1 How fast?

Rates of reaction Answers

Practice: pages 20–25

1 Answer is B. From experiments 1 and 3 the order with respect to Cl2 is 1 (the rate quadruples
–3
as the concentration doubles. Therefore, in an experiment using 0.80 mol dm of CO and
–3 –24 –3 –1
0.20 mol dm of Cl2, the rate will be halved from the 6.4 × 10 mol dm min obtained
in experiment 1. (There is no need to work out the order with respect to CO.) [1]
2 Answer is B. The concentration halves every 120 s. So, the sequence of half-lives is
2.4 → 1.2 → 0.6 → 0.3 → 0.15; that is four half-lives which is 4 × 120 s. [1]
3 Answer is C. For a zero order reaction, the rate of decomposition is a constant. [1]
2
4 Answer is A. the decomposition is Rate = k[X] [1]
2
From the data given, 0.016 = k[1] [1]
–1 –3 2
Therefore, k = 0.016 s . If [X] = 0.25 mol dm , rate = 0.016[ 0.25]
3 –1 –1
= 0.001 dm mol s [1]
1
5 Answer is B. The overall order is 2, so the units are . [1]
concentration × s

6 Answer is D. I2 has an order of zero and is not involved in the rate-determining step. Therefore, it
can be ignored. In D, [0.1][2] has a value that is greater than [0.1][1]. [1]
7 Answer is C. The slow step + the fast step must give the overall equation. I must, therefore, be
removed in the fast step in a reaction with G, and some J and K must be formed. [1]
8 Answer is B. The rate equation is Rate = k[halide] so statements 1 and 2 are correct. Raising the
temperature will increase the rate of reaction by allowing more molecules to exceed the
activation energy, but the activation energy is fixed and will not change. [1]
9 Answer is D. Increasing the amount of ozone present does not change the order with respect to
ozone. A large excess is not necessary to ensure enough ozone is present. The purpose of a large
excess is to make sure that during the reaction its concentration is virtually constant Therefore,
only statement 3 is correct. [1]
10 Answer is A. Experiments 2 and 3 give the order with respect to X as zero. Experiments 1 and 2
give the order with respect to Y as 2. So statements 1 and 2 are correct. The rate constant is
2
calculated from a set of results, for example, experiment 1 gives 0.08 = k[0.10] .
3 –1 –1
So k = 8.0 dm mmol s and statement 3 is, therefore, correct. [1]

11 a) 2N2O5(g) → 4NO2(g) + O2(g) [1]

b) i) For every 2 mol of N2O5 that reacts 4 mol of NO2 is formed. Therefore, the rate of
−4 −3 −1
formation of NO2 is twice as fast as the loss of N2O5, i.e. 7.0 × 10 mol dm s . [1]
1
ii) For oxygen, the rate of formation will be the rate of loss of N2O5,
2
–4 −3 −1
i.e. 1.75 × 10 mol dm s [1]

© Hodder & Stoughton Limited 2015

1 How fast? Rates of reaction Answers

−
12 Rate = k[ester][OH ] [1]

So, 0.000 69 = k(0.05)(0.1)

k = 0.000 69/0.005
−1 3 −1
k = 0.138 mol dm s [1] + [1]units
−3 −1 −3
13 Rate has units of mol dm s and concentrations are measured in mol dm .
a) Adding units to both sides of the equation, rate = k[A][B][C] gives:
–3 −1 −3 −3 −3
mol dm s = k(mol dm )(mol dm )(mol dm ) [1]

mol dm−3s −1
units of k =
(moldm ) (moldm )( moldm )
−3 −3 −3

−2 6 −1 6 −2 −1
= mol dm s which is better written as dm mol s [1]
2
b) If the rate equation, rate = k[A] [B] is rewritten as:

rate = k[A][A][B]

then it can be seen that this problem is similar to part a. Therefore, the units of k are the
6 −2 −1
same: dm mol s . [1]

Although it is better to deduce units using the method shown above, the answer can be
obtained using the formula:
(1−n) −1
k has units of (concentration) (time) where n is the total order for the reaction.
6 −2 −1
In both examples above the total order is 3. Therefore, the units are dm mol s .
−3 −3
14 a) When the concentration of NOCl is doubled from 0.1 mol dm to 0.2 mol dm , the initial
−10 −3 −1 −9 −3 −1
rate of the reaction increases from 4 × 10 mol dm s to 1.6 × 10 mol dm s ,
−9 −10
which is a four-fold increase (remember that 1.6 × 10 is the same as 16 × 10 ). [1]

This means that the order with respect to NOCl is 2. [1]

(The same conclusion could be reached by noticing that when doubling concentration of
−3 −3
NOCl from 0.2 mol dm to 0.4 mol dm , the rate also increases four-fold.)
2
b) The rate equation is: rate = k[NOCl]
−10 2
Using the first set of results gives 4 × 10 = k(0.1) [1]
−10 2 –8 3 −1 −1
Therefore, k = 4 × 10 /(0.1) = 4 × 10 dm mol s [1] + [1] units
−3
c) The initial rate of reaction is obtained by substituting the concentration 0.15 mol dm into
the rate equation.
−8 2 −10 −3 −1
rate = 4 × 10 × (0.15) = 9 × 10 mol dm s [1] + [1] units

© Hodder & Stoughton Limited 2015

1 How fast? Rates of reaction Answers

2− −3 −3
15 a) i) When the concentration of (COO)2 is doubled from 0.020 mol dm to 0.040 mol dm
−4 −3 −1 −4
the initial rate of the reaction increases from 0.48 × 10 mol dm min to 1.92 × 10
−3 −1
mol dm min , [1] which is a four-fold increase. This means the order with respect to
2−
(COO)2 is 2. [1]
−3 −3
ii) When the concentration of HgCl2 is halved from 0.080 mol dm to 0.040 mol dm the
−4 −3 −1 −4 −3
initial rate of reaction halves from 1.92 × 10 mol dm min to 0.96 × 10 mol dm
−1
min . [1] This means the order with respect to HgCl2 is 1. [1]
2− 2
b) i) The rate equation is: rate = k[(COO)2 ] [HgCl2] [1]
−4 2
ii) Using the first set of results gives 0.48 × 10 = k(0.020) × 0.080 [1]
−4 2 6 −2 −1
Therefore, k = 0.48 × 10 /(0.020) × 0.080 = 1.5 dm mol s [1]
−
16 a) The order with respect to Br can be obtained from the second and third sets of results.
− −3 −3
When the Br concentration is doubled from 0.1 mol dm to 0.2 mol dm the rate doubles
−3 −3 −1 −3 −3 −1
from 1.64 × 10 mol dm s to 3.28 × 10 mol dm s . [1] This means that the order with
−
respect to Br is 1. [1]
−
From the first and third sets of results, it can be seen that when the BrO3 concentration is
doubled, the rate doubles. [1]
−
Therefore, the order with respect to BrO3 is 1. [1]
+
From the second and fourth sets of results, it can be seen that when the concentration of H
is doubled, the rate increases four-fold. [1]
+
Therefore, the order with respect to H is 2. [1]

The rate equation for the reaction is:

− − + 2
rate = k[Br ][BrO3 ][H ] [1]

b) Using the rate equation and substituting the values from the first set of results:
−3 2
1.64 × 10 = k(0.1)(0.2)(0.1) [1]
−3 2 –3 –4 9 −3 −1
k = 1.64 × 10 /(0.1)(0.2)(0.1) = 1.64 × 10 /2 × 10 = 8.2 dm mol s [1]
2 –2 –3 –1
c) The initial rate = 8.2 × (0.25)(0.25)(0.25) = 3.2 × 10 mol dm s [1]
– –
17 a) i) CH3CH2CH2CH2Br + OH → CH3CH2CH2CH2OH + Br [1]
ii) Using results from experiments 1 and 3, when the concentration of hydroxide ions
1 1
is reduced by the rate is also reduced by . [1]
4 4
–
Therefore, the order with respect to OH is 1. [1]

Using results from experiments 1 and 2, when the concentration of hydroxide ions
is doubled and that of 1-bromobutane is tripled the rate increases six-fold. [1]
–
Since the order with respect to OH is 1, this would double the rate and the
1-bromobutane must triple it. [1]

© Hodder & Stoughton Limited 2015

1 How fast? Rates of reaction Answers

Therefore, the order with respect to 1-bromobutane must also be 1 [1].

–
The rate equation is: rate = k[CH3CH2CH2CH2Br][OH ] [1]
– –
b) i) CH3C(CH3)(Br)CH3 + OH → CH3C(CH3)(OH)CH3 + Br [1]
ii) Using results from experiments 1 and 3, when the concentration of hydroxide ions

is reduced by 1 the rate is unchanged. [1]

4
–
Therefore, the order with respect to OH is 0. [1]

Using results from experiments 1 and 2, when the concentration of hydroxide ions
is doubled and that of 2-bromo-2-methylpropane is tripled, the rate increases
three-fold. [1]
–
Since the order with respect to OH is 0 this would have no effect on the rate, so the
2-bromo-2-methylpropane must increase it three-fold. [1]

Therefore, the order with respect to 2-bromo-2-methylpropane must also be 1. [1]

The rate equation is: rate = k[CH3C(CH3)(Br)CH3] [1]

c) i) Nucleophilic substitution
–
ii) In experiment 1, both the OH and the 1-bromobutane are involved in the rate-
determining step [1] but in experiment 2 only 2-bromo-2-methylpropane is involved. [1]
iii) Using the first set of results in experiment 1:
0.300 = k(0.0100)(0.0100)
3 –1 –1
k = 3000 dm mol s [1]
Using the first set of results in experiment 2:
7.5 = k(0.0100)(0.0100)
–1
k = 75 000 s [1]
Therefore, the rate constant in the second experiment is 25 times greater.
(There is no need to work out the values of k as shown above, since it can be seen that
the rate in experiment 1 (7.500) is 25 times greater than that of experiment 2 (0.300).
18 First, a graph of concentration against time must be drawn. [1]
The graph is then used to establish that the reaction has a constant half-life. [1]
The graph should show, for example, that the time taken for the concentration of B to be
−3 −3
reduced from 0.800 mol dm to 0.400 mol dm is 62 s and for the concentration of B to fall
−3 −3
from 0.600 mol dm to 0.300 mol dm is also 62 s. [1]
(for this or equivalent data)
This shows that the reaction must be first order. [1]
19 a) This can be solved by plotting a graph of concentration against time. [1]
The graph is a straight line. [1] This indicates that the reaction is zero order with respect
to X. [1] In practice, the regular drop in concentration of X every 30 s can be seen directly in

© Hodder & Stoughton Limited 2015

1 How fast? Rates of reaction Answers

the table of data. This tells you that the graph will be a straight line and the reaction is
zero order with respect to X.
b) Plot a concentration–time graph. [1]
−3
It takes 58 s (strictly 58.3 s) for the concentration of Y to fall from 1.00 mol dm to
−3 −3
0.50 mol dm , [1] and 58 s for the concentration of Y to fall from 0.70 mol dm to
−3
0.35 mol dm . [1] (for this or equivalent data)
This also shows that the reaction must be first order with respect to Y. [1]
(Whenever a value is deduced from a graph, examiners allow some leeway in the value
quoted because it is difficult to read a graph precisely.)
0 1
c) i) rate = k[X] [Y] = k[Y] [1]
ii) The initial rate of the reaction is obtained by drawing a tangent to the graph at
time = 0s [1] and measuring its gradient.
−3 −1
The initial rate is 0.012 mol dm s . [1] + [1](units)
iii) 0.012 = k(1.00)
k = 0.012 s–1
20 a) The results show clearly that the reaction is first order, since it is possible to see that the
half-life is constant. [1] + [1] for data showing half-lives

–3
Concentration of H2O2/mol dm Half-life

0.1 5210

0.08 6889 – 1678 = 5210

0.06 9052 – 3841 = 5210

–4 −1
b) k = ln2/t½ = 0.693/5210 = 1.33 × 10 min . [1] + [1]units
21 a) Plot a concentration–time graph. [1]
Measuring half-lives from the graph [1], it can be seen that it takes approximately 72 min for
−3 −3
the concentration of SO2Cl2 to fall from 1.00 mol dm to 0.500 mol dm and 72 min for the
−3 −3
concentration to fall from 0.75 mol dm to 0.375 mol dm . [1] (for this or equivalent data)
Therefore, the reaction is first order. [1]
b) The rate constant requires a rate of reaction to be established for a known concentration.
−3
Taking the initial concentration of 1.00 mol dm , a tangent can be drawn to the graph. [1]
Its gradient gives the initial rate of reaction. [1]
−3 −1
The initial rate of reaction is 0.0096 mol dm min . [1]
So, 0.0096 = k[1]
−1
Therefore, k = 0.0096 min [1]units
−1
b) k = ln2/t½ = 0.693/72 = 0.0096 min [1]
This provides an easy check that a value obtained via a graph is correct.

© Hodder & Stoughton Limited 2015

1 How fast? Rates of reaction Answers

22 a) The graph [1] should show that the concentration of ammonia falls linearly with time,
hence zero order. [1]
b) 2NH3(g) → N2(g) + 3H2(g) [1]
The rate with respect to ammonia is zero. [1]
This is an unusual result which occasionally is possible when a gas decomposes on
the surface of a catalyst. So the rate depends only on the value of k, i.e. the rate
equation is rate = k. [1]
–3
c) The units of k will be the same as the units of the rate (e.g. mol dm min). [1]
23 The rate equation, rate = k[NO2(g)][F2(g)] shows that 1 mol of NO2 and 1 mol of F2 are
involved in the rate-determining step. [1]
Overall the mechanism must result in the balanced equation,
2NO2(g) + F2(g) → 2NO2F(g) being obtained. So a possible mechanism is:
NO2(g) + F2(g) → NO(g) + OF2(g) slow [1]
NO(g) + OF2(g) + NO2(g) → 2NO2F(g) fast [1]
When these equations are added together, the NO(g) and OF2(g) cancel and the overall
equation, 2NO2(g) + F2(g) → 2NO2F(g) is obtained.
It should be emphasised that you can suggest any first step involving NO2(g) + F2(g),
as long as the second step, when added to it, produces the overall equation.
For example, an alternative is
NO2(g) + F2(g) → NO2F(g) + F(g) slow [1]
NO2(g) + F(g) → NO2F(g) fast [1]
24 The equation for the reaction is:
2H2O2(aq) → 2H2O(g) + O2(g) [1]
– –
The rate equation is rate = k[H2O2(aq)][I (aq)] so 1 mol of H2O2 and 1 mol of I are involved
in the rate-determining step. [1]
This suggests a mechanism:
– –
H2O2 + I → HOI + OH slow [1]
– –
H2O2 + HOI + OH → 2H2O + O2 + I fast [1]
Another alternative is
– –
H2O2 + I → H2O + + IO slow [1]
– –
H2O2 + IO → H2O + O2 + I fast [1]
Notice that, in both steps, the overall charge has been preserved, which is always
–
an essential for an equation. Also in the second step, the I is regenerated, which is
necessary for it to be a catalyst.
25 a) The gas is likely to be N2. [1]
b) 2NO(g) + 2H2(g) → N2(g) + 2H2O(l) [1]

© Hodder & Stoughton Limited 2015

1 How fast? Rates of reaction Answers

2
c) As the rate equation is: rate = k[H2][NO] the rate-determining step must involve
1 mol of H2 and 2 mol of NO. [1]
This suggests a mechanism:
H2 + 2NO → 2NOH slow [1]
2NOH + H2 → N2 + 2H2O fast [1]
As before, there may be other valid suggestions which would gain credit in an exam.
For example:
H2 + 2NO → N2 + H2O + O slow
O + H2 → H2O fast
26 a) The rate equations are obtained from the rate-determining steps.
For mechanism X:
2
rate = k[O2][NO] [1]
For mechanism Y:
rate = k[NO][O2] [1]
For mechanism Z:
rate = k[O2] [1]
b) i) From the first two results, it can be seen that reducing the pressure from 50 kPa
to 20 kPa (a factor of 2/5) while keeping the pressure of NO constant reduces
−1 −1
the rate of reaction from 0.100 kPa h to 0.040 kPa h . [1]
Since this is also a factor of 2/5, it means that the order of reaction with respect to
O2 is 1. [1]
Using the second and third results, the initial pressure of O2 is increased three-fold
from 20 kPa to 60 kPa, while the initial pressure of NO is doubled from 50 kPa to
100 kPa. Since the order of reaction with respect to O2 is 1, the three-fold increase in
−1
pressure will triple the rate, i.e. it will increase from 0.040 to 3 × 0.040 = 0.120 kPa h .
−1
However, the rate has actually increased to 0.48 kPa h , which is a further four-fold
increase. [1]
This must be because of doubling the concentration of the NO. This indicates that the
order of reaction with respect to NO is 2. [1]
ii) Therefore, the overall rate equation is:
2
rate = k[O2][NO] [1]
This indicates that mechanism X is correct. [1]
–Ea/RT
27 k = Ae
5 –Ea/8.314 × 650
0.0450 = 3.05 × 10 × e
5
ln(0.0450) = ln(3.05 × 10 ) + (–Ea/5401.1) [1]
–3.101 = 12.628 + (–Ea/5401.1) [1]
–1
Ea = 15.729 × 5401.1 = 84 954J = 84.95 kJ mol [1]

© Hodder & Stoughton Limited 2015

1 How fast? Rates of reaction Answers

–Ea/RT
28 k = Ae
So lnk = lnA – Ea/RT [1]
T = 600 + 273 = 873 K [1]
In joules activation enthalpy is 96 000 J
ln(0.0082) = lnA – 96 000/(8.314 × 873)
lnA = –4.80 + 13.23 = 8.43 [1]
–1
A = 4582 min [1] + [1] for units
–Ea/RT
29 a) k = Ae
So lnk = lnA – Ea/RT [1]
–4
At 400 K, ln(3.2 × 10 ) = lnA – Ea/(8.314 × 400) [1]
–3
At 500 K, ln(8.4 × 10 ) = lnA – Ea/(8.314 × 500) [1]
Subtracting these two equations, [1]
Alternatively:
–4
At 400 K lnA = ln(3.2 × 10 ) + Ea/(8.314 × 400)
–3
At 500 K lnA = ln(8.4 × 10 ) + Ea/(8.314 × 500)
–4 –3
Hence, ln(3.2 × 10 ) + Ea/(8.314 × 400) = ln(8.4 × 10 ) + Ea/(8.314 × 500) [1]
–4 –3
ln(3.2 × 10 ) – ln(8.4 × 10 ) = –Ea/(8.314 × 400) – (–Ea/(8.314 × 500)
(–8.047) – (4.780) = –Ea(0.000 301) + Ea(0.000 241)
–3.267 = –0.000 0601Ea [1]
–1
Ea = 3.267/0.0000601 = 54 324 J = 54.3 kJ mol [1]
29 b) Substituting the values into the equation at 400 K
–4
ln(3.2 × 10 ) = lnA – 54 324/(8.314 × 400) [1]
ln A = –8.047 + 0.0163 = –8.031 [1]
–4 –1
A = 3.25 × 10 s [1] + [1]units
30 Complete the table of results to give values of 1/T and lnk
+6 –2 –1 –1
Temperature/K k/dm mol s lnk 1/T/K

500 0.128 –2.056 0.002 00

510 0.277 –1.284 0.001 96

515 0.367 –1.002 0.001 94

520 0.579 -0.546 0.001 92

525 0.829 -0.188 0.001 90

[1] for lnk; [1] for 1/T; [1] for consistent significant figs.
Plot a graph of lnk (y-axis) v 1/T (x-axis). [2] + [1] for line of best fit.
This gives a gradient of around –18 650 which equals Ea/R [1] for gradient

© Hodder & Stoughton Limited 2015

1 How fast? Rates of reaction Answers

–1
Ea = –18 650 × 8.314 = 155 064 J or 155 kJ mol [1]
Your graph will probably not give an x-axis value of zero, so substitution is required to
determine A.
15 –1
Depending which data you use, this should give an answer of around 2.0 × 10 s
31 a) Complete the table of results to give values of 1/T and lnk.

5 3 –1 –1 –1
Temperature T/°C k × 10 /dm mol s lnk 1/T/K

400 4.130 12.93 0.0025

450 42.05 15.25 0.0022

500 186.5 16.74 0.0020

550 1498 18.82 0.0018

600 5213 20.07 0.0017

[1] for lnk; [1] for 1/T; [1] for consistent significant figs.
Plot a graph of lnk (y-axis) v 1/T (x-axis). [2] + [1] for line of best fit
This gives a gradient of around –9091, which equals Ea/R [1] for gradient
–1
Ea = –9091 × 8.314 = 75 582 J or approx. 76 kJ mol [1]
b)

–1
Activation enthalpy of the reverse reaction will be 76 – 25.9 = 50.1 kJ mol [1]

Challenge
3
32 a) The volume of alcohol in the beer is 568 × (4.1/100) = 23.29 cm [1]
The mass of the alcohol = volume × density
= 23.29 × 0.789 = 18.37 g [1]
–1
Molar mass of ethanol = 46 g mol
Therefore, the amount, in moles of ethanol = 0.40 mol [1]
b) i) Solving this graphically, by plotting a graph of amount of moles against time,
gives a constant half-life. Therefore, the reaction is first order. [1]
ii) Note from the table of results that the time taken to reduce the amount in mol
from 0.34 mol to 0.17 mol is 4 min. This is easier than using the graph. But either
way, gives the value for the half-life of 4 minutes. [1]

© Hodder & Stoughton Limited 2015

1 How fast? Rates of reaction Answers

–1
iii) The gradient at t = 0, gives the initial rate. In this case it is 0.067 mol min [1]
Therefore, using the initial amount in mol, the rate equation is
0.067 = k[0.4]
–1
and k = 0.17 min [1]
(You could establish the value of k by noting that kt1/2 = ln2 and therefore
–1
k = 0.693/4 = 0.17 min .)
c) The alcohol transferred to the body fluids can be calculated from the amount remaining in
the stomach. The concentration will be (0.40 – x)/40 where x is the amount in mol left in the
stomach, e.g. for the second measurement after 1 min the concentration in the blood is
–3
(0.40 – 0.34)/40 = 0.0015 mol dm .
The table is therefore:
Conc of ethanol/
–3 0.00 0.0015 0.0028 0.0040 0.0058 0.0081 0.0097 0.0098
mol dm
Time/min 0 1 2 3 5 10 20 30
[1]
–1 –3 –1
d) i) The rate constant is given in units of hour so in g dm min it is 0.2/60. [1]
–1
The molar mass of ethanol is 46 g mol
–5 –3 –1
So the rate constant is (0.2/60)/46 = 7.25 × 10 mol dm min [1]
ii) Every minute the concentration of ethanol in the stomach is reduced by
–5 –3
7.25 × 10 mol dm . As the reaction is zero order, this is a constant removal and,
therefore, the ethanol remaining in the body fluids is the concentration listed in the
–5
table above minus (7.25 × 10 )t where t is the time in minutes.
–5 –3
After 3 minutes the concentration is 0.0040 – (3 × 7.25 × 10 ) = 0.0038 mol dm .

Conc of ethanol/ 0 0.0014 0.0026 0.0037 0.0053 0.0073 0.0082 0.0076

–3 (3) (1) (8) (8) (8) (7)
mol dm
Time/min 0 1 2 3 5 10 20 30
[2]
e) Plotting the graph of concentration of ethanol v time gives something similar to the curve
below, depending on the accuracy with which the calculations are done.
The answer is therefore in the region of 20 min. [1] + [1]for the graph
–3
f) Taking the concentration as being a maximum at 0.0082 mol dm
3 –3
This is 0.00082 mol per 100 cm of blood or 0.000 82 × 46 = 0.038 g dm [1]
3
which is 38 mg per 100 cm of blood. If all the assumptions in this calculation are accepted it
would be legal to drive. But it should be noted that it does not mean that it is wise to drive.

© Hodder & Stoughton Limited 2015