1.
GRADE 13
This question involves the following techniques which can be used to follow chemical
reactions in order to investigate their kinetics.
A
colorimetry
(b)
(c)
(1)
(d)
2.
rate = k[KI]
rate = k[C2H4Br2]
(Total 1 mark)
3.
For the reaction between sodium bromate(V) and sodium bromide in acidic solution, the
rate equation is:
+ 2
When the concentrations of all three reactants are doubled, the rate will increase by a
factor of
A
16
(Total 1 mark)
1.
In an experiment to determine the rate of the reaction between persulphate ions and
iodide ions in aqueous solution
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)
(i)
2
8
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)
(iii)
(2)
(iv)
Explain why the rate equation cannot be written directly from the
stoichiometric equation for the reaction.
..........................................................................................................................
..........................................................................................................................
(1)
(b)
(i)
(ii)
2.
(a)
(i)
(ii)
(b)
(i)
Give the mechanism for the SN1 reaction between 2-bromobutane and
hydroxide ions.
(3)
(ii)
(iii)
In an experiment designed to find the mechanism of the reaction between 2bromo-2-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
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)
3.
1
2
O2(g)
(b)
(ii)
The overall order of the reaction is one. Give the rate equation for the
reaction.
Rate =
(1)
(iii)
..........................................................................................................................
..........................................................................................................................
(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)
(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)
You should include the sign and units with your answer which should be
given to two significant figures.
(3)
(Total 16 marks)
4.
(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.
[NO]/mol dm
[H2]/mol dm
3 1
Rate/mol dm s
1.0
1.0
0.02
1.0
3.0
0.06
3.0
1.0
0.18
10
(i)
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)
11
(d)
State the effect of an increase in temperature on the value of the rate constant, k.
...............................................................................................................................
(1)
(e)
5.
(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)
12
(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]
Initial rate
3 1
/mol dm s
/mol dm
1.0
0.10
3.2 10
1.0
0.20
3.2 10
2.0
0.10
6.4 10
(3)
(c)
(ii)
(d)
What does the rate equation in (b) tell you about the involvement of iodine in the
rate-determining 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)
6.
This question is about the kinetics of the reaction in which ammonium cyanate,
13
(a)
Time / min
Mass of urea, mt /g
mfinal mt/g
20.3
25
12.5
7.8
50
15.7
4.6
75
17.1
3.2
100
17.5
2.8
150
18.7
1.6
200
19.1
300
20.0
14
(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)
15
(ii)
Use the half-lives to decide whether the reaction is zero order, first order or
second order. Explain how you decided the order.
Order of reaction ..............................................................................................
Explanation ......................................................................................................
.
..........................................................................................................................
..........................................................................................................................
(2)
(e)
A student thought that water might take part in the rate-determining step of the
reaction.
(i)
(ii)
7.
(a)
16
0 .3 5
0 .3 0
0 .2 5
[e s te r] / m o l d m
0 .2 0
0 .1 0
0 .0 5
0
(i)
0 .5
1 .0
1 .5
2 .0
T im e / h r
2 .5
3 .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)
17
(iv) Suggest a method by which the progress of the reaction could be followed.
..........................................................................................................................
..........................................................................................................................
(3)
(b)
(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)
8.
/mol dm
5.0 10
1.5 10
1.5 10
(a)
(i)
2.0 10
4.0 10
1.5 10
4.5 10
4.5 10
18
2-bromo-2-methylpropane ...............................................................................
sodium
hydroxide .............................................................................................
(2)
(ii)
(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)
(d)
In another series of experiments, the rate of the reaction was measured at different
temperatures. Complete the missing numbers in the table below.
temperature (T)
/K
1/temperature (1/T)
1
/K
rate
3 1
/mol dm
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
ln(rate)
8.00
7.20
6.40
5.50
19
340
350
2.94 10
9.10 10
1.66 10
4.70
(2)
(e)
On the axes below plot a graph of ln(rate) on the vertical axis against 1/T on the
horizontal axis.
(2)
20
(f)
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)
9.
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.
[OH ]
3
/mol dm
Time
/s
0.100
0.071
120
0.052
240
0.035
360
0.024
480
0.018
600
(a)
Describe how the concentration of hydroxide ions could be determined during the
reaction.
.....................................................................................................................................
.....................................................................................................................................
21
.....................................................................................................................................
.....................................................................................................................................
(3)
(b)
(i)
(2)
22
23
(ii)
Mark on your graph TWO consecutive half-lives. Measure their values and write
them below.
First halflife ..........................................................................................................
Second halflife .....................................................................................................
(1)
(iii)
What is the order of the reaction? Explain how you used your half-lives to
arrive at your answer.
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(1)
(iv)
(v)
(c)
(i)
24
(ii)
reaction.
Write equations to show the steps involved in your chosen mechanism for this
(2)
(Total 13 marks)
10.
(a)
(ii)
Rate constant
..........................................................................................................................
..........................................................................................................................
(1)
(b)
CH3I + OH CH3OH + I
(i)
[CH3I]
3
/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
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(2)
25
(ii)
(iii) Calculate the value of the rate constant for this reaction, stating its units.
(2)
(c)
The reaction
CH3CH2Br + OH CH3CH2OH + Br
(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)
26
27
11.
(a)
is shown below.
(i)
(ii)
Use the diagram to explain why the rate of a reaction increases with an
increase in temperature.
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(3)
(iii)
28
..........................................................................................................................
..........................................................................................................................
(2)
(b)
(4)
(ii)
29
(2)
(Total 15 marks)
12.
CH
C 2H
C H
C H
Br
(a)
+ O H
C 2H
CH
+ B r
O H
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
(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
30
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
1 .0 0
0 .9 0
0 .8 0
0 .7 0
0 .6 0
0 .5 0
0 .4 0
0 .3 0
0 .2 0
0 .1 0
0 .0 0
0
(ii)
10
20
30
T im e / m in
40
50
60
(2)
Show TWO successive half-life measurements on your graph and write their
values below.
First half-life
............................................................
Second half-life
............................................................
(2)
(b)
When the reaction is repeated using equal concentrations of 2-bromo-2methylbutane and aqueous sodium hydroxide, the same results are obtained.
(i)
31
(ii)
(iii)
Write a mechanism for the reaction which is consistent with your rate
equation.
(3)
(c)
13.
(a)
32
.....................................................................................................................................
Overall order of a
reaction ..........................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(b)
AB3
(i)
Initial
concentration of
A
3
/ mol dm
Initial
concentration of
B
3
/ mol dm
Initial rate of
reaction
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)
(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.
..........................................................................................................................
33
..........................................................................................................................
..........................................................................................................................
(3)
(c)
The rae constant, k, for the reaction in (b) was measured at different temperatures.
The following data were obtained.
(i)
0 .0 0 3 0 0
log10 k
1
T /K1
2.70
0.00303
3.39
0.00315
4.09
0.00327
4.43
0.00333
1
Plot a graph of log10 k against T , on the grid below.
0 .0 0 3 1 0
1
/K 1
T
0 .0 0 3 2 0
0 .0 0 3 3 0
2 .0
3 .0
lo g10k
4 .0
5 .0
(2)
34
35
(ii)
log10 k = constant
Ea 1
2.30 R T
1
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)
14.
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.
36
(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)
(i)
Time
/s
Volume of CO2
Vt/cm
/ cm
85
35
42
46
65
62
26
95
72
125
79
155
84
185
87
(Vfinal Vt)
3
(ii)
37
(iv)
80
( V fin a l V t )
/ cm 3
60
40
20
100
tim e / s
200
(2)
(v)
(1)
38
(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)
15.
(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
(1)
(ii)
39
(1)
3 1
(iii)
(2)
(b)
Further experiments were carried out and the results are shown below.
Experiment
(i)
[ 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
(ii)
2
Deduce the order of reaction with respect to peroxodisulphate ions, S 2 O 8 .
Show how you arrived at your answer.
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(1)
40
(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)
16.
(a)
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
(i)
Initial rate
3 1
/mol dm s
(3)
(ii)
41
42
(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)
(2)
(c)
The variation of the rate constant, k, with change in temperature is given by the
Arrhenius equation:
Ea 1
ln A
ln k = R 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
Ea
a straight line of slope R :
43
8
ln k
9
10
11
12
0 .0 0 2 9
0 .0 0 3 0
0 .0 0 3 1
0 .0 0 3 2
1
T
/ K
0 .0 0 3 3
0 .0 0 3 4
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)
44
17.
Experiment
Initial
concentration
of C6H12O6
3
/ mol dm
(a)
Initial
concentration
of KMnO4
3
/ mol dm
Initial
concentration
+
of H
3
/ mol dm
Rate of
reaction
/ mol dm s
3 1
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
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) ..............................................................................
(3)
45
(ii)
(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)
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)
46
(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
(2)
(Total 13 marks)
47
18.
C H 3C (C H 3)C H
+ N aO H
C H 3C (C H 3)C H
B r
+ N aB r
O H
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.
(a)
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
(i)
Sodium hydroxide
3
/ mol dm
Time /s
(ii)
3 1
A ................. mol dm s
3 1
B ................. mol dm s
(2)
48
(iii)
(v)
(vi)
From your rate equation, suggest how this reaction proceeds by giving a
possible mechanism.
(3)
(b)
49
19.
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.
30
25
20
In itia l ra te / a tm s
15
10
5
0
0 .0 5
0 .1
0 .1 5
S q u a re o f th e p a rtia l p re s s u re o f N O /a tm
(i)
0 .2
2
(ii)
50
51
(b)
ln k ln A
Ea 1
R 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)
(ii)
(2)
52
(iii)
+2
+1
2
(1)
(Total 10 marks)
20.
(CH3)3CBr + CN (CH3)3CCN + Br
(i)
What information does this rate equation give about the mechanism of this
reaction?
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
53
(ii)
Give the mechanism for this reaction consistent with the rate equation.
(3)
(Total 5 marks)
21.
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)
54
55
(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]
3
/mol dm
[I2]
3
/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
(i)
56
(ii)
(iii)
(v)
Suggest an equation for the reaction between the species in the ratedetermining step.
57