECTION C

Answer ALL the questions. Write your answers in the spaces provided.
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24 Ammonia is manufactured from nitrogen and hydrogen.

N2(g) + 3H2(g)  2NH3(g)

*(a) (i) In an experiment, 1 mol of nitrogen and 3 mol of hydrogen were placed in a
sealed vessel.
At a temperature of 450 K and a pressure of 2 atm, the system reached
equilibrium when 20% of the nitrogen had been converted into ammonia.
Calculate the value of the equilibrium constant Kp for this reaction at 450 K,
giving units in your answer.
(6)
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21
*P54560A02128* Turn over
(ii) Give the equation that relates Kp to ΔStotal and use your equation and your
answer to (a)(i) to calculate the total entropy change for the reaction at 450 K.

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[R = 8.31 J mol−1 K−1]
(2)

(b) Ammonia is a weak base which reacts with hydrochloric acid according to the
equation
NH3(aq) + HCl(aq) → NH4Cl(aq)
25.0 cm3 of aqueous ammonia with a concentration of 1.00 mol dm−3 was placed

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in a conical flask.
It was titrated with hydrochloric acid with a concentration of 0.625 mol dm−3.
(i) Calculate the volume of the acid required to react exactly with the aqueous
ammonia.
(2)

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22
*P54560A02228*
(ii) Aqueous ammonium chloride is acidic.
Write an ionic equation to show the acidic behaviour of the ammonium ion.
State symbols are not required.
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(1)

(iii) Write an expression for Ka for this dissociation.

(1)
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(iv) When all of the ammonia has just reacted with hydrochloric acid the
concentration of the ammonium chloride solution is 0.385 mol dm–3.
Calculate the pH of this solution.
[Ka = 5.6 × 10–10 mol dm–3]
(3)
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23
*P54560A02328* Turn over
(v) Using your answers to (b)(i) and (b)(iv), draw the titration curve showing the
change in pH when 50.0 cm3 of 0.625 mol dm−3 hydrochloric acid solution is
added to 25.0 cm3 of 1.00 mol dm−3 ammonia solution.

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The pH of 1.00 mol dm−3 ammonia solution is 11.6.
(4)

14 –

13 –

12 –

11 –

10 –

9–

8–

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7–
pH
6–

5–

4–

3–

2–

1–

0–
–

0 5 10 15 20 25 30 35 40 45 50
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Volume of HCI (aq) / cm3

24
*P54560A02428*
(vi) Explain, by referring to the Data Booklet, whether or not thymol blue (base)
would be a suitable indicator for this titration.
(2)
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. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(Total for Question 24 = 21 marks)

TOTAL FOR SECTION C = 21 MARKS

TOTAL FOR PAPER = 90 MARKS
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25
*P54560A02528*
Please check the examination details below before entering your candidate information
Candidate surname Other names

Centre Number Candidate Number

Pearson Edexcel
International
Advanced Level

Tuesday 4 June 2019

Afternoon (Time: 1 hour 40 minutes) Paper Reference WCH04/01

Chemistry
Advanced
Unit 4: General Principles of Chemistry I – Rates,
Equilibria and Further Organic Chemistry
(including synoptic assessment)
Candidates must have: Scientific calculator Total Marks
Data Booklet

Instructions
• Use black ink or black ball-point pen.
• centre
Fill in the boxes at the top of this page with your name,
number and candidate number.
• Answer all questions.
• Answer the questions in the spaces provided
– there may be more space than you need.

Information
• The total mark for this paper is 90.
• The marks for each question are shown in brackets
– use this as a guide as to how much time to spend on each question.
• written
Questions labelled with an asterisk (*) are ones where the quality of your
communication will be assessed
– you should take particular care with your spelling, punctuation and grammar, as
well as the clarity of expression, on these questions.
• A Periodic Table is printed on the back cover of this paper.

Advice
• Read each question carefully before you start to answer it.
• Show all your working in calculations and give units where appropriate.
• Check your answers if you have time at the end.
Turn over

P56131A
©2019 Pearson Education Ltd.

2/1/1/1/1/
*P56131A0128*
SECTION A

Answer ALL the questions in this section. You should aim to spend no more than 20 minutes on

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this section. For each question, select one answer from A to D and put a cross in the box .
If you change your mind, put a line through the box and then mark your new answer with a
cross .

1 The rate equation for the reaction of a bromoalkane, RBr, with hydroxide ions is

rate = k[RBr]

The bromoalkane that is hydrolysed according to this rate equation is most likely to be
A 1-bromohexane.
B 1-bromo-2-methylpentane.
C 2-bromo-2-methylpentane.
D 2-bromo-3-methylpentane.

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(Total for Question 1 = 1 mark)

2 Which method is most suitable for comparing the rate of hydrolysis of a primary iodoalkane
and a tertiary iodoalkane in aqueous silver nitrate?
A Measuring the increase in pH.
B Measuring the change in mass.
C Measuring the time to form a precipitate.
D Taking samples followed by titrating with sodium thiosulfate.

(Total for Question 2 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

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2
*P56131A0228*
3 The chemical equation and the rate equation for the reaction of iodine with excess propanone
in the presence of an acid catalyst are shown.
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I2 + CH3COCH3 o CH3COCH2I + HI
rate = k[CH3COCH3][H+]

Which of the following sketch graphs is correct for this reaction?

A rate

[I2]

B rate
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[I2]

C [I2]

time

D [I2]

time
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(Total for Question 3 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

3
*P56131A0328* Turn over
4 The Arrhenius equation is

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Ea 1
ln k = − × + constant
R T

The activation energy, E a , is determined from the gradient of the graph shown.

x axis

Ea
gradient = −
R
y axis

The axes on the graph are

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x axis y axis
1
A ln k
T
1
B ln k −
T
1
C ln k
T
1
D − ln k
T

(Total for Question 4 = 1 mark)

5 What are the signs of the entropy changes at 273 K when water freezes?

H2O(l) o H2O(s)
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ǻSsystem ǻSsurroundings
A negative positive
B positive negative
C negative negative
D positive positive

(Total for Question 5 = 1 mark)

4
*P56131A0428*
6 Which are the Brønsted-Lowry acids in the following equilibrium?

CH3COOH + C2H5COOH U CH3COO− + C2H5COOH2+

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A CH3COOH and C2H5COOH

B CH3COOH and C2H5COOH2+
C C2H5COOH and CH3COO−
D CH3COO− and C2H5COOH2+

(Total for Question 6 = 1 mark)

7 In a titration of hydrochloric acid with aqueous ammonia, which indicator would be

most suitable to detect the end-point?
Refer to your Data Booklet.
A Azolitmin (litmus)
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B Bromocresol purple
C Phenolphthalein
D Alizarin yellow R

(Total for Question 7 = 1 mark)

8 A solution of hydrochloric acid has pH = 2.

The solution is diluted to one tenth of its original concentration.
What is the pH of the diluted solution?
A 0.70
B 1.0
C 2.7
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D 3.0

(Total for Question 8 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

5
*P56131A0528* Turn over
9 Equal amounts of three compounds were placed in separate beakers and the same
volume of water was added to each.

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Compound 1 CH3COOH
Compound 2 CH3COCl
Compound 3 CH3COONa
Which shows the order of increasing pH in the mixtures?
A CH3COOH CH3COCl CH3COONa
B CH3COCl CH3COOH CH3COONa
C CH3COONa CH3COOH CH3COCl
D CH3COCl CH3COONa CH3COOH

(Total for Question 9 = 1 mark)

10 What are the units of Kc for the following equilibrium?

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Cu(s) + 2Ag+(aq) U Cu2+(aq) + 2Ag(s)

A mol dm−3
B dm3 mol−1
C mol2 dm−6
D no units

(Total for Question 10 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

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6
*P56131A0628*
11 The graph shows the percentage yield of a product in a gaseous equilibrium under
different conditions.
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80
70 350 °C
60
50
% yield of 450 °C
product at 40
equilibrium
30
550 °C
20
10
0
0 100 200 300 400
pressure / atm
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The forward reaction in the equilibrium is

A exothermic with the number of moles of gas decreasing.
B exothermic with the number of moles of gas increasing.
C endothermic with the number of moles of gas decreasing.
D endothermic with the number of moles of gas increasing.

(Total for Question 11 = 1 mark)

12 Which is the correct expression for R ln K ?

A R ln K = ǻSsystem − ǻH/T

B R ln K = ǻSsystem + ǻH/T

C R ln K = ǻSsystem − TǻH
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D R ln K = ǻSsystem + TǻH

(Total for Question 12 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

7
*P56131A0728* Turn over
13 Which compound is most soluble in water?
A C4H9Cl

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B C4H9Br
C C3H7COOH
D CH3COOC2H5

(Total for Question 13 = 1 mark)

14 Which compound reacts with phosphorus(V) chloride to form ethanoyl chloride?

A CH3CHO
B CH3CH2OH
C CH3COCH3
D CH3COOH

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(Total for Question 14 = 1 mark)

15 Which two compounds react together to make the compound shown?

A Ethanoyl chloride and ethylamine

B Ethanoyl chloride and propylamine
C Propanoyl chloride and ethylamine
D Propanoyl chloride and propylamine

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Use this space for any rough working. Anything you write in this space will gain no credit.

8
*P56131A0828*
16 The repeat unit of a polymer is shown.
O O
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C (CH2)2 C O (CH2)2 O

Which monomers react to make this polymer?

A HOOC(CH2)2COOH and Cl(CH2)2Cl
B ClOC(CH2)2COCl and HO(CH2)2OH
C ClOC(CH2)2COCl and HOOC(CH2)2COOH
D HOOC(CH2)2COOCH3 and ClOC(CH2)2COCl

(Total for Question 16 = 1 mark)

17 The retention time in gas chromatography is the time it takes for a compound to pass
through the chromatography column.
A column is packed with a stationary phase that is polar.
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Which of the following will have the longest retention time in the column?
A hexane
B hex-1-ene
C pentane
D pentan-1-ol

(Total for Question 17 = 1 mark)

18 A compound has the structure

CH3(CH2)4CH2 CH2(CH2)6CH2OH
C C
H H
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The systematic name of the compound is

A E-hexadec-7-en-1-ol
B Z-hexadec-7-en-1-ol
C E-hexadec-9-en-1-ol
D Z-hexadec-9-en-1-ol

(Total for Question 18 = 1 mark)

9
*P56131A0928* Turn over
19 Fats, such as the one shown, can be converted into fuels for biodiesel by transesterification.

CH2OOCC17H33

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CHOOCC17H33
CH2OOCC17H33

Which compound is used as a fuel, following the transesterification of this fat with methanol?

A C17H33COOCH3

B C17H33COOH

C CH2OOCCH3
CHOOCCH3
CH2OOCCH3

D CH2OH

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CHOH
CH2OH
(Total for Question 19 = 1 mark)

20 The type of radiation used in nmr spectroscopy is

A infrared.
B microwave.
C radio waves.
D ultraviolet.

(Total for Question 20 = 1 mark)

TOTAL FOR SECTION A = 20 MARKS

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10
*P56131A01028*
SECTION B

Answer ALL the questions. Write your answers in the spaces provided.

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21 When nitrogen(II) oxide, NO, reacts with hydrogen at high temperatures, the products
are nitrogen and water.
(a) Write an equation for this reaction. State symbols are not required.
(1)

(b) The table shows the results of a series of experiments to measure the rate of this reaction.

Experiment Initial concentration / mol dm−3

Initial rate / mol dm−3 s−1
number [NO(g)] [H2(g)]

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1 0.0020 0.020 5.5 × 10−3
2 0.0040 0.040 4.4 × 10−2
3 0.0080 0.020 8.8 × 10−2

(i) Deduce the order of reaction with respect to nitrogen(II) oxide and to hydrogen.
Justify your answers by referring to data from the table.
(3)

Order with respect to NO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...............................................

Order with respect to H2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .............................................

Justification ........... .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .............................................. .............................................................................................. . . . . . . . . . . . . . . . . . . . . . .

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. . . . . . . . . . . .................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............ ................................................................................................................................ . . . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . .................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............ ................................................................................................................................ . . . . . . . . . . . . . . . . . . . . . .

12
*P56131A01228*
(ii) Write the rate equation for the reaction.
(1)
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(iii) Calculate the value of the rate constant and give its units.
(2)

(c) There is more than one step in the reaction mechanism.

(i) Suggest why the reaction is unlikely to take place in a single step.
(1)
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. . . . . . . . . . . . .................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............ ............................................................................................................................... . . . . . . . . . . . . . . . . . . . . . . .

(ii) The first step of a three-step reaction mechanism is shown.

2NO(g) o N2O2(g)

The second step of the mechanism is the rate determining step.

Suggest an equation for the rate determining step.
Justify your suggestion.
(2)
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. . . . . . . . . . . . .................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............ ............................................................................................................................... . . . . . . . . . . . . . . . . . . . . . . .

(Total for Question 21 = 10 marks)

13
*P56131A01328* Turn over
22 Propanoic acid is a weak acid with Ka = 1.30 × 10−5 mol dm−3.
(a) (i) Write the expression for the acid dissociation constant, Ka , of propanoic acid.

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(1)

(ii) Calculate the pH of a solution of propanoic acid with a concentration of

0.120 mol dm−3.
(3)

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(b) 25.00 cm3 of propanoic acid, with a concentration of 0.120 mol dm−3, was pipetted
into a conical flask.
This solution was titrated with sodium hydroxide of concentration 0.150 mol dm−3.

CH3CH2COOH + NaOH o CH3CH2COONa + H2O

(i) Use the value of Ka to calculate the pH of the mixture in the flask when
enough sodium hydroxide has been added to react with half of the acid.
(2)
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14
*P56131A01428*
*(ii) In the region where the acid is half neutralised, the pH of the titration mixture
changes more gradually than it does when the end-point is approached.
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Explain the reason for this gradual change in pH.

(3)

. . . . . . . . . . . . .................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............ ............................................................................................................................... . . . . . . . . . . . . . . . . . . . . . . .

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. . . . . . . . . . . . .................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............ ............................................................................................................................... . . . . . . . . . . . . . . . . . . . . . . .

(iii) Calculate the minimum volume of sodium hydroxide required to react with
all of the propanoic acid.
(2)

(iv) Calculate the pH when 40 cm3 of sodium hydroxide (an excess) was added.
(3)
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15
*P56131A01528* Turn over
(c) In another titration, a solution of aqueous ammonia with a concentration of
0.120 mol dm−3 was added to 25.00 cm3 propanoic acid with a concentration of
0.120 mol dm−3.

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(i) Sketch the shape of the titration curve on the grid.
(2)

10.5

pH
7

3.5

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0 10 20 30 40

volume of ammonia / cm3

(ii) Explain why an indicator cannot be used to determine the end-point of this reaction.
(1)

. . . . . . . . . . . . .................................. .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............ ............................................................................................................................... . . . . . . . . . . . . . . . . . . . . . . .

(Total for Question 22 = 17 marks)

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16
*P56131A01628*
23 This question is about some reactions involving ethanal, CH3CHO.

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CH3CHO

Reaction A Reaction B Reaction C

I2 + NaOH HCN + KCN

CH3CH2OH Two organic Product C

products

(a) Ethanal is a carbonyl compound.

Describe the test for a carbonyl compound and give the result.
(2)

. . . . . . . . . . . . .................................. .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............ ............................................................................................................................... . . . . . . . . . . . . . . . . . . . . . . .

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. . . . . . . . . . . . .................................. .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............ ............................................................................................................................... . . . . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . .................................. .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............ ............................................................................................................................... . . . . . . . . . . . . . . . . . . . . . . .

(b) Identify, by name or formula, the reagent needed to carry out Reaction A.
(1)

. . . . . . . . . . . . .................................. .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............ ............................................................................................................................... . . . . . . . . . . . . . . . . . . . . . . .

(c) (i) Identify the two organic products of Reaction B.

(2)

. . . . . . . . . . . . .................................. .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............ ............................................................................................................................... . . . . . . . . . . . . . . . . . . . . . . .

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. . . . . . . . . . . . .................................. .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............ ............................................................................................................................... . . . . . . . . . . . . . . . . . . . . . . .

(ii) State what you would see when Reaction B is carried out.
(1)

. . . . . . . . . . . . .................................. .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............ ............................................................................................................................... . . . . . . . . . . . . . . . . . . . . . . .

18
*P56131A01828*
(d) (i) Name the reaction type and mechanism that occurs in Reaction C.
(1)
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. . . . . . . . . . . . .................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............ ............................................................................................................................... . . . . . . . . . . . . . . . . . . . . . . .

(ii) Draw the mechanism for Reaction C.

Include curly arrows, and all the relevant dipoles and lone pairs.
(4)
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(iii) The organic product of Reaction C is a racemic mixture.

State the meaning of ‘racemic mixture’.
(1)

. . . . . . . . . . . . .................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............ ............................................................................................................................... . . . . . . . . . . . . . . . . . . . . . . .

*(iv) By referring to the mechanism of Reaction C, explain why a racemic mixture

forms in this reaction.
(2)
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. . . . . . . . . . . . .................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............ ............................................................................................................................... . . . . . . . . . . . . . . . . . . . . . . .

(Total for Question 23 = 14 marks)

19
*P56131A01928* Turn over
24 This question is about compounds of iodine.
(a) Potassium iodate(V) can be decomposed by heating.

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KIO3(s) o KI(s) + 1½O2(g)

(i) Use data from your Data Booklet to calculate the enthalpy change for this reaction.
(2)

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(ii) Calculate the standard entropy change of the system, ǻS system .
[The standard molar entropy of ½O2(g) is 102.5 J mol−1 K−1]
(2)
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20
*P56131A02028*
(iii) Use your answers to (a)(i) and (a)(ii) to calculate the minimum temperature for
this reaction to be spontaneous.
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Show your working clearly.

(2)
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(iv) Explain why some reactions which are thermodynamically favourable do not
occur spontaneously.
(1)

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(b) Some data about potassium iodide and its ions are shown.
Enthalpy change of solution of KI = +20.3 kJ mol−1

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Ion Enthalpy change of hydration / kJ mol−1
K+(g) −320
I−(g) –308

(i) Use these data to calculate the lattice energy of potassium iodide.
(2)

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*(ii) Explain why the lattice energy of sodium iodide is more exothermic than that
of potassium iodide.
(2)

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(Total for Question 24 = 11 marks)

TOTAL FOR SECTION B = 52 MARKS

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*P56131A02228*
SECTION C

Answer ALL the questions. Write your answers in the spaces provided.
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25 This question is about the chemistry of methanol.

(a) Methanol can be synthesised by the reaction of carbon monoxide with hydrogen.

CO(g) + 2H2(g) U CH3OH(g)

A mixture of 18.5 mol of carbon monoxide and 13.5 mol of hydrogen was allowed
to reach equilibrium at 550 K and 60 atm pressure.
At equilibrium the mixture contained 5.5 mol of methanol.
(i) Write the expression for the equilibrium constant in terms of pressure, Kp , for
this reaction.
(1)
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(ii) Calculate the number of mol of carbon monoxide and hydrogen remaining
at equilibrium.
Hence calculate the value of Kp at 550 K.
Give your answer to three significant figures and include the units.
(5)
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(iii) The value of Kp is greater when the reaction is carried out at a lower temperature.
Use this information to deduce the sign of ǻSsurroundings for the forward reaction.

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Give your reasoning.
(2)

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(b) An organic compound, P, has the molecular formula C5H8O3 .

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A molecule of P has a carbon chain that is not branched, and contains
two different functional groups.
(i) P reacts with sodium carbonate solution, forming bubbles of a colourless gas.
There is no colour change when P is warmed with a mixture of
potassium dichromate(VI) and sulfuric acid.
Use all the information provided to identify, by name or formulae, the
two functional groups present in P.
(2)

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(ii) The mass spectrum of P has a strong peak at m / e = 43.

Suggest the structural formula of the fragment causing this peak.
(1)

24
*P56131A02428*
*(iii) When P is heated with methanol, in the presence of dilute sulfuric acid, a
pleasant smelling compound, Q, is formed.
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The high resolution proton nmr spectrum of Q is shown.

The numbers show the relative areas of the peaks.

3 3

2 2
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4.4 4.0 3.6 3.2 2.8 2.4 2.0 1.6

į / ppm

Draw the structure of Q. Justify your answer by considering the relative areas
of the four peaks, and their splitting patterns.
(4)

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(iv) Write an equation using structural formulae to show the reaction of P with
methanol in the presence of dilute sulfuric acid to form Q.
(2)

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(v) The reaction of P with methanol does not give a 100% yield of Q because of
the equilibrium position which is reached.
Suggest the formula of a compound which would react with methanol to
form Q in a reaction which is not reversible.
(1)

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(Total for Question 25 = 18 marks)

TOTAL FOR SECTION C = 18 MARKS

TOTAL FOR PAPER = 90 MARKS

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26
*P56131A02628*
Please check the examination details below before entering your candidate information
Candidate surname Other names

Centre Number Candidate Number

Pearson Edexcel
International
Advanced Level

Tuesday 29 October 2019

Morning (Time: 1 hour 40 minutes) Paper Reference WCH04/01

Chemistry
Advanced
Unit 4: General Principles of Chemistry I – Rates,
Equilibria and Further Organic Chemistry
(including synoptic assessment)
Candidates must have: Scientific calculator Total Marks
Data Booklet

P58273A
©2019 Pearson Education Ltd.

1/1/1/1/1/
*P58273A0128*
SECTION A

Answer ALL the questions in this section. You should aim to spend no more than 20 minutes on

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this section. For each question, select one answer from A to D and put a cross in the box .
If you change your mind, put a line through the box and then mark your new answer with
a cross .

1 The diagram shows four graphs in which a quantity Y has been plotted against a quantity X.

Graph 3

Graph 1

Y Graph 2

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Graph 4

(a) Which graph would be obtained when X is reactant concentration and Y is rate of
reaction for a first order reaction?
(1)
A Graph 1 DO NOT WRITE IN THIS AREA

B Graph 2
C Graph 3
D Graph 4

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(b) Which graph would be obtained when X is time and Y is product concentration
for a zero order reaction?
(1)
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A Graph 1
B Graph 2
C Graph 3
D Graph 4

(c) Which graph would be obtained when X is temperature and Y is rate of reaction?
(1)
A Graph 1
B Graph 2
C Graph 3
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D Graph 4

(Total for Question 1 = 3 marks)

2 Hydrogen iodide may be formed from the reaction of hydrogen with iodine.
The transition state is the same in both directions of the equilibrium.

H2(g) + I2(g) U 2HI(g) ¨Hreaction = +53 kJ mol−1

The activation energy for the forward reaction is 173 kJ mol−1.

The activation energy, in kJ mol−1, for the reverse reaction is

A −53
B +120
C +173
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D +226

(Total for Question 2 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

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3 Sodium chloride dissolves in water.

NaCl(s) + aq o Na+(aq) + Cl−(aq) ¨H = +3.9 kJ mol−1

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The best explanation for the fact that sodium chloride dissolves in water
spontaneously is that the process has a
A low activation energy.
B positive enthalpy change.
C positive entropy change of the surroundings, ǻS surroundings .
D positive entropy change of the system, ǻS system .

(Total for Question 3 = 1 mark)

4 Butane has a higher standard molar entropy than 2-methylpropane at 298 K and
1 atm, when both compounds are gases.
The best explanation for this fact is that butane has

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A a higher boiling temperature.
B a more positive standard molar enthalpy change of formation.
C fewer ways of distributing energy quanta.
D more ways of distributing energy quanta.

(Total for Question 4 = 1 mark)

5 Standard molar entropy is zero for

A perfect crystals at absolute zero (0 K).
B ideal gases under standard conditions (298 K and 1 atm).
C elements in their most stable states under standard conditions.
D graphite, containing only the carbon-12 isotope, under standard conditions.
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(Total for Question 5 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

4
*P58273A0428*
6 Ethanol is manufactured by the hydration of ethene at 500 K and 60 atm.

C2H4(g) + H2O(g) U C2H5OH(g) ¨H = −53.8 kJ mol−1

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(a) How does increasing the temperature to 550 K affect the activation energy and
equilibrium constant of this reaction?
(1)
Activation energy Equilibrium constant
A increases increases
B decreases decreases
C unchanged increases
D unchanged decreases

(b) How does increasing the pressure to 70 atm affect the rate of the reaction and the
equilibrium yield of ethanol?
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(1)

Rate Equilibrium yield

A increases increases
B increases decreases
C decreases increases
D decreases decreases

(c) The equilibrium constant for the hydration of ethene is given by the expression
(1)
p(C2H5OH)
A Kp =
p(C2H4 ) × p(H2O)
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p(C2H4 ) × p(H2O)
B Kp =
p(C2H5OH)

p(C2H5OH)
C Kp =
p(C2H4 )

p(C2H4 )
D Kp =
p(C2H5OH)
(Total for Question 6 = 3 marks)

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7 The Arrhenius theory defined acids as substances that
A have a sour taste.

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B react with alkalis to form a salt and water only.
C produce an excess of hydrogen ions in solution.
D accept lone pairs of electrons.

(Total for Question 7 = 1 mark)

8 The dissociation constant of water, Kw , increases with increasing temperature.

Under standard conditions pure water is neutral and has a pH = 7.
What happens to the acidity and pH of pure water when the temperature is increased?

Effect of increasing temperature

Acidity of water pH

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A increases increases
B increases decreases
C remains neutral increases
D remains neutral decreases

(Total for Question 8 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

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6
*P58273A0628*
Join now:https://t.me/igcse_files

9 When urea dissolves in liquid ammonia, an acid-base equilibrium is set up.

NH2 NH−
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NH3 + O C U NH4+ + O C
NH2 NH2

Which species are the Brønsted-Lowry acids in this equilibrium?

Acid 1 Acid 2

A NH3 NH4+

NH2
B O C NH4+
NH2
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NH−
C NH3 O C
NH2

NH2 NH−
D O C O C
NH2 NH2

(Total for Question 9 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.
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10 Limonene is a major component of the oil found in citrus fruits.

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Limonene

Limonene will show

A geometric and optical isomerism.
B geometric isomerism only.
C optical isomerism only.

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D neither geometric nor optical isomerism.

(Total for Question 10 = 1 mark)

11 Ethanal has a much higher boiling temperature and is much more soluble in water
than propane.
These differences in properties are best explained by the fact that, in addition to
London forces, ethanal forms

A hydrogen bonds in the liquid state and in aqueous solution.

B permanent dipole-dipole forces in the liquid state and hydrogen bonds in
aqueous solution.
C hydrogen bonds in the liquid state and permanent dipole-dipole forces in
aqueous solution.
D permanent dipole-dipole forces in the liquid state and in aqueous solution.
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(Total for Question 11 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

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12 Butanone may be converted into propanoic acid by
A refluxing with acidified potassium dichromate(VI).
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B warming with iodine and sodium hydroxide followed by acidifying with

sulfuric acid.
C heating with hydrogen gas in the presence of a nickel catalyst.
D heating with hydrogen cyanide and potassium cyanide followed by refluxing
with sulfuric acid.

(Total for Question 12 = 1 mark)

13 The structure of 4-hydroxybutanoic acid is

HO
O
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(a) The presence of the alcohol functional group and the carboxylic acid functional
group may be confirmed by reacting under suitable conditions
(1)
A a sample of the compound with phosphorus(V) chloride.
B a sample of the compound with sodium hydrogencarbonate solution.
C separate samples of the compound with ethanol and with ethanoic acid.
D separate samples of the compound with acidified potassium dichromate(VI)
and with 2,4-dinitrophenylhydrazine.

(b) The high resolution proton nmr spectrum of 4-hydroxybutanoic acid will have
(1)
A two singlets, two triplets and one quintet.
B two singlets and three triplets.
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C one singlet, two triplets, one quartet and one quintet.

D two singlets, two triplets, one quartet and one quintet.

(Total for Question 13 = 2 marks)

Use this space for any rough working. Anything you write in this space will gain no credit.

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14 Transesterification involves reactions in which
A alkyl groups of alcohols replace alkyl groups of esters.

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B alkyl groups of carboxylic acids replace alkyl groups of esters.
C trans isomers of long-chain esters are formed.
D diacyl chlorides and diols combine to form polyesters.

(Total for Question 14 = 1 mark)

15 The main characteristic of HPLC is the use of

A polymeric liquids.
B high pressures.
C helium-cadmium lasers.
D long columns.

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(Total for Question 15 = 1 mark)

TOTAL FOR SECTION A = 20 MARKS

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10
*P58273A01028*
SECTION B

Answer ALL the questions. Write your answers in the spaces provided.

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16 Ammonium nitrate, NH4NO3 , is used as a fertiliser.
(a) When heated gently at 160 °C , ammonium nitrate decomposes.

NH4NO3(s) o N2O(g) + 2H2O(g) ¨H = −36.0 kJ mol−1

(i) Predict the sign of the entropy change in the system, ǻS system .
Justify your answer.
(1)

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(ii) Calculate the entropy change in the system, ǻS system , for the decomposition of

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ammonium nitrate, using data from your Data Booklet.
Include a sign and units with your answer.
(3)

(iii) Calculate the entropy change in the surroundings, ǻS surroundings , for the
decomposition of ammonium nitrate at 160 °C.
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Include a sign and units with your answer.

(3)

12
*P58273A01228*
(iv) Use your answers to (a)(ii) and (a)(iii) to calculate the total entropy change,
ǻS total , for the decomposition of ammonium nitrate.
Give your answer to an appropriate number of significant figures and include
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a sign and units with your answer.

(2)

(b) When ammonium nitrate is heated rapidly, it decomposes as shown.

NH4NO3(s) o N2(g) + 2H2O(g) + ½O2(g) ¨H = −118.0 kJ mol−1

(i) The total entropy change, ǻStotal , for this decomposition of ammonium nitrate
is +555 J K−1 mol−1.
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Calculate the equilibrium constant for this decomposition.

Units are not required.
(2)

*(ii) Explain, in terms of entropy, how this equilibrium constant for the complete
decomposition of ammonium nitrate would be affected if the temperature
was increased. No calculation is required.
(2)
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(Total for Question 16 = 13 marks)

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17 The reaction of 2-bromobutane with aqueous alkali is a nucleophilic substitution.

C4H9Br + NaOH o C4H9OH + NaBr

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Depending on the conditions, the mechanism of this reaction may be SN1 or SN2.
(a) Experiments were carried out to determine the rate equation for a reaction of
2-bromobutane with aqueous sodium hydroxide.
In each experiment, the reactants were mixed and the concentration of
2-bromobutane was measured at various times as the reaction proceeded.
The initial rate of the reaction was determined using these data.
(i) Describe how the initial rate would be determined from the results of
one experiment.
(3)

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(ii) Give a reason why the concentration of sodium hydroxide used was very
much greater than the concentration of 2-bromobutane.
(1)
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*P58273A01428*
(b) The results of a set of experiments are shown.
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Experiment Initial [C4H9Br] / mol dm−3 Initial [NaOH] / mol dm−3 Initial rate / mol dm−3 s−1
1 0.020 1.0 1.5 × 10−5
2 0.030 1.0 2.3 × 10−5
3 0.040 2.0 5.9 × 10−5

(i) By referring to the data in the table, show that the reaction was first order
with respect to both C4H9Br and NaOH.
(2)

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(ii) Calculate the rate constant for the reaction.

Use the data from experiment 1 and include units with your answer.
(2)
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15
*P58273A01528* Turn over
(c) (i) State why the reaction of 2-bromobutane with aqueous sodium hydroxide
being second order indicates an SN2 mechanism.
(1)

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. . . . . . . . . . . . .................................. .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................... . . . . . . . . . . . . . . . . . . . . . .

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(ii) Draw the first step of the mechanism, showing the transition state in the
SN2 mechanism for the reaction of 2-bromobutane with aqueous sodium hydroxide.
Include curly arrows, and any relevant dipoles and lone pairs of electrons.
(3)

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16
*P58273A01628*
(d) 2-bromobutane and butan-2-ol are chiral molecules.
(i) State the meaning of the term chiral molecule.
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(1)

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*(ii) When a single enantiomer (optical isomer) of 2-bromobutane reacts with

aqueous alkali, the stereochemistry of the butan-2-ol formed depends on
whether the mechanism is SN1 or SN2.
Explain how the stereochemistry of the butan-2-ol differs with the
different mechanisms.
(4)
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(Total for Question 17 = 17 marks)

17
*P58273A01728* Turn over
18 Butanoic acid is found in milk, butter and cheese and its name comes from the
Latin word for butter. It has an unpleasant smell, which can be detected at very low
concentrations, whereas the esters of butanoic acid, such as methyl butanoate, have

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pleasant smells and tastes, and are added to food and perfumes.
(a) Some reactions of butanoic acid are shown.

Reaction 4 OH
OH
butanoic acid
Reaction 1
Reaction 3
Reaction 5
O

O O
Cl Reaction 2

O H
methyl butanoate butanal

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(i) Identify, by name or formula, the reagents and any essential conditions for
Reactions 1 to 4.
(5)

Reaction 1................. .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ . . . . . . . . . . . . . . . . . . . . .

Reaction 2................. .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ . . . . . . . . . . . . . . . . . . . . .

Reaction 3................. .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ . . . . . . . . . . . . . . . . . . . . .

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Reaction 4................. .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ . . . . . . . . . . . . . . . . . . . . .

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(ii) The reagents used in Reaction 5 are potassium dichromate(VI) and

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sulfuric acid.
State how this reaction must be carried out to ensure that the main product
is butanal.
(1)

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*P58273A01828*
(iii) Give one advantage and one disadvantage of preparing methyl butanoate
using Reactions 1 and 2 rather than Reaction 3.
(2)
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(iv) Suggest why butanal is not made from butanoic acid in a single step.
(1)

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(b) Give two ways in which the infrared spectra of butanoic acid and methyl butanoate
differ, other than in their fingerprint region.
Quote values from your Data Booklet for the wavenumber ranges of specific bonds.
(2)

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19
*P58273A01928* Turn over
(c) Butanoic acid can be detected by animals with a good sense of smell at
concentrations of 10 parts of butanoic acid vapour per billion (1 × 109) of air at
room temperature and pressure (r.t.p.).

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Calculate the minimum concentration, in mol dm−3, of butanoic acid that can be
detected by these animals.
(2)
[Molar volume of gases at r.t.p. = 24.0 dm3 mol−1]

(Total for Question 18 = 13 marks) DO NOT WRITE IN THIS AREA

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20
*P58273A02028*
19 Heating fructose with hydrochloric acid produced an aliphatic compound, G, which
has five carbon atoms in an unbranched chain.
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G gave an orange precipitate with 2,4-dinitrophenylhydrazine but no reaction when

warmed with ammoniacal silver nitrate. Addition of G to sodium hydrogencarbonate
solution resulted in vigorous effervescence.
In the mass spectrum of G, the molecular ion peak was at m / e = 116.
Draw the three possible structures of G. Explain your reasoning.
(7)
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(Total for Question 19 = 7 marks)

TOTAL FOR SECTION B = 50 MARKS

21
*P58273A02128* Turn over
SECTION C

Answer ALL the questions. Write your answers in the spaces provided.

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20 Methanoic acid, HCOOH, is a weak acid that is present in the stings of ants and nettles.
It is used as a preservative and antibacterial agent in livestock feed.
(a) An aqueous solution of methanoic acid has a concentration of 30 g dm−3.
(i) Write the equation for the dissociation of methanoic acid in water.
State symbols are not required.
(1)

(ii) Write the expression for Ka for methanoic acid.

(1)

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(iii) Calculate the pH of a solution of methanoic acid with a concentration of 30 g dm−3.
[Ka of methanoic acid = 1.70 × 10−4 mol dm−3]
(4)

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22
*P58273A02228*
(iv) State two approximations used in the calculation of the pH in (a)(iii).
(2)
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(b) A solution which contains both methanoic acid and sodium methanoate acts as a buffer.
(i) State the meaning of the term buffer.
(2)

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*(ii) Explain how a solution which contains both methanoic acid and
sodium methanoate acts as a buffer.
(4)

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23
*P58273A02328* Turn over
(c) A buffer solution Q is prepared by dissolving 1.25 mol of methanoic acid and 1.50 mol
of sodium methanoate in distilled water and making up the solution to 1.00 dm3.

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(i) Calculate the pH of Q.
[Ka of methanoic acid = 1.70 × 10−4 mol dm−3]
(3)

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(ii) Calculate the pH of Q after the addition of 2.0 g of sodium hydroxide.
Assume that the volume of Q is unchanged at 1.00 dm3.
(3)

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(Total for Question 20 = 20 marks)

TOTAL FOR SECTION C = 20 MARKS

TOTAL FOR PAPER = 90 MARKS

24
*P58273A02428*
Please check the examination details below before entering your candidate information
Candidate surname Other names

Centre Number Candidate Number

Pearson Edexcel
International
Advanced Level

Monday 13 January 2020

Afternoon (Time: 1 hour 45 minutes) Paper Reference WCH14/01

Chemistry
International Advanced Level
Unit 4: Rates, Equilibria and Further Organic Chemistry
(including synoptic assessment)
Candidates must have: Scientific calculator Total Marks
Data Booklet
Ruler

Information
• The total mark for this paper is 90.
• The marks for each question are shown in brackets
– use this as a guide as to how much time to spend on each question.
• ability
In the question marked with an asterisk (*), marks will be awarded for your
to structure your answer logically, showing how the points that you make
are related or follow on from each other where appropriate.
• A Periodic Table is printed on the back cover of this paper.

Advice
• Read each question carefully before you start to answer it.
• Checkallyouryouranswers
Show working in calculations and include units where appropriate.
• if you have time at the end.

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P60472A
©2020 Pearson Education Ltd.

1/1/1/1/1/
*P60472A0132*
SECTION A

Answer ALL the questions in this section.

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You should aim to spend no more than 20 minutes on this section.

For each question, select one answer from A to D and put a cross in the box .
If you change your mind, put a line through the box and then mark your new answer
with a cross .

1 This question is about four organic compounds each with five carbon atoms but
different functional groups.

Compound Skeletal formula

Cl
1
O

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O
2

O
3

NH2
4
O

(a) Which of these, when mixed with water, produces the solution with the lowest pH?
(1)
A compound 1
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B compound 2
C compound 3
D compound 4

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*P60472A0232*
(b) Which of these reacts with ethylamine, CH3CH2NH2 , to form an N-substituted amide?
(1)
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A compound 1
B compound 2
C compound 3
D compound 4

(c) Which of these reacts with iodine and sodium hydroxide in solution to produce a
pale yellow precipitate?
(1)
A compound 1
B compound 2
C compound 3
D compound 4
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(Total for Question 1 = 3 marks)

2 Which of these molecules can rotate the plane of plane-polarised light?

A H2NCH2COOH
B HOCH2CH2COOH
C ClCH2C(CH3)(Cl)COOH
D H2NC(CH3)2COOH

(Total for Question 2 = 1 mark)

3 A polymer is prepared by the reaction between hexanedioyl dichloride and

hexane-1-6-diamine.
What type of polymerisation occurs?
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A addition
B condensation
C hydrolysis
D substitution

(Total for Question 3 = 1 mark)

*P60472A0332*
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4 The compound HOOCCH CHCOOH reacts with excess sodium hydroxide solution.
What is the organic product formed in the reaction?

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A NaOOCCH CHCOONa
B HOOCCH CHCOONa
C NaOOCC(OH)HC(OH)HCOONa
D NaOOCCH CHCHO

(Total for Question 4 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

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*P60472A0432*
5 Which diagram shows the mechanism for the second order reaction between
1-bromoethane and potassium hydroxide in aqueous solution?
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Diagram 1
H H H
H H H
H į+ H H
C C+ C
C Br į– C C
–•• OH
H H OH H
H H + Br– H

Diagram 2
H H H
H H H
H į+ H H
C C+ C
C Br į– C –
OH C
•• OH
H H H
H H H
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–
+ Br

Diagram 3
–
H ⎡ H ⎤ H
H –•• ⎢ H Br ⎥ H
H į+ OH
C ⎢H C ⎥ H C
C Br į–
⎢ C OH ⎥ C
OH
H ⎢ H ⎥ H
H ⎣ H ⎦ H + Br–

Diagram 4
H ⎡ H ⎤
– H
H H H
H į+ –••
⎢ Br ⎥
H
C OH ⎢H C ⎥ C
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C Br į–
⎢ C OH ⎥ C
OH
H ⎢ H ⎥ H
H ⎣ H ⎦ H + Br–

A Diagram 1
B Diagram 2
C Diagram 3
D Diagram 4

(Total for Question 5 = 1 mark)

*P60472A0532*
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6 Which of these reacts directly with ethanoic acid to form ethanoyl chloride?
A chlorine

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B chloroethane
C hydrogen chloride
D phosphorus(V) chloride

(Total for Question 6 = 1 mark)

7 Which of these changes has the largest increase in the entropy of the system?
A H2O(s) → H2O(l)
B Hg(l) → Hg(g)
C H2O(l) + HCl(g) → H3O+(aq) + Cl–(aq)
D C(graphite) → C(diamond)

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(Total for Question 7 = 1 mark)

8 Equal amounts of W and X are mixed and allowed to reach equilibrium.

W+XUY+Z
The value of the equilibrium constant is Kc = 4.85. At equilibrium, the mixture
will contain
A almost all Y and Z
B almost all W and X
C W, X, Y and Z but there is less Y and Z than W and X
D W, X, Y and Z but there is more Y and Z than W and X

(Total for Question 8 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.
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9 What does X represent on the diagram?

Li+(g) + Cl–(g)
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LiCl(s)

Li+(aq) + Cl–(aq)

A sum of enthalpy changes of hydration of the gaseous ions

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B enthalpy change of formation of LiCl

C enthalpy change of solution of LiCl
D lattice energy of LiCl

(Total for Question 9 = 1 mark)

10 How are 20 cm3 of 0.05 mol dm–3 H2SO4(aq) and 20 cm3 of 0.10 mol dm–3 CH3COOH(aq) alike?
Both solutions
A have the same pH
B have the same total concentration of ions
C have the same total concentration of negative ions
D require 20 cm3 of 0.10 mol dm–3 NaOH(aq) for complete reaction
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(Total for Question 10 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

*P60472A0732*
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11 Which two solutions, both of concentration 0.10 mol dm–3, have been used to
produce this titration curve?

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pH 7

0
Volume of alkali added

A HCl(aq) and KOH(aq)

B HCOOH(aq) and KOH(aq)
C HCl(aq) and NH3(aq)

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D HCOOH(aq) and NH3(aq)

(Total for Question 11 = 1 mark)

12 A solution of sodium hydroxide of concentration 0.0080 mol dm–3 has a pH

A between 7 and 9
B between 9 and 11
C between 11 and 13
D above 13

(Total for Question 12 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.
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13 A student carried out an experiment to determine the equilibrium constant for the
reaction to form ethyl ethanoate from ethanol and ethanoic acid.
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CH3COOH + CH3CH2OH UCH3COOCH2CH3 + H2O

Different amounts of each substance were added to conical flasks, each containing
2.0 cm3 of 1.0 mol dm−3 hydrochloric acid.

Volume added / cm3

Conical
flask HCl H 2O CH3COOH CH3COOCH2CH3 CH3CH2OH
(aq) (l) (l) (l) (l)
1 2.0 1.0 0 2.0 0

2 2.0 0 5.0 0 5.0

3 2.0 0 4.0 0 3.0

4 2.0 0 0 3.0 0
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The flasks were then stoppered and left for a week to reach equilibrium.
Each mixture was then titrated with 1.0 mol dm−3 sodium hydroxide.

(a) In which flask(s) was the equilibrium approached from the right-hand side of the
equation?
(1)
A flask 1 only
B flask 4 only
C flasks 1 and 4 only
D flasks 2 and 3 only

(b) Which of these statements explains why it is possible to titrate the reaction
mixture directly to find the equilibrium concentrations?
(1)
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A the equilibrium reaction is slow

B the sodium hydroxide quickly hydrolyses the ester
C all the reactant concentrations remain constant during the titration
D a buffer solution forms in the reaction

(Total for Question 13 = 2 marks)

*P60472A0932*
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14 A reactant Q is converted into two products. Which of these graphs shows that this
reaction is first order with respect to Q?

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Graph 1 Graph 2

[Q] Rate

time [Q]

Graph 3 Graph 4

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Rate [Q]

[Q] time

A Graph 1
B Graph 2
C Graph 3 DO NOT WRITE IN THIS AREA

D Graph 4

(Total for Question 14 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

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*P60472A01032*
15 This question is about the kinetics of the reaction between nitrogen monoxide and oxygen.

2NO(g) + O2(g) → 2NO2(g)

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The rate equation for the reaction is rate = k[NO]2[O2]

(a) Which statement is not correct?
(1)
A the reaction is third order overall
B the units of the rate of the reaction are mol dm−3 s−1
C the rate of the reaction increases when the pressure is increased
D when the concentration of nitrogen monoxide doubles and the concentration
of oxygen quadruples, the rate increases by a factor of 8

(b) What are the units of the rate constant, k , for this reaction?
(1)
A dm9 mol−3 s−1
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B mol3 dm−9 s−1

C mol2 dm−6 s−1
D dm6 mol−2 s−1

(c) An experiment was carried out using 1.10 × 10−2 mol dm−3 of oxygen and some
nitrogen monoxide.
The numerical value of the initial rate and rate constant were:
• initial rate = 3.20 × 10−3
• rate constant, k = 1.70 × 103
What was the initial concentration, in mol dm−3, of the nitrogen monoxide used in
the experiment?
(1)
A 1.31 × 10−2
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B 1.71 × 10−4
C 2.02 × 10−3
D 4.50 × 10−2

(Total for Question 15 = 3 marks)

TOTAL FOR SECTION A = 20 MARKS

*P60472A01132*
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SECTION B

Answer ALL the questions.

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Write your answers in the spaces provided.

16 The compound ethyl 3-oxobutanoate, which is used in food flavouring, has the
formula CH3COCH2COOCH2CH3.
The high resolution proton (1H) NMR spectrum of this compound is

x
w

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5 4 3 2 1 0

Chemical shift, į / ppm

(a) (i) Identify which groups of hydrogen atoms are responsible for each peak in the
spectrum by adding the labels w, x, y and z to the appropriate parts of this
displayed formula to match the letters on the spectrum.
(2)

H O H O H H

H C C C C O C C H
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H H H H

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*P60472A01232*
(ii) Explain the splitting patterns of the peaks at 4.2 ppm and 1.3 ppm.
(2)
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(iii) The carbon-13 (13C) NMR spectrum of ethyl 3-oxobutanoate has six peaks.
Draw the structure of an isomer of ethyl 3-oxobutanoate that contains a
carboxylic acid group and a ketone functional group, but only has four peaks in its
carbon-13 NMR spectrum.
(1)
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*P60472A01332*
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(b) A chemist synthesising ethyl 3-oxobutanoate looked for its presence in the reaction
mixture using thin-layer chromatography. The solvent used was a mixture of
ethoxyethane, C2H5OC2H5, which is polar, and hexane.

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Under these conditions, the Rf value for ethyl 3-oxobutanoate was 0.45.
(i) Complete the diagram below, showing a chromatogram for ethyl 3-oxobutanoate,
including appropriate labels.
(3)

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(ii) Suggest why the Rf value for ethyl 3-oxobutanoate is significantly lower than 0.45
when just hexane is used as the solvent.
(2)

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(Total for Question 16 = 10 marks)

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*17 Compare and contrast the reactions of propanal and propanone with one oxidising agent,
one reducing agent and 2,4-dinitrophenylhydrazine.

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In your answer include any relevant observations for the reactions you discuss and
equations for any reactions classified as oxidation, using [O] for the oxygen from the
oxidising agent.

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(Total for Question 17 = 6 marks)

*P60472A01732*
17
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18 The rate constant for the reaction to convert cyclopropane to propene was
determined at five different temperatures.

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CH2 CH
H2 C CH3
H 2C CH2

The results are shown in the table.

Temperature (T) 1 / Temperature (1 / T) Rate constant (k)

ln k
/K / K−1 / s−1
719 1.39 × 10−3 2.49 × 10−5 –10.60

746 1.34 × 10−3 1.23 × 10−4 –9.00

791 1.26 × 10−3 1.66 × 10−3

840 1.83 × 10−2 –4.00

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889 1.12 × 10−3 1.65 × 10−1 –1.80

(a) (i) Complete the table.

(1)
(ii) Plot a graph of ln k against 1 / T.
(3)

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18
*P60472A01832*
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(iii) Use your graph to determine the activation energy, Ea , in kJ mol−1.

You should include the value and units of the gradient of the line.
The Arrhenius equation is
E 1
ln k = – a × + constant
R T (3)
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*P60472A01932*
19
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(b) The activation energy for many reactions is around +50 kJ mol–1.
Given this information, comment on your value for Ea.

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(2)

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20
*P60472A02032*
19 This question is about halides.
(a) Silicon tetrachloride, SiCl4 , is used in the manufacture of optical fibres. It can

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be made by the reaction of silicon carbide, SiC, with hydrogen chloride using a
catalyst of nickel(II) chloride.

SiC(s) + 4HCl(g) → SiCl4 (l) + CH4(g) ¨H = –631.3 kJ mol−1

The standard molar entropies S 9 , of the substances are shown in the table.

Substance SiC(s) HCl(g) SiCl4 (l) CH4(g)

S 9 / J K−1 mol−1 +16.5 +186.8 +239.7 +186.2

(i) Calculate the total entropy change, ¨Stotal , for this reaction, at 298 K, using the
information given.
Include a sign and units in your answer which should be given to an
appropriate number of significant figures.

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(5)

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22
*P60472A02232*
(ii) In industry, the reaction is carried out at 700 °C.
By considering entropy and other relevant factors, justify the use of this temperature.
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(3)

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(iii) Use your answer from (a)(i) to calculate the equilibrium constant for the
reaction at 298 K.
(2)
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*P60472A02332*
23
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(b) The following data can be used in a Born-Haber cycle for calcium iodide, CaI2.

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Letter Energy change Value / kJ mol–1

A Enthalpy change of atomisation of calcium +178.2

B First ionisation energy of calcium +590

C Second ionisation energy of calcium +1145

D Enthalpy change of atomisation of iodine (½I2(s) → I(g)) +106.8

E Electron affinity of iodine –295.4

F Lattice energy of calcium iodide –2074

(i) Complete the Born-Haber cycle by adding letters in the boxes for the energy
changes, relevant species on the blank lines and arrowheads to show the
direction of each energy change.

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(3)

Ca(g) + 2I(g)
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D ×2
Ca(g) + I2(g)

A
Ca(s) + I2(g)
Enthalpy change
of formation of
CaI2(s) calcium iodide

24
*P60472A02432*
(ii) Use the data to calculate the value for the enthalpy change of formation of
calcium iodide.
(2)
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(iii) The value for the lattice energy of calcium iodide determined experimentally
by using the Born-Haber cycle differs significantly from the theoretical
calculated value.
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Explain why the Born-Haber and the theoretical values for the lattice energies
are similar for calcium fluoride but significantly different for calcium iodide.
(4)

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*P60472A02532*
25
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(c) The electron affinity of iodine is –295.4 kJ mol–1.
Explain how the electron affinity of chlorine differs from that of iodine.

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(3)

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(Total for Question 19 = 22 marks)

TOTAL FOR SECTION B = 50 MARKS

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26
*P60472A02632*
SECTION C

Answer ALL the questions.

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Write your answers in the spaces provided.

20 This question is about ethanoic acid and some of its compounds.

(a) Three students, A, B and C, carried out an investigation to determine the amount
of isoamyl acetate, an ester of ethanoic acid, in a banana food flavouring.
They hydrolysed the ester with excess sodium hydroxide solution.
CH3COOCH2CH2CH(CH3)2 + NaOH → CH3COONa + (CH3)2CHCH2CH2OH
The amount of sodium hydroxide remaining was determined by titrating the
reaction mixture with hydrochloric acid.
(i) Give the systematic name for isoamyl acetate.
(1)
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(ii) 6.06 × 10–3 mol of sodium hydroxide reacted with the ester present in 1.07 g of
the flavouring.
Calculate the percentage by mass of the ester in the food flavouring.
(3)
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*P60472A02732*
27
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(iii) The students used 25.0 cm3 of sodium hydroxide solution with concentration
0.980 mol dm–3 for the hydrolysis.

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Calculate the pH of the reaction mixture when the hydrolysis is complete.
Assume the total volume is 25.0 cm3.
[Ionic product of water, Kw = 1.0 × 10–14 mol2 dm–6]
(3)

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(iv) Two indicators, methyl orange and phenolphthalein, were available for this titration.
Student A thought only methyl orange could be used.
Student B thought only phenolphthalein could be used.
Student C suggested either indicator could be used.
Explain which student is correct.
(2)

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28
*P60472A02832*
(v) Describe how the sodium ethanoate in the final reaction mixture could be
converted into ethanoic acid.
(1)
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*P60472A02932*
29
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(b) Ethanoic acid can be used to form buffer solutions.
(i) Calculate the pH of the buffer solution formed when 50.0 cm3 of ethanoic acid

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with concentration of 0.150 mol dm–3 is mixed with 30.0 cm3 of
sodium hydroxide solution with concentration of 0.142 mol dm–3.
[Ka for ethanoic acid = 1.70 × 10–5 mol dm–3]
(5)

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30
*P60472A03032*
(ii) Small amounts of sodium hydroxide and hydrochloric acid are added to
separate samples of the buffer solution in (b)(i).
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Explain why these samples resist change in pH.

Illustrate your answer with at least two equations.
(5)

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(Total for Question 20 = 20 marks)

TOTAL FOR SECTION C = 20 MARKS

TOTAL FOR PAPER = 90 MARKS

*P60472A03132*
31
Please check the examination details below before entering your candidate information
Candidate surname Other names

Pearson Edexcel Centre Number Candidate Number

International
Advanced Level

Tuesday 2 June 2020

Afternoon (Time: 1 hour 45 minutes) Paper Reference WCH14/01

Chemistry
International Advanced Level
Unit 4: Rates, Equilibria and Further Organic Chemistry

Candidates must have: Scientific calculator Total Marks

Data Booklet
Ruler

Information
• The total mark for this paper is 90.
• – usemarks
The for each question are shown in brackets
this as a guide as to how much time to spend on each question.
• ability
In the question marked with an asterisk (*), marks will be awarded for your
to structure your answer logically, showing how the points that you make
are related or follow on from each other where appropriate.
• A Periodic Table is printed on the back cover of this paper.

Advice
• Read each question carefully before you start to answer it.
• Checkyour
Show working in calculations and include units where appropriate.
• your answers if you have time at the end.
Turn over

*P64620A0132*
P64620A
©2020 Pearson Education Ltd.

1/1/1/1/1/
SECTION A
Answer ALL the questions in this section.
You should aim to spend no more than 20 minutes on this section.
For each question, select one answer from A to D and put a cross in the box . If you change
your mind, put a line through the box and then mark your new answer with a cross .
1 Bromine oxidises methanoic acid to carbon dioxide.
The equation for the reaction is

HCOOH(aq) + Br2(aq) → 2H+(aq) + 2Br −(aq) + CO2(g)

Which of the following methods would not be suitable for measuring the progress of
this reaction?
A colorimetry
B measuring electrical conductivity
C quenching and titrating with acid
D measuring the volume of gas
(Total for Question 1 = 1 mark)
Use this space for any rough working. Anything you write in this space will gain no credit.

2
*P64620A0232*
2 The rate of the reaction between two compounds, Y and Z, was investigated.
The results are shown.

Initial concentration of Y Initial concentration of Z Initial rate

Experiment
/ mol dm−3 / mol dm−3 / mol dm−3 s−1
1 0.64 0.24 8.00 × 10−3

2 0.64 0.48 3.20 × 10−2

3 0.32 0.48 3.20 × 10−2

What are the orders of reaction with respect to Y and Z?

Order with respect to Y Order with respect to Z

A 0 1

B 0 2

C 1 1

D 1 2

(Total for Question 2 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

3
*P64620A0332* Turn over
3 The inorganic anti-cancer drug cis-platin, Pt(NH3)2Cl2, is hydrolysed by water to make
it active. The reaction is
+
H3N NH3 H3N NH3
Pt + H2O Pt + Cl−
Cl Cl H2O Cl

The hydrolysis is first order overall. The half-life can be found from a graph of the
concentration of cis-platin against time.

Concentration of
cis-platin × 10−3 10
/ mol dm−3
8

0
0 200 400 600 800 1000 1200
Time of reaction / min

The half-life of the reaction is

A 430 min
B 460 min
C 590 min
D 600 min

(Total for Question 3 = 1 mark)

4
*P64620A0432*
4 Propanone reacts with iodine in acidic solution.

CH3COCH3(aq) + I2(aq) → CH3COCH2I(aq) + H+(aq) + I−(aq)

The rate equation for the formation of iodopropanone is found to be

rate = k[CH3COCH3(aq)][H+(aq)]

(a) Which of the following is true?

(1)

A the units for the rate constant are dm3 mol−1 s−1
B the reaction is a first order reaction overall
C the units for the rate are dm3 mol −1 s−1
D doubling the concentrations of propanone and of iodine quadruples the rate

(b) Which of the following is not true?

(1)

A the reaction rate increases if the temperature is raised

B the rate constant increases if the temperature is raised
C the addition of a small amount of sodium hydroxide decreases the
reaction rate
D the rate is unchanged when the hydrogen ion concentration is doubled

(Total for Question 4 = 2 marks)

Use this space for any rough working. Anything you write in this space will gain no credit.

5
*P64620A0532* Turn over
5 The equation shows the hydrolysis of a bromoalkane.

RBr + OH− → ROH + Br−

The rate equation is rate = k[RBr]

RBr is most likely to be

A bromomethane
B 2-bromopropane
C 1-bromo-2-methylpropane
D 2-bromo-2-methylpropane

(Total for Question 5 = 1 mark)

6 The equation for an exothermic reaction is shown.

Mg(s) + 2HCl(aq) → MgCl2(aq) + H2(g)

Which of these is true?

A ΔH is positive
B ΔSsurroundings is positive
C ΔSsystem is negative
D ΔStotal is negative

(Total for Question 6 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

6
*P64620A0632*
7 The equation for the equilibrium decomposition of hydrogen iodide into hydrogen
and iodine can be written in two ways.
2HI(g)  H2(g) + I2(g) Equilibrium constant = Kc
or
HI(g)  ½H2(g) + ½I2(g) Equilibrium constant = Kcʹ
What is the expression linking the two equilibrium constants?
A Kc = (Kcʹ )2
B Kc = Kcʹ
C Kc = 2(Kcʹ )
D Kc = K ¢c

(Total for Question 7 = 1 mark)

8 A buffer solution contains ethanoic acid, with a concentration of 0.10 mol dm−3, and
sodium ethanoate, with a concentration of 0.050 mol dm−3.
Ka for ethanoic acid = 1.7 × 10−5 mol dm−3
The pH of this buffer solution is
A 2.88

B 4.47

C 4.77

D 5.07

(Total for Question 8 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

7
*P64620A0732* Turn over
9 The graphs show the changes in pH during a series of titrations.
Each titration involves two solutions, each of concentration 0.1 mol dm−3.

Graph 1 Graph 2

14 14
12 12
10 10
8 8
pH pH
6 6
4 4
2 2
0 0
0 10 20 30 40 0 10 20 30 40
Volume of solution added / cm3 Volume of solution added / cm3

Graph 3 Graph 4

14 14
12 12
10 10
8 8
pH pH
6 6
4 4
2 2
0 0
0 10 20 30 40 0 10 20 30 40
Volume of solution added / cm3 Volume of solution added / cm3

(a) Which graph has ethanoic acid as one of the reactants?

(1)
A Graph 1
B Graph 2
C Graph 3
D Graph 4

8
*P64620A0832*
(b) Which graph shows a solution that has an acidic pH at the end-point?
(1)
A Graph 1
B Graph 2
C Graph 3
D Graph 4

(c) Which indicator is suitable for the titration shown in Graph 3?

Use your Data Booklet.
(1)
A bromocresol green
B bromothymol blue
C phenol red
D thymol blue (acid)

(Total for Question 9 = 3 marks)

Use this space for any rough working. Anything you write in this space will gain no credit.

9
*P64620A0932* Turn over
10 Which diagram shows the first step of the mechanism for the nucleophilic addition of
hydrogen cyanide to propanone in the presence of potassium cyanide?
δ−
O
δ+ O–

••
C
A H3C CH3 H3C C CH3
CN− CN

••
δ−
O
δ+ O–

••
C
B H3C CH3 H3C C CH3
CN− CN
••

δ+
O
δ− O–
••

C
C H3C CH3 H3C C CH3
CN− CN
••

δ−
O
δ+ O–
••

C
D H3C CH3 H3C C CH3
CN− CN
••

(Total for Question 10 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

10
*P64620A01032*
11 When propanone reacts with iodine in the presence of sodium hydroxide, the
precipitate formed has the formula
A CH3I
B CHI3
C CH3COCH2I
D CH3COCI3

(Total for Question 11 = 1 mark)

12 Which of the following could not be formed when methylamine is added to

ethanoyl chloride?
A HCl
B CH3NH3+Cl−
C CH3CONH2
D CH3CONHCH3

(Total for Question 12 = 1 mark)

13 In which of these esters is the percentage by mass of carbon 54.5 %?

A methyl methanoate, HCOOCH3
B methyl ethanoate, CH3COOCH3
C ethyl ethanoate, CH3COOCH2CH3
D ethyl methanoate, HCOOCH2CH3

(Total for Question 13 = 1 mark)

14 An organic compound that reacts with both lithium tetrahydridoaluminate(III)

(lithium aluminium hydride) and magnesium could be
A an aldehyde
B a carboxylic acid
C a ketone
D a tertiary alcohol

(Total for Question 14 = 1 mark)

11
*P64620A01132* Turn over
15 The following methods can be used to distinguish between pairs of organic compounds
with no further tests.
A warm each compound with Fehling’s or Benedict’s solution
B warm each compound with acidified potassium dichromate(VI) solution
C add 2,4-dinitrophenylhydrazine (Brady’s reagent) to each compound
D add a few drops of each compound, drop by drop, to water

(a) Which test would distinguish between 2-methylpropan-2-ol, (CH3)3COH, and

butanone, CH3CH2COCH3?
(1)
A
B
C
D

(b) Which test would distinguish between 2-methylpropan-2-ol, (CH3)3COH, and

butan-1-ol, CH3CH2CH2CH2OH?
(1)
A
B
C
D

(c) Which test could not be used to distinguish between 2-methylpropan-2-ol,

(CH3)3COH, and butanal, CH3CH2CH2CHO?
(1)
A
B
C
D

(Total for Question 15 = 3 marks)

TOTAL FOR SECTION A = 20 MARKS

12
*P64620A01232*
SECTION B
Answer ALL the questions. Write your answers in the spaces provided.
16 This question concerns calcium chloride, CaCl2 .
(a) Some energy changes related to calcium chloride are shown.

Energy change Value / kJ mol−1

Atomisation energy of calcium +178.2

Atomisation energy of chlorine +121.7

Electron affinity of chlorine −348.8

First ionisation energy of calcium +590.0

Standard enthalpy change of formation of calcium chloride −795.8

Experimental lattice energy of calcium chloride −2 258

Second ionisation energy of calcium To be calculated

(i) Complete the Born-Haber cycle by writing appropriate chemical formulae on

the horizontal lines. Include state symbols and relevant electrons.
(4)

∆H5 ∆H6

Ca2+(g) + 2Cl−(g)
∆H4

∆H3

∆H7
∆H2
Ca(s) + Cl2(g)

∆H1
CaCl2(s)

14
*P64620A01432*
(ii) Calculate the second ionisation energy of calcium using the cycle and the
values given in the table. Include a sign and units with your value.
(3)

(b) The theoretical lattice energy of formation of CaCl2 is −2 223 kJ mol−1.

Explain why the experimental lattice energy of CaCl2 is more exothermic than the
theoretical value.
(3)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

15
*P64620A01532* Turn over
(c) The table shows the theoretical lattice energies of some chlorides of Group 2.

magnesium calcium strontium barium

Group 2 metal chloride
chloride chloride chloride chloride

Lattice energy / kJ mol−1 −2 326 −2 223 −2 127 −2 033

Explain the trend in theoretical lattice energies on descending Group 2.

(3)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(d) Calculate the enthalpy change of solution of calcium chloride, CaCl2.

Data

∆hyd H (Ca2+) = −1 650 kJ mol−1 ∆hyd H (Cl−) = −364 kJ mol−1

Experimental lattice energy (CaCl2) = −2 258 kJ mol−1
(2)

(Total for Question 16 = 15 marks)

16
*P64620A01632*
17 This question concerns six isomers each with the molecular formula C5H10O2.
(a) Isomers A, B, C and D are structural isomers that all react with aqueous sodium carbonate
to produce carbon dioxide.
Isomer A is a straight-chain compound.
Isomer B has only two peaks in its high resolution proton NMR spectrum, both of
which are singlets.
Isomer C contains a chiral centre but isomer D does not.
Give the structures of these four isomers.
(4)

A B

C D

17
*P64620A01732* Turn over
(b) (i) Isomer E contains an ether functional group (R-O-R) and a ketone functional
group. The low resolution proton NMR spectrum of isomer E has four peaks.
The displayed formula of isomer E is

O
CH3 O CH2 CH2 C CH3
a b c d

The four hydrogen environments responsible for the four peaks are labelled.
Complete the table of information regarding these peaks including the
splitting pattern in the high resolution spectrum.
(3)

Peak a b c d

Relative peak area 3

Chemical shift
2.9 − 4.2
range, δ / ppm

Splitting singlet

(ii) State the number of peaks in the carbon-13 (13C) NMR spectrum of E.
(1)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

18
*P64620A01832*
(c) Isomer F is a neutral compound that smells of pears.
It can be formed by the reaction between compounds V and W in the presence
of concentrated sulfuric acid.
Compound V has an absorption in its infrared spectrum at 1720 cm−1 and a
broad absorption around 3050 cm−1.
Compound W can be formed directly from propanal.
(i) Identify, by name or formula, compounds V, W and F.
Justify your answer by using all the available information.
(4)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

19
*P64620A01932* Turn over
(ii) State the conditions required and the reagent needed to form compound W
from propanal.
(1)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(iii) State the role of sulfuric acid in the formation of F.

(1)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(d) State which one of the isomers A, E and F has the highest boiling temperature.
Justify your answer.
(3)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(Total for Question 17 = 17 marks)

20
*P64620A02032*
18 This question concerns acidic solutions.
(a) (i) A solution of hydrochloric acid has a pH of 1.125.
Calculate the concentration of hydrogen ions and of hydroxide ions, in mol dm−3,
in this solution.
[Kw = 1.00 × 10−14 mol2 dm−6]
(2)

(ii) Calculate the volume of water which must be added to 25.0 cm3 of this
solution to increase the pH from 1.125 to 1.500, giving your answer to an
appropriate number of significant figures.
(4)

21
*P64620A02132* Turn over
(b) Phosphoric(V) acid, H3PO4 , is a weak acid, which dissolves in water, giving the
equilibrium

Equation 1 H3PO4(aq) + H2O(l)  H2PO4− (aq) + H3O+(aq)

The H2PO4− ion formed when phosphoric(V) acid is added to water can dissociate
further into HPO2−
4 .

Equation 2 H2PO4− (aq) + H2O(l)  HPO2−

4 (aq) + H3O+(aq)

.................... .................... .................... ....................

(i) Identify the acids and bases in the spaces below Equation 2, linking the
acid-base conjugate pairs.
(2)
(ii) Explain why very little dissociation of the H2PO4− ion occurs in solutions of
phosphoric(V) acid.
(2)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

22
*P64620A02232*
(c) (i) Using Equation 1, write an expression for the acid dissociation constant, Ka1 ,
for phosphoric(V) acid, H3PO4 .
(1)

(ii) A 0.500 mol dm−3 solution of phosphoric(V) acid has a pH of 1.20.

Calculate the value of Ka1 , stating its units.
Assume that there is no further dissociation of the H2PO4− ion.
(4)

23
*P64620A02332* Turn over
(d) Phosphate buffer solutions containing hydrogenphosphate ions, HPO2− 4 , and
dihydrogenphosphate ions, H2PO4− , are commonly used in biological research.
Explain, using a relevant ionic equation, how a solution containing these ions can
act as a buffer when a small amount of alkali is added.
(3)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(Total for Question 18 = 18 marks)

TOTAL FOR SECTION B = 50 MARKS

24
*P64620A02432*
SECTION C
Answer ALL the questions. Write your answers in the spaces provided.
19 Ammonia is manufactured in the Haber Process.

N2(g) + 3H2(g)  2NH3(g)

In this process, pressures between 100 atm and 300 atm and temperatures between
675 K and 725 K are usually used.
(a) (i) Calculate ∆Ssystem for this reaction at 298 K.
Include a sign and units with your answer.
[Standard molar entropy, S , for 1 mol of each gas, in J K−1 mol−1 :
N2 = 191.6 H2 = 130.6 NH3 = 192.3]
(2)

(ii) Explain, using ideas about disorder, whether the sign of your answer to (a)(i) is
as expected.
(2)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

26
*P64620A02632*
(iii) At 700 K, the enthalpy change for this reaction is ∆H = −110.2 kJ mol−1.
Calculate the entropy change of the surroundings, ∆Ssurroundings , at 700 K.
Include a sign and units in your answer.
(2)

(iv) At 700 K, the total entropy change, ∆Stotal = −78.7 J K−1 mol−1.
Calculate ∆Ssystem for this reaction at 700 K.
Include a sign and units in your answer.
(1)

27
*P64620A02732* Turn over
*(v) Explain one advantage and one disadvantage of using a temperature higher
than 700 K in the Haber process.
Consider the effect of an increase in temperature on the rate of reaction, on the
values of ∆Ssurroundings and ∆Stotal and on the equilibrium constant.
(6)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................................... . . . . . . . . . . . . . . . . . . . .

28
*P64620A02832*
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. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

29
*P64620A02932* Turn over
(b) (i) Write the expression for the equilibrium constant, Kp , for the reaction in the
Haber Process.

N2(g) + 3H2(g)  2NH3(g)

(1)

(ii) A mixture of nitrogen, hydrogen and ammonia is at equilibrium at 255 atm

and 700 K. The partial pressure of nitrogen is 25 atm and that of hydrogen is
150 atm.
Calculate the equilibrium constant, Kp , for the formation of ammonia, at 700 K.
Include units in your answer.
(3)

30
*P64620A03032*
(iii) The pressure of the system is doubled at constant temperature.
Explain the effect of this on the yield of ammonia by considering the change
in the Kp expression and hence the position of equilibrium.
(3)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(Total for Question 19 = 20 marks)

TOTAL FOR SECTION C = 20 MARKS

TOTAL FOR PAPER = 90 MARKS

31
*P64620A03132*
Please check the examination details below before entering your candidate information
Candidate surname Other names

Centre Number Candidate Number

Pearson Edexcel
International
Advanced Level

Friday 8 January 2021

Afternoon (Time: 1 hour 45 minutes) Paper Reference WCH14/01

Chemistry
International Advanced Level
Unit 4: Rates, Equilibria and Further Organic Chemistry
(including synoptic assessment)
You must have: Total Marks
Data Booklet, scientific calculator, ruler

Instructions
• Use black ink or ball-point pen.
• centrethe
Fill in boxes at the top of this page with your name,
number and candidate number.
• Answer all questions.
• Answer the questions in the spaces provided
– there may be more space than you need.
• Show all your working in calculations and include units where appropriate.
Information
• The total mark for this paper is 90.
• –Theusemarks for each question are shown in brackets
this as a guide as to how much time to spend on each question.
• toIn the question marked with an asterisk (*), marks will be awarded for your ability
structure your answer logically, showing how the points that you make are
related or follow on from each other where appropriate.
• A Periodic Table is printed on the back cover of this paper.

Advice
• Read each question carefully before you start to answer it.
• Try to answer every question.
• your answers if you have time at the end.
Check

Turn over

P67746A
©2021 Pearson Education Ltd.

1/1/1/1/
*P67746A0128*
SECTION A

Answer ALL the questions in this section.

You should aim to spend no more than 20 minutes on this section.

For each question, select one answer from A to D and put a cross in the box .
If you change your mind, put a line through the box and then mark your new answer
with a cross .

1 Which of these has the highest standard molar entropy at 298 K and 1 atm pressure?

A carbon dioxide, CO2

B copper, Cu

C ethanol, C2H5OH

D hydrogen, H2

(Total for Question 1 = 1 mark)

2 The entropy change of the surroundings, ¨Ssurroundings , and the entropy change of the
system, ¨Ssystem , for four different reactions are given.

¨Ssurroundings ¨Ssystem
Reaction
/ J K−1 mol−1 / J K−1 mol−1
P +245 +34
Q +350 −276
R −482 +65
S −563 −128

Which of these is thermodynamically feasible?

A reaction P only

B reactions P and Q only

C reaction R only

D reactions R and S only

(Total for Question 2 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

2
*P67746A0228*
3 Which equation represents the standard enthalpy change of atomisation, ¨atH , of bromine?

A ½ Br2(l) → Br(g)

B Br2(l) → 2Br(g)

C ½ Br2(g) → Br(g)

D Br2(g) → 2Br(g)
(Total for Question 3 = 1 mark)

4 This question is about four ionic compounds.

(a) Which of these compounds would be expected to have the least exothermic
lattice energy?
(1)
A calcium chloride

B magnesium chloride

C potassium bromide

D sodium bromide

(b) Which of these compounds would be expected to have the largest difference
between their experimental (Born–Haber) and theoretical lattice energies?
(1)
A calcium chloride

B magnesium chloride

C potassium bromide

D sodium bromide

(Total for Question 4 = 2 marks)

5 The standard enthalpy change of solution of potassium chloride, KCl, is +17 kJ mol−1.
The solubility of potassium chloride in water at 298 K is 359 g dm−3.
Which of these explains the solubility of potassium chloride in water?

A the hydration enthalpy of K+ and the lattice energy of KCl are exothermic

B the hydration enthalpy of K+ and the lattice energy of KCl are endothermic

C the total entropy change when KCl dissolves is positive

D the total entropy change when KCl dissolves is negative

(Total for Question 5 = 1 mark)

*P67746A0328*
3
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6 The total entropy change, ¨Stotal , of a reaction at 298 K is −85.0 J K−1 mol−1.
What is the value of the equilibrium constant for this reaction at 298 K?
[R = 8.31 J mol−1 K−1]

A 3.61 × 10−5

B 9.07 × 10−1

C 9.66 × 10−1

D 2.77 × 104

(Total for Question 6 = 1 mark)

7 Propanone reacts with iodine in the presence of a catalyst of dilute hydrochloric acid.
The reaction occurs in aqueous solution.

CH3COCH3 + I2 → CH3COCH2I + HI
The rate equation for this reaction is

rate = k[CH3COCH3][H+]
Which is a possible mechanism for the reaction?
+
A CH3COCH3 + H+ U CH3C(O H)CH3 fast
+
CH3C(O H)CH3 → CH3C(OH) CH2 + H+ slow

CH3C(OH) CH2 + I2 → CH3COCH2I + HI fast

+
B CH3COCH3 + H+ U CH3C(O H)CH3 fast
+
CH3C(O H)CH3 → CH3C(OH) CH2 + H+ fast

CH3C(OH) CH2 + I2 → CH3COCH2I + HI slow

C CH3COCH3 → CH3COCH2− + H+ slow

I2 → ,௘+ + ,௘− slow

CH3COCH2− + I+ → CH3COCH2I fast

D I2 → ,௘+ + ,௘− slow

CH3COCH3 + ,௘− → CH3COCH2− + HI slow

CH3COCH2− + ,௘+ → CH3COCH2I fast

(Total for Question 7 = 1 mark)

4
*P67746A0428*
8 The rate equation for a reaction is

rate = k[A]2[B]0
The initial rate of reaction is 9.0 × 10−5 mol dm−3 s−1 when [A] = 0.30 mol dm−3
and [B] = 0.20 mol dm−3.
What is the value of the rate constant in dm3 mol−1 s−1?
A 8.1 × 10−6

B 3.0 × 10−4

C 1.0 × 10−3

D 5.0 × 10−3

(Total for Question 8 = 1 mark)

9 This question is about weak acids.

pKa of ethanoic acid, CH3COOH = 4.8
pKa of chloroethanoic acid, CH2ClCOOH = 2.9
(a) What is the pH of a 0.100 mol dm−3 solution of chloroethanoic acid?
(1)
A 0.27

B 1.95

C 2.90

D 3.90

(b) Which is the acid-conjugate base pair in the reaction between ethanoic acid and
chloroethanoic acid?
(1)
Acid Conjugate base

A CH3COOH CH3COO−

B CH3COOH CH3COOH2+

C CH2ClCOOH CH2ClCOO−

D CH2ClCOOH CH2ClCOOH2+

(Total for Question 9 = 2 marks)

*P67746A0528*
5
Turn over
10 A titration was carried out by adding 0.1 mol dm−3 hydrochloric acid to
0.1 mol dm−3 aqueous ammonia.

HCl(aq) + NH3(aq) o NH4Cl(aq)

The titration curve is shown.

T
U
pH
7
V

0
Volume of HCl / cm3

(a) Which region of the graph represents the most effective buffer solution?
(1)
A region T

B region U

C region V

D region W

(b) Which of these is the best indicator to use in this titration?

[Refer to the Data Booklet]
(1)
A methyl red

B phenol red

C phenolphthalein

D thymol blue

6
*P67746A0628*
(c) What is the approximate pH of an ammonium chloride solution?
(1)
A 2.0

B 5.8

C 9.7

D 11.3

(Total for Question 10 = 3 marks)

11 A diprotic acid, H2A, was titrated with sodium hydroxide solution.

H2A(aq) + 2NaOH(aq) o Na2A(aq) + 2H2O(l)
A 25.0 cm3 portion of 0.100 mol dm−3 sodium hydroxide solution required 12.80 cm3 of
the solution of the diprotic acid for complete neutralisation.
What is the concentration of H2A in mol dm−3?

A 2.56 × 10−2

B 9.77 × 10−2

C 1.95 × 10−1

D 3.91 × 10−1

(Total for Question 11 = 1 mark)

12 A sample of a bromoalkane, RBr, containing a single optical isomer reacts with

hydroxide ions in an SN1 mechanism.
RBr + OH− o ROH + Br−
The alcohol formed is a racemic mixture.
From this information, it can be deduced that RBr is most likely to be

A primary only

B secondary only

C tertiary only

D primary, secondary or tertiary

(Total for Question 12 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

*P67746A0728*
7
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13 A compound X, with molecular formula C5H10O , gave an orange precipitate with
2,4-dinitrophenylhydrazine.
X gave a silver mirror with Tollens’ reagent.
Which of these could not be X?

A B O
O

C O D

(Total for Question 13 = 1 mark)

14 Propyl ethanoate, CH3COOCH2CH2CH3 , is hydrolysed with aqueous sodium hydroxide.

Which products are formed?

A CH3COOH and CH3CH2CH2OH

B CH3COOH and CH3CH2CH2ONa

C CH3COONa and CH3CH2CH2OH

D CH3COONa and CH3CH2CH2ONa

(Total for Question 14 = 1 mark)

15 2.95 g of ethanoic acid is produced from 2.50 g of ethanol.

What is the percentage yield of ethanoic acid?
[Molar masses in g mol−1: ethanoic acid = 60 ethanol = 46]

A 65.0 %

B 84.7 %

C 90.5 %

D 118 %

(Total for Question 15 = 1 mark)

8
*P67746A0828*
16 A mixture of organic compounds was analysed using thin-layer chromatography.
The Rf value was 0.92 for one of the components in the mixture.
What can be deduced about the attractions between that component and the
stationary and mobile phases?

Attraction between Attraction between

component and component and
stationary phase mobile phase
A strong strong

B strong weak

C weak weak

D weak strong

(Total for Question 16 = 1 mark)

TOTAL FOR SECTION A = 20 MARKS

*P67746A0928*
9
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SECTION B

Answer ALL the questions.

Write your answers in the spaces provided.

17 This question is about carboxylic acids and their derivatives.

(a) Lactic acid, CH3CH(OH)COOH , is produced in muscles as a result of
anaerobic respiration.
(i) The structure of lactic acid is

H
COOH
C
HO CH3

Give a reason why lactic acid shows optical isomerism.

(1)

. . . . . . . . . . . .................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................... . . . . . . . . . . . . . . . . . . . . . .

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(ii) A laboratory sample of lactic acid does not rotate the plane of plane-polarised
monochromatic light.
Give a reason for this observation.
(1)

. . . . . . . . . . . .................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................... . . . . . . . . . . . . . . . . . . . . . .

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(iii) Give the structure of the organic product formed when lactic acid reacts with
concentrated phosphoric(V) acid, H3PO4 .
(1)

10
*P67746A01028*
(b) A reaction scheme involving butanoic acid is shown.

O O
acidified
K2Cr2O7 reagent Y
alcohol X
heat under OH Cl
reflux
butanoic acid

CH3NH2

compound Z

Identify X, Y and Z by name or formula.

(3)

Alcohol X

Reagent Y

Compound Z

*P67746A01128*
11
Turn over
(c) The repeat unit of a polyester is shown.

H H O H O
O C C O C C C C
H H H

Give the structures of the two monomers that could form this polyester.
(2)

Monomer 1 Monomer 2

(d) An organic compound E contains carbon, hydrogen and oxygen only.

(i) The accurate relative atomic masses, Ar , of the three elements in E are shown
in the table.

Element Ar

hydrogen 1.0078

carbon 12.0000

oxygen 15.9949

E contains five carbon atoms and gives a molecular ion peak at

m / z = 102.0678 in its mass spectrum.
Deduce the molecular formula of E.
(1)

12
*P67746A01228*
(ii) Aqueous sodium hydrogencarbonate is added to a sample of E.
No effervescence occurs.
State what can be deduced by this observation.
(1)

. . . . . . . . . . . . ................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................... . . . . . . . . . . . . . . . . . . . . . .

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(iii) The infrared spectrum of E has an absorption in the range 1750 – 1735 cm−1.
Name the functional group in E.
(1)

. . . . . . . . . . . . ................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................... . . . . . . . . . . . . . . . . . . . . . .

(iv) Data from the high resolution proton NMR spectrum of E is shown.

Chemical shift, į
Peak Splitting pattern Relative peak area
/ ppm for TMS
A 4.02 triplet 2

B 2.05 singlet 3

C 1.65 sextet 2

D 0.95 triplet 3

Deduce the structure of E.

Justify your answer by labelling the protons responsible for each peak.
(3)

(Total for Question 17 = 14 marks)

*P67746A01328*
13
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18 This question is about sulfuric acid and its salts.
(a) The manufacture of sulfuric acid involves the equilibrium

2SO2(g) + O2(g) U 2SO3(g) ¨rH = −197 kJ mol−1

(i) A catalyst of vanadium(V) oxide is used in this reaction.

State the effect, if any, of the catalyst on the value of the
equilibrium constant, Kp .
(1)

. . . . . . . . . . . .................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................... . . . . . . . . . . . . . . . . . . . . . .

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(ii) The temperature used for this reaction in industry is 700 K.

Explain, in terms of the equilibrium constant and the equilibrium position, the
effect of an increase in temperature on the equilibrium yield of sulfur trioxide.
(2)

. . . . . . . . . . . .................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................... . . . . . . . . . . . . . . . . . . . . . .

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(iii) Write the expression for the equilibrium constant, Kp , for this equilibrium.
State symbols are not required.
(1)

14
*P67746A01428*
(iv) A mixture of 2.00 mol of sulfur dioxide and 1.00 mol of oxygen is allowed to
reach equilibrium at 5.00 atm pressure.
1.60 mol of sulfur trioxide is formed.
Calculate the value of Kp .
Include units and give your answer to an appropriate number of
significant figures.
(4)

*P67746A01528*
15
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(b) Sulfur trioxide is used to produce sulfuric acid.
(i) Commercial concentrated sulfuric acid contains 98.5 % H2SO4 and
1.5 % water by mass.
The density of concentrated sulfuric acid is 1800 g dm−3.
Calculate the concentration of this sulfuric acid in mol dm−3.
(2)

(ii) The pH of a 0.10 mol dm−3 solution of sulfuric acid at 25 °C is 0.97.

Calculate the concentration of hydrogen ions, in mol dm−3, in this solution.
(1)

(iii) In an aqueous solution of sulfuric acid, the following equilibria exist.

H2SO4(aq) + H2O(l) U H3O+(aq) + HSO4−(aq) Ka very large
HSO4−(aq) + H2O(l) U H3O+(aq) + SO42−(aq) Ka = 0.012 mol dm−3
Explain, in terms of these equilibria, why the concentration of hydrogen ions
in a 0.10 mol dm−3 solution of sulfuric acid is not 0.20 mol dm−3.
No calculation is required.
(2)

. . . . . . . . . . . .................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................... . . . . . . . . . . . . . . . . . . . . . .

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16
*P67746A01628*
(c) A buffer solution is made from HSO4− and SO42− ions.
(i) Write two ionic equations involving HSO4− and SO42− ions to show how this
solution acts as a buffer.
State symbols are not required.
(2)

(ii) A buffer solution is formed by mixing

25.0 cm3 of a solution that is 0.150 mol dm−3 with respect to SO42− ions with
75.0 cm3 of a solution that is 0.100 mol dm−3 with respect to HSO4− ions.
Calculate the pH of this buffer solution.
[Ka for HSO4− ions = 0.012 mol dm−3]
(5)

(Total for Question 18 = 20 marks)

*P67746A01728*
17
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19 This question is about carbonyl compounds.
(a) The skeletal formula of menthone is shown.

Give the molecular formula of menthone.

(1)

. . . . . . . . . . . .................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................... . . . . . . . . . . . . . . . . . . . . . .

(b) Ethanal, CH3CHO , reacts with hydrogen cyanide in the presence of cyanide ions to
form 2-hydroxypropanenitrile.
Draw the mechanism for this reaction.
Include curly arrows, and any relevant lone pairs and dipoles.
(4)

18
*P67746A01828*
(c) A carbonyl compound, F, has the molecular formula C6H12O .
(i) F reacts with iodine in an alkaline solution to give a pale yellow precipitate.
Give the name or formula of the group in F identified by this test.
(1)

. . . . . . . . . . . . ................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................... . . . . . . . . . . . . . . . . . . . . . .

(ii) Draw the skeletal formulae of the four possible structures of

carbonyl compound F.
(2)

(iii) The carbon-13 (13C) NMR spectrum of F has four peaks.

Identify F by drawing its displayed formula.
Justify your answer by labelling the carbon atoms or groups of carbon atoms
responsible for the four peaks in the spectrum.
(2)

*P67746A01928*
19
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*(d) Explain, in terms of all the intermolecular forces involved, why butanal has a
higher boiling temperature than pentane but a lower boiling temperature than
propanoic acid.

Substance Boiling temperature / °C

butanal 76

pentane 36

propanoic acid 141

(6)

. . . . . . . . . . . .................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................... . . . . . . . . . . . . . . . . . . . . . .

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20
*P67746A02028*
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(Total for Question 19 = 16 marks)

TOTAL FOR SECTION B = 50 MARKS

*P67746A02128*
21
Turn over
SECTION C

Answer ALL the questions.

Write your answers in the spaces provided.

20 This question is about some compounds of bromine.

(a) Potassium bromate(V) decomposes to form potassium bromide and oxygen.

2KBrO3(s) o 2KBr(s) + 3O2(g) ¨rH = −67.2 kJ mol−1

The standard molar entropies of these substances are given in the table.

Substance KBrO3(s) KBr(s) O2(g)

S / J K−1 mol−1 149.2 95.9 205.0

Calculate the total entropy change, ¨Stotal , for this reaction at 298 K.
(5)

*P67746A02328*
23
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(b) Bromide ions react with bromate(V) ions in acidic solution.

5Br−(aq) + BrO3−(aq) + 6H+(aq) o 3Br2(aq) + 3H2O(l)

Two experiments are carried out.

(i) Experiment 1
The concentration of Br− ions is determined at different times.
The concentrations of BrO3− ions and H+ ions are in large excess and
effectively constant.
The graph of concentration of Br− ions against time is shown.

0.10

0.08

0.06
[Br−(aq)]
/ mol dm−3
0.04

0.02

0
0 200 400 600 800 1000
Time / s

Determine the order of the reaction with respect to bromide ions.

Show your working on the graph.
(3)

24
*P67746A02428*
(ii) Experiment 2
The initial concentrations of BrO3− ions and H+ ions are changed and the initial
rate of reaction is determined.
The initial concentration of Br− ions is constant and in large excess.

[BrO3−(aq)] [H+(aq)] Initial rate

Run
/ mol dm−3 / mol dm−3 / mol dm−3 s−1
1 0.1 0.1 3.6 × 10−3

2 0.2 0.1 7.2 × 10−3

3 0.3 0.2 4.3 × 10−2

Determine the order of reaction with respect to BrO3− ions and to H+ ions.
You must explain your working.
(3)

. . . . . . . . . . . . ................................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................... . . . . . . . . . . . . . . . . . . . . . .

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(iii) Give the overall rate equation for this reaction.

Include the units for the rate constant.
(2)

*P67746A02528*
25
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(c) The rate constant for the reaction between bromoalkane and cyanide ions is
determined at five different temperatures.
The results are given in the table.

Temperature (T ) 1/Temperature (1/T ) Rate constant (k)

ln k
/K / K−1 / s−1
300 3.33 × 10−3 3.72 × 10−5 −10.20

310 3.23 × 10−3 1.34 × 10−4 −8.92

320 3.13 × 10−3 5.48 × 10−4 −7.51

330 3.03 × 10−3 2.01 × 10−3 −6.21

340 2.93 × 10−3 7.23 × 10−3 −4.93

Plot a graph of ln k against 1/T and use it to determine the activation energy, Ea .
Include the sign and units of the gradient and the activation energy.
(7)
The Arrhenius equation can be expressed as

Ea 1
ln k = − × + constant
R T
[R = 8.31 J mol−1 K−1]

26
*P67746A02628*
TOTAL FOR SECTION C = 20 MARKS
TOTAL FOR PAPER = 90 MARKS

*P67746A02728*
27
Please check the examination details below before entering your candidate information
Candidate surname Other names

Pearson Edexcel Centre Number Candidate Number

International
Advanced Level

Time 1 hour 45 minutes

Paper
reference WCH14/01
Chemistry
International Advanced Level
UNIT 4: Rates, Equilibria and Further Organic
Chemistry
June 2021

You must have: Total Marks

Scientific calculator, Data Booklet, ruler

Instructions
• Use black ink or ball-point pen.
• Fill in the boxes at the top of this page with your name,
centre number and candidate number.
• Answer all questions.
• – there may
Answer the questions in the spaces provided
be more space than you need.
• Show all your working in calculations and include units where appropriate.
Information
• The total mark for this paper is 90.
• The marks for each question are shown in brackets
– use this as a guide as to how much time to spend on each question.
• structure
In the question marked with an asterisk (*), marks will be awarded for your ability to
your answer logically, showing how the points that you make are related or
follow on from each other where appropriate.
• A Periodic Table is printed on the back cover of this paper.

Advice
• Read each question carefully before you start to answer it.
• Checkanswer
Try to every question.
• Good luck
your answers if you have time at the end.
• with your examination.
Turn over

*P64626A0132*
P64626A
©2021 Pearson Education Ltd.

1/1/1/1/1/1/1/1
SECTION A

Answer ALL the questions in this section.

You should aim to spend no more than 20 minutes on this section.

For each question, select one answer from A to D and put a cross in the box .
If you change your mind, put a line through the box and then mark
your new answer with a cross .
1 Which of these gases would have the greatest standard molar entropy?

A NH3

B H2

C N2

D SO2

(Total for Question 1 = 1 mark)

2 What is the standard entropy change of the system, in J K–1 mol–1, for the reaction
between nitrogen and hydrogen to form ammonia?
N2 + 3H2 → 2NH3

Standard molar entropy / J K–1 mol–1

H2 130.6

N2 191.6

NH3 192.3

A –198.8

B –129.9

C +129.9

D +198.8

(Total for Question 2 = 1 mark)

2
*P64626A0232*
3 The enthalpy change of solution of sodium sulfate, Na2SO4 , may be calculated using
three pieces of data. Which of these pieces of data is not required?

A lattice energy of Na2SO4

B enthalpy change of hydration of Na+

C enthalpy change of formation of Na2SO4

D enthalpy change of hydration of SO42–

(Total for Question 3 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

3
*P64626A0332* Turn over
4 A graph of pH against volume of acid added for an acid-base titration is shown.

14
12
10

pH 8
6
4
2

Volume of acid added

(a) Which acidic solution was used in the titration?

(1)

A 0.1 mol dm–3 CH3COOH

B 1.0 mol dm–3 CH3COOH

C 0.1 mol dm–3 HCl

D 1.0 mol dm–3 HCl

(b) Which basic solution was used in the titration?
(1)
A NH3

B LiOH
C Ba(OH)2

D NaOH

4
*P64626A0432*
(c) A student suggested five indicators that might be used in this titration:
thymol blue
methyl orange
bromophenol blue
bromocresol green
phenolphthalein
How many of these indicators would be suitable? Use your Data Booklet.
(1)
A 5

B 4

C 3

D 2

(Total for Question 4 = 3 marks)

5 The halogenoalkane 2-bromo-2-methylbutane was hydrolysed with

sodium hydroxide solution, NaOH(aq).
Which suggestion about the mechanism of this reaction is correct?

Type of mechanism Number of steps in mechanism

A SN2 one

B SN2 two

C SN1 one

D SN1 two

(Total for Question 5 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

5
*P64626A0532* Turn over
6 Nitrogen monoxide and hydrogen react together to form nitrogen and water.
2NO + 2H2 → N2 + 2H2O
The steps in the mechanism of the reaction are
Step 1 2NO ⇌ N2O2 fast
Step 2 N2O2 + H2 → N2O + H2O slow
Step 3 N2O + H2 → N2 + H2O fast
Which statement about the reaction is correct?

A Step 3 is the rate determining step and the overall order is 2

B Step 3 is the rate determining step and the overall order is 4

C Step 2 is the rate determining step and the overall order is 2

D Step 2 is the rate determining step and the overall order is 3

(Total for Question 6 = 1 mark)

7 The Arrhenius equation can be shown as

Ea 1
In k = – × + constant
R T

A graph is plotted of ln k against 1/T for a reaction.

The activation energy, Ea , of this reaction equals

A – gradient ÷ R

B + gradient ÷ R
C – gradient × R

D + gradient × R

(Total for Question 7 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

6
*P64626A0632*
8 The compound menthol has the structure shown.
Some of the carbon atoms are labelled P, Q, R and S.

P
menthol
Q
R OH
S

(a) What is the number of chiral centres in a molecule of menthol?

(1)
A 1

B 2

C 3
D 4
(b) Which of the carbon atoms is responsible for a peak at 72 ppm in the
13
C NMR spectrum of menthol?
(1)
A P

B Q

C R

D S

7
*P64626A0732* Turn over
(c) Four groups of students warmed samples of menthol with sodium dichromate(VI)
in acid. They purified the reaction mixture and carried out a series of qualitative
tests on the organic product.
The findings of each group in the class are shown in the table.

menthol

Qualitative test

Add Warm with Add

Group
2,4-dinitrophenylhydrazine Fehling’s solution PCl5

One ü  ü

Two ü  

Three ü ü 

Four   ü

A tick (ü) shows a positive result, a cross () shows a negative result.
Which group recorded the results you would expect?
(1)

A One

B Two

C Three

D Four

(Total for Question 8 = 3 marks)

Use this space for any rough working. Anything you write in this space will gain no credit.

8
*P64626A0832*
9 The substance known as PHBV is a biodegradable polymer formed from
3-hydroxybutanoic acid and 3-hydroxypentanoic acid.
OH O OH O

OH OH
3-hydroxybutanoic acid 3-hydroxypentanoic acid

(a) Which of these is the repeat unit of the polymer?

(1)

A O O O

O O

B O O

O O

C O O

O O

D O O

O
O O

(b) What reaction occurs when PHBV biodegrades to its monomers?

(1)
A condensation

B hydrolysis

C hydration

D hydrogenation

(Total for Question 9 = 2 marks)

9
*P64626A0932* Turn over
10 Which reagent reacts at room temperature with methylamine, CH3NH2, to form the
compound N-methylethanamide?

A CH3COCH3

B CH3COOH

C CH3COOCH3

D CH3COCl

(Total for Question 10 = 1 mark)

11 This question is about chromatography.

(a) A spot caused by an amino acid has moved 42 mm from the baseline of a
paper chromatogram.
The Rf value for the amino acid under these conditions is 0.62.
What is the distance moved by the solvent?
(1)
A 680 mm

B 68 mm

C 42 mm

D 26 mm
(b) In gas chromatography, GC, which of these would be the most suitable
carrier gas?
(1)
A argon
B hydrogen

C methane

D oxygen

(Total for Question 11 = 2 marks)

Use this space for any rough working. Anything you write in this space will gain no credit.

10
*P64626A01032*
12 The high resolution mass spectrum of a compound X has a molecular ion peak at
m / z = 44.0632. Accurate relative atomic masses are given in the table.

Element Relative atomic mass

Hydrogen 1.0079

Carbon 12.0000

Oxygen 15.9949

Which of these compounds, with a relative molecular mass of 44, gives rise to
this peak?

A O
H
H
C
C H

B H

C OH
H C

C H
H H
H H
C
C C
H

H H

D O C O

(Total for Question 12 = 1 mark)

11
*P64626A01132* Turn over
13 How many optical isomers does this molecule have?

Br OH

A 2

B 3

C 6

D 8

(Total for Question 13 = 1 mark)

14 Which of these structures is not identical to the others?

OH H3C OH OH
Cl CH2CH3
C C C C
Cl CH2CH3 Cl CH2CH3 H3CH2C Cl
CH3 OH CH3 H3C
Structure A Structure B Structure C Structure D

A Structure A
B Structure B

C Structure C

D Structure D

(Total for Question 14 = 1 mark)

TOTAL FOR SECTION A = 20 MARKS

12
*P64626A01232*
SECTION B
Answer ALL the questions. Write your answers in the spaces provided.
15 The standard enthalpy change of solution for ammonium nitrate,
NH4NO3 , is +25.7 kJ mol–1.
(a) Calculate the value for the standard entropy change in the surroundings,
∆Ssurroundings , when ammonium nitrate dissolves in water at 298 K.
Include a sign and units with your answer.
(2)

(b) Explain what can be deduced from your answer in (a) about the sign and
the value of the standard entropy change in the system, ∆Ssystem , when
NH4NO3 dissolves.
(3)

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(Total for Question 15 = 5 marks)

13
*P64626A01332* Turn over
16 A student investigated the kinetics of the reaction between bromate(V) ions and
bromide ions in acidic conditions.
BrO3–(aq) + 5Br–(aq) + 6H+(aq) → 3Br2(aq) + 3H2O(l)
(a) In the first experiment, the student measured the initial rate of the reaction
at five different concentrations of bromate(V) ions, BrO3–. In each case, the
initial concentrations of bromide ions and hydrogen ions were constant and in
large excess. The results obtained are shown.

Initial concentration of Initial rate of reaction

bromate(V) ions / mol dm–3 / mol dm–3 s–1

0.030 4.17 × 10–7

0.060 8.34 × 10–7

0.090 1.25 × 10–6

0.120 1.67 × 10–6

0.150 2.09 × 10–6

(i) Use the results to plot a suitable graph that can be used to show that the
reaction is first order with respect to bromate(V) ions.
(3)

14
*P64626A01432*
(ii) State how your graph shows that the reaction is first order with respect to
bromate(V) ions.
(1)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(b) In the second experiment, the student determined the initial rates of the same
reaction starting with different concentrations of the reactants.

[BrO3–] [Br–] [H+] Initial rate of reaction

Run
/ mol dm–3 / mol dm–3 / mol dm–3 / mol dm–3 s–1

1 0.062 0.21 0.40 1.52 × 10–5

2 0.31 0.21 0.20 1.90 × 10–5

3 0.062 0.63 0.40 4.56 × 10–5

(i) Use these results and your answer to (a) to deduce the orders with respect to
Br– ions and H+ ions.
(2)

Br– ions. ........... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................................... . . . . . . . . . . . . . . . . . . . .

H+ ions.............. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................................... . . . . . . . . . . . . . . . . . . . .
(ii) Write the rate equation for the reaction.
(1)

(iii) Use the results for Run 1 and your rate equation from (b)(ii) to calculate the
value for the rate constant, k. Include units in your answer.
(3)

15
*P64626A01532* Turn over
(c) The presence of bromate(V) ions in drinking water is harmful to humans.
Bromate(V) ions can be converted to less harmful bromide ions by passing the
water through palladium with a reducing agent.
Describe how a heterogeneous catalyst, such as palladium, increases the
rate of a reaction.
(3)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(Total for Question 16 = 13 marks)

16
*P64626A01632*
17 This question is about an ester, Y, with the molecular formula C8H16O2 .
(a) Y contains 66.7 % carbon, 11.1 % hydrogen and 22.2 % oxygen by mass. Show that
these data are consistent with its molecular formula.
(2)

(b) The structure of compound Y is

CH3
CH3

CH2 O C

H3C C C H2 CH3

(i) Give the IUPAC name of Y.

(2)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(ii) Draw the structures of two organic compounds that would react
together to form Y.
(1)

18
*P64626A01832*
(c) The high resolution proton NMR spectrum of compound Y was obtained.
(i) Label the three remaining hydrogen environments B, C and D on
the structure.
(1)
CH3
CH3

CH2 O C

H3C C C H2 CH3

A
O

(ii) Complete the table.

(3)

Hydrogen Splitting pattern Relative

environment of peak peak area

A triplet 3

(Total for Question 17 = 9 marks)

19
*P64626A01932* Turn over
*18 The table shows the theoretical and experimental (Born-Haber) lattice energy data for
two metal halide compounds, sodium chloride and magnesium iodide.

Lattice energy / kJ mol–1

Experimental
Metal halide Theoretical
(Born-Haber)

Sodium chloride −770 −780

Magnesium iodide −1944 −2327

Using the data, compare and contrast the type and strength of bonding
in these compounds.
Give reasons for your answers.
(6)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

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20
*P64626A02032*
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(Total for Question 18 = 6 marks)

21
*P64626A02132* Turn over
19 The compound lactic acid can be synthesised from ethanal in two steps.

H H
H
Step 1 Step 2
H3C C H3C C CN H3C C COOH
KCN and HCN
O
OH OH
ethanal lactic acid

(a) (i) Give the mechanism for Step 1. Include curly arrows, and any
relevant lone pairs and dipoles.
(4)

(ii) A student predicted that the product of Step 1 would rotate the
plane of plane-polarised light.
Comment on this prediction.
(3)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

22
*P64626A02232*
(iii) Complete the table that summarises information about Step 2.
State symbols are not required for the equation.
(4)

Conversion of CH3CH(OH)CN to lactic acid

Reaction type

Reagent

Conditions

Equation

(b) Sodium hydrogencarbonate, NaHCO3 , has been used by some athletes to help
prevent lactic acid causing muscle pain during exercise.
Write an equation for the reaction between sodium hydrogencarbonate
and lactic acid.
(1)

23
*P64626A02332* Turn over
(c) Sodium hydrogencarbonate is part of a buffer in the body that controls the
pH of blood. Two of the equilibria involved in this process are shown.
Equilibrium 1 HCO3– + H3O+ ⇌ H2CO3 + H2O
Equilibrium 2 H2CO3 ⇌ CO2 + H2O
(i) Use the equilibria to explain how the buffer keeps the pH of blood nearly
constant when a small increase in the concentration of hydrogen ions occurs.
(3)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(ii) The pH of a blood sample was found to be 7.41.

Calculate the ratio of the concentration of HCO3– to H2CO3 in the blood sample.
H2CO3 + H2O ⇌ HCO3– + H3O+
Ka = 4.50 x 10–7 mol dm–3
(3)

(Total for Question 19 = 18 marks)

TOTAL FOR SECTION B = 51 MARKS

24
*P64626A02432*
SECTION C
Answer ALL the questions. Write your answers in the spaces provided.
20 The reversible reaction between hydrogen chloride and oxygen produces
water vapour and chlorine.
4HCl(g) + O2(g) ⇌ 2H2O(g) + 2Cl2(g) ∆H = –114 kJ mol–1
(a) Explain what effect, if any, each of the following changes has on the yield of
chlorine at equilibrium and on the equilibrium constant, Kp.
(i) An increase in the total pressure
(3)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(ii) An increase in the temperature

(2)

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(iii) The use of a catalyst

(2)

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25
*P64626A02532* Turn over
(b) 0.850 mol of hydrogen chloride was mixed with 0.600 mol of oxygen and allowed
to reach equilibrium in a closed flask.
At equilibrium the total pressure was 1.50 atm and there was 0.250 mol of
chlorine in the flask.
4HCl(g) + O2(g) ⇌ 2H2O(g) + 2Cl2(g)
(i) Complete the table.
(3)

Initial amount Equilibrium amount Mole fraction

Substance
/ mol / mol at equilibrium

HCl 0.850

O2 0.600

H2O 0

Cl2 0 0.250 0.189

Total moles at equilibrium =

(ii) Write the expression for the equilibrium constant, Kp .

(1)

26
*P64626A02632*
(iii) Use your answers to (b)(i) and (b)(ii) to calculate the value for Kp . Give your
answer to an appropriate number of significant figures, and include units.
(3)

(iv) Use your answer to (b)(iii) to calculate a value for the total entropy change of
the reaction, ΔStotal .
(2)

27
*P64626A02732* Turn over
(c) Draw a sketch of entropy against temperature for water to illustrate the
entropy changes as temperature increases, including when water changes state.
A scale is not required for the vertical axis
(3)

Entropy

0 100 200 300 400 500

Temperature / K

(Total for Question 20 = 19 marks)

TOTAL FOR SECTION C = 19 MARKS

TOTAL FOR PAPER = 90 MARKS

28
*P64626A02832*
Please check the examination details below before entering your candidate information
Candidate surname Other names

Centre Number Candidate Number

October 2021

Pearson Edexcel International Advanced Level

Time 1 hour 45 minutes
Paper
reference WCH14/01
Chemistry
 

International Advanced Level

UNIT 4: Rates, Equilibria and Further Organic
Chemistry
You must have: Total Marks
Scientific calculator, Data Booklet, ruler

Instructions
• Use black ink or black ball-point pen.
• Fill in the boxes at the top of this page with your name,
centre number and candidate number.
• Answer all questions.
• Answer the questions in the spaces provided
– there may be more space than you need.

Information
• The total mark for this paper is 90.
• The marks for each question are shown in brackets
– use this as a guide as to how much time to spend on each question.
• toIn the question marked with an asterisk (*), marks will be awarded for your ability
structure your answer logically, showing how the points that you make are
related or follow on from each other where appropriate.
• A Periodic Table is printed on the back cover of this paper.

*P67130A0128*
P67130A
©2021 Pearson Education Ltd.

E:1/1/1/1/
SECTION A

Answer ALL the questions in this section.

You should aim to spend no more than 20 minutes on this section.

For each question, select one answer from A to D and put a cross in the box .
If you change your mind, put a line through the box and then mark your new answer
with a cross .

1 The decomposition of ammonia is catalysed by tungsten metal.

tungsten
2NH3(g) N2(g) + 3H2(g)

This reaction has zero order kinetics.

(a) What is the rate equation for this reaction?
(1)
A rate = k
B rate = k[NH3]

C rate = k[NH3]2

D rate = k[N2][H2]3

(b) What are the units of the rate constant, k, for this zero order reaction?
(1)
A no units

B s−1
C mol dm−3 s−1

D dm3 mol−1 s−1

2
*P67130A0228* 
(c) Which of these graphs represents this zero order reaction?
(1)

Rate Rate

[NH3] [NH3]

A B

[NH3] [NH3]

Time Time

C D

(Total for Question 1 = 3 marks)

2 What is the effect of increasing temperature on the average energy of the particles in
a reaction and on the activation energy of the reaction?

Effect on the Effect on the

average energy activation energy
A unchanged decreased

B unchanged unchanged

C increased decreased

D increased unchanged

(Total for Question 2 = 1 mark)

3
 *P67130A0328* Turn over
3 Ammonium nitrate is very soluble in water.

NH4NO3(s) + aq → NH+4 (aq) + NO3−(aq) ∆H = +25.8 kJ mol−1

What is the best explanation for this?

A all ammonium salts are soluble in water

B the activation energy of the reaction is very low

C the enthalpies of hydration of the ions are very exothermic

D the entropy change of the system, ∆Ssystem , is positive

(Total for Question 3 = 1 mark)

4 The decomposition of calcium carbonate is an important reaction in the

manufacture of cement.

CaCO3(s) → CaO(s) + CO2(g) ∆H = +178 kJ mol−1

What are the signs of the entropy change of the system, ∆Ssystem , and of the
entropy change of the surroundings, ∆Ssurroundings ?

Sign of ∆Ssystem Sign of ∆Ssurroundings

A positive positive

B positive negative

C negative positive

D negative negative

(Total for Question 4 = 1 mark)

5 The standard molar entropy, S , of a substance

A is not affected by changes of state or changes in temperature

B only changes when the temperature changes

C only changes when the substance changes state

D changes when the temperature changes and when the substance changes state

(Total for Question 5 = 1 mark)

4
*P67130A0428* 
6 The water gas reaction is used in the manufacture of hydrogen.

C(s) + H2O(g)  CO(g) + H2(g) ∆H = +131.2 kJ mol−1

(a) What is the equilibrium constant, Kc , for this reaction?

(1)
[CO][H2 ]
A Kc = [CO][H2] B Kc =
[C]

[CO][H2 ] [CO][H2 ]
C Kc = D Kc =
[H2O] [H2O][C]

(b) What happens to the equilibrium constants of the forward and reverse reactions
when the temperature is increased?
(1)
Kc of forward reaction Kc of reverse reaction
A increases increases

B increases decreases

C decreases increases

D decreases decreases

(Total for Question 6 = 2 marks)

Use this space for any rough working. Anything you write in this space will gain no credit.

5
 *P67130A0528* Turn over
7 The diagram shows the Born-Haber cycle for magnesium chloride.

Mg2+(g) + 2e− + 2Cl(g)

x
y
Mg(g) + 2Cl(g)

w
Mg2+(g) + 2Cl−(g)

Mg(g) + Cl2(g)

v
LE
Mg(s) + Cl2(g)

MgCl2(s)

(a) Which of these is the electron affinity of chlorine?

(1)
A y

B y/2
C (w + y)

D (w + y)/2

(b) Which expression gives the lattice energy (LE) for magnesium chloride?
(1)
A LE = u − (v + w + x + y)

B LE = v + w + x + y − u

C LE = y − u − (v + w + x)

D LE = v + w + x − y + u

6
*P67130A0628* 
(c) Which energy change in the cycle does x represent?
(1)
A the first ionisation energy of magnesium

B the second ionisation energy of magnesium

C the sum of the first and second ionisation energies of magnesium

D the sum of the enthalpy change of atomisation and the first and second
ionisation energies of magnesium

(Total for Question 7 = 3 marks)

8 When ethanoic acid and chloroethanoic acid are mixed, an equilibrium is set up.

CH3COOH + CH2ClCOOH  CH3COOH2+ + CH2ClCOO−

The Brønsted-Lowry acids in this equilibrium are

A CH3COOH and CH2ClCOOH

B CH3COOH and CH3COOH2+

C CH2ClCOOH and CH3COOH2+

D CH3COOH2+ and CH2ClCOO−

(Total for Question 8 = 1 mark)

9 What is the pH of 0.010 mol dm−3 aqueous calcium hydroxide, Ca(OH)2(aq)?

[pKw = 14]

A 11.7

B 12.0

C 12.3

D 13.3

(Total for Question 9 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

7
 *P67130A0728* Turn over
10 Citronellol is found in rose and geranium oils.

citronellol

The type(s) of stereoisomerism shown by citronellol is

A optical and geometric isomerism

B optical isomerism only

C geometric isomerism only

D neither optical nor geometric isomerism

(Total for Question 10 = 1 mark)

11 Ethanal and propane have the same molar mass but ethanal has a much higher
boiling temperature.
Ethanal is fully miscible in water but propane is almost insoluble.
Which intermolecular forces of ethanal are mainly responsible for the differences in
these properties?

Higher boiling temperature Greater solubility in water

A hydrogen bonds hydrogen bonds

B permanent dipole forces permanent dipole forces

C hydrogen bonds permanent dipole forces

D permanent dipole forces hydrogen bonds

(Total for Question 11 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

8
*P67130A0828* 
12 An unknown aldehyde may be identified by measuring the melting temperature of
the purified precipitate formed in its reaction with

A 2,4-dinitrophenylhydrazine

B Fehling’s solution

C potassium dichromate and sulfuric acid

D Tollens’ reagent

(Total for Question 12 = 1 mark)

13 Butanoic acid may be prepared by the acid hydrolysis of

A butyl ethanoate

B 1-chlorobutane

C ethyl butanoate

D propanenitrile

(Total for Question 13 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

9
 *P67130A0928* Turn over
14 Terylene is a polyester derived from ethane-1,2-diol and terephthalic acid.

HO OH
C C

O O

terephthalic acid

What is the structure of the repeat unit of terylene?

O O

A C C
O O

O O

B C C
O O

O O
C C
C
O O

O O
C C
D
O O

(Total for Question 14 = 1 mark)

10
*P67130A01028* 
15 The formation of esters and the hydrolysis of esters are reactions that are slow under
normal laboratory conditions.
What speeds up these reactions?

Esterification Hydrolysis
A acids only acids only

B acids only acids and bases

C bases only bases only

D bases only acids and bases

(Total for Question 15 = 1 mark)

TOTAL FOR SECTION A = 20 MARKS

11
 *P67130A01128* Turn over
SECTION B
Answer ALL the questions. Write your answers in the spaces provided.
16 Compound X is used by mammals as an alternative energy source to sugars.
X is a compound of carbon, hydrogen and oxygen only.
(a) Complete combustion of a 2.50 g sample of X in dry oxygen produced
4.31 g of carbon dioxide and 1.32 g of water as the only products.
(i) Give a reason why the oxygen used must be dry.
(1)

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(ii) Show that the empirical formula of X is C4H6O3 . You must show your working.
(5)

12
*P67130A01228* 
(b) Compound X gave an orange precipitate with Brady’s reagent
(2,4-dinitrophenylhydrazine) but no reaction with Tollens’ reagent.
When X was added to a solution of sodium hydrogencarbonate, effervescence
occurred and the gas evolved turned limewater cloudy.
The carbon-13 NMR spectrum of X had only four peaks.
(i) Deduce the two possible structures of X, showing how this information
supports your answer.
(6)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

13
 *P67130A01328* Turn over
(ii) Give a chemical test which would allow you to distinguish between the two
compounds you have given in (b)(i). Include the reagents required and the
result for each of the compounds.
(3)

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14
*P67130A01428* 
(c) A simplified high resolution proton (1H) NMR spectrum of compound X is shown.

12 10 8 6 4 2 0
δ / ppm
Explain how the number of peaks in the 1H NMR spectrum, together with their
relative heights, their chemical shifts and their splitting patterns, may be used to
confirm the structure of X. Use the chemical shifts given in your Data Booklet.
(5)

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(Total for Question 16 = 20 marks)

15
 *P67130A01528* Turn over
17 The decomposition of benzenediazonium chloride is a first order reaction.

C6H5N2Cl + H2O → C6H5OH + N2 + HCl

The activation energy of this reaction was determined by measuring the rate constant
at various temperatures.
(a) In an experiment at 333 K, the concentration of a sample of
benzenediazonium chloride was measured at various times during its
decomposition. The results of this experiment are shown.

Time / s [C6H5N2Cl] / mol dm−3

0.0 0.500

40.0 0.410

100 0.285

200 0.165

280 0.100

350 0.070

400 0.050

16
*P67130A01628* 
(i) Plot a graph of concentration of benzenediazonium chloride against time.
(3)

(ii) Determine a value for the half-life, t½ , of this reaction.

You must show your working on the graph.
(1)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

17
 *P67130A01728* Turn over
(iii) Calculate the rate constant, k, for the reaction at 333 K.
Include units in your answer.
Use the expression ln 2 = kt½
(2)

(b) The experiment described in (a) was repeated for five temperatures and the data
used to plot a graph for the Arrhenius equation in the form

Ea 1
ln k = − × + constant
R T
1/T / K−1
0.0029 0.0030 0.0031 0.0032 0.0033 0.0034 0.0035
0

−2

−4

−6
ln k
−8

−10

−12

−14

(i) Use the rate constant that you have calculated in (a)(iii) to obtain data for a
point on the graph for 333 K.
(2)

18
*P67130A01828* 
(ii) Plot your data from (b)(i) on the graph.
(1)

(iii) Determine the gradient of the graph by drawing a best-fit line.

Include a sign and units in your answer.
(3)

(iv) Use the gradient determined in (b)(iii) to calculate the activation energy for
the decomposition of benzenediazonium chloride.
Include a sign and units with your answer.
(3)

(Total for Question 17 = 15 marks)

19
 *P67130A01928* Turn over
*18 The hydrolysis of halogenoalkanes by alkali is a nucleophilic substitution reaction.

RX + OH− → ROH + X−

The mechanism of this reaction for primary halogenoalkanes is different from the
mechanism for tertiary halogenoalkanes.
Describe how knowledge of the rate equations for the hydrolysis of halogenoalkanes
provides evidence for the mechanisms of these reactions.
Curly arrow mechanisms are not required.
(6)

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*P67130A02028* 
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(Total for Question 18 = 6 marks)

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 *P67130A02128* Turn over
19 Ethanol may be manufactured by the hydration of ethene.

C2H4(g) + H2O(g)  C2H5OH(g) ∆H = −45.3 kJ mol−1

(a) In a laboratory investigation of this reaction, 1.00 mol of ethene was mixed with
1.00 mol of steam at 150 °C. At equilibrium, when the total pressure of the system
was 50.0 atm, 0.450 mol of ethanol had formed.
(i) Give the expression for the equilibrium constant, Kp , for the reaction.
(1)

(ii) Calculate the equilibrium constant, Kp , for the hydration of ethene at 150 °C.
Include units with your answer.
(5)

22
*P67130A02228* 
(b) The manufacture of ethanol is carried out at 230 °C and 70 atm; the overall
conversion into ethanol is 95 % .
Comment on these conditions in relation to their effect on the equilibrium and
the overall yield of ethanol.
(3)

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(Total for Question 19 = 9 marks)

TOTAL FOR SECTION B = 50 MARKS

23
 *P67130A02328* Turn over
SECTION C
Answer ALL the questions. Write your answers in the spaces provided.
20 Sodium hydrogensulfate is a widely used acid, with applications that include
removing limescale and as a food additive. Sodium hydrogensulfate is a weak acid
because of the presence of the hydrogensulfate ion, HSO4− .
(a) (i) Write the equation for the dissociation of the hydrogensulfate ion in
aqueous solution. State symbols are not required.
(1)

(ii) A solution of sodium hydrogensulfate has pH = 1.13

Calculate the concentration of this solution, in g dm−3.
[pKa of HSO4− = 1.92]
(5)

24
*P67130A02428* 
(iii) State the assumptions you have used in (a)(ii).
(2)

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(b) A solution containing sodium hydrogensulfate and sodium sulfate is a buffer that
is used to preserve urine for steroid analysis.
(i) State what is meant by the term buffer.
(2)

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(ii) Calculate the pH of the buffer prepared by dissolving 0.750 mol of

sodium hydrogensulfate and 0.500 mol of sodium sulfate in distilled water to
make 1.00 dm3 of solution.
(3)

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 *P67130A02528* Turn over
(iii) Separate samples of 0.00500 mol of hydrochloric acid are added to 1.00 dm3
of distilled water and to the buffer in (b)(ii).
Calculate the pH changes that result in each case.
Assume that the volumes remain constant at 1.00 dm3 .
(4)

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*P67130A02628* 
(c) The titration curve obtained from the addition of sodium hydroxide solution to a
weak acid is shown. The equivalence point (E) of this titration occurred at pH = 8

pH E

Volume of NaOH / cm3

Explain the observations that would be made if methyl orange (pKIn = 3.7) were
used as the indicator for this titration.
(3)

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(Total for Question 20 = 20 marks)

TOTAL FOR SECTION C = 20 MARKS

TOTAL FOR PAPER = 90 MARKS
27
 *P67130A02728*
28
*P67130A02828* 
Please check the examination details below before entering your candidate information
Candidate surname Other names

Centre Number Candidate Number

January 2022

Pearson Edexcel International Advanced Level

Time 1 hour 45 minutes
Paper
reference WCH14/01
Chemistry
 

International Advanced Level

UNIT 4: Rates, Equilibria and Further Organic
Chemistry
You must have: Total Marks
Scientific calculator, Data Booklet, ruler

Information
• The total mark for this paper is 90.
• The marks for each question are shown in brackets
– use this as a guide as to how much time to spend on each question.
• Into the question marked with an asterisk (*), marks will be awarded for your ability
structure your answer logically, showing how the points that you make are
related or follow on from each other where appropriate.
• A Periodic Table is printed on the back cover of this paper.

*P69507A0132*
P69507A
©2022 Pearson Education Ltd.

L:1/1/1/1/
SECTION A

Answer ALL the questions in this section.

You should aim to spend no more than 20 minutes on this section.

For each question, select one answer from A to D and put a cross in the box .
If you change your mind, put a line through the box and then mark your new answer
with a cross .

1 A simplified Born‑Haber cycle for the formation of lithium iodide is shown.

–759 kJ mol–1
+
Li (g) + I (g)
–
LiI(s)

electron
+520 kJ mol–1
affinity

Li(g) + ................................... –270 kJ mol–1

+160 kJ mol–1 +107 kJ mol–1

Li(s) + ...................................

(a) The enthalpy change of atomisation of iodine (+107 kJ mol–1) is given by

the equation
(1)

A ½I2(g) → I(g)
B ½I2(s) → I(g)

C I2(g) → 2I(g)

D I2(s) → 2I(g)

(b) Use the information in the cycle to calculate the electron affinity of iodine.
(1)

A –298 kJ mol–1

B –242 kJ mol–1

C +242 kJ mol–1

D +298 kJ mol–1

(Total for Question 1 = 2 marks)

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*P69507A0232* 
2 Some energy changes are given in the table.

Energy change Value / kJ mol–1

Lattice energy for CaCl2(s) –2258

Enthalpy change of solution of CaCl2(s) –120

Enthalpy change of hydration of Cl–(g) –364

Use these data to calculate the enthalpy change of hydration of Ca2+(g).

A –1410 kJ mol–1

B –1650 kJ mol–1

C –2014 kJ mol–1

D –3106 kJ mol–1

(Total for Question 2 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

3
 *P69507A0332* Turn over
3 The reaction shown is at equilibrium. The forward reaction is endothermic.

C(s) + CO2(g)  2CO(g)

(a) Which will increase when the temperature is lowered?

(1)
A the mole fraction of carbon dioxide

B the partial pressure of carbon monoxide

C the rate of the backward reaction

D the value of Kp for the forward reaction

(b) At 680 °C and 1 atm, 52.6 % of the molecules in the gas mixture are carbon
monoxide. What is the partial pressure of carbon dioxide, in atmospheres?
(1)
A 0.237

B 0.263
C 0.474

D 0.526

(Total for Question 3 = 2 marks)

4 The equation for the precipitation of lead(II) chloride is shown.

Pb2+(aq) + 2Cl–(aq)  PbCl2(s)

What are the units of the equilibrium constant, Kc ?

A dm9 mol–3

B dm6 mol–2

C mol2 dm–6

D mol3 dm–9

(Total for Question 4 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

4
*P69507A0432* 
5 An example of a diprotic acid is cis‑butenedioic acid. Titration of this acid using
sodium hydroxide solution gave the titration curve shown.

14
12
10
8
pH
6
4
2
0
0 20 40 60 80
Volume of sodium hydroxide solution / cm3

Which indicator would be most suitable for measuring the end‑point of the
neutralisation of the proton in cis‑butenedioic acid which has a pKa = 6.33?
Use your Data Booklet.

A bromocresol green

B bromothymol blue

C litmus

D phenolphthalein

(Total for Question 5 = 1 mark)

6 At 25 °C, the pH of pure water is 7.00 and at 100 °C, the pH of pure water is 6.14.
What can be deduced from this information?

Enthalpy change of
Concentration of hydrogen ions
dissociation of water
A endothermic higher at 100 °C than at 25 °C

B endothermic lower at 100 °C than at 25 °C

C exothermic higher at 100 °C than at 25 °C

D exothermic lower at 100 °C than at 25 °C

(Total for Question 6 = 1 mark)

5
 *P69507A0532* Turn over
7 The anti‑inflammatory drug ketoprofen has the structure shown.

O OH O

What is the molecular formula of ketoprofen?

A C15H12O3

B C16H13O3

C C16H14O3

D C16H17O3

(Total for Question 7 = 1 mark)

8 Menthol has a number of medicinal uses. It can be extracted from the

peppermint plant.
The structure of menthol is

How many chiral centres are there in one molecule of menthol?

A 1

B 2

C 3

D 4

(Total for Question 8 = 1 mark)

6
*P69507A0632* 
9 Which of these reactions does not result in the formation of a racemic mixture?

A but‑2‑ene with HCl

B but‑1‑ene with HCl

C propanal with HCN

D propanone with HCN

(Total for Question 9 = 1 mark)

10 When a single enantiomer of 2‑iodobutane reacts with sodium hydroxide,

the product is a mixture of enantiomers. This is because

A the reaction is a nucleophilic substitution

B the reaction proceeds via a negatively charged transition state

C the reaction proceeds via a carbocation intermediate

D the reaction rate depends on the concentration of 2‑iodobutane

(Total for Question 10 = 1 mark)

11 How many structural isomers with the molecular formula C5H10O react
with Tollens’ reagent?

A 2

B 3

C 4
D 5

(Total for Question 11 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

7
 *P69507A0732* Turn over
12 Propanone reacts with iodine in both acidic and alkaline conditions.
(a) The products of the reactions under the stated conditions include
(1)
Acidic conditions Alkaline conditions

A CH3I CH3COO–

B CH3COCI3 CH3COO–

C CH3COCH2I CH3I

D CH3COCH2I CHI3

(b) The rate equation for the reaction between propanone and iodine
in acidic conditions is

rate = k[H+][CH3COCH3]

The reaction was carried out at two different pH values, all other conditions
remaining unchanged.
In the first reaction pH = 2.0
In the second reaction the rate was found to be 1/3 of the original value.
What was the pH of the second reaction, to 1 decimal place?
(1)
A 0.7

B 1.5
C 2.5

D 2.7

(Total for Question 12 = 2 marks)

Use this space for any rough working. Anything you write in this space will gain no credit.

8
*P69507A0832* 
13 But‑2‑ene‑1,4‑diol may be converted into 2‑oxobutanedioic acid in a two‑step
synthesis through an intermediate compound W.

steam and H2SO4

HOCH2CH CHCH2OH W HO2CCOCH2CO2H
Step 1 Step 2
but‑2‑ene‑1,4‑diol 2‑oxobutanedioic acid

Identify the intermediate compound W and the reagent for Step 2.

Compound W Reagent for Step 2

A HOCH2CH(OH)CH2CH2OH LiAlH4 in dry ether

B HOOCH2CH CHCOOH LiAlH4 in dry ether

C OHCCH(OH)CH2CHO hot acidified K2Cr2O7

D HOCH2CH(OH)CH2CH2OH hot acidified K2Cr2O7

(Total for Question 13 = 1 mark)

14 Compound X, C4H10O, is oxidised to form compound Y.

Compound Y reacts with ethanol in the presence of concentrated sulfuric acid to give
an ester, Z.
Which of these could be the formula of Z?

A CH3COOC(CH3)3

B CH3CH2COO(CH2)3CH3
C (CH3)2CHCOOCH2CH3

D CH3CH2COOCH2CH(CH3)2

(Total for Question 14 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

9
 *P69507A0932* Turn over
15 Which of these compounds is a product of the hydrolysis of CH3COOC3H7 by refluxing
with aqueous sodium hydroxide?

A CH3OH

B C3H7OH

C C3H7COOH

D C3H7COO–Na+

(Total for Question 15 = 1 mark)

16 In gas chromatography, a gas containing a mixture is passed over a liquid

stationary phase. The main reason a mixture is separated into its components is
because they have different

A boiling temperatures

B forces of attraction to the liquid

C relative molecular masses

D volatilities

(Total for Question 16 = 1 mark)

17 In HPLC, the mobile and stationary phases are

Mobile phase Stationary phase

A gas liquid

B gas solid

C liquid gas

D liquid solid

(Total for Question 17 = 1 mark)

TOTAL FOR SECTION A = 20 MARKS

10
*P69507A01032* 
SECTION B

Answer ALL the questions. Write your answers in the spaces provided.

18 Bromate(V) ions, BrO3– , oxidise bromide ions, Br–, in dilute acid.

BrO3– (aq) + 5Br– (aq) + 6H+ (aq) → 3Br2 (aq) + 3H2O(l)

Experiments to determine initial reaction rates were carried out using
different initial concentrations of the three reactants.
The results are shown in the table.

Experiment [BrO3– (aq)] [Br– (aq)] [H+ (aq)] Initial rate of reaction
number / mol dm–3 / mol dm–3 / mol dm–3 / mol dm–3 s–1

1 0.10 0.25 0.30 3.36 × 10–5

2 0.10 0.25 0.60 1.34 × 10–4

3 0.15 0.50 0.30 1.01 × 10–4

4 0.15 0.25 0.60 2.01 × 10–4

(a) The reaction is first order with respect to bromate(V) ions.

(i) Deduce the rate equation for the reaction.
Justify your answer using the data.
(4)

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*P69507A01232* 
(ii) Use the data from Experiment 4 and your answer to (a)(i)
to calculate the rate constant for the reaction. Include units in your answer.
(3)

(b) Give one possible reason why the rate equation shows that the reaction cannot
proceed in one step.
(1)

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(Total for Question 18 = 8 marks)

13
 *P69507A01332* Turn over
19 Propanal reacts very slowly with HCN at 298 K. To increase the rate of reaction
potassium cyanide, KCN, is added.
(a) (i) Complete the mechanism for this reaction by adding curly arrows, and
relevant lone pairs and dipoles to Step 1 and Step 2.
(4)

H H H H H H

Step 1 H C C C H C C C O–
O
H H H H C N
intermediate
–
C N

H C N
H H H

Step 2 H C C C O– products

H H C N

intermediate

(ii) Explain why the reaction between propanal and HCN in the absence of KCN is
very slow, referring to the value of Ka . No calculation is required.
[For HCN, Ka = 4.9 × 10–10 mol dm–3 ]
(2)

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14
*P69507A01432* 
(iii) KCN is a homogeneous catalyst in this reaction.
Justify this description by referring to the mechanism.
(2)

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(b) The organic products of this reaction are enantiomers.

Draw the three‑dimensional structures of these enantiomers.
(2)

(Total for Question 19 = 10 marks)

15
 *P69507A01532* Turn over
20 This question is about compounds with the molecular formula C6H12O2 .
(a) Hexanoic acid, C5H11COOH, is a weak acid.
(i) Write the equation for the acid dissociation constant, Ka , of hexanoic acid.
(1)

(ii) Calculate the pH of a 0.100 mol dm–3 solution of hexanoic acid.

[pKa of hexanoic acid = 4.88]
(4)

17
 *P69507A01732* Turn over
(iii) The solubility of hexanoic acid in water is 1.08 g per 100 g of water.
The isomer of hexanoic acid, butyl ethanoate, CH3CO2C4H9 , has a solubility of
0.68 g per 100 g of water.
Explain the differences in these data in terms of the hydrogen bonding
between hexanoic acid and water, and between butyl ethanoate and water.
(3)

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18
*P69507A01832* 
(b) (i) Compound A is thought to be another isomer of hexanoic acid.
10 g of compound A is found to contain 6.21 g of carbon and
1.03 g of hydrogen, with the remainder being oxygen.
Use the data to calculate the empirical formula of compound A.
You must show all your working.
(3)

(ii) State how you might use your answer to (b)(i) and a mass spectrum of
compound A to prove that compound A is an isomer of hexanoic acid.
(1)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

19
 *P69507A01932* Turn over
*(iii) A series of tests was performed on compound A.

Test Observation

1 addition of phosphorus(V) chloride misty fumes

2 addition of 2,4‑dinitrophenylhydrazine orange precipitate

3 addition of Benedict’s or Fehling’s reagent solution remains blue with no precipitate

4 addition of acidified potassium dichromate(VI) solution remains orange

5 test using polarimetry plane of plane polarised light is rotated

Deduce the structure for compound A.

Justify your answer by using all the test results.
(6)

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20
*P69507A02032* 
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21
 *P69507A02132* Turn over
(c) Compound B, another isomer with the molecular formula C6H12O2 , contains
a ring of six carbon atoms.
The carbon‑13 NMR spectrum has only two peaks, one of which is at 69 ppm.
Draw the structure of compound B.
(2)

(Total for Question 20 = 20 marks)

22
*P69507A02232* 
21 Esters are used in flavourings and perfumes.
They can be made by reactions involving alcohols.
(a) A flask containing a mixture of 0.200 mol of ethanoic acid and 0.150 mol of
ethanol was left at 25 °C, in the presence of a catalyst, until equilibrium had
been established.

CH3COOH(l) + C2H5OH(l)  CH3COOC2H5(l) + H2O(l)

The ethanoic acid present in the equilibrium mixture required 34.8 cm3 of a
2.50 mol dm–3 solution of sodium hydroxide for complete neutralisation.
(i) Calculate the value of the equilibrium constant, Kc , for this reaction at 25 °C.
(4)

(ii) The enthalpy change for this reaction is small.

Explain, by reference to the type and number of bonds being broken
and made, how this might have been predicted.
(2)

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23
 *P69507A02332* Turn over
(b) An ester which smells of raspberries can be formed by either of two
different reactions.
Reaction 1
catalyst
HCOOH + (CH3)2CHCH2OH  HCOOCH2CH(CH3)2 + H2O
Reaction 2

HCOCl + (CH3)2CHCH2OH → HCOOCH2CH(CH3)2 + HCl

(i) Name the carboxylic acid, alcohol and catalyst used in Reaction 1.
(2)
HCOOH . . . . . . . . . . . . . . . . . . . . . . . . . ...................... catalyst ...............................................

(CH3)2CHCH2OH . . . . . . . . . . . . . . . . . . . . . . . . .......................

(ii) Explain one advantage and one disadvantage of using Reaction 2 rather than
Reaction 1.
(4)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................................... . . . . . . . . . . . . . . . . . . . .

(Total for Question 21 = 12 marks)

TOTAL FOR SECTION B = 50 MARKS

24
*P69507A02432* 
SECTION C

Answer ALL the questions. Write your answers in the spaces provided.

22 The equation for the formation of ammonia in the Haber Process is shown

½N2(g) + 1½H2(g)  NH3(g)

(a) At 298 K the standard entropy change of the system, ΔS system

d
= –98 J K–1 mol–1.
Calculate the standard entropy of one mole of ammonia.
Use the value of ΔS system
d
and the data in the table.

Substance Standard molar entropy, S d / J K–1 mol–1

N2 192

H2 131

(2)

(b) The value of the total entropy change, ΔS total , varies with temperature.
Data for the value of ΔS total at different temperatures but at standard pressure of
100 kPa are given for this reaction.

Temperature / K 1/T / K–1 ΔS total / kJ K–1 mol–1

250 4.00 × 10–3 8.27 × 10–2

375 2.67 × 10–3 2.25 × 10–2

500 2.00 × 10–3 –0.764 × 10–2

625 1.60 × 10–3 –2.57 × 10–2

750 1.33 × 10–3 –3.77 × 10–2

26
*P69507A02632* 
Plot a graph of ΔS total against 1/T on the grid.
Include a line of best fit.
(2)

0.10

0.08

0.06

0.04

ΔS total
/ kJ K–1 mol–1

0.02

0 1/T
–1
0.0005 0.001 0.0015 0.002 0.0025 0.003 0.0035 0.004 0.0045 K
/

–0.02

–0.04

–0.06

27
 *P69507A02732* Turn over
(c) The relationship between ΔS total and 1/T can be found by combining the
two equations:
ΔS total = ΔS surroundings + ΔS system
and ΔS surroundings = –ΔH/T
to give
ΔS total = –ΔH/T + ΔS system
(i) Determine the gradient of the line plotted in (b), including units in
your answer.
(1)

(ii) Identify the thermodynamic quantity that can be obtained from this gradient.
(1)

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(iii) Determine the temperature at which the reaction ceases to be

thermodynamically feasible at a pressure of 100 kPa.
(1)

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28
*P69507A02832* 
(d) The industrial synthesis of ammonia

½N2(g) + 1½H2(g)  NH3(g)

is carried out at pressures of about 20 000 kPa and temperatures between 700 K
and 750 K. These temperatures are higher than the answer to (c)(iii).
(i) State the relationship between the total entropy, ΔS total , and
the equilibrium constant, K.
(1)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................................... . . . . . . . . . . . . . . . . . . . .

(ii) Calculate the value of the equilibrium constant K at 750 K.

[ΔS total at 750 K = –37.7 J K–1 mol–1 ]

(2)

(iii) Explain why ΔS total decreases with an increase in temperature.

(3)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................................... . . . . . . . . . . . . . . . . . . . .

29
 *P69507A02932* Turn over
(iv) State how the Haber Process is made economically feasible at 750 K even
though the total entropy change is negative.
(1)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(e) Ammonia from the Haber Process reacts with acids.

With phosphoric acid, H3PO4 , a number of products are formed in solution.
One of these is the fertiliser diammonium hydrogenphosphate.
(i) Write an equation for the production of this fertiliser.
State symbols are not required.
(2)

(ii) Write an ionic equation to show that ammonium ions are acidic in
aqueous solution.
State symbols are not required.
(1)

30
*P69507A03032* 
(iii) A solution containing both ammonia and ammonium ions acts as a buffer.
Explain, using a relevant ionic equation, the effect of adding a small amount
of acid to this buffer.
(3)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(Total for Question 22 = 20 marks)

TOTAL FOR SECTION C = 20 MARKS

TOTAL FOR PAPER = 90 MARKS

31
 *P69507A03132*
Please check the examination details below before entering your candidate information
Candidate surname Other names

Centre Number Candidate Number

June 2022

Pearson Edexcel International Advanced Level

Time 1 hour 45 minutes
Paper
reference WCH14/01
Chemistry
 

International Advanced Level

UNIT 4: Rates, Equilibria and Further Organic
Chemistry
You must have: Total Marks
Scientific calculator, Data Booklet, ruler

Instructions
• Use black ink or ball-point pen.
• Fill in the boxes at the top of this page with your name,
centre number and candidate number.
• Answer all questions.
• Answer the questions in the spaces provided
– there may be more space than you need.

Advice
• Read each question carefully before you start to answer it.
• Show all your working in calculations and include units where appropriate.
• Try to answer every question.
• Check your answers if you have time at the end.
Turn over

*P70967A0132*
P70967A
©2022 Pearson Education Ltd.

Q:1/1/1/1/
SECTION A

Answer ALL the questions in this section.

You should aim to spend no more than 20 minutes on this section.

For each question, select one answer from A to D and put a cross in the box . If you change
your mind, put a line through the box and then mark your new answer with a cross .

1 This question is about proton NMR spectroscopy.

(a) How many peaks are there in the low resolution proton NMR spectrum of
2‑methylpropan‑2‑ol?
(1)
A one

B two

C three

D four

(b) Which compound has three peaks with relative peak areas of 3 : 2 : 1 in its
low resolution proton NMR spectrum?
(1)
A propanal

B propane

C propan‑1‑ol

D propan‑2‑ol

B butanone

C butanal

D butan‑1‑ol

(Total for Question 1 = 3 marks)

Use this space for any rough working. Anything you write in this space will gain no credit.

2
*P70967A0232* 
2 The high resolution mass spectrum of an organic compound X has a
molecular ion peak with m / z = 58.0417 and another peak with m / z = 29.0390.
Which compound is X?
[ Ar values: H = 1.0078 C = 12.0000 O = 15.9949 ]
A CH3COCH3

B CH3CH2CHO

C CH3CH2CH2CH3

D CH3CH(CH3)CH3

(Total for Question 2 = 1 mark)

3 A high performance liquid chromatography (HPLC) system used a column with a

non‑polar stationary phase and a solvent of methanol and water.
A mixture of octane, octanal and octan‑1‑ol was placed into the HPLC column.
What is the order of retention times?

Shortest Intermediate Longest

retention time retention time retention time
A octane octanal octan‑1‑ol

B octanal octan‑1‑ol octane

C octane octan‑1‑ol octanal

D octan‑1‑ol octanal octane

(Total for Question 3 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

3
 *P70967A0332* Turn over
4 A diagram of a thin layer chromatogram of substance Y is shown.

solvent front

position of substance Y

baseline

What is the Rf value of substance Y?

A 0.25

B 0.60

C 0.75

D 1.33

(Total for Question 4 = 1 mark)

5 Which reaction cannot form a carboxylic acid?

A oxidation of primary alcohol

B acidic hydrolysis of a nitrile

C alkaline hydrolysis of an ester

D acyl chloride reacting with water

(Total for Question 5 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

4
*P70967A0432* 
6 Which alcohol could not be formed by the reduction of an aldehyde or a ketone?

A 2‑methylpentan‑1‑ol

B 3‑methylpentan‑2‑ol

C 3‑methylpentan‑3‑ol

D 2‑methylpentan‑3‑ol

(Total for Question 6 = 1 mark)

7 What is the pH of a 0.010 mol dm−3 aqueous solution of carbonic acid?

[ Ka of carbonic acid = 4.5 × 10−7 mol dm−3 at 298 K ]
A 2.00

B 4.17

C 6.35

D 8.35

(Total for Question 7 = 1 mark)

8 What is the pH of a 0.27 mol dm−3 aqueous solution of sodium hydroxide?

[ Kw = 1.0 × 10−14 mol2 dm−6 at 298 K ]
A 0.57

B 13.43

C 13.73
D 14.57

(Total for Question 8 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

5
 *P70967A0532* Turn over
9 A 0.1 mol dm−3 aqueous acid solution was added to 25 cm3 of a
0.1 mol dm−3 aqueous solution of an alkali.
The titration curve shown was obtained.

pH 7

0
0 25 50

Volume of acid added / cm3

(a) Which titration would produce this curve?

(1)
A ethanoic acid added to sodium hydroxide

B hydrochloric acid added to sodium hydroxide

C ethanoic acid added to ammonia

D hydrochloric acid added to ammonia

(b) Which indicator would be most suitable for this titration?

(1)

Indicator pH range

A malachite green 0.2–1.8

B methyl yellow 2.9–4.0

C methyl red 4.2–6.3

D thymol blue 8.0–9.6

(Total for Question 9 = 2 marks)

6
*P70967A0632* 
10 Four graphs are shown.

Graph 1 Graph 2

Graph 3 Graph 4

(a) Which graph shows the rate of reaction on the vertical axis plotted against
concentration of the reactant on the horizontal axis for a zero order reaction?
(1)
A Graph 1

B Graph 2

C Graph 3
D Graph 4

(b) Which graph shows the rate of reaction on the vertical axis plotted against
concentration of the reactant on the horizontal axis for a first order reaction?
(1)
A Graph 1

B Graph 2

C Graph 3

D Graph 4

(Total for Question 10 = 2 marks)

7
 *P70967A0732* Turn over
11 Propanone reacts with iodine in the presence of a sulfuric acid catalyst.

CH3COCH3(aq) + I2(aq) → CH3COCH2I(aq) + HI(aq)

(a) Which method would be most suitable for following this reaction?
(1)

A colorimetry

B timing how long the solution takes to go cloudy

C quenching and titrating with an acid

D quenching and titrating with starch solution

(b) The rate equation for this reaction is:

rate = k [ H+ ][ CH3COCH3 ]

Two experiments were carried out. In both experiments the concentration

of propanone and iodine remained the same but the concentration of the
sulfuric acid was changed.
The initial rate in the first experiment was three times faster than the initial rate in
the second experiment.
In the first experiment the initial pH was 1.50
What is the initial pH in the second experiment?
(1)
A 1.02
B 1.98

C 2.28

D 4.50

(Total for Question 11 = 2 marks)

Use this space for any rough working. Anything you write in this space will gain no credit.

8
*P70967A0832* 
12 A series of experiments was carried out to determine the rate constant, k, of the
reaction between bromate(V) ions and bromide ions at different temperatures, T.

1
A graph of ln k was plotted against . The gradient of the line was −4670 K.
T
The Arrhenius equation may be written as

Ea 1
ln k = − × + constant R = 8.31 J mol−1 K−1
R T

What is the activation energy of this reaction?

A +38.8 kJ mol−1

B +38.8 J mol−1 K−1

C +562 J mol−1

D +562 J mol−1 K−1

(Total for Question 12 = 1 mark)

13 Solid vanadium(V) oxide catalyses the equilibrium shown.

2SO2(g) + O2(g)  2SO3(g) ∆H = −196 kJ mol−1

Which statement is correct?

A vanadium(V) oxide is a homogeneous catalyst

B decreasing the pressure would increase the equilibrium yield of

sulfur trioxide
C increasing the surface area of the catalyst would increase the equilibrium
yield of sulfur trioxide
D decreasing the temperature would increase the equilibrium yield of
sulfur trioxide

(Total for Question 13 = 1 mark)

14 In which series does the standard molar entropy of the compounds increase?

A CaO(s) < H2O(l) < CO2(g) < SO2(g)

B CaO(s) < H2O(l) < SO2(g) < CO2(g)

C SO2(g) < CO2(g) < H2O(l) < CaO(s)

D CO2(g) < SO2(g) < H2O(l) < CaO(s)

(Total for Question 14 = 1 mark)

9
 *P70967A0932* Turn over
15 Experimental lattice energy values determined using the Born‑Haber cycle often
differ from calculated theoretical values.
The ionic radii and charges of some ions are shown.
P, Q, R and S are not the chemical symbols of the elements.

Ion Ionic radius / nm

P+ 0.076

Q+ 0.167

R− 0.133

S− 0.220

Which of these compounds would be expected to show the largest percentage

difference between the experimental and theoretical lattice energies?

A PR

B PS

C QR

D QS

(Total for Question 15 = 1 mark)

TOTAL FOR SECTION A = 20 MARKS

10
*P70967A01032* 
SECTION B
Answer ALL the questions. Write your answers in the spaces provided.
16 This question is about ammonia and ammonium chloride.
(a) Ammonia is produced by reacting nitrogen and hydrogen as shown.

N2(g) + 3H2(g)  2NH3(g)

(i) Write the expression for the equilibrium constant, Kp .

(1)

11
 *P70967A01132* Turn over
(ii) An equilibrium was established by mixing nitrogen and hydrogen in a
1 : 3 ratio by volume, at a temperature of 450 °C and pressure of 200 atm.
The equilibrium mixture contained 28 % of ammonia by volume.
Complete the table.
(3)

Substance Mole fraction Partial pressure / atm

NH3 0.28 56

(iii) Calculate the equilibrium constant.

Give your answer to an appropriate number of significant figures and
include units, if required.
(3)

(iv) When the temperature was reduced to 400 °C at the same pressure, the
equilibrium mixture contained 36 % of ammonia.
Explain what can be deduced about this reaction from this information.
(2)

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12
*P70967A01232* 
(b) Ammonium chloride can be produced by reacting ammonia with
hydrogen chloride.
Ammonium chloride is a white solid that is very soluble in water.
Hess’s Law can be used to calculate the enthalpy of solution of
ammonium chloride, using hydration enthalpies and lattice energy.
(i) Complete the Hess cycle by filling in the empty box.
(1)

NH4+(g) + Cl−(g)

Lattice
ΔhydH
energy

NH4Cl(s)
ΔsolH

(ii) Complete the expression for the enthalpy change of solution using the
hydration enthalpies and lattice energy.
(1)
ΔsolH =

(iii) Calculate the enthalpy change of solution, using your expression in (b)(ii) and
these data.
Enthalpy change of hydration of NH4+ = −307 kJ mol−1
Enthalpy change of hydration of Cl− = −378 kJ mol−1
Lattice energy of NH4Cl = −705 kJ mol−1
(2)

13
 *P70967A01332* Turn over
(iv) A student suggested that the enthalpy change of solution of
ammonium bromide would be of a similar magnitude to the enthalpy change
of solution of ammonium chloride.
Comment on this suggestion in terms of the hydration enthalpies and
lattice energies of these two compounds.
(3)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(c) Write an ionic equation to show why aqueous solutions of ammonium chloride
are acidic. State symbols are not required.
(1)

(Total for Question 16 = 17 marks)

14
*P70967A01432* 
17 This question is about carbonyl compounds.
(a) Three carbonyl compounds, A, B and C, are straight‑chain structural isomers,
with the formula C5H10O.
Only isomer A reacts with Tollens’ reagent to give a silver mirror.
Only isomer B reacts with iodine in the presence of alkali to produce
pale yellow crystals.
Draw the displayed structures of these three isomers.
(3)

(b) Another carbonyl compound, propanal, reacts with HCN in the presence of KCN
to form a racemic mixture of two optical isomers of CH3CH2CH(OH)CN.
(i) Give the IUPAC name for CH3CH2CH(OH)CN.
(1)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(ii) Describe how you could distinguish between pure samples of

the two optical isomers.
(1)

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15
 *P70967A01532* Turn over
(iii) Explain, with reference to the reaction mechanism, why this reaction produces
a racemic mixture.
(2)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(c) (i) Propanone, an isomer of propanal, also reacts with HCN in the presence
of KCN.
Draw the skeletal formula of the product of this reaction.
(1)

(ii) State why the product formed in (c)(i) does not show optical isomerism.
(1)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

16
*P70967A01632* 
13
(d) C NMR spectroscopy provides information about the structures of propanal
and propanone.
(i) Identify the chemical shift range and carbon environment of one peak you
would expect to see in both spectra.
(1)

Chemical shift range Carbon environment

(ii) State the number of peaks you would expect to see in each 13C NMR spectrum.
(1)

Propanal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .................

Propanone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ......................

(Total for Question 17 = 11 marks)

17
 *P70967A01732* Turn over
*18 Compare and contrast the reactions of ethanoyl chloride with water, with ethanol
and with ammonia.
Refer to the structural features of the molecules that determine the type of reaction.
Identify the products of the reactions. You may include equations in your answers.
(6)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

18
*P70967A01832* 
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(Total for Question 18 = 6 marks)

19
 *P70967A01932* Turn over
19 This question is about methanoic acid and propanoic acid.
(a) A student carried out a titration to find the concentration of an aqueous solution
of potassium hydroxide.
25.00 cm3 of 0.150 mol dm−3 aqueous methanoic acid was pipetted
into a conical flask. Potassium hydroxide was added from a burette
while measuring the pH. The titration curve is shown.

14
13
12
11
10
9
8
pH 7
6
5
4
3
2
1
0
0 5 10 15 20 25 30 35 40 45 50

Volume of KOH added / cm3

(i) Complete the equation for the reaction taking place in this titration.
State symbols are not required.
(1)
HCOOH +

(ii) Calculate the concentration of the potassium hydroxide solution, using your
equation in (i) and the titration curve.
(2)

20
*P70967A02032* 
(iii) Use the titration curve to determine a value for the acid dissociation constant,
Ka , of methanoic acid.
(3)

(b) A student prepared a buffer by mixing together equimolar aqueous solutions of

propanoic acid, CH3CH2COOH, and sodium propanoate, CH3CH2COONa.
The acid dissociation constant, Ka , for propanoic acid is 1.3 × 10−5 mol dm−3 .
Calculate the volume ratio of propanoic acid to sodium propanoate needed to
produce a buffer solution with a pH of 4.6
(2)

(Total for Question 19 = 8 marks)

21
 *P70967A02132* Turn over
20 This question is about the hydrolysis of 2‑bromobutane with
aqueous sodium hydroxide at 298 K.
The equation for the reaction is:

CH3CH2CHBrCH3 + OH− → CH3CH2CHOHCH3 + Br −

(a) The data shown were obtained in an experiment to investigate the kinetics of
this reaction.

Initial concentration / mol dm−3

Initial rate
Experiment number
/ mol dm−3 s−1
[CH3CH2CHBrCH3 ] [OH− ]

1 0.100 0.100 1.01 × 10−3

2 0.200 0.100 2.02 × 10−3

3 0.100 0.200 1.01 × 10−3

(i) Deduce the order of reaction with respect to 2‑bromobutane and with respect
to hydroxide ions. Justify your answers.
(2)

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(ii) Write the rate equation for the reaction using your answer to (a)(i).
(1)

22
*P70967A02232* 
(iii) Calculate the rate constant for Experiment 1.
Include units in your answer.
(2)

(b) Draw the mechanism for this reaction that is consistent with your rate equation.
Include curly arrows, and any relevant dipoles and lone pairs of electrons.
(3)

(Total for Question 20 = 8 marks)

TOTAL FOR SECTION B = 50 MARKS

23
 *P70967A02332* Turn over
SECTION C
Answer ALL the questions. Write your answers in the spaces provided.
21 This question is about oxides of iron.
(a) The equation for the reduction of iron(III) oxide by carbon is shown.

Fe2O3(s) + 3C(s) → 2Fe(s) + 3CO(g)

Some data relating to this reaction are shown.

Substance Fe2O3 C Fe CO

∆fH / kJ mol−1 −824.2 0 0 −110.5

S / J K−1 mol−1 87.4 5.7 27.3 197.6

(i) Calculate the standard enthalpy change, ∆rH , for the reduction of
iron(III) oxide by carbon.
(2)

(ii) Calculate the entropy change, ∆Ssystem , for this reaction.

(3)

24
*P70967A02432* 
(iii) Calculate the temperature at which this reaction becomes feasible, using your
answers from (a)(i) and (a)(ii).
(3)

(b) The equation for the reduction of iron(III) oxide by carbon monoxide is shown.

Fe2O3(s) + 3CO(g) → 2Fe(s) + 3CO2(g) ∆H = −24.8 kJ mol−1

The entropy change, ∆S system , for this reaction is +15.2 J mol−1 K−1 .
(i) Explain why the reaction should be feasible at any temperature.
(2)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(ii) Explain how an increase in temperature would affect ∆S total of this reaction.
No calculation is required.
(3)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

25
 *P70967A02532* Turn over
(c) Iron also forms iron(II) oxide. The data in the table can be used to construct a
Born‑Haber cycle for iron(II) oxide, FeO.

Value
Letter Enthalpy change
/ kJ mol−1

A Enthalpy change of atomisation of iron +416

B First ionisation energy of iron +759

C Second ionisation energy of iron

D Enthalpy change of formation of iron(II) oxide −272

E First electron affinity of oxygen −141

F Second electron affinity of oxygen +798

G Lattice energy of iron(II) oxide −3920

H Enthalpy change of atomisation of oxygen (½O2(g) → O(g)) +249

26
*P70967A02632* 
(i) Complete the Born‑Haber cycle by putting letters in the boxes to label the
energy changes.
(3)

Fe2+(g) + O2−(g)

Fe2+(g) + O(g)

Fe2+(g) + ½O2(g) Fe2+(g) + O−(g)

Fe+(g) + ½O2(g)

Fe(g) + ½O2(g)

Fe(s) + ½O2(g)

FeO(s)

(ii) Calculate the value for second ionisation energy of iron, C.

(2)

27
 *P70967A02732* Turn over
(iii) Suggest why the second electron affinity of oxygen is positive.
(2)

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(Total for Question 21 = 20 marks)

TOTAL FOR SECTION C = 20 MARKS

TOTAL FOR PAPER = 90 MARKS

28
*P70967A02832* 
BLANK PAGE

30
*P70967A03032* 
Please check the examination details below before entering your candidate information
Candidate surname Other names

Centre Number Candidate Number

October 2022

Pearson Edexcel International Advanced Level

Time 1 hour 45 minutes
Paper
reference WCH14/01
Chemistry
 

International Advanced Level

UNIT 4: Rates, Equilibria and Further Organic
Chemistry
You must have: Total Marks
Scientific calculator, Data Booklet, ruler

*P71863A0132*
P71863A
©2022 Pearson Education Ltd.

B:1/1/1/1/1/
SECTION A
Answer ALL the questions in this section.
You should aim to spend no more than 20 minutes on this section.
For each question, select one answer from A to D and put a cross in the box .
If you change your mind, put a line through the box and then mark your new answer
with a cross .
1 Which continuous monitoring method could be used to obtain rate data for the
reaction shown?

C4H9Cl(l) + H2O(l) → C4H9OH(aq) + H+(aq) + Cl−(aq)

A electrical conductivity

B colorimetry

C mass change

D titration with alkali

(Total for Question 1 = 1 mark)

2 Nitrogen monoxide is reduced by hydrogen.

2NO(g) + 2H2(g) → N2(g) + 2H2O(g)

The rate equation for the reaction is

rate = k [NO]2 [H2]

(a) The concentrations of both reactants are tripled.

By what factor does the rate of reaction increase?
(1)
A 3

B 9

C 18

D 27

2
*P71863A0232* 
(b) Which graph is correct for this reaction?
(1)

A B
[H2] Rate

Time [H2]

C D
[NO] Rate

Time [NO]2

(c) The reaction mechanism occurs in three steps.

Step 1 NO + NO  N2O2
Step 2 N2O2 + H2 → N2O + H2O
Step 3 N2O + H2 → N2 + H2O
Which is the rate-determining step in the mechanism?
(1)
A Step 1

B Step 2

C Step 3

D cannot be deduced from the information provided

(Total for Question 2 = 3 marks)

Use this space for any rough working. Anything you write in this space will gain no credit.

3
 *P71863A0332* Turn over
3 The Born–Haber cycle for strontium iodide, SrI2 , is shown.
All values are in kJ mol−1 . The cycle is not to scale.

Sr2+(g) + 2I(g) + 2e–

–590
Sr2+(g) + 2I –(g)

+1614

Sr(g) + 2I(g)

–1963
Sr(g) + I2 (s)

+164 Sr(s) + I2 (s)

–561
SrI2(s)

(a) Which of the following statements is not true?

(1)
A the lattice energy of strontium iodide is exothermic

B the first electron affinity of iodine is −295 kJ mol−1

C the second ionisation energy of strontium is +1614 kJ mol−1

D t he standard enthalpy change of atomisation of strontium

is +164 kJ mol−1

(b) Using the Born–Haber cycle, it can be calculated that the

standard enthalpy change of atomisation of iodine, in kJ mol−1 , is
(1)
A +542

B +271

C +214

D +107

4
*P71863A0432* 
(c) Theoretical lattice energies are calculated assuming only ionic bonding is present.
Which of these is most likely to be the theoretical lattice energy of
strontium iodide?
(1)
−1
A −561 kJ mol

B −1937 kJ mol−1

C −1963 kJ mol−1

D −1989 kJ mol−1

(Total for Question 3 = 3 marks)

4 Which of these statements is true?

A the enthalpy change of hydration of an ion is always negative

B the enthalpy change of solution of an ionic compound is always negative

C an endothermic enthalpy change of solution indicates that an
ionic compound will be insoluble
D the more exothermic the lattice energy of an ionic compound, the more
soluble it is likely to be

(Total for Question 4 = 1 mark)

5 Which sequence shows the elements in order of increasing standard entropy?

A He(g) < O2(g) < Hg(l) < Os(s)

B O2(g) < He(g) < Hg(l) < Os(s)

C Os(s) < Hg(l) < He(g) < O2(g)

D Os(s) < Hg(l) < O2(g) < He(g)

(Total for Question 5 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

5
 *P71863A0532* Turn over
6 This question is about the equilibrium system used in the industrial production
of nitric acid.

4NH3(g) + 5O2(g)  4NO(g) + 6H2O(g) ∆H = −905 kJ mol−1

The process is carried out at a temperature of 800 °C, a total pressure of 10 atm and
in the presence of a platinum-rhodium catalyst.
(a) Which conditions of temperature and pressure would be expected to give the
greatest equilibrium yield of NO?
(1)
A high temperature and high pressure

B high temperature and low pressure

C low temperature and high pressure

D low temperature and low pressure

(b) Which of these statements best explains why only a small amount of energy is
required to maintain this process?
(1)
A the catalyst increases the equilibrium yield of NO

B the catalyst decreases the activation energy

C the reaction is thermodynamically feasible

D the reaction is highly exothermic

A atm−1

B atm

C dm3 mol−1

D mol dm−3

(Total for Question 6 = 3 marks)

Use this space for any rough working. Anything you write in this space will gain no credit.

6
*P71863A0632* 
7 In which equation is H2O acting only as a Brønsted–Lowry acid?

A CH3COOH + H2O → CH3COO− + H3O+

B NH4+ + H2O → H3O+ + NH3

C NH3 + H2O → NH4+ + OH−

D 2H2O → H3O+ + OH−

(Total for Question 7 = 1 mark)

8 What is the pH of a 0.050 mol dm−3 solution of barium hydroxide, Ba(OH)2 ?

A 13.3

B 13.0

C 12.7

D 12.4

(Total for Question 8 = 1 mark)

9 What is the pH of a solution containing 0.100 mol dm−3 CH3COOH and

0.200 mol dm−3 CH3COONa ?
[pKa CH3COOH = 4.76]

A 5.06

B 4.76

C 4.46
D 2.88

(Total for Question 9 = 1 mark)

10 Which of these indicators is most suitable for the titration of ammonia solution
with hydrochloric acid?

A methyl violet (pKin = 0.8)

B bromocresol green (pKin = 4.7)

C thymol blue (pKin = 8.9)

D alizarin yellow (pKin = 12.5)

(Total for Question 10 = 1 mark)

7
 *P71863A0732* Turn over
11 Which compound is both completely miscible in water and has a
higher boiling temperature than water?

A CH3COOH

B CH3COCH3

C CH3CH2CH2CHO

D CH3CH2COOCH2CH3

(Total for Question 11 = 1 mark)

12 Which compound forms a precipitate with Fehling's or Benedict’s solutions and with
iodine in the presence of alkali?

A methanal

B ethanal

C propanone
D butanone

(Total for Question 12 = 1 mark)

13 Which reaction does not produce a tertiary alcohol as one of the products?

A (CH3)2C=CH2 + H2O

B (CH3)3CBr + H2O
C (CH3)3CCOC(CH3)3 + LiAlH4

D (CH3)3CCOOC(CH3)3 + NaOH

(Total for Question 13 = 1 mark)

14 Which change decreases the retention time in gas chromatography?

A decreasing the column temperature

B increasing the carrier gas flow rate

C decreasing the amount of sample

D increasing the column length

(Total for Question 14 = 1 mark)

TOTAL FOR SECTION A = 20 MARKS

8
*P71863A0832* 
SECTION B
Answer ALL the questions. Write your answers in the spaces provided.
15 This question is about lactic acid, CH3CH(OH)COOH .
(a) Give the IUPAC name of lactic acid.
(1)

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(b) Lactic acid is a chiral molecule, existing as a pair of non-superimposable

mirror images called enantiomers.
Complete the 3D diagrams of the enantiomers of lactic acid.
(2)

C C

(c) Racemic lactic acid is synthesised in a two-step process.

In Step 1, ethanal, CH3CHO , is reacted with hydrogen cyanide, HCN , in the
presence of KCN to form compound X.

In Step 2, compound X is hydrolysed using dilute acid.

Step 1 Step 2
CH3CHO + HCN compound X CH3CH(OH)COOH

(i) State what is meant by racemic lactic acid.

(1)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

10
*P71863A01032* 
(ii) Complete the mechanism for the formation of X in Step 1.
Include curly arrows, and any relevant lone pairs and dipoles.
(4)

CN–

(iii) Write the ionic equation for the hydrolysis of X in Step 2.

State symbols are not required.
(2)

(iv) Explain, with reference to your mechanism in (c)(ii), why the lactic acid formed
in this process is racemic.
(2)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

11
 *P71863A01132* Turn over
(d) Lactic acid is a weak acid.
(i) Calculate the mass, in g, of lactic acid, HA , required to make 1.00 dm3 of an
aqueous solution with a pH of 3.00 .
Assume:
• [HA]initial = [HA]equilibrium
• [H+] = [A−]
[Lactic acid data: pK a = 3.86 M r = 90.0]
(4)

12
*P71863A01232* 
(ii) In practice, the initial concentration of lactic acid does not equal its
equilibrium concentration.
Explain how this affects the mass of acid needed to make a solution with a
pH of 3.00 . No calculation is required.
(2)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(iii) Lactic acid is a stronger acid than ethanoic acid.

H
H O H O
O
H C C C H C C

H H O H H O H

lactic acid ethanoic acid

Give a possible reason why lactic acid is the stronger acid.

(1)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(Total for Question 15 = 19 marks)

13
 *P71863A01332* Turn over
16 Azomethane, CH3N2CH3 , decomposes to form nitrogen and ethane.

CH3N2CH3(g) → N2(g) + C2H6(g)

(a) Write the rate equation for this first order reaction.
(1)

(b) The concentration of azomethane, [CH3N2CH3] , was measured at various times

during its decomposition at 573 K .
A graph of the data obtained is shown.

6
[CH3N2CH3]
5
/ 10–3 mol dm–3
4

0
0 30 60 90 120 150 180 210 240 270 300
Time / minutes

14
*P71863A01432* 
(i) Determine values for the half-life, t 1/2 , of the decomposition of azomethane
from the graph, stating whether or not these data confirm that the reaction is
first order.
You must show your working on the graph.
(2)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(ii) Calculate the rate constant, k, in s−1 , for the decomposition of azomethane at
573 K , using your answer to (b)(i) and the expression shown.

ln2
t1/2 =
k
(2)

15
 *P71863A01532* Turn over
(c) The rate constant for the decomposition of azomethane is 1.1 × 10−6 s−1 at 523 K
and 3.5 × 10−3 s−1 at 623 K.
(i) Explain why the rate constant for this reaction is higher at 623 K than at 523 K .
(2)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(ii) The rate constant changes with temperature according to the

expression shown.

k  E  1 1
log10  1  = − a  − 
 k2  2.3 R  T1 T2 

Calculate the activation energy, Ea , for the decomposition of azomethane

using this expression and the values for k at 523 K and 623 K .
Include units and give your answer to two significant figures.
[R = 8.31 J mol−1 K −1]
(3)

16
*P71863A01632* 
(d) The activation energy for the decomposition of azomethane is high because the
reaction involves covalent bond fission.
Identify on the structure of azomethane the covalent bond (or bonds) that break
in this decomposition.
(1)

H H
C
H N=N H
C
H H

(Total for Question 16 = 11 marks)

17
 *P71863A01732* Turn over
17 This question is about reactions of carboxylic acids and their derivatives.
(a) Molecule A reacts in two ways in the presence of an acid catalyst.

molecule A

Reaction 1 is intramolecular, in which one molecule of A forms a cyclic ester B.

Reaction 2 is intermolecular, in which a condensation polymer C forms.
(i) Draw the structure of the cyclic ester B.
(1)

(ii) Draw the structure of the condensation polymer C, showing two repeat units.
(2)

(iii) Explain why the entropy change of the system, ΔSsystem , is greater for
Reaction 1 than for Reaction 2.
(2)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................................... . . . . . . . . . . . . . . . . . . . .

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 *P71863A01932* Turn over
(b) The molecule shown is a triester, used as a food additive.

O O

(i) Give the molecular formula of this triester.

(1)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(ii) Complete the equation for the alkaline hydrolysis of this triester with
excess aqueous sodium hydroxide, showing the structures of the products.
(3)

O + ................ NaOH
O

O O

20
*P71863A02032* 
(c) Some reactions of ethanoyl chloride, CH3COCl , are shown.

Reagent P

O
O O
Reagent S Reaction Q
N
Cl NH2

Reagent R

(i) Identify Reagent P, by name or formula.

(1)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(ii) Write a balanced equation for Reaction Q.

State symbols are not required.
(2)

(iii) Suggest the structural formula of Reagent R.

(1)

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(iv) Draw the skeletal formula of Reagent S.

(1)

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 *P71863A02132* Turn over
*(d) Sodium ethanoate, CH3COONa , reacts with 2-methylpropanoyl chloride,
(CH3)2CHCOCl , to form organic compound Z and sodium chloride, NaCl .
The molecular ion peak in the mass spectrum of Z is at m / z = 130.
The infrared spectrum of Z has peaks at 1820 cm−1 and 1754 cm−1 .
The carbon-13 NMR spectrum of Z has five peaks.
A simplified high resolution proton NMR spectrum of Z is shown.
The number of protons in each environment is indicated on the spectrum.

3H 6H

3.0 2.5 2.0 1.5 1.0 0.5 0.0

δ / ppm

Deduce the structure of Z, showing how your answer is consistent with all the
information provided.
(6)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

22
*P71863A02232* 
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(Total for Question 17 = 20 marks)

TOTAL FOR SECTION B = 50 MARKS

23
 *P71863A02332* Turn over
SECTION C
Answer ALL the questions. Write your answers in the spaces provided.
18 This question is about the homogeneous system

H2(g) + I2(g)  2HI(g)

(a) Write the expression for the equilibrium constant, Kc , of this system.
(1)

(b) Chemist A carried out an experiment to determine Kc .

0.00500 mol of H2 and 0.0100 mol of I2 were heated in a sealed container of
volume 1.00 dm3 .
At equilibrium, the mixture was found to contain 0.00968 mol of HI .
Calculate Kc , using these data and your expression from (a).
Include units, if any.
Give your answer to an appropriate number of significant figures.
(4)

25
 *P71863A02532* Turn over
(c) Chemist B determined the value of Kc at five different temperatures.

Temperature, T / K 1 / T (K−1) Kc ln Kc

523 122 4.80

577 0.00173 99.2

620 0.00161 86.5 4.46

669 0.00149 75.6 4.33

721 0.00139 66.8 4.20

(i) Complete the table of data.

(2)
(ii) Plot a graph of ln Kc against 1 / T .
Include a line of best fit.
(3)

ln Kc

1 / T (K–1)

(iii) Determine the gradient of your graph.

You must show your working on the graph.
(1)

26
*P71863A02632* 
(iv) The gradient of the graph from (c)(iii) is related to the enthalpy change of the
reaction, ∆H .

ΔH
gradient = −
R
Calculate ∆H , in J mol−1 , using your value for the gradient.
(2)

(v) The free energy change for the reaction, ∆G , is related to entropy and can be
calculated from Kc .

∆G = −RT ln Kc

Calculate ∆G at 620 K , using this equation and data from the table.
Include units.
(2)

(vi) The equation relating ∆G, ∆H and ∆Ssystem is shown.

∆G = ∆H − T∆Ssystem

Calculate ∆Ssystem at 620 K , using your answers to (c)(iv) and (c)(v).

(2)

27
 *P71863A02732* Turn over
(d) Explain, in terms of the total entropy change, ∆Stotal , why this reaction is feasible
at any temperature.
Assume that both ∆H and ∆Ssystem are independent of temperature.
(3)

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(Total for Question 18 = 20 marks)

TOTAL FOR SECTION C = 20 MARKS

TOTAL FOR PAPER = 90 MARKS

28
*P71863A02832* 
Please check the examination details below before entering your candidate information
Candidate surname Other names

Centre Number Candidate Number

January 2023

Pearson Edexcel International Advanced Level

Time 1 hour 45 minutes
Paper
reference WCH14/01
Chemistry
 

International Advanced Level

UNIT 4: Rates, Equilibria and Further Organic
Chemistry
You must have: Total Marks
Scientific calculator, Data Booklet, ruler

Instructions
• Use black ink or ball‑point pen.
• IfFillpencil is used for diagrams/sketches/graphs it must be dark (HB or B).
• centre number
in the boxes at the top of this page with your name,
and candidate number.
• Answer all questions.
• Answer the questions in the spaces provided
– there may be more space than you need.

Advice
• Read each question carefully before you start to answer it.
• Show all your working in calculations and include units where appropriate.
• Try to answer every question.
• your answers if you have time at the end.
Check
Turn over

J:1/1/1/1/
SECTION A

Answer ALL the questions in this section.

You should aim to spend no more than 20 minutes on this section.

For each question, select one answer from A to D and put a cross in the box . If you change
your mind, put a line through the box and then mark your new answer with a cross .

1 Two ways of writing an equation for the reaction between nitrogen monoxide and
oxygen are shown.

2NO + O2 → 2NO2 Equation 1

NO + ½O2 → NO2 Equation 2

(a) Which pair of rate equations could be correct for this reaction?
(1)

Equation 1 Equation 2

A rate = k[NO]2[O2] rate = k[NO]2[O2]

B rate = k[NO]2[O2] rate = k[NO][O2]½

C rate = k[NO2]2 rate = k[NO2]2

D rate = k[NO2]2 rate = k[NO2]

(b) Which two methods can be used for continuous monitoring of the progress of
this reaction?
(1)
A colorimetry and titration

B colorimetry and volume change

C mass change and volume change

D mass change and titration

(Total for Question 1 = 2 marks)

Use this space for any rough working. Anything you write in this space will gain no credit.

2
*P71887A0232* 
2 The half‑life of a first order chemical reaction is

A half the time taken for the reaction to be complete

B the time taken for the value of the rate constant to halve

C the time taken for the concentration of a reactant to halve

D the time taken for the concentration of a product to double

(Total for Question 2 = 1 mark)

3 Two chemicals, E and F, react to form products G and H.

E + 2F → G + H

The mechanism for the reaction occurs in two steps via the formation of an
intermediate J.

E + F → J slow

J + F → G + H fast

What is the rate equation for the reaction?

A rate = k[E][F]

B rate = k[E][F]2

C rate = k[F][J]

D rate = k[E][F]2[J]

(Total for Question 3 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

3
 *P71887A0332* Turn over
4 Which graph shows the entropy of a substance as it changes state
from solid to liquid to gas?

Graph 1 Graph 2

Entropy Entropy

Temperature Temperature

Graph 3 Graph 4

Entropy Entropy

Temperature Temperature

A Graph 1
B Graph 2

C Graph 3

D Graph 4

(Total for Question 4 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

4
*P71887A0432* 
5 Two flasks, P and Q, are connected by a tube fitted with a tap.

P Q

Flask P contains argon gas and flask Q is in vacuum.

Assume argon behaves as an ideal gas and therefore has no intermolecular forces
between its atoms.
How do the entropy and energy of the system change when the tap is opened and
the argon fills both flasks?

Entropy of the system Energy of the system

A increases decreases
B decreases decreases
C increases unchanged
D decreases unchanged

(Total for Question 5 = 1 mark)

6 When hydrogen and oxygen are mixed in a flask, there is no reaction.

When a platinum gauze is added to the flask, the mixture explodes.
It can be deduced that, in the absence of a platinum gauze,
the mixture of hydrogen and oxygen is

A kinetically stable and thermodynamically stable

B kinetically stable and thermodynamically unstable

C kinetically unstable and thermodynamically stable

D kinetically unstable and thermodynamically unstable

(Total for Question 6 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

5
 *P71887A0532* Turn over
7 The diagram shows the Born–Haber cycle for sodium oxide.

2Na+(g) + 2e– + O(g)

x
y
2Na(g) + O(g)

w 2Na+(g) + O2–(g)

2Na(g) + ½O2(g)

v
z
2Na(s) + ½O2(g)

Na2O(s)

(a) Which energy change in the cycle does y represent?

(1)
A the first electron affinity of oxygen

B the second electron affinity of oxygen

C the sum of the first and second electron affinities of oxygen

D t he sum of the enthalpy change of atomisation of oxygen and the first

and second electron affinities of oxygen

(b) Which expression gives the enthalpy change of formation of sodium oxide, Δf H?
(1)
A Δf H = v + w + x – y – z

B Δf H = v + w + x + y – z

C Δf H = v + w + x – y + z

D Δf H = v + w + x + y + z

(Total for Question 7 = 2 marks)

6
*P71887A0632* 
8 An ionic compound is found to have some degree of covalent bonding.

What will be the cause of the covalency and how will the lattice energy obtained
from a Born–Haber cycle differ from the theoretical value obtained from
electrostatic theory?

Born–Haber lattice energy compared

Cause of covalency
with theoretical value
A cation polarised by anion Born–Haber more exothermic

B anion polarised by cation Born–Haber less exothermic

C cation polarised by anion Born–Haber less exothermic

D anion polarised by cation Born–Haber more exothermic

(Total for Question 8 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

7
 *P71887A0732* Turn over
9 The equation for the reaction between iron and steam is shown.

3Fe(s) + 4H2O(g)  Fe3O4(s) + 4H2(g) ΔH = –151.2 kJ mol–1

(a) What is the equilibrium constant expression for this reaction?

(1)
[Fe3O 4 ] × [H2 ]4
A Kc =
[Fe]3 × [H2 O]4

[Fe3O 4 ] × [H2 ]4
B Kc =
[H2 O]4

[H2 ]4
C Kc =
[Fe]3 × [H2 O]4

[H2 ]4
D Kc =
[H2 O]4

(b) What is the effect on the equilibrium constant for this reaction if small pieces of
iron are replaced by iron powder and if the temperature is increased?
(1)

Iron powder used Temperature increased

A Kc increases Kc increases

B Kc unchanged Kc increases

C Kc increases Kc decreases

D Kc unchanged Kc decreases

(Total for Question 9 = 2 marks)

Use this space for any rough working. Anything you write in this space will gain no credit.

8
*P71887A0832* 
10 Equal amounts of ethanoic acid and methanoic acid are mixed.
[pKa values: ethanoic acid = 4.8 methanoic acid = 3.8]
What are the conjugate acid‑base pairs in the mixture?

acid 1 base 1 acid 2 base 2

A HCOOH HCOO– CH3COOH2+ CH3COOH

B CH3COOH CH3COO– HCOOH2+ HCOOH

C HCOOH CH3COOH CH3COOH2+ HCOO–

D CH3COOH HCOOH HCOOH2+ CH3COO–

(Total for Question 10 = 1 mark)

11 A 1 mol dm–3 solution of ethanoic acid is gradually diluted by the addition of

distilled water.
What happens to the degree of dissociation of the acid and the pH of the solution as
the distilled water is added?

Degree of dissociation pH
A increases increases
B increases decreases
C decreases increases
D decreases decreases

(Total for Question 11 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

9
 *P71887A0932* Turn over
12 The solubility of magnesium hydroxide is 1.1 × 10–4 mol dm–3 at 25 °C and
4.0 × 10–3 mol dm–3 at 100 °C.

[Kw = 1.0 × 10–14 mol2 dm–6 at 25 °C Kw = 5.5 × 10–14 mol2 dm–6 at 100 °C]

(a) What is the pH of a saturated solution of magnesium hydroxide at 25 °C?

(1)
A 9.7

B 10.0

C 10.3

D 12.0

(b) Saturated solutions of magnesium hydroxide at 25 °C and 100 °C are compared.

How do the concentrations of hydroxide ions and the pH values of these
solutions differ?
(1)

Concentration of hydroxide ions at 100 °C pH at 100 °C

A higher lower

B higher higher

C lower higher

D lower lower

(Total for Question 12 = 2 marks)

Use this space for any rough working. Anything you write in this space will gain no credit.

10
*P71887A01032* 
13 Propanal has a much higher boiling temperature than butane even though both
compounds have the same molar mass.
The main reason for the difference in boiling temperature is that in the liquid state
A propanal forms much stronger London forces than butane

B propanal forms permanent dipole‑permanent dipole forces

C propanal forms hydrogen bonds

D propanal forms hydrogen bonds and

permanent dipole‑permanent dipole forces

(Total for Question 13 = 1 mark)

14 The structure of an ester is shown.

Which two compounds react to form this ester?

A butanoyl chloride and 2‑methylbutan‑2‑ol

B butanoyl chloride and 3‑methylbutan‑2‑ol

C propanoyl chloride and 2‑methylbutan‑2‑ol

D propanoyl chloride and 3‑methylbutan‑2‑ol

(Total for Question 14 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

11
 *P71887A01132* Turn over
15 Samples of ethanal and propanone are added to separate test tubes containing
iodine dissolved in aqueous potassium hydroxide and the mixtures are heated gently.

A pale yellow precipitate will be formed with

A ethanal and propanone

B ethanal only

C propanone only

D neither ethanal nor propanone

(Total for Question 15 = 1 mark)

16 The chromatogram of a substance X is shown.

solvent front

substance X

baseline

What is the Rf value for substance X?

A 0.28

B 0.62

C 0.70

D 0.86

(Total for Question 16 = 1 mark)

TOTAL FOR SECTION A = 20 MARKS

12
*P71887A01232* 
SECTION B

Answer ALL the questions. Write your answers in the spaces provided.

17 The reaction between hydrogen peroxide and iodide ions in acid conditions is known
as the Harcourt–Esson reaction after the scientists who first studied its kinetics.

H2O2(aq) + 2I–(aq) + 2H+(aq) → 2H2O(l) + I2(aq)

(a) A student carried out experiments to determine the rate equation for this
reaction at 293 K.

(i) The rate of this reaction may be obtained by adding a fixed volume of
sodium thiosulfate solution and a few drops of starch solution to the
reaction mixture.
Explain how this method gives the rate of reaction.
(3)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

13
 *P71887A01332* Turn over
(ii) The student’s results are shown.

Run [H2O2(aq)] / mol dm–3 [I–(aq)] / mol dm–3 [H+(aq)] / mol dm–3 Rate / mol dm–3 s–1

1 0.0210 0.0198 0.00105 0.00181

2 0.0105 0.0400 0.00105 0.00181

3 0.0105 0.0797 0.00099 0.00364

4 0.0210 0.0801 0.00201 0.00730

Deduce the rate equation for this reaction.

(3)

(iii) Calculate the rate constant for this reaction at 293 K, using the results from
Run 1. Include units with your answer.
(3)

14
*P71887A01432* 
(b) The student carried out a second series of experiments with this reaction at 313 K.
The rate of reaction was found to be 4.45 times faster at 313 K than at 293 K.
Calculate the activation energy, Ea , for this reaction, using the Arrhenius equation.
Give your answer to an appropriate number of significant figures and
include units.

Ea
ln k = – + constant
RT
(4)

(Total for Question 17 = 13 marks)

15
 *P71887A01532* Turn over
18 Lactic acid is formed in muscles and in sour milk.

OH OH
CH3 C C

H O

Lactic acid may be obtained from ethanal in the laboratory by the two‑step
synthesis shown.

OH OH OH
O
Step 1 Step 2
CH3 C CH3 C C N CH3 C C
HCN / CN– HCl(aq)
H H H O

*(a) Explain why lactic acid formed in muscles is optically active while lactic acid
obtained using the laboratory synthesis is not.
You should define any terms you use.
(6)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

16
*P71887A01632* 
. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

17
 *P71887A01732* Turn over
(b) Poly(lactic acid) is a polyester derived from lactic acid as the only monomer.
Poly(lactic acid), which is often referred to as PLA, may be obtained from
renewable resources and is also biodegradable.
(i) Draw the structure of a section of PLA showing two repeat units.
(2)

(ii) Lactic acid is converted into compound X which is then polymerised to

form PLA.
The empirical formula of X is C3H4O2 and its molar mass is 144 g mol–1.
Determine the molecular formula of X.
(1)

18
*P71887A01832* 
(iii) A simplified high resolution proton NMR spectrum of X is shown.
The numbers above the peaks are the relative peak areas.
Note that the chemical shifts for X are different from the general values in the
Data Booklet.

12 10 8 6 4 2 0
δ / ppm

State what the number of peaks, their relative peak areas and splitting
patterns show about the structure of X.
(3)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

19
 *P71887A01932* Turn over
(iv) A simplified carbon‑13 NMR spectrum of X is shown.

200 160 120 80 40 0

δ / ppm

State what additional information about the structure of X is given by

this spectrum.
(2)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(v) Draw the structure of X using the information from (b)(ii) to (b)(iv).
(1)

(Total for Question 18 = 15 marks)

20
*P71887A02032* 
19 Carbonyl compounds are usually reduced in the laboratory using complex
metal hydrides such as lithium tetrahydridoaluminate(III), LiAlH4 .
The metal hydrides react by supplying hydride ions, H–, which then react with the
carbonyl group to form an intermediate.
The addition of a strong acid in aqueous solution to the intermediate produces the
reduction product.
(a) State the essential condition for using LiAlH4 .
(1)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(b) Complete the mechanism for the reduction of propanone with LiAlH4 , showing
the structure of the intermediate and of the final product.
Include curly arrows, and relevant lone pairs and dipoles.
(4)
H3C
C O
H3C

H–

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(Total for Question 19 = 8 marks)

21
 *P71887A02132* Turn over
20 Cracking reactions are used to obtain more useful compounds from the alkanes
found in crude oil. An equation for the cracking of butane is shown.

C4H10(g) → C2H6(g) + C2H4(g)

Thermodynamic data for the compounds in this reaction are given in the table.

C4H10(g) C2H6(g) C2H4(g)

Standard molar entropy S d / J K–1 mol–1 310.1 229.5 219.5

Standard molar enthalpy change of formation Δf H d / kJ mol–1 –126.5 –84.7 +52.2

(a) (i) Calculate the entropy change in the system, ΔS system

d
, for the
cracking of butane.
Include a sign and units with your answer.
(2)

(ii) Calculate the enthalpy change of reaction, Δ r H d , for the cracking of butane.
Include a sign and units with your answer.
(2)

22
*P71887A02232* 
(iii) Calculate the entropy change in the surroundings, ΔS surroundings
d
, at 298 K for the
cracking of butane, using your answer to (a)(ii).
Include a sign and units with your answer.
(2)

(iv) Calculate the total entropy change, ΔS total

d
, at 298 K for the cracking of butane,
using your answers to (a)(i) and (a)(iii).
Include a sign and units with your answer.
(1)

(v) Calculate the temperature at which the cracking reaction becomes feasible.
(2)

23
 *P71887A02332* Turn over
(b) 5 mol of butane is cracked at 750 K. At equilibrium, 4.45 mol of ethene is formed
and the total pressure is 1.20 atm.

C4H10(g)  C2H6(g) + C2H4(g)

(i) Give the expression for the equilibrium constant, Kp , for this reaction.
(1)

(ii) Calculate the value of Kp , including units if required.

(5)

(Total for Question 20 = 15 marks)

TOTAL FOR SECTION B = 51 MARKS

24
*P71887A02432* 
SECTION C

Answer ALL the questions. Write your answers in the spaces provided.

21 Gluconic acid is a weak acid which occurs in fruit and honey and is widely used as a
food additive.

OH OH OH

OH OH OH
gluconic acid

(a) A solution of gluconic acid was prepared by dissolving 4.75 g of the solid in water
and making the solution up to 250.0 cm3 in a volumetric flask.

(i) Write the equation for the acid dissociation constant, Ka , of gluconic acid.
Use RCOOH for gluconic acid.
(1)

(ii) Calculate the pH of the solution of gluconic acid.

[Mr (gluconic acid) = 196 Ka (gluconic acid) = 1.38 × 10–4 mol dm–3 ]
(4)

25
 *P71887A02532* Turn over
(b) A solution of 0.105 mol dm–3 sodium hydroxide was titrated against 25.0 cm3 of the
gluconic acid solution prepared in (a).
The titration curve is shown. The curve is not to scale.

0
0 10 20 30 40
Volume of NaOH / cm3

(i) Explain why phenol red is an appropriate indicator for this titration.
Refer to the titration curve and the Data Booklet.
(2)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

26
*P71887A02632* 
(ii) Calculate the pH of the titration mixture after the addition of 35.0 cm3 of
sodium hydroxide solution.
The value required cannot be obtained from the titration curve in (b).
(5)

27
 *P71887A02732* Turn over
(c) Mixtures of gluconic acid and sodium gluconate are buffers.
(i) Explain how a solution that contains both gluconic acid and sodium gluconate
acts as a buffer.
Use RCOOH for the formula of gluconic acid.
(4)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

28
*P71887A02832* 
(ii) The concentration of a solution of gluconic acid is 1.55 mol dm–3.
Calculate the number of moles of sodium gluconate that must be added to
1.00 dm3 of this solution to give a buffer with pH = 3.71.
Assume that the volume of the solution is unchanged.
(3)

(Total for Question 21 = 19 marks)

TOTAL FOR SECTION C = 19 MARKS

TOTAL FOR PAPER = 90 MARKS
29
 *P71887A02932*
Please check the examination details below before entering your candidate information
Candidate surname Other names

Centre Number Candidate Number

Pearson Edexcel International Advanced Level

Friday 2 June 2023
Morning (Time: 1 hour 45 minutes) Paper
reference WCH14/01
Chemistry
 

International Advanced Level

UNIT 4: Rates, Equilibria and Further Organic
Chemistry
You must have: Total Marks
Scientific calculator, Data Booklet, ruler

Instructions
• Use black ink or ball-point pen.
• IfFillpencil is used for diagrams/sketches/graphs it must be dark (HB or B).
• centrein the boxes at the top of this page with your name,
number and candidate number.
• Answer the
Answer all questions.
• – there may questions in the spaces provided
be more space than you need.

Information
• The total mark for this paper is 90.
• – usemarks
The for each question are shown in brackets
this as a guide as to how much time to spend on each question.
• Into the question marked with an asterisk (*), marks will be awarded for your ability
structure your answer logically, showing how the points that you make are
related or follow on from each other where appropriate.
• A Periodic Table is printed on the back cover of this paper.

Advice
• Read each question carefully before you start to answer it.
• Show all your working in calculations and include units where appropriate.
• Checkanswer
Try to every question.
• your answers if you have time at the end. Turn over

N:1/1/1/1/
SECTION A
Answer ALL the questions in this section.
You should aim to spend no more than 20 minutes on this section.
For each question, select one answer from A to D and put a cross in the box .
If you change your mind, put a line through the box and then mark your new answer
with a cross .
1 A homogeneous equilibrium is shown.

W + X  2Y + Z

What is the Kc expression for this equilibrium?

2 Y Z
A Kc =
W X

Y 2 Z
B Kc =
W X

W X
C Kc =
2 Y Z

W X
D Kc =
Y 2 Z

(Total for Question 1 = 1 mark)

2 The reaction shown occurs at 360 °C and 1 atm.

CO + H2O  CO2 + H2 ΔH = –41.2 kJ mol–1

What is the type of equilibrium and how is Kc affected by an increase in temperature?

Effect of increasing
Type of equilibrium
temperature on Kc
A heterogeneous decreases

B homogeneous decreases

C heterogeneous increases

D homogeneous increases

(Total for Question 2 = 1 mark)

2
*P71942A0232* 
3 What are the units of Kp for the equilibrium shown?

N2(g) + 3H2(g)  2NH3(g)

–1
A atm

B atm

C atm–2

D atm2

(Total for Question 3 = 1 mark)

4 High-performance liquid chromatography (HPLC) is used to separate a mixture into

its three components.
The resulting chromatogram is shown.

G
E

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

(a) Which is correct for the labels on the axes?

(1)

x-axis y-axis

A absorption time

B Rf absorption

C time Rf

D time absorption

3
 *P71942A0332* Turn over
(b) Which is correct for the components E, F and G ?
(1)
Most attracted to
Most abundant
stationary phase
A E E

B G E

C E F

D G F

(Total for Question 4 = 2 marks)

5 Which pair of compounds can form a racemic mixture when mixed?

CH2OH CH2OH

A H H
C2H5 CH2OH
HO H3C

CH2OH CH2OH

B H H
C2H5 C2H5
HO HO

CH3 CH3

C H HO
C2H4OH CH2OH
HO H3C

CH2OH CH2OH

D H H
C2H5 H5C2
HO OH

(Total for Question 5 = 1 mark)

4
*P71942A0432* 
6 Metoprolol is a drug used to treat heart problems.
The structure of metoprolol is shown.

OH
H
O N CH3

CH3
H3C O

How many chiral centres are there in a molecule of metoprolol?

A 0

B 1

C 2

D 3

(Total for Question 6 = 1 mark)

7 The decomposition of hydrogen peroxide is catalysed by iodide ions.

I–
2H2O2(aq) 2H2O(l) + O2(g)

The mechanism for this reaction is shown.

Step 1: H2O2(aq) + I –(aq)  IO–(aq) + H2O(l) fast

Step 2: H2O2(aq) + IO–(aq) → I –(aq) + H2O(l) + O2(g) slow

What is the rate equation for this reaction?

A rate = k[H2O2]2[I – ]

B rate = k[H2O2][I – ]

C rate = k[H2O2]2[I – ][IO– ]

D rate = k[H2O2][IO– ]

(Total for Question 7 = 1 mark)

5
 *P71942A0532* Turn over
8 The two monomers shown react to form a polymer.

HO O

O
OH
HO OH

monomer 1 monomer 2

Which is a repeat unit of the resulting polymer?

O O

A
O
O

O O

B O
O

C
O
O

O
D O
O
O

(Total for Question 8 = 1 mark)

6
*P71942A0632* 
9 A partial mechanism of the reaction between ethanoyl chloride and
concentrated aqueous ammonia is shown.

O–

••
Oδ– O
δ+
CH3 C CH3 C Cl CH3 C + Cl–

••
Clδ– + H N
+
H
H N H
••
H N H H
H
H
O O
CH3 C CH3 C
+
H N H H N H

H
NH+4
••
H N H

(a) How many curly arrows are needed to complete the mechanism?
(1)
A 4

B 5

C 6

D 8

(b) What is the IUPAC name for the organic product?

(1)
A amino ethanone

B ethanamide

C ethanoyl amine

D methanamide

(Total for Question 9 = 2 marks)

Use this space for any rough working. Anything you write in this space will gain no credit.

7
 *P71942A0732* Turn over
10 How do the boiling temperature and the solubility in water of butanoic acid compare
with the values for hexane?

Boiling temperature Solubility in water

A lower lower

B lower higher

C higher lower

D higher higher

(Total for Question 10 = 1 mark)

11 Which acid would be produced by the hydrolysis of the molecule shown?

A 2-hydroxy-3-methylbutanoic acid

B 3-hydroxy-2-methylbutanoic acid

C 3-hydroxy-2,3-dimethylpropanoic acid

D 4-hydroxypentanoic acid

(Total for Question 11 = 1 mark)

12 Which is produced after the polyester shown is hydrolysed with excess

sodium hydroxide?

O O H H

O C C O C C

H H n

A benzene-1,4-dicarboxylic acid

B ethane-1,2-diol

C sodium ethanedioate

D water

(Total for Question 12 = 1 mark)

8
*P71942A0832* 
13 The titration curve shown is produced when a base is added to an acid.
12

pH 7

2
0 1 2 3 4 5 6 7 8 9 10 11 12

Volume of base / cm3

(a) Which indicators could be used for this titration? Use your Data Booklet.
(1)
A bromocresol green, methyl red and phenolphthalein

B bromothymol blue, phenol red and phenolphthalein

C methyl red, bromothymol blue and phenol red

D thymol blue, screened methyl orange and bromophenol blue

(b) Which acid and base could produce this curve?

(1)
A CH3COOH and NaOH

B CH3COOH and NH3

C HCl and NaOH

D HCl and NH3

(Total for Question 13 = 2 marks)

9
 *P71942A0932* Turn over
14 The structure of maleic acid is shown.
OH HO

O C C O
C C
H H
(a) Which could be the titration curve when sodium hydroxide is added to
maleic acid?
(1)
14
12
10
8
pH
A 6
4
2
0
0 20 40 60 80
Volume of NaOH / cm3
14
12
10
8
pH
B 6
4
2
0
0 20 40 60 80
Volume of NaOH / cm3
14
12
10
8
pH
C 6
4
2
0
0 20 40 60 80
Volume of NaOH / cm3
14
12
10
8
pH
D 6
4
2
0
0 20 40 60 80
Volume of NaOH / cm3

10
*P71942A01032* 
(b) What is the IUPAC name for maleic acid?
(1)

OH HO

O C C O
C C
H H

maleic acid

A (E)-but-2-enedioic acid

B (Z)-but-2-enedioic acid

C (E)-1,2-ethenedioic acid

D (Z)-1,2-ethenedioic acid

(Total for Question 14 = 2 marks)

15 Which is not a conjugate acid-base pair?

A NH3 , NH2–

B NH4+ , NH3

C H2CO3 , CO32–

D H2CO3 , HCO3–

(Total for Question 15 = 1 mark)

16 What is the pH of the solution when 2.15 g of barium hydroxide is dissolved in

200 cm3 of deionised water?
[molar mass of barium hydroxide = 171.3 g mol–1 Kw = 1.00 × 10–14 mol2 dm–6 ]

A 10.1

B 12.1

C 12.8

D 13.1

(Total for Question 16 = 1 mark)

TOTAL FOR SECTION A = 20 MARKS

11
 *P71942A01132* Turn over
SECTION B
Answer ALL the questions. Write your answers in the spaces provided.
17 A Born–Haber cycle for calcium chloride is shown.

Ca2+(g) + 2Cl(g)
2 × +122 kJ mol–1
Ca2+(g) + Cl2(g)
2 × –349 kJ mol–1

Ca2+(g) + 2Cl–(g)
+1145 kJ mol–1

Ca+(g) + Cl2(g)

+590 kJ mol–1

–2258 kJ mol–1
Ca(g) + Cl2(g)

Ca(s) + Cl2(g) +178 kJ mol–1

CaCl2(s)

(a) State the value of the ΔatH for calcium.

(1)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(b) Calculate the enthalpy change of formation for calcium chloride.

(2)

12
*P71942A01232* 
(c) Some energy data are shown.

Theoretical lattice energy Experimental lattice energy

Compound
/ kJ mol–1 / kJ mol–1

CaCl2 –2223 –2258

CaI2 –1905 –2074

Explain why the difference between the theoretical and the experimental
values for lattice energy is very much greater for calcium iodide than for
calcium chloride.
(4)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

13
 *P71942A01332* Turn over
(d) Calcium chloride is soluble in water.
(i) Complete the energy cycle including labelled arrows.
(2)

ΔsolH
CaCl2(s) Ca2+(aq) + 2Cl–(aq)

(ii) Calculate the enthalpy change of solution, ΔsolH, for calcium chloride using the
data given and the completed energy cycle in (d)(i).
(2)

Data Energy change / kJ mol–1

LE (CaCl2(s)) –2258

ΔhydH (Ca2+(g)) –1579

ΔhydH (Cl–(g)) –378

(Total for Question 17 = 11 marks)

14
*P71942A01432* 
18 This question is about the reaction between nitrogen monoxide and oxygen.
NO(g) + ½O2(g)  NO2(g)
(a) The results of a series of kinetics experiments are shown.

Initial [NO] Initial [O2] Initial rate

Experiment
/ mol dm–3 / mol dm–3 / mol dm–3 s–1
1 0.010 0.050 0.040

2 0.020 0.050 0.160

3 0.030 0.050 0.360

4 0.040 0.050 0.641

5 0.050 0.050 1.001

6 0.020 0.025 0.080

The data for experiments 1–5 were plotted on a graph.

1.2

1.0

0.8

Initial rate
0.6
/ mol dm–3 s–1

0.4

0.2

0
0 0.01 0.02 0.03 0.04 0.05 0.06

[NO] / mol dm–3

(i) Draw a best-fit line on the graph.
(1)

15
 *P71942A01532* Turn over
(ii) State how the graph shows that the reaction is not first order with respect to
nitrogen monoxide.
(1)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(iii) Deduce the orders of reaction with respect to NO and O2 , using the data from
experiments 1–6.
(2)

Order with respect to NO = ..............................................................

Order with respect to O2 = ..............................................................

(iv) Write the rate equation for the reaction, using your answer to (a)(iii).
(1)

(v) Calculate the rate constant for this reaction using the data from experiment 1
and your rate equation. Include units in your answer.
(2)

(b) The equilibrium constant, Kp , for the reaction at 298 K is 1.55 × 106 atm–½.
State what this value of the equilibrium constant indicates about the position of
the equilibrium. Justify your answer.
(2)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................................... . . . . . . . . . . . . . . . . . . . .

(Total for Question 18 = 9 marks)

16
*P71942A01632* 
19 This question is about some bromoalkanes.
(a) There are three straight-chain structural isomers with the
molecular formula C5H11Br.
(i) Complete the table for these three isomers.
(3)

Number of peaks in
Isomer Skeletal formula 13
C NMR spectrum

...........................

17
 *P71942A01732* Turn over
*(ii) The high resolution proton NMR spectrum of one of these isomers is shown.

5 4 3 2 1 0
Chemical shift, δ / ppm

Deduce which isomer is present in the sample, explaining the splitting

patterns and chemical shifts seen in the spectrum.
Include the name of the isomer and the relative peak areas.
Use your Data Booklet.
(6)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

18
*P71942A01832* 
. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

19
 *P71942A01932* Turn over
(b) Draw the SN2 mechanism for the reaction of 1-bromopropane with hydroxide ions
in aqueous solution.
Include curly arrows, and relevant dipoles and lone pairs.
(4)

(Total for Question 19 = 13 marks)

20
*P71942A02032* 
20 Nitrous oxide, N2O, decomposes at high temperature to form nitrogen and oxygen.

N2O(g)  N2(g) + ½O2(g)

(a) (i) Some standard molecular entropy data are shown.

Standard molecular entropy S

Substance
/ J K–1 mol–1

nitrogen, N2 192

oxygen, O2 205

nitrous oxide, N2O 220

Calculate the standard entropy change of the system for the

decomposition shown.
Include a sign and units in your answer.
(2)

(ii) The standard enthalpy change of the forward reaction is –82 kJ mol–1.
Calculate the entropy change of the surroundings at 2048 K.
Include a sign and units in your answer.
(2)

(iii) Calculate the total entropy change of the reaction at 2048 K.

Include a sign and units in your answer.
(1)

21
 *P71942A02132* Turn over
(b) Rate experiments on the decomposition of nitrous oxide produced the
following graph.

1 –1
/K
T
0.0064 0.0065 0.0066 0.0067 0.0068
–188

–190

–192

ln k

–194

–196

–198

Calculate the activation energy for the reaction in kJ mol–1.

Include the value of the gradient.
Ea 1
ln k = – + constant
R T
R = 8.31 J K–1 mol–1
(2)

22
*P71942A02232* 
(c) Explain whether or not this reaction occurs at 2048 K by considering the values
calculated in (a) and (b).
(2)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(Total for Question 20 = 9 marks)

23
 *P71942A02332* Turn over
21 Hexane-2,5-dione, CH3COCH2CH2COCH3 , is a toxic compound formed in the
human body if hexane is consumed.
(a) Complete the table for hexane-2,5-dione.
Name the organic product formed if a reaction takes place.
(2)

Reaction
Reagent and conditions Name of organic product (if formed)
( / )

refluxed with excess

acidified potassium dichromate(VI)

excess lithium
tetrahydridoaluminate(III)
in dry ether

(b) State the observation when hexane-2,5-dione reacts with iodine in the presence
of alkali.
(1)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(c) Hexane-2,5-dione reacts with excess hydrogen cyanide, HCN, in the presence of
potassium cyanide, KCN.
(i) Name the type and mechanism of this reaction.
(1)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(ii) Draw the structure of the product.

(1)

24
*P71942A02432* 
(d) (i) Give the observation when 2,4-dinitrophenylhydrazine (Brady’s reagent)
reacts with hexane-2,5-dione.
(1)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(ii) Describe, in outline, how the product of this reaction may be used to confirm
the identity of hexane-2,5-dione. Experimental details are not required.
(2)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(Total for Question 21 = 8 marks)

TOTAL FOR SECTION B = 50 MARKS

25
 *P71942A02532* Turn over
SECTION C
Answer ALL the questions. Write your answers in the spaces provided.
22 The alkaline compound tris(hydroxymethyl)aminomethane, known as Tris, is used to
make a buffer for biological research.

HO NH2

Tris

(a) Sketch the low resolution proton NMR spectrum of Tris (C4H11NO3).
Use your Data Booklet.
(3)

10 9 8 7 6 5 4 3 2 1 0
Chemical shift, δ / ppm

26
*P71942A02632* 
(b) Tris is a Brønsted–Lowry base and its conjugate acid is formed as shown.

OH OH

HO NH2 + H+  HO NH3+

OH OH

(i) Explain how a mixture of Tris and its conjugate acid acts as a buffer solution
when a small amount of acid is added.
(3)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

27
 *P71942A02732* Turn over
(ii) Write the expression for the Ka of the conjugate acid of Tris (C4H12NO3+).
(1)

(iii) When hydrochloric acid is added to Tris, the acid salt is formed.
The acid salt is a solid, which has the formula C4H12NO3+Cl–, and contains the
conjugate acid of Tris.
When 100 g of the acid salt is mixed with 500 cm3 of 0.200 mol dm–3 Tris,
an alkaline buffer is formed.
Calculate the pH of this buffer, assuming that there is no change in volume
when the solid is added.
Ka for the conjugate acid of Tris is 8.413 × 10–9 mol dm–3.
(5)

28
*P71942A02832* 
(c) A solution of chloroethanoic acid is prepared for titration with Tris.
0.0150 g of chloroethanoic acid (Mr = 94.5) is dissolved in 1500 cm3 of
distilled water. The resulting solution has a pH of 3.42.
Calculate the Ka of chloroethanoic acid.
(4)

(d) A titration curve of Tris with chloroethanoic acid is shown.

7
pH
6

3
0 2 4 6 8 10 12 14 16 18 20 22 24 26
Volume of acid added / cm3

29
 *P71942A02932* Turn over
(i) Explain how this graph shows Tris and its conjugate acid act as a buffer.
(2)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(ii) Use the graph to estimate the pH of the salt formed when Tris is neutralised
with chloroethanoic acid.
(1)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................ ................ . . . . . . . . . . . . . . . . . . . .

(iii) Suggest a reason why buffers are so important in biological systems.

(1)

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(Total for Question 22 = 20 marks)

TOTAL FOR SECTION C = 20 MARKS

TOTAL FOR PAPER = 90 MARKS

30
*P71942A03032* 
Please check the examination details below before entering your candidate information
Candidate surname Other names

Centre Number Candidate Number

Pearson Edexcel International Advanced Level

Friday 20 October 2023
Morning (Time: 1 hour 45 minutes) Paper
reference WCH14/01
Chemistry  

International Advanced Level

UNIT 4: Rates, Equilibria and Further Organic
Chemistry

You must have: Total Marks

Scientific calculator, Data Booklet, ruler

Instructions
•• Use black ink or ball‑point pen.
If pencil is used for diagrams/sketches/graphs it must be dark (HB or B).
• Fill in the boxes at the top of this page with your name,
centre number and candidate number.
•• Answer all questions.
Answer the questions in the spaces provided
– there may be more space than you need.
Information
•• The total mark for this paper is 90.
The marks for each question are shown in brackets
– use this as a guide as to how much time to spend on each question.
• Instructure
the question marked with an asterisk (*), marks will be awarded for your ability to
your answer logically, showing how the points that you make are related or
follow on from each other where appropriate.
• A Periodic Table is printed on the back cover of this paper.
Advice
•• Read each question carefully before you start to answer it.
Show all your working in calculations and include units where appropriate.
•• Try to answer every question.
Check your answers if you have time at the end.
Turn over

Answer ALL the questions in this section.

DO NOT WRITE IN THIS AREA DO NOT WRITE IN THIS AREA DO NOT WRITE IN THIS AREA
You should aim to spend no more than 20 minutes on this section.

For each question, select one answer from A to D and put a cross in the box .
If you change your mind, put a line through the box and then mark your new answer
with a cross .
1 Which method would be most suitable to investigate the kinetics of the
reactions shown?
(a) (CH3)2C CH2(g) + HI(g) → (CH3)3CI(g)
(1)
A colorimetry

B measurement of change in volume

C measurement of change in mass

D quenching with ice‑cold water followed by titrating with acid

(b) HCOOCH3(aq) + NaOH(aq) → HCOONa(aq) + CH3OH(aq)

(1)
A colorimetry

B measurement of change in volume

C measurement of change in mass

D quenching with ice‑cold water followed by titrating with acid

(Total for Question 1 = 2 marks)

2 The equation for the reaction of bromate(V) ions with bromide ions in acid solution
is shown.
BrO–3(aq) + 5Br –(aq) + 6H+ → 3Br2(aq) + 3H2O(l )
The rate equation for the reaction is
rate = k[BrO–3][Br –][H+]2
The concentrations of all the reactants are doubled.
By what factor does the rate of reaction increase?

A 2

B 4

C 8

D 16
(Total for Question 2 = 1 mark)

2
*P75068A0236* 
3 This question is about rates of chemical reactions.
(a) Which graph shows a reaction that is zero order with respect to reactant Q?
DO NOT WRITE IN THIS AREA DO NOT WRITE IN THIS AREA DO NOT WRITE IN THIS AREA

(1)

[Q]
A

Time

B Rate

[Q]

[Q]
C

Time

Rate
D

[Q]

(b) The equation for a gas phase reaction is shown.

A(g) → B(g) + C(g)
The reaction is first order.
When the initial pressure of A is 2 atm the half‑life of the reaction is 20 s.
What is the half‑life of the reaction when the initial pressure of A is 4 atm?
(1)
A 10 s

B 20 s

C 40 s

D 400 s
(Total for Question 3 = 2 marks)

3
 *P75068A0336* Turn over
4 The graph shown can be used to obtain a value for the activation energy, Ea , of
a reaction.

DO NOT WRITE IN THIS AREA DO NOT WRITE IN THIS AREA DO NOT WRITE IN THIS AREA
1 –1
/K
T

ln(rate constant)

The activation energy is related to the rate constant by the equation

Ea 1
ln(rate constant) = – × + constant
R T
From the graph, the Ea is equal to

( −gradient)
A
R
( −gradient)
B
RT

C (–gradient) × R

D (–gradient) × RT
(Total for Question 4 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

4
*P75068A0436* 
5 The energy cycle for dissolving calcium chloride in water is shown.

Ca2+(g) + 2Cl–(g)
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LE = –2258 kJ mol–1

CaCl2(s)

Δsol H = –120 kJ mol–1

Ca2+(aq) + 2Cl–(aq)

(a) The enthalpy change of hydration of the calcium ion is –1650 kJ mol–1.
What is the enthalpy change of hydration, in kJ mol–1, of the chloride ion?
(1)
A –728

B –364

C +364
D +728

(b) Why is the enthalpy change of hydration for magnesium ions more exothermic
than that for calcium ions?
(1)
A magnesium ions have a larger radius

B magnesium ions form stronger ionic bonds

C magnesium ions have a higher charge density

D magnesium has higher first and second ionisation energies

(Total for Question 5 = 2 marks)

5
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6 Heating copper(II) nitrate results in the equilibrium shown.

2Cu(NO3)2(s)  2CuO(s) + 4NO2(g) + O2(g)

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Which is the expression for Kp?

2( pCuO) × 4( pNO2 ) × ( pO2 )

A Kp =
2( pCu(NO3 )2 )

( pCuO)2 × ( pNO2 )4 × ( pO2 )

B Kp =
( pCu(NO3 )2 )2

C Kp = 4( pNO2) × ( pO2)

D Kp = ( pNO2)4 × ( pO2)
(Total for Question 6 = 1 mark)

7 When concentrated hydrochloric acid is added to methanoic acid, an acid‑base

reaction occurs.

HCl + HCOOH  Cl– + HCOOH2+

What are the Brønsted‑Lowry acid‑base conjugate pairs in this equilibrium?

Conjugate base Conjugate base

Acid 1 Acid 2
of Acid 1 of Acid 2
A HCl HCOOH HCOOH2+ Cl–
B HCl HCOOH2+ HCOOH HCOOH2+
C HCl Cl– HCOOH HCOOH2+
D HCl Cl– HCOOH2+ HCOOH

(Total for Question 7 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

6
*P75068A0636* 
8 At 100 °C, pure water has a pH of 6, but at 25 °C it has a pH of 7.
This is because
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A the dissociation of water is endothermic, so the concentration of

hydrogen ions is lower at 100 °C than at 25 °C

B the dissociation of water is exothermic, so the concentration of

hydrogen ions is lower at 100 °C than at 25 °C

C the dissociation of water is endothermic, so the concentration of

hydrogen ions is higher at 100 °C than at 25 °C

D the dissociation of water is exothermic, so the concentration of

hydrogen ions is higher at 100 °C than at 25 °C
(Total for Question 8 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

7
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9 Four beakers each contain equal volumes of four solutions.
Beaker 1 contains 0.01 mol dm–3 NaOH

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Beaker 2 contains 0.01 mol dm–3 NH3
Beaker 3 contains 0.1 mol dm–3 NaOH
Beaker 4 contains 0.1 mol dm–3 Ba(OH)2
The pH of the four solutions was measured.
Which of the following gives the order of decreasing pH?

A 1, 2, 3, 4

B 2, 1, 3, 4

C 3, 4, 1, 2

D 4, 3, 1, 2
(Total for Question 9 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

8
*P75068A0836* 
10 This question is about the reaction scheme shown.

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OH

O Reaction 2
Reaction 1 + PCl5

Cl
OH

Reaction 3 Reaction 4
+ (CH3)2CHCOOH + (CH3)2CHCH2OH
+ H+

(a) Which reagent is required for Reaction 1?

(1)
A acidified potassium dichromate(VI)

B concentrated sulfuric acid

C hydrogen with a nickel catalyst

D lithium tetrahydridoaluminate(III)

(b) Reaction 1 has a yield of 90 %.

What mass of 2‑methylpropanoic acid is required to produce 6.66 g
of 2‑methylpropan‑1‑ol?
[Mr values 2‑methylpropanoic acid = 88 2‑methylpropan‑1‑ol = 74]
(1)
A 6.22 g

B 7.13 g

C 7.92 g

D 8.80 g

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*P75068A01036* 
(c) Which condition is essential for Reaction 2?
(1)
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A acid catalyst

B anhydrous

C high temperature

D ether solvent

(d) Reactions 3 and 4 produce the same ester.

Which is an advantage of using Reaction 4 to produce this ester in the laboratory?
(1)
A it can be carried out at room temperature

B it requires a catalyst

C the atom economy is higher

D hydrogen chloride is a product

(Total for Question 10 = 4 marks)

11 Which diagram shows two repeat units of the polymer formed by the polymerisation
of propane‑1,3‑diol and benzene‑1,4‑dicarboxylic acid?

O O

A O CH2CH2CH2 O C C

O O

B O CH2CH2CH2 O C C O CH2CH2CH2

O O O O

C O C CH2CH2CH2 C O O C CH2CH2CH2 C O

O O O O

D O CH2CH2CH2 O C C O CH2CH2CH2 O C C

(Total for Question 11 = 1 mark)

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12 Polymer waste may be disposed of by incineration.
At a plant carrying out this process with poly(propene), a waste gas was produced

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that was thought to be either propane or carbon dioxide. These compounds have the
same molecular ion peak in a low resolution mass spectrometer but can be separated
at high resolution.

Atom Relative atomic mass, Ar

1
H 1.0079
12
C 12.0000
16
O 15.9949

Which are the correct relative molecular masses?

propane carbon dioxide

A 29.0395 27.9949

B 27.9949 29.0395

C 43.9898 44.0632

D 44.0632 43.9898

(Total for Question 12 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

12
*P75068A01236* 
13 A thin‑layer chromatogram of a mixture of two compounds, X and Y, is shown.

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Solvent front

Baseline

(a) What is the Rf value for compound X?

(1)
A 0.33

B 0.38

C 0.60

D 0.62

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*P75068A01436* 
(b) Y travelled further than X. How do the attractions between Y and X to the
stationary and mobile phases compare?
(1)
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Attraction between Y and the Attraction between Y and the

stationary phase mobile phase
is stronger than the attraction between is stronger than the attraction between
A
X and the stationary phase X and the mobile phase
is stronger than the attraction between is weaker than the attraction between X
B
X and the stationary phase and the mobile phase
is weaker than the attraction between X is stronger than the attraction between
C and the stationary phase X and the mobile phase
is weaker than the attraction between X is weaker than the attraction between X
D and the stationary phase and the mobile phase

(Total for Question 13 = 2 marks)

TOTAL FOR SECTION A = 20 MARKS

15
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SECTION B

Answer ALL the questions. Write your answers in the spaces provided.

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14 This question is about the nucleophilic addition reaction between ethanal and
hydrogen cyanide in the presence of potassium cyanide as a catalyst.
The equation for the reaction is shown.

CH3CHO + HCN → CH3CH(OH)CN

(a) (i) Give the IUPAC name of the organic product.

(1)

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(ii) Complete the mechanism for this two‑step reaction, showing the structure
of the intermediate and including curly arrows, and relevant lone pairs
and dipoles.
(4)

H O
–
Step 1 C C N

H C H

+ HCN

Step 2 H C N

CH3CH(OH)CN + CN–

16
*P75068A01636* 
(a) (iii) Justify the use of the term ‘nucleophilic addition’ to describe the mechanism
of this reaction.
(2)
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(b) Explain why the product of the reaction is not optically active even though it
contains a chiral carbon atom.
(2)

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(Total for Question 14 = 9 marks)

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15 A reaction vessel contained nitrogen monoxide and oxygen in a 2 : 1 molar ratio.
The mixture was allowed to come to equilibrium forming nitrogen dioxide.
The equation for the reaction is shown.

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2NO + O2  2NO2

The volume of the vessel was 15 dm3 and the reaction was carried out at a
constant temperature and at a pressure of 200 000 Pa.
At equilibrium there was a total of 0.69625 mol of gas in the reaction vessel and the
mass of oxygen was 7.000 g.

(a) (i) Calculate the number of moles of each substance at equilibrium.

(3)

(ii) Calculate the value of Kc under these conditions.

Include units in your answer.
(4)

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*P75068A01836* 
(b) Calculate the temperature, in K, of the reaction mixture at equilibrium under
these conditions.
Use the equation pV = nRT and the data at the start of the question.
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(3)

Experiment number Initial [NO] / mol dm–3 Initial [O2] / mol dm–3 Initial rate / mol dm–3 s–1

1 6.50 × 10–2 1.25 × 10–2 6.87 × 10–4

The rate equation for this reaction is

rate = k[NO]2[O2]

(i) Give the reason why colorimetry can be used to monitor the rate of
the reaction.
(1)

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(ii) Use the data from Experiment 1 to find the value of the rate constant, k.
Include units in your answer.
(2)

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(iii) State why the reaction is unlikely to proceed in a single step.
(1)

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(iv) A student proposed the mechanism shown for this reaction.

2NO  N2O2 slow

N2O2 + O2 → 2NO2 fast

Justify whether or not this mechanism is consistent with the overall equation
for the reaction and with the rate equation.
(2)

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(Total for Question 15 = 16 marks)

20
*P75068A02036* 
16 Iron, lead and zinc can be extracted using a blast furnace but aluminium cannot.

In a blast furnace, iron is extracted from iron(III) oxide, Fe2O3 , at high temperature.

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Some standard enthalpy changes of formation, Δf H d , and standard molar entropies,
S d , are shown.

Substance Al(s) Al2O3(s) CO(g) CO2(g) Fe(s) Fe2O3(s)

Δf H d / kJ mol–1 0 –1676 –111 –394 0 –824

S d / J K–1 mol–1 28.3 50.9 197.6 213.6 27.3 87.4

(a) The main reaction occurring in the blast furnace to form iron is shown.

Fe2O3(s) + 3CO(g) → 2Fe(s) + 3CO2(g)

This reaction is feasible at all temperatures.

(i) Calculate the standard entropy change of the system for this reaction.
(3)

(ii) Calculate the standard enthalpy change for this reaction.

.(3)

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*P75068A02236* 
(iii) Explain how your answers to (a)(i) and (a)(ii) show that this reaction is feasible
at all temperatures.
(3)
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(b) The main reduction reaction of aluminium oxide in a blast furnace is shown.

Al2O3 + 3CO → 2Al + 3CO2

(i) Calculate the temperature at which this reaction becomes feasible.

(4)

(ii) Suggest why aluminium is not extracted from its oxide using a blast furnace.
(1)

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(Total for Question 16 = 14 marks)

23
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17 This question is about four isomers with the molecular formula C4H8O2 .

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Name Skeletal formula

O
butanoic acid
OH

H
4‑hydroxybutanal OH
O

O
ethyl ethanoate
O

3‑hydroxybutanone

*(a) These four isomers can be identified using three chemical tests.
Each test gives a positive result for only one isomer.
All three tests give a negative result for the fourth isomer.
Deduce the three chemical tests required. For each test
• identify the reagent
• give the positive observation in each test
• identify the functional group of the isomer that gives the positive result.
(6)

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24
*P75068A02436* 
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(b) The four isomers can also be distinguished using NMR spectroscopy.

(i) State why it is not possible to distinguish any of these isomers from the

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number of peaks in their 13C NMR spectra.
(1)

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(ii) Complete the table below to give the number of peaks in a low resolution
1
H NMR spectrum of each isomer.
(3)

Name Skeletal formula Number of peaks

O
butanoic acid
OH

H
4‑hydroxybutanal OH
O

O
ethyl ethanoate
O

3‑hydroxybutanone

26
*P75068A02636* 
(iii) One of the 1H NMR spectra has a peak with a chemical shift, δ,
greater than 10 ppm.
Identify the isomer, and the proton environment responsible for this peak.
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(1)

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(iv) The high resolution 1H NMR spectrum of one of the isomers contains a
multiplet of five peaks (a quintet).
Explain, with reference to the structure of one of the isomers, the presence of
the quintet.
(2)

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(Total for Question 17 = 13 marks)

TOTAL FOR SECTION B = 52 MARKS

27
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SECTION C

Answer ALL the questions. Write your answers in the spaces provided.

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18 Pentanoic acid, C4H9COOH, is a carboxylic acid with Ka = 1.38 × 10–5 mol dm–3.
A student was asked to titrate 25.0 cm3 of 0.120 mol dm–3 pentanoic acid solution with
0.100 mol dm–3 potassium hydroxide solution.
The equation for the reaction is shown.

C4H9COOH + KOH → C4H9COO–K+ + H2O

The teacher asked the student to sketch a graph showing the expected changes in
pH as potassium hydroxide solution is added.
The student first identified four key points for the sketch graph,
using four calculations and one chemical equation. These points are shown.

12 Key point 4
11

9
Key point 3
8
pH
7

4
Key point 2
3

2 Key point 1

0
0 5 10 15 20 25 30 35 40 45 50
3
Volume of KOH(aq) / cm

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*P75068A02836* 
(a) (i) At Key point 1, before any potassium hydroxide has been added, the pH = 2.9.
Use a calculation to justify this value.
(3)
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(ii) The student deduced that the pH at Key point 4 must be less than 13.
Use a calculation to justify the student’s deduction.
You are not required to calculate the exact pH of the solution.
(2)

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(iii) The student deduced that the neutralisation point of the graph at Key point 3
would be at 30 cm3.
Use a calculation to justify the student’s deduction.
(2)

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(iv) The student deduced that when equal amounts of pentanoic acid and
potassium hydroxide have been mixed at Key point 3, the pH would be
greater than 7.

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Justify the student’s deduction.
(1)

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(v) The student deduced that at Key point 2, 15.0 cm3 of potassium hydroxide
would have been added and the pH would be 4.9.
Justify the student’s deductions using a calculation.
(2)

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This question continues on page 32 after the blank page.

30
*P75068A03036* 
(b) The student then completed the sketch graph by linking these four points to
show how the pH would change as potassium hydroxide was added.

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14

12 Key point 4
11

9
Key point 3
8
pH
7

4
Key point 2
3

2 Key point 1

0
0 5 10 15 20 25 30 35 40 45 50
Volume of KOH(aq) / cm3

Explain why the student drew the line so that in the section of the graph between
5 cm3 and 25 cm3 the pH changes very little as the potassium hydroxide is added.
No calculation is required.
(3)

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*P75068A03236* 
(c) (i) The student carried out the titration using methyl orange as an indicator.
The experiment did not give a satisfactory colour change at the neutralisation
point, and the student continued adding potassium hydroxide until 50 cm3
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had been added.

Describe the colour of the solution during this titration experiment with
particular reference to the key points on the sketch graph.
Use the Data Booklet.
(3)

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(ii) The student found a bottle labelled ‘Acid‑base indicator solution’ in the store
cupboard. The student, having checked with the teacher, used this as the
indicator for the titration.
The initial yellow solution turned green at the neutralisation point of
the titration.
Suggest the identity of the indicator solution including a justification for the
colour observed at the neutralisation point.
Use the Data Booklet.
(2)

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(Total for Question 18 = 18 marks)

TOTAL FOR SECTION C = 18 MARKS

TOTAL FOR PAPER = 90 MARKS

33
 *P75068A03336*
Please check the examination details below before entering your candidate information
Candidate surname Other names

Centre Number Candidate Number

Pearson Edexcel International Advanced Level

Monday 8 January 2024
Morning (Time: 1 hour 45 minutes) Paper
reference WCH14/01
Chemistry  

International Advanced Level

UNIT 4: Rates, Equilibria and Further Organic
Chemistry

You must have: Total Marks

Scientific calculator, Data Booklet, ruler

Answer ALL the questions in this section.

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You should aim to spend no more than 20 minutes on this section.

For each question, select one answer from A to D and put a cross in the box . If you change
your mind, put a line through the box and then mark your new answer with a cross .

1 The equation for a reaction is shown.

A(g) + 2B(g)  3C(s) + 4D(g)

(a) Some collisions between reactant molecules do not lead to the formation
of products.
What is the best explanation for this?
(1)
A the reactant concentrations are too low

B the collisions do not have sufficient energy

C the reaction is at equilibrium

D the molecules do not collide in the correct ratio

(b) What are the units of the equilibrium constant, Kp , for this reaction?
(1)
A atm

B atm–1

C atm4
D atm–4
(Total for Question 1 = 2 marks)

2 Nitrogen(V) oxide, N2O5 , decomposes in a first order reaction.

At 45 °C, the half‑life for this reaction is 1400 s.
In an experiment, the initial concentration of nitrogen(V) oxide is 1.0 mol dm–3.
What is the concentration, in mol dm–3, of nitrogen(V) oxide after 4200 s?
A 0.875

B 0.500

C 0.250

D 0.125
(Total for Question 2 = 1 mark)

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*P73456A0228* 
3 Ammonia is produced by the reaction of nitrogen with hydrogen in the presence of
an iron catalyst.
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N2(g) + 3H2(g)  2NH3(g) ΔH = –92 kJ mol–1

(a) Which of the following statements about the catalyst is not correct?
(1)
A it lowers the activation energy of the reaction

B it has no effect on the equilibrium constant for the reaction

C it alters the enthalpy change of the reaction

D it reduces the energy cost of the reaction

(b) Which conditions favour the highest percentage of ammonia in an equilibrium

mixture from identical amounts of nitrogen and hydrogen?
(1)
A a temperature of 400 K and a pressure of 200 kPa

B a temperature of 400 K and a pressure of 200 atm

C a temperature of 400 °C and a pressure of 200 kPa

D a temperature of 400 °C and a pressure of 200 atm

(Total for Question 3 = 2 marks)

4 The equations for three reactions involving hydrogen are shown.

J N2(g) + 3H2(g) → 2NH3(g)

K N2(g) + 2H2(g) → N2H4(l )
L I2(s) + H2(g) → 2HI(g)
What is the order of increasing standard entropy change of the system, ΔS system
d
, for
these reactions?

A J, K, L

B K, L, J

C K, J, L

D L, K, J
(Total for Question 4 = 1 mark)
Use this space for any rough working. Anything you write in this space will gain no credit.

3
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5 Methane reacts with steam to produce carbon dioxide and hydrogen.

CH4(g) + 2H2O(g) → CO2(g) + 4H2(g)

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The standard molar entropies of the reactants and products are given in the table.

Substance S d / J K–1 mol–1

CH4(g) 186

H2O(g) 189

CO2(g) 214

H2(g) 131

The value of ΔS system

d
for this reaction, in J K–1 mol–1, is

A –174
B –30

C +30

D +174
(Total for Question 5 = 1 mark)

6 What are the signs of the entropy changes at 373 K when water vapour condenses?

H2O(g) → H2O(l )

ΔSsystem ΔSsurroundings

A positive positive

B positive negative

C negative positive

D negative negative

(Total for Question 6 = 1 mark)

Use this space for any rough working. Anything you write in this space will gain no credit.

4
*P73456A0428* 
7 At 50 °C, the ionic product of water, Kw , is 5.5 × 10–14 mol2 dm–6.
At this temperature, water is
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A neutral with a pH of 7.0

B neutral with a pH of 6.6

C acidic with a pH of 6.6

D alkaline with a pH of 7.4

(Total for Question 7 = 1 mark)

8 Equimolar solutions of four acids are prepared. Which solution has the lowest pH?
Use electronegativity values from the Data Booklet.

A CH3COOH

B CH2ClCOOH

C CH2BrCOOH
D CH2ICOOH
(Total for Question 8 = 1 mark)

9 Some equations for acid‑base equilibria are shown.

H3PO4 + H2O  H2PO4– + H3O+

H2PO4– + H2O  HPO42– + H3O+

HPO42– + H2O  PO43– + H3O+

What is the conjugate acid of HPO42– ?

A H3PO4

B H3O+

C H2PO4–

D PO43–
(Total for Question 9 = 1 mark)
Use this space for any rough working. Anything you write in this space will gain no credit.

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10 What is the pH of a 0.200 mol dm–3 solution of strontium hydroxide, Sr(OH)2?

Kw = 1.00 × 10–14 mol2 dm–6

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A 14.0

B 13.6

C 13.3

D 12.6
(Total for Question 10 = 1 mark)

11 Carvone is an oil used in aromatherapy.

(a) Carvone shows

(1)
A geometric and optical isomerism

B geometric isomerism only

C optical isomerism only

D neither geometric nor optical isomerism

(b) Which reagent gives a positive result when added to carvone?

(1)
A ammoniacal silver nitrate (Tollens’ reagent)

B aqueous sodium carbonate

C iodine in the presence of an alkali

D 2,4‑dinitrophenylhydrazine

B 9

C 8

D 7
(Total for Question 11 = 3 marks)

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*P73456A0628* 
12 From which two reactants could CH3(CH2)2COO(CH2)4CH3 be made?

A butanoic acid and pentan‑1‑ol

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B butanoyl chloride and butan‑1‑ol

C butanal and pentan‑1‑ol

D pentanoic acid and butan‑1‑ol

(Total for Question 12 = 1 mark)

13 The reaction between ethanoic acid and lithium tetrahydridoaluminate(III) is best

described as

A elimination

B oxidation

C reduction

D substitution
(Total for Question 13 = 1 mark)

14 Which substance is the least soluble in water?

A propanal

B propan‑1‑ol

C propanoic acid

D sodium propanoate
(Total for Question 14 = 1 mark)
Use this space for any rough working. Anything you write in this space will gain no credit.

7
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15 (a) The mass spectrum of compound X shows a large peak at m/z = 59.

This peak is due to the fragmentation of the molecular ion.

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Which compound is most likely to be X?
(1)
A 2‑methylpropan‑2‑ol

B pentane

C propanal

D propanone

(b) Compound Y does not react with acidified aqueous sodium dichromate.
The infrared spectrum of Y is shown.

100

% Transmittance

0
3000 2000 1000
–1
Wavenumber / cm

Which compound is most likely to be Y? Refer to the Data Booklet.

(1)
A 2‑methylpropan‑2‑ol

B pentane

C propanal

D propanone
(Total for Question 15 = 2 marks)

TOTAL FOR SECTION A = 20 MARKS

8
*P73456A0828* 
SECTION B

Answer ALL the questions. Write your answers in the spaces provided.
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16 A group of students investigated the kinetics of a ‘clock’ reaction.

The reaction investigated was that between hydrogen peroxide and iodide ions in the
presence of acid.

Reaction 1 H2O2(aq) + 2H+(aq) + 2I–(aq) → 2H2O(l ) + I2(aq)

In this ‘clock’ reaction, a fixed volume of aqueous sodium thiosulfate, Na2S2O3 , and a
small amount of starch were added to the reaction mixture.
The added thiosulfate ions react with the iodine produced in Reaction 1.

Reaction 2 2S2O32–(aq) + I2(aq) → S4O62–(aq) + 2I –(aq)

When all the thiosulfate ions have reacted, the presence of iodine is detected by the
formation of a starch‑iodine complex. The students recorded the time taken for this
complex to form.
(a) (i) State the final colour of the mixture containing the starch‑iodine complex.
(1)

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(ii) Under appropriate conditions, the reciprocal of time can be used as an

approximate measure of the initial rate of the reaction.
Explain why the concentration of the sodium thiosulfate must be low
compared with the initial concentrations of the other reagents.
(2)

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(b) Four reaction mixtures, with different initial concentrations of hydrogen peroxide,
hydrogen ions and iodide ions, were prepared.

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Each mixture had the same volume and contained the same amount of
sodium thiosulfate and starch.

[H2O2] [H+] [I–] Time 1 ÷ time

Mixture
/ mol dm–3 / mol dm–3 / mol dm–3 /s / s–1

1 5.4 × 10–2 1.7 × 10–5 8.2 × 10–3 195 5.13 × 10–3

2 2.7 × 10–2 1.7 × 10–5 8.2 × 10–3 391 2.56 × 10–3

3 5.4 × 10–2 1.7 × 10–5 1.6 × 10–2 97 1.03 × 10–2

4 5.4 × 10–2 1.7 × 10–4 8.2 × 10–3 204 4.90 × 10–3

(i) Use the results in the table to deduce the order of Reaction 1 with respect to
hydrogen peroxide, hydrogen ions and iodide ions.
Justify each answer by referring to relevant data from the table.
(3)

Hydrogen peroxide .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................................ . . . . . . . . . . . . . . . . . . . .

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Hydrogen ions .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............................................................................................................................................................ . . . . . . . . . . . . . . . . . . . .

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Iodide ions .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................................... . . . . . . . . . . . . . . . . . . . .

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(ii) Write the overall rate equation for Reaction 1 using your answers to (b)(i).
(1)

(iii) All four mixtures contained 8.50 × 10–5 mol of sodium thiosulfate.
Calculate the amount of iodine that had reacted with the sodium thiosulfate
when the colour changed in Reaction 2.
(1)

10
*P73456A01028* 
(iv) Calculate the rate of reaction, in mol dm–3 s–1, with respect to
hydrogen peroxide using the answer from (b)(iii), the stoichiometry of
Reaction 1 and data from Mixture 1.
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The total volume of each Mixture was 0.050 dm3.

(2)

(v) Calculate a value for the rate constant of Reaction 1 using data from
Mixture 1 and your answers to (b)(ii) and (b)(iv).
Include the units of the rate constant.
(2)

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(c) The activation energy for Reaction 1 may be found by repeating the experiment
at different temperatures.
Each student carried out an experiment at a different temperature.

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One of the students misread the thermometer in their experiment.

1÷T
ln rate T/K
/ K–1

–1.8 333 0.00300

–2.5 323 0.00310

–3.6 308 0.00325

–4.0 307 0.00326

–4.7 291.5 0.00343

–6.0 278 0.00360

The activation energy, Ea , for a reaction may be found by plotting a graph of

ln rate against 1/T.
The gradient of the resulting line of best fit can be used in the Arrhenius equation
to determine a value for Ea , in kJ mol–1.
(i) Determine the value for Ea for Reaction 1 by plotting a graph using the
axes provided.
You should take into account the error made by one of the students.

Ea 1
ln rate = – × + constant R = 8.31 J K–1 mol–1
R T
(5)

12
*P73456A01228* 
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Ea ............................................... ............... kJ mol–1

(ii) The students all used thermometers capable of reading to the same precision.
Use your graph to deduce the temperature that the student who made the
error should have read on their thermometer.
(2)

(Total for Question 16 = 19 marks)

13
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17 The question is about lattice energies.
The table shows energy values used in a Born–Haber cycle for

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magnesium chloride, MgCl2.

Energy change Label Value / kJ mol–1

Enthalpy change of atomisation of magnesium A +148

First ionisation energy of magnesium B +738

Second ionisation energy of magnesium C +1451

Enthalpy change of atomisation of chlorine D +122

Lattice energy of magnesium chloride E –2526

Enthalpy change of formation of magnesium chloride F –641

(a) (i) Complete the Born–Haber cycle for magnesium chloride by adding
labels for each of the four energy changes and writing formulae in the
two empty boxes.
(3)

Mg2+(g) + 2Cl(g) + 2e–

................................

Mg2+(g) + Cl2(g) + 2e– 2 × electron affinity (Cl)

Mg2+(g) + 2Cl–(g)
................................

................................

Mg(s) + Cl2(g)

MgCl2(s)

14
*P73456A01428* 
(ii) Calculate a value for the electron affinity of chlorine, in kJ mol–1, using the data
in the table and the completed Born–Haber cycle.
(2)
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(iii) Explain why, when magnesium reacts with chlorine, MgCl2 is formed rather
than MgCl3.
(2)

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(iv) Calculate the standard molar enthalpy change of solution of

magnesium chloride, in kJ mol–1, using the data shown and the value for the
lattice energy, LE[MgCl2], given in the table.

Data ΔhydH d [Mg2+(g)] = –1920 kJ mol–1 ΔhydH d [Cl–(g)] = –364 kJ mol–1

(2)

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*(b) Lattice energies from the Born–Haber cycle are based on experimental values.
Theoretical lattice energies can also be calculated. Experimental and theoretical
values for three different crystal lattices are shown.

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Experimental lattice energy Theoretical lattice energy
Compound
/ kJ mol–1 / kJ mol–1
sodium fluoride NaF –918 –912
magnesium fluoride MgF2 –2957 –2913
magnesium chloride MgCl2 –2526 –2326

Discuss the reasons for the differences in these six values of lattice energy in
terms of the structure and bonding in these three substances.
(6)

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16
*P73456A01628* 
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(Total for Question 17 = 15 marks)

17
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18 Methyl 2‑hydroxypropanoate is used as an industrial solvent.
It may be prepared in three steps using ethanal as the starting material.

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Step 1 Step 2 Step 3
CH3CHO CH3CH(OH)CN CH3CH(OH)COOH CH3CH(OH)COOCH3

(a) Name the reagent(s) in Step 1 and Step 2.

(2)
Step 1

Reagent(s).. ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................... ................ . . . . . . . . . . . . . . . . . . . .

Step 2

Reagent(s).. ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........................................................................................................................................... ................ . . . . . . . . . . . . . . . . . . . .

(b) (i) Complete the mechanism for Step 1, using curly arrows and relevant
lone pairs, charges and dipoles.
(4)

H H

H C C O

–
C N

18
*P73456A01828* 
(ii) Explain why the 2‑hydroxypropanoic acid, CH3CH(OH)COOH, produced
is not optically active.
(3)
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(c) (i) State the type of reaction in Step 3.

(1)

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(ii) A small amount of a polymeric compound is formed during Step 3.

Deduce the structure for the repeat unit of the polymer formed.
(1)

19
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(d) The high‑resolution proton nuclear magnetic resonance (NMR) spectrum of
methyl 2‑hydroxypropanoate gives four peaks, J, K, L and M.
Peaks L and M are singlets with relative intensities of one and three respectively.

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(i) Label the displayed formula to show the protons responsible for these
two peaks.
(2)

H H O H

H C C C O C H

H O H
H

(ii) Complete the table to show the expected number of hydrogen atoms and
expected splitting pattern for peaks J and K.
(2)

Number of Splitting
Peak δ / ppm
hydrogen atoms pattern
J 1.3
K 4.1
L 3.6 1 singlet
M 3.7 3 singlet

(Total for Question 18 = 15 marks)

TOTAL FOR SECTION B = 49 MARKS

20
*P73456A02028* 
SECTION C

Answer ALL the questions. Write your answers in the spaces provided.
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19 (a) Ethyl propanoate, CH3CH2COOCH2CH3 , smells of pineapple and is used as a

flavouring. It may be hydrolysed using hydrochloric acid as a catalyst to produce
propanoic acid and ethanol.

CH3CH2COOCH2CH3(l ) + H2O(l )  CH3CH2COOH(l ) + CH3CH2OH(l )

A mixture was prepared using 0.100 mol of ethyl propanoate and 0.200 mol of water
containing the catalyst.
The mixture was left to reach equilibrium at 25 °C.
The equilibrium mixture contained 0.0440 mol of propanoic acid.
(i) Calculate the value for Kc for this equilibrium at 25 °C.
Give your answer to an appropriate number of significant figures.
(4)

(ii) The standard enthalpy change, ΔrH d , for this reaction is close to, but not
exactly zero. Explain this statement by considering the type and number of
bonds being broken and made. No calculations are required.
(2)

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(iii) Deduce the effect of increasing the temperature on the total entropy change
of this reaction, ΔStotal , and on the value of the equilibrium constant, Kc .
Assume that ΔSsystem does not change with temperature.

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(3)

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(b) Propanoic acid is a weak acid.

(i) State the difference between a weak acid and a strong acid such as
hydrochloric acid.
(1)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .......................... ................................................................................................................................. . . . . . . . . . . . . . . . . . . . .

(ii) Calculate the pH of 0.500 mol dm–3 hydrochloric acid at 25 °C.

(1)

22
*P73456A02228* 
(iii) Calculate the pH of 0.500 mol dm–3 propanoic acid at 25 °C.
Ka (propanoic acid) = 1.30 × 10–5 mol dm–3 at 25 °C.

DO NOT WRITE IN THIS AREA DO NOT WRITE IN THIS AREA DO NOT WRITE IN THIS AREA

(3)

(c) The number of moles of propanoic acid in a solution may be determined by

titration with aqueous sodium hydroxide.
(i) Calculate the pH at the point in the titration where half the acid has been
neutralised. You must show your working.
(2)

23
 *P73456A02328* Turn over
(ii) Sketch the titration curve showing the change in pH when
50 cm3 of 0.500 mol dm–3 sodium hydroxide is added to
25.0 cm3 of propanoic acid of the same concentration, using your answers to

DO NOT WRITE IN THIS AREA DO NOT WRITE IN THIS AREA DO NOT WRITE IN THIS AREA
(b)(iii) and (c)(i).
(3)
14

pH
8

0
0 10 20 30 40 50
Volume of sodium hydroxide / cm3

(iii) Suggest a suitable indicator for this titration. Justify your choice by referring to
your titration curve in (c)(ii).
Use the Data Booklet.
(2)

. . . . . . . . . . . ..................... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .......................... ................................................................................................................................. . . . . . . . . . . . . . . . . . . . .

(Total for Question 19 = 21 marks)

TOTAL FOR SECTION C = 21 MARKS

TOTAL FOR PAPER = 90 MARKS
24
*P73456A02428* 

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