870 20 Chemical kinetics

CHAPTER 20 Chemical kinetics

TOPIC 20A The rates of chemical reactions

Discussion question
20A.1 Summarize the characteristic of zeroth-order, first-order, second-
order, and pseudofirst-order reactions.
20A.2 When can a reaction order not be ascribed?
20A.3 What are the advantages of ascribing an order to a reaction?
20A.4 Summarize the experimental procedures that can be used to monitor
the composition of a reaction system.

Exercises
20A.1(a) Predict how the total pressure varies during the gas-phase reaction
2 ICl(g) + H2(g) → I2(g) + 2 HCl(g) in a constant-volume container.
20A.1(b) Predict how the total pressure varies during the gas-phase reaction
N2(g) + 3 H2(g) → 2 NH3(g) in a constant-volume container.
20A.2(a) The rate of the reaction A + 2 B → 3 C + D was reported as
2.7 mol dm−3 s−1. State the rates of formation and consumption of the
participants.
20A.2(b) The rate of the reaction A + 3 B → C + 2 D was reported as
2.7 mol dm−3 s−1. State the rates of formation and consumption of the
participants.
20A.3(a) The rate of formation of C in the reaction 2 A + B → 2 C + 3 D
is 2.7 mol dm−3 s−1. State the reaction rate, and the rates of formation or
consumption of A, B, and D.
20A.3(b) The rate of consumption of B in the reaction A + 3 B → C + 2 D
is 2.7 mol dm−3 s−1. State the reaction rate, and the rates of formation or
consumption of A, C, and D.
20A.4(a) The rate law for the reaction in Exercise 20A.2(a) was found to be
v = kr[A][B]. What are the units of kr when the concentrations are in moles per
cubic decimetre? Express the rate law in terms of the rates of formation and
consumption of (i) A, (ii) C.
20A.4(b) The rate law for the reaction in Exercise 20A.2(b) was found to be
v = kr[A][B]2. What are the units of kr when the concentrations are in moles
per cubic decimetre? Express the rate law in terms of the rates of formation
and consumption of (i) A, (ii) C.
20A.5(a) The rate law for the reaction in Exercise 20A.3(a) was reported as
d[C]/dt = kr[A][B][C]. Express the rate law in terms of the reaction rate v;
what are the units for kr in each case when the concentrations are in moles per
cubic decimetre?
20A.5(b) The rate law for the reaction in Exercise 20A.3(b) was reported as
d[C]/dt = kr[A][B][C]−1. Express the rate law in terms of the reaction rate v;
what are the units for kr in each case when the concentrations are in moles per
cubic decimetre?
20A.6(a) If the rate laws are expressed with (i) concentrations in moles per
cubic decimetre, (ii) pressures in kilopascals, what are the units of the second-
order and third-order rate constants?
20A.6(b) If the rate laws are expressed with (i) concentrations in molecules per
cubic metre, (ii) pressures in pascals, what are the units of the second-order
and third-order rate constants?

Problems
20A.1 At 400 K, the rate of decomposition of a gaseous compound initially [complex]/(mmol dm−3) 8.01 9.22 12.11
at a pressure of 12.6 kPa, was 9.71 Pa s −1 when 10.0 per cent had reacted (i) 125 144 190
v0 /(mol dm−3 s−1)
and 7.67 Pa s −1 when 20.0 per cent had reacted. Determine the order of the
reaction. (ii) 640 730 960

20A.2 The following initial-rate data were obtained on the rate of binding
20A.4 The following kinetic data (v0 is the initial rate) were obtained for the
of glucose with the enzyme hexokinase present at a concentration of
reaction 2 ICl(g) + H2(g) → I2(g) + 2 HCl(g):
1.34 mmol dm−3. What is (a) the order of reaction with respect to glucose,
(b) the rate constant? Experiment [ICl]0 /(mmol dm−3 ) [H2 ]0 /(mmol dm−3 ) v0 /(mol dm−3 s−1 )

[C6H12O6]/(mmol dm−3) 1.00 1.54 3.12 4.02 1 1.5 1.5 3.7 ×10−7
v0 /(mol dm−3 s−1) 5.0 7.6 15.5 20.0 2 3.0 1.5 7.4 ×10−7
3 3.0 4.5 22 ×10−7
20A.3 The following data were obtained on the initial rates of a reaction of a
d-metal complex with a reactant Y in aqueous solution. What is (a) the order 4 4.7 2.7 ?
of reaction with respect to the complex and Y, (b) the rate constant? For the
(a) Write the rate law for the reaction. (b) From the data, determine the value of
experiments (i), [Y] = 2.7 mmol dm−3 and for experiments (ii) [Y] =
the rate constant. (c) Use the data to predict the reaction rate for experiment 4.
6.1 mmol dm−3.
 Exercises and problems 871

TOPIC 20B Integrated rate laws

Discussion questions
20B.1 Describe the main features, including advantages and disadvantages, 20B.2 Write the rate law that corresponds to each of the following expressions:
of the following experimental methods for determining the rate law of a (a) [A] = [A]0 −krt, (b) ln([A]/[A]0) = −krt, and (c) [A] = [A]0/(1 + krt[A]0).
reaction: the isolation method, the method of initial rates, and fitting data
to integrated rate law expressions.

Exercises
20B.1(a) At 518 °C, the half-life for the decomposition of a sample
of gaseous acetaldehyde (ethanal) initially at 363 Torr was 410 s. When the
pressure was 169 Torr, the half-life was 880 s. Determine the order of the
reaction.
20B.1(b) At 400 K, the half-life for the decomposition of a sample of a gaseous
compound initially at 55.5 kPa was 340 s. When the pressure was 28.9 kPa, the
half-life was 178 s. Determine the order of the reaction.
20B.2(a) The rate constant for the first-order decomposition of N2O5 in the
reaction 2 N2O5(g) → 4 NO2(g) + O2(g) is kr = 3.38 ×10−5 s−1 at 25 °C. What is
the half-life of N2O5? What will be the pressure, initially 500 Torr, after (i) 50 s,
(ii) 20 min after initiation of the reaction?
20B.2(b) The rate constant for the first-order decomposition of a compound A
in the reaction 2 A → P is kr = 3.56 ×10−7 s−1 at 25 °C. What is the half-life of
A? What will be the pressure, initially 33.0 kPa after (i) 50 s, (ii) 20 min after
initiation of the reaction?
20B.3(a) The second-order rate constant for the reaction CH3COOC2H5(aq) +
OH−(aq) → CH3CO2−(aq) + CH3CH2OH(aq) is 0.11 dm3 mol−1 s−1. What is the
concentration of ester (CH3COOC2H5) after (i) 20 s, (ii) 15 min when ethyl
acetate is added to sodium hydroxide so that the initial concentrations are
[NaOH] = 0.060 mol dm−3 and [CH3COOC2H5] = 0.110 mol dm−3?
20B.3(b) The second-order rate constant for the reaction A + 2 B → C + D
is 0.34 dm3 mol−1 s−1. What is the concentration of C after (i) 20 s, (ii)
15 min when the reactants are mixed with initial concentrations of
[A] = 0.027 mol dm−1 and [B] = 0.130 mol dm−3?
20B.4(a) A reaction 2 A → P has a second-order rate law with kr = 4.30 ×10−4
dm3 mol−1 s−1. Calculate the time required for the concentration of A to
change from 0.210 mol dm−3 to 0.010 mol dm−3.
20B.4(b) A reaction 2 A → P has a third-order rate law with kr = 6.50 ×10−4
dm6 mol−2 s−1. Calculate the time required for the concentration of A to
change from 0.067 mol dm−3 to 0.015 mol dm−3.

Problems
20B.1 For a first-order reaction of the form A → n B (with n possibly
fractional), the concentration of the product varies with time as
[B] = n[B]0 (1− e − krt ) . Plot the time dependence of [A] and [B] for the cases
n = 12 , 1, and 2.
20B.2 For a second-order reaction of the form A → n B (with n possibly
fractional), the concentration of the product varies with time as
[B] = nkrt[A]20 /(1 + krt[A]0 ) . Plot the time dependence of [A] and [B] for the
cases n = 12 , 1, and 2.
20B.6 A second-order reaction of the type A + 2 B → P was carried out in a
solution that was initially 0.050 mol dm−3 in A and 0.030 mol dm−3 in B. After
1.0 h the concentration of A had fallen to 0.010 mol dm−3. (a) Calculate the
rate constant. (b) What is the half-life of the reactants?
20B.7‡ The oxidation of HSO3−by O2 in aqueous solution is a reaction
of importance to the processes of acid rain formation and flue gas
desulfurization. R.E. Connick et al. (Inorg. Chem. 3 4, 4543 (1995)) report
that the reaction 2 HSO3−(aq) + O2(g) → 2 SO2− 4 (aq) + 2 H (aq) follows the rate
+

law v = kr[HSO4− ]2[H+ ]2. Given pH = 5.6 and an oxygen molar concentration
20B.3 The data below apply to the formation of urea from ammonium cyanate,
of 0.24 mmol dm−3 (both presumed constant), an initial HSO3− molar
NH4CNO → NH2CONH2. Initially 22.9 g of ammonium cyanate was dissolved
concentration of 50 μmol dm−3, and a rate constant of 3.6 ×106 dm9 mol−3 s−1,
in enough water to prepare 1.00 dm3 of solution. Determine the order of the
what is the initial rate of reaction? How long would it take for HSO3−to reach
reaction, the rate constant, and the mass of ammonium cyanate left after
half its initial concentration?
300 min.
20B.8 Pharmacokinetics is the study of the rates of absorption and elimination
t/min 0 20.0 50.0 65.0 150 of drugs by organisms. In most cases, elimination is slower than absorption
m(urea)/g 0 7.0 12.1 13.8 17.7 and is a more important determinant of availability of a drug for binding to its
target. A drug can be eliminated by many mechanisms, such as metabolism
in the liver, intestine, or kidney followed by excretion of breakdown products
20B.4 The data below apply to the reaction, (CH3)3CBr + H2O → (CH3)3COH +
through urine or faeces. As an example of pharmacokinetic analysis, consider
HBr. Determine the order of the reaction, the rate constant, and the molar
the elimination of beta adrenergic blocking agents (beta blockers), drugs used
concentration of (CH3)3CBr after 43.8 h.
in the treatment of hypertension. After intravenous administration of a beta
blocker, the blood plasma of a patient was analysed for remaining drug and
t/h 0 3.15 6.20 10.00 18.30 30.80
the data are shown below, where c is the drug concentration measured at a
[(CH3)3CBr]/(10−2 mol dm−3) 10.39 8.96 7.76 6.39 3.53 2.07 time t after the injection.

20B.5 The thermal decomposition of an organic nitrile produced the following t/min 30 60 120 150 240 360 480
data:
c/(ng cm−3) 699 622 413 292 152 60 24
t/(103 s) 0 2.00 4.00 6.00 8.00 10.00 12.00 ∞
(a) Is removal of the drug a first- or second-order process? (b) Calculate
[nitrile]/ 1.50 1.26 1.07 0.92 0.81 0.72 0.65 0.40
the rate constant and half-life of the process. Comment: An essential
(mol dm−3)
Determine the order of the reaction and the rate constant. ‡ These problems were supplied by Charles Trapp and Carmen Giunta.
872 20 Chemical kinetics

aspect of drug development is the optimization of the half-life of

t/ms 0.12 0.62 0.96 1.60 3.20 4.00 5.75
elimination, which needs to be long enough to allow the drug to find and
act on its target organ but not so long that harmful side effects become [ClO]/(μmol dm−3) 8.49 8.09 7.10 5.79 5.20 4.77 3.95
important. Determine the rate constant of the reaction and the half-life of a ClO radical.
20B.9 The following data have been obtained for the decomposition of
20B.14 Cyclopropane isomerizes into propene when heated to 500 °C in the
N2O5(g) at 67 °C according to the reaction 2 N2O5(g) → 4 NO2(g) + O2(g). gas phase. The extent of conversion for various initial pressures has been
Determine the order of the reaction, the rate constant, and the half-life. It is followed by gas chromatography by allowing the reaction to proceed for a
not necessary to obtain the result graphically; you may do a calculation using time with various initial pressures:
estimates of the rates of change of concentration.
p0/Torr 200 200 400 400 600 600
t/min 0 1 2 3 4 5 t/s 100 200 100 200 100 200
[N2O5]/(mol dm−3) 1.000 0.705 0.497 0.349 0.246 0.173 p/Torr 186 173 373 347 559 520

20B.10 The gas phase decomposition of acetic acid at 1189 K proceeds by way
where p0 is the initial pressure and p is the final pressure of cyclopropane.
of two parallel reactions: What is the order and rate constant for the reaction under these conditions?

(1) CH3COOH → CH4 + CO2 k1 = 3.74 s−1 20B.15 The addition of hydrogen halides to alkenes has played a fundamental
role in the investigation of organic reaction mechanisms. In one study
(2) CH3COOH → CH2CO + H2O k2 = 4.65 s−1
(M.J. Haugh and D.R. Dalton, J. Amer. Chem. Soc. 97, 5674 (1975)), high
pressures of hydrogen chloride (up to 25 atm) and propene (up to 5 atm) were
What is the maximum percentage yield of the ketene CH2CO obtainable at examined over a range of temperatures and the amount of 2-chloropropane
this temperature? formed was determined by NMR. Show that if the reaction A + B → P
20B.11 Sucrose is readily hydrolysed to glucose and fructose in acidic solution. proceeds for a short time δt, the concentration of product follows [P]/[A] =
The hydrolysis is often monitored by measuring the angle of rotation of plane- kr[A]m −1[B]nδt if the reaction is mth-order in A and nth-order in B. In a
polarized light passing through the solution. From the angle of rotation the series of runs the ratio of [chloropropane] to [propene] was independent of
concentration of sucrose can be determined. An experiment on the hydrolysis [propene] but the ratio of [chloropropane] to [HCl] for constant amounts
of sucrose in 0.50 m HCl(aq) produced the following data: of propene depended on [HCl]. For δt ≈ 100 h (which is short on the time
scale of the reaction) the latter ratio rose from zero to 0.05, 0.03, 0.01 for
t/min 0 14 39 60 80 110 140 170 210 p(HCl) = 10 atm, 7.5 atm, 5.0 atm. What are the orders of the reaction with
respect to each reactant?
[sucrose]/ 0.316 0.300 0.274 0.256 0.238 0.211 0.190 0.170 0.146
(mol dm−3) 20B.16 Show that t1/2 is given by eqn 20B.6 for a reaction that is nth order in A.
Then deduce an expression for the time it takes for the concentration of a
Determine the rate constant of the reaction and the half-life of a sucrose substance to fall to one-third the initial value in an nth-order reaction.
molecule. 20B.17 Derive an integrated expression for a second-order rate law v = kr[A]
20B.12 The composition of a liquid phase reaction 2 A → B was followed by a [B] for a reaction of stoichiometry 2 A + 3 B → P.
spectrophotometric method with the following results: 20B.18 Derive the integrated form of a third-order rate law v = kr[A]2[B] in which
the stoichiometry is 2 A + B → P and the reactants are initially present in (a) their
t/min 0 10 20 30 40 ∞ stoichiometric proportions, (b) with B present initially in twice the amount.
[B]/(mol dm−3) 0 0.089 0.153 0.200 0.230 0.312
20B.19 Show that the ratio t1/2/t3/4, where t1/2 is the half-life and t3/4 is the time
for the concentration of A to decrease to 3/4 of its initial value (implying that
Determine the order of the reaction and its rate constant. t3/4 < t1/2), can be written as a function of n alone, and can therefore be used as
20B.13 The ClO radical decays rapidly by way of the reaction, 2 ClO → Cl2 + O2. a rapid assessment of the order of a reaction.
The following data have been obtained:

TOPIC 20C Reactions approaching equilibrium

Discussion questions
20C.1 Describe the strategy of a temperature-jump experiment. What 20C.2 What feature of a reaction would ensure that its rate would respond to a
parameters of a reaction are accessible from this technique? pressure jump?

Exercises
20C.1(a) The equilibrium NH3(aq) + H2O(l) ⇌ NH4+ (aq) + OH−(aq) at 25 °C is
subjected to a temperature jump which slightly increased the concentration
of NH4+ (aq) and OH−(aq). The measured relaxation time is 7.61 ns.
The equilibrium constant for the system is 1.78 ×10 −5 at 25 °C, and the
equilibrium concentration of NH3(aq) is 0.15 mol dm−3. Calculate the rate
constants for the forward and reverse steps.
20C.1(b) The equilibrium A ! B + C at 25 °C is subjected to a temperature
jump which slightly increases the concentrations of B and C. The measured
 Exercises and problems 873

relaxation time is 3.0 μs. The equilibrium constant for the system is 2.0 ×10−16 0.20 mmol dm−3. Calculate the rate constants for the forward and reverse
at 25 °C, and the equilibrium concentrations of B and C at 25 °C are both steps.

Problems
20C.1 Show by differentiation that eqn 20C.4 is a solution of eqn 20C.3. 1
= ka′ 2 + 8ka ka′ [A]tot
20C.2 Set up the rate equations and plot the corresponding graphs for the τ2
approach to an equilibrium of the form A ! 2 B.
(b) Describe the computational procedures that lead to the determination
20C.3 The reaction A ! 2 B is first-order in both directions. Derive an of the rate constants ka and ka′ from measurements of τ for different values of
expression for the concentration of A as a function of time when the [A]tot. (c) Use the data provided below and the procedure you outlined in part
initial molar concentrations of A and B are [A]0 and [B]0. What is the final (b) to calculate the rate constants ka and ka′, and the equilibrium constant K for
composition of the system? formation of hydrogen-bonded dimers of 2-pyridone:
20C.4 Show that eqn 20C.8 is an expression for the overall equilibrium
[P]/(mol dm−3) 0.500 0.352 0.251 0.151 0.101
constant in terms of the rate constants for the intermediate steps of a reaction
mechanism. To facilitate the task, begin with a mechanism containing three τ/ns 2.3 2.7 3.3 4.0 5.3
steps, and then argue that your expression may be generalized for any number
of steps. 20C.6 Consider the dimerization 2 A " A 2 with forward rate constant kr
20C.5 Consider the dimerization 2 A " A 2 , with forward rate constant
and backward rate constant ka′ . Show that the relaxation time is
ka and backward rate constant ka′ . (a) Derive the following expression τ = 1/(kr′ + 4 kr[A]eq ).
for the relaxation time in terms of the total concentration of protein,
[A]tot = [A] + 2[A2]:

TOPIC 20D The Arrhenius equation

Discussion question
20D.1 Define the terms in and discuss the validity of the expression 20D.2 What might account for the failure of the Arrhenius equation at low
ln k r = ln A −Ea/RT. temperatures?

Exercises
20D.1(a) The rate constant for the decomposition of a certain substance 20D.2(a) The rate of a chemical reaction is found to triple when the
is 3.80 ×10 −3 dm3 mol−1 s −1 at 35 °C and 2.67 ×10 −2 dm3 mol−1 s −1 at 50 °C. temperature is raised from 24 °C to 49 °C. Determine the activation energy.
Evaluate the Arrhenius parameters of the reaction. 20D.2(b) The rate of a chemical reaction is found to double when the
20D.1(b) The rate constant for the decomposition of a certain substance temperature is raised from 25 °C to 35 °C. Determine the activation energy.
is 2.25 ×10−2 dm3 mol−1 s−1 at 29 °C and 4.01 ×10−2 dm3 mol−1 s−1 at 37 °C.
Evaluate the Arrhenius parameters of the reaction.

Problems
20D.1 Show that the definition of Ea given in eqn 20D.3 reduces to eqn 20D.1 organic waste matter), and industrial processes (such as food production and
for a temperature-independent activation energy. fossil fuel use). Reaction with the hydroxyl radical OH is the main path by
which CH4 is removed from the lower atmosphere. T. Gierczak et al. (J. Phys.
20D.2 A first-order decomposition reaction is observed to have the following
Chem. A 1 0 1 , 3125 (1997)) measured the rate constants for the elementary
rate constants at the indicated temperatures. Estimate the activation energy.
bimolecular gas-phase reaction of methane with the hydroxyl radical over a
kr/(10−3 s−1) 2.46 45.1 576 range of temperatures of importance to atmospheric chemistry. Deduce the
Arrhenius parameters A and Ea from the following measurements:
θ/°C 0 20.0 40.0
T/K 295 223 218 213 206 200 195
20D.3 The second-order rate constants for the reaction of oxygen atoms with
kr/(106 dm3 3.55 0.494 0.452 0.379 0.295 0.241 0.217
aromatic hydrocarbons have been measured (R. Atkinson and J.N. Pitts, mol−1 s−1)
J. Phys. Chem. 79, 295 (1975)). In the reaction with benzene the rate constants
are 1.44 ×107 dm3 mol−1 s−1 at 300.3 K, 3.03 ×107 dm3 mol−1 s−1 at 341.2 K,
20D.5‡ As we saw in Problem 20D.4, reaction with the hydroxyl radical
and 6.9 ×107 dm3 mol−1 s−1 at 392.2 K. Find the pre-exponential factor and
OH is the main path by which CH4, a by-product of many natural and
activation energy of the reaction.
industrial processes, is removed from the lower atmosphere. T. Gierczak
20D.4‡ Methane is a by-product of a number of natural processes (such as et al. (J. Phys. Chem. A 1 0 1 , 3125 (1997)) measured the rate constants for
digestion of cellulose in ruminant animals, anaerobic decomposition of the bimolecular gas-phase reaction CH4(g) + OH(g) → CH3(g) + H2O(g) and
874 20 Chemical kinetics

found A = 1.13 ×109 dm3 mol−1 s−1 and Ea = 14.1 kJ mol−1 for the Arrhenius consumed by this reaction (which is slightly less than the amount introduced
parameters. (a) Estimate the rate of consumption of CH4. Take the average to the atmosphere) given an effective volume for the Earth’s lower atmosphere
OH concentration to be 1.5 ×10−21 mol dm−3, that of CH4 to be 40 nmol dm−3, of 4 ×1021 dm3.
and the temperature to be −10 °C. (b) Estimate the global annual mass of CH4

TOPIC 20E Reaction mechanisms

Discussion questions
20E.1 Distinguish between reaction order and molecularity.
20E.2 Assess the validity of the statement that the rate-determining step is the
slowest step in a reaction mechanism.
20E.3 Distinguish between a pre-equilibrium approximation and a steady-state
approximation. Why might they lead to different conclusions?
20E.4 Explain and illustrate how reaction orders may change under different
circumstances.
20E.5 Distinguish between kinetic and thermodynamic control of a reaction.
Suggest criteria for expecting one rather than the other.
20E.6 Explain how it is possible for the activation energy of a reaction to be
negative.

Exercises
20E.1(a) The reaction mechanism for the decomposition of A 2 involves an intermediate. Deduce the rate law for the reaction in two
ways by (i) assuming a pre-equilibrium and (ii) making a steady-state
A 2 ! A + A (fast ) approximation.

A + B → P (slow ) 20E.2(a) The mechanism of a composite reaction consists of a fast pre-

involves an intermediate A. Deduce the rate law for the reaction in two ways by
(i) assuming a pre-equilibrium and (ii) making a steady-state approximation.
20E.1(b) The reaction mechanism for renaturation of a double helix from its
strands A and B:
A + B ! unstable helix (fast )
Unstable helix → stable double helix (slow )
equilibrium step with forward and reverse activation energies of 25 kJ mol−1
and 38 kJ mol−1, respectively, followed by an elementary step of activation
energy 10 kJ mol−1. What is the activation energy of the composite reaction?
20E.2(b) The mechanism of a composite reaction consists of a fast pre-
equilibrium step with forward and reverse activation energies of 27 kJ mol−1
and 35 kJ mol−1, respectively, followed by an elementary step of activation
energy 15 kJ mol−1. What is the activation energy of the composite reaction?

Problems
20E.1 Use mathematical software or a spreadsheet to examine the time HCl + HCl ! (HCl)2 K1
k k
dependence of [I] in the reaction mechanism A ⎯⎯ a
→ I ⎯⎯
b
→ P . In all of
HCl + CH3CHaCH2 ! complex K2
the following calculations, use [A]0 = 1 mol dm−3 and a time range of 0 to 5 s.
(a) Plot [In] against t for ka = 10 s −1 and kb = 1 s −1. (b) Increase the ratio kb/ka (HCl)2 + complex → CH3CHClCH3 + HCl + HCl kr (slow)
steadily by decreasing the value of ka and examine the plot of [I] against t at
each turn. What approximation about d[I]/dt becomes increasingly valid? 20E.5 Show that the following mechanism can account for the rate law of the
reaction in Problem 20B.15:
20E.2 Use mathematical software or a spreadsheet to investigate the effects on
[A], [I], [P], and tmax of decreasing the ratio ka/kb from 10 (as in Fig. 20E.1) to What further tests could you apply to verify this mechanism?
0.01. Compare your results with those shown in Fig. 20E.3.
20E.6 Polypeptides are polymers of amino acids. Suppose that a long
20E.3 Set up the rate equations for the reaction mechanism: polypeptide chain can undergo a transition from a helical conformation to a
random coil. Consider a mechanism for a helix–coil transition that begins in
ka kb the middle of the chain:
⎯⎯
A← ⎯
→B ←
⎯ ⎯⎯⎯
→C
⎯
k a′ kb′
hhhh... " hchh...
Show that, under specific circumstances, the mechanism is equivalent to hchh... " cccc ...

⎯⎯
A← ⎯
→C
kr in which h and c label, respectively, an amino acid in a helical or coil part of
⎯ k′r the chain. The first conversion from h to c, also called a nucleation step, is
relatively slow, so neither step may be rate determining. (a) Set up the rate
20E.4 Derive an equation for the steady state rate of the sequence of reactions equations for this mechanism. (b) Apply the steady-state approximation
A " B " C " D , with [A] maintained at a fixed value and the product D and show that, under these circumstances, the mechanism is equivalent to
removed as soon as it is formed. hhhh... " cccc ...

TOPIC 20F Examples of reaction mechanisms
Discussion questions
20F.1 Discuss the range of validity of the expression k r = k a kb[A]/(kb + k a′[A])
for the effective rate constant of a unimolecular reaction according to the
Lindemann–Hinshelwood mechanism.
Exercises
20F.1(a) The effective rate constant for a gaseous reaction which has a
Lindemann–Hinshelwood mechanism is 2.50 ×10 −4 s −1 at 1.30 kPa and
2.10 ×10 −5 s −1 at 12 Pa. Calculate the rate constant for the activation step in
the mechanism.
20F.1(b) The effective rate constant for a gaseous reaction which has a
Lindemann–Hinshelwood mechanism is 1.7 ×10−3 s−1 at 1.09 kPa and
2.2 ×10−4 s−1 at 25 Pa. Calculate the rate constant for the activation step in the
mechanism.
20F.2(a) Calculate the fraction condensed and the degree of polymerization at
t = 5.00 h of a polymer formed by a stepwise process with kr = 1.39 dm3 mol−1
s−1 and an initial monomer concentration of 10.0 mmol dm−3.
Problems
20F.1 The isomerization of cyclopropane over a limited pressure range was
examined in Problem 20B.14. If the Lindemann mechanism of unimolecular
reactions is to be tested we also need data at low pressures. These have been
obtained (H.O. Pritchard et al., Proc. R. Soc. A 2 1 7, 563 (1953)):
p/Torr 84.1 11.0 2.89 0.569 0.120 0.067
104 kr/s−1 2.98 2.23 1.54 0.857 0.392 0.303
Test the Lindemann–Hinshelwood theory with these data.
TOPIC 20G Photochemistry
Discussion questions
20G.1 Consult literature sources and list the observed ranges of timescales
during which the following processes occur: radiative decay of excited
electronic states, molecular rotational motion, molecular vibrational
motion, proton transfer reactions, energy transfer between fluorescent
Exercises
20G.1(a) In a photochemical reaction A → 2 B + C, the quantum yield
with 500 nm light is 210 mol einstein−1 (1 einstein = 1 mol photons). After
exposure of 300 mmol of A to the light, 2.28 mmol of B is formed. How
many photons were absorbed by A?
20G.1(b) In a photochemical reaction A → B + C, the quantum yield with
500 nm light is 120 mol einstein−1 (1 einstein = 1 mol photons). After exposure
Exercises and problems 875
20F.2 Bearing in mind distinctions between the mechanisms of stepwise
and chain polymerization, describe ways in which it is possible to control
the molar mass of a polymer by manipulating the kinetic parameters of
polymerization.
20F.2(b) Calculate the fraction condensed and the degree of polymerization
at t = 10.00 h of a polymer formed by a stepwise process with
kr = 2.80 ×10−2 dm3 mol−1 s−1 and an initial monomer concentration of
50.0 mmol dm−3.
20F.3(a) Consider a polymer formed by a chain process. By how much does
the kinetic chain length change if the concentration of initiator increases by a
factor of 3.6 and the concentration of monomer decreases by a factor of 4.2?
20F.3(b) Consider a polymer formed by a chain process. By how much does
the kinetic chain length change if the concentration of initiator decreases by a
factor of 10.0 and the concentration of increases by a factor of 5.0?
20F.2 Calculate the average polymer length in a polymer produced by a chain
mechanism in which termination occurs by a disproportionation reaction of
the form M⋅ + ⋅M → M + :M.
20F.3 Derive an expression for the time dependence of the degree of
polymerization for a stepwise polymerization in which the reaction is acid-
catalysed by the −COOH acid functional group. The rate law is
d[A]/dt = −kr[A]2[OH].
molecules used in FRET analysis, electron transfer events between complex
ions in solution, and collisions in liquids.
20G.2 Discuss experimental procedures that make it possible to differentiate
between quenching by energy transfer, collisions, and electron transfer.
of 200 mmol A to the light, 1.77 mmol B is formed. How many photons were
absorbed by A?
20G.2(a) Consider the quenching of an organic fluorescent species with
τ0 = 6.0 ns by a d-metal ion with kQ = 3.0 ×108 dm3 mol−1 s−1. Predict the
concentration of quencher required to decrease the fluorescence intensity of
the organic species to 50 per cent of the unquenched value.
876 20 Chemical kinetics

20G.2(b) Consider the quenching of an organic fluorescent species with concentration of quencher required to decrease the fluorescence intensity of
τ0 = 3.5 ns by a d-metal ion with kQ = 2.5 ×109 dm3 mol−1 s−1. Predict the the organic species to 75 per cent of the unquenched value.

Problems
20G.1 In an experiment to measure the quantum yield of a photochemical
pN2 = 0.0 atm
reaction, the absorbing substance was exposed to 320 nm radiation from a
87.5 W source for 28.0 min. The intensity of the transmitted radiation was Relative fluorescence intensity 1.000 0.606 0.360 0.22 0.135
0.257 that of the incident radiation. As a result of irradiation, 0.324 mol of t/μs 0.0 5.0 10.0 15.0 20.0
the absorbing substance decomposed. Determine the quantum yield.
20G.2‡ Ultraviolet radiation photolyses O3 to O2 and O. Determine the rate at pN2 = 9.7 4 × 1 0 −4 atm
which ozone is consumed by 305 nm radiation in a layer of the stratosphere
of thickness 1.0 km. The quantum yield is 0.94 at 220 K, the concentration Relative fluorescence intensity 1.000 0.585 0.342 0.200 0.117
about 8 nmol dm−3, the molar absorption coefficient 260 dm3 mol−1 cm−1, t/μs 0.0 3.0 6.0 9.0 12.0
and the flux of 305 nm radiation about 1 ×1014 photons cm−2 s−1. Data from
W.B. DeMore et al., Chemical kinetics and photochemical data for use in
You may assume that all gases are perfect. Determine the rate constant for the
stratospheric modeling: Evaluation Number 11, JPL Publication 94–26 (1994).
energy transfer process.
20G.3 Dansyl chloride, which absorbs maximally at 330 nm and fluoresces
20G.6 An amino acid on the surface of an enzyme was labelled covalently
maximally at 510 nm, can be used to label amino acids in fluorescence
with 1.5-I AEDANS and it is known that the active site contains a tryptophan
microscopy and FRET studies. Tabulated below is the variation of the
residue. The fluorescence quantum yield of tryptophan decreased by 15 per
fluorescence intensity of an aqueous solution of dansyl chloride with time after
cent due to quenching by 1.5-I AEDANS. What is the distance between the
excitation by a short laser pulse (with I0 the initial fluorescence intensity). The
active site and the surface of the enzyme?
ratio of intensities is equal to the ratio of the rates of photon emission.
20G.7 The Förster theory of resonance energy transfer and the basis for the
t/ns 5.0 10.0 15.0 20.0 FRET technique can be tested by performing fluorescence measurements on
a series of compounds in which an energy donor and an energy acceptor are
If/I0 0.45 0.21 0.11 0.05
covalently linked by a rigid molecular linker of variable and known length. L.
Stryer and R.P. Haugland (Proc. Natl. Acad. Sci. USA 58, 719 (1967)) collected
(a) Calculate the observed fluorescence lifetime of dansyl chloride in water.
the following data on a family of compounds with the general composition
(b) The fluorescence quantum yield of dansyl chloride in water is 0.70. What
dansyl-(l-prolyl)n-naphthyl, in which the distance R between the naphthyl
is the fluorescence rate constant?
donor and the dansyl acceptor was varied from 1.2 nm to 4.6 nm by increasing
20G.4 When benzophenone is exposed to ultraviolet radiation it is excited into the number of prolyl units in the linker:
a singlet state. This singlet changes rapidly into a triplet, which phosphoresces.
Triethylamine acts as a quencher for the triplet. In an experiment in R/nm 1.2 1.5 1.8 2.8 3.1 3.4 3.7 4.0 4.3 4.6
the solvent methanol, the phosphorescence intensity varied with amine
ηT 0.99 0.94 0.97 0.82 0.74 0.65 0.40 0.28 0.24 0.16
concentration as shown below. A time-resolved laser spectroscopy experiment
had also shown that the half-life of the fluorescence in the absence of
quencher is 29 μs. What is the value of kQ?
Are the data described adequately by eqn 20G.10? If so, what is the value of R0
[Q]/(mmol dm−3) 1.0 5.0 10.0 for the naphthyl–dansyl pair?

If/(arbitrary units) 0.41 0.25 0.16
20G.5 An electronically excited state of Hg can be quenched by N2 according
to Hg*(g) + N2(g, v = 0) → Hg(g) + N2(g, v = 1) in which energy transfer from
Hg* excites N2 vibrationally. Fluorescence lifetime measurements of samples
of Hg with and without N2 present are summarized below (for T = 300 K):
20G.8 The first step in plant photosynthesis is absorption of light by
chlorophyll molecules bound to proteins known as ‘light-harvesting
complexes’, where the fluorescence of a chlorophyll molecule is quenched by
nearby chlorophyll molecules. Given that for a pair of chlorophyll a molecules
R0 = 5.6 nm, by what distance should two chlorophyll a molecules be separated
to shorten the fluorescence lifetime from 1 ns (a typical value for monomeric
chlorophyll a in organic solvents) to 10 ps?

TOPIC 20H Enzymes

Discussion questions
20H.1 Discuss the features, advantages, and limitations of the Michaelis–
Menten mechanism of enzyme action.
20H.2 A plot of the rate of an enzyme-catalysed reaction against
temperature has a maximum, in an apparent deviation from the
behaviour predicted by the Arrhenius equation (Topic 20D). Suggest
an interpretation.
20H.3 Distinguish between competitive, non-competitive, and uncompetitive
inhibition of enzymes. Discuss how these modes of inhibition may be
detected experimentally.
20H.4 Some enzymes are inhibited by high concentrations of their own
products. Sketch a plot of reaction rate against concentration of substrate for
an enzyme that is prone to product inhibition.
 Exercises and problems 877

Exercises
20H.1(a) Consider the base-catalysed reaction 1.04 mmol dm−3 s−1 when the substrate concentration is 0.105 mol dm−3. What
is the maximum velocity of this reaction?
k
⎯⎯
(1) AH + B ← ⎯
a
⎯→ BH + + A − (both fast) 20H.2(b) The enzyme-catalysed conversion of a substrate at 25 °C has
ka′
a Michaelis constant of 0.032 mol dm−3. The rate of the reaction is
k
(2 ) A − + AH ⎯⎯
b
→ product (slow) 0.205 mmol dm−3 s−1 when the substrate concentration is 0.875 mol dm−3.
What is the maximum velocity of this reaction?
Deduce the rate law.
20H.3(a) Consider an enzyme-catalysed reaction that follows Michaelis–
20H.1(b) Consider the acid-catalysed reaction
Menten kinetics with KM = 3.0 mmol dm−3. What concentration of a
competitive inhibitor characterized by KI = 20 μmol dm−3 will reduce the rate
k
⎯⎯
(1) HA + H + ← ⎯
a
⎯→ HAH + (both fast) of formation of product by 50 per cent when the substrate concentration is
ka′
held at 0.10 mmol dm−3?
k
(2 ) HAH + + B ⎯⎯
b
→ BH + + AH (slow) 20H.3(b) Consider an enzyme-catalysed reaction that follows Michaelis–
Menten kinetics with KM = 0.75 mmol dm−3. What concentration of a
Deduce the rate law. competitive inhibitor characterized by KI = 0.56 mmol dm−3 will reduce the
rate of formation of product by 75 per cent when the substrate concentration
20H.2(a) The enzyme-catalysed conversion of a substrate at 25 °C has
is held at 0.10 mmol dm−3?
a Michaelis constant of 0.046 mol dm−3. The rate of the reaction is

Problems
20H.1 Michaelis and Menten derived their rate law by assuming a rapid 20H.4 The enzyme-catalysed conversion of a substrate at 25 °C has a Michaelis
pre-equilibrium of E, S, and ES. Derive the rate law in this manner, and constant of 90 μmol dm−3 and a maximum velocity of 22.4 μmol dm−3 s−1 when
identify the conditions under which it becomes the same as that based on the enzyme concentration is 1.60 nmol dm−3. (a) Calculate kcat and η. (b) Is
the steady-state approximation (eqn 20H.1). the enzyme ‘catalytically perfect’?
20H.2 (a) Use the Michaelis–Menten equation (eqn 20H.1) to generate two 20H.5 The following results were obtained for the action of an ATPase on ATP
families of curves showing the dependence of v on [S]: one in which KM varies at 20 °C, when the concentration of the ATPase was 20 nmol dm−3:
but vmax is constant, and another in which vmax varies but KM is constant. (b)
Use eqn 20H.7 to explore the effect of competitive, uncompetitive, and non- [ATP]/(μmol dm−3) 0.60 0.80 1.4 2.0 3.0
competitive inhibition on the shapes of the plots of v against [S] for constant
v/(μmol dm−3 s−1) 0.81 0.97 1.30 1.47 1.69
KM and vmax. Use mathematical software, a spreadsheet, or the Living graphs
on the web site of this book.
Determine the Michaelis constant, the maximum velocity of the reaction, the
20H.3 For many enzymes, the mechanism of action involves the formation of turnover number, and the catalytic efficiency of the enzyme.
two intermediates:
20H.6 Some enzymes are inhibited by high concentrations of their own
substrates. (a) Show that when substrate inhibition is important the reaction
E + S → ES v = ka[E][S] rate v is given by
ES → E + S v = ka′ [ES]
ES → ES′ v = kb[ES] vmax
v=
1+ K M /[S]0 +[S]0 /K I
ES′ → E + P v = kc[ES′]

where KI is the equilibrium constant for dissociation of the inhibited enzyme–

Show that the rate of formation of product has the same form as that shown in
substrate complex. (b) What effect does substrate inhibition have on a plot of
eqn 20H.1, but with vmax and KM given by
1/v against 1/[S]0?

kbkc[E]0 kc (ka′ + kb )
vmax = and K M =
kb + kc ka (kb + kc )

Integrated activities
20.1 Autocatalysis is the catalysis of a reaction by the products. For example,
for a reaction A → P it may be found that the rate law is v = k r[A][P] and the
reaction rate is proportional to the concentration of P. The reaction gets
started because there are usually other reaction routes for the formation of
some P initially, which then takes part in the autocatalytic reaction proper.
(a) Integrate the rate equation for an autocatalytic reaction of the form
A → P, with rate law v = k r[A][P], and show that
[P] (1 + b)eat
=
[P]0 1 + beat
where a = ([A]0 + [P]0)kr and b = [P]0/[A]0. Hint: Starting with the expression
v = −d[A]/dt = kr[A][P], write [A] = [A]0 −x, [P] = [P]0 + x and then write the
expression for the rate of change of either species in terms of x. To integrate
the resulting expression, use integration by the method of partial fractions
878 20 Chemical kinetics
(The chemist’s toolbox 20B.1). (b) Plot [P]/[P]0 against at for several values of
b. Discuss the effect of autocatalysis on the shape of a plot of [P]/[P]0 against
t by comparing your results with those for a first-order process, in which
[P]/[P]0 = 1 − e −krt . (c) Show that for the autocatalytic process discussed
in parts (a) and (b), the reaction rate reaches a maximum at tmax =
−(1/a) ln b. (d) An autocatalytic reaction A → P is observed to have the rate
law d[P]/dt = kr[A]2[P]. Solve the rate law for initial concentrations [A]0 and
[P]0. Calculate the time at which the rate reaches a maximum. (e) Another
reaction with the stoichiometry A → P has the rate law d[P]/dt = kr[A][P]2;
integrate the rate law for initial concentrations [A]0 and [P]0. Calculate the
time at which the rate reaches a maximum.
20.2 Many biological and biochemical processes involve autocatalytic steps
(Problem 20.1). In the SIR model of the spread and decline of infectious
diseases the population is divided into three classes; the ‘susceptibles’, S, who
can catch the disease, the ‘infectives’, I, who have the disease and can transmit
it, and the ‘removed class’, R, who have either had the disease and recovered,
are dead, are immune, or isolated. The model mechanism for this process
implies the following rate laws:
dS dI dR
= −rSI = rSI − aI = aI
dt dt dt
Which are the autocatalytic steps of this mechanism? Find the conditions on
the ratio a/r that decide whether the disease will spread (an epidemic) or die
out. Show that a constant population is built into this system, namely that
S + I + R = N, meaning that the time scales of births, deaths by other causes,
and migration are assumed large compared to that of the spread of the disease.
20.3‡ J. Czarnowski and H.J. Schuhmacher (Chem. Phys. Lett. 1 7, 235 (1972))
suggested the following mechanism for the thermal decomposition of F2O in
the reaction 2 F2O(g) → 2 F2(g) + O2(g):
(1) F2O + F2O → F + OF + F2O ka
(2) F + F2O → F2 + OF kb
(3) OF + OF → O2 + F + F kc
(4) F + F + F2O → F2 + F2O kd
(a) Using the steady-state approximation, show that this mechanism is
consistent with the experimental rate law −d[F2O]/dt = kr[F2O]2 + k′[Fr 2O] .
3/2
(b) The experimentally determined Arrhenius parameters in the range
501–583 K are A = 7.8 ×1013 dm3 mol−1 s−1, Ea/R = 1.935 ×104 K for kr and A =
2.3 ×1010 dm3 mol−1 s−1, Ea/R = 1.691 ×104 K for k′.r At 540 K, ΔfH<(F2O) =
+ 24.41 kJ mol−1, D(F–F) = 160.6 kJ mol−1, and D(O–O) = 498.2 kJ mol−1.
Estimate the bond dissociation energies of the first and second F–O bonds in
F2O and the Arrhenius activation energy of reaction 2.
20.4 Express the root mean square deviation {〈M2〉 −〈M〉2}1/2 of the molar mass
of a condensation polymer in terms of the fraction p, and deduce its time-
dependence.
20.5 Calculate the ratio of the mean cube molar mass to the mean square
molar mass in terms of (a) the fraction p, (b) the chain length.
20.6 Conventional equilibrium considerations do not apply when a reaction
is being driven by light absorption. Thus the steady-state concentration of
products and reactants might differ significantly from equilibrium values. For
instance, suppose the reaction A → B is driven by light absorption, and that its
rate is Ia, but that the reverse reaction B → A is bimolecular and second order
with a rate kr[B]2. What is the stationary state concentration of B? Why does
this ‘photostationary state’ differ from the equilibrium state?
20.7 The photochemical chlorination of chloroform in the gas phase has been
found to follow the rate law d[CCl4]/dt = kr[Cl2]1/2Ia1/2. Devise a mechanism
that leads to this rate law when the chlorine pressure is high.