Chapter 10 Chemical Kinetics II PDF

10
Chemical Kinetics II.

CHAPTER Composite Mechanisms
LAIDLER . MEISER . SANCTUARY

Physical Chemistry
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Problems and Solutions

Chapter 10: Chemical Kinetics II. Composite Mechanisms Composite Mechanisms and Rate Equations
Chapter 10
Composite Mechanisms and Rate Equations
10.1. Suppose that a reaction of stoichiometry A + 2B = Y + Z is believed to occur by the mechanism:
Where X is an intermediate. Write the expression for the rate of formation of Y.
Solution
10.2. Suppose that a reaction A + 2B = 2Y + 2Z is believed to occur according to the mechanism:
Obtain an expression for the rate of formation of the product Y.
Solution
10.3. Suppose that a reaction of stoichiometry A + B = Y + Z is believed to occur according to the mechanism:
Apply the steady-state treatment and obtain an expression for the rate. To what expressions does the general rate equation reduce if;
a. The second reaction is slow, the initial equilibrium being established very rapidly?
b. The second reaction is very rapid compared with the first reaction in either direction?
Solution
10.4. A reaction of stoichiometry:

A+B=Y+Z
is found to be second order in A and zero order in B. Suggest a mechanism that is consistent with this behavior.
Solution
10-2
10.5. The rate of formation of the product of a reaction is found to give a nonlinear Arrhenius plot, the line being convex to the 1/T axis
(i.e., the activation energy is higher at higher temperatures). Suggest a reason for this type of behavior.
(Hint: For this and the following problem, consider the possibility of two parallel reactions and of two consecutive reactions having
different activation energies.)
Solution
10.6. An Arrhenius plot is concave to the 1/T axis (i.e., it exhibits a lower activation energy at higher temperatures). Suggest a reason for
this type of behavior.
Solution
10.7. Nitrogen pentoxide reacts with nitric oxide in the gas phase according to the stoichiometric equation:
N2O5 + NO = 3NO2
The following mechanism has been proposed:
Assume that the steady-state treatment can be applied to NO3, and derive an equation for the rate of consumption of N2O5.
Solution
10.8. The reaction 2NO + O2 2NO2 is believed to occur by the mechanism:
Assume N2O2 to be in a steady state and derive the rate equation. Under what conditions does the rate equation reduce to second-
order kinetics in NO and first-order kinetics in O2?
Solution
*10.9. The gas-phase reaction:

Cl2 + CH4 CH3Cl + HCl
proceeds by a free-radical chain reaction in which the chain propagators are Cl and CH3 (but not H), and the chain-ending step is 2Cl
Cl2. Write the mechanism, identify the initiation reaction and the chain-propagating steps, and obtain an expression for the rate of
the overall reaction.
Solution
10-3
10.10. The following mechanism has been proposed for the thermal decomposition of pure ozone in the gas phase:
Derive the rate equation.
Solution
*10.11. A reaction occurs by the mechanism:
and the concentration of X is sufficiently small compared with the concentrations of A and B that the steady-state treatment applies.
Prove that the activation energy Ea at any temperature is given by:
k ( E E2 E1 ) k2 E1
Ea 1 1
k 1 k2
that is, is the weighted mean of the values E1 + E2 E1, and E1, which apply, respectively, to the limiting cases of k1 k2 and k2
k1.
Solution
10.12. F. A. Lindemann [Trans. Faraday Soc., 17, 598(1922)] proposed the following mechanism for a unimolecular gas reaction:
The species A* is an energized molecule that is present in low concentrations. Apply the steady-state treatment to A* and obtain an
expression for the rate in terms of [A], k1, k1, and k2. Show that the mechanism predicts first-order kinetics at higher A
concentrations and second-order kinetics at lower ones.
Solution
10-4
*10.13. Certain polymerizations involve esterification reactions between COOH groups on one molecule and OH groups on another.
Suppose that the concentration of such functional groups is c and that the rate of their removal by esterification obeys the equation:
dc
kc 2
dt
Obtain an equation relating the time t to the fraction f of functional groups remaining and to the initial concentration c0 of functional
groups.
Solution
*10.14. Show that the mechanism:
leads to the result that the rate equation for the overall reaction is = k[H2][I2].
Solution
10.15. Apply the steady-state treatment to the following mechanism, in which Y and Z are final products and X is a labile intermediate:
Obtain an expression for the rate of formation of the product Z. What rate equations are obtained if (a) A and (b) B are present in
great excess?
Solution
10-5
Chapter 10: Chemical Kinetics II. Composite Mechanisms Photochemistry and Radiation Chemistry
Photochemistry and Radiation Chemistry

10.16. Calculate the maximum wavelength of the radiation that will bring about dissociation of a diatomic molecule having a dissociation
energy of 390.4 kJ mol1.
Solution
10.17. Hydrogen iodide undergoes decomposition into H2 + I2 when irradiated with radiation having a wavelength of 207 nm. It is found
that when 1 J of energy is absorbed, 440 g of HI is decomposed. How many molecules of HI are decomposed by 1 photon of
radiation of this wavelength? Suggest a mechanism that is consistent with this result.
Solution
10.18. A 100-watt mercury-vapor lamp emits radiation of 253.7 nm wavelength and may be assumed to operate with 100% efficiency. If all
the light emitted is absorbed by a substance that is decomposed with a quantum yield of unity, how long will it take for 0.01 mol to
be decomposed?
Solution
10.19. Suppose that the radiation emitted by the lamp in Problem 10.18 is all absorbed by ethylene, which decomposes into C2H2 + H2 with
a quantum yield of unity. How much ethyne will be produced per hour?
Solution
10.20. A 1000-watt mercury vapor flash lamp emits radiation of 253.7 nm wavelength, and the duration of the flash is 1 s. Suppose that
all of the radiation of a single flash is absorbed
by mercury vapor; how many atoms of excited mercury are formed?
Solution
10-6
*10.21. The photochemical reaction between chlorine and chloroform in the gas phase follows the stoichiometric equation:
CHCl3 + Cl2 = CCl4 + HCl
It is believed to occur by the mechanism:
Assume the rate of formation of Cl atoms in the initiation reaction to be 2Ia, where Ia is the intensity of light absorbed, and obtain an
expression for the overall rate in terms of Ia and [CHCl3].
Solution
*10.22. When water vapor is irradiated with a beam of high-energy electrons, various ions such as H+ and O appear. Calculate the
minimum energies required for the formation of these ions, given the following thermochemical data:
Are the results you obtain consistent with the experimental appearance potentials of
19.5 eV for H+ and 7.5 eV for O?
Solution
10-7
10.23. The mercury-photosensitized hydrogenation of ethylene in the presence of mercury vapor is first-order with respect to ethylene and
half-order with respect to H2. Its rate is proportional to the square root of the intensity of the light absorbed. The following
mechanism has been suggested to account for these observations:
Applying the steady-state approximation to [H] and [C2H5], verify that the mechanism indeed supports the observations. What is the
observed rate constant in terms of the rate constants of the elementary reactions?
Solution
Catalysis
10.24. The hydrolysis of a substance is specifically catalyzed by hydrogen ions, and the rate constant is given by:
k/dm3 mol1 s1 = 4.7 102([H+]/mol dm3)
When the substance was dissolved in a 103 M solution of an acid HA, the rate constant was 3.2 105 dm3 mol1 s1. Calculate the
dissociation constant of HA.
Solution
*10.25. The following is a slightly simplified version of the mechanism proposed in 1937 by G. K. Rollefson and R. F. Faull [J. Amer.
Chem. Soc., 59, 625(1937)] to explain the iodine-catalyzed decomposition of acetaldehyde:
I2 2I
I + CH3CHO HI + CH3CO
CH3CO CH3 + CO
CH3 + HI CH4 + I
2I I2
Apply the steady-state treatment to I, CH3CO, and CH3 and obtain an expression for the rate.
Solution
10-8
*10.26. Suppose that a reaction is catalyzed by a series of homologous acids and that the Hammett equation (9.130) applies:
log10 ka = log10 k0 +
where is the substituent constant and is the reaction constant. Suppose that the corresponding equation for the dissociation of the
acid is:
log10 Ka = log10 K0 + '
where ' is the reaction constant for the dissociation; the substituent constants are the same in both equations. Prove that the
Brnsted equation:
ka Ga K a
applies. How does relate to the reaction constants and '?
Solution
10.27. The hydrolysis of ethyl acetate catalyzed by hydrochloric acid obeys the rate equation:
= k[ester][HCl]
and the reaction essentially goes to completion. At 25 C the rate constant is 2.80 105 dm3 mol1 s1. What is the half-life of the
reaction if [ester] = 0.1 M and [HCl] = 0.01 M?
Solution
10.28. The following mechanism has been proposed for the alkaline hydrolysis of Co(NH3)5Cl2+:
Co(NH3)5Cl2+ + OH Co(NH3)4(NH2)Cl+ + H2O
Co(NH3)4(NH2)Cl+ Co(NH2)4(NH2)2+ + Cl
Co(NH3)4(NH2)2+ + H2O Co(NH3)5(OH)2+
Assume Co(NH3)4(NH2)Cl+ and Co(NH3)4(NH2)2+ to be in the steady state and derive an expression for the rate of reaction.
Experimentally, the rate is proportional to [Co(NH)5Cl2+] [OH]; does this fact tell us anything about the relative magnitudes of the rate
constants?
Solution
10-9
10.29. Confirm that Eq. 10.68,

1
[H ]min (kOH K w / kH ) 2
follows from Eq. 10.66,
kOH K w
k k0 kH [H ]
[H ]
Solution
10.30. The following results have been obtained by D. B. Dahlberg and F. A. Long [J. Amer. Chem. Soc., 95, 3825(1973)] for the base-
catalyzed enolization of 3-methyl acetone.
Catalyst ClCH2COO CH3COO HPO 2
4
Ka/mol dm3 1.39 103 1.80 105 6.25 108

k/dm3 mol1 s1 1.41 103 1.34 102 0.26
Estimate the Brnsted coefficient .
Solution
10.31. Suggest a plausible mechanism for the bromination of acetone catalyzed by hydroxide ions. As with the acid-catalyzed reaction
discussed in Section 10.9, the rate is independent of the bromine concentration.
Solution
10.32. It was found by J. Halpern and coworkers [J. Phys. Chem., 60, 1455(1956)] that the rate equation for the oxidation of molecular
hydrogen by dichromate ions (Cr2 O72 ) catalyzed by Cu2+ ions is of the form:
k[H 2 ][Cu 2 ]2

[H 2 ] k [Cu 2 ]
(**Note that the rate is independent of the concentration of dichromate ions.)
Suggest a mechanism consistent with this behavior, and apply the steady-state treatment to obtain the rate expression. Comment on
rate-controlling steps corresponding to special cases of the mechanism.
Solution
10-10
10.33. For the oxidation of molecular hydrogen by dichromate ions catalyzed by Ag+ ions, A. H. Webster and J. Halpern [J. Phys. Chem.,
60, 280(1956)] obtained the rate equation:
k [H 2 ][Ag ]2
k[H 2 ][Ag ]2
[H 2 ] k [Ag ]
The existence of two terms suggests that two mechanisms are occurring in parallel. Suggest the two mechanisms, applying the
steady-state treatment to obtain the second term in the rate equation.
Solution
10.34. The reaction:

Tl+ + 2Ce4+ Tl3+ + 2Ce3+
is catalyzed by Ag+ ions. Under certain conditions the rate is proportional to
[Ce4+][Tl+][Ag+]/[Ce3+]
Suggest a mechanism consistent with this behavior.
Solution
10-11
Chapter 10: Chemical Kinetics II. Composite Mechanisms Enzyme-Catalyzed Reactions
Enzyme-Catalyzed Reactions
10.35. The following rates have been obtained for an enzyme-catalyzed reaction at various substrate concentrations:
103[S]/mol dm3 Rate, /(arbitrary units)
0.4 2.41
0.6 3.33
1.0 4.78
1.5 6.17
2.0 7.41
3.0 8.70
4.0 9.52
5.0 10.5
10.0 12.5
Plot against [S], 1/ against 1/[S], and /[S] against , and from each plot estimate the Michaelis constant. Which plot appears to give the
most reliable value?
Solution
10.36. The following data have been obtained for the myosin-catalyzed hydrolysis of ATP, at 25 C and pH 7.0.
105[ATP]/mol dm3 106/mol dm3 s1

7.5 0.067
12.5 0.095
20.0 0.119
32.5 0.149
62.5 0.185
155.0 0.191
320.0 0.195
10-12
Plot against [S], 1/ against 1/[S], and /[S] against , and from each plot calculate the Michaelis constant Km and the limiting rate V.
Solution
*10.37. The following values of V (limiting rate at high substrate concentrations) and Km have been obtained at various temperatures for the
hydrolysis of acetylcholine bromide, catalyzed by acetylcholinesterase.
T/C 106V/mol dm3 s1 Km 104/mol dm3
20.0 1.84 4.03
25.0 1.93 3.75
30.0 2.04 3.35
35.0 2.17 3.05
a. Assuming the enzyme concentration to be 1.00 1011 mol dm3, calculate the energy of activation, the enthalpy of activation, the
Gibbs energy of activation, and the entropy of activation for the breakdown of the enzyme-substrate complex at 25 C.
k 1
b. Assuming Km to be the dissociation constant k1/k1 for the enzyme-substrate complex (ES E S), determine the following
k1
thermodynamic quantities for the formation of the enzyme-substrate complex at 25 C: G, H, S.

c. From the results obtained in parts (a) and (b), sketch a Gibbs energy diagram and an enthalpy diagram for the reaction.
Solution
10-13
*10.38. The following data relate to an enzyme reaction:

103[s]/mol dm3 105V/mol dm3 s1
2.0 13
4.0 20
8.0 29
12.0 33
16.0 36
20.0 38
The concentration of the enzyme is 2.0 g dm3, and its molecular weight is 50 000. Calculate Km, the maximum rate V, and kc.
Solution
10.39. The following data have been obtained for the myosin-catalyzed hydrolysis of ATP.
Temperature/C kc 106/s1
39.9 4.67
43.8 7.22
47.1 10.0
50.2 13.9
Calculate, at 40 C, the energy of activation, the enthalpy of activation, the Gibbs energy of activation, and the entropy of activation.
Solution
10-14
*10.40. The following is a simplified version of the mechanism that has been proposed by H. Theorell and Britton Chance for certain
enzyme reactions involving two substrates A and B.
Assume that the substrates A and B are in excess of E so that the steady-state treatment can be applied to EA and EZ, and obtain an
expression for the rate.
Solution
*10.41.When an inhibitor I is added to a single-substrate enzyme system, the mechanism is sometimes:
This is known as a competitive mechanism, since S and I compete for sites on the enzyme.
a. Assume that the substrate and inhibitor are present in great excess of the enzyme, apply the steady-state treatment, and obtain the
rate equation.
b. Obtain an expression for the degree of inhibition defined as:

= 0
0
where is the rate in the presence of inhibitor and 0 is the rate in its absence.
Solution
10-15
*10.42. Obtain the rate equation corresponding to the mechanism:
Assume ES and ES to be in the steady state and the substrate concentration to be much higher than the enzyme concentration.
Express the catalytic constant kc and the Michaelis constant Km in terms of k1, k1, k2, and k3.
Solution
*10.43. Enzyme-catalyzed reactions frequently follow an equation of the form of Eq. 10.85. Suppose that kc and Km show the following
temperature dependence:
kc = Ac exp(Ec/RT ) and Km = B exp(Hm /RT )
where Ac, B, Ec, and Hm are temperature-independent parameters. Explain under what conditions, with [S] held constant, the rate
may pass through a maximum as the temperature is raised.
Solution
10.44. Some enzyme reactions involving two substrates A and B occur by the following mechanism:
k1
E A EA
k 1
k2 k3
EA + B EAB E Y Z
(This is known as the ordered ternary-complex mechanism; A must add first to E, and the resulting complex EA reacts with B; the
complex EB is not formed.)
The concentrations of A and B are much greater than the concentration of E. Apply the steady-state treatment and obtain an
expression for the rate.
Solution
10-16
Chapter 10: Chemical Kinetics II. Composite Mechanisms Polymerization
10.45. The following ping-pong mechanism appears sometimes to apply to an enzyme-catalyzed reaction between two substrates A and
B to give the final products Y and Z:
k1 k2
E A EA EA + Y
k 1
k3 k4
EA + B EAB E Z
It can be assumed that the substrates are present in great excess of the enzyme and that steady-state conditions apply. Obtain an
expression for the rate of reaction.
Solution
Polymerization
10.46. The polymerization of styrene [M] catalyzed by benzoyl peroxide [C] obeys a kinetic equation of the form:
d [M]
k[M]3/ 2 [C]1/ 2
dt
Obtain an expression for the kinetic chain length, in terms of [M], [C], and the rate constants for initiation, propagation, and
termination.
Solution
10.47. The polymerization of ethylene [M] photosensitized by acetone occurs by the mechanism:
hv
CH3COCH3 CO + 2CH3
kp
CH3 + C2H4 CH3CH2CH2
kp
CH3CH2CH2 + C2H4 CH3CH2CH2CH2CH2
kr
Rn + Rm Mn + m
where one quantum gives 2CH3.
Show that the rate equation is:
1/ 2
d [M] 2I
k p [M]
dt kt
where I is the intensity of light absorbed and kp and kt are the rate constants for the propagation and termination steps, respectively.
Solution
10-17
Chapter 10: Chemical Kinetics II. Composite Mechanisms Essay Questions
Essay Questions
10.48. Explain the essential features of a chain reaction.
10.49. Give an account of catalysis by acids and bases, distinguishing between specific and general catalysts.
10.50. Will the rate of an enzyme-catalyzed reaction usually be more sensitive to temperature than that of the same reaction when it is
uncatalyzed? Discuss.
10.51. Explain how you would determine the parameters Km and kc for an enzyme reaction involving a single substrate.
10.52. Explain clearly the difference between collisions and encounters. What significance does this distinction have in chemical kinetics?
10.53. Explain clearly the kind of reasoning involved in deciding what might be the rate-controlling step in a chemical reaction.
10.54. Give a qualitative description of the electronic double-layer theories of Helmholtz, Gouy and Chapman, and Stern.
10-18
Chapter 10: Chemical Kinetics II. Composite Mechanisms Solutions
Solutions
10.1. Suppose that a reaction of stoichiometry A + 2B = Y + Z is believed to occur by the mechanism:
Where X is an intermediate. Write the expression for the rate of formation of Y.
Solution:
A B
k1
X very slow
X B Y Z k2
very fast
Because the second reaction is very fast, X is consumed once produced. So steady state approximation may be applied.
d X
X k1 A B k2 X B 0
dt
k1 A B
X
k2 B
k1 A
X
k2
Similarly
d Y
Y k2 X B
dt
d Y k1 k2 A B

dt k2
d Y
k1 A B
dt
BacktoProblem10.1 BacktoTop
10-19
10.2. Suppose that a reaction A + 2B = 2Y + 2Z is believed to occur according to the mechanism:
Obtain an expression for the rate of formation of the product Y.
Solution:
2X very rapid equilibrium

k1
A
k 1
X B
k2
Y Z slow
Adjust for the stoichiometric coefficients, we can write the reactions as follows:
1 X very rapid equilibrium

k1
A
2 k1
X B k2
Y Z slow
The overall reaction becomes:
1 k1
Y Z
A B
2 k 1
Let us write out the rate of formation for substance X and Y.
d X
k1 A 2 k 1 X k2 X B
1
dt
d Y
k2 X B
dt
Since X is an intermediate, steady state approximation can be applied.
10-20
d X
k1 A 2 k1 X k2 X B 0
1
dt
k1 A k 1 X k2 X B
1
2
k1 A X k 1 k2 B
1
2
k1 A 2
1

X
k 1 k2 B
Plug the above expression into the expression for the rate of formation of Y
d Y
k2 X B
dt
d Y k2 k1 A 2 B
1

dt k 1 k2 B
In this particular reaction, since the first step reaches equilibrium very rapidly, it is safe to assume that k1 k2 .
d Y k2 k1 A 2 B
1

dt k 1 k 2 B
d Y k 1/2
Y k2 1 A B
dt k 1
10-21
10.3. Suppose that a reaction of stoichiometry A + B = Y + Z is believed to occur according to the mechanism:
Apply the steady-state treatment and obtain an expression for the rate. To what expressions does the general rate equation reduce if;
a. The second reaction is slow, the initial equilibrium being established very rapidly?
b. The second reaction is very rapid compared with the first reaction in either direction?
Solution:
A
k1

k 1

X fast equilibrium
X B
k2
Y Z slow
We will begin by writing out the rate of formation and consumption for each species involved.
d A
k1 A k1 X
dt
d X
k1 A k1 X k2 X B
dt
d B
k2 X B
dt
d Y
k2 X B
dt
d Z
k2 X B
dt
d X
According to the steady-state treatment, we can assume that 0 to a good approximation. This will enable us to find an expression for X .
dt
10-22
k1 A k1 X k2 X B
k1 A X k1 k2 B
k1 A
X
k 1 k 2 B
a) The information above leads us to believe that k1 k2 which means that,
k1 A
X
k 1 k 2 B
k1 A
Y k2 B
k1 k2 B
k1k2 A B
Y this term can be dropped
k1 k2 B
k1k2 A B
Y
k1
b) The information above leads us to believe that k2 k1 which means that,
10-23
k1 A
X
k 1 k 2 B
k1 A
Y k2 B
k1 k2 B
k k A B
Y 1 2 this term can be dropped
k1 k2 B
k1 k2 A B
Y
k 2 B
Y k1 A
10-24
10.4. A reaction of stoichiometry:

A+B=Y+Z
is found to be second order in A and zero order in B. Suggest a mechanism that is consistent with this behavior.
Solution:
Given that,
k1

A B
Y Z
k1
K A B since B 1 then,
2 0 0
K A
2
This means that substance B should not appear in the rate determining step.
1 2A X very slow
2 X 2B 2Y 2Z very fast
3 2A 2B 2Y 2Z
2
4 A B Y Z
10-25
10.5. The rate of formation of the product of a reaction is found to give a nonlinear Arrhenius plot, the line being convex to the 1/T axis (i.e., the
activation energy is higher at higher temperatures). Suggest a reason for this type of behavior.
(Hint: For this and the following problem, consider the possibility of two parallel reactions and of two consecutive reactions having different
activation energies.)
Solution:
We are told that a plot of lnk against 1/T produces a non-linear curve that is convex to the x-axis. The following diagram is a sketch of what this would
look like.
Based on the information given above, we can assume that two reactions are occurring simultaneously and that there is competition for a particular
reactant.
lnk
1/T
10-26
10.6. An Arrhenius plot is concave to the 1/T axis (i.e., it exhibits a lower activation energy at higher temperatures). Suggest a reason for this type of
behavior.
Solution:
Two consecutive reactions may be taking place here.
10-27
10.7. Nitrogen pentoxide reacts with nitric oxide in the gas phase according to the stoichiometric equation:
N2O5 + NO = 3NO2
The following mechanism has been proposed:
Assume that the steady-state treatment can be applied to NO3, and derive an equation for the rate of consumption of N2O5.
Solution:
Let us begin by writing out the rate of formation and consumption for each species involved in the reaction.
k1

N 2O5 NO
3NO 2
k1
1 N 2O5
k1
NO 2 NO3
2 NO 2 NO3
k2
N 2O5
3 NO NO3
k3
2NO 2
Since the first two equations can be combined to a single equilibrium, we can write,
1 NO 2 NO3
k1
N 2O5
k1
2 NO NO3
k2
2NO2
d N 2 O5
N 2O5 k1 N 2O5 k 1 NO 2 NO3
dt
d NO3
NO3 k1 N 2O5 k 1 NO 2 NO3 k2 NO NO3
dt
d NO
NO k2 NO NO3
dt
According to the steady-state approximation,
10-28
d NO3
NO3 k1 N 2O5 k 1 NO 2 NO3 k2 NO NO3 0
dt
k1 N 2O5 k 1 NO 2 NO3 k2 NO NO3
k1 N 2O5 NO3 k 1 NO 2 k2 NO
k1 N 2O5
NO3
k1 NO2 k2 NO
This can be substituted into the rate of consumption for N 2 O5 and simplified.
N O k1 N 2O5 k 1 NO 2 NO3
2 5
k1 N 2O5
N O k1 N 2O5 k 1 NO 2
2 5 k1 NO2 k2 NO

k k NO2 N 2O5
N O k1 N 2O5 1 1
2 5
k1 NO2 k2 NO
k1 N 2O5 k1 NO2 k2 NO k1k1 NO2 N 2O5
N O
2 5
k NO k NO
1 2 2
k1k1 NO 2 N 2O5 k1k2 N 2O5 NO k1k 1 NO 2 N 2O5

N O
2 5
k NO k NO
1 2 2
k1k2 N 2O5 NO
N O 2 5
k 1 NO2 k2 NO
10-29
10.8. The reaction 2NO + O2 2NO2 is believed to occur by the mechanism:
Assume N2O2 to be in a steady state and derive the rate equation. Under what conditions does the rate equation reduce to second-order kinetics
in NO and first-order kinetics in O2?
Solution:
Given: see above
Required: Under what conditions does the rate equation reduce to second-order kinetics in NO and first-order kinetics in O2?
2NO O 2 2NO 2
1 2NO k
N 2O21
2 N 2O 2 k
2NO 1
3 N 2O 2 O 2 k
2
2NO 2
d NO 2
NO2 k2 O 2 N 2 O 2
dt
d N 2O2
N2O2 k1 NO k1 N 2O 2 k2 O2 N 2 O 2
2
dt
According to the steady state approximation,
d N 2O2
N2O2 k1 NO k1 N 2 O 2 k2 O 2 N 2O 2 0
2
dt
k1 NO k1 N 2O 2 k2 O 2 N 2O 2
2
k1 NO N 2 O 2 k1 k2 O 2
2
k1 NO
2
N 2O2
k 1 k2 O 2
10-30
Substituting into the expression defining the rate of formation of NO 2 ,
NO k2 O2 N 2 O2
2
k1 NO2
NO k2 O 2
2
k1 k2 O2

k1k2 O 2 NO
2
NO 2
k 1 k2 O 2
In order for the rate equation reduce to second-order kinetics in NO and first-order kinetics in O2, k1 k2 so that we may eliminate a terms in the
denominator. This yields the following:
k1k2 O 2 NO
2
NO 2
k 1 k2 O 2
k1k2
O2 NO
2
NO 2
k1
Thus, the rate equation will be second-order kinetics in NO and first-order kinetics in O2 when,
k1 k2
10-31
*10.9. The gas-phase reaction:

Cl2 + CH4 CH3Cl + HCl
proceeds by a free-radical chain reaction in which the chain propagators are Cl and CH3 (but not H), and the chain-ending step is 2Cl Cl2.
Write the mechanism, identify the initiation reaction and the chain-propagating steps, and obtain an expression for the rate of the overall
reaction.
Solution:
Following the method outlined in Section 10.5 Free Radical Reactions,
Cl2 CH 4 CH3Cl HCl
Initiation: Cl2
k1
Cl Cl

Propagation: Cl CH4
k2
HCl CH3

CH3 Cl2
k3
CH3Cl Cl

Termination: 2Cl
k1
Cl2
It is important to remember that the termination reaction always involves the regeneration of the initial species (the one that forms the free radicals in the
first place).
We can apply the steady-state approximation for the chlorine and CH3 radicals in order to obtain an expression for the overall rate of reaction.
d Cl
Cl k1 Cl 2 k2 Cl CH 4 k3 Cl 2 CH 3Cl k1 Cl
2
dt
d CH 3
CH k2 Cl CH 4 k3 Cl 2 CH 3Cl
dt 3
d HCl
HCl k2 Cl CH 4
dt
10-32
d Cl
Cl k1 Cl 2 k2 Cl CH 4 k3 Cl 2 CH 3Cl k1 Cl 0
2
(1)
dt
d CH 3
CH k2 Cl CH 4 k3 Cl 2 CH 3Cl 0 (2)
dt 3
We recognize that the equations (1) and (2) have some common terms, such as k2 Cl CH 4 and k3 Cl 2 CH 3Cl . Since both equations equal to 0,
we can add them together in order those terms, and their sum still adds up to 0.
(1) (2) :
k1 Cl 2 k2 Cl CH 4 k3 Cl 2 CH 3Cl k 1 Cl k2 Cl CH 4 k3 Cl 2 CH 3Cl 0
2
k1 Cl 2 k 1 Cl =0
2
1/2
k
Cl 1

Cl2 1/2
k 1
Substituting into the rata equation for the formation of HCl,
HCl k2 Cl CH 4
k 1/2
k2 1 Cl 2 CH 4
1/2
HCl
k 1

1/2
k
HCl k2 1 CH 4 Cl2 1/2
k 1
10-33
10.10. The following mechanism has been proposed for the thermal decomposition of pure ozone in the gas phase:
Derive the rate equation.
Solution:
Following the same method as we have done for the previous problems;
1 2O 3
k1
O3 O2 O
2 O O 3
k2
2O 2
d O2
O2 k1 O3 k2 O O3
2
dt
d O
O k1 O3 k2 O O3
2
dt
Applying the steady state approximation to O,
d O
O k1 O3 k2 O O3 0
2
dt
k1 O3 k2 O O3
2
k1 O3
2
O
k2 O3
k
O 1 O3
k2
Substitution into the expression for the rate of formation of oxygen yields,
10-34
O k1 O3 k2 O O3
2
2
k
O k1 O3 k2 O3 O 3
2 1
2 k2

O k1 O3 k1 O3
2 2
2
O 2k1 O3
2
2
10-35
*10.11. A reaction occurs by the mechanism:
and the concentration of X is sufficiently small compared with the concentrations of A and B that the steady-state treatment applies. Prove that
the activation energy Ea at any temperature is given by:
k 1 ( E1 E2 E1 ) k2 E1
Ea
k 1 k2
that is, is the weighted mean of the values E1 + E2 E1, and E1, which apply, respectively, to the limiting cases of k1 k2 and k2 k1.
Solution:
k1

A B
X
k2
Z
k 1
d X
X k1 A B k1 X k2 X
dt
d Z
Z k2 X
dt
Applying the steady state approximation to substance X,
d X
X k1 A B k1 X k2 X 0
dt
k1 A B k1 X k2 X
k1 A B X k1 k2
k1 A B
X
k1 k2
Substitution into the expression for the rate of formation of substance Z yields,
10-36
Z k2 X
k1 A B
Z k2
k1 k2
k1k2 A B
Z
k 1 k 2
k1k2
Let the rate constant K and taking the natural log we obtain,
k1 k2
kk
ln K ln 1 2
k 1 k 2
ln K ln k1 ln k2 ln k 1 k2
Differentiating both sides with respect to temperature leads to,
d ln K ln k1 1 dk2 1 d k 1 k 2

dT dT k2 dT k 1 k2 dT
d ln K ln k1 1 dk2 1 dk 1 1 dk2

dT dT k2 dT k 1 k2 dT k 1 k2 dT
d ln K ln k1 dk2 1 1 k 1 dk 1

dT dT dT k2 k 1 k2 k 1 k 1 k2 dT
d ln K ln k1 dk2 k 1 k2 k2 k 1 ln k 1

dT dT dT k2 k 1 k2 k 1 k2 dT
d ln K ln k1 k 1 d ln k2 k 1 ln k 1

dT dT k 1 k2 dT k 1 k2 dT
Recall that Eq. 9.63 states,
ln k1 E
C 12
dT RT
10-37
Rearranging to isolate the activation energy,
ln k1 ln k1 ln k2
E1 RT 2 similarly, E1 RT 2 and E2 RT 2
dT dT dT
Substituting these expressions into the differentiated expression above yields,
d ln K
E RT 2 and therefore,
dT
k1 k1
E E1 E2 E1
k1 k2 k1 k2
We can combine the terms by putting them over a common denominator.
E1 k 1 k2 Ek E k
E 2 1 1 1
k 1 k2 k 1 k 2 k 1 k 2
E1k 1 E1k2 E2 k 1 E1k 1
E
k 1 k 2
Further simplification leads to the desired equation,
E1k2 k1 E1 E2 E1
E
k1 k2
10-38
10.12. F. A. Lindemann [Trans. Faraday Soc., 17, 598(1922)] proposed the following mechanism for a unimolecular gas reaction:
The species A* is an energized molecule that is present in low concentrations. Apply the steady-state treatment to A* and obtain an expression
for the rate in terms of [A], k1, k1, and k2. Show that the mechanism predicts first-order kinetics at higher A concentrations and second-order
kinetics at lower ones.
Solution:
Given: see above
Required: expression for rate, k1, k1, k2
d A
A k1 A k1 A A
2
dt
d A
A k1 A k1 A A k2 A
2
dt
Applying the Steady-State treatment to A we obtain the following expression:
d A
0
dt
A k1 A k1 A A k2 A 0
2

Rearranging and simplifying we obtain,
k1 A k1 A A k2 A
2
k1 A A k1 A k2
2
k1 A
2
k 1 A k 2
10-39
The rate is given by,
k2 A
We may substitute the above expression for A which yields,
k1k2 A
2
k A k
1 2
At high pressures, we can work under the assumption that k1 A k2 therefore enabling us to remove the k2 term in the denominator and further
simplify the expression.
k1k2 A k1k2 A
2 2

k A k
1 2 k1 A
(a first order rate equation)
k1k2
A
k1
At low pressure, we can work under the assumption that k2 k1 A and thus,
k1k2 A k1 k2 A
2 2

k1 A k2 k2 (a second order rate equation)
k1 A
2
10-40
*10.13. Certain polymerizations involve esterification reactions between COOH groups on one molecule and OH groups on another. Suppose that the
concentration of such functional groups is c and that the rate of their removal by esterification obeys the equation:
dc
kc 2
dt
Obtain an equation relating the time t to the fraction f of functional groups remaining and to the initial concentration c0 of functional groups.
Solution:
dc
Given the differential equation kc 2 , we can start by choosing the boundary condition that at t = 0, c = c0. Rearranging the above expression and
dt
taking the integral of both sides, we obtain,
dc
kdt
c2
dc
2 kdt
c
1
kt I
c
Applying the boundary conditions to solve for I,
1
kt I
c
1
I
c0
Substituting this back into the integrated expression,
1 1
kt
c c0
This can be rewritten as,
10-41
c0 c
kt
cc0
The expression for the fraction of functional groups remaining is therefore,
c0 c
f
c0
Let us derive an expression relation the fraction of functional groups remaining to the initial concentration only,
c0 c c0 c
f c0 c0 c c
0 c0kt
1 f c0 c0 c c c
c0 c0 c0
Inverting the above expression:
1 f 1

f c0kt
1 1
1
f c0kt
1 1 1 c0kt
1
f c0kt c0kt
c0kt
f
1 c0kt
10-42
*10.14. Show that the mechanism:
leads to the result that the rate equation for the overall reaction is = k[H2][I2].
Solution:
Recall that when reactions occur as fast equilibriums, we may write,
I
2
k
1 K 1
k1 I 2
k2 H 2 I
2 K
k2 I H 2
Let us now rearrange these expressions in order to isolate I and H2I as they are important reagents in the rate determining step. Finding expressions for
these will allow us to determine the rate equation.
k1 I
2

k1 I 2
k1
I I2
2

k1
1
k 2 1
I 1 I2 2
k1
k2

H 2 I
k2 I H 2
k2
H 2 I I H 2
k2
10-43
Now substitute the expression for I into the above to obtain,

1
k k 2 1
H 2 I 2 1 I2 2 H 2
k2 k1
The overall rate is given by the rate determining step which is the slow reaction in this case.
k3 H 2 I I
Substitution yields,
1 1
k k 2 1 k 2 1
k3 2 1 I 2 2 H 2 1 I 2 2
k2 k1 k1
Simplification yields,
1 1
k2 k1 2 1 k1 2 1
k3 I2 H 2
2
I2 2
k2 k1 k1
k3k2k1
I 2 H 2
k2k1
k3k2k1
letting k , we obtain the final expression for the rate equation
k 2k 1
k I 2 H 2
10-44
10.15. Apply the steady-state treatment to the following mechanism, in which Y and Z are final products and X is a labile intermediate:
Obtain an expression for the rate of formation of the product Z. What rate equations are obtained if (a) A and (b) B are present in great excess?
Solution:
Given: see above
Required: expression for rate of formation of Z, a), b)
We will begin by writing out the rates of consumption or production for each of the reacting species involved. We do know, however, that X is the
species for which we will be applying the steady-state treatment.
d A
A k1 A B k1 X k2 A X
dt
d B
B k1 A B k1 X k3 B X
dt
d X
X k1 A B k1 X k2 A X k3 B X
dt
Applying the steady-state treatment for X, we obtain,
d X
0
dt
k1 A B k1 X k2 A X k3 B X 0
k1 A B k1 X k2 A X k3 B X
This can be simplified by factoring out X from the right hand side.
10-45
k1 A B X k1 k2 A k3 B
k1 A B
X
k 1 k 2 A k3 B
Now we may write out the rates of formation for the product Z.
d Z
Z k3 B X
dt
Substituting what we have found (while applying the steady-state treatment to X) above into the expression for the rate of formation of Z we obtain,
Z k3 B X
k1 A B
Z k3 B
k 1 k 2 A k3 B
k1k3 A B
2
Z
k 1 k 2 A k3 B
a) If reagent A is present in great excess, then we can work under the assumption that k2 A k1 k3 B which allows us to simplify the rate
equation given above.
k1k3 A B
2
Z
k 1 k 2 A k3 B
k1k3 A B
2
Z (a second order rate equation)

k2 A
k1k3
B
2
Z
k2
10-46
b) If the reagent B is present in great excess then we can work under the assumption k3 B k1 k2 A thus,
k1k3 A B
2
Z
k 1 k 2 A k3 B
k1 k3 A B
2
Z (a second order rate equation)

k3 B
Z k1 A B
Since this simplified rate equation has the same form as that originally derived, the first reaction is rate determining.
10-47
10.16. Calculate the maximum wavelength of the radiation that will bring about dissociation of a diatomic molecule having a dissociation energy of
390.4 kJ mol1.
Solution:
Given: Ediss 390.4 kJ mol

1
Required: max
We know that the dissociation energy given above is the total dissociation energy per mole. It is important to determine the dissociation energy in
Joules. In order to do this, we will divide the dissociation energy by Avogadros number.
390.4 kJ mol1
Ediss
6.022 1023 mol1
Ediss 6.482 896 1022 kJ
Ediss 6.482 896 1019 J
With this energy, we can determine the corresponding frequency by using the following expression,
E hv
E
v
h
Where h is Plancks constant and is measured in J s.
6.482 896 1019 J

v
6.626 1034 J s
v 9.784 027 1014 s 1
The simple wave equation that relates the speed of light to wavelength and frequency can be used in order to determine the wavelength.
c v
c
v
Where c is the speed of light measured in m s-1.
10-48
2.998 108 m s 1
9.784 027 1014 s 1

3.06 107 m
Since wavelengths are typically expressed in terms on nanometers, we can write,
1 nm
3.06 107 m 9
110 m
306 nm
This wavelength corresponds to the maximum wavelength that will cause dissociation of this diatomic molecule.
10-49
10.17. Hydrogen iodide undergoes decomposition into H2 + I2 when irradiated with radiation having a wavelength of 207 nm. It is found that when 1 J
of energy is absorbed, 440 g of HI is decomposed. How many molecules of HI are decomposed by 1 photon of radiation of this wavelength?
Suggest a mechanism that is consistent with this result.
Solution:
Given: 207 nm, E 1 J, m 440 g
Required: number of molecules of HI decomposed
It is first important to determine the number of moles of HI in 440 g. We can do this by using the molar mass of HI.
m
n
M
440 g 440 106 g
440 106 g
n
127.9 g mol1
n 3.440 188 106 mol
With this, we are able to determine the number of molecules of HI by using Avogadros number.

# molecules 3.440 188 106 mol 6.022 1023 mol1
# molecules 2.071 681 1018
Given the wavelength, we can determine the corresponding frequency as was done in the previous problem.
c v
c 2.998 108 m s 1
v
207 109 m
v 1.448 309 1015 s 1
Using E hv , we can determine the energy associated with this frequency and wavelength.
10-50
E hv

E 6.626 1034 J s 1.448 309 1015 s 1
E 9.596 497 1019 J
1 Joule of radiation will correspond to the following number of photons,
1 J
# photons
9.596 497 1019 J
# photons 1.04 1018
# molecules 2.071 681 1018

A single photon will then be able to decompose 1.99 . Which is approximately 2 molecules of HI.
# photons 1.04 1018
The German photochemist Emil Gabriel Warburg found for this reaction, a quantum yield of 2 (as we have just done). In order to explain this, he
proposed the following mechanism:
HI hv H I
H HI H 2 I
I I I2
When all three steps are added together, we obtain the following:
2HI hv H 2 I 2
10-51
10.18. A 100-watt mercury-vapor lamp emits radiation of 253.7 nm wavelength and may be assumed to operate with 100% efficiency. If all the light
emitted is absorbed by a substance that is decomposed with a quantum yield of unity, how long will it take for 0.01 mol to be decomposed?
Solution:
Given: P 100 W, 253.7 nm, n 0.01 mol
Required: t required to decompose
Let us first determine the frequency associated with the radiation of 253.7 nm.
c v
c2.998 108 m s 1
v
253.7 109 m
v 1.181 7111015 s 1
The energy can be found using the following expression:
E hv

E 6.626 1034 J s 1.181 7111015 s 1
E 7.830 1019 J
We know that a 100-W lamp emits 100 Joules per second (definition of a watt). Using this information, we can determine the number of photons
emitted per second.
P 100 J s 1
# photons per second
E 7.830 1019 J
# photons per second 1.277 137 1020
Since we are working in moles, let us change the above into molar units.
1.277 137 1020 s 1

1
2.120 785 104 moles of photons per second
6.022 10 mol
23
In order for 0.01 moles of this substance to be decomposed, it will require
10-52
0.01 mol
t 47.15 s 47 s
2.120785 104 mol s 1
10-53
10.19. Suppose that the radiation emitted by the lamp in Problem 10.18 is all absorbed by ethylene, which decomposes into C2H2 + H2 with a quantum
yield of unity. How much ethyne will be produced per hour?
Solution:
Given: Problem 10.18: P 100 W, 253.7 nm, n 0.01 mol
Required: amount of ethylene produced per hour
The lamp in the previous problem was found to produce,
1.277 137 1020 s 1

1
2.120 785 104 moles of photons per second
6.022 10 mol
23
Knowing this, we can determine how many moles of photons would be produced in 1 hour.
60 s 60 min
1 hour 3600 s
min hour
s
n 2.120 785 104 mol s 1 3600
hour
mol
n 0.76
hour
Since ethylene is also a substance with a quantum yield of unity, then 0.76 moles of ethylene will be produced per hour.
10-54
10.20. A 1000-watt mercury vapor flash lamp emits radiation of 253.7 nm wavelength, and the duration of the flash is 1 s. Suppose that all of the
radiation of a single flash is absorbed by mercury vapor; how many atoms of excited mercury are formed?
Solution:
Given: flash lamp: P 1000 W, 253.7 nm, t 1 s
Required: N Hg produced
We will begin by determining the frequency and energy associated with this wavelength.
c v
c2.998 108 m s 1
v
253.7 109 m
v 1.181 711 1015 s 1
E hv

E 6.626 1034 J s 1.181 7111015 s 1
E 7.830 1019 J
Again, we know that a 1000-W lamp will emit 1000 Joules per second. With this, we can determine the number of photons emitted per second.
P 1000 J s 1
# photons per second
E 7.830 1019 J
# photons per second 1.277 137 1021
In a single microsecond, which is equal to, 1 s 110
6
s we will see that,

# photons 1.277 137 1021 photons s 1 110 s
6
# photons 1.277 1015 emitted

Supposing that all of the radiation of a single flash (1 microsecond) is absorbed by mercury vapor, the number of photons emitted in this time will be
equal to the number of excited mercury atoms formed.
N Hg 1.28 1015 atoms
10-55
*10.21. The photochemical reaction between chlorine and chloroform in the gas phase follows the stoichiometric equation:
CHCl3 + Cl2 = CCl4 + HCl

It is believed to occur by the mechanism:
Assume the rate of formation of Cl atoms in the initiation reaction to be 2Ia, where Ia is the intensity of light absorbed, and obtain an expression
for the overall rate in terms of Ia and [CHCl3].
Solution:
We will begin by writing down the steady-state expressions for Cl and CCl3.
d Cl
2 I a k2 Cl CHCl3 k3 CCl3 Cl2 k4 Cl
2
dt
d Cl
0
dt
2 I a k2 Cl CHCl3 k3 CCl3 Cl2 k4 Cl 0
2
2 I a k3 CCl3 Cl2 k2 Cl CHCl3 k4 Cl

2
d CCl3
k2 Cl CHCl3 k3 CCl3 Cl2
dt
d CCl3
0
dt
k2 Cl CHCl3 k3 CCl3 Cl2 0
k2 Cl CHCl3 k3 CCl3 Cl2
10-56
Adding the two steady-state expressions, we obtain the following:
2 I a k2 Cl CHCl3 k3 CCl3 Cl2 k4 Cl 0

2
k2 Cl CHCl3 k3 CCl3 Cl2 0
2 I a k4 Cl 0
2
Solving for Cl,
2 I a k4 Cl
2
2I a
Cl
2

k4
1
2I a 2
Cl
k4
The overall rate equation is given by,
HCl k2 Cl CHCl3
Substituting the expression for Cl into the above yields,
1
2Ia 2
k2 CHCl3
k4
10-57
*10.22. When water vapor is irradiated with a beam of high-energy electrons, various ions such as H+ and O appear. Calculate the minimum energies
required for the formation of these ions, given the following thermochemical data:
Are the results you obtain consistent with the experimental appearance potentials of
19.5 eV for H+ and 7.5 eV for O?
Solution:
Hydrogen ions are quite easily formed according to the following process:
H2O e H OH 2e
This reaction can be generated through the addition of the following two equations:
1 H 2O H OH
2 e H H 2e
The standard enthalpy of formation for the original reaction is therefore given by,
H o H o rxn 1 H o rxn 2
H o 498.7 1312.2 kJ mol 1
H o 1810.9 kJ mol 1
1 eV 96.47 kJ mol 1
1 eV
H o 1810.9 kJ mol 1
96.47 kJ mol 1
H o 18.77 163 885 eV 18.8 eV
10-58
The above value is lower than the observed value of 19.5 eV, indicating that the system passes through a state of higher energy. The OH radical
probably dissipates energy in the form of translational, vibrational, and rotational energy.
O- ions are most easily formed by
H 2O e 2H O
This reaction can be generated through the addition of the following three equations:
4 H 2O H OH
5 OH H O
6 O + e O
The standard enthalpy of formation for the original reaction is therefore given by,
H o H o rxn 4 H o rxn 5 H o rxn 6

H o 498.7 428.2 213.4 kJ mol 1
H o 713.5 kJ mol 1
1 eV 96.47 kJ mol 1
1 eV
H o 713.5 kJ mol 1
96.47 kJ mol 1
H o 7.396 081 683 eV 7.4 eV
The above value is close to the observed appearance potential of 7.5 eV.
10-59
10.23. The mercury-photosensitized hydrogenation of ethylene in the presence of mercury vapor is first-order with respect to ethylene and half-order
with respect to H2. Its rate is proportional to the square root of the intensity of the light absorbed. The following mechanism has been suggested
to account for these observations:
Applying the steady-state approximation to [H] and [C2H5], verify that the mechanism indeed supports the observations. What is the observed
rate constant in terms of the rate constants of the elementary reactions?
Solution:
Applying the steady-state approximation for H, we obtain,
d H
H 2k1 Hg H 2 k2 H C2 H 4 k3 C 2 H 5 H 2 k 4 H
2
dt
Applying the steady-state approximation to C2H5, we obtain,
d C2 H5
C2 H5 k2 H C2 H 4 k3 C 2 H 5 H 2
dt
Let us simplify both equations.
10-60
d H
0
dt
2k1 Hg H 2 k2 H C2 H 4 k3 C2 H 5 H 2 k4 H 0
2
2k1 Hg H 2 k3 C2 H5 H 2 k2 H C2 H 4 k4 H
2
d C2 H5
0
dt
k2 H C2 H 4 k3 C2 H5 H 2 0
k2 H C2 H 4 k3 C2 H5 H 2
Adding both equations we obtain,
2k1 Hg H 2 k3 C2 H 5 H 2 k2 H C2 H 4 k4 H
2
k2 H C2 H 4 k3 C2 H 5 H 2
2k1 Hg H 2 k4 H
2
Isolating for H will yield,
2k1 Hg H 2 k4 H
2
2k1 Hg H 2
H
2

k4
1
2k1 Hg H 2 2
H

k4

Substituting this expression into the steady-state approximation for C2H5,
10-61
d C2 H 5
C2 H5 k2 H C2 H 4 k3 C2 H 5 H 2 0
dt
k2 H C2 H 4 k3 C2 H 5 H 2
k2 H C2 H 4
C2 H 5
k3 H 2
1
k2 C2 H 4 2k1 Hg H 2 2

C2 H 5
k3 H 2 k4

The rate of formation of ethane is given by,
d C2 H 6
C2 H6 k3 C 2 H 5 H 2
dt
This can also be written as,
1
d C2 H 6 k2 H 2 C2 H 4 2k1 Hg H 2 2
C2 H 6 k3
dt k3 H 2

k4

1
d C2 H 6 2k1 Hg H 2 2
C2 H 6 k2 C 2 H 4
dt k4

The rate is indeed first order with respect to ethylene and half-order with respect to Hg* and H2. Since the number of moles of Hg* produced is directly
proportional to the intensity of the light absorbed, the rate is also proportional to the square root of the intensity of the light. The observed rate constant
is therefore given by,
1
2k 2
kobs k2 1
k4
10-62
10.24. The hydrolysis of a substance is specifically catalyzed by hydrogen ions, and the rate constant is given by:
k/dm3 mol1 s1 = 4.7 102([H+]/mol dm3)

When the substance was dissolved in a 10 M solution of an acid HA, the rate constant was 3.2 105 dm3 mol1 s1. Calculate the dissociation
3
constant of HA.
Solution:
Given: k0 4.7 10 dm3mol 1 s 1 , C 103 M, kHA 3.2 105 dm3 mol 1 s 1

2
Required:
The concentration of H+ ions in the solution is:
3.2 105
2
6.81 104 mol dm 3
4.7 10
The dissociation constant is therefore
Ka
6.81 10 4 2
4.64 104 mol dm 3

3
10
10-63
*10.25. The following is a slightly simplified version of the mechanism proposed in 1937 by G. K. Rollefson and R. F. Faull [J. Amer. Chem. Soc., 59,
625(1937)] to explain the iodine-catalyzed decomposition of acetaldehyde:
I2 2I
I + CH3CHO HI + CH3CO
CH3CO CH3 + CO
CH3 + HI CH4 + I
2I I2
Apply the steady-state treatment to I, CH3CO, and CH3 and obtain an expression for the rate.
Solution:
We can first associate reaction constants to the above reactions as k1, k2, k3, k4, and k5. Then we can write out the rate of formation or consumption for
the intermediate species I, CH3CO, and CH3. By the steady-state approximation, the rate of formation or consumption of these species equal to 0.
d I
I 2k1 I 2 k2 I CH 3CHO k4 CH 3 HI k 1 I
2
dt
d I
I 0
dt
2k1 I 2 k2 I CH 3CHO k4 CH 3 HI k1 I 0
2
d CH 3CO
CH3CO k2 I CH 3CHO k3 CH 3CO
dt
d CH 3CO
CH3CO 0
dt
k2 I CH 3CHO k3 CH 3CO 0
d CH 3
CH3 k3 CH 3CO k4 CH 3 HI
dt
d CH 3
CH3 0
dt
k3 CH 3CO k4 CH 3 HI 0
10-64
All three of these steady-state approximations can be added together in order to eliminate terms. This process yields the following result:
2k1 I 2 k2 I CH 3CHO k4 CH 3 HI k 1 I 0
2
k2 I CH 3CHO k3 CH 3CO 0
k3 CH 3CO k4 CH 3 HI 0
2k1 I 2 k 1 I 0
2
Rearrange and simplify to isolate I.
2k 1 I k1 I 2
2
k1
I 2 I2
2k1
1
k1 2 1

I 2 2
I
2 k 1
The overall rate is given by,
CO k3 CH3CO k2 I CH3CHO
Making the substitution for I, we will get,
1
k 2 1
CO k2 1 I 2 2 CH 3CHO
2k 1
10-65
*10.26. Suppose that a reaction is catalyzed by a series of homologous acids and that the Hammett equation (9.130) applies:
log10 ka = log10 k0 +
where is the substituent constant and is the reaction constant. Suppose that the corresponding equation for the dissociation of the acid is:
log10 Ka = log10 K0 + '
where ' is the reaction constant for the dissociation; the substituent constants are the same in both equations. Prove that the Brnsted equation:
ka Ga K a
applies. How does relate to the reaction constants and '?
Solution:
The first two equations above may be written in the following manner:
1 1
log10 ka log10 k0

1 1
log10 K a log10 K 0
" "
Subtracting the second equation from the first yields,
1 1
log10 ka log K constant
" 10 a
Combine the terms to obtain,
1 1
log10 ka log K constant
" 10 a
1 1
"
log10 k a log10 K a constant
1

ka
log10 1
constant
"
Ka
This can also be written as,
10-66
ka
log10
constant
"
Ka
Rearranging this expression to isolate ka,
ka

10constant G
"
Ka

"
ka GK a

Note that thus,
"
ka GK a
represents the ratio of the two reaction constants.
10-67
10.27. The hydrolysis of ethyl acetate catalyzed by hydrochloric acid obeys the rate equation:
= k[ester][HCl]
and the reaction essentially goes to completion. At 25 C the rate constant is
2.80 105 dm3 mol1 s1. What is the half-life of the reaction if [ester] = 0.1 M and
[HCl] = 0.01 M?
Solution:
Given: k ester HCl , T 25 C, k 2.80 10 5 dm3 mol 1 s 1 , ester 0.1 M,
HCl 0.01 M
Required: t1/2
Since the reaction essentially goes to completion, we can assume that the concentration of hydrochloric acid remains unchanged throughout. We have
also been given the rate equation which is first order with respect to HCl but is overall second order. We can use the concentration of HCl in order to
determine the pseudo-first order rate constant.
Remembering that first order reactions have a rate constant with the units s-1 (Table 9.1),
k 2nd order 2.80 10 5 dm3 mol 1 s 1

HCl 0.01 M
1 M mol L1 , 1 L 1 dm3 therefore,
HCl 0.01 M 0.01 mol dm 3
k ' k 2nd order HCl

k ' 2.80 10 5 dm3 mol 1 s 1 0.01 mol dm 3
k ' 2.80 107 s 1
The half life for a first order reaction is given by Eq. 9.40:
ln 2
t1/2
k
10-68
This expression is also found in Table 9.1. Now, making the substitution of the pseudo-first order rate constant into Eq. 9.40 we obtain,
6.931 472
t1/2
2.80 107 s 1
t1/2 2.48 106 s
10-69
10.28. The following mechanism has been proposed for the alkaline hydrolysis of Co(NH3)5Cl2+:
Co(NH3)5Cl2+ + OH Co(NH3)4(NH2)Cl+ + H2O

Co(NH3)4(NH2)Cl+ Co(NH2)4(NH2)2+ + Cl
Co(NH3)4(NH2)2+ + H2O Co(NH3)5(OH)2+
Assume Co(NH3)4(NH2)Cl+ and Co(NH3)4(NH2)2+ to be in the steady state and derive an expression for the rate of reaction.
Experimentally, the rate is proportional to [Co(NH)5Cl2+] [OH]; does this fact tell us anything about the relative magnitudes of the rate
constants?
Solution:
Lets make a couple of substitutions in order to simplify the list of reactions.
A Co NH 3 5 Cl2
X Co NH 3 4 NH 2 Cl
Y Co NH 2 4 NH 2
2
Z Co NH 3 5 OH
2
Rewriting the above reaction sequence we obtain,
1 A OH
k1
X H 2O
2 X
k2
Y Cl
3 Y H 2 O
k3
Z
Applying the steady state approximation to substance X,
10-70
d X
X k1 A OH k2 X
dt
d X
X 0
dt
k1 A OH k2 X
k
X 1 A OH
k2
Applying the steady state approximation to substance Y,
d Y
Y k2 X k3 Y H 2O
dt
d Y
Y 0
dt
k2 X k3 Y H 2O
k2 X
Y
k 3 H 2O
k2 k1 A OH
Y
k3 k 2 H 2O

k1 A OH

Y
k3 H 2O
The overall rate of reaction is therefore,
10-71
Z k3 Y H 2O
k1 A OH

Z k3 H 2O
k3 H 2O
Z k1 A OH
Z k1 Co NH 3 5 Cl 2 OH
10-72
10.29. Confirm that Eq. 10.68,

1

[H ]min ( kOH K w / kH ) 2
follows from Eq. 10.66,

kOH K w
k k0 kH [H ]
[H ]
Solution:
We have been told that,
kOH K w
k k0 kH [H ]
[H ]

This expression may be differentiated with respect to [H ] . This process yields,
dk d k Kw

0
k kH [H ] OH
d [H ] d [H ] [H ]
dk k Kw

kH OH 2
d [H ] [H ]

Setting this expression equal to zero will allow us to further simplify and isolate for [H ] min.
kOH K w
kH 0
[H ]2
kOH K w
kH
[H ]2
k Kw
[H ]2 OH
kH
1
k Kw 2
[H ] OH
k
H
10-73
10.30. The following results have been obtained by D. B. Dahlberg and F. A. Long [J. Amer. Chem. Soc., 95, 3825(1973)] for the base-catalyzed
enolization of 3-methyl acetone.

4
Ka/mol dm3 1.39 103 1.80 105 6.25 108

k/dm3 mol1 s1 1.41 103 1.34 102 0.26
Estimate the Brnsted coefficient .
Solution:
Given: see above
Required: Brnsted coefficient

14
Recall that K w [H ][OH ] 10 . Since we have been given the acid dissociation constants and we require the base dissociation constants given
by,
[HB ][OH ] A H
Kb and K a
B HA
We can convert the acid dissociation constants into base dissociation constants by dividing 10-14 by each value.
[H ][OH ]
[H
] [OH
]
HA
A H A H
HA
[H ][OH ]

HA [OH ]
A H A
HA
10-74
which can be expressed as:
HA [OH ] K
[HB ][OH ]
A
b
B
We should also take the natural log of Kb and k in order to plot them against each other. By doing this, we will produce a straight-line graph whose
slope is equal to the Brnsted coefficient.

4
Kb 7.19 1012 5.56 1010 1.60 107

k 1.41 103 1.34 102 0.26
ln Kb -25.66 -21.31 -15.65
lnk -6.56 -4.31 -1.35
10-75
From the equation of the line generated by Microsoft Excels trendline option, we can see that the slope of the curve is equal to,
m 0.5206
m 0.52
10-76
10.31. Suggest a plausible mechanism for the bromination of acetone catalyzed by hydroxide ions. As with the acid-catalyzed reaction discussed in
Section 10.9, the rate is independent of the bromine concentration.
Solution:
The hydroxide ion is assumed to abstract a proton from the acetone molecule, giving the ion CH3COCH2-, which exists in a resonant state. If its
resonance structure reacts rapidly with a bromine molecule, the rate is independent of the bromine concentration.
10-77
10.32. It was found by J. Halpern and coworkers [J. Phys. Chem., 60, 1455(1956)] that the rate equation for the oxidation of molecular hydrogen by
dichromate ions (Cr2 O72 ) catalyzed by Cu2+ ions is of the form:
k[H 2 ][Cu 2 ]2

[H 2 ] k [Cu 2 ]
(**Note that the rate is independent of the concentration of dichromate ions.)
Suggest a mechanism consistent with this behavior, and apply the steady-state treatment to obtain the rate expression. Comment on rate-
controlling steps corresponding to special cases of the mechanism.
Solution:
Since we know that the rate is independent of the concentration of dichromate ions, we will begin with the reaction that occurs between the hydrogen
molecule and Cu2+. This reaction can likely be said to reach equilibrium rapidly. The balanced reactions are as follows:
k1

Cu 2 H 2
CuH H

k 1
CuH Cu 2
k2
2Cu H
We can assume that the second step is the rate controlling step. Also, it should be noted that a third reaction (rapid) takes place with the dichromate ion.
We will apply the steady state approximation for the CuH ion.
d CuH
CuH k1 Cu 2 H 2 k1 CuH H k2 CuH Cu 2
dt
d CuH
0
dt
k1 Cu 2 H 2 k1 CuH H k2 CuH Cu 2 0
k1 Cu 2 H 2 k1 CuH H k2 CuH Cu 2

k1 Cu 2 H 2 CuH k1 H k2 Cu 2
k1 Cu 2 H 2
CuH

k 1
H k2 Cu 2
10-78
The overall rate can then be written as:
2Cu k2 CuH Cu 2

Making the appropriate substitutions into the above, we obtain,
k1 Cu 2 H 2
2Cu k2 Cu 2
k1 H k2 Cu
2

This expression simplifies to the following:
k1k2 H 2 Cu 2
2
k 1 H k2 Cu 2
10-79
10.33. For the oxidation of molecular hydrogen by dichromate ions catalyzed by Ag+ ions, A. H. Webster and J. Halpern [J. Phys. Chem., 60,
280(1956)] obtained the rate equation:
k [H 2 ][Ag ]2
k[H 2 ][Ag ]2
[H 2 ] k [Ag ]
The existence of two terms suggests that two mechanisms are occurring in parallel. Suggest the two mechanisms, applying the steady-state
treatment to obtain the second term in the rate equation.
Solution:
In the previous problem, this particular reaction was catalyzed by copper ions (please refer back to it in order to review the reactions). However, here,
we can see from the overall rate equation that there is an additional term (which means that two mechanisms are occurring in parallel).
It is safe to assume that the first term in the rate equation derives from a single step reaction involving a single hydrogen molecule and two Ag+ ions.
Normally, we would not suggest that the order of each species is directly related to the stoichiometric values, but we will make this assumption in this
particular case. We can write the reaction as follows:
2Ag H 2
k1
2AgH
AgH ' k1 Ag H 2
2

This reaction can then be followed by the rapid reduction of the dichromate ion by the former product. Conversely, we can say that the AgH is rapidly
oxidized by the dichromate ion. The next terms can be explained in the same way that the previous problem involving copper was.
k2

Ag H 2
AgH H

k2
AgH Ag
k3
AgH Ag
Applying the steady-state approximation to reactions two and three we obtain,
10-80
d AgH
AgH k2 Ag H 2 k 2 AgH H k3 AgH Ag
dt
d AgH
0
dt
k2 Ag H 2 k 2 AgH H k3 AgH Ag 0
k2 Ag H 2 k 2 AgH H k3 AgH Ag

k2 Ag H 2 AgH k 2 H k3 Ag
k2 Ag H 2
AgH
k 2
H k3 Ag
The overall rate equation can then be written as:
AgH k3 AgH Ag

Making the substitution for the AgH molecule into the expression above, we obtain,
k2 Ag H 2
AgH k3 Ag

k 2 H k3 Ag

This can be re-written as:
k2 k3 Ag H 2
2
''
k 2
H k3 Ag
Putting both rate equations together, we will obtain the true rate equation.
10-81
' ''
k2k3 H 2 Ag
2
2k1 H 2 Ag
2
k 2 H k3 Ag
10-82
10.34. The reaction:

Tl+ + 2Ce4+ Tl3+ + 2Ce3+
+
is catalyzed by Ag ions. Under certain conditions the rate is proportional to
[Ce4+][Tl+][Ag+]/[Ce3+]
Suggest a mechanism consistent with this behavior.
Solution:
We are given that,
Ce4 Tl Ag
and Tl 2Ce 4 Tl3 2Ce3
Ce3
Since the overall rate equation consists of a ratio, we know that there must be more than a single reaction taking place. We can also guess that the first
reaction is a rapid equilibrium and the second reaction is the rate controlling step (slow). We are also told that there is a catalyst involved so this will
take part in the initial fast equilibrium reaction.
k1

Ag Ce 4 3
Ce Ag
2
k 1
The newly oxidized silver ion will then react with Tl+ through an oxidation/reduction.
Ag 2 Tl
k2
Tl2 Ag
Since we know that the silver can only stably return to the +1 oxidation state via oxidation/reduction, we know that there must be a third step that
involves Tl 2 in order to bring it to the fully oxidized form of +3. This next reaction will occur fairly quickly. From the first step, we can use the
remaining Ce4+ as an oxidizing agent (which will in turn be reduced to Ce3+).
Tl2 Ce4
k3
Tl3 Ce3
Let us verify our assumptions by adding up all of the reactions and checking to see whether all of the reactants and products are satisfied.
10-83
k1

Ag Ce 4 3
Ce Ag
2
k1
Ag 2 Tl
k2
Tl2 Ag
Tl2 Ce 4
k3
Tl3 Ce3
2Ce4 Tl 2Ce3 Tl3
Recall that:
k1 Ag Ce
2 3
K
k1 Ag Ce4
The overall rate of the reaction will be defined by the limiting step and is therefore;
k2 Ag 2 Tl
Making the appropriate rearrangements and simplifications to eliminate Ag2+ (by substitution from the equilibrium constant expression) we obtain,
K Ag Ce 4
k2 Tl
Ce3
This can be re-written in as,
k1k2 Ag Ce Tl
4
k1 Ce3
Thus proving that,
Ce4 Tl Ag
Ce3
10-84
10.35. The following rates have been obtained for an enzyme-catalyzed reaction at various substrate concentrations:
103[S]/mol dm-3 Rate, /(arbitrary units)

0.4 2.41
0.6 3.33
1.0 4.78
1.5 6.17
2.0 7.41
3.0 8.70
4.0 9.52
5.0 10.5
10.0 12.5

Plot against [S], 1/ against 1/[S], and /[S] against , and from each plot estimate the Michaelis constant. Which plot appears to give the most
reliable value?
Solution:
In order to create all of these plots, let us first write out a table that includes all of the values that we will be required to use.
103[S] (mol dm-3) 1/ 1/[S] (10-3 mol dm-3) /[S] (10-3 mol dm-3)
0.4 2.41 0.4149 2.500 6.025
0.6 3.33 0.3003 1.667 5.550
1.0 4.78 0.2092 1.000 4.780
1.5 6.17 0.1621 0.667 4.113
2.0 7.41 0.1350 0.500 3.705
3.0 8.7 0.1149 0.333 2.900
10-85
4.0 9.52 0.1050 0.250 2.380

5.0 10.5 0.0952 0.200 2.100
10.0 12.5 0.0800 0.100 1.250
Plot 1: against [S]
v max
Km
The Michaelis-Menten equation (Eq. 10.82) states that,
10-86
max S
K m S
In this expression, Km = MichaelisMenten rate constant, [S] = substrate concentration, v = initial rate of production of the product, and v max = maximum
initial rate of production of the product.
Notice that this plot produces a curved line which is not easy to work with. It essentially produces a saturation curve which is mostly only useful to
examine the relationship between the concentration of substrate and the rate of reaction. Here, we would need to look at the steepest part of the slope
which we can call a straight line. The highest point of this straight line would be equal to v max. From this point ( v max), we could then draw a
straight line down to the x-axis. This gives us the value of the Michaelis-Menten rate constant, Km.
As you can guess, this particular method is not going to provide the most accurate or precise results due to the fact that there is a lot of guesswork and
3
estimation involved. From the plot above, we have determined that Km 2 10 mol dm3 .
Plot 2: 1/ against 1/[S]
10-87
v max
1/Km
max S
K m S
The type of plot that you see here is called a double reciprocal plot. It is quite often used in enzyme kinetics and therefore the student should become
acquainted with this type of curve. Double reciprocal plots give us two pieces of critical information, v max and 1/Km. They give us this information in
terms of y and x-intercept respectively. They can therefore be determined quite reliably (especially when using graphing programs). It is also interesting
to examine plots for enzyme inhibition at a variety of concentrations in order to see the effects on v max and 1/Km (usually as the concentration increases).
Double reciprocal plots also by their shape- allow us to determine the type of enzyme inhibition/catalysis occurring in our experiment.
10-88
This plot has told us that, 1/ K m 0.5 therefore,
1
K m 0.5 K m 2 103 mol dm 3
Plot 3: /[S] against
max S
K m S
10-89
The final plot above produces a beautiful straight line graph which will allow us to perform a linear regression and obtain the exact value for the
Michaelis-Menten rate constant. Since we have plotted /[S] against , we can use the Michaelis-Menten equation to help us determine what we need to
be looking for on the plot to give us our Km value. It turns out that the slope of this plot allows us to determine Km.
Upon performing a linear regression (using Microsoft Excels linest function) we obtain the following regression statistics:
Linear Regression Statistics
m -0.479 7.123 b
Sm 0.011 0.087 Sb
R2 0.996 0.104 Sy
F 1924.562 7 DF
The numerical value in the first row and column provides the exact value of the slope (for the third curve). Therefore,
1/ K m 0.479
1
K m 0.479
K m 2.09 103 mol dm 3
So what is the difference between the second and third curves? As can be seen, the second plot is highly sensitive to increasingly large values of [S]
because there is bunching and crowding of the data points in that range. Looking at the far right of the plot, we can see that the double reciprocal
method is less sensitive to small values of [S] and therefore does not produce an evenly populated curve.
The third curve is actually the best since it is both evenly populated and allows for proper statistical analysis such as a linear regression. Using the linear
regression method, it is possible to determine (more precisely and accurately) the value for the Michaelis-Menten rate constant. It is the preferred
method when working quantitatively in enzyme catalysis.
10-90
10.36. The following data have been obtained for the myosin-catalyzed hydrolysis of ATP, at
25 C and pH 7.0.
105[ATP]/mol dm3 106/mol dm3 s1
7.5 0.067
12.5 0.095
20.0 0.119
32.5 0.149
62.5 0.185
155.0 0.191
320.0 0.195

Plot against [S], 1/ against 1/[S], and /[S] against , and from each plot calculate the Michaelis constant Km and the limiting rate V.
Solution:
We will use the same method in this problem as we did in the previous.
105[ATP]/mol dm3 106/mol dm3 s1 1/ 1/[S] /[S]
7.5 0.067 14.925 0.133 8.933E-03
12.5 0.095 10.526 0.080 7.600E-03
20.0 0.119 8.403 0.050 5.950E-03
32.5 0.149 6.711 0.031 4.585E-03
62.5 0.185 5.405 0.016 2.960E-03
155.0 0.191 5.236 0.006 1.232E-03
10-91
320.0 0.195 5.128 0.003 6.094E-04
Note that the limiting rate here is actually v max in plots two and three and is better described as twice the value at which saturation occurs in the first
plot.
Plot 1: against [ATP]
v max
Km
Km 16.7 105 mol dm3 and vmax 0.22 106 mol dm 3 s 1
Plot 2: 1/ against 1/[ATP]
10-92
v max
1/Km
1
1 / K m 0.06 K m 0.06 K m 16.67 105 mol dm 3
1 / vmax 4.7 vmax 1 / 4.7 vmax 0.21 106 mol dm 3 s 1
Plot 3: /[ATP] against
10-93
v max/Km
v max
Linear regression statistics:
Linear Regression Statistics
m -0.061 0.013 b
Sm 0.005 0.001 Sb
R2 0.968 0.001 Sy
F 149.196 5 DF
The numerical value located in the first row and column provides us with the value for the slope. As we have previously seen, the slope is equal to
1/ K m therefore,
1/ K m 0.061
1
K m 0.061
K m 16.39 105 mol dm 3
10-94
From the plot above, we can see that,
vmax 0.22 106 mol dm 3 s 1
10-95
*10.37. The following values of V (limiting rate at high substrate concentrations) and Km have been obtained at various temperatures for the hydrolysis
of acetylcholine bromide, catalyzed by acetylcholinesterase.
.
T/C 106V/mol dm3 s1 Km 104/mol dm3
20.0 1.84 4.03
25.0 1.93 3.75

30.0 2.04 3.35
35.0 2.17 3.05

a. Assuming the enzyme concentration to be 1.00 1011 mol dm3, calculate the energy of activation, the enthalpy of activation, the Gibbs
energy of activation, and the entropy of activation for the breakdown of the enzyme-substrate complex at 25 C.
k 1
b. Assuming Km to be the dissociation constant k1/k1 for the enzyme-substrate complex (ES E S), determine the following thermodynamic
k1
quantities for the formation of the enzyme-substrate complex at 25 C: G, H, S.

c. From the results obtained in parts (a) and (b), sketch a Gibbs energy diagram and an enthalpy diagram for the reaction.
Solution:
Remember that we should change the temperature units to Kelvin! We will now construct a table that includes all of the values that we will need to
generate the desired plots.
T (K) V (mol dm-3 s-1) Km (mol dm-3) 1/T (K) Log10(V) (mol Log10(Km) (mol
dm-1 s-1) dm-3)
293 1.84E-06 4.03E-04 3.413E-03 -5.735 -3.395
298 1.93E-06 3.75E-04 3.356E-03 -5.714 -3.426
303 2.04E-06 3.35E-04 3.300E-03 -5.690 -3.475
308 2.17E-06 3.05E-04 3.247E-03 -5.664 -3.516
10-96
a) Slope of plot of log10V against 1/T=-430.9K
E ln10 R slope
E 19.14 430.9 8247.426 J mol 1
E 8.25 kJ mol 1
RT at 25oC = 8.314 298 = 2478 J mol 1 2.48 kJ mol 1
H E RT
H 8.25 2.48
H 5.77 kJ mol 1
10-97
G 19.14 7.51 298.15

G 42 864.76 623 J mol 1
G 42.9 kJ mol 1
5700 42 856
S
298.15
S 124 J K 1 mol 1
At 25.0oC, V 1.93 106 dm 3 mol 1 s 1

E0 1.0 1011 mol dm3
kc V / E 0 1.93 105 s 1
k BT k BT 1.3806503 1023 m 2 kg s 2 K 1 298 K

kc exp G / RT ;

at 25.0 C
o
34
6.21 1012 s 1
h h 6.626 10 m kg / s
2
h 1.93 105 s 1
exp G / RT kc 3.108 108 107.51
k BT 6.21 1012 s 1

G ln exp G / RT RT
G ln 107.51 8.314 298.15
G ln 10 7.51 8.314 298.15
b) Slope of log10Km against 1/T plot=742.91
10-98
H o (for dissociation) ln10 R slope

H o (for dissociation) 19.14 742.91
H o (for dissociation) 14 219.2974 J mol 1
H o (for dissociation) 14.2 kJ mol 1
At 25.0oC, log10 K m 3.426
G o (for dissociation) ln K m RT
G o (for dissociation) 19.14 298.15 3.426
G o (for dissociation) 19 550.78 077 J mol 1
10-99
For association,
G o 19.6 kJ mol 1
H o 14.2 kJ mol 1
G o H o 14 219 19 551
S o 113.265 135 J K 1 mol 1
T 298.15
S o 113.3 J K 1 mol 1
c)
10-100
*10.38. The following data relate to an enzyme reaction:

103[s]/mol dm3 105V/mol dm3 s1
2.0 13
4.0 20
8.0 29
12.0 33
16.0 36
20.0 38
The concentration of the enzyme is 2.0 g dm3, and its molecular weight is 50 000 g/mol. Calculate Km, the maximum rate V, and kc.
Solution:
1
Given: C 2.0 g dm , M 50 000 g mol
3
Required: determine Km, the maximum rate V, and kc.
103[s] (mol dm-3) 105V (mol dm-3 s1) 1/[s] (1/mol dm-3) 1/V (1/ mol dm-3 s1)
2 13 500 7692
4 20 250 5000
8 29 125 3448
12 33 083 3030
16 36 62.5 2778
20 38 50.0 2630
10-101
1/Km
1/v max
The equation of the line generated is:
y 11.291x 2081.8
This means that 1/v max is equal to the y-intercept, thus,
1 / vmax 2081.8 mol 1 dm3 s

vmax 1 / 2081.8 mol 1 dm3 s
vmax 4.804 104 mol dm 3 s 1
Conversely, the value for 1/Km is equal to the x-intercept which can be determined by looking at the plot above (or by setting y = 0 and solving for x).
10-102
y 11.291x 2081.8
11.291x 2081.8 0
11.291x 2081.8
2081.8
x
11.291
x 1 / K m 184.3769374
1
K m 184.3769374
K m 5.42 103 mol dm 3
It should be remembered that the Eq. 10.82 is not always the best way to represent the rate for a particular reaction. When we know that the Michaelis-
Menten equation can be applied but we are unsure of the mechanism, we should use Eq. 10.85 which state that:
kc E o S
K m S
It is possible to then say that,
max kc E o
max
kc
E o
Let us now determine the value of the enzyme concentration.
2 g dm 3
E o
50 000 g mol1
E o 4.0 105 mol dm 3
10-103
4.804 104 mol dm 3 s 1

kc
4.0 105 mol dm 3
kc 12.01 s 1
10-104
10.39. The following data have been obtained for the myosin-catalyzed hydrolysis of ATP.
Temperature/C kc 106/s1
39.9 4.67
43.8 7.22
47.1 10.0
50.2 13.9
Calculate, at 40 C, the energy of activation, the enthalpy of activation, the Gibbs energy of activation, and the entropy of activation.
Solution:
Given: see table above
Required: H, S, and G at 40 C
Recall that,
k Ae Ea / RT
Ea
ln k ln A
RT
1
So we can plot ln k vs. in order to determine the activation energy (which appears in the slope portion of the equation for the line). The k that
T
will be used is actually kc.
10-105
T /C T/K 1/T K-1 kc /s1 lnkc

39.90 313.05 3.19E-03 4.67E-06 -12.274
43.80 316.95 3.16E-03 7.22E-06 -11.839
47.10 320.25 3.12E-03 1.00E-05 -11.513
50.20 323.35 3.09E-03 1.39E-05 -11.184
From the equation of the line, we see that the slope is m = -10 657. From this, we can determine the activation energy.
Ea
m 10 567
R

Ea 10 567 K 8.3145 J K 1
mol1
Ea 87 859 J mol1
Ea 87.9 kJ mol1
10-106
From the previous chapter we know that,
H Ea RT therefore,

H 87 859 J mol1 8.3145 J K 1 mol1 313.15 K
H 85 255 J mol1
H 85.26 kJ mol1
Also, we know that,

k T G
kc B e RT
h
Which can be rearranged to solve for G.
kBT G
ln kc ln
h RT
G

kT
ln B ln kc
RT h

1.381 1023 J K 1 313.15 K

G 8.3145 J K
1
mol 1

313.15 K ln

6.626 1034 J s
ln 4.72 10 s
6 1

G 2603.686 J mol1 41.771
G 108 758 J mol1

G 108.8 kJ mol 1
Using the equation G H T S we can determine the value for the entropy of activation.
10-107
T S H G
H G
S
T
S
85 255 108 758 J mol 1
313.15 K
S 75.05 kJ K 1 mol 1
10-108
*10.40. The following is a simplified version of the mechanism that has been proposed by H. Theorell and Britton Chance for certain enzyme reactions
involving two substrates A and B.
Assume that the substrates A and B are in excess of E so that the steady-state treatment can be applied to EA and EZ, and obtain an expression
for the rate.
Solution:
Given: see above
Required: overall rate equation
Applying the steady-state approximation for EA, we obtain,
d EA
EA k1 E A k1 EA k2 EA B
dt
d EA
0
dt
k1 E A k1 EA k2 EA B 0
Applying the steady-state approximation for EZ, we obtain,
d EZ
EZ k2 EA B k3 EZ
dt
d EZ
0
dt
k2 EA B k3 EZ 0
We can now formulate an equation representing the initial concentration of the enzyme.
10-109
E o E EA EZ
With this, it is obvious that the steady-state approximation for EA should be solved for E so that it can be expressed in terms of EA and substituted into
the equation for the initial concentration of the enzyme.
k1 E A k1 EA k2 EA B
k1 EA k2 EA B
E
k1 A
k1 EA k2 EA B
E o EA EZ
k1 A
The steady-state approximation for EZ should be solved for EZ in order to express it in terms of EA which can also be substituted into the equation
representing the initial concentration of the enzyme.
k2 EA B k3 EZ
k2 EA B
EZ
k3
k1 EA k2 EA B k2 EA B
E o EA
k1 A k3
The final expression above can be factored which yields,
k1 k2 B k2 B
E o EA 1
k1 A k3
The overall rate is given by,
k2 EA B
Therefore,
10-110
E o
EA
k1 k2 B k B
1 2
k1 A k3
E o
k2 B
k1 k2 B k2 B
1
k1 A k3
k2 E o B
k1 k2 B k B
1 2
k1 A k3
This can be simplified to the following expression:
k1k2 k3 A E o B
k1k3 k1k3 A k2 k3 B k1k2 A B
10-111
*10.41. When an inhibitor I is added to a single-substrate enzyme system, the mechanism is sometimes:
This is known as a competitive mechanism, since S and I compete for sites on the enzyme.
a. Assume that the substrate and inhibitor are present in great excess of the enzyme, apply the steady-state treatment, and obtain the rate
equation.
b. Obtain an expression for the degree of inhibition defined as:
0
=
0
where is the rate in the presence of inhibitor and 0 is the rate in its absence.
Solution:
a) We will apply the steady-state approximation to both ES and EI.
d ES
ES k1 S E k1 ES k2 ES
dt
d ES
0
dt
k1 S E k1 ES k2 ES 0
d EI
EI ki I E k i EI
dt
d EI
0
dt
ki I E k i EI 0
Solving the first equation for ES we obtain,
10-112
k1 S E
ES
k1 k2
Solving the second equation for EI we obtain,
ki I E ki EI
ki I E
EI
k i
Solving the first equation again but this time in order to isolate E;
k1 S E k1 ES k2 ES
k1 S E ES k1 k2
ES k1 k2
E
k1 S
The initial enzyme concentration is given by,
E o E ES EI
Substituting the expressions found for E, ES and EI we obtain to following:
ES k1 k2 ES ki I E
E o
k1 S k i
However, we can see here that we cannot further simplify this expression due to the presence of E. In order to eliminate this term, we can perform the
following operations:
10-113
ki I
ES k1 k2
k1 S
EI
k i
ki I ES k1 k2
EI
k i k1 S
ES k1 k2 ES ki I ES k1 k2
E o
k1 S k i k1 S
We will now factor out the ES term to obtain,
k1 k2 ki I k1 k2
E o ES 1
k1 S k i k1 S
k2 ES
Written in terms of the initial concentration of enzyme the rate equation becomes,
k2 E o
k1 k2 1 ki I k1 k2
k1 S ki k1 S
It is possible to further simplify the denominator by multiplying all terms by the concentration S.
k2 E o S
k1 k2 S I ki k1 k2

k1 ki k1
Let us combine the terms in the denominator,
10-114
k1 k2 ki k1 k2
I S
k1 ki k1
Recall that,
k1 k2 K and K i
ki
therefore,
m
k1 ki
I
K m 1 S
Ki
k2 E o S
I
K m 1 S
Ki
0
b) Given that ,
0
0
1
0 0 0
k2 E o S
I
K m 1 S
Ki K m S k2 E o S
1
k2 E o S k2 E o S I
K m 1 S
K m S Ki
10-115
K m S
1
I
K m 1 S
Ki
Km
I
Ki
I
K m 1 S
Ki
10-116
*10.42. Obtain the rate equation corresponding to the mechanism:
Assume ES and ES to be in the steady state and the substrate concentration to be much higher than the enzyme concentration. Express the
catalytic constant kc and the Michaelis constant Km in terms of k1, k1, k2, and k3.
Solution:
Given: see mechanism above
Required: overall rate equation
We will solve this problem in a similar manner as we did for the previous one. Let us begin by applying the steady-state treatment for ES and ES.
10-117
d ES
ES k1 S E k1 ES k2 ES
dt
d ES
0
dt
k1 S E k1 ES k2 ES
k1 S E ES k1 k2
k1 S E
ES
k1 k2
ES k1 k2
E
k1 S
d ES'
ES' k2 ES k3 ES'
dt
d ES'
0
dt
k2 ES k3 ES'
k2 ES
ES'
k3
E o E ES ES'
ES k1 k2 ES k2 ES
E o
k1 S k3
k k k
E o ES 1 2 1 2
k1 S k3
10-118
k2 ES
k2 E o
k1 k2 1 k2
k1 S k3
k 2 k3
Eo S
k 2 k3
k 1 k 2 k 3
S
k1 k2 k3
When S is large
k1k2
Eo
k 1 k2
and the catalytic constant is therefore
k1k2
kc
k 1 k2
K m is the first term in the denominator of the rate equation:
k 1 k 2 k 3
Km
k1 k2 k3
10-119
*10.43. Enzyme-catalyzed reactions frequently follow an equation of the form of Eq. 10.85. Suppose that kc and Km show the following temperature
dependence:
kc = Ac exp(Ec/RT ) and Km = B exp(Hm /RT )

where Ac, B, Ec, and Hm are temperature-independent parameters. Explain under what conditions, with [S] held constant, the rate may pass
through a maximum as the temperature is raised.
Solution:
Given: Eq. 10.85, kc = Ac exp(Ec/RT ) and Km = B exp(Hm /RT )
Required: when is [S] held constant?
Suppose that Hm is positive:
Km will then increase accordingly with an increase in temperature (linearly) and at sufficiently low temperature it will be much smaller that the
concentration of the substrate. The effective activation energy is therefore given by Ec and its rate will increase as the temperature increases.
At sufficiently high temperatures, Km will be much larger than the concentration of the substrate and the effective activation energy will be given by Ec -
Hm.
If Hm is larger than Ec, effective activation energy will be negative. This would mean that the rate has gone through a maximum as the temperature was
increased.
If Hm is smaller than Ec, effective activation energy will be positive. This does not indicate that the rate has gone through a maximum! However, the
observed activation energy will be lower at higher temperatures. An Arrhenius plot will therefore show curvature (ie. bending away from the axes).
10-120
10.44. Some enzyme reactions involving two substrates A and B occur by the following mechanism:
k1
E A EA
k 1
k2 k3
EA + B EAB E Y Z
(This is known as the ordered ternary-complex mechanism; A must add first to E, and the resulting complex EA reacts with B; the complex EB
is not formed.)
The concentrations of A and B are much greater than the concentration of E. Apply the steady-state treatment and obtain an expression for the
rate.
Solution:
Since we are told that the concentrations of A and B are much greater than the concentration E, we can apply the steady-state treatment to complexes EA
and EAB.
d EA
EA k1 E A k1 EA k2 EA B
dt
d EA
0
dt
k1 E A k1 EA k2 EA B
k1 E A EA k1 k2 B
k1 E A
EA
k 1 k 2 B
EA k1 k2 B
E
k1 A
10-121
d EAB
EAB k2 EA B k3 EAB
dt
d EAB
0
dt
k2 EA B k3 EAB
k2 EA B
EAB
k3
k3 EAB
EA
k 2 B
Since E o E EA EAB then we can write:
EA k1 k2 B k3 EAB
E o EAB
k1 A k 2 B
k3 EAB
k 2 B
k1 k2 B k EAB
E o 3 EAB
k1 A k 2 B
k EAB k1 k2 B k3 EAB
E o 3 EAB
k2 B k1 A k 2 B
k k k B
E o EAB 3 1 2
k
3 1
k2 B k1 A k2 B
k3 EAB
Which can be written in the following manner:
10-122
Eo
EAB
k3 k1 k2 B k
3 1
k2 B k1 A k2 B
k3 E o
k3 k1 k2 B k
3 1
k2 B k1 A k2 B
k1k2k3 E o A B
k3 k1 k2 B k3k1 A k1k2 B A
10-123
10.45. The following ping-pong mechanism appears sometimes to apply to an enzyme-catalyzed reaction between two substrates A and B to give the
final products Y and Z:
k1 k2
E A EA EA + Y
k 1
k3 k4
EA + B EAB E Z
It can be assumed that the substrates are present in great excess of the enzyme and that steady-state conditions apply. Obtain an expression for
the rate of reaction.
Solution:
Let us apply the steady-state approximation to EA, EA and EAB. This procedure yields;
10-124
d EA
EA k1 E A k1 EA k2 EA
dt
d EA
0
dt
k1 E A k1 EA k2 EA 0
k1 E A k1 EA k2 EA
k1 E A EA k1 k2
d EA'
EA' k2 EA k3 EA' B
dt
d EA'
0
dt
k2 EA k3 EA' B 0
k2 EA k3 EA' B
d EA'B
EA'B k3 EA' B k4 EA'B
dt
d EA'B
0
dt
k3 EA' B k4 EA'B 0
k3 EA' B k4 EA'B
Since the overall rate equation is given by,
k3 EA' B
We should define the initial enzyme concentration in terms as of EA but making the appropriate substitutions and rearrangements.
10-125
E o E EA EA' EA'B
k1 E A EA k1 k2
EA k1 k2
E
k1 A
k2 EA k3 EA' B
k EA' B
EA 3
k2
k3 EA' B k4 EA'B
k3 EA' B
EA'B
k4
EA k1 k2 k3 EA' B EA' k3 EA' B
E o
k1 A k2 k4
Since the first term does not involve EA, we will need to make a second substitution.
k3 EA' B
k1 k2 k k k EA' B
EA k1 k2 k2 or k1 k2 k3 B
3 1 2 EA'
k1 A k1 A k2 k1 A k1 A k2
thus, E o EA'
k1 k2 k3 B k3 EA' B EA' k3 EA' B

k1 A k2 k2 k4
k k k B k B k B
Eo EA' 1 2 3 3 1 3
k1 A k2 k2 k4
k3 EA' B
10-126
k3 E o B
k1 k2 k3 B k3 B 1 k3 B
k1 A k2 k2 k4
Simplification yields,
k1k 2 k3k4 E o A B
k1k 2 k 4 A k3k 4 k 1 k2 B k1k3 k 2 k 4 A B
10-127
10.46. The polymerization of styrene [M] catalyzed by benzoyl peroxide [C] obeys a kinetic equation of the form:
Obtain an expression for the kinetic chain length, in terms of [M], [C], and the rate constants for initiation, propagation, and termination.
Solution:
d [M]
Given: k[M]3/ 2 [C]1/ 2
dt
Required: expression for the kinetic chain length
Eq. 10.97,
1
d M k 2 3 1
k p i M 2 C 2
dt kt
defines the polymerization rate for the rate of initiation, i ki M C (Eq. 10.96). The chain length is therefore equal to,
1
k p M 2
1
ki 2
C
kt
10-128
10.47. The polymerization of ethylene [M] photosensitized by acetone occurs by the mechanism:
hv
CH3COCH3 CO + 2CH3
kp
CH3 + C2H4 CH3CH2CH2
kp
CH3CH2CH2 + C2H4 CH3CH2CH2CH2CH2
kr
Rn + Rm Mn + m
where one quantum gives 2CH3.

Show that the rate equation is:
1/ 2
d [M] 2I
k p [M]
dt kt
where I is the intensity of light absorbed and kp and kt are the rate constants for the propagation and termination steps, respectively.
Solution:
Given: rate of formation of CH3 is 2I
Required: see above
The steady-state equations are
2 I k p CH 3 M kt CH 3 R n 0
From Eq. 20.2,
k p CH 3 M k p CH 3CH 2CH 2 M kt CH 3CH 2CH 2 R n 0
and so on.
The sum of all the equations is
10-129
2 I kt R n 0
2
so that
1
2I 2
R n k
t
the rate of removal of monomer is

d [M]
v k p M R n
dt
1
d [M] 2I 2
kp M
dt kt
10-130

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10

Chemical Kinetics II.

LAIDLER . MEISER . SANCTUARY

Problems and Solutions

Where X is an intermediate. Write the expression for the rate of formation of Y.

10.2. Suppose that a reaction A + 2B = 2Y + 2Z is believed to occur according to the mechanism:

Obtain an expression for the rate of formation of the product Y.

10.4. A reaction of stoichiometry:

10.8. The reaction 2NO + O2 2NO2 is believed to occur by the mechanism:

*10.9. The gas-phase reaction:

Derive the rate equation.

*10.11. A reaction occurs by the mechanism:

*10.14. Show that the mechanism:

Photochemistry and Radiation Chemistry

10.29. Confirm that Eq. 10.68,

Ka/mol dm3 1.39 103 1.80 105 6.25 108

Estimate the Brnsted coefficient .

10.34. The reaction:

105[ATP]/mol dm3 106/mol dm3 s1

thermodynamic quantities for the formation of the enzyme-substrate complex at 25 C: G, H, S.

*10.38. The following data relate to an enzyme reaction:

*10.41.When an inhibitor I is added to a single-substrate enzyme system, the mechanism is sometimes:

*10.42. Obtain the rate equation corresponding to the mechanism:

Where X is an intermediate. Write the expression for the rate of formation of Y.

10.2. Suppose that a reaction A + 2B = 2Y + 2Z is believed to occur according to the mechanism:

Obtain an expression for the rate of formation of the product Y.

2X very rapid equilibrium

1 X very rapid equilibrium

Let us write out the rate of formation for substance X and Y.

a) The information above leads us to believe that k1 k2 which means that,

b) The information above leads us to believe that k2 k1 which means that,

10.4. A reaction of stoichiometry:

Two consecutive reactions may be taking place here.

The following mechanism has been proposed:

k1k1 NO 2 N 2O5 k1k2 N 2O5 NO k1k 1 NO 2 N 2O5

10.8. The reaction 2NO + O2 2NO2 is believed to occur by the mechanism:

Given: see above

Substituting into the expression defining the rate of formation of NO 2 ,

*10.9. The gas-phase reaction:

Following the method outlined in Section 10.5 Free Radical Reactions,

Cl2 CH 4 CH3Cl HCl

Derive the rate equation.

*10.11. A reaction occurs by the mechanism:

Differentiating both sides with respect to temperature leads to,

Recall that Eq. 9.63 states,

Rearranging to isolate the activation energy,

We can combine the terms by putting them over a common denominator.

Further simplification leads to the desired equation,

Given: see above

Required: expression for rate, k1, k1, k2

Applying the Steady-State treatment to A we obtain the following expression:

Rearranging and simplifying we obtain,

The rate is given by,

We may substitute the above expression for A which yields,

Substituting this back into the integrated expression,

This can be rewritten as,

The expression for the fraction of functional groups remaining is therefore,

*10.14. Show that the mechanism:

Recall that when reactions occur as fast equilibriums, we may write,

Now substitute the expression for I into the above to obtain,

Given: see above

Required: expression for rate of formation of Z, a), b)

Z (a second order rate equation)