School of Chemistry and Physics, University of KwaZulu-Natal, Westville Campus, Durban

Chemical Reactivity CHEM120

Tutorial 7 (Kinetics) 11 and 13 September 2013

1. For a first order reaction, the following

three graphs for experiments done at two
different temperatures were obtained.
(a) Which two lines represent experiments
done at the same temperature? What
accounts for the difference in these two
lines? In what way are they the same?
(b) Which two lines represent experiments
done with the same starting concentration
but at different temperatures? Which line
probably represents the lower temperature?
How do you know?
For a first-order reaction, a plot of ln[A] vs. time is linear, as shown in the diagram. The
slope is k, and the intercept is [A]0. According to the Arrhenius equation, k increases with
increasing temperature.
(a) Lines 1 and 2 have the same slope, and thus the same rate constant, k. These experiments
are done at the same temperature. The y-intercepts of the two lines are different; the
experiments had different initial concentrations of A.
(b) Lines 2 and 3 have the same y-intercept and thus the same starting concentration of A.
The slopes of the two lines are different, so their rate constants are different and they occur at
different temperatures. Line 3, with the smaller slope and k value will occur at the lower
temperature.
2. (a) Consider the combustion of H2(g): 2 H2(g) + O2(g) 2 H2O(g).
If hydrogen is burning at the rate of 0.85 mol/s, what is the rate of consumption of oxygen?
What is the rate of formation of water vapour?
(b) The reaction 2 NO(g) + Cl2(g) 2 NOCl(g) is carried out in a closed vessel. If the partial
pressure of NO is decreasing at a rate of 23 Pa/min, what is the rate of change of the total
pressure of the vessel.

Relate the rate of disappearance of reactants to the rate of appearance of products. Use this

relationship to calculate desired quantities.

(a)

[H2O]/2t = [H2]/2t = [O2]/t

H2 is burning, [H2]/t = 0.85 mol/s

O2 is consumed, [O2]/t = [H2]/2t = 0.85 mol/s/2 = 0.43 mol/s
H2O is produced, +[H2O]/t = [H2]/t = 0.85 mol/s
(b)
The change in total pressure is the sum of the changes of each partial pressure. NO
and Cl2 are disappearing and NOCl is appearing.
PNO/t = 23 Pa/min
PCl 2 / t PNO / 2t 11.5 Pa/min

+PNOCl/t = PNO/t = +23 Pa/min

PT/t = 23 Pa/min 11.5 Pa/min + 23 Pa/min = 11.5 = 12 Pa/min
3. Consider the reaction of peroxydisulfate ion (S2O82-) with iodide ion (I-) in aqueous
solution:
S2O82- (aq) + 3 I-(aq) 2 SO42-(aq) + I3- (aq).
At a particular temperature the rate of disappearance of S2O82- varies with reactant
concentrations in the following manner:
Experiment
1
2
3
4

[S2O82-] (M)
0.018
0.027
0.036
0.050

[I-] (M)
0.036
0.036
0.054
0.072

Initial Rate (M/s)

2.6 x 10-6
3.9 x 10-6
7.8 x 10-6
1.4 x 10-5

(a) Determine the rate law for the equation.

(b) What is the average value of the rate constant for the disappearance of S2O82- based on the
four sets of data?
(c)How is the rate of disappearance of S2O82- related to the rate of disappearance of I-?
(d) What is the rate of disappearance of I- when [S2O82-] = 0.015 M and [I-] = 0.040 M?

(a) Increasing [S2O8 ] by a factor of 1.5 while holding [I ] constant increases the rate by a
2

factor of 1.5 (Experiments 1 and 2). Doubling [S2O8 ] and increasing [I ] by a factor of 1.5
triples the rate (2 1.5 = 3, experiments 1 and 3). Thus the reaction is first order in both
2

[S2O8 ] and [I ]; rate = k [S2O8 ] [I ].

2

(b) k = rate/[S2O8 ] [I ]
6

k1 = 2.6 10

M/s/(0.018 M)(0.036 M)

= 4.01 10 = 4.0 10
3

1 1

k2 = 3.9 10 /(0.027)(0.036) = 4.01 10 = 4.01 10 = 4.0 10

1 1

k3 = 7.8 10 /(0.036)(0.054) = 4.01 10 = 4.01 10 = 4.0 10

k4 = 1.4 10 /(0.050)(0.072) = 3.89 10 = 3.9 10
3

kavg = 3.98 10 = 4.0 10

1 1

1 1

1 1

(c) [S2O8 ]/t = [I ]/3t; the rate of disappearance of S2O8

disappearance of I .

is one-third the rate of

(d) Note that the data are given in terms of disappearance of S2O8 .
3[S 2O82 ]
[I ]

3(3.98 10 3 M 1s 1 ) (0.015 M)(0.040 M) 7.2 10 6

t
t

M/s

4. Sucrose (C12H22O11), which is commonly known as table sugar, reacts in dilute acid
solutions to form two simpler sugars, glucose and fructose, both of which have the formula
C6H12O6. At 23C and in 0.5 M HCl, the following data were obtained for the disappearance of
sucrose:
Time (min)
0
39
80
140
210

[C12H22O11] (M)
0.316
0.274
0.238
0.190
0.146

(a) Is the reaction first order or second order with respect to [C12H22O11]?
(b) What is the value of the rate constant?
(a)

Make both first- and second-order plots to see which is linear.

time(min)

[C12H22O11](M)

ln[C12H22O11]

1/[C12H22O11]

0.316

1.152

3.16

39

0.274

1.295

3.65

80

0.238

1.435

4.20

140

0.190

1.661

5.26

210

0.146

1.924

6.85

The plot of ln [C12H22O11] is linear, so the reaction is first order in C12H22O11.

(b)

k = slope = [1.924 (1.295)] / 171 min = 3.68 10 min

3

(The slope of the best-fit line is 3.67 10 min .)

5. The gas-phase reaction Cl(g) + HBr(g) HCl(g) + Br(g) has an overall enthalpy change of
-66 kJ. The activation energy for the reaction is 7kJ.
(a) Sketch the energy profile for the reaction and label Ea and E.
(b) What is the activation energy for the reverse reaction?
Use the definitions of activation energy (Emax Ereact) and E (Eprod Ereact) to sketch the
graph and calculate Ea for the reverse reaction.
(a)
Cl(g) + HBr(g)

HCl (g) + Br(g)

(b) Ea(reverse) = 73 kJ

6. The following mechanism has been proposed for the gas-phase reaction of H2 and ICl:
H2(g) + ICl(g) HI(g) + HCl(g)
HI(g) + ICl(g) I2(g) + HCl(g).
(a) Write the balanced equation for the overall reaction.
(b) Identify any intermediates in the mechanism.
(c) Write rate laws for each elementary reaction in the mechanism.
(d) If the first step is slow and the second one is fast, what rate law do you expect to be
observed for the overall reaction?
(a) H2 (g) ICl(g) HI(g) HCl(g)
HI(g) ICl(g) I 2 (g) HCl(g)
H 2 (g) 2ICl(g) I 2 (g) 2HCl(g)

(b) Intermediates are species produced and consumed during a reaction. HI is the
intermediate.
(c) Both reactions are bimolecular. Thus,the rate law is first order in each reactant and second
order overall:
First step: rate = k1[H2][ICl]

Second step: rate = k2[HI][ICl]

(d) The slow step determines the rate law for the overall reaction. If the first step is slow, the
observed rate law is: rate = k[H2][ICl].
7. NO catalyses the decomposition of N2O, possibly by the following mechanism:
NO(g) + N2O(g) N2(g) + NO2(g)
2 NO2(g) 2 NO(g) + O2(g)
(a) What is the chemical equation for the overall reaction?
(b) Why is NO considered a catalyst and not an intermediate?
(c) If experiments show that, during the decomposition of N2O, NO2 does not accumulate in
measurable quantities, does this rule out the proposed mechanism? Explain.
(a)

2[NO(g) N2 O(g) N2 (g) NO 2 (g)]

2NO 2 (g) 2NO(g) O 2 (g)
2N 2 O(g) 2N 2 (g) O 2 (g)

(b) An intermediate is produced and then consumed during the course of the reaction. A
catalyst is consumed and then reproduced. In other words, the catalyst is present when the
reaction sequence begins and after the last step is completed. In this reaction, NO is the
catalyst and NO2 is an intermediate.
(c) No. The proposed mechanism cannot be ruled out, based on the behavior of NO2. NO2
functions as an intermediate; it is produced and then consumed during the reaction. That there
is no measurable build-up of NO2 indicates the first step is slow relative to the second; as
soon as NO2 is produced by the slow first step, it is consumed by the faster second step.