CHAPTER 13

CHEMICAL KINETICS

13.1

1 mol N 2
(a) rate (N 2 ) = rate(H 2 )
3 mol H 2

1
= rate(H 2 )
3

2 mol NH 3 2
(b) rate (NH 3 ) = rate(H 2 )
= rate(H 2 )
3 mol H 2 3
2 mol NH 3
(c) rate (NH 3 ) = rate(N 2 )
= 2 rate(N 2 )
1
mol
N
2

13.3

(a) The rate of formation of dichromate ions =

0.14 mol Cr2 O72- 2 mol CrO 42-
= 0.28 mol L s -1

2-
L
s

1
mol
Cr
O
2 7

(b) 0.14 mol L1 s 1 1 = 0.14 mol L1 s 1

13.5

mol NO 2 1 mol O 2
(a) rate of formation of O2 = 6.5 103

L s 2 mol NO 2

= 3.3 103 (mol O 2 ) L1 s 1

(b) 6.5 103 mol L1 s 1 2 = 3.3 103 mol L1 s 1

SM-394

(a) and (c)

-1

Concentration (mmol L )

13.7

12
[I2],
mmol/L
[I2],
mmolL-1

10

[HI],
mmol/L
[HI],
mmolL-1

8
6
4
2
0
0

1000

2000

3000

4000

5000

6000

Time (s)

Note that the curves for the [I 2 ] and [H 2 ] are identical and only the [I 2 ]
curve is shown.
(b) The rates at individual points are given by the slopes of the lines
tangent to the points in question. If these are determined graphically, there
may be some variation from the numbers given below.
time, s rate, mmol L1 s 1
0

20.0060

1000 20.003
2000 20.000 98
3000 20.000 61
4000 20.000 40
5000 20.000 31

13.9

For A
products, rate = (mol A) L1 s 1
(a) rate
[(mol A) L1 s 1 ] = k0 [A]0 = k0 ,so units of k0 are (mol A) L1 s 1
(same as the units for the rate, in this case)
(b) rate
[(mol A) L1 s 1 ] = k1 [A], so units of k1 are

SM-395

(mol A) L1 s 1
= s 1
1
(mol A) L

(c) rate
[(mol A) L1 s 1 ] = k1 [A]2 , so units of k1 are

(mol A) L1 s 1
(mol A) L1

= L (mol A) 1 s 1

13.11 From the units of the rate constant, k , it follows that the reaction is first

order, thus rate = k[N 2 O5 ].

3.45 g N 2 O5 1 mol N 2 O5
1
[N 2 O5 ] =
= 0.0426 mol L

0.750 L 108.02 g N 2 O5

rate = 5.2 103 s 1 0.0426 mol L1 = 2.2 104 (mol N 2 O5 ) L1 s 1

13.13 (a) From the units of the rate constant, it follows that the reaction is

second order; therefore,

rate = k[H 2 ][I 2 ]
0.52 g H 2 1 mol H 2 0.19 g I 2 1 mol I 2
= (0.063 L mol1 s 1 )

0.750 L 2.016 g H 2 0.750 L 253.8 g I 2

= 2.2 105 mol L1 s 1
(b) rate(new) = k 2 [H 2 ]initial [I 2 ] = 2 rate(initial), so, by a factor of 2

13.15 Because the rate increased in direct proportion to the concentrations of

both reactants, the rate is first order in both reactants.

rate = k[CH 3 Br][OH ]

13.17 When the concentration of ICl is doubled, the rate doubles (experiments 1

and 2). Therefore, the reaction is first order in ICl. When the concentration
of H 2 is tripled, the rate triples (experiments 2 and 3); thus, the reaction is
first order in H 2 .
(a) rate = k[ICl][H 2 ]

SM-396

 22 107 mol

L
L
(b) k =

3
3
Ls

3.0 10 mol 4.5 10 mol

= 0.16 L mol1 s 1
0.16 L 4.7 103 mol 2.7 103 mol
(c) rate =

L
L
mol s

6
1
1
= 2.0 10 mol L s

13.19 (a) Doubling the concentration of A (experiments 1 and 2) doubles the

rate; therefore, the reaction is first order in A. Increasing the concentration

of B by the ratio 3.02/1.25 (experiments 2 and 3) increases the rate by
(3.02/1.25) 2 ; hence, the reaction is second order in B. Tripling the
concentration of C (experiments 3 and 4) increases the rate by 32 = 9;
thus, the reaction is second order in C. Therefore, rate = k[A][B]2 [C]2 .
(b) overall order = 5
(c) k =

rate
[A][B]2 [C]2

Using the data from experiment 4, we get

2

0.457 mol
L
L
L
k =

3
3
3
L s 1.25 10 mol 3.02 10 mol 3.75 10 mol
= 2.85 1012 L4 mol4 s 1
From experiment 3, we get
5.08 102 mol

L
L
k =

3
3
Ls

1.25 10 mol 3.02 10 mol

2

3
1.25 10 mol
= 2.85 1012 L4 mol4 s 1 (Checks!)

SM-397

 2.85 1012 L4 3.01 103 mol 1.00 103 mol

(d) rate =

4
L
L
mol s

1.15 103 mol

2
= 1.13 10 mol L1 s 1

13.21 (a) k =

0.693 0.693
=
= 6.93 104 s 1
t1/2
1000 s

[A]0
(b) We use ln
[A]t

= kt and solve for k .

0.67 mol L1
ln

0.53 mol L1
ln ([A]0 /[A]t )

=
= 9.4 103 s 1
k=
t
25 s
0.153 mol A 2 mol A 0.034 mol B
(c) [A]t =

L
L

1 mol B

= 0.085 (mol A) L1

0.153 mol L1
ln

0.085 mol L1

= 5.1 103 s 1
k=
115 s

13.23 (a) t1/ 2 =

0.693 0.693 s 1 min 1 h

=

= 5.2 h
5
k
3.7 10 60 s 60 min

(b) [A]t = [A]0 e kt

t = 3.5 h 3600 s h 1 = 1.3 104 s
[N 2 O5 ] = 0.0567 mol L1 e (3.7 10

s 1 ) (1.3 104 s)

= 3.5 102 mol L1

[A]0
(c) Solve for t from ln
= kt , which gives
[A]t

SM-398

 [A]
[N O ]
ln 0 ln 2 5 0 ln 0.0567
[A]t
[N O ]
0.0135
t=
= 2 5 t=
= 3.9 104 s
5 1
k
k
3.7 10 s
1 min
2
= (3.9 104 s)
= 6.5 10 min
60
s

13.25 (a)

[A] 1 1
= = ; so the time elapsed is 2 half-lives.
[A]0 4 2

t = 2 355 s = 710 s
(b) Because 15% is not a multiple of 12 , we cannot work directly from the
half-life. But k = 0.693/ t1/ 2
so k =

0.693
= 1.95 103 s 1
355 s

Then [see the solution to Exercise 13.23(c)],

[ A]0
1

ln
ln

[
A
]
0.15
t

=
= 9.7 10 2 s
t=
3 1
k
1.95 10 s

ln
(c) t =

13.27 (a) t1/ 2 =

[A]0
1
ln 9
9 [A]0
=
= 1.1 103 s
3 1
k
1.95 10 s

0.693
0.693
=
= 247 min
k
2.81 103 min 1

(b) See the solutions to Exercises 13.31(c) and 13.33(c).

[SO 2 Cl2 ]0
ln

[SO 2 Cl2 ]t
ln 10

=
= 819 min
t=
k
2.81 103 min 1
(c) [A]t = [A]0 e kt
Because the vessel is sealed, masses and concentrations are proportional,
and we write

SM-399

(mass left)t = (mass)0 e kt

= 14.0 g e (2.81 10

min 1 60 min h 1 1.5 h)

= 10.9 g
Note: Knowledge of the volume of the vessel is not required. However, we
could have converted mass to concentration, solved for the new
concentration at 1.5 h. and finally converted back to the new (remaining)
mass. But this is not necessary

13.29 (a) We first calculate the concentration of A at 3.0 min.

1 mol A
[A]t = [A]0
[B]t
3 mol B
1 mol A
1
= 0.015 mol L1
0.018 (mol B) L
3 mol B

= 0.009 mol L1

The rate constant is then determined from the first-order integrated rate
law.
[A]
ln 0 ln 0.015
[A]t
0.009
=
= 0.17 min 1
k=
3.0 min
t
1 mol A
1
(b) [A]t = 0.015 mol L1
0.030 (mol B) L
3 mol B
= 0.005 mol L1
[A]
ln 0 ln 0.015
[A]t
0.005
=
= 6.5 min
t=
k
0.17 min 1

additional time = 6.5 min 3.0 min = 3.5 min

SM-400

13.31 (a)
35.00

-1

1/[HI] (Lmol )

30.00
25.00
20.00
15.00

1/[HI] = (0.0078 t) + 1.0

10.00
5.00
0.00
0

1000

2000

3000

4000

5000

Time (s)

Equation 17.b in the text can be rearranged as

1 + [A]0 kt
1
1
=
=
+ kt
[A]t
[A]0
[A]0

Thus, if the reaction is second order, a plot of 1/[HI] against time should
give a straight line of slope k .
As can be seen from the graph, the data fit the equation for a second-order
reaction quite well. The slope is determined by a least squares fit of the
data by the graphing program.
(b) i. The rate constant for the rate law for the loss of HI is simply the
slope of the best fit line, 7.8 103 L mol1 s 1 . ii. Since two moles of
HI are consumed per mole of reaction, the rate constant for the unique rate
law is half the slope or 3.9 103 L mol1 s 1 .

13.33 It is convenient to obtain an expression for the half-life of a second-order

reaction. We work with Eq. 17.b.

[A]t =

[A]t 1/ 2
[A]0

[A]0
(17.b)
1 + [A]0 kt

1
1
=
2 1 + [A]0 kt1/ 2

SM-401

Therefore, 1 + [A]0 kt1/ 2 = 2, or [A]0 kt1/ 2 = 1, or

t1/ 2 =

1
1
and k =
k[A]0
t1/ 2 [A]0

It is also convenient to rewrite Eq. 17.b to solve for t. We take

reciprocals:
1
1
=
+ kt
[A]t [A]0
giving
1
1

[A]t [A]0
t=
k
(a) k =

1
1
=
= 0.024 L mol1 s 1
1
t1/ 2 [A]0 (50.5 s) (0.84 mol L )

1
1
16
1

[A] [A]0 [A]0 [A]0

15
t=
=
=
k
k
k[A]0
=

15
= 7.4 102 s
(0.024 L mol s 1 ) (0.84 mol L1 )
1

4
1

[A]0 [A]0
3
(b) t =
=
k
k[A]0
=

3
= 1.5 102 s
1
1
(0.024 L mol s ) (0.84 mol L )
1

5
1

[A]0 [A]0
4
(c) t =
=
k
k[A]0
=

4
= 2.0 102 s
1
1
(0.024 L mol s ) (0.84 mol L )
1

13.35 See the solution to Exercise 13.33 for the derivation of the formulas

needed here.

SM-402

1
1
1L
1L

[A] [A]0
0.080 mol 0.10 mol
=
= 1.7 102 min
(a) t =
1
1
k
0.015 L mol min
(b) [A] =

0.15 mol A 0.19 mol B 1 mol A

L
L
2 mol B

= 0.055(mol A) L1 = 0.37[A]0

1
1

[A]t [A]0
t=
k
1
1

1
0.055 mol L
0.15 mol L1
=
0.0035 L mol1 min 1
= 3.3 103 min

13.37 (a) rate =

1 d[A]
= k[A]
a dt

d[A]
= ak dt
[A]
integrate from [A]0 at t = 0 to [A]t at t :
t
d[A]
= ak dt
[A]0 [A]
0
[A]t
= akt , and [A]t = [A]0 exp(akt )
ln
[A]0

[A]t

(b) at t1/2 , [A]t = 1 [A]0 . Therefore:

2
[A]0
ln
= ln 2 = akt1/ 2 , and
[A]t
t1/ 2 =

ln 2
ak

SM-403

13.39

d[A]
= k[A]3 , we can derive an expression for the amount
dt
of time needed for the inital concentration of A, [A]0 , to decrease
Given:

by 1/2. Begin by obtaining the integrated rate law for a third-order

reaction by separation of variables:
[A]t
t
1
-3
2
2
=
[A]
d[A]
[A]0
0 kdt = 2 [A]t [A]0 = kt
To obtain an expression for the half-life, let [A]t = 1 2 [A]0 and t = t1/2 :
1
( 12 [A]0 ) 2 [A]02 = kt1/ 2
2
solving for the half-life:
3
t1/ 2 =
2k[A]02

13.41 The overall reaction is CH2=CHCOOH + HCl ClCH2CH2COOH. The

intermediates include chloride ion, CH2=CHC(OH)2+ and

ClCH 2 CHC(OH) 2 .

13.43 The first elementary reaction is the rate-controlling step, because it is the

slow step. The second elementary reaction is fast and does not affect the
overall reaction order, which is second order as a result of the fact that the
rate-controlling step is bimolecular.
rate = k[NO][Br2 ]

13.45 If mechanism (a) were correct, the rate law would be rate = k[NO2][CO].

But this expression does not agree with the experimental result and can be
eliminated as a possibility. Mechanism (b) has rate = k[NO2]2 from the
slow step. Step 2 does not influence the overall rate, but it is necessary to
achieve the correct overall reaction; thus this mechanism agrees with the
experimental data. Mechanism (c) is not correct, which can be seen from
the rate expression for the slow step, rate = k[NO3][CO]. [CO] cannot be
eliminated from this expression to yield the experimental result, which
does not contain [CO].
SM-404

13.47 (a) True;

(b) False. At equilibrium, the rates of the forward and reverse

reactions are equal, not the rate constants.

(c) False. Increasing the

concentration of a reactant causes the rate to increase by providing more

reacting molecules. It does not affect the rate constant of the reaction.
13.49 The overall rate of formation of A is rate = - k[A] + k [B] . The first term

accounts for the forward reaction and is negative as this reaction reduces
[A]. The second term, which is positive, accounts for the back reaction
which increases [A]. Given the 1:1 stoichiometry of the reaction, if no B
was present at the beginning of the reaction, [A] and [B] at any time are
related by the equation: [A] + [B] = [A]o where [A]o is the initial
concentration of A. Therefore, the rate law may be written:
d[A]
= k[A] + k ([A]o [A]) = (k + k )[A] + k [A]o
dt
The solution of this first-order differential equation is:
[A] =

k + ke-(k + k )t
[A]o
k + k

As t the exponential term in the numerator goes to zero and the

concentrations reach their equilibrium values given by:

k [A]o
k[A]o
and [B]eq = [A]o [A] =
k + k
k + k
taking the ratio of products over reactants we see that:
[B]eq
k
= = K where K is the equilibrium constant for the reaction.
[A]eq k

[A]eq =

SM-405

13.51
0

ln(k )

-2
-4
-6
y = -32700 x + 35.0

-8
-10
0.0011

0.00115

0.0012

0.00125

0.0013

0.00135

-1

1 / T (K )

(a) Given the Arrhenius equation, ln k = ln A Ea / RT , we see that the

slope of the best fit line to the data ( 3.27 10 4 K) is Ea / R and the yintercept (35.0) is ln A. Therefore,

E a = (3.27 10 4 K )(8.31 10 3 kJ mol 1 K 1 ) = 2.72 10 2 kJ mol 1 .

(b) At 600 oC (or 873 K), the rate constant is:
ln(k ) = ( 3.27 104 K )

1
+ 35.0 = 2.46
873 K

k = 0.088
k E 1 1 E T T
13.53 We use ln = a = a

k R T T R T T
0.87 s 1
k
ln = ln
1
k
0.76 s

1030 K 1000 K
Ea
=

3
1
1
8.31 10 kJ K mol 1030 K 1000 K
Ea =

(8.31 10 3 kJ K 1 mol 1 )(1000 K )(1030 K ) 0.87 s 1

ln
1
(1030 K 1000 K )
0
.
76
s

= 39 kJ mol 1
k E
1 1 E T T
13.55 We use ln = a = = a

k R T T R TT

SM-406

k = rate constant at 700C, T = (700 + 273) K = 973 K

973 K 1073 K
315 kJ mol1
k
ln =

3
1
k 8.314 10 kJ mol 973 K 1073 K
k
= 3.63;
= 0.026
k
k = 0.026 9.7 1010 L mol1 s 1 = 2.5 109 L mol1 s 1
k E 1 1 E T T
13.57 ln = a = a

k R T T R TT

323 K 318 K
103 kJ mol1
=
= 0.60
3
1
1
8.314 10 kJ K mol 318 K 323 K
k
= 1.8
k
k = 1.8 5.1 104 s 1 = 9.2 104 s 1

13.59 (a) The equilibrium constant will be given by the ratio of the rate constant

of the forward reaction to the rate constant of the reverse reaction:

K=

k 265 L mol1 min 1

=
= 0.676
k 392 L mol1 min 1

(b) The reaction profile corresponds to a plot similar to that shown in Fig.
13.31a. The reaction is endothermicthe reverse reaction has a lower
activation barrier than the forward reaction.
(c) Raising the temperature will increase the rate constant of the reaction
with the higher activation barrier more than it will the rate constant of the
reaction with the lower energy barrier. We expect the rate of the forward
reaction to go up substantially more than for the reverse reaction in this
case. k will increase more than k and consequently the equilibrium
constant K will increase. This is consistent with Le Chateliers principle.
75
13.61 (a) cat = catalyzed, uncat = uncatalyzed Ea,cat = 125
Ea,uncat = 0.60 Ea,uncat

SM-407

(0.60) E

/ RT

/ RT

a ,uncat
k
rate(cat )
Ae a ,cat
e
= cat = Ea ,uncat / RT =
E
/ RT
rate(uncat ) kuncat Ae
e a ,uncat

=e

( 0.60 +1.00) Ea ,uncat / RT

= e[(0.60)(125 kJ mol

=e

(0.60) Ea ,uncat / RT

) /(8.314103 kJ K 1 mol 1 298 K )]

= 4 1013

(b) The last step of the calculation in (a) is repeated with T = 350 K.
e[(0.60)(125 kJ mol

) /(8.314103 kJ K 1 mol 1 350 K )]

= 2 1011

The rate enhancement is lower at higher temperatures.

13.63 cat = catalyzed

E
/ RT
E
/ RT
kcat
rate(cat)
e a,cat
Ae a,cat
=
= 1000 =
= Ea / RT
rate(uncat) kuncat
e
Ae Ea / RT

ln 1000
Ea,cat = Ea RT ln 1000
= 98 kJ mol1 (8.31 103 kJ K 1 mol1 ) (298 K) (ln 1000)
= 81 kJ mol1

13.65 The overall reaction is RCN + H 2 O

RC(RO)NH 2 . The

intermediates include
The hydroxide ion serves as a catalyst for the reaction.

13.67 (a) False. A catalyst increases the rate of both the forward and reverse

reactions by providing a completely different pathway. (b) True,

although a catalyst may be poisoned and lose activity.
(c) False. There is a completely different pathway provided for the
reaction in the presence of a catalyst.
(d) False. The position of the equilibrium is unaffected by the presence of
a catalyst.

SM-408

13.69 (a) To obtain the Michaelis-Menten rate equation, we will begin by

employing the steady-state approximation, setting the rate of change in the

concentration of the ES intermediate equal to zero:
d[ ES]
= k1 [ E][S] k'1 [ ES] k 2 [ ES] = 0.
dt
Rearranging gives:

k + k'1
[ ES] = K M [ ES].
[ E ][S] = 2
k1

The total bound and unbound enzyme concentration, [E]0, is given by:
[E]0 = [E] + [ES], and, therefore, [E] = [ES] [E]0.
Substituting this expression for [E] into the preceding equation, we obtain:
([ES] [E]0)[S] = KM [ES].
Rearranging to obtain [ES] gives:

[ ES] =

[ E]0 [S]
.
K M + [S]

From the mechanism, the rate of appearance of the product is given by

rate = k2[ES]. Substituting the preceding equation for [ES], we obtain:
Rate =

k 2 [ E]0 [S]
,
K M + [S]

the Michaelis-Menten rate equation, which can be rearranged to obtain:

KM
1
1
=
+
.
rate k 2 [ E]0 [S] k 2 [ E] 0

If one plots

will be

KM
1
1
, the slope will be
and the y-intercept
versus
[S]
k 2 [ E]0
rate

1
.
k 2 [ E]0

SM-409

(b)

1/rate

slope =

km
k 2 [E] 0

y-intercept =

1
k 2 [E]0

0
1/[S]

13.71 (a) The easiest way to solve this problem is to set up a system of

simultaneous equations.
[H 2 SeO3 ]

[I ]

[H + ]

Rate, mol L1 s 1

0.020

0.020

0.010

8.0 106

0.020

0.010

0.020

4.0 106

0.020

0.030

0.030

2.4 104

0.010

0.020

0.020

1.6 105

We have the following general relationship:

rate = k[H 2 SeO3 ]x [I ] y [H + ]z , which can be rewritten for ease of
computation as
ln (rate) = ln k + x ln [H 2 SeO3 ] + y ln [I ] + z ln [H + ]
Using the data above, we can create four equations, which should be
enough to solve the system of four unknown variables:
ln(8.0 106 ) = ln k + x ln 0.020 + y ln 0.020 + z ln 0.010
ln(4.0 106 ) = ln k + x ln 0.020 + y ln 0.010 + z ln 0.020
ln(2.4 104 ) = ln k + x ln 0.020 + y ln 0.030 + z ln 0.030
ln(1.6 105 ) = ln k + x ln 0.010 + y ln 0.020 + z ln 0.020
which give, upon calculating the numerical logarithms:

SM-410

11.74 = ln k 3.91 x 3.91 y 4.60 z (1)

12.40 = ln k 3.91 x 4.60 y 3.91 z (2)
8.33 = ln k 3.91 x 3.51 y 3.51 z (3)
11.04 = ln k 4.60 x 3.91 y 3.91 z (4)
Solving this set of simultaneous equations and rounding the x, y, and z
answers to the nearest whole number gives x = 1, y = 3, and z = 2, with
k = 5.0 105 L5 mol5 s 1 .
(b) With
[H 2 SeO3 ] = 0.030 mol L1 , [I ] = 0.025 mol L1 and [H + ] = 0.015 mol L1 ,
rate = (5.0 105 L5 mol5 s 1 ) (0.030 mol L1 )1 (0.025 mol L1 )3

(0.015 mol L1 ) 2

rate = 5.3 105 mol L1 s 1

1
1
1
1

1
[A]t [A]0
0.0050 mol L
0.040 mol L1
k
=
=
13.73 (a)
12 h
t
= 15 L mol1 h 1
(b) [EX 2 ] = 0.040

mol EX 2
mol X 1 mol EX 2
0.070

L
L 2 mol X

= 0.005 mol L1
1
1
1
1

1
[EX 2 ]t [EX 2 ]0
0.005 mol L
0.040 mol L1
=
k=
15 h
t
= 10 L mol1 h 1 (1 sf )

SM-411

Potential Energy

13.75

Effect of
catalyst
(new
pathway
lowers Ea)

First
activated
complex

Second
activated
complex

Intermediate

Ea,2

Ea,1

Progress of reaction

13.77 x = amount of original sample = 25.0 mg

n = number of half -lives

n

1
x = amount remaining
2
10.9
= 0.886 half -lives
12.3

1

2

0.886

25.0 mg = 13.5 mg

13.79 The anticipated rate for mechanism (i) is: rate = k[C12H22O11], while the

expected rate for mechanism (ii) is: rate = k[C12H22O11][H2O]. The rate for
mechanism (ii) will be pseudo-first-order in dilute solutions of sucrose
because the concentration of water will not change. Therefore, in dilute
solutions kinetic data can not be used to distinguish between the two
mechanisms. However, in a highly concentrated solution of sucrose, the
concentration of water will change during the course of the reaction. As a

SM-412

result, if mechanism (ii) is correct the kinetics will display a first-order

dependence on the concentration of H2O while mechanism (i) predicts that
the rate of the reaction is independent of [H2O].
13.81 (a) The objective is to reproduce the observed rate law. If step 2 is the

slow step, if step 1 is a rapid equilibrium, and if step 3 is fast also, then our
proposed rate law will be rate = k2 [N 2 O 2 ][H 2 ]. Consider the equilibrium
of Step 1: k1 [NO]2 = k1 9[N 2 O 2 ]
[N 2 O 2 ] =

k
[NO]2 Substituting in our proposed rate law, we have
k1 9

k
rate = k2 1 [NO]2 [H 2 ] = k[NO]2 [H 2 ] where k = k2
k1 9

k1

k1 9

The assumptions made above reproduce the observed rate law; therefore,
step 2 is the slow step.

Potential Energy

(b)

Ea,2

Ea,3

Ea,1
Reactants

Products

Progress of reaction

SM-413

Note: The dips that represent the formation of the intermediate

N 2 O 2 and N 2 O will not be at the same energy, but we have no
information to determine which should be lower.

13.83

rate at 28C k t 48 h
= = =
rate at 5C
k t 4 h

k E 1 1
We use ln = a and solve for Ea .
k R T T
k
48
R ln (8.314 103 kJ K 1 mol1 ) ln
k=
4 = 75 kJ mol1
Ea =
1 1
1
1

T T
278 K 301 K

13.85

(a) To obtain the Michaelis-Menten rate equation assuming a

pre-equilibrium between the bound and unbound states of the substrate
we begin with the expression for the equilibrium constant of the fast
equilibrium between the bound and unbound substrate:
[ES]
K=
, solving for [ES] we obtain: [ES] = K [E][S]
[E][S]
as before in problem 13.69, the total bound and unbound enzyme
concentration, [E]0 , is given by:
[E]0 = [E]+[ES], and, therefore,
[E]=[E]0 [ES]
Substituting this expression for [E] into the equation above we obtain:
K ([E]0 -[ES])[S] = [ES].
Rearrainging to obtain [ES]:
K [E]0 [S] [E]0 [S]
= 1
[ES]=
1+K [S]
K +[S]
From the mechanism, the rate of appearance of the product is given by:
rate = k2 [ES]. Substituting the equation above for [ES] one obtains:
rate =

k2 [E]0 [S]
, the Michaelis-Menten rate equation.
K 1 +[S]

13.87 (a) ClO is the reaction intermediate; Cl is the catalyst.

SM-414

(b) Cl, ClO, O, O 2

(c) Step 1 and step 2 are propagating.

Cl2
(d) Cl + Cl

13.89 For a third-order reaction,

t1/ 2

1
constant
or t1/2 =
2
[A 0 ]
[A 0 ]2

(a) The time necessary for the concentration to fall to one-half of the
initial concentration is one half-life:
first half-life = t1 = t1/ 2 =

constant
[A 0 ]2

(b) This time, t1/ 4 , is two half-lives, but because of different starting
concentrations, the half-lives are not the same:
second half -life = t2 =

constant 4(constant)
=
= 4t1
( 12 [A 0 ]) 2
[A 0 ]2

total time =t1 + t2 = t1 + 4t1 = 5t1 = t1/ 4

(c) This time, t1/16 , is four half-lives; again, the half-lives are not the
same:
third half -life = t3 =

constant 16(constant)
=
= 16t1
( 14 [A 0 ]) 2
[A 0 ]2

fourth half -life = t4 =

constant 64(constant)
=
= 64t1
( 18 [A 0 ]) 2
[A 0 ]2

total time = t1 + t2 + t3 + t4 = t1 + 4t1 + 16t1 + 64t1 = 85t1 = t1/16

If t1 is known, the times t1/ 4 and t1/16 can be calculated easily.

13.91 By analogy with the reaction in Exercise 13.82, the overall reaction here is

CH 4 (g) + Cl2 (g)

CH3 Cl + HCl

2 Cl
(a) Initiation: Cl2
Propagation: Cl + CH 4
CH 3 Cl + H

SM-415

H + Cl2
HCl + Cl
Termination: Cl + Cl
Cl2
H + H
H2
H + Cl
HCl
(b) CH 3 Cl and HCl

13.93 The strategy for working this problem is to obtain the equilibrium

constants for the reaction at two or more temperatures and then use those
values to calculate H r and S r . From Table 13.1 we can obtain K
values at 4 temperatures:
K=

k
k

K 500 =

K 600

6.4 109 L mol1 s 1

= 0.015
4.3 107 L mol1 s 1

9.7 106 L mol1 s 1

=
= 0.022
4.4 104 L mol1 s 1

K 700 =

1.8 103 L mol1 s 1

= 0.028
6.3 102 L mol1 s 1

K 700 =

9.7 102 L mol1 s 1

= 0.037
2.6 L mol1 s 1

We can choose to calculate the desired quantities from any two of these
points, or we can plot the data and determine the values from the slope and
intercept of the graph:
ln K =

H r
R

1 S r
+
R
T1

The plot should be ln K versus

intercept will be

H r
1
. The slope will be
and the
R
T

S r
.
R

SM-416

T (K)

1 1
(K )
T

ln K

500

0.0200

0.015

4.20

600

0.001 67

0.022

3.82

700

0.001 43

0.028

3.58

800

0.001 25

0.037

3.30

H r
= 1177, H r = 9.8 kJ mol1
R

S r
= 1.86, S r = 15 J K 1 mol1
R

13.95 In order for the reaction to be catalyzed heterogeneously, the reacting

species must attach themselves to the surface of the catalyst. The

concentration of the reactants is usually much greater than the number of
active sites available on the catalyst so that the rate is determined by the
surface area of the catalyst and not by the concentrations or pressures of
reactants.

k1

13.97 (a) OCl + H 2 O U HOCl + OH

fast equilibrium

k1
k2
HOCl + I
HOI + Cl

k3
HOI + OH U OI + H 2 O

very slow

fast equilibrium

k3
The overall reaction is OCl + I
OI + Cl
(b) The rate law will be based upon the slow step of the reaction:
rate = k2 [HOCl][I ]
Even though HOCl is a stable species because it is an intermediate in the
reaction as written, technically we should not leave the rate law in this

SM-417

form. The concentration of HOCl can be expressed in terms of the

reactants and products using the fast equilibrium approach:

K=

k1 [HOCl][OH ]
=
k1 9
[OCl ]

[HOCl] =

k1 [OCl ]
k1 9 [OH ]

k2 k1 [OCl ][I ]
rate =
k1 9 [OH ]
(c) An examination of the rate law shows that the rate is dependent upon
the concentration of OH , which means that the rate will be dependent
upon the pH of the solution.
(d) If the reaction is carried out in an organic solvent, then H 2 O is no
longer the solvent and its concentration must be included in calculating the
equilibrium concentration of HOCl:

K=

k1 [HOCl][OH ]
=
k1 9 [OCl ][H 2 O]

k1 [OCl ][H 2 O]
[HOCl] =
k1 9 [OH ]
rate =

k 2 k1 [OCl ][I ][H O]

2
k1 9
[OH ]

The rate of reaction will then show a dependence upon the concentration
of water, which will be obscured when the reaction is carried out with
water as the solvent.
13.99 Concentration (mol L1 )

2 N 2 O5

4 NO 2

initial

P0

change

+2x

at time t

P0 x

2x

SM-418

O2
0

+ 0.5 x
0.5x

Therefore, Ptotal at time t = P0 + 1.5 x. This allows calculation of x at each

time, which in turn allows calculation of PN2O5 (= P0 x) at these times.
Converting the units to atmospheres by dividing by
101.325 kPa atm 1 and to [N 2 O5 ] by dividing by RT allows us to make
the following table:
t , min x, kPa

PN2O5 , kPa

PN 2O5 , atm

[N 2 O5 ], mol L1

ln [N 2 O5 ]

27.3

0.269

0.0100

4.605

10.9

16.4

0.162

6.01 103

5.114

10

17.5

9.85

0.0972

3.61 103

5.624

15

21.4

5.9

0.058

2.2 103

6.12

20

23.8

3.5

0.035

1.3 103

6.65

30

26.0

1.3

0.013

4.8 104

7.64

The data fit closely to a straight line; therefore, this is a first-order

reaction. The rate constant can be obtained from the slope, which is

4.605 (7.64)
= 0.101 min 1 = k
30 min
rate = k[N 2 O5 ] = 0.101 min 1 [N 2 O5 ], which gives the results in the table
below.

t, min

rate, mol L1 min 1

1.01 103

6.07 104

10

3.65 104

15

2.2 104

20

1.3 104

30

4.8 105

SM-419