SM-394

CHAPTER 13
CHEMICAL KINETICS



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

= =



(b)
3
3 2 2
2
2mol NH 2
rate(NH ) rate(H ) rate(H )
3mol H 3

= =



(c)
3
3 2 2
2
2mol NH
rate(NH ) rate(N ) 2 rate(N )
1mol N

= =




13.3 (a) The rate of formation of dichromate ions =
2- 2-
-1 2 7 4
2-
2 7
0.14 mol Cr O 2 mol CrO
0.28 mol L s
L s 1 mol Cr O

=

(b)
1 1 1 1
0.14mol L s 1 0.14mol L s

=

13.5 (a)
3 2 2
2
2
3 1 1
2
mol NO 1mol O
rate of formation of O 6.5 10
L s 2mol NO
3.3 10 (mol O ) L s

=

(b)
3 1 1 3 1 1
6.5 10 mol L s 2 3.3 10 mol L s

=








SM-395
13.7 (a) and (c)









Note that the curves for the
2
[I ] and
2
[H ] are identical and only the
2
[I ]
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,
1 1
mmol L s


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
1 1
(mol A) L s

=
(a) rate
1 1 0 1 1
0 0 0
[(mol A) L s ] [A] ,sounitsof are(mol A) L s k k k

= =
(same as the units for the rate, in this case)
(b) rate
1 1
1 1 1
1 1
1
(mol A) L s
[(mol A) L s ] [A], sounitsof are s
(mol A) L
k k

= =

0
2
4
6
8
10
12
0 1000 2000 3000 4000 5000 6000
Time (s)
C
o
n
c
e
n
t
r
a
t
i
o
n

(
m
m
o
l

L
-
1
)
[I2], mmol/L
[HI], mmol/L
[I
2
], mmolL
-1
[HI], mmolL
-1
SM-396
(c) rate
1 1
1 1 2
1 1
2
1
1 1
(mol A) L s
[(mol A) L s ] [A] , sounitsof are
(mol A) L
L (mol A) s
k k

=


=


13.11 From the units of the rate constant, , k it follows that the reaction is first
order, thus rate
2 5
[N O ]. k =
1 2 5 2 5
2 5
2 5
3.45gN O 1mol N O
[N O ] 0.0426mol L
0.750L 108.02gN O


= =



3 1 1 4 1 1
2 5
rate 5.2 10 s 0.0426mol L 2.2 10 (mol N O ) L s

= =

13.13 (a) From the units of the rate constant, it follows that the reaction is
second order; therefore,
2 2
rate [H ][I ] k =
1 1 2 2 2 2
2 2
5 1 1
0.52gH 1mol H 0.19gI 1mol I
(0.063L mol s )
0.750L 2.016gH 0.750L 253.8gI
2.2 10 mol L s



=


=
(b) rate(new)
2 initial 2
2 [H ] [I ] 2 rate(initial), k = = 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
3
[CH Br][OH ] k

=

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
2
H is tripled, the rate triples (experiments 2 and 3); thus, the reaction is
first order in
2
H .
(a)
2
rate [ICl][H ] k =
SM-397
(b)
7
3 3
1 1
22 10 mol L L
L s 3.0 10 mol 4.5 10 mol
0.16L mol s
k

=



=

(c)
3 3
6 1 1
0.16L 4.7 10 mol 2.7 10 mol
rate
mol s L L
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
2
(3.02/1.25) ; hence, the reaction is second order in B. Tripling the
concentration of C (experiments 3 and 4) increases the rate by
2
3 9; =
thus, the reaction is second order in C. Therefore, rate
2 2
[A][B] [C] . k =
(b) overall order 5 =
(c)
2 2
rate
[A][B] [C]
k =
Using the data from experiment 4, we get
2 2
3 3 3
12 4 4 1
0.457mol L L L
L s 1.25 10 mol 3.02 10 mol 3.75 10 mol
2.85 10 L mol s
k



=



=

From experiment 3, we get
2
2
3 3
2
3
12 4 4 1
5.08 10 mol L L
L s 1.25 10 mol 3.02 10 mol
L
1.25 10 mol
2.85 10 L mol s (Checks!)
k

=

SM-398
(d)
2
12 4 3 3
4
2
3
2 1 1
2.85 10 L 3.01 10 mol 1.00 10 mol
rate
L L mol s
1.15 10 mol
L
1.13 10 mol L s

=


13.21 (a)
4 1
1/2
0.693 0.693
6.93 10 s
1000s
k
t

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

=


and solve for . k
1
1
3 1 0
0.67mol L
ln
0.53mol L ln([A] /[A] )
9.4 10 s
25s
t
k
t

= = =
(c)
1
0.153mol A 2mol A 0.034mol B
[A]
L 1mol B L
0.085(mol A) L
t

=



=

1
1
3 1
0.153mol L
ln
0.085mol L
5.1 10 s
115s
k

= =

13.23 (a)
1/ 2
5
0.693s 1min 1h 0.693
5.2h
60s 60min 3.7 10
t
k


= = =

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

=
1 4
3.5h 3600s h 1.3 10 s t

= =
5 1 4
1 (3.7 10 s )(1.3 10 s) 2 1
2 5
[N O ] 0.0567mol L e 3.5 10 mol L


= =
(c) Solve for
0
[A]
fromln , whichgives
[A]
t
t kt

=



SM-399
0 2 5 0
2 5 4
5 1
4 2
[A] [N O ]
0.0567
ln ln
ln
[A] [N O ]
0.0135
3.9 10 s
3.7 10 s
1min
(3.9 10 s) 6.5 10 min
60s
t t
t
k k






= = = =

= =




13.25 (a)
2
0
[A] 1 1
;
[A] 4 2

= =


so the time elapsed is 2 half-lives.
2 355s 710s t = =
(b) Because 15% is not a multiple of
1
2
, we cannot work directly from the
half-life. But
1/ 2
0.693/ k t =
so
3 1
0.693
1.95 10 s
355s
k

= =
Then [see the solution to Exercise 13.23(c)],
s 10 7 . 9
s 10 95 . 1
15 . 0
1
ln
] A [
] A [
ln
2
1 3
0
=

=

k
t
t

(c)
0
1
3 0 9
3 1
[A]
ln
[A] ln9
1.1 10 s
1.95 10 s
t
k

= = =

13.27 (a)
1/ 2
3 1
0.693 0.693
247min
2.81 10 min
t
k

= = =

(b) See the solutions to Exercises 13.31(c) and 13.33(c).
2 2 0
2 2
3 1
[SO Cl ]
ln
[SO Cl ]
ln10
819min
2.81 10 min
t
t
k




= = =

(c)
0
[A] [A] e
kt
t

=
Because the vessel is sealed, masses and concentrations are proportional,
and we write
SM-400
0
(massleft) (mass) e
kt
t

=
3 1 1
(2.81 10 min 60min h 1.5h)
14.0g e


=
10.9g =
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.
0
1mol A
[A] [A] [B]
3mol B
t t

=



1 1
1mol A
0.015mol L 0.018(mol B) L
3mol B


=



1
0.009mol L

=
The rate constant is then determined from the first-order integrated rate
law.
0
1
[A]
0.015
ln
ln
[A]
0.009
0.17min
3.0min
t
k
t

= = =
(b)
1 1
1
1mol A
[A] 0.015mol L 0.030(mol B) L
3mol B
0.005mol L
t

=


=

0
1
[A]
0.015
ln
ln
[A]
0.005
6.5min
0.17min
t
t
k






= = =
additional time 6.5min 3.0min 3.5min = =




SM-401
13.31 (a)










Equation 17.b in the text can be rearranged as
0
0 0
1 [A] 1 1
[A] [A] [A]
t
kt
kt
+
= = +
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,
3 1 1
7.8 10 L mol s

. 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 1 1
3.9 10 L mol s

.

13.33 It is convenient to obtain an expression for the half-life of a second-order
reaction. We work with Eq. 17.b.

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

1/ 2
0 0 1/2
[A]
1 1
[A] 2 1 [A]
t
kt
= =
+

0.00
5.00
10.00
15.00
20.00
25.00
30.00
35.00
0 1000 2000 3000 4000 5000
Time (s)
1
/
[
H
I
]

(
L

m
o
l
-
1
)
1/[HI] =(0.0078 t) +1.0
SM-402
Therefore,
0 1/ 2 0 1/ 2
1 [A] 2, or [A] 1, or kt kt + = =

1/ 2
0 1/ 2 0
1 1
and
[A] [A]
t k
k t
= =
It is also convenient to rewrite Eq. 17.b to solve for . t We take
reciprocals:

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

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

=
(a)
1 1
1
1/ 2 0
1 1
0.024L mol s
[A] (50.5s)(0.84mol L )
k
t

= = =

0 0 0
0
2
1 1 1
1 1 16 1
[A] [A] [A] [A] 15
[A]
15
7.4 10 s
(0.024L mol s )(0.84mol L )
t
k k k


= = =
= =


(b)
0 0
0
4 1
[A] [A] 3
[A]
t
k k

= =

2
1 1 1
3
1.5 10 s
(0.024L mol s )(0.84mol L )

= =


(c)
0 0
0
2
1 1 1
5 1
[A] [A] 4
[A]
4
2.0 10 s
(0.024L mol s )(0.84mol L )
t
k k

= =
= =



13.35 See the solution to Exercise 13.33 for the derivation of the formulas
needed here.
SM-403
(a)
2 0
1 1
1 1 1L 1L
[A] [A] 0.080mol 0.10mol
1.7 10 min
0.015L mol min
t
k


= = =


(b)
1
0
0.15mol A 0.19mol B 1mol A
[A]
L L 2mol B
0.055(mol A) L 0.37[A]

=



= =


0
1 1
1 1
3
1 1
[A] [A]
1 1
0.055mol L 0.15mol L
0.0035L mol min
3.3 10 min
t
t
k

=

=


13.37 (a)
1d[A]
[A]
d
rate k
a t
= =
















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

1/2 0
0
1/ 2
1/ 2
1
(b) at , [A] [A] . Therefore:
2
[A]
ln ln2 , and
[A]
ln2
t
t
t
akt
t
ak
=
= =
=
SM-404
13.39











13.41 The overall reaction is CH
2
=CHCOOH +HCl ClCH
2
CH
2
COOH. The
intermediates include chloride ion, CH
2
=CHC(OH)
2
+
and
2 2
ClCH CHC(OH) .

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.

2
rate [NO][Br ] k =

13.45 If mechanism (a) were correct, the rate law would be rate =k[NO
2
][CO].
But this expression does not agree with the experimental result and can be
eliminated as a possibility. Mechanism (b) has rate =k[NO
2
]
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[NO
3
][CO]. [CO] cannot be
eliminated from this expression to yield the experimental result, which
does not contain [CO].
3
0
d[A]
Given: [A] , we can derive an expression for the amount
d
of time needed for the inital concentration of A, [A] , to decrease
by 1/2. Begin by obtaining the integrated rate law for a third-orde
k
t
=
t
0
[A]
-3 2 2
0
[A] 0
1
2 0 1/2
2 2
1
0 0 1/ 2 2
r
reaction by separation of variables:
1
[A] d[A] d [A] [A]
2
To obtain an expression for the half-life, let [A] [A] and = :
1
( [A] ) [A]
2
solving
t
t
t
k t kt
t t
kt


= = =

=
=


1/ 2
2
0
for the half-life:
3
2 [A]
t
k
=
SM-405
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 =- [A] [B] k k + . 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:
o
[A] [B] [A] + = where
o
[A] is the initial
concentration of A. Therefore, the rate law may be written:
o o
d[A]
[A] ([A] [A]) ( )[A] [A]
dt
k k k k k = + = + +
The solution of this first-order differential equation is:
-( )
o
e
[A] [A]
k k t
k k
k k
+
+
=
+

As t the exponential term in the numerator goes to zero and the
concentrations reach their equilibrium values given by:
o o
eq eq o
eq
eq
[A] [A]
[A] and [B] [A] [A]
taking the ratio of products over reactants we see that:
[B]
where is the equilibrium constant for the reaction.
[A]
k k
k k k k
k
K K
k

= = =
+ +
= =

SM-406
13.51









(a) Given the Arrhenius equation,
a
ln lnA / k E RT = , we see that the
slope of the best fit line to the data (
4
10 27 . 3 K) is E
a
/ R and the y-
intercept (35.0) is ln A. Therefore,
. mol kJ 10 72 . 2 ) K mol kJ 10 31 . 8 )( K 10 27 . 3 (
1 2 1 1 3 4
a

= = E
(b) At 600
o
C (or 873 K), the rate constant is:
( )
4
1
ln( ) 3.27 10 K 35.0 2.46
873 K
0.088
k
k
= + =
=


13.53 We use ln
a a
1 1 E E k T T
k R T T R T T

= =




ln
1
1
a
3 1 1
0.87s
ln
0.76s
1030K 1000K
1030K 1000K 8.31 10 kJ K mol
k
k
E

=




=




1
1
1 1 1 3
a
mol kJ 39
s 76 . 0
s 87 . 0
ln
) K 1000 K 1030 (
) K 1030 )( K 1000 )( mol K kJ 10 31 . 8 (

= E


13.55 We use ln
a a
1 1 E E T T k
k R T T R TT

= = =




y =-32700 x +35.0
-10
-8
-6
-4
-2
0
0.0011 0.00115 0.0012 0.00125 0.0013 0.00135
1 / T (K
-1
)
l
n
(
k
)
SM-407
rate constant at 700 C, (700 273) K 973K k T = = + =

1
3 1
315kJ mol 973K 1073K
ln
973K 1073K 8.314 10 kJ mol
3.63; 0.026
k
k
k
k

= =

10 1 1 9 1 1
0.026 9.7 10 L mol s 2.5 10 L mol s k

= =

13.57 ln
a a
1
3 1 1
1 1
103kJ mol 323K 318K
0.60
318K 323K 8.314 10 kJ K mol
E E T T k
k R T T R TT

= =




= =




4 1 4 1
1.8
1.8 5.1 10 s 9.2 10 s
k
k
k

=
= =


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:
1 1
1 1
265L mol min
0.676
392L mol min
k
K
k



= = =


(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.

13.61 (a) cat =catalyzed, uncat =uncatalyzed
75
a,cat a,uncat a,uncat 125
0.60 E E E = =
SM-408
, ,
, ,
, ,
/ (0.60) /
/ /
( 0.60 1.00) / (0.60) /
( )
( )
a cat a uncat
a uncat a uncat
a uncat a uncat
E RT E RT
cat
E RT E RT
uncat
E RT E RT
k rate cat Ae e
rate uncat k Ae e
e e


+
= = =
= =

1 3 1 1
[(0.60)(125 )/(8.314 10 298 )] 13
4 10
kJ mol kJ K mol K
e


= =

(b) The last step of the calculation in (a) is repeated with T =350 K.
1 3 1 1
[(0.60)(125 )/(8.314 10 350 )] 11
2 10
kJ mol kJ K mol K
e


=

The rate enhancement is lower at higher temperatures.

13.63 cat =catalyzed
a,cat a,cat
a a
/ /
cat
/ /
uncat
rate(cat) e e
1000
rate(uncat) e e
E RT E RT
E RT E RT
k A
k A


= = = =

ln 1000
a,cat a
1 3 1 1
1
ln1000
98kJ mol (8.31 10 kJ K mol )(298K)(ln1000)
81kJ mol
E E RT

=
=
=


13.65 The overall reaction is
2 2
RCN H O RC( O)NH . + R 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-409
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:
. 0 ] ES [ ] ES [ ] S ][ E [
dt
] ES [ d
2 1 1
= = k k' k
Rearranging gives: ]. ES [ ] ES [ ] S ][ E [
M
1
1 2
K
k
k' k
=

+
=
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] =K
M
[ES].
Rearranging to obtain [ES] gives: .
] S [
] S [ ] E [
] ES [
M
0
+
=
K

From the mechanism, the rate of appearance of the product is given by
rate =k
2
[ES]. Substituting the preceding equation for [ES], we obtain:
,
] S [
] S [ ] E [
Rate
M
0 2
+
=
K
k

the Michaelis-Menten rate equation, which can be rearranged to obtain:
.
] E [
1
] S [ ] E [ rate
1
0 2 0 2
M
k k
K
+ =
If one plots
rate
1
versus
] S [
1
, the slope will be
0 2
M
] E [ k
K
and the y-intercept
will be .
] E [
1
0 2
k








SM-410
(b)










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

2 3
[H SeO ] [I ]

[H ]
+
Rate,
1 1
mol L s


0.020 0.020 0.010
6
8.0 10

0.020 0.010 0.020
6
4.0 10

0.020 0.030 0.030
4
2.4 10

0.010 0.020 0.020
5
1.6 10

We have the following general relationship:
2 3
rate [H SeO ] [I ] [H ] ,
x y z
k
+
= which can be rewritten for ease of
computation as
2 3
ln (rate) ln ln[H SeO ] ln[I ] ln[H ] k x y z
+
= + + +
Using the data above, we can create four equations, which should be
enough to solve the system of four unknown variables:
6
ln(8.0 10 ) ln ln0.020 ln0.020 ln0.010 k x y z

= + + +
6
ln(4.0 10 ) ln ln0.020 ln0.010 ln0.020 k x y z

= + + +
4
ln(2.4 10 ) ln ln0.020 ln0.030 ln0.030 k x y z

= + + +
5
ln(1.6 10 ) ln ln0.010 ln0.020 ln0.020 k x y z

= + + +
which give, upon calculating the numerical logarithms:
0
1/[S]
1
/
r
a
t
e
2 0
slope =
[E]
m
k
k
2 0
1
y-intercept =
[E] k
SM-411
11.74 ln 3.91 3.91 4.60 (1)
12.40 ln 3.91 4.60 3.91 (2)
8.33 ln 3.91 3.51 3.51 (3)
11.04 ln 4.60 3.91 3.91 (4)
k x y z
k x y z
k x y z
k x y z
=
=
=
=

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
5
5.0 10 k =
5 5 1
L mol s .


(b) With
1 1 1
2 3
[H SeO ] 0.030mol L , [I ] 0.025mol L and[H ] 0.015mol L ,
+
= = =

5 5 5 1 1 1 1 3
1 2
rate (5.0 10 L mol s )(0.030mol L ) (0.025mol L )
(0.015mol L )

=



5 1 1
rate 5.3 10 mol L s

=

13.73 (a)
1 1
0
1 1
1 1 1 1
[A] [A] 0.0050mol L 0.040mol L
12h
15L mol h
t
k
t




= =
=

(b)
2 2
2
1
mol EX 1mol EX mol X
[EX ] 0.040 0.070
L L 2mol X
0.005mol L

=



=


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




= =
=







SM-412
13.75














13.77 amount of original sample 25.0mg x = =
number of half -lives n =

1
amount remaining
2
n
x

=




10.9
0.886half -lives
12.3
=

0.886
1
25.0mg 13.5mg
2

=




13.79 The anticipated rate for mechanism (i) is: rate =k[C
12
H
22
O
11
], while the
expected rate for mechanism (ii) is: rate =k[C
12
H
22
O
11
][H
2
O]. 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
First
activated
complex
Second
activated
complex
Intermediate
Effect of
catalyst
(new
pathway
lowers E
a
)
A
B
E
a,1

E
a,2
Progress of reaction
P
o
t
e
n
t
i
a
l

E
n
e
r
g
y

H
SM-413
result, if mechanism (ii) is correct the kinetics will display a first-order
dependence on the concentration of H
2
O while mechanism (i) predicts that
the rate of the reaction is independent of [H
2
O].

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
2 2 2 2
[N O ][H ]. k = Consider the equilibrium
of Step
2
1 1 2 2
1: [NO] [N O ] k k = 9
2
2 2
1
[N O ] [NO]
k
k
=
9
Substituting in our proposed rate law, we have
2 2 1 1
2 2 2 2
1 1
rate [NO] [H ] [NO] [H ] where
k k
k k k k
k k

= = =


9 9

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













Products
E
a,1

Progress of reaction
P
o
t
e
n
t
i
a
l

E
n
e
r
g
y

H
E
a,2 E
a,3
Reactants
SM-414
Note: The dips that represent the formation of the intermediate
2 2 2
N O andN O will not be at the same energy, but we have no
information to determine which should be lower.

13.83
rateat 28 C 48h
rateat 5 C 4h
k t
k t

= = =


We use
a
a
1 1
ln andsolvefor .
E k
E
k R T T

3 1 1
1
a
48
ln (8.314 10 kJ K mol ) ln
4
75kJ mol
1 1
1 1
278K 301K
k
R
k
E
T T

= = =

13.85
















13.87 (a) ClO is the reaction intermediate; Cl is the catalyst.
(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
eq
0
uilibrium between the bound and unbound substrate:
[ES]
, solving for [ES] we obtain: [ES] [E][S]
[E][S]
as before in problem 13.69, the total bound and unbound enzyme
concentration, [E] , is
K K = =
0
0
0
0 0
given by:
[E] [E]+[ES], and, therefore,
[E]=[E] [ES]
Substituting this expression for [E] into the equation above we obtain:
([E] -[ES])[S] [ES].
Rearrainging to obtain [ES]:
[E] [S] [E] [S]
[ES]=
1+ [S]
K
K
K
=

=
=
1
2
2 0
1
+[S]
From the mechanism, the rate of appearance of the product is given by:
rate [ES]. Substituting the equation above for [ES] one obtains:
[E] [S]
rate = , the Michaelis-Menten rate equati
+[S]
K
k
k
K

=
on.
SM-415
(b) Cl, ClO, O,
2
O
(c) Step 1 and step 2 are propagating.
(d)
2
Cl Cl Cl +

13.89 For a third-order reaction,

1/ 2 1/2
2 2
0 0
1 constant
or
[A ] [A ]
t t =
(a) The time necessary for the concentration to fall to one-half of the
initial concentration is one half-life:
first half-life
1 1/ 2
2
0
constant
[A ]
t t = = =
(b) This time,
1/ 4
, t is two half-lives, but because of different starting
concentrations, the half-lives are not the same:
second
2 1
2 2
1
0 0 2
constant 4(constant)
half -life 4
( [A ]) [A ]
t t = = = =
total
1 2 1 1 1 1/ 4
time 4 5 t t t t t t = + = + = =
(c) This time,
1/16
, t is four half-lives; again, the half-lives are not the
same:
third
3 1
2 2
1
0 0 4
constant 16(constant)
half -life 16
( [A ]) [A ]
t t = = = =
fourth
4 1
2 2
1
0 0 8
constant 64(constant)
half -life 64
( [A ]) [A ]
t t = = = =
total time
1 2 3 4 1 1 1 1 1 1/16
4 16 64 85 t t t t t t t t t t = + + + = + + + = =
If
1
t is known, the times
1/ 4
t and
1/16
t can be calculated easily.

13.91 By analogy with the reaction in Exercise 13.82, the overall reaction here is
4 2 3
CH (g) Cl (g) CH Cl HCl + +
(a) Initiation:
2
Cl 2Cl
Propagation:
4 3
Cl CH CH Cl H + +
SM-416

2
H Cl HCl Cl + +
Termination:
2
Cl Cl Cl +

2
H H H +
H Cl HCl +
(b)
3
CH Cl andHCl

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
r r
and . H S From Table 13.1 we can obtain K
values at 4 temperatures:

k
K
k
=

9 1 1
500
7 1 1
6.4 10 L mol s
0.015
4.3 10 L mol s
K



= =



6 1 1
600
4 1 1
9.7 10 L mol s
0.022
4.4 10 L mol s
K



= =



3 1 1
700
2 1 1
1.8 10 L mol s
0.028
6.3 10 L mol s
K



= =



2 1 1
700
1 1
9.7 10 L mol s
0.037
2.6L mol s
K



= =


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:

r r
1
1
ln
H S
K
R T R

= +



The plot should be ln K versus
1
.
T
The slope will be
r
H
R

and the
intercept will be
r
.
S
R


SM-417
(K) T
1
1
(K )
T

K 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

1 r
r
1177, 9.8kJ mol
H
H
R

= =

1 1 r
r
1.86, 15J K mol
S
S
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.

13.97 (a)
1
2
1
OCl H O HOCl OH

+ +

k
k
fast equilibrium

2
HOCl I HOI Cl
k
+ + very slow

3
2
3
HOI OH OI H O

+ +

k
k
fast equilibrium
The overall reaction is OCl I OI Cl

+ +
(b) The rate law will be based upon the slow step of the reaction:

2
rate [HOCl][I ] k

=
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-418
form. The concentration of HOCl can be expressed in terms of the
reactants and products using the fast equilibrium approach:

1
1
[HOCl][OH ]
[OCl ]
k
K
k

= =
9


1
1
[OCl ]
[HOCl]
[OH ]
k
k

=
9


2 1
1
[OCl ][I ]
rate
[OH ]
k k
k

=
9

(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
2
H O is no
longer the solvent and its concentration must be included in calculating the
equilibrium concentration of HOCl:

1
1 2
[HOCl][OH ]
[OCl ][H O]
k
K
k

= =
9


1 2
1
[OCl ][H O]
[HOCl]
[OH ]
k
k

=
9

rate =
1
2
2
1
[OCl ][I ][H O]
[OH ]
k k
k

9

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
1
2 5 2 2
(mol L ) 2N O 4NO O

+
initial
0
P 0 0
change x 2x + 0.5x +
at time t
0
P x 2x 0.5x
SM-419
Therefore,
total 0
at time 1.5 . P t P x = + This allows calculation of x at each
time, which in turn allows calculation of
2 5
N O 0
( ) P P x = at these times.
Converting the units to atmospheres by dividing by
1
2 5
101.325kPa atm andto[N O ]

by dividing by RT allows us to make

the following table:
, t min , kPa x
2 5
N O
, kPa P
2 5
N O
, atm P
1
2 5
[N O ], mol L

2 5
ln[N O ]
0 0 27.3 0.269 0.0100 4.605
5 10.9 16.4 0.162
3
6.01 10

5.114
10 17.5 9.85 0.0972
3
3.61 10

5.624
15 21.4 5.9 0.058
3
2.2 10

6.12
20 23.8 3.5 0.035
3
1.3 10

6.65
30 26.0 1.3 0.013
4
4.8 10

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

1
4.605 ( 7.64)
0.101min
30min
k

= =
1
2 5 2 5
rate [N O ] 0.101min [N O ], k

= = which gives the results in the table
below.
t, min rate,
1 1
mol L min


0
3
1.01 10

5
4
6.07 10

10
4
3.65 10

15
4
2.2 10

20
4
1.3 10

30
5
4.8 10