Chapter 09 Chemical Kinetics I

CHAPTER
9 Chemical Kinetics I.
The Basic Ideas
LAIDLER . MEISER . SANCTUARY

Physical Chemistry
Electronic Edition
Publisher: MCH Multimedia Inc.
Problems and Solutions

Chapter 9: Chemical Kinetics I. The Basic Ideas Rate Constants and Order of Reaction
Chapter 9
*problems with an asterisk are slightly more demanding
Rate Constants and Order of Reaction

9.1. The stoichiometric equation for the oxidation of bromide ions by hydrogen peroxide in acid solution is:
2Br– + H 2 O 2 + 2H+ → Br 2 + 2H 2 O
Since the reaction does not occur in one stage, the rate equation does not correspond to this stoichiometric equation but is
υ = k[H 2 O 2 ][H+][Br–]
a. If the concentration of H 2 O 2 is increased by a factor of 3, by what factor is the rate of consumption of Br– ions increased?
b. If the rate of consumption of Br– ions is 7.2 × 10–3 mol dm–3 s–1, what is the rate of consumption of hydrogen peroxide? What is
the rate of formation of bromine?
c. What is the effect on the rate constant k of increasing the concentration of bromide ions?
d. If by the addition of water to the reaction mixture the total volume were doubled, what would be the effect on the rate of change
of the concentration of Br–? What would be the effect on the rate constant k?
Solution
9.2. A reaction obeys the stoichiometric equation:
A + 2B → 2Z
Rates of formation of Z at various concentrations of A and B are as follows:
[A]/mol dm–3 [B]/mol dm–3 Rate/mol dm–3 s–1

3.5 × 10–2 2.3 × 10–2 5.0 × 10–7
7.0 × 10–2 4.6 × 10–2 2.0 × 10–6
7.0 × 10–2 9.2 × 10–2 4.0 × 10–6
9-2
What are α and β in the rate equation and what is the rate constant k?
υ = k[A]α[B]β
Solution
9.3. Some results for the rate of a reaction between two substances A and B are shown in the following table. Deduce the order α with
respect to A, the order β with respect to B, and the rate constant.

1.4 × 10–2 2.3 × 10–2 7.40 × 10–9
2.8 × 10–2 4.6 × 10–2 5.92 × 10–8
2.8 × 10–1 4.6 × 10–2 5.92 × 10–6
Solution
9.4. A substance decomposes at 600 K with a rate constant of 3.72 ×10– 5 s–1.
a. Calculate the half-life of the reaction.
b. What fraction will remain undecomposed if the substance is heated for 3 h at 600 K?
Solution
9.5. How does the time required for a first-order reaction to go to 99% completion relate to the half-life of the reaction?
Solution
9.6. The rate constant for the reaction H + OH → H 2 O is 1.3 × 10 dm mol s . Calculate the half-life for the neutralization process if
+ – 11 3 –1 –1
(a) [H]+ = [OH–] = 10–1 M and (b) [H+] = [OH–] = 10–4 M.

Solution
9.7. The isotope 90Sr emits radiation by a first-order process (as is always the case with radioactive decay) and has a half-life of 28.1
years. When ingested by mammals it becomes permanently incorporated in bone tissue. If 1 μg is absorbed at birth, how much of
this isotope remains after (a) 25 years, (b) 50 years, (c) 70 years?
Solution
9-3
9.8. The first-order decomposition of nitramide in the presence of bases, NH 2 NO 2 → N 2 O(g) + H 2 O(l), is conveniently analyzed by
collecting the gas evolved during the reaction. During an experiment, 50.0 mg of nitramide was allowed to decompose at 15 °C. The
volume of dry gas evolved after 70.0 min. was measured to be 6.59 cm3 at 1 bar pressure. Find the rate constant and the half-life for
nitramide decomposition.
Solution
9.9. The reaction:
2NO(g) + Cl2(g) → 2NOCl(g)
is second order in NO and first order in Cl 2 . In a volume of 2 dm3, 5 mol of nitric oxide and 2 mol of Cl 2 were brought together, and
the initial rate was 2.4 × 10–3 mol dm–3 s–1. What will be the rate when one-half of the chlorine has reacted?
Solution
9.10. Measuring the total pressure is a convenient way to monitor the gas phase reaction:
2NOCl(g) → 2NO(g) + Cl 2 (g)
However, the rate depends on the concentration of the reactant, which is proportional to the partial pressure of the reactant. Derive
an expression relating the rate of this reaction to the initial pressure, P 0 , and the total pressure, P t , at time t. Assume that the reaction
follows second-order kinetics.
Solution
9.11. The following results were obtained for the rate of decomposition of acetaldehyde:
% decomposed:
0 5 10 15 20 25 30 35 40 45 50
Rate/Torr min–1
8.53 7.49 6.74 5.90 5.14 4.69 4.31 3.75 3.11 2.67 2.29
Employ van’t Hoff’s differential method to obtain the order of reaction.
Solution
9-4
32
9.12. The isotope 15 P emits radiation and has a half-life of 14.3 days. Calculate the decay constant in s–1. What percentage of the initial
activity remains after (a) 10 days, (b) 20 days, (c) 100 days?
Solution
35
9.13. The following counts per minute were recorded on a counter for the isotope 16 S at various times:
Time/d Counts/min
0 4280
1 4245
2 4212
3 4179
4 4146
5 4113
10 3952
15 3798
Determine the half-life in days and the decay constant in s–1. How many counts per minute would be expected after (a) 60 days and (b) 365
days?
Solution
9.14. The reaction:
cis -Cr(en) 2 (OH) +2  trans -Cr(en) 2 (OH) +2
is first order in both directions. At 25 °C the equilibrium constant is 0.16 and the rate constant k 1 is 3.3 × 10–4 s–1. In an experiment
starting with the pure cis form, how long would it take for half the equilibrium amount of the trans isomer to be formed?
Solution
9-5
9.15. Suppose that a gas phase reaction 2A(g) → 2B(g) + C(g) follows second-order kinetics and goes to completion. If the reaction is
allowed to proceed in a constant volume vessel at an initial pressure of 2 bar (only A is initially present), what will be the partial
pressures of A, B, and C and the total pressure at t = t 1/2 , 2t 1/2 , 3t 1/2 , and infinity?
Solution
9.16. Derive the following relationship for the half-life t 1/2 of a reaction of order n, with all reactants having an initial concentration a 0 :
2n –1 –1
t1/ 2 =
ka0n –1 (n –1)
Solution
9.17. Vaughan [J. Am. Chem. Soc. 54, 3867(1932)] reported the following pressure measurements as a function of time for the
dimerization of 1,3-butadiene (C 4 H 6 ) under constant volume conditions at 326 °C:
t/min 3.25 12.18 24.55 42.50 68.05

P/Torr 618.5 584.2 546.8 509.3 474.6
The initial amount of butadiene taken would have exerted a pressure of 632.0 Torr. Find whether the reaction follows first- or second-order
kinetics and evaluate the rate constant.
Solution
9.18. A drug administered to a patient is usually consumed by a first-order process. Suppose that a drug is administered in equal amounts
at regular intervals and that the interval between successive doses is equal to the (1/n)-life for the disappearance process (i.e., to the
time that it takes for the fraction 1/n to disappear). Prove that the limiting concentration of the drug in the patient’s body is equal to n
times the concentration produced by an individual dose.
Solution
9.19. Equation 9.45 applies to a second-order reaction of stoichiometry A + B → Z. Derive the corresponding equation for a second-order
reaction of stoichiometry 2A + B →Z.
Solution
9-6
9.20. Derive the integrated rate equation for an irreversible reaction of stoichiometry 2A + B → Z, the rate being proportional to [A]2[B]
and the reactants present in stoichiometric proportions; take the initial concentration of A as 2a 0 and that of B as a 0 . Obtain an
expression for the half-life of the reaction.
Solution
9.21. Prove that for two simultaneous (parallel) reactions
[Y] k1
= at all times.
[Z] k2
Solution
*9.22. Prove that for two consecutive first-order reactions; A → B → C the rate of formation of C is given by:
 k e – k1t – k1e – k2t 

=
[C] [A]0 1 + 2 
 k1 – k2 
where [A] 0 is the initial concentration of A.

(Hint: The solution of the differential equation):
dx
= abe – bt – cx
dt
where a, b, and c are constants, is
ab – bt
=x (e – e – ct ) + I
c–b
Solution
9-7
*9.23. a. Derive the integrated rate equation for a reversible reaction of stoichiometry:
k1
AY + Z
k –1
The reaction is first order from left to right and second order from right to left. Take the initial concentration of A as a 0 and the
concentration at time t as a 0 – x.
b. Obtain the integrated equation in terms of k, and the equilibrium constant K = k 1 /k –1 .
c. A reaction to which this rate equation applies is the hydrolysis of methyl acetate. Newling and Hinshelwood, J. Chem. Soc., 1936,
1357(1936), obtained the following results for the hydrolysis of 0.05 M ester at 80.2 °C in the presence of 0.05 M HCl, which
catalyzes the reaction:
Time, s 1350 2070 3060 5340 7740 ∞

Percent hydrolysis 21.2 30.7 43.4 59.5 73.45 90.0
Obtain values for the rate constants k 1 and k –1 .

Solution
*9.24. The dissociation of a weak acid HA + H 2 O  H 3 O+ + A– can be represented as:
A  Y+Z
The rate constants k 1 and k –1 cannot be measured by conventional methods but can be measured by the T-jump technique (Section
9.5). Prove that the relaxation time is given by:
1
t *=
k1 + 2k –1 xe
where the concentration of the ions (Y and Z) is at equilibrium.

Solution
9-8
Chapter 9: Chemical Kinetics I. The Basic Ideas Temperature Dependence
Temperature Dependence
9.25. The rate constant for a reaction at 30 °C is found to be exactly twice the value at 20 °C. Calculate the activation energy.
Solution
Solution
9.27. The following data for a first-order decomposition reaction in aqueous medium was reported by E. O. Wiig [J. Phys. Chem. 34,
596(1930)].
t/ºC 0 20 40 60
–5 –1
k/10 min 2.46 43.5 575 5480
Find the activation energy and the preexponential factor.

Solution
9.28. Two second-order reactions have identical preexponential factors and activation energies differing by 20.0 kJ mol–1. Calculate the
ratio of their rate constants (a) at 0 °C and (b) at 1000 °C.
Solution
9.29. The gas-phase reaction between nitric oxide and oxygen is third order. The following rate constants have been measured:
T/K 80.0 143.0 228.0 300.0 413.0 564.0

9 6 –1 –1
k × 10 /cm mol s 41.8 20.2 10.1 7.1 4.0 2.8
The behavior is interpreted in terms of a temperature-dependent preexponential factor; the rate equation is of the form:
k = aTne–E/RT
where a and n are constants. Assume the activation energy to be zero and determine n to the nearest half-integer.
Solution
9-9
9.30. The definition of activation energy E a is generally considered to be given by an extension of Eq. 9.91:
 d ln k 
Ea = RT 2  
 dT 
Problem 9.29 shows that for certain reactions, the temperature dependence of the reaction rate constant is better described by an
expression of the type
k = aTne–E/RT
Using the definition for E a given here, derive an expression for the activation energy from this expression.
Solution
9.31. The water flea Daphnia performs a constant number of heartbeats and then dies. The flea lives twice as long at 15 °C as at 25 °C.
Calculate the activation energy for the reaction that controls the rate of its heartbeat.
Solution
9.32. A sample of milk kept at 25 °C is found to sour 40 times as rapidly as when it is kept at 4 °C. Estimate the activation energy for the
souring process.
Solution
*9.33. Experimentally, the rate constant for the O(3P) + HCl reaction in the gas phase is found to have a temperature dependence given by:
k (cm3 molecule–1 s–1) = 5.6 × 10–21T 2.87 e–1766 K/T
in the range 350 – 1480 K [Mahmud, Kim, and Fontijn, J. Phys. Chem. 94, 2994(1990)].
a. Using the results of Problem 9.30, find the value of E a at 900 K, which is approximately the middle of this range.
b. Using variational transition-state theory (an extension of the transition-state theory described in Section 9.9), the theoretical rate
constant for this reaction is found to behave according to the equation:
k (cm3 molecule–1 s–1) = 6.9 × 10–20T2.60e–2454 K/T
in the same temperature range [T. C. Allison, B. Ramachandran, J. Senekowitsch, D. G. Truhlar, and R. E. Wyatt, J. Mol. Structure,
Theochem, 454, 307, 1998.] Compare the experimental and theoretical rate constants at 900 K.
Solution
9-10
9.34. The activation energy for the reaction:

H + CH 4 → H 2 + CH 3
has been measured to be 49.8 kJ mol–1. Some estimates of enthalpies of formation, ∆ f H°, are:
H 218.0 kJ mol–1
CH 4 –74.8 kJ mol–1
CH 3 139.5 kJ mol–1
Estimate a value for the activation energy of the reverse reaction.

Solution
*9.35. By a treatment similar to that given for relaxation methods for the case A  Z, derive the rate equations for analyzing the reaction
A + B  Z by carrying out the steps below.
a. Show that at equilibrium, k 1 a e b e = k –1 z e , where the subscript e indicates equilibrium concentrations.
dx
=
b. Show that k1 (ae – x)(be – x) – k –1 ( ze + x) , where x represents a change from equilibrium.
dt
dx
c. Show that for small x, = – [k1 (ae + be ) + k –1 ]x . [Hint: Use the result of part (a).]
dt
d. The displacement from equilibrium x always follows the first-order process x = x 0 exp(–t/t*), where t* is the relaxation time.
Show that dx/dt = –x/t*.
1
e. Comparing the results of parts (c) and (d), show that= 2k1ae + k –1 if a e = b e .
t*
1 k z
f. For the case a e = b e , show=
that 2 k1k –1 ze + k –1 . [Hint: Use the result of part (e) and the fact that 1 = e . ]
t* k –1 aebe
Solution
9-11
Chapter 9: Chemical Kinetics I. The Basic Ideas Collision Theory and Transition-State Theory
9.36. A reaction of the type A + B  Z has been studied by relaxation methods. Some of the available data relating equilibrium
concentrations of the product to the relaxation times are given below.
z e /M 0.001 0.002 0.005 0.010 0.025 0.05 0.10

t*/ms 4.08 3.74 2.63 1.84 1.31 0.88 0.674
Determine k 1 , k –1 , and K = k 1 /k –1 .
Solution
9.37. The equilibrium H 2 O  H– + OH has a relaxation time of about 40 μs at 25 °C. Find the values of the forward and reverse rate
constants. K w = [H+][OH–] = 10–14.
1
(Hint: For this case, using steps similar to those of Problem 9.25, it can be shown that =
k1 + k –1 ([H + ]e + [OH – ]e ) .)
t*
Solution
Collision Theory and Transition-State Theory Formatted: Heading 1, Left, Indent:

Left: 0", First line: 0"
9.38. Two reactions of the same order have identical activation energies and their entropies of activation differ by 50 J K–1 mol–1.
Calculate the ratio of their rate constants at any temperature.
Solution
9.39. The gas-phase reaction:
H 2 + I 2 → 2HI
is second order. Its rate constant at 400 °C is 2.34 × 10–2 dm3 mol–1 s–1, and its activation energy is 150 kJ mol–1. Calculate ∆‡H°,
∆‡S°, and ∆‡G° at 400 °C, and the preexponential factor.
Solution
9-12
Chapter 9: Chemical Kinetics I. The Basic Ideas Collision Theory and Transition-State Theory
9.40. A substance decomposes according to first-order kinetics; the rate constants at various temperatures are as follows:
Temperature/°C Rate constant, k/s–1

15.0 4.18 × 10–6
20.0 7.62 × 10–6
25.0 1.37 × 10–5
30.0 2.41 × 10–5
37.0 5.15 × 10–5
Calculate the activation energy. Calculate also, at 25 °C, the enthalpy of activation, the Gibbs energy of activation, the preexponential
factor, and the entropy of activation.
Solution
9.41. The following data have been obtained for the hydrolysis of adenosine triphosphate, catalyzed by hydrogen ions:

39.9 4.67 × 10–6
43.8 7.22 × 10–6
47.1 10.0 × 10–6
50.2 13.9 × 10–6
Calculate, at 40 °C, the Gibbs energy of activation, the energy of activation, the enthalpy of activation, the preexponential factor, and the
entropy of activation.
Solution
9.42. The half-life of the thermal denaturation of hemoglobin, a first-order process, has been found to be 3460 s at 60 °C and 530 s at 65
°C. Calculate the enthalpy of activation and entropy of activation at 60 °C, assuming the Arrhenius equation to apply.
Solution
9-13
Chapter 9: Chemical Kinetics I. The Basic Ideas Ionic-Strength Effects
*9.43. a. Using Eq. 9.73, calculate the collision density for 6.022 ×1023 molecules of hydrogen iodide present in a volume 1 m3 at 300 K.
Take d AA = 0.35 nm.
b. If the activation energy for the decomposition of HI is 184 kJ mol–1, what rate constant does kinetic theory predict at 300 °C? To
what entropy of activation does this result correspond?
Solution
–9 –1 –1
9.44. The rate constant for a first-order reaction is 7.40 × 10 s at 25 °C, and the activation energy is 112.0 kJ mol . Calculate, at 25 °C,
the preexponential factor A, the enthalpy of activation ∆‡H°, the Gibbs energy of activation ∆‡G°, and the entropy of activation ∆‡S°.
Solution
9.45. The rate constant for a second-order reaction in solution is 3.95 × 10–4 dm3 mol–1 s–1 at 25 °C, and the activation energy is 120.0 kJ
mol–1. Calculate, at 25 °C, the preexponential factor A, the enthalpy of activation ∆‡H°, the Gibbs energy of activation ∆‡G°, and the
entropy of activation ∆‡S°.
Solution
Ionic-Strength Effects Formatted: Heading 1
9.46. The rate constant k for the reaction between persulfate ions and iodide ions varies with ionic strength I as follows:
I/10–3 mol dm–3 2.45 3.65 4.45 6.45 8.45 12.4

3 –1 –1
k/dm mol s 1.05 1.12 1.16 1.18 1.26 1.39
Estimate the value of z A z B .

Solution
9-14
Chapter 9: Chemical Kinetics I. The Basic Ideas Ionic-Strength Effects
9.47. The following constants were obtained by Brønsted and Livingstone [J. Amer. Chem. Soc., 49, 435(1927)] for the reaction:
[CoBr(NH 3 ) 5 ]2+ + OH– → [Co(NH 3 ) 5 OH]2+ + Br–
under the following conditions:
Concentration/mol dm–1 k
2+
[CoBr(NH 3 ) 5 ] NaOH NaCl dm mol –1 s –1
3
–4 –4
5.0 × 10 7.95 × 10 0 1.52
–4 –3
5.96 × 10 1.004 × 10 0 1.45
–4 –3
6.00 × 10 0.696 × 10 0.005 1.23
–4 –3
6.00 × 10 0.696 × 10 0.020 0.97
–4 –3
6.00 × 10 0.691 × 10 0.030 0.91
Make an estimate of the rate constant of the reaction at zero ionic strength. Are the results consistent with z A z B = –2?
Solution
9.48. Suppose that the rates of ionic reactions in solution were proportional to the activity rather than the concentration of activated
complexes. Derive an equation relating the logarithm of the rate constant to the ionic strength and the charge numbers of the ions
and contrast it with Eq. 9.124. Can the results in Figure 9.22 be reconciled with the equation you have derived?
Solution
9-15
Chapter 9: Chemical Kinetics I. The Basic Ideas Pressure Effects
9.49. When the subatomic species muonium (Mu) was first discovered in 1960, it was not known whether it bore an electric charge. The
answer was provided by a kinetic study of the ionic strength effect on the reaction Mu + Cu2+ in aqueous solution. The following
rate constants were measured at two ionic strengths:
I=0 k = 6.50 × 109 dm3 mol–1 s–1

I = 0.9 M k = 6.35 × 109 dm3 mol–1 s–1
Suppose that muonium had a single negative charge; what would k be expected to be at an ionic strength of 0.9 M? What do you deduce
about the actual charge on muonium?
Solution
9.50. The rate constants of a second-order reaction in aqueous solution at 25 °C had the following values at two ionic strengths:
I/mol dm–3 k/dm3 mol–1 s–1

2.5 × 10–3 1.40 × 10–3
2.5 × 10–2 2.35 × 10–3
Formatted: Space After: 0 pt
Make an estimate of the value of z A z B , the product of the charge numbers.
Solution
9.51. A reaction of the type:
A+ + B2– → products
was found at 25 °C to have a rate constant of 2.8 × 10–4 dm3 mol–1 s–1 at an ionic strength of 1.0 × 10–3 M. Assume the Debye-Hückel
limiting law to apply and estimate the rate constant at zero ionic strength.
Solution
Pressure Effects Formatted: Heading 1, Left
9.52. The rate of a reaction at 300 K is doubled when the pressure is increased from 1 bar to 2000 bar. Calculate ∆‡V°, assuming it to be
independent of pressure.
9-16
Chapter 9: Chemical Kinetics I. The Basic Ideas Pressure Effects
Solution
9.53. The following results were obtained for the solvolysis of benzyl chloride in an acetone-water solution at 25 °C:
P/102 kPa 1.00 345 689 1033

–6 –1
k/10 s 7.18 9.58 12.2 15.8
Make an appropriate plot and estimate ∆‡V°.

Solution
9.54. The fading of bromphenol blue in alkaline solution is a second-order reaction between hydroxide ions and the quinoid form of the
dye:
quinoid form (blue) + OH– → carbinol form (colorless)
The following results show the variation of the second-order rate constant k with the hydrostatic pressure P at 25 °C:
P/104 kPa 101.3 2.76 5.51 8.27 11.02

–4 –1 –1
k/10 M s 9.30 11.13 13.1 15.3 17.9
Estimate ∆‡V°.
Solution
9.55. Use Figure 9.23 to make approximate estimates of the volumes of activation for the alkaline hydrolyses of methyl acetate, ethyl
acetate, and propionamide, at 25 °C.
Solution
9-17
Chapter 9: Chemical Kinetics I. The Basic Ideas Essay Questions
Essay Questions Formatted: Heading 1, Indent: Left:

0", First line: 0"
9.56. Explain clearly the difference between the order and the molecularity of a reaction.
9.57. Give an account of experimental methods that might be used to study the kinetics of (a) a reaction having a half-life of about 10–1 s
and (b) a reaction having a half-life of about 10–7 s.
9.58. Predict the effects of (a) increasing the dielectric constant of the solvent, (b) increasing the ionic strength, and (c) increasing the
pressure on the reactions of the following types:
A 2+ + B– → X +
A + + B2+ → X 3+
A + B → A + B–
Give a clear explanation in each case. What can you say about the entropy of activation to be expected in each case?
9.59. Van’t Hoff’s differential method can be applied to kinetic data in two different ways:
1. Rates can be determined at various stages of a single reaction.
2. Initial rates can be measured at a variety of initial concentrations, the reaction being run a number of times. In each case log 10
(rate) can be plotted against log 10 (concentration of a reactant). Can you suggest why a different order of reaction might be obtained
when these two different procedures are used?
Formatted: Heading 1
9-18
Chapter 9: Chemical Kinetics I. The Basic Ideas Solutions
Solutions
9.1. The stoichiometric equation for the oxidation of bromide ions by hydrogen peroxide in acid solution is:
2Br– + H 2 O 2 + 2H+ → Br 2 + 2H 2 O
Since the reaction does not occur in one stage, the rate equation does not correspond to this stoichiometric equation but is
υ = k[H 2 O 2 ][H+][Br–]
a. If the concentration of H 2 O 2 is increased by a factor of 3, by what factor is the rate of consumption of Br– ions increased?
b. If the rate of consumption of Br– ions is 7.2 × 10–3 mol dm–3 s–1, what is the rate of consumption of hydrogen peroxide? What is
the rate of formation of bromine?
c. What is the effect on the rate constant k of increasing the concentration of bromide ions?
d. If by the addition of water to the reaction mixture the total volume were doubled, what would be the effect on the rate of change
of the concentration of Br–? What would be the effect on the rate constant k?
Solution:
It is important to note that rather than considering the species as themselves, we can make the rate equation more simple by introducing the
following substitutions.
H 2O2 = A
H+ = B
Br – = C
a) We can start off by writing down the rate of reaction for each species involved. Recall from section 9.2 that the rate of reaction is
independent of which reactant or product species is chosen. For the reaction: aA + bB → yY + zZ occurring at constant volume, the
rate of reaction is given as;
1 d [A] 1 d [ B] 1 d [ Y ] 1 d [ Z ]
v=
− =
− = =
a dt b dt y dt z dt
Let us now apply this to our particular case. This will yield;
9-19
d [A] 1 d [ B] 1 d [ C]
vA =
− , vB =
− , vC =
−
dt 2 dt 2 dt
If the concentration of H 2 O 2 is increased by a factor of 3, then we can say that vB will remain fixed and vC will also increase by a
factor of three.
vC will ↑ by a factor of 3
b) We are given that v=

C 7.2 ×10 –3 mol dm –3 s –1 (bromide ion). With this information, we are able to determine the rate of
consumption of species A and B. It is possible to also write the rate of reaction in a manner that expresses the rates of consumption
or formation for each species.
vA vB vY vZ
=
v = = =
a b y z
vA vC vBr2
=
v = =
1 2 1
vA 7.2 ×10 –3 mol dm –3 s –1 vBr2
=
v = =
1 2 1
vA = 0.0036 mol dm –3 s –1
v=
A 3.6 ×10 –3 mol dm –3 s –1
vBr=
2
3.6 ×10 –3 mol dm –3 s –1
c) Recall from section 9.3 that the rate constant k, is independent of concentration (as well as time). This means that there will be no
change in its value if one increases the concentration of bromide ions.
no change in k
d) If we add enough water into the mixture to double the total volume, we will at the same time, be diluting all of the concentrations by
one half. Recall that for the bromide ion, we originally we have;
9-20
1 d [ C] 1 d [ C]  1  1 d [ C]
vC = − multiplied by one half will produce vC =
−  = −
2 dt 2 dt  2  4 dt
vC will have a rate of disappearance that is 4x slower
no change in k
Back to Problem 9.1 Back to Top
9-21
9.2. A reaction obeys the stoichiometric equation:

A + 2B → 2Z
Rates of formation of Z at various concentrations of A and B are as follows:

3.5 × 10–2 2.3 × 10–2 5.0 × 10–7
7.0 × 10–2 4.6 × 10–2 2.0 × 10–6
7.0 × 10–2 9.2 × 10–2 4.0 × 10–6
What are α and β in the rate equation and what is the rate constant k?
υ = k[A]α[B]β
Solution:
Let us begin by determining the total order of the reaction by using the rate at a variety of concentrations.
v ( C3 ) 4.0 ×10−6 mol dm –3 s –1

=v =
v ( C2 ) 2.0 ×10−6 mol dm –3 s –1
v=2
This tells us that the overall order of the reaction will be 2nd order. Since both A and B are included in the rate equation, we can assume
that,
α 1,=
= β 1
v = k [ A ] [ B]
1 1
The rate constant may be determined by rearranging the above expression and simply substituting in experimental values given above at the
same concentration (for each species).
9-22
v
k=
[ A ] [ B]
1 1
v ( C1 ) 5.0 ×10−7 mol dm –3 s –1

= =
[ A ] [ B] ( 3.5 ×10–2 mol dm –3 ) ( 2.3 × 10–2 mol )
k 1 1
dm –3
−4
=
k 6.2 ×10 3 –1
dm mol s –1
9-23
9.3. Some results for the rate of a reaction between two substances A and B are shown in the following table. Deduce the order α with
respect to A, the order β with respect to B, and the rate constant.

v1 1.4 × 10–2 2.3 × 10–2 7.40 × 10–9
v2 2.8 × 10–2 4.6 × 10–2 5.92 × 10–8
v3 2.8 × 10–1 4.6 × 10–2 5.92 × 10–6
Solution:
Given: see above
Required: α, β, k
We will solve this problem in the same way that problem 9.2 was done.
Let us begin by determining the total order of the reaction by examining the concentrations of each species in conjunction with the change
in the rate (at each different concentration).
1.
α β
v3  2.8 ×10−1   4.6 ×10−2 
=   
v2  2.8 ×10−2   4.6 ×10−2 
 5.92 ×10−6  α
 = 10
−8 
= 100
 5.92 ×10 
α =2
2.
2 β
v2  2.8 ×10−2   4.6 ×10−2 
=   
v1  1.4 ×10−2   2.3 ×10−2 
 5.92 ×10−8 
 −9 
= 8= 4 × 2 β
 7.4 × 10 
β =1
9-24
3.
v = k [ A ] [ B]
2
2
7.4 ×10−9 = k1 1.4 ×10−2   2.3 ×10−2 
=k1 1.641 526 176 ×10−3
2
5.92 ×10−8= k2  2.8 ×10−2   4.6 ×10−2 
=k2 1.641 526 176 ×10−3
2
5.92 ×10−6= k3  2.8 ×10−1   4.6 ×10−2 
=k3 1.641 526 176 ×10−3
k1 + k2 + k3
k=
3
=k 1.642 ×10−3
9-25
9.4. A substance decomposes at 600 K with a rate constant of 3.72 ×10– 5 s–1.
a. Calculate the half-life of the reaction.
b. What fraction will remain undecomposed if the substance is heated for 3 h at 600 K?
Solution:
Given: T =
600 K, k =×
3.72 10 – 5 s –1 , t =
3hrs
Required: t1/2 , fraction undecomposed
By looking at the units for the rate constant, it is often possible to determine the order of the reaction. This information will greatly
facilitate the calculation of the half life as there are different equations that should be used depending on the order of the reaction. Since the
units are in s–1, we have seen in Table 9.1 that this corresponds to a 1st order reaction.
a) The half life will then be:
ln 2
t1/2 =
k
ln 2
t1/2 =
3.72 ×10 –5 s −1
0.693 147
t1/2 =
3.72 ×10 –5 s −1
t1/2 = 18 632.988 72 s
=
t1/2 1.86 ×104 s
1 min 1 hr
=
t1/2 1.86 ×104 s × ×
60 s 60 min
t1/2 = 5.18 hrs
b) The undecomposed fraction after three hours will be:
1 a
If k = ln 0 then we can rearrange this expression in order to solve for the fraction of substance that is undecomposed.
t a0 − x
9-26
a0
kt = ln
a0 − x
 a 
exp ( kt ) = ln e  0 
 a0 − x 
a0 − x  60 min 60 s 
exp ( −kt=
) = fraction undecomposed=exp  −3.72 ×10 –5 s –1 × 3 hrs × ×  = 0.669
a0  1 hr 1 min 
fraction undecomposed = 0.669
9-27
9.5. How does the time required for a first-order reaction to go to 99% completion relate to the half-life of the reaction?
Solution:
From Table 9.1 we are given the following information,
1st order reaction:

1 a ln 2
=k = ln 0 , t1/2
t a0 − x k
With this we know that after the half life, there is only 50 percent of the substance left. This means that the fraction undecomposed is equal
to 0.5.
a0 − x
At t1/2 , 0.5 exp ( −kt1/2 )
= 0.5 and =
a0
If the reaction goes to 99 percent completion, this would mean that the fraction undecomposed will be equal to 0.01 and therefore,
a0 − x
At t99 , = exp ( −kt99 )
= 0.01 and 0.01
a0
Let us now rearrange these expressions in order to isolate for the time variable.
1
= exp ( kt1/2 )
0.5
ln 2 = ln e ( kt1/2 )
ln 2
t1/2 =
k
1
= exp ( kt99 )
0.01
ln100 = ln e ( kt99 )
ln100
t99 =
k
9-28
Taking the ratio of these two expressions will show us how the time required for a first-order reaction to go to 99% completion relates to the
half-life of the reaction.
ln100
t99 k ln100 k ln100 t
= = × = → 99 = 6.64
t1/2 ln 2 k ln 2 ln 2 t1/2
k
9-29
9.6. The rate constant for the reaction H+ + OH– → H 2 O is 1.3 × 1011 dm3 mol–1 s–1. Calculate the half-life for the neutralization process if
(a) [H]+ = [OH–] = 10–1 M and (b) [H+] = [OH–] = 10–4 M.
Solution:
1.3 ×1011 dm3 mol –1 s –1 , [ H ] =

+
Given: k = OH  =
10 –1 M,  H +  =
OH –  =
–
10 –4 M
Required: t1/2 in each case
We will again look at the rate constant in order to determine the overall order of the reaction. Since the units are dm3 mol–1 s–1, from Table
9.1 we can see that the reaction is 2nd order.
a) The half life for the neutralization process [H]+ = [OH–] = 10–1 M is therefore,
1
t1/2 =
ka0
1
t1/2 =
(1.3 × 1011
dm 3
mol s )(10−1 M )
−1 −1
1 M = 1 mol L−1
1 L = 1 dm3
1
t1/2 =
(1.3 ×1011 3
dm mol −1
)(
s −1 10−1 mol dm −3 )
= 7.7 ×10−11 s
t1/2
b) The half life for the neutralization process [H]+ = [OH–] = 10–4 M is therefore,
9-30
1
t1/2 =
ka0
1
t1/2 =
(1.3 × 1011
dm 3
mol s )(10−4 M )
−1 −1
1 M = 1 mol L−1
1 L = 1 dm3
1
t1/2 =
(1.3 ×1011 3
dm mol −1
)(
s −1 10−4 mol dm −3 )
= 7.7 ×10−8 s
t1/2
9-31
9.7. The isotope 90Sr emits radiation by a first-order process (as is always the case with radioactive decay) and has a half-life of 28.1
years. When ingested by mammals it becomes permanently incorporated in bone tissue. If 1 μg is absorbed at birth, how much of
this isotope remains after (a) 25 years, (b) 50 years, (c) 70 years?
Solution:
=
Given: 90
=
Sr: t1/2 28.1 years, m 1 µ g
Required: fraction remaining in each case

It is first important to determine the rate constant. Since we are told that the radioactive decay is a 1st order process, we can use Table 9.1 in
order to calculate its value.
ln 2
t1/2 =
k
ln 2
k=
t1/2
t1/2 = 28.1 yrs
0.693147
k=
28.1 yrs
k = 0.024 667 yrs −1
Now we will use the integrated form in order to isolate for the fraction undecomposed after a certain period of time.
1 a
k = ln 0
t a0 − x
a0
kt = ln
a0 − x
 a 
exp ( kt ) = ln e  0 
 a0 − x 
a −x
exp ( −kt= ) 0 = fraction undecomposed
a0
9-32
a) After 25 years,
a0 − x
(
= exp −0.024 667 yrs −1 × 25 yrs
a0
)
a0 − x
= 0.540 µ g
a0
0.540 µ g remain after 25 years
b) After 50 years
a0 − x
(
= exp −0.024 667 yrs −1 × 50 yrs
a0
)
a0 − x
= 0.291 µ g
a0
c) After 70 years,
a0 − x
(
= exp −0.024 667 yrs −1 × 70 yrs
a0
)
a0 − x
= 0.178 µ g
a0
9-33
9-34
9.8. The first-order decomposition of nitramide in the presence of bases, NH 2 NO 2 → N 2 O(g) + H 2 O(l), is conveniently analyzed by
collecting the gas evolved during the reaction. During an experiment, 50.0 mg of nitramide was allowed to decompose at 15 °C. The
volume of dry gas evolved after 70.0 min. was measured to be 6.59 cm3 at 1 bar pressure. Find the rate constant and the half-life for
nitramide decomposition.
Solution:
Given: Nitramide: m =50.0 mg, T =15 °C, V =6.59 cm3 , P =1 bar, t =70.0 min
Required: k , t1/2
When given this type of problem, it is essential that the number of moles of substance in found before the rate constant as well as the half
life can be determined. Let us begin by using the Ideal Gas Law in order to do this.
PV = nRT
m 50 ×10−3 g
n= =
M 62.023 g mol−1
0
n0 8.06 ×10−4 mol

=
PV
nreacted ( 70 min ) =
RT
nreacted ( 70 min ) =
(1 bar ) ( 6.59 cm ) 3
( 0.083145 dm 3
)(
bar K −1 mol−1 288 K )
1 cm = 0.001 dm
3 3
6.59 cm3 0.001 dm3

nreacted ( 70 min ) = −1
×
23.945 76 dm3 mol 1 cm3
nreacted ( 70 min
= ) 2.75 ×10−4 mol
Now that we have the initial number of moles and the number of moles reacted after 70 minutes, we can use this bit of information in the
integrated rate law as the fraction of undecomposed substance.
9-35
1 a 1 n0
=k =ln 0 ln
t a0 − x t n0 − nreacted
1 8.06 ×10−4 mol
k= ln
70 min ( 8.06 ×10−4 − 2.75 ×10−4 ) mol
k 5.96 ×10−3 min −1

=
The half life for the reaction may now be determined using the above value.
ln 2
t1/2 =
k
0.693147
t1/2 =
5.96 ×10−3 min −1
t1/2 = 116 min
9-36
9.9. The reaction:

2NO(g) + Cl 2 (g) → 2NOCl(g)
is second order in NO and first order in Cl 2 . In a volume of 2 dm3, 5 mol of nitric oxide and 2 mol of Cl 2 were brought together, and
the initial rate was 2.4 × 10–3 mol dm–3 s–1. What will be the rate when one-half of the chlorine has reacted?
Solution:
Given: [ NO ] , [ Cl2 ] , V
= 2 dm3 , nNO
= 5 mol, nCl= 2 mol, k= 2.4 × 10 –3 mol dm –3 s –1
2 1
2 0
Required: k when half of chlorine reacted
Let us first write out the rate law for this reaction (given that the reaction is second order in NO and first order in Cl 2 ).
v = k [ NO ] [ Cl2 ]
2 1
The easiest way to solve this problem is to construct a table which will enable us to examine the initial amounts of each species in addition
to the amount after half of the chlorine is reacted.
2NO + Cl2 → 2NOCl

initial 5 2 0 mol
reacted 1
final 3 1 2 mol
The rate of reaction is therefore equal to:
9-37
rate1 = k1 [ NO ] [ Cl2 ]
2 1
k1 [5] [ 2]
2.4 ×10−3 =
2 1
2.4 ×10−3
=
k1 = 4.8 ×10−5
50
When one-half of the chlorine has reacted:
rate2 = k1 [3] [1]
2 1
rate2 =4.8 ×10−5 × 9

=
rate2 4.32 ×10−4 mol dm −3 s −1
9-38
9.10. Measuring the total pressure is a convenient way to monitor the gas phase reaction:
2NOCl(g) → 2NO(g) + Cl 2 (g)
However, the rate depends on the concentration of the reactant, which is proportional to the partial pressure of the reactant. Derive an
expression relating the rate of this reaction to the initial pressure, P 0 , and the total pressure, P t , at time t. Assume that the reaction follows
second-order kinetics.
Solution:
Let us begin by mentioning that we will making reference to all quantities in terms of the number of moles. Let n 0 denote the initial amount
of NOCl and we will say that 2x is the number of moles reacted after a period of time, t. We can again construct a table to facilitate our
problem solving process.
2NOCl ( g ) → 2NO ( g ) + Cl2 ( g )

initial n0 0 0
reacted − 2x 2x x
final n0 − 2 x 2x x
We can see that the total amount of gas at any given time (t) is equal to:
n0 −2 x +2x + x = n0 + x
With this information, we can now calculate the concentrations. We will make use of the Ideal Gas Law which states that,
PV = nRT
n0 RT
P0 =
V
n
initial concentration →
V
n0 P
= 0
V RT
9-39
Let us now derive the expression for the concentration at the time t.



total number of moles
RT
=Pt ( n0 + x )
V
Pt n x
= 0+
RT V V
x Pt n0
= −
V RT V
n0 P
Substituting the original expression = 0 into the expression for the concentration at time t, we get,
V RT
x Pt n0 Pt P
= − = − 0
V RT V RT RT
x P − P0
= t= [Cl
= ]2 2 [ NO]
V RT
And
n0 − 2 x P0  2Pt − 2P0  3P0 − 2Pt

= − = = [ NOCl]
V RT  RT  RT
−d [ NOCl] k [3P0 − 2Pt ]
2
= = k= [ NOCl]
2
rate
dt R 2T 2
9-40
9.11. The following results were obtained for the rate of decomposition of acetaldehyde:
% decomposed:
0 5 10 15 20 25 30 35 40 45 50
Rate/Torr min–1
8.53 7.49 6.74 5.90 5.14 4.69 4.31 3.75 3.11 2.67 2.29
Employ van’t Hoff’s differential method to obtain the order of reaction.

Solution:
It is best to solve this type of problem using Microsoft Excel or any other math program that will enable you to plot this curve. Employing
the Van’t Hoff method, we obtain the following values:
% ν Torr log 10 (% log 10 (ν Torr
decomposed min–1 remaining) min-1)
0 8.53 2.00 0.931
5 7.49 1.98 0.874
10 6.74 1.95 0.829
15 5.9 1.93 0.771
20 5.14 1.90 0.711
25 4.69 1.88 0.671
30 4.31 1.85 0.634
35 3.75 1.81 0.574
40 3.11 1.78 0.493
45 2.67 1.74 0.427
50 2.29 1.70 0.360
We can now plot log 10 (ν/Torr min-1) versus log 10 (% remaining). The slope will then be the order of the reaction (with respect to time).
9-41
Using the slope function on Microsoft Excel we obtain,
slope = 1.865272965
slope = 2.0 to the nearest half integer
9-42
32
9.12. The isotope 15 P emits radiation and has a half-life of 14.3 days. Calculate the decay constant in s–1. What percentage of the initial
activity remains after (a) 10 days, (b) 20 days, (c) 100 days?
Solution:
Given: 32
15 P : t1/2 = 14.3 days
Required: decay constant, percentage of initial activity

Let us begin by determining the rate constant. According to Table 9.1,
ln 2
t1/2 =
k
24 hrs 60 min 60 s
t1/2 = 14.3 days × × ×
1 day 1 hr 1 min
t1/2 = 1 235 520 s
0.693 147
k=
1 235 520 s
k 5.61×10−7 s −1 or,
=
0.693 147
k=
14.3 days
k = 0.0485 days −1
a) Percentage of initial activity remaining after 10 days
9-43
1 a
k = ln 0
t a0 − x
a0
kt = ln
a0 − x
 a 
exp ( kt ) = ln e  0 
 a0 − x 
a0 − x
exp ( − kt ) =
a0
a0 − x
(
= exp −0.0485 days −1 ×10 days
a0
)
a0 − x
= 0.615 697 × 100%
a0
62% active
b) Percentage of initial activity remaining after 20 days
9-44
1 a
k = ln 0
t a0 − x
a0
kt = ln
a0 − x
 a 
exp ( kt ) = ln e  0 
 a0 − x 
a0 − x
exp ( − kt ) =
a0
a0 − x
(
= exp −0.0485 days −1 × 20 days
a0
)
a0 − x
= 0.379 083 ×100%
a0
38% active
c) Percentage of initial activity remaining after 100 days
9-45
1 a
k = ln 0
t a0 − x
a0
kt = ln
a0 − x
 a 
exp ( kt ) = ln e  0 
 a0 − x 
a0 − x
exp ( −kt ) =
a0
a0 − x
(
= exp −0.0485 days −1 ×100 days
a0
)
a0 − x
= 0.007 828 ×100%
a0
0.78% active
9-46
35
9.13. The following counts per minute were recorded on a counter for the isotope 16 S at various times:
Time/d Counts/min Formatted: Line spacing: Exactly 12

pt
0 4280 Formatted: Line spacing: Exactly 12
pt
1 4245
Formatted: Line spacing: Exactly 12
2 4212 pt
pt
4 4146
5 4113 pt
10 3952 pt
pt
Determine the half-life in days and the decay constant in s–1. How many counts per minute would be expected after (a) 60 days and (b) 365 Formatted: Line spacing: Exactly 12
pt
days?
pt
Solution:
Formatted: Space After: 0 pt
35
Given: 16 S : see above
Required: t1/2 , decay constant in each case
In order to plot this graph, we will use roughly the same method as we did in problem 9.11.
t (days) n (min) ln(n 0 /n)

0 4280 0.00E+00
1 4245 8.21E-03
2 4212 1.60E-02
3 4179 2.39E-02
4 4146 3.18E-02
5 4113 3.98E-02
10 3952 7.97E-02
15 3798 1.19E-01
9-47
We can plot ln(n 0 /n) against t in order to find the slope, k. It is equally possible to simply calculate the slope based on the rise over run principle.
rise 0.119
=
slope = = 7.93 ×10−3 days −1
run 15
k= 7.93 ×10−3 days −1 → k= 9.18 ×10−8 s −1
This plot indicates that the reaction is first order.
Now that we have determined the value of the decay constant, we can find the half life.
0.693 147
t1/2 =
7.93 ×10−3 days −1
t1/2 = 87 days
a) The number of counts per minute expected after 60 days,
9-48
n0  0.693 
ln = kt=  t
n(t )  87 
=
kt60 ( 7.93 ×10 −3
days −1 ) ( 60 days )
n0
= = ln
kt60 0.4758
n
n0
exp ( 0.4758 ) = ln e
n
n0
= 1.609 301
n
n0 4280
=n = = 2659.5
1.609 301 1.609 301
n = 2660 counts
b) The number of counts per minute expected after 365 days,
=
kt60 ( 7.93 ×10 −3
days −1 ) (365 days )
n0
= =
kt60 2.894 45 ln
n
n0
exp ( 2.894 45 ) = ln e
n
n0
= 18.073 558
n
n0 4280
=n = = 236.8
18.073 558 18.073 558
n = 237 counts
9-49
9.14. The reaction:
cis -Cr(en) 2 (OH) +2  trans -Cr(en) 2 (OH) +2
is first order in both directions. At 25 °C the equilibrium constant is 0.16 and the rate constant k 1 is 3.3 × 10–4 s–1. In an experiment
starting with the pure cis form, how long would it take for half the equilibrium amount of the trans isomer to be formed?
Solution:
Given: T =
25 °C, keq =
0.16, k1 =
3.3 × 10 –4 s –1
Required: see above

It is important to realize that these are two opposing reactions occurring at the same time. We are told that they are 1st order in both
directions therefore for the reaction A ←k1
→ Z , if the experiment is starting with the pure cis form of the isomer of concentration a 0 and if

k−1
after time t, the concentration of the trans form of the isomer has the concentration x, then that of the cis form will be equal to a 0 -x.
If the forward reaction were to occur in isolation, it’s rate equation could be written as;
=v1 k1 ( a0 − x )
While the rate of the reverse reaction would be written as;
v−1 = k−1 x
Since these reactions are in opposite directions, we can define the net rate of change of concentration of the trans isomer as:
dx
= k1 ( a0 − x ) − k−1 x
dt
If x e is the concentration of the trans isomer at equilibrium (this is when the net rate is zero), then we know that,
k1 ( a0 − x ) − k−1 x =
0
k1 ( a0 − x ) =
k−1 x
k1 xe
= k=
k−1
eq
( 0 − xe )
a
9-50
It is possible to eliminate k−1 in order to obtain the following Eq. 9.47:
dx k a
= 1 0 ( xe − x )
dt xe
Integration of this equation, subject to the boundary condition that x = 0 when t = 0 gives the rate equation corresponding to Eq. 9.48:
x xe a kt
k1t = e ln or 0 1 =ln xe − ln ( xe − x )
a0 ( xe − x ) xe
xe
For half of the equilibrium amount of product to be formed, it would mean that x = . Making this substitution into the above will yield,
2
xe xe
k1t1/2 = ln
a0  xe 
 xe − 2 
 
xe xe
k1t1/2 = ln
a0  xe 
2
 
x  2 
k1t1/2 = e ln  xe × 
a0  xe 
x
k1t1/2 = e ln 2
a0
Having been given the equilibrium constant as well as the rate constant for the forward reaction, we can now do a few more calculations in
order to determine how long it would take for half the equilibrium amount of the trans isomer to be formed.
9-51
xe
=keq = 0.16
( a0 − xe )
=
1 (=
a0 − xe ) 1
keq xe 0.16
( a0 − xe ) = a0
− 1=
1
xe xe 0.16
a0 1
= 1+
xe 0.16
a0
= 7.25
xe
xe
k1t1/2 = ln 2
a0
xe
ln 2
a0 ln 2
=
t1/2 =
k1 a0
k1
xe
0.693147
t1/2 =
( 7.25 × 3.3 ×10−4 s−1 )
t1/2 = 289.7 s
t1/2 = 290 s
9-52
9.15. Suppose that a gas phase reaction 2A(g) → 2B(g) + C(g) follows second-order kinetics and goes to completion. If the reaction is
allowed to proceed in a constant volume vessel at an initial pressure of 2 bar (only A is initially present), what will be the partial
pressures of A, B, and C and the total pressure at t = t 1/2 , 2t 1/2 , 3t 1/2 , and infinity?
Solution:
Given: 2A(g) → 2B(g) + C(g) (second order), P0 = 2 bar
Required: PA , PB , PC , Ptot at t = t 1/2 , 2t 1/2 , 3t 1/2 and infinity
Recall from section 9.4 that if we have a reaction of either of the following forms:
2A → Z or A + B → Z
We can write the rate equation in its differential form according to Eq. 9.31 and Eq. 9.32.
dx
= k ( a0 − x )
2
dt
dx
kdt =
( a0 − x )
2
Eq. 9.32 can then be integrated in order to obtain the following:
1
kt + I =
( a0 − x )
I = constant of integration
when= x 0,= t 0
1
I=
( a0 )
x 1 1
=
kt →=
kt −
a0 ( a0 − x ) a0 − 2 x ( a0 )
Let us assume that 2x moles of substance A are consumed in each step. For a 2nd order reaction, we can check Table 9.1 or look at Eq. 9.40
in order to find the expression for the half life.
9-53
1
t1/2 =
( a0 ) k
Since all of the times asked for are written in multiples of the half life, we can write,
n 1 1
kt = = − where n =
1, 2,3, ∞
a0 a0 − 2 x ( a0 )
Further simplification of this expression gives,
n 1 1
+ =
a0 ( a0 ) a0 − 2 x
n +1 1
=
a0 a0 − 2 x
a0
= a0 − 2 x
n +1
a
2=
x a0 − 0
n +1
a0  n 
x=  
2  n +1 
Using simple stoichiometry, we can see that,
PA ∝ a0 − 2 x
PB ∝ 2 x
PC ∝ x
9-54
a0
Since = a0 − 2 x, then
n +1
P
PA = 0
n +1
a
Since 2=x a0 − 0 then
n +1
n
PB = P0
n +1
a  n 
Since x = 0   then
2  n +1 
P  n 
PC = 0  
2  n +1 
Using the above three expressions, we can construct a table which will give the partial pressures for each species in addition to the total
pressure at each temperature.
P tot
t P A (bar) P B (bar) P C (bar) (bar)
t0 2.000 0.000 0.000 2.000
t 1/2 1.000 1.000 0.500 2.500
2t 1/2 0.667 1.333 0.667 2.667
3t 1/2 0.500 1.500 0.750 2.750
t infinity 0.000 2.000 1.000 3.000
9-55
9-56
9.16. Derive the following relationship for the half-life t 1/2 of a reaction of order n, with all reactants having an initial concentration a 0 :
2n –1 –1
t1/ 2 =
ka0n –1 (n –1)
Solution:
From Table 9.1, we are given the general expression for a reaction of the nth order. We can separate the variables and integrate this in order
to generate the above equation for the half life of an nth order reaction.
dx
= k ( a0 − x )
n
dt
dx
kdt =
( a0 − x )
n
dx
∫ kdt = ∫ ( a − x)
n
0
(a − x)
1− n
kt =
( n − 1)
1  1 1 
k=  − n −1 
t ( n − 1)  ( a0 − x ) n −1
a 0 
a0
Recall that at the half life, x = and therefore,
2
9-57
 
 
1  1 1 
k −
t1/2 ( n − 1)   a 
n −1
a 0n −1 
  a0 − 0  
 2 
 
 
1  1 1 
=k −
t1/2 ( n − 1)   a0 n −1 a 0n −1 
  
 2  
 
 
1  1 1 
=t1/2 −
k ( n − 1)   a0 n −1 a 0n −1 
  
 2  
Further simplification will yield,
1  a0 1− n 1− n 
=t1/2   − a 0 
k ( n − 1)  2  
 a0 1− n 1− n 
 a 0 2 − a 0 = a 0 ( 2 − 1)
1− n n −1 1− n 1− n n −1
  − a 0 =
 
2 
t1/2 =
(2 n −1
− 1)
n −1
ka 0 ( n − 1)
9-58
9.17. Vaughan [J. Am. Chem. Soc. 54, 3867(1932)] reported the following pressure measurements as a function of time for the
dimerization of 1,3-butadiene (C 4 H 6 ) under constant volume conditions at 326 °C:
t/min 3.25 12.18 24.55 42.50 68.05

P/Torr 618.5 584.2 546.8 509.3 474.6
The initial amount of butadiene taken would have exerted a pressure of 632.0 Torr. Find whether the reaction follows first- or second-order
kinetics and evaluate the rate constant.
Solution:
Given: see above
Required: first or second order kinetics? k
First we should write out the balanced reaction for this process.
2C4 H 6 → C8 H12
initial n0 0
time t n0 − 2 x x
We are again assuming that 2x moles are being consumed in each step (problem 9.15). From this, we can determine the number of moles at
any given time, t.
n0 − 2 x + x = n0 − x
n0 − x at time t
Using the Ideal Gas Law, we can derive expressions for the number of moles in both instances.
9-59
PV = nRT
n RT
P0 = 0
V
( n − x ) RT
Pt = 0
V
n0 RT ( n0 − x ) RT
P0 − =
Pt −
V V
RT 
P0 − Pt = n0 − n0 − x 
V 
(  )
xRT
P0 − Pt =
V
The partial pressure of butadiene at a time t, can therefore be expressed as,
PC4 H6 = 2 Pt − P0 =
( n0 − 2 x ) RT
V
e.g. at time 3.25min, P t =618.5 Torr
PC4 H6 (3.25) =
2 × 618.5 − 632 =
605 etc.
Re-tabulating the given data in terms of the partial pressure of butadiene will yield,
t/min 3.25 12.18 24.55 42.50 68.05
= 2 Pt − Po
PC4 H6 /Torr 605.0 536.4 461.6 386.6 317.2
 PC H 
ln  4 6  -0.0437 -0.1640 -0.3142 -0.4915 -0.6894
 Po 
9-60
In order to determine whether the reaction proceeds according to 1st or 2nd order kinetics, one should first plot PC4 H6 vs. t . This plot yields
curved line.
This means that the reaction does NOT proceed according to 1st order kinetics and therefore, we must now try to plot the inverse of the
pressure versus time.
9-61
This straight-line plot indicates that the reaction follows 2nd order kinetics. It is also possible to perform a linear regression (using
Microsoft Excel Linest Function) in order to reveal the integrated rate law.
2nd order kinetics
linear regression statistics:

2.31869E-05 0.001586
2.66985E-07 1.01E-05
0.999602407 1.38E-05
7542.405387 3
1
= 2.31869 ×10−5t + 0.001586
PC4 H6
Remember that the slope of this line will be equal to the rate constant, k.
=k 2.31869 ×10−5
9-62
9-63
9.18. A drug administered to a patient is usually consumed by a first-order process. Suppose that a drug is administered in equal amounts
at regular intervals and that the interval between successive doses is equal to the (1/n)-life for the disappearance process (i.e., to the
time that it takes for the fraction 1/n to disappear). Prove that the limiting concentration of the drug in the patient’s body is equal to n
times the concentration produced by an individual dose.
Solution:
When the concentration has reached nc, where c is the concentration produced by a single dose, the concentration will fall to ( n − 1) c during
the interval between successive doses. The next dose restores the concentration to ( n − 1) c + c which when simplified is equal to nc. This
indicates that the steady state has been reached.
9-64
9.19. Equation 9.45 applies to a second-order reaction of stoichiometry A + B → Z. Derive the corresponding equation for a second-order
reaction of stoichiometry 2A + B →Z.
Solution:
2A + B → Z
a0 b0 0
a0 − 2 x b0 − x x
dx
= k ( a0 − 2 x )( b0 − x )
dt
dx
kdt =
( a0 − 2 x )( b0 − x )
dx  1 1  dx
=kdt =  − 
( a0 − 2 x )( b0 − x )  ( a0 − 2 x ) 2 ( b0 − x )  2b0 − a0

1 1  dx
=∫ kdt ∫ (a − 
 0 − 2 x ) 2 ( b0 − x )  2b0 − a0
1  1 1 
=
kt  − ln ( a0 − 2 x ) + ln 2 ( b0 − x )  + I
2b0 − a0  2 2 
when=
x 0,=
t 0
 1 
I=
1
2b0 − a0
( ) 1
( )
 − 2 ln a0 − 2 x + 2 ln 2 b0 − x 
1 1 a0 1 2 b0 
=kt  ln − ln 
2b0 − a0  2 ( a0 − 2 x ) 2 2 ( b0 − x ) 
1 a (b − x )
kt = ln 0 0
2 ( 2b0 − a0 ) b0 ( a0 − 2 x )
9-65
9-66
9.20. Derive the integrated rate equation for an irreversible reaction of stoichiometry 2A + B → Z, the rate being proportional to [A]2[B]
and the reactants present in stoichiometric proportions; take the initial concentration of A as 2a 0 and that of B as a 0 . Obtain an
expression for the half-life of the reaction.
Solution:
2A + B → Z
2a0 b0 0
2a0 − 2 x b0 − x x
v = k [ A ] [ B]
2
[ A ]0 = 2a0
[ B]0 = b0
dx
=k ( 2a0 − 2 x ) ( b0 − x )
2
dt
For simplicity, we will say that ( b0 − x ) = ( a0 − x ) . Making this substitution into the above yield,
9-67
( 2a0 − 2 x ) = ( 2a0 − 2 x )( 2a0 − 2 x )

2
( 2a0 − 2 x ) =4a 2 − 4a0 x − 4a0 x + 4 x 2 =4 ( a 2 − 2a0 x + x 2 )

2
0 0
( 2a0 − 2 x ) = 4 ( a0 − x )
2 3
dx
= 4k ( a0 − x )
3
dt
dx
4kdt =
( a0 − x )
3
dx
4 ∫ kdt = ∫
( a0 − x )
3
1
4kt + I =
2 ( a0 − x )
2
when=x 0,=t 0
1 1
I= = 2
( )
2
2 a0 − x 2 a0
1 1
=4kt −
2 ( a0 − x )
2
2a 02
a0
at t1/2 , x = hence,
2
9-68
1 1 1 1
=
4kt1/2 2
=
− 2 2
− 2
 a  2a 0  a  2a 0
2  a0 − 0  2 0
 2   2
1 1 2 1 4 1
4kt1/2 = 2 − 2 =2− 2 = 2− 2
a 0 2a 0 a 0 2a 0 2a 0 2a 0
2
3
4kt1/2 = 2
2a 0
3
2a 02 3 1
=
t1/2 = ×
4k 2a 02 4k
3
t1/2 =
8ka 02
9-69
9.21. Prove that for two simultaneous (parallel) reactions
[Y] k1
= at all times.
[Z] k2
Solution:
Let us begin by writing out the rate equations for each individual reaction.
d [Y] d [ Z]
= k= 1 [ A ] and k2 [ A ]
dt dt
Setting these expressions equal to one another it is possible to eliminate the concentration of A.
d [Y] d [ Z]
[A]
= k1= = k2 [ A ]
dt dt
k1 d [ Y ]
=
k2 d [ Z]
Integrate both sides of the equation to obtain,
k1
∫ k d [ Z] = ∫ d [ Y ]
2
k1
[ Z] + I =[Y]
k2
Note that under the boundary condition t = 0, then [ Y ] = [ Z] therefore, I = 0 hence;
9-70
k1
[ Z] + I =[Y]
k2
I =0
k1
[ Z] + 0 =[Y]
k2
k1 [ Y ]
=
k2 [ Z]
9-71
*9.22. Prove that for two consecutive first-order reactions; A → B → C the rate of formation of C is given by:
 k e – k1t – k1e – k2t 
=[C] [A]0 1 + 2 
 k1 – k2 
where [A] 0 is the initial concentration of A.
(Hint: The solution of the differential equation):
dx
= abe – bt – cx
dt
where a, b, and c are constants, is
ab – bt
= x (e – e – ct ) + I
c–b
Solution:
A 
k1
→ B 
k2
→C
a0 0 0
a0 − x x 0
b0 − x x
Writing out the rates of consumption and formation for each species, we will obtain,
−d [ A ]
= k1 [ A ]
dt
d [ B]
= k1 [ A ] − k2 [ B]
dt
d [ C]
= k 2 [ B]
dt
Let us integrate the first expression after separating the variables.
9-72
At −d [ A ]
∫
A0
[A] ∫ 1
= k dt
ln [ A ] A = k1t
A t
ln [ A ]t − ln [ A ]0 = k1t
[ A ]t
ln =kt
[ A ]0 1
[ A ]t
ln e = exp ( −k1t )
[ A ]0
[ A ]t [ A ]0 exp ( −k1t )
=
This expression can be substituted into the rate of formation for substance B. This will yield,
d [ B]
= k1 [ A ]0 exp ( −k1t ) − k2 [ B]
dt
With the boundary condition t = 0, this means that [ B] = 0 which allows us to further simplify the above.
d [ B]
= k1 [ A ]0 exp ( −k1t ) −= k 2 [ B] 0
dt
k1 [ A ]0 exp ( −k1t ) =
k 2 [ B]
k1 [ A ]0 exp ( −k1t )
[ B] = and integrate to obtain,
k2
=[ B] [ A ]0
k1
k2 − k1
(
e( − 1 ) − e( − 2 )
kt k t
)
9-73
[ A ]0 = [ A ] + [ B] + [C]
[C] = [ A ]0 − [ A ] − [ B]
[C] = [ A ]0 − [ A ]0 exp ( −k1t ) − [ A ]0
k1
k2 − k1
(
e( − k1t ) − e( − k2t ) )
Simplify by method of factoring the above to get the appropriate expression (that which is sought after).
 k e – k1t – k1e – k2t 

=
[C] [A]0 1 + 2 
 k1 – k2 
9-74
*9.23. a. Derive the integrated rate equation for a reversible reaction of stoichiometry:
k1
AY + Z
k –1
The reaction is first order from left to right and second order from right to left. Take the initial concentration of A as a 0 and the
concentration at time t as a 0 – x.
b. Obtain the integrated equation in terms of k, and the equilibrium constant K = k 1 /k –1 .
c. A reaction to which this rate equation applies is the hydrolysis of methyl acetate. Newling and Hinshelwood, J. Chem. Soc., 1936,
1357(1936), obtained the following results for the hydrolysis of 0.05 M ester at 80.2 °C in the presence of 0.05 M HCl, which
catalyzes the reaction:
Time, s 1350 2070 3060 5340 7740 ∞
Percent hydrolysis 21.2 30.7 43.4 59.5 73.45 90.0
Obtain values for the rate constants k 1 and k –1 .
Solution:
k1
A  Y + Z
k –1
initial a0 0 0
time t a0 − x x x
a) We can write out the rate equation with respect to the rate of consumption of the concentration of A.
d [A]
− = k1 [ A ] − k−1 [ Y ][ Z]
dt
At a time t, this can then be written in the following form:
dx
= k1 ( a0 − x ) − k−1 x 2
dt
dx
Recall that at equilibrium, = 0 therefore,
dt
9-75
k1 ( a0 − xe ) − k−1 x e2 =
0
k1 ( a0 − xe ) =
k−1 x e2
k1 ( a0 − xe )
k−1 = ( †)
xe2
Insertion of this expression into the first equation yields,
k a −x 
dx (
= k1 ( a0 − x ) −  1 0 2 e  x 2
)
dt  xe 
 
2
xe dx
= xe2 k1 ( a0 − x ) − x e2 k1 ( a0 − xe ) x 2
dt
xe2 dx
= k1  xe2 ( a0 − x ) − x e2 ( a0 − xe ) x 2 
dt
xe2 dx
= k1dt
 xe2 ( a0 − x ) − x e2 ( a0 − xe ) x 2 
Integration of the LHS of this expression can be carried out after resolution into partial fractions.
p q
=
LHS +
a0 − x a0 xe + a0 x − xe x
xe xe ( a0 − xe )
=p = and q
2a0 − xe 2a0 − xe
The integration is now straightforward although rather lengthy. We will use the boundary conditions t = 0, x = 0 which gives the
following result.
9-76
xe a x + x ( a0 − xe )
k1 = ln 0 e ( *)
( 2a0 − xe ) t a0 ( xe − x )
Readers wishing further mathematical details/explanation are referred to C. Capellos and B.H.T Bielski, Kinetic Systems (New York:
Wiley, Interscience, 1972) pp.41-43.
b) Knowing that the equilibrium constant is K = k 1 /k –1 , we may also write, from ( † )
k1 ( a0 − xe ) − k−1 x e2 =
0
k1 ( a0 − xe ) k−1 xe
2
=
k−1 k−1
k1 ( a0 − xe ) xe2
=
k−1 ( a0 − xe ) ( a0 − xe )
k1 xe2
=
K =
k−1 ( a0 − xe )
c) In order to deal with the numerical data which are in terms of percent hydrolysis, it is convenient to define,
x x
r≡ and re ≡ e
a0 a0
Substituting this into the integrated rate law derived in part A, (*)
re r + r (1 − re )
k1 = ln e
( 2 − re ) t ( re − r )
9-77
re + r (1 − re )
From the data given in the problem, we have re = 0.90 . We may now construct a table which will allow us to plot ln versus
( re − r )
time. Remember that the slope of this line will enable us to find the forward and reverse rate constant values.
 r + r (1 − re )   k1 (2 − re ) 
ln  e  =t 
 (re − r )   re 
slope
time (s) r r e + r(1-r e ) r e -r ln(r e +r(1-r e ))/(r e -r)

1350 0.212 0.9212 0.688 0.2919
2070 0.307 0.9307 0.593 0.4507
3060 0.434 0.9434 0.466 0.7053
5340 0.595 0.9595 0.305 1.1461
7740 0.7345 0.97345 0.1655 1.7719
1.64 − 0.35 k ( 2 − re )
slope = 1.843 ×10−4 s −1 =1
=
7000 s re
9-78
Solving for k1 we obtain,
k1 ( 2 − re ) ( 2 − 0.90 )
= k1
re 0.90
k1 ( 2 − re )
= 1.222
=k1 1.843 ×10−4 s −1
re
1.843 ×10−4 s −1
k1 =
1.222
k1 1.51× 10−4 s −1
=
This is done at constant catalyst concentration of 0.05 M HCl and makes k 1 [0.05] 1st order. The 2nd order rate constant is therefore,
1
1.51× 10−4 s −1 ×
k1 =
0.05 mol dm −3
k1 ( 2nd order
= ) 3.02 ×10−3 dm3 mol−1 s−1
At equilibrium,
k1
A  Y + Z
k –1
0.05 ( 0.1) 0.05 ( 0.9 ) 0.05 ( 0.9 )
9-79
[ Y ][ Z=] ( 0.05 ( 0.9 ) )

2
k1
=
K =
k−1 [A] 0.05 ( 0.1)
K = 0.405 mol dm −3
k1 1.51×10−4 s −1
k−= =
K 0.405 mol dm −3
1
k−1 3.73 ×10−4 dm3 mol−1 s −1

=
k−1 ( 2nd order ) =

1
3.73 ×10−4 dm3 mol−1 s −1 ×
0.05 mol dm −3
k−1 ( 2nd order
= ) 7.46 ×10−3 dm6 mol−2 s−1
9-80
*9.24. The dissociation of a weak acid HA + H 2 O  H 3 O+ + A– can be represented as:

A  Y+Z
The rate constants k 1 and k –1 cannot be measured by conventional methods but can be measured by the T-jump technique (Section
9.5). Prove that the relaxation time is given by:
1
t *=
k1 + 2k –1 xe
where the concentration of the ions (Y and Z) is at equilibrium.
Solution:
If a 0 is the initial concentration of substance A and x is the concentration of ions at equilibrium, then the corresponding rate law is the same
one as we have seen in the previous problem.
dx
= k1 ( a0 − x ) − k−1 x 2
dt
dx
At equilibrium, =0
dt
k1 ( a0 − xe ) − k−1 xe 2 =0
The deviation from the equilibrium can be defined as: ∆x = x − xe and we may also write,
d ∆x dx
= = k1 ( a0 − x ) − k−1 x 2
dt dt
Subtraction of the second expression from the above yields
d ∆x
=−k1∆x − k−1 ( ∆x ) − 2k−1 xe ∆x
2
dt
Since ∆x is very small, the term in the ( ∆x ) may be ignored. This will omission will produce,
2
d ∆x
=−k1∆x − 2k−1 xe ∆x
dt
d ∆x
=( −k1 − 2k−1 xe ) ∆x
dt
9-81
Integrate this expression to obtain,
d ∆x
∫ = ( −k1 − 2k−1 xe )dt
∆x ∫
ln ∆x = ( −k1 − 2k−1 xe ) t + I
Using the boundary condition t = 0, ∆x =∆x0 ,
( ∆x )0
ln =( −k1 − 2k−1 xe ) t
∆x
By definition, the relaxation time t ∗ is the time that corresponds to,
( ∆x )0
= e=since ln ( e ) 1 then,
∆x
1 =( −k1 − 2k−1 xe ) t ∗
1
t∗ =
( k1 + 2k−1 xe )
9-82
Solution:
Given: k30 °C = 2k20 °C
Required: Ea
We are told that T 1 = 293.15 K and T 2 = 303.15 K. Let us take the inverse of these two temperatures in order to plot ln(k) versus 1/T. If
this plot yields a straight line, then we know that the slope of this line is equal to the activation energy divided by R. We know that this is
true according to the Arrhenius equation,
k = Ae − Ea / RT
− Ea / RT
ln k = ln A ln e
Ea
=
ln k ln A −
RT
E
ln A − a
k20 °C RT1
ln = therefore, ln k = ln 2
k30 °C ln A − Ea
RT2
9-83
1 1
= = 3.411×10−3 K −1
T1 293.15 K
1 1
= = 3.299 ×10−3 K −1
T2 303.15 K
ln 2 0.693147
=m =
1 1
− ( 3.299 ×10 − 3.411×10−3 ) K −1
−3
T2 T1
Ea
m=
−6160 K =
R
Ea =− R × m= − 8.3145 J K −1 mol−1 × −6160 K
Ea = 51 217.32 J mol−1
Ea = 51.2 kJ mol−1
9-84
Solution:
Given: k230 °C = 2k220 °C
Required: Ea
k = Ae − Ea / RT
− Ea / RT
ln k = ln A ln e
Ea
=
ln k ln A −
RT
E
ln A − a
k220 °C RT1
k230 °C ln A − Ea
RT2
9-85
1 1
= = 2.028 ×10−3 K −1
T1 493.15 K
1 1
= = 1.987 ×10−3 K −1
T2 503.15 K
ln 2 0.693147
=m =
1 1
− (1.987 ×10 − 2.028 ×10−3 ) K −1
−3
T2 T1
Ea
= =
m 17196 K
R
Ea = 17 196 K × 8.3145 J K −1 mol−1
Ea = 142 976.142 J mol−1
Ea = 143 kJ mol−1
9-86
9.27. The following data for a first-order decomposition reaction in aqueous medium was reported by E. O. Wiig [J. Phys. Chem. 34,
596(1930)].
t/ºC 0 20 40 60
k/10–5 min–1 2.46 43.5 575 5480
Find the activation energy and the preexponential factor.

Solution:
Given: see above
Required: Ea , A
Let us first change the temperature from Celsius to Kelvin, then proceed by taking the inverse value of each temperature and the lnk for
each value given above. We will then plot lnk versus 1/T. Since we have been told that this is a 1st order decomposition, this straight line
will give us a slope which will enable us to determine the activation energy and in turn the pre-exponential factor.
T (K) 1/T (K-1) k (10–5 min–1) lnk

273.15 0.003661 2.46 -10.6128
293.15 0.003411 43.5 -7.74016
313.15 0.003193 575 -5.15856
333.15 0.003002 5480 -2.90407
It is either possible to perform a linear regression or simply add a trendline to the plot using Microsoft Excel in order to determine the
equation of the line. Either method will produce the same results.
9-87
k = Ae − Ea / RT
− Ea / RT
ln k = ln A ln e
Ea
=
ln k ln A −
RT
Ea
When plotting lnk versus 1/T, you will find that ln A is the y-intercept and that is the slope.
R
Ea 11 703
ln k = ln A − = 32.217 −
RT T
Ea = 11 703 K × 8.3145 J K −1 mol−1
Ea = 97 304.59 J mol−1
Ea = 97.3 kJ mol−1
9-88
ln A = 32.217
ln e A = e32.217
A 9.81×1013 min −1
=
A 1.63 ×1012 s −1
=
9-89
9.28. Two second-order reactions have identical preexponential factors and activation energies differing by 20.0 kJ mol–1. Calculate the
ratio of their rate constants (a) at 0 °C and (b) at 1000 °C.
Solution:
Given: two second order reactions: =

A1 A2 , E=
a2 Ea1 + 20.00 kJ mol−1
k1
Required: in each case
k2
a) The ratio of their rate constants at 0 °C.
= e − Ea / RT1 and k2 Ae − Ea / RT2

k1 A=
k1 A e − Ea / RT this is true since both pre-exponential factors are identical.
=
ratio =
k2 A e − Ea / RT
=
k1 ∆Ea / RT
e= e
20 000 (
J mol−1 / 8.3145 J K −1 mol−1 )( 273.15 K )
k2
k1
( 273.15 =
K ) 6.68 ×103
k2
b) The ratio of their rate constants at 1000 °C
= e − Ea / RT1 and k2 Ae − Ea / RT2

k1 A=
k1 A e − Ea / RT this is true since both pre-exponential factors are identical.
=
ratio =
k2 A e − Ea / RT
=
k1 ∆Ea / RT
e= e
20 000 ( )(
J mol−1 / 8.3145 J K −1 mol−1 1273.15 K )
k2
k1
(1273.15 K ) = 6.62
k2
9-90
9-91
9.29. The gas-phase reaction between nitric oxide and oxygen is third order. The following rate constants have been measured:
T/K 80.0 143.0 228.0 300.0 413.0 564.0
k × 109/cm6 mol–1 s–1 41.8 20.2 10.1 7.1 4.0 2.8
The behavior is interpreted in terms of a temperature-dependent preexponential factor; the rate equation is of the form:
k = aTne–E/RT
where a and n are constants. Assume the activation energy to be zero and determine n to the nearest half-integer.
Solution:
Given: see above
Required: n to the nearest half-integer
We will begin by calculating the ln(T) as well as the ln(k) for each value given above.
T (K) ln(T) k (cm6 mol–1 s–1) ln(k)

80 4.382 4.18E+10 24.4562
143 4.963 2.02E+10 23.7289
228 5.429 1.01E+10 23.0358
300 5.704 7.10E+09 22.6834
413 6.023 4.00E+09 22.1096
564 6.335 2.80E+09 21.7529
9-92
k = aT n e – E / RT
since a and n are constants and the activation energy is zero,
Ea
ln k =ln a + n ln T −
RT
ln=
k ln a + n ln T
This means that a plot of ln(k) versus ln(T) will create a line with a slope equal to n and the y-intercept is equal to lna.
=
ln k 30.68 − 1.410 x
n = −1.4
9-93
9.30. The definition of activation energy E a is generally considered to be given by an extension of Eq. 9.91:
 d ln k 
Ea = RT 2  
 dT 
Problem 9.29 shows that for certain reactions, the temperature dependence of the reaction rate constant is better described by an Formatted: Space After: 6 pt
expression of the type
k = aTne–E/RT Formatted: Space After: 6 pt, Don't
adjust space between Latin and Asian
Using the definition for E a given here, derive an expression for the activation energy from this expression. text
Solution: Formatted: Space After: 6 pt
 d ln k 
Given that Ea = RT 2   , we can write;
 dT 
k = aT n e – E / RT
Ea
ln k =ln a + n ln T −
RT
Take the derivative with respect to the temperature to obtain,
 E 
d 
− 
d ln k d ln a nd ln T RT 
= +
dT dT dT dT
d ln k n E
= +
dT T RT 2
 d ln k  d ln k n E
E=
a RT 2   and = + then,
 dT  dT T RT 2
n E 
=Ea RT 2  + 2 
 T RT 
nRT 2 E RT 2
Ea = +
T RT 2
=
Ea nRT + E
9-94
9-95
9.31. The water flea Daphnia performs a constant number of heartbeats and then dies. The flea lives twice as long at 15 °C as at 25 °C.
Calculate the activation energy for the reaction that controls the rate of its heartbeat.
Solution:
Given: Daphnia: lives twice as long at 15 °C as at 25 °C
Required: Ea
k = Ae − Ea / RT
− Ea / RT
ln k = ln A ln e
Ea
=
ln k ln A −
RT
E
ln A − a
2k15 °C RT1
ln =
k25 °C E
ln A − a
RT2
9-96
1 1
= = 3.470 ×10−3 K −1
T1 288.15 K
1 1
= = 3.354 ×10−3 K −1
T2 298.15 K
k25 °C = 2k15 °C therefore,
ln 2 0.693147
=m =
1 1
− ( 3.354 × 10 −3
− 3.470 ×10−3 ) K −1
T2 T1
Ea
= =
m 5974 K
R
Ea = 5974 K × 8.3145 J K −1 mol−1
Ea = 49 670.823 J mol−1
Ea = 49.7 kJ mol−1
9-97
9.32. A sample of milk kept at 25 °C is found to sour 40 times as rapidly as when it is kept at 4 °C. Estimate the activation energy for the
souring process.
Solution:
Given: milk: see above
Required: Ea
k = Ae − Ea / RT
− Ea / RT
ln k = ln A ln e
Ea
=
ln k ln A −
RT
E
ln A − a
k4 °C RT1
k25 °C ln A − Ea
RT2
9-98
1 1
= = 3.608 ×10−3 K −1
T1 277.15 K
1 1
= = 3.354 ×10−3 K −1
T2 298.15 K
ln 40 0.693147
=m =
1 1
− ( 3.354 ×10 − 3.608 ×10−3 ) K −1
−3
T2 T1
Ea
= =
m 14 500 K
R
Ea = 14 500 K × 8.3145 J K −1 mol−1
Ea = 120 560.25 J mol−1
Ea = 121 kJ mol−1
9-99
*9.33. Experimentally, the rate constant for the O(3P) + HCl reaction in the gas phase is found to have a temperature dependence given by:
k (cm3 molecule–1 s–1) = 5.6 × 10–21T 2.87 e–1766 K/T
in the range 350 – 1480 K [Mahmud, Kim, and Fontijn, J. Phys. Chem. 94, 2994(1990)].
a. Using the results of Problem 9.30, find the value of E a at 900 K, which is approximately the middle of this range.
b. Using variational transition-state theory (an extension of the transition-state theory described in Section 9.9), the theoretical rate
constant for this reaction is found to behave according to the equation:
k (cm3 molecule–1 s–1) = 6.9 × 10–20T2.60e–2454 K/T
in the same temperature range [T. C. Allison, B. Ramachandran, J. Senekowitsch, D. G. Truhlar, and R. E. Wyatt, J. Mol. Structure,
Theochem, 454, 307, 1998.] Compare the experimental and theoretical rate constants at 900 K.
Solution:
Given: see above, problem 9.30
Required: Ea ( 900 K ) , compare k theoretical with kexperimental
a) From the equation obtained by Mahmud, et al.,
E = 1766 K × 8.3145 J K −1 mol−1

E = 14 683.407 J mol−1
Using the expression derived in problem 9.30, we can determine the activation energy for this process at 900 K.
=
Ea nRT + E
since k ( cm3 molecule –1 s –1 ) =
5.6 ×10 –21 T 2.87 e –1766 K /T and k =
aT n e – E / RT
n = 2.87
( )( )
Ea = ( 2.87 ) 8.3145 J K −1 mol−1 900 K + 14 683.407 J mol−1
−1
Ea = 36 159.7605 J mol
Ea = 36.2 kJ mol−1
9-100
b) Using variational transition-state theory in the same temperature range we find that,
k ( cm3 molecule –1 s –1=

) 5.6 ×10–21 T 2.87 e –1766 K /T
) 5.6 ×10–21 ( 9002.87 ) e –1766/900
k ( cm3 molecule –1 s=
–1
) 2.37 ×10−13
2.37 ×10−13 cm3 molecule –1 s –1 → experimental
k=
) 6.9 ×10–20 T 2.60 e – 2454 K /T
) 6.9 ×10–20 ( 9002.60 ) e – 2454/900
k ( cm3 molecule –1 s=
–1
) 2.17 ×10−13
=k 2.17 ×10−13 cm3 molecule –1 s –1 → theoretical
The theoretical value is slightly smaller than the experimental value. It is possible to perform a statistical analysis in order to determine
the significance of this difference.
9-101
9.34. The activation energy for the reaction:

H + CH 4 → H 2 + CH 3
has been measured to be 49.8 kJ mol–1. Some estimates of enthalpies of formation, ∆ f H°, are:
H 218.0 kJ mol–1
CH 4 –74.8 kJ mol–1
CH 3 139.5 kJ mol–1
Estimate a value for the activation energy of the reverse reaction.

Solution:
Given: see above
Required: Ea ( reverse reaction )
H + CH 4 → H 2 + CH 3
∆ f H ° ( kJ mol −1
) 218 − 74.8 139.5
Let us begin by determining the standard enthalpy for the reaction.
∆H ° = ∑ ∆ f H ° ( products ) − ∑ ∆ f H ° ( reactants )
∆ f H ° ( CH 3 ) −  ∆ f H ° ( CH 4 ) + ∆ f H ° ( H ) 
∆H ° =
∆H ° 139.5 − ( −74.8 + 218 )  kJ mol−1
=
∆H ° = −3.7 kJ mol−1
From Figure 9.11, we can see that E 1 – E –1 = ∆U (Eq. 9.70). In this particular instance it is possible to say that E A − E– A =∆H ° . Since we
have been given the value for the activation energy for the forward reaction, we can use this expression to determine the activation energy
for the reverse reaction.
Rearrange the above to obtain,
9-102
E A − E– A =∆H °
E–=
A E A − ∆H °
E=
–A  49.8 − ( −3.7 )  kJ mol−1
E– A = 53.5 kJ mol−1
9-103
*9.35. By a treatment similar to that given for relaxation methods for the case A  Z, derive the rate equations for analyzing the reaction
A + B  Z by carrying out the steps below.
a. Show that at equilibrium, k 1 a e b e = k –1 z e , where the subscript e indicates equilibrium concentrations.
dx
= b. Show that k1 (ae – x)(be – x) – k –1 ( ze + x) , where x represents a change from equilibrium.
dt
dx
c. Show that for small x, = – [k1 (ae + be ) + k –1 ]x . [Hint: Use the result of part (a).]
dt
d. The displacement from equilibrium x always follows the first-order process x = x 0 exp(–t/t*), where t* is the relaxation time.
Show that dx/dt = –x/t*.
1
e. Comparing the results of parts (c) and (d), show that= 2k1ae + k –1 if a e = b e .
t*
1 k z
f. For the case a e = b e , show= that 2 k1k –1 ze + k –1 . [Hint: Use the result of part (e) and the fact that 1 = e . ]
t* k –1 aebe
Solution:
A + B 
k1
 
 Z
k−1
a0 b0 0
a0 − x b0 − x x
a) First write out the rate law with respect to the rate of consumption of substances A and B.
dx
= k1 [ A ][ B] − k−1 [ Z] and at a time t, we obtain:
dt
dx
= k1 ( a0 − x )( b0 − x ) − k−1 x however, at equilibrium,
dt
9-104
dx a0 b0
= 0= and xe , , ze
dt 2 2
dx
= k1 ( a0 − x )( b0 − x ) − k−1 x
dt
 a  b 
k1  a0 − 0  b0 − 0  − k−1 ze = 0
 2  2
a b
k1 0 0 = k−1 ze
2 2
a b0
=
Let 0 a=
e and be to simplify this expression further → k1aebe =
k−1 ze
2 2
b) Since Z is formed as A and B are consumed, for a change in a e and b e by an amount –x, we obtain the following expression:
d ( ze + x ) dx
= = k1 ( ae − x )( be − x ) − k−1 ( ze + x )
dt dt
dx
c) Show that for small x, = – [k1 (ae + be ) + k –1 ]x .
dt
We can multiply out the expression from part B to obtain,
dx
= k1 ( ae − x )( be − x ) − k−1 ( ze + x )
dt
= k1 ( aebe − ae x − be x + x 2 ) − k−1 ( ze + x )
dx
dt
= k1 ( aebe − ( ae + be ) x + x 2 ) − k−1 ( ze + x )
dx
dt
Since we are working under the assumption that x is small, we are able to drop a term from this equation.
9-105
dx
( )
small x → = k1 aebe − ( ae + be ) x + x 2 − k−1 ( ze + x )
dt
= k1 ( aebe − ( ae + be ) x ) − k−1 ( ze + x )
dx
dt
Using the results from part A we find that,
dx
= k1aebe − k1 ( ae + be ) x − k−1 ze − k−1 x
dt
k1aebe = k−1 ze therefore,
dx
−k1 ( ae + be ) x −k1aebe − k−1 x + k1aebe
=
dt
dx
−  k1 ( ae + be ) + k−1  x
=
dt
d) Show that dx/dt = –x/t*.
 −t  dx x
Since x = x0 exp  ∗  we can differentiate both sides to obtain = − ∗.
t  dt t
e) When comparing this result to that found in part C, we observe that,
x
−  k1 ( ae + be ) + k−1  x = −
t∗
1
= k1 ( ae + be ) + k−1
t∗
Let us assume for simplicity sake that be = ae .
9-106
1
= 2k1ae + k−1
t∗
1
f) Show=
that 2 k1k –1 ze + k –1 .
t*
k1 z
For the equilibrium constant, we are told that = e . We will use this fact in addition to the result obtained in part e) in order to
k –1 aebe
prove the above statement.
k1 ze
=
K = but when =
be ae ,
k –1 aebe
k1 ze
=
K =
k –1 a e2
a e2 ze zk ze k –1 zk
= → a e2 = e –1 → ae = and k1 = e 2–1
k –1 k1 k1 k1 ae
Substituting this into the expression generated in the previous section,
1 zk ze k –1
= ∗
2 e –1 + k−1
t ze k –1 k1
k1
1 zk
= ∗
2k1 e –1 + k−1
t k1
1
= 2 k1k –1 ze + k−1
t∗
9-107
9.36. A reaction of the type A + B  Z has been studied by relaxation methods. Some of the available data relating equilibrium
concentrations of the product to the relaxation times are given below.
z e /M 0.001 0.002 0.005 0.010 0.025 0.05 0.10
t*/ms 4.08 3.74 2.63 1.84 1.31 0.88 0.674
Determine k 1 , k –1 , and K = k 1 /k –1 .
Solution:
Given: z e /M and t*/ms given above
Required: k 1 , k –1 , K = k 1 /k –1
Recall from the previous problem,
k1 ze
=
K = but when =
be ae ,
k –1 aebe
k1 ze
=
K =
k –1 a e2
a e2 ze k –1 zk ze k –1 zk
= → a e2= e –1 → ae= and k1= e 2–1
k –1 k1 k1 k1 ae
1 zk ze k –1
= 2 e 2–1 + k−1
t∗ ae k1
1
= 2 k1k –1 ze + k−1
t∗
9-108
1
From the above expression, we can see that the plot of ze vs. will generate a straight line.
t∗
ze t* (s) 1/t* (s-1) sqrt(z e )

0.001 4.08E-03 2.4510E+02 0.03162
0.002 3.74E-03 2.6738E+02 0.04472
0.005 2.63E-03 3.8023E+02 0.07071
0.010 1.84E-03 5.4348E+02 0.10000
0.025 1.31E-03 7.6336E+02 0.15811
0.050 8.80E-04 1.1364E+03 0.22361
0.100 6.74E-04 1.4837E+03 0.31623
It is possible to perform a linear regression on the data above in order to generate the equation for this line or one may use Microsoft
Excel’s trendline option which will display the equation of the line on the chart.
9-109
From the line equation, it can be observed that the y-intercept is equal to the rate constant for the reverse reaction (k -1 ).
k−1 = 81.3 s −1
Linear Regression Statistics
m 4497.93 81.29022158 b
Sm 122.255 20.3000768 Sb
R2 0.99632 31.27065583 Sy
F 1353.59 5 DF
From the linear regression statistics, we find the that the rate constant for the forward reaction is equal to the regression error (third box
from the top in the second column).
k1 = 32.3 M −1 s −1
Therefore,
k1 32.3 M −1 s −1
=
K =
k−1 81.3 s −1
K = 0.385 M −1
9-110
9.37. The equilibrium H 2 O  H– + OH has a relaxation time of about 40 μs at 25 °C. Find the values of the forward and reverse rate
constants. K w = [H+][OH–] = 10–14.
1
(Hint: For this case, using steps similar to those of Problem 9.25, it can be shown that =
k1 + k –1 ([H + ]e + [OH – ]e ) .)
t*
Solution:
Given: see above
Required: k1 , k−1
Let us begin by writing down the rate of consumption of water for this reaction.
d [ H 2O]
− = k1 [ H 2 O ] − k−1  H +  OH − 
dt
From the equilibrium condition we may write,
k1 [ H 2 O ]e − k−1  H +  OH −  =0
e e
k1 [ H 2 O ]e = k−1  H +  OH − 
e e
k1  H  e OH  e
+ −
=
K =
k−1 [ H 2O]e
=K w =H +  OH −  10−14 therefore,
e e
Kw
K=
[ H 2O]e
For 1 L of pure water,
n m 1000 g
=
C ,=
n = = 55.5087 mol
V M 18.0152 g mol−1
55.5087 mol
[ H 2O]e
= = 55.51 M
1L
9-111
Kw 10−14 M 2
=K = = 1.801 52 ×10−16 M
[ 2 ]e
H O 55.51 M
Since k1 = Kk−1 , then the equation that relates the relaxation time to the concentration can be written in the following manner:
1
=
Kk−1 + k –1 ([H + ]e + [OH – ]e )
t*
Factor to obtain,
1
= k−1  K + ([H + ]e + [OH – ]e ) 
t*
K w =
Using the fact that, = H +  OH −  we can further simplify to get,
e e
1
= k−1  K + 2 K w 
t*
This expression will enable us to solve for the rate constant belonging to the reverse reaction.
1
= k−1  K + 2 K w 
t*
1
k−1 =
t *  K + 2 K w 
1
k−1 =
40 ×10−6 s 1.801 52 ×10−16 M + 2 10−14 M 2 
 
k−1 1.25 ×1011 M −1 s −1
=
9-112
k1
K=
k−1
= =
k1 Kk −1 (1.801 52 ×10 −16
)(
M 1.25 ×1011 M −1 s −1 )
k1 2.25 ×10−5 s −1
=
Formatted: Space After: 6 pt, Don't

adjust space between Latin and Asian
text
9-113
9.38. Two reactions of the same order have identical activation energies and their entropies of activation differ by 50 J mol–1. Calculate
the ratio of their rate constants at any temperature.
Solution: Formatted: Space After: 6 pt
Given: E=
a1 Ea 2 , S=
a2 S a1 + 50 J K mol –1 –1
k1
Required: at any temperature
k2
Using the Arrhenius equation, k = Ae − Ea / RT we can formulate an expression which will enable us to determine the ratio of the rate constants
at any temperature. For simplicity, we will allow the temperature to be 273.15 K.
k T   ∆‡ S o   − Ea 
k = e2  B  exp   exp  
 h   R   RT 
k T   ∆‡ S1o   − Ea 
k1 = e 2  B  exp   exp  
 h   R   RT 
k T   ∆‡ S 2o   − Ea 
k2 = e 2  B  exp   exp  
 h   R   RT 
k T   ∆‡ S1o   − Ea 
e2  B  exp   exp  
k1  h   R   RT 
=
k2 k T   ∆ S2 
‡ o
 − Ea 
e 2  B  exp   exp  
 h   R   RT 
k1  ∆‡ S1o − ∆‡ S 2o 
= exp  
k2  R 
k1  −50 J K −1 mol−1 
= exp  
k2  8.3145 J K −1 mol−1
 
k1
= 2.445 ×10−3
k2
9-114
9-115
9.39. The gas-phase reaction:

H 2 + I 2 → 2HI
is second order. Its rate constant at 400 °C is 2.34 × 10–2 dm3 mol–1 s–1, and its activation energy is 150 kJ mol–1. Calculate ∆‡H°,
∆‡S°, and ∆‡G° at 400 °C, and the preexponential factor.
Solution:
Given: second order: T = 400 °C, k = 2.34 ×10 –2 dm3 mol –1 s –1 , Ea = 150 kJ mol –1
Required: ∆‡H°, ∆‡S°, ∆‡G°, A

It is easiest to determine the pre-exponential factor by using the given information in conjunction with the Arrhenius equation.
k = Ae − Ea / RT
Ea
=
ln k ln A −
RT
E
ln=
A ln k + a
RT
150 000 J mol−1
ln ( 2.34 ×10 –2 dm3 mol –1 s –1 ) +
ln A =
(8.3145 J K −1 mol−1 ) ( 673.15 K )
ln A = 23.045 504 dm3 mol –1 s –1 
23.045 504 dm3 mol –1 s –1 
A=e  
=
A 1.02 ×1010 dm3 mol –1 s –1
According to Eq. 9.100,
Ea = ∆‡ H ° + 2 RT
Knowing the value for the activation energy, we can rearrange this expression in order to solve for ∆‡ H ° .
9-116
∆‡ H =
° Ea − 2 RT
= (
∆‡ H ° 150 000 J mol –1 − 2 × 8.3145 J K –1 mol –1 × 673.15 K )
∆ H ° =138 806.1887 J mol
‡ –1
∆‡ H ° =138.8 kJ mol –1
From Eq. 9.100, it follows that the rate constant may be written as,
k T  ∆‡S °/ R − Ea / RT
k = e2  B e e (Eq. 9.101)
 h 
This can be rearranged in order to solve for ∆‡S°. This procedure yields,
9-117
k T  ‡
k = e 2  B  e ∆ S °/ R e − Ea / RT
 h 
k k T  ‡
= e2  B  e∆ S °/ R
e − Ea / RT  h 
2.34 ×10 –2 dm3 mol –1 s –1
= e 2 ( )
 1.381×10−23 J K −1 673.15 K  ‡
 e∆ S °/ R
( −150 000 J mol−1 ) / ( 8.3145 J K −1 mol−1 )( 673.15 K )  6.626 ×10−34 J s 
e  
(1.036 676 s –1 ) e∆ S °/ R
1.019 847 ×1010 dm3 mol –1 s –1 =
‡
1.019 847 ×1010 dm3 mol –1 s –1

e∆ S °/ R =
‡
1.036 676 s –1
∆‡ S °  1.019 847 ×1010 dm3 mol –1 s –1 
= ln  
R  1.036 676 s –1
 
∆‡ S °
= −9.226 707
R
∆‡ S ° = −9.226 707 × 8.3145 J K −1 mol−1
∆‡ S ° = −76.72 J K −1 mol−1
Recall from Chapter 3 that ∆‡G° = ∆‡ H ° − T ∆‡ S ° therefore,
=∆‡G° 139 000 J mol –1 − 673.15 K ( ) ( −76.72 J K −1

mol−1 )
∆ G° =190 641 J mol
‡ –1
∆‡G° =190.6 kJ mol
9-118
9.40. A substance decomposes according to first-order kinetics; the rate constants at various temperatures are as follows:

15.0 4.18 × 10–6
20.0 7.62 × 10–6
25.0 1.37 × 10–5
30.0 2.41 × 10–5
37.0 5.15 × 10–5
Calculate the activation energy. Calculate also, at 25 °C, the enthalpy of activation, the Gibbs energy of activation, the preexponential
factor, and the entropy of activation.
Solution:
Given: see above
Required: Ea , ∆‡ H °, ∆‡ S °, ∆‡G°, A at T= 25 °C
Since we are dealing with a substance that decomposes according to 1st order kinetics, we may use the method of plotting lnk versus 1/T in
order to generate a straight line curve.
T (K) k (s-1) 103/T (K-1) ln(k)

288.15 4.18E-06 3.470415 -12.3852
293.15 7.62E-06 3.411223 -11.7847
298.15 1.37E-05 3.354016 -11.1981
303.15 2.41E-05 3.298697 -10.6333
310.15 5.15E-05 3.224246 -9.87393
9-119
A linear regression may be performed in order to generate the equation for the line.
m -10.2071 23.03635974 b
Sm 0.008403 0.028173779 Sb
R2 0.999998 0.001609684 Sy
F 1475487 3 DF
The slope is therefore, m = -10.2071. Recall that from the Arrhenius equation, we are able to determine the activation energy once we
know the slope.
9-120
 −E 
k = Aexp  a 
 RT 
E
=
ln k ln A − a
RT
E
m= a
R
= =
Ea mR 10.2071×103 K × 8.3145 J K −1 mol−1
Ea = 84 866.933 J mol−1
Ea = 84.9 kJ mol−1
We will use the same methods employed in the previous problem to solve for the remaining variables.
Ea = ∆‡ H ° + RT (Eq. 9.95)
∆‡ H =
° Ea − RT
= (
∆‡ H ° 84 867 J mol−1 − 8.3145 J K −1 mol−1 × 298.15 K )
−1
∆ H ° =82 388.03 J mol
‡
∆‡ H ° =82.4 kJ mol−1
From Eq. 9.87 we know that,
k T   −∆‡G° 
k =  B  exp  
 h   RT 
Rearrange to obtain,
9-121
k  −∆‡G° 
= exp  
 kBT   RT 
 
 h 
 −∆‡G°  1.37 ×10−5 s −1

exp  =
(
 RT  1.381×10−23 J K −1 298.15 K )( )
−34
6.626 ×10 J s
 −∆ G°  ‡
−18
exp =  2.204 670 ×10
 RT 
−∆‡G°
= ln ( 2.204 670 ×10−18 )
RT
( )( )
∆‡G° = − 8.3145 J K −1 mol−1 298.15 K ln ( 2.204 670 ×10−18 )
∆‡G° =100 785 J mol−1

∆‡G° =100.8 kJ mol−1
∆‡G° = ∆‡ H ° − T ∆‡ S ° can be rearranged to obtain,
T ∆‡ S ° = ∆‡ H ° − ∆‡G°
∆‡ H ° − ∆‡G° 82 388 J mol−1 − 100 785 J mol−1
=∆‡ S ° =
T 298.15 K
∆‡ S ° = −61.7 J K −1 mol−1
For unimolecular gas reactions, the pre-exponential factor is given by Eq. 9.98.
9-122
k T   ∆‡ S ° 
A = e B  exp  
 h   R 
 1.381× 10−23 ( 313.15 )   −61.7 
A = e −34  exp  
 6.626 × 10   8.3145 
A=e ( 6.526 715 ×1012 )( 5.97 249 ×10−4 )
A 1.01×1010 s −1
=
9-123
9.41. The following data have been obtained for the hydrolysis of adenosine triphosphate, catalyzed by hydrogen ions:

39.9 4.67 × 10–6
43.8 7.22 × 10–6
47.1 10.0 × 10–6
50.2 13.9 × 10–6
Calculate, at 40 °C, the Gibbs energy of activation, the energy of activation, the enthalpy of activation, the preexponential factor, and the
entropy of activation.
Solution:
Given: see above
Required: Ea , ∆‡ H °, ∆‡ S °, ∆‡G°, A at T= 40 °C
T (K) k (s-1) 103/T (K-1) ln(k)

-
313.05 4.67E-06 3.194378 12.2744
-
316.95 7.22E-06 3.155072 11.8387
-
320.25 1.00E-05 3.12256 11.5129
-
323.35 1.39E-05 3.092624 11.1836
9-124
m -10.6571 21.77330432 b
Sm 0.14652 0.460276149 Sb
R2 0.999622 0.011088537 Sy
F 5290.36 2 DF
9-125
 −E 
k = Aexp  a 
 RT 
E
=
ln k ln A − a
RT
E
m= a
R
= =
Ea mR 10.6571×103 K × 8.3145 J K −1 mol−1
Ea = 88 608.45 795 J mol−1
Ea = 88.6 kJ mol−1
Ea = ∆‡ H ° + RT ( Eq. 9.95)
∆ H=
‡
° Ea − RT
= (
∆‡ H ° 88 608 J mol−1 − 8.3145 J K −1 mol−1 × 313.15 K )
∆‡ H ° =86 003 J mol−1

∆‡ H ° =86.0 kJ mol−1
From Eq. 9.87 we know that,
k T   −∆‡G° 
k = B  exp  
 h   RT 
Rearrange to obtain,
k  −∆‡G° 
= exp  
 kBT   RT 
 
 h 
We will estimate the rate constant at 40 °C by the rate constant given at 313.05 K.
9-126
 −∆‡G°  4.67 ×10−6 s −1

exp  =
(
 RT  1.381×10−23 J K −1 313.15 K )( )
−34
6.626 ×10 J s
 −∆ G° 
‡
−19
exp =  7.155 207 ×10
 RT 
−∆‡G°
= ln ( 7.155 207 ×10−16 )
RT
( )( )
∆‡G° = − 8.3145 J K −1 mol−1 313.15 K ln ( 7.155 207 ×10−16 )
∆‡G° =108 785 J mol−1

∆‡G° =108.8 kJ mol−1
T ∆‡ S ° = ∆‡ H ° − ∆‡G°
∆‡ H ° − ∆‡G° 86 003 J mol−1 − 108 785 J mol−1
=∆‡ S ° =
T 313.15 K
∆‡ S ° = −72.751 J K −1 mol−1
9-127
k T   ∆‡ S ° 
A = e B  exp  
 h   R 
 1.381×10−23 ( 313.15 )   −72.751 
A = e −34  exp  
 6.626 × 10   8.3145 
e ( 6.526 715 ×1012 )(1.584 780 021×10−4 )
A=
A 2.81×109 s −1
=
9-128
9.42. The half-life of the thermal denaturation of hemoglobin, a first-order process, has been found to be 3460 s at 60 °C and 530 s at 65
°C. Calculate the enthalpy of activation and entropy of activation at 60 °C, assuming the Arrhenius equation to apply.
Solution:
1/2 ( 60 °C )
Given: first order: t= 1/2 ( 65 °C )
3460 s, t= 530 s
Required: ∆‡ H °, ∆‡ S ° at T= 60 °C
ln 2
Since this is a 1st order process, we know that t1/2 = . Let us determine the values of the rate constant at 60 °C and 65 °C.
k
ln 2 0.693 147
k (=
60 °C ) =
t1/2 ( 60 °C ) 3460 s
k ( 60
= °C ) 2.003 316 ×10−4 s −1
ln 2 0.693 147
k (=
65 °C ) =
t1/2 ( 65 °C ) 530 s
k ( 65=
°C ) 1.307 825 × 10−3 s −1
Taking the inverse of both temperatures will enable us to generate a straight line plot. As previously seen, the slope of this curve allows us
to calculate the activation energy.
T (K) 1/T (K-1) k 1 (s-1) k2 (s-1) ln(k 1 ) ln(k 2 ) ln(k 2 /k 1 )

333.15 0.003002 2.00E-04 1.31E-03 -8.51554 -6.63939 1.876147
338.15 0.002957
9-129
rise ln k2 − ln k1 1.876 147

=
m = =
run 1/ T2 − 1/ T1 ( 2.957 ×10−3 − 3.002 ×10−3 ) K −1
E
m=
−42 271 K =
− a
R
Ea = ( −42 271 K ) ( −8.3145 J K −1
mol−1 )
Ea = 351 444 J mol−1
Ea = 351.4 kJ mol−1
Ea = ∆‡ H ° + RT (Eq. 9.95)
∆‡ H =
° Ea − RT
= (
∆‡ H ° 351 444 J mol−1 − 8.3145 J K −1 mol−1 × 333.15 K )
−1
∆ H ° =348 674 J mol
‡
∆‡ H ° =348.7 kJ mol−1
9-130
k T   −∆‡G°  k  −∆‡G° 
=k  B  exp  =→ exp  
 h   RT   kBT   RT 
 
 h 
 −∆‡G°  2.003 316 ×10−4 s −1
exp  =
(
 RT  1.381×10−23 J K −1 333.15 K )( )
−34
6.626 ×10 J s
 −∆‡G°  −17
exp =  2.885 143 × 10
 RT 
−∆‡G°
= ln ( 2.885 143 ×10−17 )
RT
( )( )
∆‡G° = − 8.3145 J K −1 mol−1 333.15 K ln ( 2.885 143 × 10−17 )
∆‡G° =105 493 J mol−1
T ∆ ‡ S ° = ∆ ‡ H ° − ∆ ‡G °
∆‡ H ° − ∆‡G° 348 674 J mol−1 − 105 493 J mol−1
=∆‡ S ° =
T 333.15 K
∆‡ S ° =729.95 J K −1 mol−1
9-131
*9.43. a. Using Eq. 9.73, calculate the collision density for 6.022 ×1023 molecules of hydrogen iodide present in a volume 1 m3 at 300 K.
Take d AA = 0.35 nm.
b. If the activation energy for the decomposition of HI is 184 kJ mol–1, what rate constant does kinetic theory predict at 300 °C? To
what entropy of activation does this result correspond?
Solution:
Given: Eq. 73, 6.022 ×1023 molecules of HI, V = 1 m3, T = 300 K, d AA = 0.35 nm
E a = 184 kJ mol–1, T = 300 °C
Required: Z AA , ∆‡ S °
Eq. 9.73 defines the collision density,
π kBT
ZAA = 2d 2 N A2
m
a) First we need to find the mass of hydrogen iodide.
M 127.904 g mol−1
=
m =
N A 6.022 ×1023 mol−1
=m 2.123 946 ×10−22 g
=m 2.123 946 ×10−25 kg
Now we can simply substitute all appropriate values into Eq. 9.73 to obtain the collision density.
2 ( 0.35 ×10
ZAA = −9
m ) ( 6.022 ×10 m
2 23
)
−3 2
(
π 1.381×10−23 J K −1 ) (573.15 K )
2.123 946 ×10−25 kg
ZAA 3.040 ×1031 m −3 s −1
=
b) We can now use a version of Eq. 9.78 in order to determine the value of the rate constant.
9-132
ν = ZAA e − E a / RT
=ν ( 3.040 ×10 31
m −3 s −1 ) e −184 000/ (8.3145×573.15)
=ν 5.179 ×1014 m −3 s −1
−22
m 2.123 946 ×10 g
=
n =
M 127.904 g mol−1
n = 1.660 578 mol
ν=
5.179 ×1014 m −3 s −1 ×1.660 578 mol
=ν 8.600 135 ×10−10 mol m −3 s −1
According to the rate equation,
ν = k [ HI]
2
ν 8.600 135 ×10−10 mol m −3 s −1

=k =
[ HI] (1 mol m )
2 −3 2
1000 dm3
=k 8.600 135 ×10−10 m3 mol−1 s −1 ×
1 m3
=k 8.600 135 ×10−7 dm3 mol−1 s −1
The collision frequency factor (ie. pre-exponential factor) is given by,
k 8.600 135 ×10−7 dm3 mol−1 s −1

=A=
e − Ea / RT e −184 000/ (8.3145×573.15)
=A 5.048 238 ×1010 dm3 mol−1 s −1
In order to obtain the value for the entropy of activation we may use Eq. 9.98 but for a bimolecular molecule.
k T  ‡ ∆S / R
A = e2  B e
 h 
Rearranging,
9-133
∆S / R 5.048 238 ×1010 dm3 mol−1 s −1

=
‡
e
e
(
2
)
 1.381×10−23 J K −1 573.15 K 

 6.626 ×10−34 J s 
 
e ∆S / R 5.719 266 ×10−4 dm3 mol−1
=
‡
∆‡ S ° (8.3145 J K −1
mol−1 ) ln ( 5.719 266 × 10−4 )
∆‡ S ° = −62.1 J K −1 mol−1
9-134
9.44. The rate constant for a first-order reaction is 7.40 × 10–9 s–1 at 25 °C, and the activation energy is 112.0 kJ mol–1. Calculate, at 25 °C,
the preexponential factor A, the enthalpy of activation ∆‡H°, the Gibbs energy of activation ∆‡G°, and the entropy of activation ∆‡S°.
Solution:
Given: first order: k =7.40 ×10 –9 s –1 , T =25 °C, Ea =

112.0 kJ mol –1
Required: ∆‡ H °, ∆‡ S °, ∆‡G°, A at T= 25 °C
Given the rate constant, we may first solve for the Gibbs energy of activation using Eq. 9.87.
k T  −∆‡G °/ RT
k = B e
 h 
7.40 ×10−9 s −1
e −∆ G °/ RT =
‡
(1.381×10 −23
J K −1 ) ( 298.15 K )
6.626 ×10−34 J s
e −∆ G °/ RT 1.190 843 ×10−21
=
‡
−∆‡G°
= ln (1.190 843 × 10−21 )
RT
( )( )
∆‡G° = − 8.3145 J K −1 mol−1 298.15 K ln (1.190 843 × 10−21 )
∆‡G° =119 436 J mol−1

∆‡G° =119.4 kJ mol−1
Given the activation energy, we may first solve for the enthalpy of activation using Eq. 9.95.
Ea = ∆‡ H ° + RT (Eq. 9.95)
9-135
∆‡ H =
° Ea − RT
= (
∆‡ H ° 112 000 J mol−1 − 8.3145 J K −1 mol−1 × 298.15 K )
−1
∆ H ° =109 521 J mol
‡
∆‡ H ° =109.5 kJ mol−1
T ∆‡ S ° = ∆‡ H ° − ∆‡G°
∆‡ H ° − ∆‡G° 109 521 J mol−1 − 119 436 J mol−1
=∆‡ S ° =
T 298.15 K
∆‡ S ° = −33.25 J K −1 mol−1
k T  ∆‡ S ° / R
A = e B e
 h 
 1.381×10−23 ( 298.15 )  ( −33.254 966) / (8.3145)
A = e e
 6.626 ×10−34 
=A e ( 6.214 083 ×1012 ) ( 0.018 322 )
A 3.09 ×1011 s −1
=
9-136
9.45. The rate constant for a second-order reaction in solution is 3.95 × 10–4 dm3 mol–1 s–1 at 25 °C, and the activation energy is 120.0 kJ
mol–1. Calculate, at 25 °C, the preexponential factor A, the enthalpy of activation ∆‡H°, the Gibbs energy of activation ∆‡G°, and the
entropy of activation ∆‡S°.
Solution:
Given: first order: k =3.95 ×10 –4 dm3 mol –1s –1 , T =25 °C, Ea =
120.0 kJ mol –1
Required: ∆‡ H °, ∆‡ S °, ∆‡G°, A at T= 25 °C
Given the rate constant, we may first solve for the Gibbs energy of activation using Eq. 9.87.
k T  −∆‡G °/ RT
k = B e
 h 
3.95 ×10−4 dm3 mol−1 s −1

e −∆ G °/ RT =
‡
(1.381×10 −23
J K −1 ) ( 298.15 K )
6.626 ×10−34 J s
e −∆ G °/ RT 6.356 529 ×10−17
=
‡
−∆‡G°
= ln ( 6.356 529 ×10−17 )
RT
( )( )
∆‡G° = − 8.3145 J K −1 mol−1 298.15 K ln ( 6.356 529 ×10−17 )
∆‡G° =92 452 J mol−1

∆‡G° =92.45 kJ mol−1
Given the activation energy, we may first solve for the enthalpy of activation using Eq. 9.95.
Ea = ∆‡ H ° + RT (Eq. 9.95)
9-137
∆‡ H =
° Ea − RT
= (
∆‡ H ° 120 000 J mol−1 − 8.3145 J K −1 mol−1 × 298.15 K )
−1
∆ H ° =117 521 J mol
‡
∆‡ H ° =117.5 kJ mol−1
T ∆‡ S ° = ∆‡ H ° − ∆‡G°
∆‡ H ° − ∆‡G° 117 521 J mol−1 − 92 452 J mol−1
=∆‡ S ° =
T 298.15 K
∆‡ S ° =84.08 J K −1 mol−1
k T  ‡
A = e  B  e∆ S °/ R
 h 
 1.381×10−23 ( 298.15 )  (84.08) / (8.3145)
A = e e
 6.626 ×10−34 
=A e ( 6.214 083 ×1012 ) ( 24 654 )
A 4.16 ×1017 dm3 mol−1 s −1

=
9-138
9.46. The rate constant k for the reaction between persulfate ions and iodide ions varies with ionic strength I as follows:
I/10–3 mol dm–3 2.45 3.65 4.45 6.45 8.45 12.4

3 –1 –1
k/dm mol s 1.05 1.12 1.16 1.18 1.26 1.39
Estimate the value of z A z B .

Solution:
We know that this reaction follows 2nd order kinetics by examining the units associated with the rate constant. Recall that information
regarding the rate law, rate constant and half life are condensed in Table 9.1.
According to the Debye-Huckel limiting law (Section 7.10) the activity coefficient of an ion is related to its valency, z and the ionic
strength, I. By Eq. 7.104,
log10 γ = − Bz 2 I (Eq. 9.121)
Introduction of the above into the rate equation (Eq. 9.120) gives,
γ Aγ B
=
log10 k log10 k0 + log10 (Eq. 9.120)
γ‡
log10 k = log10 k0 + log10 γ A + log10 γ B − log10 γ ‡

log10=k log10 k0 − B  z A2 + z B2 − ( zA + zB )  I
2
 
=
log10 k

2
( 2
)
log10 k0 − B  z A + z B − z A + 2zA zB + z B2  I
2

=
log10 k log10 k0 + 2 BzA zB I
The value of B is approximately 0.51 dm-3/2 mol-1/2 for aqueous solutions at 25 °C. Therefore,
=
log10 k log10 k0 + 1.02 zA zB I / mol dm −3 (Eq. 9.125)
I (10–3 mol dm–3) k (dm3 mol–1 s–1) sqrt(I) log 10 (k)
9-139
2.45 1.05 0.049497 0.021189

3.65 1.12 0.060415 0.049218
4.45 1.16 0.066708 0.064458
6.45 1.18 0.080312 0.071882
8.45 1.26 0.091924 0.100371
1.24 1.39 0.111355 0.143015
m 1.850795931 -0.066937665 b
Sm 0.144547247 0.011480668 Sb
R2 0.976182639 0.007300432 Sy
F 163.9447163 4 DF
9-140
log10 k − log10 k0 ≈ zA zB I / mol dm −3
Therefore, a plot of log10 k against I / mol dm −3 will yield a slope that is approximately equal to zA zB . From the regression statistics, we
see that m = 1.850 796
1.850 795 931

=zA zB = 1.814 505 814
1.02
zA zB ≈ 1.814
9-141
9.47. The following constants were obtained by Brønsted and Livingstone [J. Amer. Chem. Soc., 49, 435(1927)] for the reaction:
[CoBr(NH 3 ) 5 ]2+ + OH– → [Co(NH 3 ) 5 OH]2+ + Br–
under the following conditions:
Concentration/mol dm–1 k
2+
[CoBr(NH 3 ) 5 ] NaOH NaCl dm mol –1 s –1
3
–4 –4
5.0 × 10 7.95 × 10 0 1.52
–4 –3
5.96 × 10 1.004 × 10 0 1.45
–4 –3
6.00 × 10 0.696 × 10 0.005 1.23
–4 –3
6.00 × 10 0.696 × 10 0.020 0.97
–4 –3
6.00 × 10 0.691 × 10 0.030 0.91
Make an estimate of the rate constant of the reaction at zero ionic strength. Are the results consistent with z A z B = –2?
Solution:
Let us begin by determining the ionic strengths of each reaction mixture. Recall that the ionic strength of a solution represents a function of
all ions present into the given solution.
1 n
I= ∑ cB z B2
2 B=1
where c B = molar concentration of each ion and z B = charge number of that particular ion.
9-142
( 22 × 5.0 ×10 –4 ) + (1.0 ×10−3 ) + ( 2 × 7.95 ×10 –4 ) 

1
(1) =
I
2 
= I 2.295 ×10 M –3
( 22 × 5.96 ×10 –4 ) + (11.92 ×10−4 ) + ( 2 ×1.004 ×10 –3 ) 

1
( 2) =I
2 
= I 2.79 ×10 –3 M
( 22 × 6.0 ×10 –4 ) + (12.0 ×10−4 ) + ( 2 × 0.696 ×10 –3 ) + 0.01

1
( 3) =I
2 
= I 7.496 ×10 M–3
( 24.0 ×10 –4 ) + (12.0 ×10−4 ) + (1.392 ×10 –3 ) + 0.04 

1
( 4) =
I
2 
= I 22.50 ×10 M–3
( 24.0 ×10 –4 ) + (12.0 ×10−4 ) + (1.392 ×10 –3 ) + 0.06 

1
( 5) =I
2 
=I 32.50 ×10 –3 M

2.30E-03 1.52 0.047906 0.181844
2.79E-03 1.45 0.052820 0.161368
7.50E-03 1.23 0.086579 0.089905
2.25E-02 0.97 0.150000 -0.013228
3.25E-02 0.91 0.180278 -0.040959
9-143
-1.683623642 0.250069168
0.122806104 0.014277339
0.984289358 0.01453188
187.9533719 3
From the regression statistics, we can see that the y-intercept is equal to log10 k0 = 0.250 0691 68 .
We may now make an estimate of the rate constant.
k0 = 100.250 0691 68
k0 = 1.778 562 651
k0 = 1.78 dm3 mol−1 s −1
Again from the regression statistics, the slope was given to be m = -1.683 623 642. We already know that the slope is equal to 1.02zA zB for
an aqueous solution at 25 °C. Therefore,
9-144
m=
−1.683 623 642 =
1.02zA zB
−1.683 623 642

zA zB = = −1.650 611 414
1.02
zA zB = −1.65
When rounded to a single significant figure, zA zB = −2 which is in fact consistent with the statement given in the question.
9-145
9.48. Suppose that the rates of ionic reactions in solution were proportional to the activity rather than the concentration of activated
complexes. Derive an equation relating the logarithm of the rate constant to the ionic strength and the charge numbers of the ions
and contrast it with Eq. 9.124. Can the results in Figure 9.22 be reconciled with the equation you have derived?
Solution:
Let the following reaction occur as follows,
A + B → X‡ → products
The basis of the ionic strength treatment is that the rate of a reaction is proportional to the concentration of the activated complexes, X‡ and
NOT to their activity. The rate equation is thus,
ν = k  X‡ 
The equilibrium between the activated complexes and the reactants A and B may then be expressed as,
a‡  X‡  γ ‡
=
K‡ = (Eq. 9.118)
aA bB [ A ][ B] γ Aγ B
Remember that a and b are the activities and γ represents the activity coefficient. We will now introduce Eq. 9.118 into a modified rate
equation (from the one given above). Suppose that,
ν = k  X‡  γ ‡
γ γ
 X‡  = K ‡ [ A ][ B] A ‡ B
γ
 γ Aγ B  ‡
ν = k  K ‡ [ A ][ B] γ
 γ ‡ 

ν = kK ‡ [ A ][ B] γ Aγ B
Let
=kK k=
0 and k kK ‡ [ A ][ B] γ Aγ B
9-146
Taking the logarithm of each part of the equation, we obtain,
=
log10 k log10 k0 + log10 γ Aγ B
Using the fact that log10 γ = − Bz 2 I we can make a substitution to get,
log10 k = log10 k0 − B  zA2 + zB2  I
In this particular situation, plotting log10 k against I will always yield a line with a negative slope. This conclusion is inconsistent with
the results presented in Figure 9.22.
9-147
9.49. When the subatomic species muonium (Mu) was first discovered in 1960, it was not known whether it bore an electric charge. The
answer was provided by a kinetic study of the ionic strength effect on the reaction Mu + Cu2+ in aqueous solution. The following
rate constants were measured at two ionic strengths:
I=0M k = 6.50 × 109 dm3 mol–1 s–1

I = 0.9 M k = 6.35 × 109 dm3 mol–1 s–1
Suppose that muonium had a single negative charge; what would k be expected to be at an ionic strength of 0.9 M? What do you deduce
about the actual charge on muonium?
Solution:
If there were a single negative charge on the muonium ion, the slope of the plot of log10 k against I would yield a slope of approximately -
2. Thus, zA zB = −2 . According to Eq. 9.124,
=
log10 k log10 k0 + 2 BzA zB I which can be rearranged to obtain,
log10 k − log10 k0 =
2 BzA zB I
k 
log10   =1.02 × ( −2 ) × ( 0.9 ) =−6.12
1/2
 0
k
k  −6.12 −7
=  10 = 7.59 ×10 ????
 0
k
I have no clue what the previous author did here. There is absolutely no explanation as to where he got his numbers from. I cannot finish
this problem.
9-148
9-149
9.50. The rate constants of a second-order reaction in aqueous solution at 25 °C had the following values at two ionic strengths:
I/mol dm–3 k/dm3 mol–1 s–1
2.5 × 10–3 1.40 × 10–3
2.5 × 10–2 2.35 × 10–3
Make an estimate of the value of z A z B , the product of the charge numbers.
Solution:
Given: see above
Required: estimate z A z B
Let us plot log10 k against I.

2.50E-03 1.40E-03 0.05000 -2.8539
2.50E-02 2.35E-03 0.15811 -2.6289
9-150
m 2.080582256 -2.957901077 b
Sm 0 0 Sb
R2 1 0 Sy
F NA 0 DF
The slope of the plot above is equal to m = 2.080 582 256. This means that,
2.080 582 256 = 1.02 zA zB

2.080 582 256
zA zB =
1.02
zA zB = 2.04
An approximation to one significant figure yields, zA zB ≈ 2 .
9-151
9.51. A reaction of the type:

A+ + B2– → products
was found at 25 °C to have a rate constant of 2.8 × 10–4 dm3 mol–1 s–1 at an ionic strength of 1.0 × 10–3 M. Assume the Debye-Hückel
limiting law to apply and estimate the rate constant at zero ionic strength.
Solution:
Given: k =2.8 ×10 –4 dm3 mol –1 s –1 , T =25 °C, I =1.0 × 10−3 M
Required: k at I 0 ( k0 )
The Debye-Hückel limiting law states that,
=
This can be rearranged to solve for k 0 upon substitution of the appropriate values.
=
=
log10 k0 log10 k − 2 BzA zB I
k0 log10 ( 2.8 ×10 –4 dm3 mol –1 s –1 ) − 1.02 ( −2 ) 1.0 ×10 –3 M
log10 =
log10 k0 =
−3.552 842 + 0.064 510
log10 k0 = −3.488 332
k0 = 10−3.488 332
=
k0 3.25 ×10 –4 dm3 mol –1 s –1
9-152
9.52. The rate of a reaction at 300 K is doubled when the pressure is increased from 1 bar to 2000 bar. Calculate ∆‡V°, assuming it to be
independent of pressure.
Solution:
=
Given: =
T 300 K, P0 1=
bar, Pf 2000 bar
Required: ∆‡V° (pressure independent)
∆‡V °
According to Eq. 9.129 we know that, ln k =ln k0 − ∆P .
RT
We are told that the rate of the reaction increases 2-fold when the pressure is increased from 1 bar to 2000 bar. This would mean that,
ν 1 = k0
ν2 = k
ν2 k ∆‡V °
ln =
ln 2 =
ln = − ∆P
ν1 k0 RT
∆‡V °
ln 2 =
− ∆P
RT
Rearrange this expression to isolate ∆‡V ° ,
− ln 2 ( RT )
∆‡V ° =
P
Substitution yields,
9-153
∆ V° =
‡
( )(
−0.693 147 8.3145 J K −1 mol−1 300 K )
( 2000 − 1) bar
∆ V ° = −0.864 908 J bar −1 mol−1
‡
1 bar =
105 Pa, 1 atm =×
1.013 25 105 Pa, 1 atm dm3 =
101.325 J
1 bar 1.013 25 ×105 Pa 1 atm dm3
∆‡V ° = −0.864 908 J bar −1 mol−1 × × ×
105 Pa 1 atm 101.325 J
∆‡V ° = −8.649 081× 10−3 dm3 mol−1
9-154
1 dm3 = 0.001 m3
0.001 m3
∆‡V ° = −8.649 081× 10−3 dm3 mol−1 ×
1 dm3
∆‡V ° = −8.65 ×10−6 m3 mol−1
9-155
9.53. The following results were obtained for the solvolysis of benzyl chloride in an acetone-water solution at 25 °C:
P/102 kPa 1.00 345 689 1033

–6 –1
k/10 s 7.18 9.58 12.2 15.8
Make an appropriate plot and estimate ∆‡V°.

Solution:
Given: se above
Required: plot and estimate ∆‡V°
P/102 kPa k/10–6 s–1 lnk

1.00 7.18 -11.844
3.45 9.58 -11.556
6.89 1.22 -11.314
10.3 1.58 -11.056
9-156
m 7.58108E-06 -11.83434645 b
Sm 1.89127E-07 0.012186716 Sb
R2 0.998756818 0.014547781 Sy
F 1606.774843 2 DF
∆‡V °
According to Eq. 9.129 we know that, ln= k ln k0 − P . This means that a plot of lnk against P will yield a slope that is equal to
RT
∆‡V °
− . This information will allow us to determine the value of ∆‡V ° .
RT
9-157
∆‡V °
m= − = 7.581 08 ×10−6 kPa −=
1
7.581 08 × 10−9 Pa −1
RT
(
−∆‡V ° 7.581 08 × 10−9 Pa −1 8.3145 J K −1 mol−1 × 298.15 K
= )
−5 −1 −1
∆ V ° = −1.879 ×10
‡
J Pa mol
−1
1 J Pa = 1 m therefore,
3
∆‡V ° = −1.88 ×10−5 m3 mol−1
9-158
9.54. The fading of bromphenol blue in alkaline solution is a second-order reaction between hydroxide ions and the quinoid form of the
dye:
quinoid form (blue) + OH– → carbinol form (colorless)
The following results show the variation of the second-order rate constant k with the hydrostatic pressure P at 25 °C:
P/104 kPa 101.3 2.76 5.51 8.27 11.02
k/10–4 M–1 s–1 9.30 11.13 13.1 15.3 17.9
Estimate ∆‡V°.
Solution:
Given: second order: P/104 kPa and k/10–4 M–1 s–1 above
Required: ∆‡V°
We will use the same method as we did in the previous problem. We should first begin by adjusting the units to simplify our results.
1 M = 1 mol L−1
=1 L 1=
m3 , 1 m3 1000 dm3
1 L 1 m3
1 M = 1 mol L−1 × ×
1 m3 1000 dm3
= 1.0 ×10−3 mol dm −3
1M
(1 M )
−1
= 1000 dm3 mol−1
(10 M) 000 dm3 mol−1 and (10−4 M ) s −1 104 dm3 mol−1 s −1

−4 −1 −1
=
10
The rate constant can now be expressed in the following form,
k /10−4 M −1 s −1 = k /104 dm3 mol−1 s −1
P/ kPa k/10-4 M–1 s–1 k/dm3 mol-1 s–1 lnk
1013000.00 9.30E-04 9.30 2.2300
9-159
27600.00 1.11E-03 11.13 2.4096
55100.00 1.31E-03 13.10 2.5726
82700.00 1.53E-03 15.30 2.7279
110200.00 1.79E-03 17.90 2.8848
5.9127E-06 2.238955304
1.0317E-07 0.006964007
0.99908744 0.008981709
3284.45091 3
∆ V°
‡
According to Eq. 9.129 we know that, ln= k ln k0 − P . This means that a plot of lnk against P will yield a slope that is equal to
RT
∆‡V °
− . This information will allow us to determine the value of ∆‡V ° .
RT
9-160
∆‡V °
m=
− 5.9127 ×10−9 Pa −1
=
RT
−∆
= ‡
(
V ° 5.9127 ×10−9 Pa −1 8.3145 J K −1 mol−1 × 298.15 K )
−5 −1 −1
∆ V ° = −1.466 ×10
‡
J Pa mol
−1
1 J Pa = 1 m therefore,
3
∆‡V ° = −1.47 ×10−5 m3 mol−1
9-161
9.55. Use Figure 9.23 to make approximate estimates of the volumes of activation for the alkaline hydrolyses of methyl acetate, ethyl
acetate, and propionamide, at 25 °C.
Solution:
Given: Figure 9.23, =
T 25 °C
Required: estimate ∆‡V° in each case
k
From Figure 9.23, at 10 000 lb per square inch, the values of log10 are:
k0
Ethyl acetate: 0.105

Methyl acetate: 0.11
Propionamide: 0.20
k
The value of log10 when the pressure is 10 000 pounds per square inch is approximately 0.105. The slope of a plot in which natural
k0
logarithms were used would therefore be,
k 2.303 × 0.105
ln =
k0 10 000 psi
1=psi 6.89 ×103 Pa therefore,
k 2.303 × 0.105
ln =
k0 6.89 × 103 Pa
10 000 psi ×
1 psi
k 2.303 × 0.105
ln =
k0 10 000 × 6.89 ×103 Pa
k
=
log10 3.509 651× 10−9 Pa −1
k0
According to Eq. 9.129 (for ethyl acetate),
9-162
∆‡V ° Formatted: Space After: 6 pt

=
ln k ln k0 − P
RT
∆‡V ° k ∆‡V ° ∆‡V °
ln k − ln k0 =
− P → ln = − P since mP =
−
RT k0 RT RT
(
−∆‡V ° 3.509 651×10−9 Pa −1 8.3145 J K −1 mol−1 298.15 K
= )( )
∆‡V ° = −8.69 979 ×10−6 J Pa −1 mol−1 → since1 J Pa −1 = 1 m3 therefore,
∆‡V ° = −8.70 ×10−6 m3 mol−1
Similarly, for methyl acetate;
∆‡V °
=
ln k ln k0 − P
RT
∆‡V ° k ∆‡V ° ∆‡V °
ln k − ln k0 =
− P → ln = − P since m = −
RT k0 RT RT
( )(
V ° 3.68 ×10−9 Pa −1 8.3145 J K −1 mol−1 298.15 K
−∆‡= )
∆‡V ° = −9.122 602 884 ×10−6 J Pa −1 mol−1 → since1 J Pa −1 = 1 m3 therefore,
∆‡V ° = −9.12 ×10−6 m3 mol−1
For proprionamide the slope is;
∆‡V °
=
ln k ln k0 − P
RT
∆‡V ° k ∆‡V ° ∆‡V °
ln k − ln k0 =
− P → ln = − P since m = −
RT k0 RT RT
−∆=
‡
( )(
V ° 6.685 ×10−9 Pa −1 8.3145 J K −1 mol−1 298.15 K )
∆‡V ° = −1.657 190 225 ×10−5 J Pa −1 mol−1 → since1 J Pa −1 = 1 m3 therefore,
∆‡V ° = −1.66 ×10−5 m3 mol−1
9-163
9-164

Chapter 09 Chemical Kinetics I

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Chapter 09 Chemical Kinetics I

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CHAPTER

LAIDLER . MEISER . SANCTUARY

Problems and Solutions

Rate Constants and Order of Reaction

[A]/mol dm–3 [B]/mol dm–3 Rate/mol dm–3 s–1

[A]/mol dm–3 [B]/mol dm–3 Rate/mol dm–3 s–1

(a) [H]+ = [OH–] = 10–1 M and (b) [H+] = [OH–] = 10–4 M.

cis -Cr(en) 2 (OH) +2  trans -Cr(en) 2 (OH) +2

t/min 3.25 12.18 24.55 42.50 68.05

 k e – k1t – k1e – k2t 

where [A] 0 is the initial concentration of A.

Time, s 1350 2070 3060 5340 7740 ∞

Obtain values for the rate constants k 1 and k –1 .

*9.24. The dissociation of a weak acid HA + H 2 O  H 3 O+ + A– can be represented as:

where the concentration of the ions (Y and Z) is at equilibrium.

Find the activation energy and the preexponential factor.

T/K 80.0 143.0 228.0 300.0 413.0 564.0

9.34. The activation energy for the reaction:

Estimate a value for the activation energy of the reverse reaction.

a. Show that at equilibrium, k 1 a e b e = k –1 z e , where the subscript e indicates equilibrium concentrations.

z e /M 0.001 0.002 0.005 0.010 0.025 0.05 0.10

Collision Theory and Transition-State Theory Formatted: Heading 1, Left, Indent:

Temperature/°C Rate constant, k/s–1

Temperature/°C Rate constant, k/s–1

Ionic-Strength Effects Formatted: Heading 1

I/10–3 mol dm–3 2.45 3.65 4.45 6.45 8.45 12.4

Estimate the value of z A z B .

I=0 k = 6.50 × 109 dm3 mol–1 s–1

I/mol dm–3 k/dm3 mol–1 s–1

Pressure Effects Formatted: Heading 1, Left

P/102 kPa 1.00 345 689 1033

Make an appropriate plot and estimate ∆‡V°.

P/104 kPa 101.3 2.76 5.51 8.27 11.02

Essay Questions Formatted: Heading 1, Indent: Left:

b) We are given that v=

vC will have a rate of disappearance that is 4x slower

Back to Problem 9.1 Back to Top

9.2. A reaction obeys the stoichiometric equation:

[A]/mol dm–3 [B]/mol dm–3 Rate/mol dm–3 s–1

v ( C3 ) 4.0 ×10−6 mol dm –3 s –1

v ( C1 ) 5.0 ×10−7 mol dm –3 s –1

Back to Problem 9.2 Back to Top

[A]/mol dm–3 [B]/mol dm–3 Rate/mol dm–3 s–1

Back to Problem 9.3 Back to Top

Required: t1/2 , fraction undecomposed

b) The undecomposed fraction after three hours will be:

Back to Problem 9.4 Back to Top

1st order reaction:

1.3 ×1011 dm3 mol –1 s –1 , [ H ] =

Required: t1/2 in each case

Back to Problem 9.6 Back to Top

Required: fraction remaining in each case

Back to Problem 9.7 Back to Top

n0 8.06 ×10−4 mol

6.59 cm3 0.001 dm3

k 5.96 ×10−3 min −1

Back to Problem 9.8 Back to Top

9.9. The reaction:

Required: k when half of chlorine reacted

2NO + Cl2 → 2NOCl

rate2 =4.8 ×10−5 × 9

Back to Problem 9.9 Back to Top

2NOCl ( g ) → 2NO ( g ) + Cl2 ( g )