University of Oxford

Department of Chemistry

1st Year Physical Chemistry Tutorials

1.4 Chemical Kinetics

Suggested texts:
Atkins, De Paula & Keeler, Physical Chemistry, 11th ed.
Vallance, An Introduction to Chemical Kinetics
Pilling & Seakins, Reaction Kinetics, OUP
Cox, Modern Liquid Kinetics, OUP Primer

Relevant lecture courses:

Chemical Kinetics – HT Year 1

You may want to cover the following points in your revision notes:

a) Rates of reaction: Order of reaction, molecularity, mechanisms, rate laws, rate

constants (and units of).

b) Experimental techniques for measuring reaction rates.

c) Collision theory: its use and failings.

d) The steady-state approximation: its validity and use in simplifying complex

rate laws.

e) Specific mechanisms: e.g. Lindemann theory for unimolecular reactions, Michaelis-

Menten equation for enzyme kinetics.

f ) Temperature dependence of rate constants: the Arrhenius equation, its in-

terpretation and implications.

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A. Discussion questions

1. Explain the terms order, overall order and molecularity as applied to the kinetics
of a chemical reaction.

2. (a) Explain the key requirements for an experiment designed to measure the rate
of a chemical reaction.
(b) Outline experimental methods to determine the rate of a chemical reaction
occuring on a timescale of:
i. seconds to minutes
ii. milliseconds or faster.

3. In the gas phase the reaction H2 + Br2 −−→ 2 HBr has the rate law:

3
ka [H2 ][Br2 ] 2
ν=
[Br2 ] + kb [HBr]

If the concentrations are measured in molecules cm−3 and time in seconds, what
are the units of ka and kb ?
k
4. For the elementary second order reaction O + O3 −−1→ 2 O2 , write down expressions
for the rate of change of each species in terms of the rate constant and concentrations
of the reactants.
d[A]
5. For the reaction A → products, where dt
= −k[A]n , derive expressions for:

(a) the integrated rate law of the reaction when it is:

i. first-order with respect to A (n = 1),
ii. second-order with respect to A (n = 2),
and derive a general integrated rate law when n ≥ 2.
(b) the half-life of A when the reaction is:
i. first-order with respect to A (n = 1),
ii. second-order with respect to A (n = 2),
and derive a general expression for half-life when n ≥ 2.

6. Explain what is meant by the steady-state approximation in chemical kinetics. Why

is it useful and under what conditions is it valid?

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7. According to simple collision theory, the rate law for a bimolecular reaction is given
by:
 
d[A] ZAB Ea
− = k[A][B] = P exp −
dt NAv RT

(a) Outline the origin of this equation and explain the meaning of P , ZAB and the
exponential term. NAv is Avogadro’s constant.
(b) Show that the rate constant can be written as:
  12  
8kB T Ea
k = Pσ NAv exp −
πµ RT

defining µ and σ.

8. For the general enzyme-substrate reaction:

k1 k
−−
E+S)−*
2
− ES −−→ P + E
k−1

derive the Michaelis-Menten equation, which describes the rate of an enzyme-

catalysed reaction:

dP k2 [E]0 [S]
= k[E]0 =
dt KM + [S]

defining KM in terms of the elementary reaction rate constants k1 , k−1 and k2 .

([E]0 = [E] + [ES] is the total enzyme concentration.)
The rate constant k as a function of substrate concentration [S] is given below:

[S] / 10−6 m 2 5 10 20
k /s−1 3.5 5.3 6.5 7.3

Using an appropriate graph determine k2 and KM .

9. Outline the Lindemann mechanism for the unimolecular decomposition of azomethane:

H3 CNNCH3 −−→ N2 + C2 H6

Under what conditions would this reaction show second-order kinetics?

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B. Numerical problems

1. The Arrhenius equation:

 
Ea
k = A exp −
RT

yields the temperature dependence of the reaction rate constant.

(a) By comparison with simple collision theory determine the expression for the
pre-exponential factor, A, and state its temperature dependence.
(b) Calculate the % change in A when the temperature increases from 20 to 30 °C.
(c) Calculate the % change in k when the temperature increases from 20 to 30 °C.
Assume an activation energy of 100 kJ mol−1 (why is this a reasonable value?).
(d) Comment on the relative importance of the pre-exponential factor’s tempera-
ture dependence.

2. (a) Why does the rate of most chemical reactions increase as the temperature is
raised?
(b) The rate constant for the decomposition of HI into H2 and I2 shows the fol-
lowing temperature dependence:

T /K 550 625 700 830

k /dm3 mol−1 s−1 3.13 × 10−6 7.90 × 10−5 3.20 × 10−3 0.10

Determine the activation energy and the pre-exponential factor for the reac-
tion.
(c) What is the overall reaction order for the decomposition? What justification
does the information in the table above give for the form of the rate equation?
(d) The reaction between hydrogen and iodine to form hydrogen iodide is believed
to proceed via a chain mechanism. Using this reaction as an example, explain
the meanings of the terms initiation, propagation and termination.
(e) For the reaction between nitric oxide and oxygen:
2 NO + O2 −−→ 2 NO2
the rate law is k[NO]2 [O2 ] and the rate of reaction is found to fall as tempera-
ture is increased. Propose a mechanism for the reaction that is consistent with
this rate law and temperature dependence.

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3. For the elementary gas phase reaction H + C2 H4 −−→ C2 H5 the second-order rate
constant varies with temperature in the following way:

T /K 198 298 400 511 604

1012 k /cm3 molecule−1 s−1 0.20 1.13 2.83 4.27 7.69

(a) Determine the activation energy and the pre-exponential factor for the reac-
tion.
(b) Estimate σ for the reaction at 400 K.
(c) Compare the value obtained with an estimate of 4.0 × 10−19 m2 for the collision
cross section.

(Take the atomic masses of H and C to be 1.0 amu and 12 amu respectively.)

4. The gas phase reaction of fluorine atoms with bromine follows the stoichiometric
equation:

F + Br2 −−→ FBr + Br

For an initial fluorine atom concentration of [F] = 4 × 10−9 mol dm−3 the following
concentrations of Br2 were observed as a function of time at 298 K:

t /ms 0 0.7 1.3 2.7 3.9

[Br2 ] / 10−9 mol dm−3 0.100 0.066 0.048 0.022 0.011

(a) Show that the reaction is first-order with respect to [Br2 ].

(b) Given that the reaction is also first-order with respect to fluorine atoms, cal-
culate the overall second-order rate constant.

5. The reaction Cl2 + CO −−→ COCl2 is believed to proceed via the following mecha-
nism:

−−
Cl2 )−*
− 2 Cl
Cl + CO −)−
−*
− COCl
COCl + Cl2 −−→ COCl2 + Cl

Assuming that the first two steps are much faster than the third step (i.e. pre-
equilibrium conditions), deduce a rate law for the formation of COCl2 .

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6. The following mechanism has been proposed for the thermal decomposition of
NO2 Cl:

k
NO2 Cl −−1→ NO2 + Cl
k−1
NO2 + Cl −−→ NO2 Cl
k
NO2 Cl + Cl −−2→ NO2 + Cl2

(a) Derive an expression for the rate of decomposition of NO2 Cl in terms of the
concentrations of NO2 Cl and NO2 and the three rate constants k1 , k−1 and k2 .
(b) Discuss the conditions under which the overall reaction will exhibit kinetics
that are:
i. first-order with respect to NO2 Cl,
ii. second-order with respect to NO2 Cl.
(c) How would you expect the reaction rate to vary with temperature in b) i.?

7. A possible ion-molecule reaction mechanism for synthesis of ammonia in interstellar

gas clouds is shown below:

N+ + H 2 −−→ NH+ + H k1
NH+ + H2 −−→ NH2 + + H k2
NH2 + + H2 −−→ NH3 + + H k3
NH3 + + H2 −−→ NH4 + + H k4
NH4 + + e− −−→ NH3 + H k5
NH4 + + e− −−→ NH2 + 2 H k6

(a) Use the steady-state approximation to derive equations for the concentrations
of the intermediates NH+ , NH2 + , NH3 + and NH4 + in terms of the reactant
concentrations [N+ ], [H2 ] and [e – ]. Treat the electrons as you would any other
reactant.
(b) Show that the overall rate of production of NH3 is given by

d[NH3 ] k1 k5
= [N+ ][H2 ]
dt k5 + k6

(c) What is the origin of the activation energy in chemical reactions?

(d) The rates of many ion-molecule reactions show virtually no dependence on
temperature.

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 i. What does this imply about their activation energy?
ii. What relevance does this have to reactions occurring in the interstellar
medium?
k k
8. Consider two sequential first-order reactions: A −−1→ B −−2→ C

(a) Write down expressions for the rate of change of each species and derive the
integrated rate expression for [A].
(b) Show that:

k1 [A]0  −k1 t
− e−k2 t

[B](t) = e
k2 − k1

and derive an expression for [C](t).

(c) Under conditions k2  k1 and k2 t  1 compare your expressions for [B] and
[C] with those obtained by assuming B is in steady-state. Comment on the
result.

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Numerical answers

A. Discussion questions B. Numerical problems

8. k2 = 8.3 s−1 1. (b) +1.7 %

KM = 2.75 µm (c) +294 %

2. (b) A = 9.6 × 107 dm3 mol−1 s−1

Ea = 143 kJ mol−1

3. (a) A = 3.8 × 10−11 cm3 mol−1 s−1

Ea = 8.67 kJ mol−1

(b) σ = 1.28 A
2

(c) P = 0.032

4. (b) k = 1.4 × 1011 dm3 mol−1 s−1