Gases A and B react as shown in the following equation.

1
2A(g) + B(g) C(g) + D(g)

The initial rate of the reaction was measured in a series of experiments at a constant
temperature. The following rate equation was determined.

rate = k[A]2

An incomplete table of data for the reaction between A and B is shown in the table.

Experiment Initial [A] / mol dm−3 Initial [B] / mol dm−3 Initial rate / mol dm−3 s−1

1 4.2 × 10−3 2.8 × 10−3 3.3 × 10−5

2 7.9 × 10−3 2.8 × 10−3

3 5.6 × 10−3 1.8 × 10−4

(a) Use the data from Experiment 1 to calculate a value for the rate constant, k, at this
temperature.
Deduce the units of k.

Calculation ......................................................................................................

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

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

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

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

Units ...............................................................................................................

........................................................................................................................
(3)

(b) Use your value of k from (a) to complete the table for the reaction between A and B.
(If you have been unable to calculate an answer for (a), you may assume a value of 2.3.
This is not the correct answer.)
(2)

Page 1 of 64
 (c) The reaction is zero order with respect to B.

State the significance of this zero order for the mechanism of the reaction.

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

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

........................................................................................................................
(1)
(Total 6 marks)

This question involves the use of kinetic data to deduce the order of a reaction and calculate a
2 value for a rate constant.

The data in Table 1 were obtained in a series of experiments on the rate of the reaction between
compounds A and B at a constant temperature.

Table 1

Experiment Initial concentration Initial concentration Initial rate

of A / mol dm−3 of B / mol dm−3 / mol dm−3 s−1

1 0.12 0.26 2.10 × 10−4

2 0.36 0.26 1.89 × 10−3

3 0.72 0.13 3.78 × 10−3

(a) Show how these data can be used to deduce the rate expression for the reaction between
A and B.

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

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

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

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

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

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(3)

Page 2 of 64
 The data in Table 2 were obtained in two experiments on the rate of the reaction between
compounds C and D at a constant temperature.

Table 2

Experiment Initial concentration Initial concentration Initial rate

of C / mol dm−3 of D / mol dm−3 / mol dm−3 s−1

4 1.9 × 10−2 3.5 × 10−2 7.2 × 10−4

5 3.6 × 10−2 5.4 × 10−2 To be calculated

The rate equation for this reaction is

rate = k[C]2[D]

(b) Use the data from experiment 4 to calculate a value for the rate constant, k, at this
temperature. Deduce the units of k.

k = ............................... Units = ...............................

(3)

(c) Calculate a value for the initial rate in experiment 5.

Initial rate = ............................... mol dm−3 s−1

(1)

Page 3 of 64
(d) The rate equation for a reaction is

rate = k[E]

Explain qualitatively why doubling the temperature has a much greater effect on the rate of
the reaction than doubling the concentration of E.

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

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

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

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

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

........................................................................................................................
(3)

(e) A slow reaction has a rate constant k = 6.51 × 10−3 mol−1 dm3 at 300 K.

Use the equation ln k = ln A – Ea / RT to calculate a value, in kJ mol−1, for the activation

energy of this reaction.

The constant A = 2.57 × 1010 mol−1 dm3.

The gas constant R = 8.31 J K−1 mol−1.

Activation energy = ...............................

(2)
(Total 12 marks)

Page 4 of 64
 Butadiene dimerises according to the equation
3
2C4H6 C8H12

The kinetics of the dimerisation are studied and the graph of the concentration of a sample of
butadiene is plotted against time. The graph is shown below.

(a) Draw a tangent to the curve when the concentration of butadiene is 0.0120 mol dm−3.
(1)

Page 5 of 64
 (b) The initial rate of reaction in this experiment has the value 4.57 × 10−6 mol dm−3 s−1.

Use this value, together with a rate obtained from your tangent, to justify that the order of
the reaction is 2 with respect to butadiene.

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

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

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

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

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

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

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

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

........................................................................................................................
(5)
(Total 6 marks)

The rate equation for the hydrogenation of ethene

4
C2H4(g) + H2(g) C2H6(g)

is Rate = k[C2H4][H2]

At a fixed temperature, the reaction mixture is compressed to triple the original pressure.

What is the factor by which the rate of reaction changes?

A 6

B 9

C 12

D 27
(Total 1 mark)

Page 6 of 64
 (a) The table shows the results of three experiments to investigate the rate of reaction between
5 compounds A and B dissolved in a given solvent.
All three experiments were carried out at the same temperature.

Experiment 1 Experiment 2 Experiment 3

Initial concentration of A / mol

1.60 × 10–2 2.40 × 10–2 3.60 × 10–2
dm–3

Initial concentration of B / mol

4.20 × 10–2 6.30 × 10–2 6.30 × 10–2
dm–3

Initial rate /mol dm–3 s–1 8.00 × 10–5 1.80 × 10–4 4.05 × 10–4

(i) Deduce the order of reaction with respect to A.

Tick (✓) one box.

Order of reaction Tick

with respect to A ✓)
(✓

2
(1)

(ii) Deduce the order of reaction with respect to B.

Tick (✓) one box.

Order of reaction Tick

with respect to B ✓)
(✓

2
(1)

Page 7 of 64
(b) The reaction between two different compounds, C and D, is studied at a given temperature.
The rate equation for the reaction is found to be

rate = k[C][D]2

(i) When the initial concentration of C is 4.55 × 10–2 mol dm–3 and the initial
concentration of D is 1.70 × 10–2 mol dm–3, the initial rate of reaction is
6.64 × 10–5 mol dm–3 s–1.

Calculate the value of the rate constant at this temperature and deduce its units.

Calculation ............................................................................................

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

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

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

Units of rate constant ............................................................................

...............................................................................................................
(3)

(ii) The experiment in part (i) is repeated at the same temperature but after the addition
of extra solvent so that the total volume of the mixture is doubled.

Deduce the new initial rate of reaction.

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

...............................................................................................................
(1)
(Total 6 marks)

Page 8 of 64
 This question involves the use of kinetic data to calculate the order of a reaction and also a value
6 for a rate constant.

(a) The data in this table were obtained in a series of experiments on the rate of the reaction
between compounds E and F at a constant temperature.

Initial concentration Initial concentration Initial rate of reaction

Experiment −3 −3
of E / mol dm of F / mol dm / mol dm−3 s−1

1 0.15 0.24 0.42 × 10−3

2 0.45 0.24 3.78 × 10−3

3 0.90 0.12 7.56 × 10−3

(i) Deduce the order of reaction with respect to E.

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

(Space for working) ...............................................................................

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

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

...............................................................................................................
(1)

(ii) Deduce the order of reaction with respect to F.

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

(Space for working) ...............................................................................

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

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

...............................................................................................................
(1)

Page 9 of 64
(b) The data in the following table were obtained in two experiments on the rate of the reaction
between compounds G and H at a constant temperature.

Initial concentration Initial concentration Initial rate of reaction

Experiment −3 −3
of G / mol dm of H / mol dm / mol dm−3 s−1

4 3.8 × 10−2 2.6 × 10−2 8.6 × 10−4

5 6.3 × 10−2 7.5 × 10−2 To be calculated

The rate equation for this reaction is

rate = k[G]2[H]

(i) Use the data from Experiment 4 to calculate a value for the rate constant k at this
temperature. Deduce the units of k.

Calculation ............................................................................................

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

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

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

Units ......................................................................................................

...............................................................................................................
(3)

(ii) Calculate a value for the initial rate of reaction in Experiment 5.

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

...............................................................................................................
(1)
(Total 6 marks)

Page 10 of 64
 (a) The data in the following table were obtained in two experiments about the rate of the
7 reaction between substances B and C at a constant temperature.

Initial concentration Initial concentration

Experiment −3 Initial rate / mol dm−3 s−1
of B / mol dm of C / mol dm−3

1 4.2 × 10−2 2.6 × 10−2 8.4 × 10−5

2 6.3 × 10−2 7.8 × 10−2 To be calculated

The rate equation for this reaction is known to be

rate = k[B]2[C]

(i) Use the data from Experiment 1 to calculate a value for the rate constant k at this
temperature and deduce its units.

Calculation ............................................................................................

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

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

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

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

Units ......................................................................................................

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

(Extra space) ........................................................................................

...............................................................................................................
(3)

(ii) Calculate a value for the initial rate in Experiment 2.

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

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

...............................................................................................................
(1)

Page 11 of 64
(b) The data in the following table were obtained in a series of experiments about the rate of
the reaction between substances D and E at a constant temperature.

Initial concentration Initial concentration

Experiment −3 Initial rate /mol dm−3 s−1
of D / mol dm of E / mol dm−3

3 0.13 0.23 0.26 × 10−3

4 0.39 0.23 2.34 × 10−3

5 0.78 0.46 9.36 × 10−3

(i) Deduce the order of reaction with respect to D.

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

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

...............................................................................................................
(1)

(ii) Deduce the order of reaction with respect to E.

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

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

...............................................................................................................
(1)

(c) The compound (CH3)3CBr reacts with aqueous sodium hydroxide as shown in the
folfollowing equation.

(CH3)3CBr + OH− (CH3)3COH + Br−

This reaction was found to be first order with respect to (CH3)3CBr but zero order with
respect to hydroxide ions.

The following two-step process was suggested.

Step 1 (CH3)3CBr (CH3)3C+ + Br−

Step 2 (CH3)3C+ + OH− (CH3)3COH

(i) Deduce the rate-determining step in this two-step process.

...............................................................................................................
(1)

Page 12 of 64
 (ii) Outline a mechanism for this step using a curly arrow.

(1)
(Total 8 marks)

Gases P and Q react as shown in the following equation.

8
2P(g) + 2Q(g) R(g) + S(g)

The initial rate of the reaction was measured in a series of experiments at a constant
temperature. The following rate equation was determined.

rate = k[P]2[Q]

(a) Complete the table of data for the reaction between P and Q.

Experiment Initial [P] / mol dm–3 Initial [Q] / mol Initial rate / mol dm–3 s–1
dm–3

1 2.5 × 10–2 1.8 × 10–2 5.0 × 10–5

2 7.5 × 10–2 1.8 × 10–2

3 5.0 × 10–2 5.0 × 10–5

4 5.4 × 10–2 4.5 × 10–4

(Space for working) .......................................................................................

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

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

........................................................................................................................
(3)

Page 13 of 64
 (b) Use the data from Experiment 1 to calculate a value for the rate constant (k) at this
temperature. Deduce the units of k.

Calculation .....................................................................................................

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

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

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

Units ...............................................................................................................

........................................................................................................................
(3)
(Total 6 marks)

The initial rate of the reaction between two gases P and Q was measured in a series of
9 experiments at a constant temperature. The following rate equation was determined.

rate = k[P]2[Q]

(a) Complete the table of data below for the reaction between P and Q.

Experiment Initial [P] /mol dm–3 Initial [Q] /mol dm–3 Initial rate /mol dm–3 s–1

1 0.20 0.30 1.8 = 10–3

2 0.40 0.60

3 0.60 5.4 = 10–3

4 0.90 12.2 = 10–3

(Space for working) .......................................................................................

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

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

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

........................................................................................................................
(3)

Page 14 of 64
(b) Use the data from Experiment 1 to calculate a value for the rate constant k and deduce its
units.

Calculation .....................................................................................................

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

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

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

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

Units ...............................................................................................................

........................................................................................................................
(3)

(c) Consider the graphs E, F, G and H below.

Write in the box below the letter of the graph that shows how the rate constant k varies with
temperature.

(1)
(Total 7 marks)

Page 15 of 64
 (a) In the presence of the catalyst rhodium, the reaction between NO and H2 occurs according
10 to the following equation.

2NO(g) + 2H2(g) N2(g) + 2H2O(g)

The kinetics of the reaction were investigated and the rate equation was found to be

rate = k[NO]2[H2]

The initial rate of reaction was 6.2 × 10–6 mol dm–3 s–1 when the initial concentration of NO
was 2.9 × 10–2 mol dm–3 and the initial concentration of H2 was 2.3× 10–2 mol dm–3.

(i) Calculate the value of the rate constant under these conditions and give its units.

Calculation ..........................................................................................

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

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

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

Units ....................................................................................................

.............................................................................................................
(3)

(ii) Calculate the initial rate of reaction if the experiment is repeated under the same
conditions but with the concentrations of NO and of H2 both doubled from their
original values.

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

.............................................................................................................
(1)

Page 16 of 64
 (b) Using the rate equation and the overall equation, the following three-step mechanism for
the reaction was suggested. X and Y are intermediate species.

Step 1 NO + NO X

Step 2 X + H2 Y

Step 3 Y + H2 N2 + 2H2O

Suggest which one of the three steps is the rate-determining step.

Explain your answer.

Rate-determining step..................................................................................

Explanation ..................................................................................................

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

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

(Extra space) ...............................................................................................

......................................................................................................................
(2)
(Total 6 marks)

The rate of hydrolysis of an ester X (HCOOCH2CH2CH3) was studied in alkaline conditions at a

11 given temperature. The rate was found to be first order with respect to the ester and first order
with respect to hydroxide ions.

(a) (i) Name ester X.

.............................................................................................................
(1)

(ii) Using X to represent the ester, write a rate equation for this hydrolysis reaction.

.............................................................................................................
(1)

Page 17 of 64
(iii) When the initial concentration of X was 0.024 mol dm–3 and the initial concentration
of hydroxide ions was 0.035 mol dm–3, the initial rate of the reaction was
8.5 × 10–5 mol dm–3 s–1.
Calculate a value for the rate constant at this temperature and give its units.

Calculation ..........................................................................................

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

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

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

Units ....................................................................................................

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(3)

(iv) In a second experiment at the same temperature, water was added to the original
reaction mixture so that the total volume was doubled.
Calculate the initial rate of reaction in this second experiment.

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

.............................................................................................................
(1)

(v) In a third experiment at the same temperature, the concentration of X was half that
used in the experiment in part (a) (iii) and the concentration of hydroxide ions was
three times the original value.
Calculate the initial rate of reaction in this third experiment.

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

.............................................................................................................
(1)

(vi) State the effect, if any, on the value of the rate constant k when the temperature is
lowered but all other conditions are kept constant. Explain your answer.

Effect …...............................................................................................

Explanation .........................................................................................
(2)

Page 18 of 64
 (b) Compound A reacts with compound B as shown by the overall equation

A + 3B → AB3

The rate equation for the reaction is

rate = k[A][B]2

A suggested mechanism for the reaction is

Step 1 A + B → AB

Step 2 AB + B → AB2

Step 3 AB2 + B → AB3

Deduce which one of the three steps is the rate-determining step.

Explain your answer.

Rate-determining step .................................................................................

Explanation ..................................................................................................

......................................................................................................................
(2)
(Total 11 marks)

A reaction mechanism is a series of steps by which an overall reaction may proceed.

12 The reactions occurring in these steps may be deduced from a study of reaction rates.
Experimental evidence about initial rates leads to a rate equation. A mechanism is then proposed
which agrees with this rate equation.
Ethanal dimerises in dilute alkaline solution to form compound X as shown in the following
equation.

2CH3CHO → CH3CH(OH)CH2CHO
X

A chemist studied the kinetics of the reaction at 298 K and then proposed the following rate
equation.

Rate = k [CH3CHO][OH–]

(a) Give the IUPAC name of compound X.

......................................................................................................................
(1)

Page 19 of 64
(b) The initial rate of the reaction at 298K was found to be 2.2 × 10–3 mol dm–3 s–1 when the
initial concentration of ethanal was 0.10 mol dm–3 and the initial concentration of sodium
hydroxide was 0.020 mol dm–3.
Calculate a value for the rate constant at this temperature and give its units.

Calculation ...................................................................................................

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

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

Units .............................................................................................................
(3)

(c) The sample of X produced consists of a racemic mixture (racemate). Explain how this
racemic mixture is formed.

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

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

......................................................................................................................
(2)

(d) A three-step mechanism has been proposed for this reaction according to the following
equations.

Step
1

Step
2

Step
3

(i) Using the rate equation, predict which of the three steps is the rate-determining step.
Explain your answer.

Rate-determining step ........................................................................

Explanation .........................................................................................

.............................................................................................................
(2)

Page 20 of 64
 (ii) Deduce the role of ethanal in Step 1.

.............................................................................................................
(1)

(iii) Use your knowledge of reaction mechanisms to deduce the type of reaction
occurring in Step 2.

.............................................................................................................
(1)

(iv) In the space below draw out the mechanism of Step 2 showing the relevant curly
arrows.

(2)

(e) In a similar three-step mechanism, one molecule of X reacts further with one molecule of
ethanal. The product is a trimer containing six carbon atoms.

Deduce the structure of this trimer.

(1)
(Total 13 marks)

Page 21 of 64
 Hydrogen peroxide is a powerful oxidising agent. Acidified hydrogen peroxide reacts with iodide
13 ions to form iodine according to the following equation.

H2O2(aq) + 2H+(aq) + 2I−(aq) → I2(aq) + 2H2O(l)

The initial rate of this reaction is investigated by measuring the time taken to produce sufficient
iodine to give a blue colour with starch solution.

A series of experiments was carried out, in which the concentration of iodide ions was varied,
while keeping the concentrations of all of the other reagents the same. In each experiment the
time taken (t) for the reaction mixture to turn blue was recorded.

The initial rate of the reaction can be represented as ( ), and the initial concentration of iodide
ions can be represented by the volume of potassium iodide solution used.

A graph of log10 ( ) on the y-axis against log10 (volume of KI(aq)) is a straight line. The gradient
of this straight line is equal to the order of the reaction with respect to iodide ions.

The results obtained are given in the table below. The time taken for each mixture to turn blue
was recorded on a stopclock graduated in seconds.

Volume of log10 (volume of

Expt. Time / s
KI(aq) / cm3 KI(aq)) log10 ( )

1 5 0.70 71 −1.85

2 8 0.90 46 −1.66

3 10 1.00 37 −1.57

4 15 1.18 25 −1.40

5 20 1.30 19 −1.28

6 25 1.40 14 −1.15

Page 22 of 64
(a) Use the results given in the table to plot a graph of log10 ( ) on the y-axis against log10
(volume of KI(aq)).

Draw a straight line of best fit on the graph, ignoring any anomalous points.

(5)

Page 23 of 64
 (b) Determine the gradient of the line you have drawn. Give your answer to two decimal
places. Show your working.

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

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

........................................................................................................................
(3)

(c) Deduce the order of reaction with respect to iodide ions.

........................................................................................................................
(1)

(d) A student carried out the experiment using a flask on the laboratory bench. The
student recorded the time taken for the reaction mixture to turn blue. State one way
this method could be improved, other than by repeating the experiment or by
improving the precision of time or volume measurements. Explain why the accuracy
of the experiment would be improved.

Improvement .................................................................................................

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

Explanation ....................................................................................................

........................................................................................................................
(2)
(Total 11 marks)

Propanone and iodine react in acidic conditions according to the following equation.
14
CH3COCH3 + I2 → ICH2COCH3 + HI

A student studied the kinetics of this reaction using hydrochloric acid and a solution containing
propanone and iodine. From the results the following rate equation was deduced.

rate = k[CH3COCH3][H+]

(a) Give the overall order for this reaction.

......................................................................................................................
(1)

Page 24 of 64
(b) When the initial concentrations of the reactants were as shown in the table below, the initial
rate of reaction was found to be 1.24 × 10–4 mol dm–3 s–1.

initial concentration / mol dm–3

CH3COCH3 4.40

I2 5.00 × 10–3

H+ 0.820

Use these data to calculate a value for the rate constant, k, for the reaction and give its
units.

Calculation ...................................................................................................

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

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

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

Units .............................................................................................................
(3)

(c) Deduce how the initial rate of reaction changes when the concentration of iodine is doubled
but the concentrations of propanone and of hydrochloric acid are unchanged.

......................................................................................................................
(1)

Page 25 of 64
(d) The following mechanism for the overall reaction has been proposed.

Use the rate equation to suggest which of the four steps could be the rate-determining
step. Explain your answer.

Rate-determining step .................................................................................

Explanation ..................................................................................................

......................................................................................................................
(2)

(e) Use your understanding of reaction mechanisms to predict a mechanism for Step 2 by
adding one or more curly arrows as necessary to the structure of the carbocation below.

(1)
(Total 8 marks)

Page 26 of 64
 Kinetic studies enable chemists to suggest mechanisms for reactions.
15
(a) The following data were obtained in a series of experiments on the rate of the reaction
between compounds A and B at a constant temperature.

Experiment Initial concentration Initial concentration Initial rate/

of A/mol dm–3 of B/mol dm–3 mol dm–3 s–1

1 0.12 0.15 0.32 × 10–3

2 0.36 0.15 2.88 × 10–3

3 0.72 0.30 11.52 × 10–3

(i) Deduce the order of reaction with respect to A.

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

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

(ii) Deduce the order of reaction with respect to B.

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

.............................................................................................................
(2)

Page 27 of 64
(b) The following data were obtained in a series of experiments on the rate of the reaction
between NO and O2 at a constant temperature.

Experiment Initial concentration of Initial concentration of Initial rate/

–3 –3
NO/mol dm O2/mol dm mol dm–3 s–1

4 5.0 × 10–2 2.0 × 10–2 6.5 × 10–4

6.5 × 10–2 3.4 × 10–2 To be

5
calculated

The rate equation for this reaction is

rate = k[NO]2[O2]

(i) Use the data from Experiment 4 to calculate a value for the rate constant, k, at this
temperature, and state its units.

Value of k ............................................................................................

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

Units of k .............................................................................................

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

(ii) Calculate a value for the initial rate in Experiment 5.

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

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

(iii) Using the rate equation, a scientist suggested a mechanism for the reaction which
consisted of the two steps shown below.

Step 1 NO + NO → N2O2

Step 2 N2O2 + O2 → 2NO2

Which did the scientist suggest was the rate–determining step?

.............................................................................................................
(5)
(Total 7 marks)

Page 28 of 64
 The hydrolysis of methyl propanoate was studied in acidic conditions at 25°C and the rate
16 equation was found to be

rate = k[CH3CH2COOCH3][H+]

(a) Use the data below to calculate the value of the rate constant, k, at this temperature.
Deduce its units.

Initial rate of reaction / Initial concentration of methyl Initial concentration of

mol dm–3 s–1 propanoate / mol dm–3 hydrochloric acid / mol dm–3

1.15 × 10–4 0.150 0.555

Rate constant ...............................................................................................

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

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

Units .............................................................................................................

......................................................................................................................
(3)

(b) The reaction in part (a) was repeated at the same temperature, but water was added so
that the volume of the reaction mixture was doubled. Calculate the initial rate of reaction
under these conditions.

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

......................................................................................................................
(1)

Page 29 of 64
 (c) A third experiment was carried out at a different temperature. Some data from this
experiment are shown in the table below.

Initial rate of reaction / Value of rate constant at Initial methyl propanoate /

mol dm s –3 –1 this different temperature mol dm–3

4.56 × 10–5 8.94 × 10–4 0.123

Calculate the initial pH of the reaction mixture. Give your answer to two decimal places.

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

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

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

......................................................................................................................
(3)
(Total 7 marks)

The initial rate of the reaction between the gases NO and H2 was measured in a series of
17 experiments at a constant temperature and the following rate equation was determined.

rate = k[NO]2[H2]

(a) Complete the table of data below for the reaction between NO and H2

Experiment Initial [NO] / mol dm–3 Initial [H2] / mol dm–3 Initial rate / mol dm–3 s–1

1 3.0 × 10–3 1.0 × 10–3 1.8 × 10–5

2 3.0 × 10–3 7.2 × 10–5

3 1.5 × 10–3 1.0 × 10–3

4 0.50 × 10–3 8.1 × 10–5

(3)

Page 30 of 64
 (b) Using the data from experiment 1, calculate a value for the rate constant, k, and state
its units.

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

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

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

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

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

......................................................................................................................
(3)
(Total 6 marks)

(a) Compound A, HCOOCH2CH2CH3, is an ester. Name this ester and write an equation for its
18 reaction with aqueous sodium hydroxide.

Name ……….................................................................................................

Equation .......................................................................................................
(2)

Page 31 of 64
(b) The initial rate of reaction between ester A and aqueous sodium hydroxide was measured
in a series of experiments at a constant temperature. The data obtained are shown below.

Experiment Initial concentration Initial concentration Initial rate

–3 –3
of NaOH / mol dm of A / mol dm / mol dm–3 s–1

1 0.040 0.030 4.0 × 10–4

2 0.040 0.045 6.0 × 10–4

3 0.060 0.045 9.0 × 10–4

4 0.120 0.060 to be calculated

Use the data in the table to deduce the order of reaction with respect to A and the order of
reaction with respect to NaOH. Hence calculate the initial rate of reaction in Experiment 4.

Order with respect to A ................................................................................

Order with respect to NaOH .........................................................................

Initial rate in Experiment 4 ............................................................................

......................................................................................................................
(3)

(c) In a further experiment at a different temperature, the initial rate of reaction was found to be
9.0 × 10–3 mol dm–3 s–1 when the initial concentration of A was 0.020 mol dm–3 and the initial
concentration of NaOH was 2.00 mol dm–3.
Under these new conditions with the much higher concentration of sodium hydroxide, the
reaction is first order with respect to A and appears to be zero order with respect to sodium
hydroxide.

(i) Write a rate equation for the reaction under these new conditions.

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

(ii) Calculate a value for the rate constant under these new conditions and state its units.

Calculation ..........................................................................................

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

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

Units ....................................................................................................

Page 32 of 64
 (iii) Suggest why the order of reaction with respect to sodium hydroxide appears to be
zero under these new conditions.

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

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

.............................................................................................................
(6)

(d) A naturally-occurring triester, shown below, was heated under reflux with an excess of
aqueous sodium hydroxide and the mixture produced was then distilled. One of the
products distilled off and the other was left in the distillation flask.

(i) Draw the structure of the product distilled off and give its name.

Structure

Name ..................................................................................................

(ii) Give the formula of the product left in the distillation flask and give a use for it.

Formula ...............................................................................................

Use ......................................................................................................
(4)
(Total 15 marks)

Page 33 of 64
 (a) The following table shows the results of three experiments carried out at the same
19 temperature to investigate the rate of the reaction between compounds P and Q.

Experiment 1 Experiment 2 Experiment 3

Initial concentration of P/mol dm–3 0.50 0.25 0.25

Initial concentration of Q/mol dm–3 0.36 0.36 0.72

Initial rate/mol dm–3 s–1 7.6 × 10–3 1.9 × 10–3 3.8 × 10–3

Use the data in the table to deduce the order with respect to P and the order with respect
to Q.

Order with respect to P ................................................................................

Order with respect to Q ................................................................................

(2)

(b) In a reaction between R and S, the order of reaction with respect to R is one, the order
of reaction with respect to S is two and the rate constant at temperature T1 has a value of
4.2 × 10–4 mol–2 dm6 s–1.

(i) Write a rate equation for the reaction. Calculate a value for the initial rate of reaction
when the initial concentration of R is 0.16 mol dm–3 and that of S is
0.84 mol dm–3.

Rate equation ....................…..............................................................

Calculation ..........................................................................................

(ii) In a second experiment performed at a different temperature, T2, the initial

rate of reaction is 8.1 × 10–5 mol dm–3s–1 when the initial concentration of R is
0.76 mol dm–3 and that of S is 0.98 mol dm–3. Calculate the value of the rate constant
at temperature T2.

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

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

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

(iii) Deduce which of T1 and T2 is the higher temperature.

.............................................................................................................
(6)
(Total 8 marks)

Page 34 of 64
 (a) The initial rate of the reaction between compounds A and B was measured in a series of
20 experiments at a fixed temperature. The following rate equation was deduced.

rate = k[A][B]2

(i) Complete the table of data below for the reaction between A and B.

Expt Initial [A] Initial [B] Initial rate

–3 –3
/mol dm /mol dm /mol dm–3 s–1

1 4.80 × 10–2 6.60 × 10–2 10.4 × 10–3

2 4.80 × 10–2 3.30 × 10–2

3 13.2 × 10–2 5.20 × 10–3

4 1.60 × 10–2 10.4 × 10–3

(ii) Using the data for experiment 1, calculate a value for the rate constant, k, and state
its units.

Calculation ..........................................................................................

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

Units ....................................................................................................
(6)

(b) State how the value of the rate constant, k, would change, if at all, if the concentration of A
were increased in a series of experiments.

......................................................................................................................
(1)
(Total 7 marks)

Page 35 of 64
 (a) The following data were obtained in a series of experiments on the rate of the reaction
21 between compounds A and B at a constant temperature.

Experiment Initial concentration Initial concentration Initial rate/mol dm–3

–3 –3
of A/mol dm of B/mol dm s–1

1 0.12 0.15 0.32 × 10–3

2 0.36 0.15 2.88 × 10–3

3 0.72 0.30 11.52 × 10–3

(i) Deduce the order of reaction with respect to A.

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

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

(ii) Deduce the order of reaction with respect to B.

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

.............................................................................................................
(2)

Page 36 of 64
 (b) The following data were obtained in a series of experiments on the rate of the reaction
between NO and O2 at a constant temperature.

Experiment Initial concentration Initial concentration Initial rate/mol dm–3

–3 –3
of NO/mol dm of O2/mol dm s–1

4 5.0 × 10–2 2.0 × 10–2 6.5 × 10–4

5 6.5 × 10–2 3.4 × 10–2 To be calculated

The rate equation for this reaction is

rate = k[NO]2[O2]

(i) Use the data from experiment 4 to calculate a value for the rate constant, k, at this
temperature, and state its units.

Value of k ............................................................................................

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

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

Units of k .............................................................................................

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

(ii) Calculate a value for the initial rate in experiment 5.

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

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

.............................................................................................................
(4)
(Total 6 marks)

The rate of the reaction between substance A and substance B was studied in a series of
22 experiments carried out at the same temperature. In each experiment the initial rate was
measured using different concentrations of A and B. These results were used to deduce the
order of reaction with respect to A and the order of reaction with respect to B.

(a) What is meant by the term order of reaction with respect to A?

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

......................................................................................................................
(1)

Page 37 of 64
 (b) When the concentrations of A and B were both doubled, the initial rate increased by a
factor of 4. Deduce the overall order of the reaction.

......................................................................................................................
(1)

(c) In another experiment, the concentration of A was increased by a factor of three and the
concentration of B was halved. This caused the initial rate to increase by a factor of nine.

(i) Deduce the order of reaction with respect to A and the order with respect to B.

Order with respect to A .......................................................................

Order with respect to B ........................................................................

(ii) Using your answers from part (c)(i), write a rate equation for the reaction and suggest
suitable units for the rate constant.

Rate equation .....................................................................................

Units for the rate constant ...................................................................

.............................................................................................................
(4)
(Total 6 marks)

This question is about the reaction between propanone and an excess of ethane-1,2-diol, the
23 equation for which is given below.

In a typical procedure, a mixture of 1.00 g of propanone, 5.00 g of ethane-1,2-diol and 0.100 g of

benzenesulphonic acid, C6H5SO3H, is heated under reflux in an inert solvent. Benzenesulphonic
acid is a strong acid.

When the concentration of benzenesulphonic acid is doubled, the rate of the reaction doubles. It
can be deduced that

A the reaction is first order overall.

B the reaction is third order overall.

C the reaction is acid-catalysed.

D units for the rate constant, k, are mol−2 dm6 s−1.

(Total 1 mark)

Page 38 of 64
 (a) The initial rate of the reaction between substances P and Q was measured in a series of
24 experiments and the following rate equation was deduced.

rate = k[P]2[Q]

(i) Complete the table of data below for the reaction between P and Q.

Experiment Initial [P] / mol dm–3 Initial [Q] / mol dm–3 Initial rate / mol dm–3 s–1

1 0.20 0.30 4.8 × 10–3

2 0.10 0.10

3 0.40 9.6 × 10–3

4 0.60 19.2 × 10–3

(ii) Using the data from experiment 1, calculate a value for the rate constant, k, and
deduce its units.

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

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

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

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

.............................................................................................................
(6)

(b) What change in the reaction conditions would cause the value of the rate constant to
change?

......................................................................................................................
(1)
(Total 7 marks)

Page 39 of 64
 Iodine and propanone react in acid solution according to the equation
25
I2 + CH3COCH3 → CH3COCH2I + HI

The rate equation for the reaction is found to be

rate = k [CH3COCH3][H+]

(a) Deduce the order of reaction with respect to iodine and the overall order of reaction.

Order with respect to iodine .........................................................................

Overall order ................................................................................................

(2)

(b) At the start of the experiment, the rate of reaction was found to be 2.00 × 10–5 mol dm–3 s–1
when the concentrations of the reactants were as shown below.

Reactant Concentration / mol dm–3

CH3COCH3 1.50

I2 2.00 × 10–2

H+ 3.00 × 10–2

Use these data to calculate a value for the rate constant and deduce its units.

Rate constant ...............................................................................................

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

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

Units .............................................................................................................
(3)

(c) How can you tell that H+ acts as a catalyst in this reaction?

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

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

......................................................................................................................
(2)

Page 40 of 64
 (d) Calculate the initial rate of reaction if the experiment were to be repeated at the same
temperature and with the same concentrations of iodine and propanone as in part (b) but at
a pH of 1.25

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

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

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

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

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

......................................................................................................................
(3)
(Total 10 marks)

(a) The following data were obtained in a series of experiments on the rate of the reaction
26 between compounds A and B at a constant temperature.

Experiment Initial concentration Initial concentration Initial

–3 –3
of A/mol dm of B/mol dm rate/mol dm–3 s–1

1 0.15 0.24 0.45 × 10–5

2 0.30 0.24 0.90 × 10–5

3 0.60 0.48 7.20 × 10–5

(i) Show how the data in the table can be used to deduce that the reaction is first-order
with respect to A.

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

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

(ii) Deduce the order with respect to B.

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

.............................................................................................................
(2)

Page 41 of 64
(b) The following data were obtained in a second series of experiments on the rate of the
reaction between compounds C and D at a constant temperature.

Experiment Initial concentration Initial concentration Initial

–3 –3
of A/mol dm of B/mol dm rate/mol dm–3 s–1

4 0.75 1.50 9.30 × 10–5

5 0.20 0.10 To be calculated

The rate equation for this reaction is

rate = k[C]2[D]

(i) Use the data from Experiment 4 to calculate a value for the rate constant, k, at this
temperature. State the units of k.

Value for k ...........................................................................................

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

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

Units of k .............................................................................................

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

(ii) Calculate the value of the initial rate in Experiment 5.

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

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

......................................................................................................................
(4)
(Total 6 marks)

Page 42 of 64
 The equation and rate law for the reaction of substance P with substance Q are given below.
27
2P + Q → R + S
rate = k[P]2[H+]

Under which one of the following conditions, all at the same temperature, would the rate of
reaction be slowest?

[P] / mol dm−3 pH

A 0.1 0

B 1 2

C 3 3

D 10 4
(Total 1 mark)

Rate = k [A]2 [B]

28
Correct units for the rate constant in the rate equation above are

A mol dm−3 s−1

B mol−1 dm−3 s−1

C mol2 dm−6 s−1

D mol−2 dm6 s−1

(Total 1 mark)

Page 43 of 64
Mark schemes

1
(a) k = rate / [A]2 or
1

= 1.87 or 1.9
Answer scores 2
1.90 scores first mark only (incorrect rounding)
1

mol−1dm3s−1
Any order and independent of calculation
1

(b) Expt 2 rate = 1.167 × 10−4 − 1.2 × 10−4 (mol dm−3 s−1)
If answers in table are not those given here, check their value of k
in part (a) or use of alternative k.
1

Expt 3 [A] = 9.7 × 10−3 − 9.8(1) × 10−3 (mol dm−3)

If their k is incorrect in part (a) mark this part consequentially e.g. if
k = 7.9 × 10−3 due to lack of squaring in (a)

Using alternative value for k

expt 2 4.9 × 10−7

Expt 2 rate = 1.4(4) × 10−4 (mol dm−3 s−1)

expt 3 1.5 ×10−1

Expt 3 [A] = 8.85 × 10−3 (mol dm−3)

(expt 2 6.24 × 10−5 × their k)
(expt 3 0.0134 / √k)
1

(c) Slow step or rds involves only A

OR
B does not appear in the slow step or the rds
OR
B only appears after the slow step or the rds
Not B has no effect on the rate or B is not in the rate equation
Allow “it” for B
1
[6]

(a) Consider experiments 1 and 2: [B constant]

2
[A] increases × 3: rate increases by 32 therefore 2nd order with respect to A
1

Page 44 of 64
 Consider experiments 2 and 3:

[A] increases × 2: rate should increase × 22 but only increases × 2

Therefore, halving [B] halves rate and so 1st order with respect to B
1

Rate equation: rate = k[A]2[B]

1

(b) rate = k [C]2[D] therefore k = rate / [C]2[D]

1

Allow consequential marking on incorrect transcription

1

mol–2 dm+6 s–1

Any order
1

(c) rate = 57.0 × (3.6 × 10–2)2 × 5.4 × 10–2 = 3.99 × 10–3 (mol dm–3 s–1)

OR

Their k × (3.6 × 10–2)2 × 5.4 × 10–2

1

(d) Reaction occurs when molecules have E>Ea

1

Doubling T by 10 °C causes many more molecules to have this E

1

Whereas doubling [E] only doubles the number with this E

1

(e) Ea = RT(lnA – lnk) / 1000

Mark is for rearrangement of equation and factor of 1000 used
correctly to convert J into kJ
1

Ea = 8.31 × 300 (23.97 – (–5.03)) / 1000 = 72.3 (kJ mol–1)

1
[12]

Page 45 of 64
 (a) Gradient drawn on graph
3

Line must touch the curve at 0.012 but must not cross the curve.
1

(b) Stage 1: Rate of reaction when concentration = 0.0120 mol dm–3

From the tangent

Change in [butadiene] = –0.0160 – 0 and change in time = 7800 – 0

Extended response
1

Gradient = –(0.0160 – 0) / (7800 – 0) = –2.05 × 10–6

Rate = 2.05 × 10–6 (mol dm–3 s–1)

1

Stage 2: Comparison of rates and concentrations

Initial rate / rate at 0.0120 = (4.57 × 10–6) / (2.05 × 10–6) = 2.23

Marking points in stage 2 can be in either order
1

Inital concentration / concentration at point where tangent drawn = 0.018 / 0.012 =

1.5
1

Page 46 of 64
 Stage 3: Deduction of order

If order is 2, rate should increase by factor of (1.5)2 = 2.25 this is approximately equal
to 2.23 therefore order is 2nd with respect to butadiene
1
[6]

B
4 [1]

(a) (i) 2
5 1

(ii) 0
1

(b) (i) K=

Correct answer for k with or without working scores 2.

First mark is for insertion of numbers into a correctly rearranged
rate equ , k = etc.
1

= 5.05 (range allowed 5.03−5.07)

AE (−1) for copying numbers wrongly or swapping two numbers.
1

mol−2 dm+6 s−1

Mark units separately, ie only these units but can be in any order.
1

(ii) 8.3 × 10−6 (mol dm−3 s−1)

Allow 0.83 × 10−5.
Ignore units.

OR if not 8.3 × 10−6, look at their k in part(i) and if not 5.05

Allow ecf for their (incorrect) k × (1.64 × 10−6)

1
[6]

(a) (i) 2 or two or second or [E]2

6
1

(ii) 1 or one or first or [F]1 or [F]

1

Page 47 of 64
 (b) (i) k=
mark is for insertion of numbers into a correctly rearranged rate equ
, k = etc.
AE (−1) for copying numbers wrongly or swapping two numbers.
1

= 22.9 (Allow 22.9 − 24 after correct rounding)

1

mol−2dm+6 s&8722;1
Any order.
1

(ii) 6.8(2) × 10−3 (mol dm&8722;3s−1)

OR if their k is wrong, award the mark consequentially
a quick check can be achieved by using
their answer = 2.9768 × 10−4 Allow 2.9 − 3.1 × 10−4 for the mark
their k
Allow 6.8 × 10−3 to 6.9 × 10−3
Ignore units.
1
[6]

7
(a) (i)

Mark is for insertion of numbers into a correctly rearranged rate equ

, k = etc.
If upside down, score only units mark from their k
AE (−1) for copying numbers wrongly or swapping two numbers
1

= 1.8(3)
1

mol−2 dm+6 s−1

Any order
If k calculation wrong, allow units consequential to their
k = expression
1

(ii) 5.67 × 10−4 (mol dm−3 s−1) OR their k × 3.1 × 10−4

Allow 5.57 × 10−4 to 5.7 × 10−4
1

(b) (i) 2 or second or [D]2

1

Page 48 of 64
 (ii) 0 or zero or [E]0
1

(c) (i) Step 1 or equation as shown

Penalise Step 2 but mark on
1

(ii)

Ignore correct partial charges, penalise full / incorrect partial charges

If Step 2 given above, can score the mark here for

allow: OH− (must show lp)

If SN2 mechanism shown then no mark (penalise involvement of
:OH− in step 1)
Ignore anything after correct step 1
1
[8]

(a) Exp 2 4.5 ×10–4

8
Min 2sf
1

Exp 3 4.5 ×10–3

If three wrong answers, check their value of k in (b).
1

Exp 4 0.043 OR 4.3 ×10–2 OR 0.044 OR 4.4 ×10–2

They can score all 3 if they have used their (incorrect) value of k.
see below.
Exp 2 rate = k × (1.0125 × 10–4)
Exp 3 [Q] = 0.02/k
Exp 4 [P] = 0.0913/√k
1

(b)

Mark is for insertion of numbers into a correctly rearranged rate equ

, k = etc
If upside down, score only units mark from their k
AE (-1) for copying numbers wrongly or swapping two numbers
1

= 4.4(4) (allow 40/9)

1
Page 49 of 64
 mol–2dm+6s–1
Any order
If k calculation wrong, allow units conseq to their k expression
1
[6]

(a) Exp 2 14.(4) ×10–3 OR 1.4(4) ×10–2 or 0.014

9
Allow 2sf
1

Exp 3 0.1(0)
1

Exp 4 0.3(0)
If three wrong answers, check their value of k in 1(b).
They can score all 3 if they have used their (incorrect) value of k.
see below.
Exp 2 rate = 0.096 × k
Exp 3 [Q] = 0.015/k
Exp 4 [P] = 0.116/√k
1

(b)

mark is for insertion of numbers into a correctly rearranged rate equ

, k = etc
1

= 0.15 (min 2sfs) (allow )

if upside down, score only units mark

AE (–1) for copying numbers wrongly or swapping two numbers
1

mol–2 dm+6 s–1

Any order
If k calculation wrong, allow units conseq to their k
1

(c) G
1
[7]

Page 50 of 64
10 (a) (i)

mark is for insertion of numbers into a correctly

rearranged rate equ, k = etc
AE (-1) for copying numbers wrongly or swapping two numbers
1

= 0.32 (min 2sfs)

1

mol–2 dm6 s–1 Units must be conseq to their k

Any order
If k calculation wrong, allow units conseq to their k
1

(ii) 4.95 × 10–5 to 4.97 × 10–5 or 5.0 × 10–5 (min 2 sfs)

(ignore units)
rate = their k × 1.547 × 10–4
1

(b) Step 2
If wrong no further mark
1

One H2 (and two NO) (appear in rate equation)

or species (in step 2) in ratio/proportion as in the rate equation
1
[6]

(a) (i) propyl methanoate

11
must be correct spelling
1

(ii) rate = k[X][OH–]

allow HCOOCH2CH2CH3 (or close) for X
allow ( ) but penalise missing minus
1

Page 51 of 64
(iii) k=

In (a)(iii), if wrong orders allow

mark is for insertion of numbers in correct expression for k
If expression for k is upside down, only score units conseq to their
expression
1

= 0.10(12) 2sf minimum

1 for conseq answer
1

mol–1 dm3 s–1

1 for conseq units
any order
1

(iv) 2.1(3) × 10–5

or 2.1(2) × 10–5 ignore units
allow 2 sf
NB If wrong check the orders in part (a)(iii) and allow (a)(iv) if
conseq to wrong k
See * below
1

(v) 1.3 ×10–4 (1.28 ×10–4)

allow (1.26 × 10–4) to (1.3 × 10–4) ignore units
allow 2 sf
NB If wrong check the orders in part (a)(iii) and allow (a)(iv) if
conseq to wrong k
See ** below
1

For example, if orders given are 1st in X and second in OH–

[The mark in a(ii) and also first mark in a(iii) have already been lost]

So allow mark * in (iv) for rate = their k × (0.012)(0.0175)2 = their k ×(3.7 × 10–6)
(allow answer to 2sf)
** in (v) for rate = their k × (0.012)(0.105)2 = their k ×(1.32 × 10–4)
(allow answer to 2sf)

The numbers will of course vary for different orders.

Page 52 of 64
 (vi) Lowered
if wrong, no further mark
1

fewer particles/collisions have energy > Ea

OR
fewer have sufficient (activation) energy (to react)
not just fewer successful collisions
1

(b) Step 2
1

(this step with previous) involves one mol/molecule/particle

A and two Bs

or 1:2 ratio or same amounts (of reactants) as in rate equation

if wrong, no further mark
1
[11]

(a) 3-hydroxybutanal
12
ignore number 1 i.e. allow 3-hydroxybutan-1-al
not hydroxyl
1

(b)

= 1.1
1

mol–1 dm3 s–1

1

(c) planar or flat C=O or molecule

allow planar molecule
1

equal probability of attack from above or below

must be equal; not attack of OH–
1

(d) (i) Step 1 if wrong – no mark for explanation.

1

involves ethanal and OH– or species/ “molecules”

in rate equation
1
Page 53 of 64
 (ii) (B-L) acid or proton donor
not Lewis acid
1

(iii) nucleophilic addition

QOL
1

(iv)

not allow M2 before M1, but allow M1 attack on C+ after

non-scoring carbonyl arrow
ignore error in product
2

(e)

1
[13]

(a) Log (1 / time) on the y-axis + log (vol) on x-axis

13
If axes unlabelled use data to decide that log (1 / time) is on the
y-axis
1

Sensible scales
Lose this mark if the plotted points do not cover at least half of the
paper
Lose this mark if the graph plot goes off the squared paper
Lose this mark if plots a non-linear / broken scale
Lose this mark if uses an ascending y-axis of negative numbers
1

Plots points correctly ± one square

1

Line through the points is smooth

Lose this mark if the candidate’s line is doubled
1

Page 54 of 64
 Line through the points is best fit – ignores last point
Must recognise that point at 25 cm3 is an anomaly
If wrong graph, mark consequentially on anomaly if correctly
plotted.
A kinked graph loses smooth and best fit marks
1

(b) Uses appropriate x and y readings

Allow taken from table or taken or drawn on graph

Must show triangle on graph or such as

1

Correctly calculates gradient 0.95 ± 0.02

Ignore positive or negative sign
Correct answer only with no working scores this mark
1

Answer given to 2 decimal places

1

(c) First order or order is 1

Allow consequential answer from candidate’s results
1

(d) Thermostat the mixture / constant temperature / use a water bath

or Colorimeter / uv-visible spectrometer / light sensor to monitor colour change
1

Reaction / rate affected by temperature change

or Eliminates human error in timing / more accurate time of colour change
1
[11]

(a) 2 or two or second

14 1

(b) k=

mark is for insertion of numbers into a correctly rearranged rate

equ, k = etc
if upside down, (or use of I2 data) score only units mark
1

= 3.44 × 10–5 (min 3sfs)

1

mol–1 dm3 s–1

any order
1

Page 55 of 64
 (c) no change or no effect or stays the same or 1.24 × 10–4
1

(d) 1 or 2 or 1 and 2
if wrong no further mark but mark on from no answer
1

rate equ doesn’t involve I 2 or only step which includes 2

species in rate equ
1

(e)

any second arrow loses the mark

1
[8]

(a) (i) 2
15 1

(ii) 0
1

(b) (i) rate/[NO2]2[O2]

1

13
1

mol dm–3
1

(ii) 1.9 × 10–3

1

(iii) Step 2
1
[7]

Page 56 of 64
 (a) k = rate/[CH3CH2COOCH3][H+]
16
1

or

= 1.38 × 10–3 to 1.4 × 10–3

1

mol–1 dm3 s–1

1

(b) ans = rate constant × (½ × 0.150) × (½ × 0.555)

ignore units

= rate constant × 0.0208

2.88 × 10–5 (1.38 × 10–3 gives 2.87 × 10–5)

Allow 2.87 – 2.91 × 10–5 (1.4 × 10–3 gives 2.91 × 10–5)
1

(c) [H+] = rate/ k[CH3COOCH2CH3]

1

= 0.415 (0.4146)
1

pH = 0.38 mark independently

[H+] = 0.41 gives pH = 0.39
1
[7]

(a) exp2 4.0 × 10–3

17
1

exp3 0.45 × 10–5

1

exp4 9.0 × 10–3

1

Page 57 of 64
 (b)

2000
1

mol–2 dm6 s–1

1
[6]

(a) propyl methanoate;

18
HCOOC3H7 + OH– → HCOO– + C3H7OH
1

OR

HCOOC3H7 + NaOH → HCOONa + C3H7OH;

1

(b) order wrt A = 1;

1

order wrt NaOH = 1;

1

Initial rate in Exp 4 = 2.4 × 10–3;

1

(c) (i) r(ate) = k[A]

OR

r(ate) = k[A][NaOH]0;
(penalise missing [ ] but mark on)
(penalise missing [ ] once per paper)
(if wrong order, allow only units mark conseq on their rate eqs)
(penalise ka or kw etc)
1

(ii) ;

= 0.45;
1

s–1;
l

Page 58 of 64
 (iii) (large) excess of OH– or [OH–] is large/high;
1

[OH–] is (effectively) constant

OR

[A] is the limiting factor (Q of L mark)

1

(d) (i)

propan(e)-1,2,3-triol

OR

1,2,3-propan(e)triol

OR

Glycerol;
1

(ii) CH3(CH2)16COONa or C17H35COONa or C18H35O2Na;

(ignore 3 in front of formula but not if indicating trimer)
1

(not just anion and penalise Na shown as covalently bonded) soap -

allow with detergent but not detergent alone;
1
[15]

(a) order with respect to P is 2

19 1

order with respect to Q is 1

1

Page 59 of 64
 (b) (i) rate = k[R][S]2
(if wrong expression, no further marks)
1

rate = (4.2 × 10–4) × 0.16 × 0.842

1

= 4.7 × 10–5 (mol dm–3 s–1)

ignore units even if wrong
1

(ii)

= 1.1 × 10–4
1

(iii) T1
*If calculated value for k > 4.2 × 10–4, then answer to (iii) is T2
1
[8]

(a) (i) Experiment 2 2.60 × 10–3

20
1

Experiment 3 0.60 × 10–2

1

Experiment 4 11.4 × 10–2

1

(ii) k=

= 49.7
(Allow 49.8 and 50)
1

mol–2 dm6 s–1

1

Page 60 of 64
 (b) No change
1
[7]

(a) (i) 2 (1)

21
(ii) 0 (1) 2

(b) (i) Value of k: k = = = 13

Units of k: mol–2 dm6 s–1 (1)

(ii) rate = 13 (6.5 × 10–2)2 (3.4 × 10–2)

= 1.9 × 10–3 (mol dm–3 s–1) (1)
If k wrong, the mark in (ii) may be gained conseq for their
k × 1.437 × 10–4
4
[6]

(a) Power (or index or shown as x in [ ]x) of concentration term

22
(in rate equation) (1)
1

(b) 2 (1)
1

(c) (i) Order with respect to A: 2 (1)

Order with respect to B: 0 (1)

(ii) Rate equation: (rate =) k [A]2 (1)

Allow conseq on c(i)

Units for rate constant: mol–1 dm3 s–1 (1)

conseq on rate equation
4
[6]

Page 61 of 64
 Organic points

(1) Curly arrows: must show movement of a pair of electrons,

i.e. from bond to atom or from lp to atom / space
e.g.

(2) Structures

penalise sticks (i.e. ) once per paper

Penalise once per paper

allow CH3– or –CH3 or or CH3

or H3C–

C
23 [1]

(a) (i) Experiment 2: 0.4(0) × 10–3 (1)

24
Experiment 3: 0.15 (1)
Experiment 4: 0.28 (1)

(ii) k= = 0.4(0) mol–2 dm6 s–1

(1) (1) (1)

6

Page 62 of 64
 (b) (change in) temperature (1)
1
[7]

(a) Order with respect to iodine: 0 (1)

25 Overall order: 2 (1)
2

(b) Rate constant: k = = 4.4(4) × 10–4 (1)

Units: mol–1 dm3 s–1 (1)

3

(c) Appears in rate equation (1)

OR implied by mention of concentration or order

does not appear in (stoichiometric / overall) equation (1)

2

(d) pH = –log10 [H+] (1)

= 1.25
[H+] = 0.056(2) (1)

rate = (4.44 × 10–4) × (1.50) × (0.0562)

= 3.75 × 10–5 (1) (mol dm3 s–1)

(3.7 — 3.8)
Can score all 3 conseq on k from part (b)
3
[10]

(a) (i) (Experiment 1 → 2) [A] doubled, ([B] constant,)

26 rate doubled (1)
stated or shown numerically

(ii) 2 (1)
or shown as ... [B]2
2

Page 63 of 64
 (b) (i) k= = 1.1(0) × 10–4
(1) (1)

units of k: mol–2 dm6 s–1 (1)

(ii) rate = (1.10 × 10–4) × (0.20)2 × (0.10)

= 4.4(1) × 10–7 (mol dm–3 s–1)
(1) for the answer
Ignore units
Conseq on (i)
Upside down expression for k scores zero in (i) for 9073
but rate = 9073 × (0.2)2 × (0.1) = 36(.3)
conseq scores (1) in (ii)
4
[6]

C
27 [1]

D
28 [1]

Page 64 of 64