GCE A2 CHEMISTRY KINETICS

The kinetics of the hydrolysis of the halogenoalkane RCH2Cl with aqueous sodium hydroxide
(where R is an alkyl group) was studied at 50 C. The following results were obtained:

3 1

Experiment

[RCH2Cl]

[OH ]

0.050

0.10

4.0 10

0.15

0.10

1.2 10

0.10

0.20

1.6 10

(i)

Initial rate/mol dm s

Deduce the order of reaction with respect to the halogenoalkane, RCH2Cl, and with

respect to the hydroxide ion, OH , giving reasons for your answers.

(4)

(ii)

Hence write the rate equation for the reaction.

(1)

(iii)

Calculate the value of the rate constant with its units for this reaction at 50 C.
(2)

(iv)

Using your answer to part (ii), write the mechanism for this reaction.
(3)
(Total 10 marks)

In an experiment to determine the rate of the reaction between persulphate ions and iodide ions
in aqueous solution
2

S2O 8 + 2I 2SO 4 + I2
the following data were obtained:

C o n c e n tra tio n /m o l d m

In itia l ra te
/m o l d m 3 s 1

0 .1 0 0

0 .1 0 0

0 .3 6

0 .2 0 0

0 .1 0 0

0 .7 2

0 .2 0 0

0 .2 0 0

1 .4 4

S2O

(a)

2
8

(i)
Deduce the order of reaction with respect to each of the reagents and
hence write the rate equation for the reaction.
(3)

(ii)

With reference to this reaction state what is meant by the overall order of a
reaction.
(1)

Page

2.

(iii) Calculate the rate constant including units.

(2)

(iv) Explain why the rate equation cannot be written directly from the stoichiometric
equation for the reaction.
(1)

(b)

(i)
Suggest a suitable experimental technique that would enable you to
determine the rate of the reaction given opposite.
(1)

(ii)

Suggest a necessary condition that would help to ensure accurate results.

(1)

(iii)

Suggest one advantage or disadvantage of your chosen experimental method.

(1)
(Total 10 marks)

4.

(a)

(i)

Explain what is meant by the following terms.

Rate of reaction
Overall order of a reaction
(2)

(ii)

Explain why the order of reaction cannot be deduced from the stoichiometric
equation for a reaction.
(1)

(b)

Substitution reactions of halogenoalkanes, can proceed via an SN1 or SN2 mechanism.

When 1-bromobutane, CH3CH2CH2CH2Br, 2-bromobutane, CH3CH2CHBrCH3, and
2-bromo-2-methylpropane, (CH3)3CBr, are reacted separately with aqueous sodium
hydroxide solution each gives the corresponding alcohol.
(i)

Give the mechanism for the SN1 reaction between 2-bromobutane and
hydroxide ions.
(3)

(ii)

Explain why the product mixture is not optically active.

(2)

(iii) In an experiment designed to find the mechanism of the reaction between 2-bromo2-methylpropane and hydroxide ions the following data were obtained at constant
temperature.
Initial concentration of
2-bromo-2-methylpropane
3
/mol dm

Initial concentration of

3
OH / mol dm

0.10

0.10

1.2 10

0.20

0.10

2.4 10

0.30

0.20

3.6 10

Initial rate of reaction

3 1
/mol dm s

Use the data to deduce the rate equation for the reaction of 2-bromo-2methylpropane with sodium hydroxide solution.

(3)

(c)

Suggest, in outline, a method you could use to follow the progress of the reaction between
a bromoalkane and aqueous sodium hydroxide.
(3)
(Total 14 marks)

5.

Manganate(VII) ions react with ethanedioate ions in acidic solution.

2+

2MnO4 (aq) + 16H (aq) + 5C2O4 (aq) 2Mn (aq) + 8H2O(l) + 10CO2(g)
(a)

In a particular experiment 200 cm of aqueous potassium manganate(VII), KMnO4,

3

of concentration 0.0500 mol dm were mixed with 50.0 cm of ethanedioic acid,

3
3
3
HOOCCOOH, of concentration 0.500 mol dm , and 80 cm of 1.0 mol dm sulphuric
acid.
(i)

Show by calculation that the starting concentration of the manganate(VII) ions was
2
3
3.03 10 mol dm .
(1)

(ii)

The concentration of the manganate(VII) ions was determined over a period

of time.
Time / s

Concentration of manganate(VII) ions/ mol dm

3.03 10

400

2.98 10

800

2.86 10

1200

2.75 10

1600

1.90 10

2000

7.50 10

2400

2.50 10

Plot a graph of the concentration of manganate(VII) ions against time and from it
determine the initial rate of the reaction and the rate at 1600 s.
(5)

(b)

A second experiment was set up involving the same chemicals in the same concentrations
as in experiment 1 but this time some solid manganese(II) sulphate was dissolved in the
3

c o n c e n tr a tio n /m o l d m

ethanedioic acid before the potassium manganate (VII) solution was poured in. The plot
of the concentration of manganate(VII) ions against time is given below:

3 .5 1 0

3 .0 1 0

2 .5 1 0

2 .0 1 0

1 .5 1 0

1 .0 1 0

5 .0 1 0

(i)

400

800

1200 1600 2000 2400

tim e / s

Determine the order of the reaction with respect to manganate(VII) ions by

considering the time taken for the concentration to fall by half, using the
concentrations at 0, 800 and 1600 s.
(3)

(ii)

Compare this graph with the one you plotted in (a) (ii) and give two pieces of
evidence that manganese(II) sulphate is a catalyst for this reaction.
(2)

(c)

(i)
Carrying out a flame test on potassium manganate(VII) gives a lilac
flame.
What does this show?
(1)

(ii)

Describe how aqueous sodium hydroxide solution could be used to show that
manganese(II) ions had been produced in the reaction between manganate (VII)
ions and ethanedioate ions in acidic solution.
(2)
(Total 14 marks)

6.

Hydrogen peroxide decomposes to form water and oxygen.

H2O2(aq) H2O(l) +
(a)

1
2

O2(g)

Suggest a method for following the rate of this reaction.

(2)

(b)

The reaction is first order with respect to hydrogen peroxide.

(i)

Explain what is meant by the term first order.

(1)

(ii)

The overall order of the reaction is one. Give the rate equation for the reaction.
Rate =
(1)

(iii) How would you use a graph of hydrogen peroxide concentration against time to
show that the reaction is first order?
(2)

(c)

The data in the table show the effect of temperature on the rate of this reaction.
T
/K

(i)

Rate
3 1
/ mol dm s

1/T
1
/K

ln(rate)

293

1.6 10

3.41 10

13.3

302

4.2 10

3.31 10

12.4

314

14.4 10

3.19 10

11.1

323

33.8 10

3.10 10

10.3

On the axes below, sketch graphs for two temperatures, T1 and T2, where T2 is
greater than T1, and use them to explain why increasing temperature has a dramatic
effect on the rate of this reaction.

(4)

(ii)

Plot a graph of ln(rate), on the vertical axis, against 1/temperature, on the

5

horizontal axis, on the grid below.

(3)

(iii)

Use your graph and the equation below to calculate the activation energy, EA, for
this reaction.
EA
ln(rate) = constant R

(1/T)

where R = 8.31 J K mol

You should include the sign and units with your answer which should be given to
two significant figures.

(3)
(Total 16 marks)

7.

(a) In a rate of reaction experiment between two substances, A and B, the overall order
of the reaction was found to be 2. Write three possible rate equations for such a second
order reaction between A and B.
(3)

(b)

At a certain temperature the rate of reaction between nitrogen monoxide, NO, and
hydrogen, H2, was investigated. The following data were obtained.
3

[NO]/mol dm

(i)

[H2]/mol dm

1.0

1.0

1.0

3.0

3.0

1.0

3 1

Rate/mol dm s
0.02
0.06
0.18

Use the data above to deduce the rate equation for this reaction.
(3)

(ii)

Use your answer to (b)(i) above to calculate the value of the rate constant, with
units.
(2)

(c)

The investigation described in part (b), above, was repeated, but at a higher temperature,
and the rate of the reactions increased. Explain, in terms of particles, why an increase in
temperature increases the rate of a reaction.
(3)

(d)

State the effect of an increase in temperature on the value of the rate constant, k.
(1)

(e)

Explain the effect of a catalyst on the rate of a reaction.

(3)
(Total 15 marks)

8.

This question is about the hydrolysis of 2-bromo-2-methylbutane.

C5H11Br + H2O C5H11OH + HBr
(a)

15 cm of water was mixed with 15 cm of ethanol. 1.0 cm of 2-bromo-2-methylbutane

was added to this mixture. The conductivity of this mixture was measured and rose from
0 to 200 microsiemens in 600 s.
3

The experiment was repeated using equal volumes of water and ethanol, with 2.0 cm of
3
2-bromo-2-methylbutane in the 31 cm of mixture. The conductivity of the mixture rose
from 0 to 400 microsiemens in 600 s.
(i)

Explain why the conductivity of the mixture increases during these reactions.
(1)

(ii)

Why was an ethanol/water mixture used for this reaction rather than water on its
own?
(1)

(iii)

What is the effect on the rate of the reaction of doubling the concentration of
2-bromo-2-methylbutane?
(1)

(iv)

Deduce the order of the reaction with respect to 2-bromo-2-methylbutane.

(1)

(v)

Explain why this is the order of reaction with respect to 2-bromo-2-methylbutane

and not the overall order of the reaction.
(1)

(b)

The table below shows the results from another experiment where a solution of
2-bromo-2-methylbutane is reacted with varying concentrations of hydroxide ions.
A few drops of an acid-alkali indicator are added to the mixture and the time for the
indicator to change to the acidic colour is measured.

[C5H11Br]
2

/10 mol dm

(i)

[OH ]
3
3
/10 mol dm

Time
/s

1.5

0.75

1.5

1.50

1.5

2.25

14
3 1

Calculate the rate of the reaction, in mol dm s , for each concentration of

hydroxide ions.
(2)

(ii)

What effect does doubling the concentration of hydroxide ions have on the rate of
the reaction?
(1)

(iii) What is the order of the reaction with respect to the hydroxide ions?
(1)

(c)

When 2-bromo-2-methylbutane reacts with water, or hydroxide ions, the mechanism for
the reaction is the same.
(i)

Use your answers to (a)(iv) and (b)(iii) to write the rate equation for the reaction
with hydroxide ions.
Rate =
(1)

(ii)

Write a mechanism for the reaction which is consistent with your rate equation.
(2)
(Total 12 marks)

9.

In an acidic solution, propanone reacts with iodine as follows:

CH3COCH3 + I2 CH3COCH2I + HI
The rate of this reaction can be followed by removing portions of the reaction mixture at known
times, adding them to a solution of sodium hydrogen carbonate to stop the reaction and then
titrating the mixture with standard sodium thiosulphate solution.
(a)

(i)
Write the ionic equation for the reaction of thiosulphate ions with
iodine in aqueous solution.
(2)

(ii)

State which indicator is used in this titration, and describe what you would see at
the end point.
(2)

(b)

Use the following data to deduce the rate equation for the reaction of propanone with
+
iodine in acidic solution, given that the order with respect to [H ] is one.
[CH3COCH3]
3

/mol dm

[I2]
/mol dm

Initial rate
3 1
/mol dm s

1.0

0.10

3.2 10

1.0

0.20

3.2 10

2.0

0.10

6.4 10

(3)

(c)

What is meant by:

(i)

order of reaction with respect to a particular reactant

(1)

(ii)

overall order of reaction.

(1)

(d)

What does the rate equation in (b) tell you about the involvement of iodine in the ratedetermining step, and hence about the least number of steps in the reaction?
(2)

(e)

Sodium hydroxide cannot be used to stop the reaction, because very alkaline conditions
cause another reaction to occur between propanone and iodine.
Write the equation for this reaction.
(3)
(Total 14 marks)

10.

This question is about the kinetics of the reaction in which ammonium cyanate, NH4CNO, turns
into urea, NH2CONH2, in aqueous solution.
9

NH4CNO(aq) 2CONH2(aq)
The table below shows the mass of urea, mt, which formed at different times in a solution of
ammonium cyanate of known starting concentration.
When the reaction stopped the mass of urea, mfinal, was 20.3 g.

(a)

Time / min

Mass of urea, mt /g

25

12.5

50

15.7

75

17.1

100

17.5

150

18.7

200

19.1

300

20.0

mfinal mt/g
20.3
7.8
4.6
3.2
2.8
1.6

Complete the final column of the table.

(1)

(b)

Plot a graph of mfinal mt (on the vertical axis) against time (on the horizontal axis).

(2)

(c)

The graph can be used to work out a rate equation for the reaction.
What term in the rate equation for the reaction is proportional to mfinal mt?
(1)

(d)

(i)
Show THREE successive half-life measurements on your graph, and
give their values.
(ii)

Use the half-lives to decide whether the reaction is zero order, first order or second
order. Explain how you decided the order.
(2)

(iii) Suggest a possible rate equation for the reaction.

(1)

(e)

A student thought that water might take part in the rate-determining step of the reaction.
(i)

What is meant by the rate-determining step?

(1)

(ii)

The solution of ammonium cyanate used in the experiment initially contained 0.35
3
moles of ammonium cyanate in approximately 1 dm (55.5 moles) of water.
Is the order you calculated in (d)(ii) an order with respect to ammonium cyanate, or
could it include the water as well? Explain your answer.
(2)
(Total 12 marks)

11

11.

(a)

The ester methyl ethanoate reacts with water as follows:

CH3COOCH3 + H2O CH3COOH + CH3OH

An experiment to investigate the kinetics of this hydrolysis showed that the concentration
of methyl ethanoate varied as shown in the graph below.
The water in this reaction is not only a reagent but is also the solvent and is therefore in
large excess.

[ e s t e r ]

. 3

. 3

. 2

0 . 2
/3 m

0
o

. 1

. 0

(i)

. 51

. 0 1 . 5 2 . 0 2 . 5 3
T i m
e
/ h r

. 0

Show, under these conditions, that the reaction is first order in methyl ethanoate.
(2)

(ii)

Explain with a reason whether or not the overall order of reaction must also be one.
(1)

(iii) Assuming the reaction is first order, use the graph to calculate the rate constant, k.
Include the units in your answer.
(3)

(iv) Suggest a method by which the progress of the reaction could be followed.
(3)

(b)

The Arrhenius equation

ln k = ln A Ea/RT
relates the rate constant k to the activation energy Ea for a reaction. A is a constant, R is
the gas constant.
(i)

Comment on the relative values of the rate constant k at a given arbitrary

temperature T for two reactions, one of which has an activation energy of about
1
1
180 kJ mol , the other of which has an activation energy of about 50 kJ mol . No
calculation is expected.
(1)

(ii)

Suppose that these two different values of activation energy were for the same
overall reaction at the same temperature. Suggest a way in which the conditions

are different for the two reactions.

(1)
(Total 11 marks)

12.

2-bromo-2-methylpropane reacts with aqueous sodium hydroxide as shown in the equation

below.
(CH3)3CBr + NaOH (CH3)3COH + NaBr
A series of experiments was carried out to investigate the kinetics of this reaction.
Initial concentration of
(CH3)3CBr
/mol dm
5.0 10

1.5 10

1.5 10
(a)

(i)

Initial concentration of
NaOH
/mol dm
2.0 10

2.0 10

4.0 10

Initial rate of reaction

3 1

/mol dm s
1.5 10

4.5 10

4.5 10

Give the order of the reaction with respect to

2-bromo-2-methylpropane ...............................................................................
sodium hydroxide .............................................................................................
(2)

(ii)

Write the rate equation for this reaction.

(1)

(b)

Use one set of the data to calculate the rate constant for this reaction. Include the unit of
the rate constant in your answer.
(2)

(c)

The slowest step of the mechanism is the following reaction

+

(CH3)3CBr (CH3)3C +Br

Is your rate equation consistent with this information? Explain your answer.
(1)

(d)

In another series of experiments, the rate of the reaction was measured at different
13

temperatures. Complete the missing numbers in the table below.

temperature (T)
/K

1/temperature (1/T)
1
/K

rate

3 1

/mol dm s

8.00

7.20

6.40

5.50

4.70

300

3.33 10

3.35 10

310

3.23 10

7.47 10

320

3.13 10

1.66 10

330

3.03 10

4.09 10

340

2.94 10

9.10 10

350

ln(rate)

1.66 10

(2)

(e)

On the axes below plot a graph of ln(rate) on the vertical axis against 1/T on the
horizontal axis.

(2)

Time
/s

[OH ]
3
/mol dm

0.100

120

0.071

240

0.052

360

0.035

480

0.024

600

0.018

(f)

Use the Arrhenius equation

EA
ln(rate) = constant R (1/T)

to calculate the value of the activation energy, EA, for the reaction.
1

[R = 8.31 J K mol ].
Show your working clearly and give your answer to 2 significant figures.
(2)
(Total 12 marks)

13.

This question is about the kinetics of the reaction between 2-bromo-2-methylpropane and
sodium hydroxide in a suitable solvent.
(CH3)3CBr + NaOH (CH3)3COH + NaBr
3

Equal volumes of 0.200 mol dm solutions of the two reactants were mixed together and
maintained at a constant temperature of 30 C. The concentration of hydroxide ions was
determined at different times. The results are shown in the table below.

(a)

Describe how the concentration of hydroxide ions could be determined during the
reaction.
(3)

(b)

(i)
Plot a graph of hydroxide ion concentration (vertical axis) against time
(horizontal axis) on the grid below.

15

(2)

(ii)

Mark on your graph TWO consecutive half-lives. Measure their values and write
them below.
First half-life ..........................................................................................................
Second half-life .....................................................................................................
(1)

(iii)

What is the order of the reaction? Explain how you used your half-lives to arrive at
your answer.
(1)

(iv) Explain why your answer to (iii) is an overall order.

(1)

(v)

Suggest a rate equation for this reaction.

Rate =
(1)

(c)

(i)
answer.

What mechanism is likely to be operating in this reaction? Justify your

(2)

(ii)

Write equations to show the steps involved in your chosen mechanism for this
reaction.
(2)
(Total 13 marks)

14.

(a)

Define the terms

(i)

Overall order of reaction

(1)

(ii)

Rate constant
(1)

(b)

In a kinetic study of the reaction

CH3I + OH CH3OH + I

At a certain temperature the following data were obtained:

Experiment

[CH3I]
/mol dm

[OH ]
3
/mol dm

Initial rate
3 1
/mol dm s

0.1

0.1

1 10

0.2

0.1

2 10

0.1

0.2

2 10

(i)

State the order of reaction with respect to CH3I and with respect to OH ions.
Give your reasons.
(2)

(ii)

Write the rate equation for the reaction.

(1)

(iii) Calculate the value of the rate constant for this reaction, stating its units.
17

(2)

(c)

The reaction

CH3CH2Br + OH CH3CH2OH + Br

has an SN2 mechanism that proceeds through a transition state.

(i)

Draw the mechanism, showing the structure of the transition state.

(3)

(ii)

Draw a reaction profile for this exothermic reaction. Show the energy level of the
transition state on the profile.
(2)
(Total 12 marks)

15.

Persulphate ions, S2O 8 slowly oxidise arsenic(III) acid, H3AsO3 in aqueous solution according
to the equation
2

S2O 8 + H3AsO3 + H2O 2SO 4 + H3AsO4 + 2H

3

25 cm of a 1.0 mol dm solution of potassium persulphate was mixed with 25 cm of a

solution of arsenic(III) acid of the same concentration.
At timed intervals, small potions of the reation mixture were analysed to determine the
2

concentration of persulphate ion, [S2O 8 ].

The results are shown below.
2

[ S 2 O 8 ]
3
/ mol dm
1.0

0.76

10

0.62

15

0.52

20

0.44

30

0.35

Time
/ minutes

(a)

[ S2
/ m

(i)
On the grid below, plot a graph of the concentration of persulphate
ions against time.

. 0

. 9

o 3l

. 8

. 7

. 6

. 5

. 4

. 3
0

0
T

(ii)

1 5
i m
e

2
/

0
m

i n

(2)
3

Draw a tangent to the curve at the point where [S2O 8 ] = 0.50 mol dm and use it
to calculate the slope of the curve at that point. Give your answer to two significant
figures.
Slope: ..............................
(4)

(b)

The rate of the reaction at a particular concentration of reactant can be measured from the
slope of the graph at that concentration.
2

The initial rate, which is the rate when the concentrations of persulphate ions, S2O 8 ,
3

and arsenic(III) acid, H3AsO3, are both 1.0 mol dm , was found to be 0.060 mol dm
19

min .

(i)

Use your answer to (a)(ii) to show that the ratio of the initial rate to the rate when
2

[S2O 8 ] and [H3AsO3] are 0.50 mol dm is approximately 4:1. Use this ratio to
deduce the overall order of reaction.
(3)

(ii)

Suggest TWO rate equations that agree with the order of the reaction that you have
deduced in (i). How could the experiment be adapted to distinguish between these
two rate equations?
(5)
(Total 14 marks)

16.

(a) The distribution of the energy of particles in a gas at temperature T1 is shown

below.

(i)

On the diagram above, draw the distribution of energy of particles at a lower

temperature, T2.
(2)

(ii)

Use the diagram to explain why the rate of a reaction increases with an increase in
temperature.
(3)

(iii) Explain fully why a catalyst increases the rate of a reaction.

(2)

(b)

The fermentation of glucose is an exothermic reaction and is catalysed by enzymes in

yeast.
C6H12O6(aq) 2C25(aq) + 2CO2(g)
The reaction is slow at room temperature.
(i)

Describe, with the aid of a diagram, an experiment you could do to follow the

progress of this reaction at different temperatures.

(4)

(ii)

Would you expect Ssystem to be positive or negative for this reaction? Justify your
answer with TWO pieces of evidence.
(2)

(iii) Deduce the sign of Ssurroundings. Show your reasoning.

(2)
(Total 15 marks)

17.

2-bromo-2-methylbutane reacts with aqueous sodium hydroxide in a substitution reaction.

C
C

3H

H C
B

(a)

C
C

3H

+ O

3H

H C
O

3H

+ B

The rate of reaction can be followed by measuring the concentration of 2-bromo-2methylbutane at various times.
In one such experiment, a known amount of 2-bromo-2-methylbutane was added to a
large excess of aqueous sodium hydroxide. The following results were obtained.
Time/min
0

(i)

Concentration of 2-bromo-2-methylbutane/mol dm
0.96

10

0.61

20

0.38

30

0.24

40

0.15

50

0.10

Plot a graph of the concentration of 2-bromo-2-methylbutane on the y (vertical)

axis against time on the x (horizontal) axis.

21

. 0

. 9

. 8

. 7

. 6

. 5

. 4

. 3

. 2

. 1

. 0

C o n c e n tra tio n o f 2 -b ro m o -2 -m e th y lb u ta n e / m o l d m

0
T

(ii)

3 0
i m

4
e

0
m

i n

(2)

Show TWO successive half-life measurements on your graph and write their values
below.
(2)

(iii) What is the order of reaction with respect to 2-bromo-2-methylbutane?

Give a reason for your answer.
(2)

(b)

When the reaction is repeated using equal concentrations of 2-bromo-2-methylbutane and

aqueous sodium hydroxide, the same results are obtained.
(i)

What is the order of reaction with respect to hydroxide ions?

(1)

(ii)

Write the rate equation for the reaction.

(1)

(iii)

Write a mechanism for the reaction which is consistent with your rate equation.
(3)

(c)

The reaction between 2-bromobutane, C2H5CHBrCH3, and aqueous sodium hydroxide

proceeds by the same mechanism as in (b)(iii).
Use the mechanism to explain why the reaction of a single optical isomer of 2bromobutane produces a mixture that is no longer optically active.
(3)
(Total 14 marks)

18.

One step in the manufacture of nitric acid is the reaction between nitrogen(II) oxide and oxygen

to form nitrogen(IV) oxide.

2NO(g) + O2(g)

H = 114 kJ mol

2NO2(g)

(i)
Use the equation to suggest the sign of Ssystem for the
forward reaction. Justify your answer.

(a)

(2)

(ii) What is the sign of Ssurroundings for the forward reaction? Justify your answer.
(2)

(b)

(i)
Write the expression for Kp for this reaction.
What are the units of Kp in this reaction?
Units ..............................................
(2)

(ii)

Suggest how the temperature and pressure could be altered to make nitrogen(IV)
oxide more economically. Justify your suggestions by considering both yield and
rate.
Temperature
Pressure
(4)

(c)

(i)
What property would allow you to follow the progress of this
reaction? Justify your answer.
(2)

(ii)

In a series of experiments, the following results were obtained.

Experiment

[O2(g)]

[NO(g)]
3
/mol dm

/mol dm

Initial rate
3 1
/mol dm s

1.0 10

1.0 10

8.0 10

2.0 10

1.0 10

3.2 10

2.0 10

2.0 10

6.4 10

What is the order of the reaction with respect to NO(g)? Justify your answer.

(2)

What is the order of the reaction with respect to O2(g)?

(1)

(iii) What is the rate equation for this reaction?

(1)

(iv)

What is the overall order for this reaction?

(1)

23

(v)

Calculate the rate constant, k, for this reaction. Include units with your answer.
(2)

(d)

Suggest why this reaction takes place quickly at room temperature and pressure.
(1)
(Total 20 marks)

19.

(a)

Explain what is meant by the following terms.

Rate of reaction
Overall order of a reaction
(2)

(b)

Two gases, A and B, react according to the equation

A + 3B

AB3

A series of experiments carried out at 298 K gave the following results.

Experiment

(i)

Initial rate of
reaction

Initial
concentration of
A
3
/ mol dm

Initial
concentration of
B
3
/ mol dm

0.100

0.100

0.00200

0.100

0.200

0.00798

0.200

0.100

0.00399

/ mol dm min

State the order of reaction with respect to each of the reactants. Justify your
answer.
Reactant A
Reactant B
(3)

(ii)

Write the rate equation for the reaction between A and B.

(1)

(iii)

Use the experimental data from Experiment 1 to calculate the rate constant,
including units.

(2)

(iv)

Suggest a possible mechanism for the reaction between A and B, leading to the
formation of AB3. Identify the rate-determining step.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)

(c)

The rae constant, k, for the reaction in (b) was measured at different temperatures.
The following data were obtained.

2.70

1
T /K1
0.00303

3.39

0.00315

4.09

0.00327

4.43

0.00333

log10 k

25

1
Plot a graph of log10 k against T , on the grid below.

(i)

. 0 0
2 . 0

. 0

1
/ K 1
T
0 . 0

. 0

. 0

l o 1 kg0

. 0

. 0
(2)

(ii)

The Arrhenius equation can be written

log10 k = constant

Ea 1

2.30 R T
1

where R = 8.31 J mol K .

Ea
1
A graph of log10 k against T has a gradient of 2.30 R .
Calculate the gradient of the graph and hence calculate the value of activation
energy, Ea.

(2)
(Total 15 marks)

20.

This question is about the reaction between calcium carbonate and hydrochloric acid.
CaCO3(s) + 2HCl(aq) CaCl2(aq) + CO2(g) + H2O(l)
One method of studying the kinetics of this reaction is to measure the volume of carbon dioxide
given off at various timed intervals when using an excess of calcium carbonate.

27

(a)

Suggest TWO other methods for following this reaction. Explain your choices.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)

(b)

Suggest why the volume of carbon dioxide given off in the first few seconds of the
reaction is an unreliable measure of the initial rate of the reaction.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(1)

(c)

In an experiment, the following results were obtained.

(i)

(Vfinal Vt)

Time
/s

Volume of CO2

85

35

42

46

65

62

26

95

72

125

79

155

84

185

87

Vt/cm

/ cm

What was the final volume, Vfinal?

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

(ii)

Complete the table.

(1)

(iii)

To what is (Vfinal Vt) proportional?

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

(iv)

Plot these results on the grid below.

1

8
( Vf

i n

a lt

c3 m
6

1 0
t i m

0
(2)

(v)

On your graph measure and record THREE successive half-lives. Deduce the order
of the reaction. Justify your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)

(vi)

Give the rate equation for this reaction.

29

(1)

(vii) What are the units of the rate constant?

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

(d)

What would you expect the signs of Ssystem and Stotal to be for the reaction between
calcium carbonate and hydrochloric acid? Justify your answers.
Ssystem ..........................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
Stotal ............................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(4)
(Total 17 marks)

21.

The reaction between peroxodisulphate and iodide ions occurs as follows:

S 2 O 82 (aq) + 2I (aq)
2SO 24 (aq) + I 2 (aq)
Initial rates for this reaction can be determined by a method known as an iodine clock.
A mixture of potassium iodide, sodium thiosulphate and starch is made up, and a clock started
when a solution of potassium peroxodisulphate is added. When enough iodine has been formed
to react with all the sodium thiosulphate, the excess iodine suddenly forms a blue-black
complex with the starch. At this point the clock is stopped, and the time taken.

(a)

In one particular experiment, the volumes of the reactants used were as follows:

Volume of
K2S2O8(aq)
3

/ cm

10.0

(i)

Volume of
3
KI(aq) / cm
10.0

Volume of
Na2S2O3(aq)
/ cm

Volume of
starch solution /
3
cm

Volume of
3
water / cm

Time taken
/s

5.0

1.0

14.0

The concentration of the sodium thiosulphate used was 0.010 mol dm . Calculate
2
the number of moles of thiosulphate ions, S 2 O 3 , in the mixture.

(1)

(ii)

Iodine reacts with thiosulphate ions as shown below:

I 2 (aq) + 2S 2 O 32 (aq)
2I (aq) + S 4 O 62 (aq)
Calculate the number of moles of iodine which had reacted when the clock was
stopped.

(1)

31

(iii)

3 1

Calculate the rate of formation of iodine in mol dm s .

(2)

(b)

Further experiments were carried out and the results are shown below.

Experiment

[ S 2 O 8 (aq)] / mol dm

[I (aq)] / mol dm

3 1

Rate / mol dm s

0.0100

0.0200

2.74 10

0.0100

0.0400

5.47 10

0.0300

0.0800

3.28 10

(i)

What is the order of reaction with respect to iodide ions, I ?

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

(ii)

2
Deduce the order of reaction with respect to peroxodisulphate ions, S 2 O 8 .
Show how you arrived at your answer.

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

(iii)

Use your answers to (i) and (ii) to write an overall rate equation for the reaction.

(1)

(iv)

Use the data from experiment 1 to calculate the rate constant for this reaction.
Give the units for the rate constant.

(2)
(Total 9 marks)

22.

Two gases, A and B, react according to the equation

A(g) + 2B(g) AB2(g)
A series of kinetics experiments performed at constant temperature gave the following results:
Experiment

Initial concentration of
3
A /mol dm

Initial concentration of
3
B /mol dm

0.0500

0.100

1.00 10

0.0500

0.200

3.92 10

0.1000

0.100

1.95 10

(a)

Initial rate
3 1
/mol dm s

(i)
Calculate, showing your working, the order of reaction with respect to
A and to B.

(3)

(ii)

Write the rate equation for the reaction.

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

33

(iii)

Calculate the rate constant, k, for the reaction in experiment 3, stating its units.
(2)

(b)

(i)
Explain, in terms of collision theory, why the rate of reaction
increases with an increase in temperature.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)

(ii)

Suggest, with an explanation, the least number of steps which is likely to exist in
the mechanism of the reaction between A and B.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(c)

The variation of the rate constant, k, with change in temperature is given by the Arrhenius
equation:
Ea

ln k = R

1
+ ln A
T

where A is a constant.
In a series of experiments performed at various temperatures T to determine the rate
constant, k, for the decomposition of a gas X, a graph of ln k against 1/T gave a straight
Ea
line of slope R :

l nk

1 1

1 2
0 . 0

0
1
T

. 0

35

3
1

. 0

. 0

Use the graph to calculate the value of the activation energy, in kJ mol , for the
1
1
decomposition of X. The value of the gas constant R = 8.31 J K mol .

(4)
(Total 15 marks)

23.

In the presence of hydrogen ions, H , glucose, C6H12O6, can be oxidised by a solution of

potassium manganate(VII), KMnO4, which is purple in colour.
A series of experiments was carried out to determine the rate of reaction and the results are
shown below.

Experiment

Initial
concentration
of C6H12O6
/ mol dm

Initial
concentration
of KMnO4
/ mol dm

Initial
concentration
+
of H
3
/ mol dm

Rate of
reaction
3 1

/ mol dm s

1.0

0.01

0.5

2.0 10

1.0

0.005

0.5

1.0 10

0.5

0.005

0.5

1.0 10

1.0

0.02

1.0

8.0 10

(a)

Describe how the rate of this reaction may have been measured.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)

(b)

(i)
Give the order of reaction with respect to each reactant. In the case of
potassium manganate(VII) and hydrogen ions explain how you arrived at your
answer.
Glucose ................................................
Potassium manganate(VII) ...............................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
Hydrogen ions ..................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)

(ii)

Write the rate equation for this reaction.

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

37

(iii)

Using the data from experiment 1, calculate the rate constant for the reaction.
Include the units of the rate constant in your final answer.

(2)

(c)

Additional experiments were carried out to investigate the effect of temperature on the
rate of reaction.
(i)

Complete the missing data in the table below.

Temperature (T)
/K

1/ temperature (1/T)
1
/K

Rate constant

ln (rate constant)

295

3.39 10

2.88 10

5.85

305

3.28 10

1.01 10

4.60

1.83 10

311
320

3.13 10

4.98 10

3.00

333

3.00 10

2.02 10

1.60
(1)

(ii)

Plot a graph of ln (rate constant) on the vertical axis against 1/T on the horizontal
axis using the axes below.

(2)

(iii)

EA 1

T + constant, together with your

Use the Arrhenius equation ln (rate) = R
graph to calculate a value of the activation energy, EA, for this reaction.
Show all steps in your working. Include units in your final answer, which should be
given to two significant figures.
1
1
[Gas constant, R = 8.31 J K mol ]

(2)
(Total 13 marks)

39

24.

The principal reaction occurring when 2-bromo-2-methylpropane reacts with aqueous sodium
hydroxide is as follows:
3C

( C

) C

CH

HC

3 3 H+

CN
B

( a C+ O 3 H NH

a) CB

3 Hr

Several experiments were carried out in order to follow the kinetics of this alkaline hydrolysis.
A few drops of phenolphthalein were added to a sample of sodium hydroxide, and, after the
addition of a measured amount of 2-bromo-2-methylpropane, the mixture was vigorously
shaken and a clock was immediately started. The time was taken when the pink colour due to
the indicator disappeared.
This experiment was repeated twice using different concentrations of the two reactants.
All experiments were carried out at the same temperature.
The results are shown in the table below.
Experiment

2-bromo-2-methylpropane
3
/ mol dm

0.011

8.0 10

33

0.022

8.0 10

16

0.022

1.2 10

24

(a)

(i)

Sodium hydroxide
3
/ mol dm

Time /s

Identify the attacking species responsible for this alkaline hydrolysis.

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

(ii)

Assuming that the final concentration of sodium hydroxide is zero, calculate the
3 1
average rates of reaction in mol dm s for experiments A and B.

3 1

A ................. mol dm s

3 1

B ................. mol dm s

(2)

(iii)

Deduce the order of reaction with respect to 2-bromo-2-methylpropane. Justify

your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)

(iv)

By comparing the average rates of reaction between experiments B and C, deduce

the order of reaction with respect to sodium hydroxide.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(v)

Write the rate equation for the reaction.

Rate =
(1)

(vi)

From your rate equation, suggest how this reaction proceeds by giving a possible
mechanism.

(3)

41

(b)

Explain briefly why 1-bromobutane, an isomer of 2-bromo-2-methylpropane, reacts by a

different mechanism when it is hydrolysed.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 12 marks)

25.

This question concerns the reaction between nitrogen monoxide and oxygen:
2NO(g) + O2(g) 2NO2(g)

(a)

In a series of experiments designed to find the rate equation for this reaction, the
following data were obtained. In each experiment the partial pressure of oxygen was the
same.

I n

i t i a l

a1

2 0
t e / a t m
1 5
1

0
5
0

0
S

0
q

. 0

a r e

0
o

t h

. 1

a r2 t i a l

0
p

r e s s u

. 1
r e

5
o

(i)

What is the order of reaction with respect to nitrogen monoxide?

Justify your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(ii)

A new series of readings is taken with the partial pressure of oxygen doubled.
The gradient of the line doubles.
State, with a reason, the order of reaction with respect to oxygen.
...........................................................................................................................
...........................................................................................................................
(1)

(iii)

Hence write the rate equation for the reaction.

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

(iv)

State the units of the rate constant.

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

43

(b)

The rate of the decomposition of nitrous oxide

2N2O(g) 2N2(g) + O2(g)
has been studied at different temperatures. The rate constant k was determined at each
temperature.
The relationship between the rate constant and the temperature T is given by the
Arrhenius equation:

ln k = ln A

Ea
R

1

T

where Ea is the activation energy for the reaction, R is the gas constant, and k is the rate
constant at temperature T.

(i)

Given values of k at different temperatures T, what graph would you plot and how
would you use it to determine the activation energy?
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)

(ii)

A plot of the data gave a straight line with gradient 2.95 10 K .

Find the activation energy for the reaction, in kJ mol1, to three significant
figures.
1
1
[The value of R is 8.314 J K mol ]

(2)

(iii)

What is the oxidation number of nitrogen in nitrous oxide, N2O?

Put a cross ( ) in the box of the correct answer. If you change your mind about an
answer, put a line through the box ( ) and then mark your new answer with a
cross ( ).
A

+2

+1

2
(1)
(Total 10 marks)

26.

Cyanide ions react with 2-bromo-2-methylpropane in the following way:

(CH3)3CBr + CN (CH3)3CCN + Br
The rate equation for this reaction is
rate = k[(CH3)3CBr]

(i)

What information does this rate equation give about the mechanism of this reaction?
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)

45

(ii)

Give the mechanism for this reaction consistent with the rate equation.

(3)
(Total 5 marks)

27.

This question is about the reaction of iodine with propanone.

+

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

(a)

Suggest, in outline, THREE different methods for following the rate of this reaction.
State which of the reactants or products could be measured by each method you choose.
Method 1
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
Method 2
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
Method 3
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)

(b)

The reaction is extremely slow at room temperature in the absence of H+ ions as a

catalyst.
Suggest how you would quench the reaction before carrying out a titration method to
determine the concentration of iodine at different times.
Justify your answer.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)

(c)

A series of experiments was carried out, varying the concentrations of the reactants and
the catalyst. The following results were obtained.
Experiment

[CH3COCH3]
/mol dm

[I2]
/mol dm

[H ]
3
/mol dm

Initial rate
3 1
/mol dm s

1.00

0.010

0.10

2.8 10

1.00

0.010

0.20

5.6 10

1.50

0.010

0.20

8.4 10

1.50

0.020

0.10

4.2 10

The reaction is first order with respect to hydrogen ions, H .

(i)

Deduce the order of the reaction with respect to propanone, CH3COCH3. Justify
your answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)

47

(ii)

Deduce the order of the reaction with respect to iodine, I2.

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

(iii)

Hence give the rate equation for this reaction.

(1)

(iv)

Which species are involved in the rate-determining step?

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

(v)

Suggest an equation for the reaction between the species in the rate-determining
step.

Explain why this step is likely to take place.

...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(Total 13 marks)

28.

This question is about the reaction of magnesium with hydrochloric acid which takes place
rapidly at room temperature.
Mg(s) + 2HCl(aq) MgCl2(aq) + H2(g)
mol

H = 467 kJ

(a)

Rewrite the equation omitting spectator ions.

(1)

(b)

Suggest the sign of the following entropy changes for this reaction. Justify each of your
answers.
(i)

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

(ii)

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

(iii)

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

49

(c)

A student carried out this experiment at five different temperatures in order to calculate
the activation energy of the reaction. The students laboratory record is shown below.

Method
Clean a strip of magnesium weighing 0.100 g with sand paper. Measure the temperature of
3

20 cm of 1.00 mol dm hydrochloric acid in a 100 cm beaker. Add the magnesium ribbon, stir
continuously, and time how long it takes for the magnesium to disappear. Repeat the
experiment at four other temperatures.
Assumption: the initial rate of reaction is proportional to 1/time.
Results
1/T
Temperature
Temperature
time
1
/C
/K
/s
/K

1/time
/s

ln 1/time

45

0.0222

3.81

25

0.0400

3.22

11

0.0909

-2.40

0.1667

-1.79

122

0.0082

-4.80

24

297

3.37 10

33

306

3.27 10

45

318

3.14 10

56

329

3.04 10

10

283

3.53 10

The Arrhenius equation is ln k = Ea/R (1/T) + constant

ln 1/time is proportional to ln k and so a graph of ln 1/time will have the same gradient as
that of the Arrhenius plot of ln k against 1/Temperature
The student plotted the graph of ln 1/time against 1/Temperature and from this the
1
activation energy, EA, was calculated as + 51.3 kJ mol .
(i)

Suggest the reason for cleaning the magnesium ribbon with sand paper.
(1)

(ii)

Calculate the number of moles of hydrochloric acid used up when all the
magnesium reacts in one experiment. Hence comment on whether the change in
concentration during the reaction will have a significant effect on the validity of the
assumption that the initial rate of reaction is proportional to 1/time. How would
you overcome this potential error?
[Take the relative atomic mass of magnesium as 24 in this and subsequent
calculations.]
(5)

51

(iii)

Use the value of H and other information given in the question to calculate the
temperature change in an experiment assuming no energy is lost to the
surroundings. Hence comment on whether this change in temperature will have a
significant effect. How would you overcome this potential error?
1

[H = 467 kJ mol .
heat produced = mass specific heat capacity change in temperature.
1

Assume that the specific heat capacity of the solution is 4.18 J K g ]

(4)

(iv)

The most difficult thing to measure accurately is the time it takes for the
magnesium to disappear and the time measured can be up to 2 seconds out.
Assuming this error, calculate the shortest time at 56 C and the longest time at
10 C for this reaction.
Complete the table for these times. Plot the two points on the grid below and join
them with a straight line. From the gradient, which equals EA/R, of this line
calculate another value for the activation energy.
1/T
1
/K

Temperature
/ C

Temperature
/K

time
/s

56

329

3.04 10

10

283

3.53 10

1/time
1
/s

ln 1/time

ln 1 / t
(v)

0 . 0 0
1 . 0

. 5

. 0

. 5

. 0

. 5

. 0

. 5

. 0

1
. 0

/ T )1 ( K
0 3 1

. 0

. 0

If the reaction mixture is not stirred, the magnesium tends to float on the surface of
the acid.
Suggest how this would affect the measurements of the rate of the reaction.
(1)

(vi) Suggest two other improvements the student could do to this experiment to
improve the accuracy or validity of the results.
(2)

(vii) If ethanoic acid of the same concentration and at the same temperature is used
instead of hydrochloric acid, explain how the rate would differ.
(1)
(Total 24 marks)

53

29.

One step in the production of nitric acid is the oxidation of ammonia.

4NH3 + 5O2 4NO + 6H2O
This is carried out at 900 C over a platinum-rhodium catalyst and is an example of
heterogeneous catalysis.
Explain in terms of collision frequency and collision energy how the rate would change if the
temperature were increased, and which of these causes the greater effect.
What is the difference between a heterogeneous and a homogeneous catalyst? Suggest one
advantage of using a heterogeneous catalyst in processes such as this.
(Total 6 marks)