CHAPTER 15

CHEMICAL KINETICS

Reaction Rates
10.

The reaction rate is defined as the change in concentration of a reactant or product per unit
time. Consider the general reaction:
aA products where rate =

d[A]
dt

If we graph [A] vs. t, it would usually look like the solid line in the following plot.

[A]

b
c
0

t1

t2

time

An instantaneous rate is the slope of a tangent line to the graph of [A] vs. t. We can determine
the instantaneous rate at any time during the reaction. On the plot, tangent lines at t 0 and t
= t1 are drawn. The slope of these tangent lines would be the instantaneous rates at t 0 and t
= t1. We call the instantaneous rate at t 0 the initial rate. The average rate is measured over
a period of time. For example, the slope of the dashed line connecting points a and c is the
average rate of the reaction over the entire length of time 0 to t2 (average rate = [A]/t). An
average rate is determined over some time period, whereas an instantaneous rate is
determined at one specific time. The rate that is largest is generally the initial rate. At t 0,
the slope of the tangent line is greatest, which means the rate is largest at t 0.
The initial rate is used by convention so that the rate of reaction only depends on the forward
reaction; at t 0, the reverse reaction is insignificant because no products are present yet.

613

614
11.

CHAPTER 15

CHEMICAL KINETICS

Using the coefficients in the balanced equation to relate the rates:

d[ NH3 ]
d[H 2 ]
d[ N 2 ]
d[ N 2 ]
3
and
2
dt
dt
dt
dt
So :

d[ NH3 ]
1 d[H 2 ]
1 d[ NH3 ]
2 d[H 2 ]

or

3 dt
2 dt
dt
3 dt

Ammonia is produced at a rate equal to 2/3 of the rate of consumption of hydrogen.

12.

The coefficients in the balanced reaction relate the rate of disappearance of reactants to the
rate of production of products. From the balanced reaction, the rate of production of P 4 will
be 1/4 the rate of disappearance of PH3, and the rate of production of H2 will be 6/4 the rate
of disappearance of PH3. By convention, all rates are given as positive values.
Rate

[PH3 ] (0.0048 mol/ 2.0 L)

= 2.4 103 mol L1 s1

t
s

[P4 ]
1 [PH3 ]

= 2.4 103/4 = 6.0 104 mol L1 s1

t
4 t
[H 2 ]
6 [PH3 ]

= 6(2.4 103)/4 = 3.6 103 mol L1 s1

t
4 t
13.

0.0120/0.0080 = 1.5; reactant B is used up 1.5 times faster than reactant A. This corresponds to a 3 to 2 mole ratio between B and A in the balanced equation. 0.0160/0.0080 = 2;
product C is produced twice as fast as reactant A is used up. So the coefficient for C is twice
the coefficient for A. A possible balanced equation is 2A + 3B 4C.

14.

1.24 1012 cm3

1L
6.022 1023 molecules
= 7.47 108 L mol1 s1

3
molecules s
mol
1000 cm

15.

mol
mol
k
Rate = k[Cl] [CHCl3],

Ls
L

16.

a. The units for rate are always mol L1 s1.

1/ 2

1/2

c. Rate = k[A],

mol
mol
k

Ls
L

k must have units of s-1.

e. L2 mol2 s1

mol
1/2
-1/2
1

; k must have units of L mol s .

L
b. Rate = k; k has units of mol L1 s1.
2

d. Rate = k[A] ,

mol
mol
k

Ls
L

k must have units L mol1 s1.

CHAPTER 15

CHEMICAL KINETICS

615

Rate Laws from Experimental Data: Initial Rates Method

17.

a. In the first two experiments, [NO] is held constant and [Cl2] is doubled. The rate also
doubled. Thus the reaction is first order with respect to Cl2. Or mathematically: Rate =
k[NO]x[Cl2]y
0.36
k (0.10) x (0.20) y
(0.20) y
, 2.0 = 2.0y, y = 1

x
y
y
0.18
k (0.10) (0.10)
(0.10)

We can get the dependence on NO from the second and third experiments. Here, as the
NO concentration doubles (Cl2 concentration is constant), the rate increases by a factor of
four. Thus, the reaction is second order with respect to NO. Or mathematically:
1.45
k (0.20) x (0.20)
(0.20) x
, 4.0 = 2.0x, x = 2; so, Rate = k[NO]2[Cl2].

0.36
k (0.10) x (0.20)
(0.10) x

Try to examine experiments where only one concentration changes at a time. The more
variables that change, the harder it is to determine the orders. Also, these types of
problems can usually be solved by inspection. In general, we will solve using a
mathematical approach, but keep in mind that you probably can solve for the orders by
simple inspection of the data.
b. The rate constant k can be determined from the experiments. From experiment 1:
2

0.18 mol
0.10 mol 0.10 mol
2
2
1
k

, k = 180 L mol min
L min
L
L

From the other experiments:

k = 180 L2 mol2 min1 (second exp.); k = 180 L2 mol2 min1 (third exp.)
The average rate constant is kmean = 1.8 102 L2 mol2 min1.
18.

Rate = k[NO]x[O2]y; Comparing the first two experiments, [O2] is unchanged, [NO] is tripled,
and the rate increases by a factor of nine. Therefore, the reaction is second order in NO (3 2 =
9). The order of O2 is more difficult to determine. Comparing the second and third
experiments:
3.13 1017
k (2.50 1018 ) 2 (2.50 1018 ) y

1.80 1017
k (3.00 1018 ) 2 (1.00 1018 ) y
1.74 = 0.694(2.50)y, 2.51 = 2.50y, y = 1
Rate = k[NO]2[O2]; from experiment 1:
2.00 1016 molecules cm3 s1 = k(1.00 1018 molecules/cm3)2
(1.00 1018 molecules/cm3)

616

CHAPTER 15

CHEMICAL KINETICS

k = 2.00 1038 cm6 molecules2 s1 = kmean

2

Rate =

6.21 1018 molecules

7.36 1018 molecules
2.00 1038 cm6

cm3
cm3
molecules2 s

Rate = 5.68 1018 molecules cm3 s1

19.

a. Rate = k[ClO2]x[OH]y; From the first two experiments:

2.30 101 = k(0.100)x(0.100)y and 5.75 102 = k(0.0500)x(0.100)y
(0.100) x
= 2.00x, x = 2
(0.0500) x

Dividing the two rate laws: 4.00 =

Comparing the second and third experiments:

2.30 101 = k(0.100)(0.100)y and 1.15 101 = k(0.100)(0.0500)y
Dividing: 2.00 =

(0.100) y
= 2.0y, y = 1
y
(0.050)

The rate law is: Rate = k[ClO2]2[OH]

2.30 101 mol L1 s1 = k(0.100 mol/L)2(0.100 mol/L), k = 2.30 102 L2 mol2 s1
= kmean
2

b. Rate =
20.

2.30 102 L2 0.175 mol

0.0844 mol

= 0.594 mol L1 s1

2
L
L
mol s

a. Rate = k[Hb]x[CO]y
Comparing the first two experiments, [CO] is unchanged, [Hb] doubles, and the rate
doubles. Therefore, x = 1, and the reaction is first order in Hb. Comparing the second
and third experiments, [Hb] is unchanged, [CO] triples, and the rate triples. Therefore, y
= 1 and the reaction is first order in CO.
b. Rate = k[Hb][CO]
c. From the first experiment:
0.619 mol L1 s1 = k(2.21 mol/L)(1.00 mol/L), k = 0.280 L mol1 s1
The second and third experiments give similar k values, so kmean = 0.280 L mol1 s1.
d. Rate = k[Hb][CO] =

0.280 L 3.36 mol

2.40 mol

= 2.26 mol L1 s1
mol s
L
L

CHAPTER 15
21.

CHEMICAL KINETICS

617

a. Rate = k[NOCl]n; using experiments two and three:

2.66 104
k (2.0 1016 ) n

, 4.01 = 2.0n, n = 2; Rate = k[NOCl]2

3
16 n
6.64 10
k (1.0 10 )
2

3.0 1016 molecules

5.98 104 molecules

, k = 6.6 1029 cm3 molecules1 s1

k
3

cm3 s
cm

b.

The other three experiments give (6.7, 6.6, and 6.6) 1029 cm3 molecules1 s1,
respectively. The mean value for k is 6.6 1029 cm3 molecules1 s1.
6.6 1029 cm3
1L
6.022 1023 molecules 4.0 108 L
=

molecules s
mol
mol s
1000 cm3

c.
22.

Rate = k[N2O5]x; the rate laws for the first two experiments are:
2.26 103 = k(0.190)x and 8.90 104 = k(0.0750)x
Dividing the two rate laws: 2.54 =
k

(0.190) x
= (2.53)x, x = 1; Rate = k[N2O5]
(0.0750) x

Rate
8.90 104 mol L1 s 1
= 1.19 102 s1

[ N 2 O5 ]
0.0750 mol / L

The other experiments give similar values for k. kmean = 1.19 102 s1
23.

Rate = k[I]x[OCl]y[OH]z; Comparing the first and second experiments:

18.7 103
k (0.0026) x (0.012) y (0.10) z
, 2.0 = 2.0x, x = 1

9.4 103
k (0.0013) x (0.012) y (0.10) z

Comparing the first and third experiments:

9.4 103
k (0.0013)(0.012) y (0.10) z
, 2.0 = 2.0y, y = 1

4.7 103
k (0.0013)(0.0060) y (0.10) z

Comparing the first and sixth experiments:

4.8 103
k (0.0013)(0.012)(0.20) z
, 1/2 = 2.0z, z = 1

9.4 103
k (0.0013)(0.012)(0.10) z

Rate =

k[I ][OCl ]
; the presence of OH decreases the rate of the reaction.

[OH ]

618

CHAPTER 15

CHEMICAL KINETICS

For the first experiment:

9.4 103 mol
(0.0013 mol/ L) (0.012 mol/ L)
, k = 60.3 s 1 = 60. s 1
k
Ls
(0.10 mol/ L)

For all experiments, kmean = 60. s 1 .

24.

[A]
Rate2
k[A]2x

2
x
Rate1
k[A]1
[A]1

The rate doubles as the concentration quadruples:

2 = (4)x, x = 1/2
The order is 1/2 (the square root of the concentration of reactant).
For a reactant that has an order of 1 and the reactant concentration is doubled:

Rate2
1
(2) 1
Rate1
2
The rate will decrease by a factor of 1/2 when the reactant concentration is doubled for a 1
order reaction. Negative orders are seen for substances that hinder or slow down a reaction.
25.

Rate = k[H2SeO 3 ]x [H ] y [I ]z ; comparing the first and second experiments:

3.33 107
7

1.66 10

k (2.0 104 ) x (2.0 102 ) y (2.0 102 ) z

4 x

2 y

2 z

k (1.0 10 ) (2.0 10 ) (2.0 10 )

, 2.01 = 2.0x, x = 1

Comparing the first and fourth experiments:

6.66 107
1.66 107

k (1.0 104 )(4.0 102 ) y (2.0 102 ) z

k (1.0 104 )(2.0 102 ) y (2.0 102 ) z

, 4.01 = 2.0y, y = 2

Comparing the first and sixth experiments:

13.2 107
1.66 107

k (1.0 104 )(2.0 102 ) 2 (4.0 102 ) z

k (1.0 104 )(2.0 102 ) 2 (2.0 102 ) z

7.95 = 2.0 z , log(7.95) = z log(2.0), z =

Rate = k[H2SeO3][H+]2[I]3

log (7.95)
= 2.99 3
log(2.0)

CHAPTER 15

CHEMICAL KINETICS

619

Experiment 1:
2

1.0 104 mol 2.0 102 mol 2.0 102 mol

1.66 107 mol

Ls
L
L
L

k = 5.19 105 L5 mol-5 s-1 = 5.2 105 L5 mol-5 s-1 = kmean

Integrated Rate Laws

26.

Zero order:

d[A]
k,
dt
[ A ]t

[ A]

[ A ]t

[ A ]0

d[A] k dt
t

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

[ A ]0

First order:

d[A]
k[A],
dt
[ A ]t

ln[A]

[ A ]t

d[A]
[A] k dt
[ A ]0
0

kt, ln[A]t ln[A]0 kt, ln[A]t = kt + ln[A]0

[ A ]0

Second order:

d[A]
k[A]2 ,
dt

27.

1
[ A]

[ A ]t

[ A ]t

kt,

[ A ]0

Zero order: t1/2 =

d[A]
[A]2 k dt
[ A ]0
0

[ A ]0
;
2k

1
1
1
1

kt,
kt
[A]t [A]0
[ A]t
[A]0
first order: t1/2 =

ln 2
1
; second order: t1/2 =
k[A]0
k

For a first-order reaction, if the first half-life equals 20. s, the second half-life will also be 20.
s because the half-life for a first-order reaction is concentration-independent. The second
half-life for a zero-order reaction will be 1/2(20.) = 10. s. This is because the half-life for a
zero-order reaction has a direct relationship with concentration (as the concentration
decreases by a factor of 2, the half-life decreases by a factor of 2). Because a second-order
reaction has an inverse relationship between t1/2 and [A]0, the second half-life will be 40. s
(twice the first half-life value).

620
28.

CHAPTER 15

CHEMICAL KINETICS

a. Because the 1/[A] versus time plot was linear, the reaction is second order in A. The
slope of the 1/[A] versus time plot equals the rate constant k. Therefore, the rate law, the
integrated rate law, and the rate constant value are:
Rate = k[A]2;

1
1
= kt +
; k = 3.60 10-2 L mol-1 s-1
[ A ]0
[A]

b. The half-life expression for a second-order reaction is: t1/2 =

For this reaction: t1/2 =

1
k[A]0

1
2

3.60 10

L mol s

2.80 10 mol/ L

= 9.92 103 s

Note: We could have used the integrated rate law to solve for t1/2, where
[A] = (2.80 103 /2) mol/L.
c. Because the half-life for a second-order reaction depends on concentration, we must use
the integrated rate law to solve.

1
1
1
3.60 102 L
1
= kt +
,

t
4
[A]
[ A ]0 7.00 10 M
mol s
2.80 103 M
1.43 103 357 = (3.60 102)t, t = 2.98 104 s
29.

a. Because the ln[A] versus time plot was linear, the reaction is first order in A. The slope
of the ln[A] versus time plot equals k. Therefore, the rate law, the integrated rate law,
and the rate constant value are:
Rate = k[A]; ln[A] = kt + ln[A]0; k = 2.97 102 min1
b. The half-life expression for a first order rate law is:
t1/2 =

0.6931
ln 2
0.6931

, t1/2 =
= 23.3 min
k
k
2.97 10 2 min 1

c. 2.50 103 M is 1/8 of the original amount of A present initially, so the reaction is 87.5%
complete. When a first-order reaction is 87.5% complete (or 12.5% remains), then the
reaction has gone through 3 half-lives:
100% 50.0% 25.0% 12.5%; t = 3 t1/2 = 3 23.3 min = 69.9 min
t1/2
t1/2
t1/2
Or we can use the integrated rate law:
2.50 103 M
[ A]
2
1

kt, ln
ln
2.00 102 M = (2.97 10 min )t
[
A
]
0

CHAPTER 15

CHEMICAL KINETICS

t=
30.

621

ln(0.125)
= 70.0 min
2.97 10 2 min 1

a. Because the [C2H5OH] versus time plot was linear, the reaction is zero order in C2H5OH.
The slope of the [C2H5OH] versus time plot equals -k. Therefore, the rate law, the
integrated rate law, and the rate constant value are: Rate = k[C2H5OH]0 = k; [C2H5OH]
= kt + [C2H5OH]0; k = 4.00 105 mol L1 s1
b. The half-life expression for a zero-order reaction is t1/2 = [A]0/2k.
t1/2 =

[C 2 H 5OH]0
1.25 102 mol/ L
= 156 s

2k
2 4.00 105 mol L1 s 1

Note: We could have used the integrated rate law to solve for t1/2, where
[C2H5OH] = (1.25 102/2) mol/L.
c. [C2H5OH] = kt + [C2H5OH]0 , 0 mol/L = (4.00 105 mol L1 s1)t +
1.25 102 mol/L
t=
31.

1.25 102 mol/ L

= 313 s
4.00 105 mol L1 s 1

The first assumption to make is that the reaction is first order. For a first order reaction, a
graph of ln[H2O2] versus time will yield a straight line. If this plot is not linear, then the
reaction is not first order, and we make another assumption.
Time
(s)

[H2O2]
(mol/L)

0
120.
300.
600.
1200.
1800.
2400.
3000.
3600.

1.00
0.91
0.78
0.59
0.37
0.22
0.13
0.082
0.050

ln[H2O2]
0.000
0.094
0.25
0.53
0.99
1.51
2.04
2.50
3.00

Note: We carried extra significant figures in some of the natural log values in order to reduce
round-off error. For the plots, we will do this most of the time when the natural log function
is involved.

622

CHAPTER 15

CHEMICAL KINETICS

The plot of ln[H2O2] versus time is linear. Thus the reaction is first order. The differential
d[H 2 O 2 ]
rate law and integrated rate law are Rate =
= k[H2O2] and ln[H2O2] = kt +
dt
ln[H2O2]0.
We determine the rate constant k by determining the slope of the ln[H2O2] versus time plot
(slope = k). Using two points on the curve gives:
slope = k =

y
0 (3.00)

= 8.3 104 s1, k = 8.3 104 s1

x
0 3600.

To determine [H2O2] at 4000. s, use the integrated rate law, where [H2O2]0 = 1.00 M.

[H 2 O 2 ]
= kt
ln[H2O2] = kt + ln[H2O2]0 or ln
[H 2 O 2 ]0

[H O ]
ln 2 2 = 8.3 104 s1 4000. s, ln[H2O2] = 3.3, [H2O2] = e3.3 = 0.037 M
1.00
32.

The first assumption to make is that the reaction is first order. For a first-order reaction, a
graph of ln[C4H6] versus t should yield a straight line. If this isn't linear, then try the second
order plot of 1/[C4H6] versus t. The data and the plots follow:
Time

195

604

1246

2180

[C4H6]

1.6 102

1.5 102

1.3 102

1.1 102

ln[C4H6]
1/[C4H6]

4.14
62.5

4.20
66.7

4.34
76.9

4.51
90.9

6210 s
0.68 102 M
4.99
147 M 1

Note: To reduce round-off error, we carried extra significant figures in the data points.

The natural log plot is not linear, so the reaction is not first order. Because the second order
plot of 1/[C4H6] versus t is linear, we can conclude that the reaction is second order in
butadiene. The differential rate law is:

CHAPTER 15

CHEMICAL KINETICS

623

Rate = k[C4H6]2
For a second-order reaction, the integrated rate law is

1
1
= kt +
.
[C 4 H 6 ]0
[C 4 H 6 ]

The slope of the straight line equals the value of the rate constant. Using the points on the
line at 1000. and 6000. s:
k = slope =
33.

144 L / mol 73 L / mol

= 1.4 102 L mol1 s1
6000. s 1000. s

From the data, the pressure of C2H5OH decreases at a constant rate of 13 torr for every 100. s.
Since the rate of disappearance of C2H5OH is not dependent on concentration, the reaction is
zero order in C2H5OH.
k=

13 torr
1 atm

= 1.7 104 atm/s

100. s
760 torr

The rate law and integrated rate law are:

1 atm
= kt + 0.329 atm
Rate = k = 1.7 104 atm/s; PC2 H5OH = kt + 250. torr
760 torr
At 900. s:
PC2 H5OH = 1.7 104 atm/s 900. s + 0.329 atm = 0.176 atm = 0.18 atm = 130 torr

34.

a. Because the 1/[A] versus time plot is linear with a positive slope, the reaction is second
order with respect to A. The y intercept in the plot will equal 1/[A]0. Extending the plot,
the y intercept will be about 10, so 1/10 = 0.1 M = [A]0.
b. The slope of the 1/[A] versus time plot will equal k.
Slope = k =

(60 20) L / mol

= 10 L mol1 s1
(5 1) s

1
10 L
1
1

9s
= kt +
= 100, [A] = 0.01 M
[ A ]0
mol s
0.1 M
[A]
c. For a second-order reaction, the half-life does depend on concentration: t1/2 =
First half-life: t1/2 =

1
10 L
0.1 mol

mol s
L

=1s

Second half-life ([A]0 is now 0.05 M): t1/2 = 1/(10 0.05) = 2 s

Third half-life ([A]0 is now 0.025 M): t1/2 = 1/(10 0.025) = 4 s

1
k[A]0

624
35.

CHAPTER 15

CHEMICAL KINETICS

Assume the reaction is first order and see if the plot of ln[NO2] versus time is linear. If this
isnt linear, try the second order plot of 1/[NO2] versus time. The data and plots follow.
Time (s)

[NO2] (M)

ln[NO2]

0
1.20 103
3.00 103
4.50 103
9.00 103
1.80 104

0.500
0.444
0.381
0.340
0.250
0.174

0.693
0.812
0.965
1.079
1.386
1.749

1/[NO2] (M -1)
2.00
2.25
2.62
2.94
4.00
5.75

The plot of 1/[NO2] versus time is linear. The reaction is second order in NO2. The differential rate law and integrated rate law are Rate = k[NO2]2 and

1
1
= kt +
.
[ NO 2 ]
[ NO 2 ]0

The slope of the plot 1/[NO2] versus time gives the value of k. Using a couple of points on
the plot:
slope = k =

y
(5.75 2.00) M 1
= 2.08 104 L mol1 s1

x
(1.80 104 0) s

To determine [NO2] at 2.70 104 s, use the integrated rate law, where 1/[NO2]0= 1/0.500 M =
2.00 M 1.
1
1
1
2.08 104 L
= kt +
,
=
2.70 104 s + 2.00 M 1
[ NO 2 ]
[ NO 2 ]0 [ NO 2 ]
mol s

1
= 7.62, [NO2] = 0.131 M
[ NO 2 ]

CHAPTER 15
36.

CHEMICAL KINETICS

625

a. First, assume the reaction to be first order with respect to O. Hence a graph of ln[O]
versus t would be linear if the reaction is first order.
t (s)
0
10. 103
20. 103
30. 103

[O] (atoms/cm3)

ln[O]

5.0 109
1.9 109
6.8 108
2.5 108

22.33
21.37
20.34
19.34

Because the graph is linear, we can conclude the reaction is first order with respect to O.
b. The overall rate law is: Rate = k[NO2][O]
Because NO2 was in excess, its concentration is constant. Thus for this experiment, the
rate law is Rate: k[O], where k = k[NO2]. In a typical first-order plot, the slope equals
k. For this experiment, the slope equals k = k[NO2]. From the graph:
slope =

19.34 22.23
= 1.0 102 s1, k = slope = 1.0 102 s1
3
(30. 10 0) s

To determine k, the actual rate constant:

k = k[NO2], 1.0 102 s1 = k(1.0 1013 molecules/cm3)
k = 1.0 1011 cm3 molecules1 s1
37.

a. We check for first-order dependence by graphing ln[concentration] versus time for each
set of data. The rate dependence on NO is determined from the first set of data since the
ozone concentration is relatively large compared to the NO concentration, so it is
effectively constant.

626

CHAPTER 15
Time (ms)
0
100.
500.
700.
1000.

[NO] (molecules/cm3)
8

6.0 10
5.0 108
2.4 108
1.7 108
9.9 107

CHEMICAL KINETICS

ln[NO]
20.21
20.03
19.30
18.95
18.41

Because ln[NO] versus t is linear, the reaction is first order with respect to NO.
We follow the same procedure for ozone using the second set of data. The data and plot
are:
Time (ms)

[O3] (molecules/cm3)

ln[O3]

0
50.
100.
200.
300.

1.0 1010
8.4 109
7.0 109
4.9 109
3.4 109

23.03
22.85
22.67
22.31
21.95

The plot of ln[O3] versus t is linear. Hence the reaction is first order with respect to
ozone.
b. Rate = k[NO][O3] is the overall rate law.

CHAPTER 15

CHEMICAL KINETICS

627

c. For NO experiment, Rate = k[NO] and k = (slope from graph of ln[NO] versus t).
k = slope =

18.41 20.21
= 1.8 s1
(1000. 0) 103 s

For ozone experiment, Rate = k[O3] and k = (slope from ln[O3] versus t).
k = slope =

(21.95 23.03)
= 3.6 s1
(300. 0) 103 s

d. From NO experiment, Rate = k[NO][O3] = k[NO] where k = k[O3].

k = 1.8 s1 = k(1.0 1014 molecules/cm3), k = 1.8 1014 cm3 molecules1 s1
We can check this from the ozone data. Rate = k[O3] = k[NO][O3], where k = k[NO].
k = 3.6 s1 = k(2.0 1014 molecules/cm3), k = 1.8 1014 cm3 molecules1 s1
Both values of k agree.
38.

This problem differs in two ways from previous problems:

1. A product is measured instead of a reactant.
2. Only the volume of a gas is given and not the concentration.
We can find the initial concentration of C6H5N2Cl from the amount of N2 evolved after
infinite time when all the C6H5N2Cl has decomposed (assuming the reaction goes to
completion).
n=

PV 1.00 atm (58.3 103 L)

= 2.20 103 mol N2

0.08206L atm
RT
323 K
K mol

Because each mole of C6H5N2Cl that decomposes produces one mole of N2, the initial
concentration (t = 0) of C6H5N2Cl was:
2.20 103 mol
= 0.0550 M
40.0 103 L

We can similarly calculate the moles of N2 evolved at each point of the experiment, subtract
that from 2.20 103 mol to get the moles of C6H5N2Cl remaining, and then calculate
[C6H5N2Cl] at each time. We would then use these results to make the appropriate graph to
determine the order of the reaction. Because the rate constant is related to the slope of the
straight line, we would favor this approach to get a value for the rate constant.
There is a simpler way to check for the order of the reaction that saves doing a lot of math.
The quantity (V Vt ), where V = 58.3 mL N2 evolved and Vt = mL of N2 evolved at time
t, will be proportional to the moles of C6H5N2Cl remaining; (V Vt ) will also be

628

CHAPTER 15

CHEMICAL KINETICS

proportional to the concentration of C6H5N2Cl. Thus we can get the same information by
using (V Vt ) as our measure of [C6H5N2Cl]. If the reaction is first order, a graph of ln(V
Vt ) versus t would be linear. The data for such a graph are:
t (s)

Vt (mL)

0
6
9
14
22
30.

0
19.3
26.0
36.0
45.0
50.4

(V Vt )

ln(V Vt )

58.3
39.0
32.3
22.3
13.3
7.9

4.066
3.664
3.475
3.105
2.588
2.07

We can see from the graph that this plot is linear, so the reaction is first order. The differential rate law is d[C6H5N2Cl]/dt = Rate = k[C6H5N2Cl], and the integrated rate law is
ln[C6H5N2Cl] = kt + ln[C6H5N2Cl]0. From separate data, k was determined to be 6.9 102
s1.
39.

Because [V]0 > > [AV]0, the concentration of V is essentially constant in this experiment.
We have a pseudo-first-order reaction in AV:
Rate = k[AV][V] = k[AV], where k = k[V]0
The slope of the ln[AV] versus time plot is equal to k.
k = slope = 0.32 s1; k

40.

k
0.32 s 1

1.6 L mol-1 s-1

[V]0
0.20 mol/L

[A]
ln 2
0.6931
= kt; k =
ln

= 4.85 102 d1
t 1/ 2
14.3 d
[A]0
If [A]0 = 100.0, then after 95.0% completion, [A] = 5.0.

CHAPTER 15

CHEMICAL KINETICS

629

5.0
2
1
ln
= -4.85 10 d t, t = 62 days
100
.
0

41.

Comparing experiments 1 and 2, as the concentration of AB is doubled, the initial rate

increases by a factor of 4. The reaction is second order in AB.
Rate = k[AB]2, 3.20 103 mol L1 s 1 = k1(0.200 M)2
k = 8.00 102 L mol1 s 1 = kmean
For a second-order reaction:
1
1

t1/2 =
= 12.5 s
2
1 1
k[AB]0
8.00 10 L mol s 1.00 mol/ L

42.

Box a has 8 NO2 molecules. Box b has 4 NO2 molecules, and box c has 2 NO2 molecules.
Box b represents what is present after the first half-life of the reaction, and box c represents
what is present after the second half-life.
a. For first order kinetics, t1/2 = 0.693/k; the half-life for a first order reaction is concentration independent. Therefore, the time for box c, the time it takes to go through two
half-lives, will be 10 + 10 = 20 minutes.
b. For second order kinetics, t1/2 = 1/k[A]0; the half-life for a second order reaction is inversely proportional to the initial concentration. So if the first half-life is 10 minutes, the
second half-life will be 20 minutes. For a second order reaction, the time for box c will
be 10 + 20 = 30 minutes.
c. For zero order kinetics, t1/2 = [A]0/2k; the half-life for a zero order reaction is directly
related to the initial concentration. So if this reaction was zero order, then the second
half-life would decrease from 10 min to 5 min. The time for box c will be 10 + 5 = 15
minutes if the reaction is zero order.

43.

For a first-order reaction, the integrated rate law is ln([A]/[A]0) = kt. Solving for k:

0.250 mol/ L
= k 120. s, k = 0.0116 s1
ln
1.00 mol/ L

0.350 mol/ L
= 0.0116 s1 t, t = 150. s
ln
2.00 mol/ L
44.

Successive half-lives increase in time for a second-order reaction. Therefore, assume

reaction is second order in A.
t1/2 =

1
1
1
, k=
=
= 1.0 L mol1 min1
t1/ 2 [A]0
10.0 min(0.10 M )
k[A]0

630

CHAPTER 15

a.

CHEMICAL KINETICS

1
1
1.0 L
1

= kt +
80.0 min +
= 90. M 1, [A] = 1.1 102 M
[A]
[A]0
0.10 M
mol min

b. 30.0 min = 2 half-lives, so 25% of original A is remaining.

[A] = 0.25(0.10 M) = 0.025 M
45.

a. The integrated rate law for this zero-order reaction is [HI] = kt + [HI]0.
1.20 104 mol
25 min 60 s 0.250 mol
[HI] = kt + [HI]0, [HI] =

Ls
min
L

[HI] = 0.18 mol/L + 0.250 mol/L = 0.07 M

b. [HI] = 0 = kt + [HI]0, kt = [HI]0, t =
t=

46.

0.250 mol/L
1.20 104 mol L-1 s -1

[HI]0
k

= 2080 s = 34.7 min

a. The integrated rate law for a second order reaction is 1/[A] = kt + 1/[A]0, and the halflife expression is t1/2 = 1/k[A]0. We could use either to solve for t1/2. Using the integrated rate law:

1
1
1.11 L / mol 0.555 L
= k 2.00 s +
, k=
=
(0.900/2)mol/L
0.900 mol/ L
2.00 s
mol s
b.
47.

8.9 L / mol
1
1
= 0.555 L mol1 s1 t +
, t=
= 16 s
0.100 mol/ L
0.900 mol/ L
0.555 L mol1 s 1

a. When a reaction is 75.0% complete (25.0% of reactant remains), this represents two halflives (100% 50% 25%). The first-order half-life expression is t1/2 = (ln 2)/k. Because there is no concentration dependence for a first-order half-life, 320. s = two halflives, t1/2 = 320./2 = 160. s. This is both the first half-life, the second half-life, etc.
b. t1/2 =

ln 2
ln 2
ln 2
, k

= 4.33 103 s 1
k
t 1/ 2
160. s

At 90.0% complete, 10.0% of the original amount of the reactant remains, so [A] =
0.100[A]0.

[ A]
0.100[A]0
ln(0.100)
kt, ln
(4.33 103 s 1 )t, t
532 s
ln
[A]0
4.33 103 s 1
[A]0
48.

Because [B]0 >> [A]0, the B concentration is essentially constant during this experiment, so
rate = k[A] where k = k[B]2. For this experiment, the reaction is a pseudo-first-order
reaction in A.

CHAPTER 15

a.

CHEMICAL KINETICS

631

3.8 103 M
[A]
= k 8.0 s, k = 0.12 s 1
= kt, ln
ln
2

[A]0
1.0 10 M

For the reaction: k = k[B]2, k = 0.12 s1/(3.0 mol/L)2 = 1.3 102 L2 mol2 s1
b. t1/2 =

c.

ln 2
0.693

= 5.8 s
k'
0.12 s 1

[A]
[ A]
= 0.12 s 1 13.0 s,
= e0.12(13.0) = 0.21
ln
2
2

1
.
0

10
M
1
.
0

10

[A] = 2.1 103 M

d. [A] reacted = 0.010 M 0.0021 M = 0.008 M
[C] reacted = 0.008 M

2 mol C
= 0.016 M 0.02 M
1 mol A

[C]remaining = 2.0 M 0.02 M = 2.0 M; as expected, the concentration of C basically

remains constant during this experiment since [C]0 >> [A]0.
49.

a. Because [A]0 << [B]0 or [C]0, the B and C concentrations remain constant at 1.00 M for
this experiment. Thus, rate = k[A]2[B][C] = k[A]2 where k = k[B][C].
For this pseudo-second-order reaction:

1
1
1
1
,
= kt +
= k(3.00 min) +
5
[A]
[A]0 3.26 10 M
1.00 10 4 M
k = 6890 L mol1 min1 = 115 L mol1 s1
k = k[B][C], k =

k
115 L mol1 s 1
= 115 L3 mol3 s1
, k
[B][C]
(1.00 M )(1.00 M )

b. For this pseudo-second-order reaction:

1
1

= 87.0 s
1 1
k'[A]0
115 L mol s (1.00 104 mol/ L)
1
1
1
= kt +
= 115 L mol1 s1 600. s +
= 7.90 104 L/mol
4
[A]
[ A ]0
1.00 10 mol/ L
Rate = k[A]2, t1/2 =

c.

[A] = 1/7.90 104 L/mol = 1.27 105 mol/L

632

CHAPTER 15

CHEMICAL KINETICS

From the stoichiometry in the balanced reaction, 1 mol of B reacts with every 3 mol of A.
Amount A reacted = 1.00 104 M 1.27 105 M = 8.7 105 M
Amount B reacted = 8.7 105 mol/L

1 mol B
= 2.9 105 M
3 mol A

[B] = 1.00 M 2.9 105 M = 1.00 M

As we mentioned in part a, the concentration of B (and C) remain constant because the A
concentration is so small compared to the B (or C) concentration.
50.

The integrated rate law for each reaction is:

ln[A] = -4.50 104 s1(t) + ln[A]0 and ln[B] = 3.70 103 s1(t) + ln[B]0
Subtracting the second equation from the first equation (ln[A]0 = ln[B]0):
[A]
= 3.25 103(t)
ln[A] ln[B] = 4.50 104(t) + 3.70 103(t), ln
[
B
]

When [A] = 4.00 [B], ln(4.00) = 3.25 103(t), t = 427 s.

51.

The consecutive half-life values of 24 hours, then12 hours, show a direct relationship with
concentration; as the concentration decreases, the half-life decreases. Assuming the drug
reaction is either zero, first, or second order, only a zero order reaction shows this direct
relationship between half-life and concentration. Therefore, assume the reaction is zero order
in the drug.
t1/2

[A]0
[A]0
2.0 103 mol/L
, k

4.2 105 mol L-1 h-1

2k
2t1/2
2(24 h)

Reaction Mechanisms
52.

For a mechanism to be acceptable, the sum of the elementary steps must give the overall
balanced equation for the reaction, and the mechanism must give a rate law that agrees with
the experimentally determined rate law. A mechanism can never be proven absolutely. We
can only say it is possibly correct if it follows the two requirements just described.
Most reactions occur by a series of steps. If most reactions were one step, then all reactants
would appear in the overall rate law, and these orders would be the coefficients in the
balanced equation. This is not the case.

53.

In a unimolecular reaction, a single reactant molecule decomposes to products. In a

bimolecular reaction, two molecules collide to give products. The probability of the
simultaneous collision of three molecules with enough energy and the proper orientation is
very small, making termolecular steps very unlikely.

CHAPTER 15
54.

CHEMICAL KINETICS

633

a. An elementary step (reaction) is one for which the rate law can be written from the
molecularity, i.e., from coefficients in the balanced equation.
b. The molecularity is the number of species that must collide to produce the reaction
represented by an elementary step in a reaction mechanism.
c. The mechanism of a reaction is the series of proposed elementary reactions that may
occur to give the overall reaction. The sum of all the steps in the mechanism gives the
balanced chemical reaction.
d. An intermediate is a species that is neither a reactant nor a product but that is formed and
consumed in the reaction sequence.
e. The rate-determining step is the slowest elementary reaction in any given mechanism.

55.

For elementary reactions, the rate law can be written using the coefficients in the balanced
equation to determine the orders.
a. Rate = k[CH3NC]

b. Rate = k[O3][NO]

c. Rate = k[O3]

d. Rate = k[O3][O]

e. Rate = k
56.

C or Rate = kN, where N = the number of

14
6

14
6C

atoms (convention)

The rate law is Rate = k[NO]2[Cl2]. If we assume the first step is rate-determining, we would
expect the rate law to be Rate = k1[NO][Cl2]. This isn't correct. However, if we assume the
second step to be rate-determining, Rate = k2[NOCl2][NO]. To see if this agrees with
experiment, we must substitute for the intermediate NOCl2 concentration. Assuming a fastequilibrium first step (rate reverse = rate forward):
k
k-1[NOCl2] = k1[NO][Cl2], [NOCl2] = 1 [NO][Cl2]; substituting into the rate equation:
k 1

k 2 k1
k k
[NO]2[Cl2] = k[NO]2[Cl2] where k = 2 1
k 1
k 1
This is a possible mechanism with the second step the rate-determining step because the
derived rate law agrees with the experimentally determined rate law.
Rate =

57.

Let's determine the rate law for each mechanism. If the rate law derived from the mechanism
is the same as the experimental rate law, then the mechanism is possible (assuming the sum
of all the steps in the mechanism gives the overall balanced equation). When deriving rate
laws from a mechanism, we must substitute for all intermediate concentrations.
a. Rate = k1[NO][O2]; not possible
b. Rate = k2[NO3][NO] and k1[NO][O2] = k1[NO3] or [NO3] =
Rate =

k 2 k1
[NO]2[O2];
k 1

possible

k1
[NO][O2]
k 1

634

CHAPTER 15
c. Rate = k1[NO]2; not possible

CHEMICAL KINETICS

d. Rate = k2[N2O2] and [N2O2] =

Rate =

k1
[NO]2
k 1

k 2 k1
[NO]2 ; not possible
k 1

Only the mechanism in b is consistent, so only mechanism b is a possible mechanism for this
reaction.
58.

From experiment (Exercise 31), we know the rate law is Rate = k[H2O2]. A mechanism
consists of a series of elementary reactions where the rate law for each step can be
determined using the coefficients in the balanced equation for each respective step. For a
plausible mechanism, the rate law derived from a mechanism must agree with the rate law
determined from experiment. To derive the rate law from the mechanism, the rate of the
reaction is assumed to equal the rate of the slowest step in the mechanism.
This mechanism will agree with the experimentally determined rate law only if step 1 is the
slow step (called the rate-determining step). If step 1 is slow, then Rate = k[H2O]2 which
agrees with experiment.
Another important property of a mechanism is that the sum of all steps must give the overall
balanced equation. Summing all steps gives:
H2O2 2 OH
H2O2 + OH H2O + HO2
HO2 + OH H2O + O2

____________________________________

2 H2O2 2 H2O + O2
59.

A mechanism consists of a series of elementary reactions in which the rate law for each step
can be determined using the coefficients in the balanced equations. For a plausible mechanism, the rate law derived from a mechanism must agree with the rate law determined from
experiment. To derive the rate law from the mechanism, the rate of the reaction is assumed to
equal the rate of the slowest step in the mechanism.
Because step 1 is the rate determining step, the rate law for this mechanism is Rate =
k[C4H9Br]. To get the overall reaction, we sum all the individual steps of the mechanism.
Summing all steps gives:
C4H9Br C4H9+ + Br
C4H9+ + H2O C4H9OH2+
C4H9OH2+ + H2O C4H9OH + H3O+

___________________________________________________________

C4H9Br + 2 H2O C4H9OH + Br + H3O+

Intermediates in a mechanism are species that are neither reactants nor products but that are
formed and consumed during the reaction sequence in the mechanism. The intermediates for
this mechanism are C4H9+ and C4H9OH2+.

CHAPTER 15
60.

CHEMICAL KINETICS

635

a. This rate law occurs when the first step is assumed rate determining.
Rate = k1[Br2] = k[Br2]
b. This rate law occurs when the second step is assumed rate-determining and the first step
is a fast- equilibrium step.
Rate = k2[Br][H2]; from the fast-equilibrium first step (rate forward = rate reverse):
k1[Br2] = k-1[Br]2, [Br] = (k1/k-1)1/2[Br2]1/2
Substituting into the rate equation:
Rate = k2(k1/k-1)1/2[Br2]1/2[H2] = k[H2][Br2]1/2
c. From a, k = k1; from b, k = k2(k1/k-1)1/2.

61.

Rate = k2[I][HOCl]; from the fast-equilibrium first step:

k1[OCl] = k-1[HOCl][OH], [HOCl] =

Rate =
62.

k1[OCl ]
; substituting into the rate equation:
k 1 [OH ]

k 2 k1[I ][OCl ]
k[I ][OCl ]

k 1[OH ]
[OH ]

a. Rate = k3[COCl][Cl2]; from the fast-equilibrium reactions 1 and 2:

k
[COCl ]
k
2 , [COCl] = 2 [CO][Cl]
[Cl ][CO ] k 2
k 2
1/ 2

k
[Cl ]2
1 , [Cl ] 1 [Cl 2 ]
[Cl 2 ] k 1
k 1

1/ 2

k k
Thus [COCl] = 2 1
k 2 k 1

[CO][Cl2]1/2; Substituting into rate law:

1/ 2

k k
Rate = k 3 2 1
k 2 k 1

[CO][Cl2]3/2 = k[CO][Cl2]3/2

b. Cl and COCl are intermediates.

63.

Rate = k3[Br][H2BrO3+]; we must substitute for the intermediate concentration. Because

steps 1 and 2 are fast-equilibrium steps, rate forward reaction = rate reverse reaction.
k2[HBrO3][H+] = k-2[H2BrO3+]; k1[BrO3][H+] = k-1[HBrO3]

636

CHAPTER 15
[HBrO3] =

Rate =

64.

CHEMICAL KINETICS

k k
k
k1
[BrO3][H+]; [H2BrO3+] = 2 [HBrO3][H+] = 2 1 [BrO3][H+]2
k 2 k 1
k 2
k 1

k 3 k 2 k1
[Br][BrO3-][H+]2 = k[Br][BrO3][H+]2
k 2 k 1

Rate = k[BrO3][SO32][H+]; first step: SO32 + H+ HSO3

(fast)

The rate law contains BrO3, SO32 and H+. In order to incorporate all these ions into the rate
law, the rate-determining step could contain BrO3 and HSO3 (the intermediate produced in
the first step). A possible second step is:
BrO3 + HSO3 products

(slow)

A likely choice is: BrO3 + HSO3 SO42 + HBrO2

(slow)

Followed by: HBrO2 + SO32 HBrO + SO42 (fast);

HBrO + SO32 SO42 + H+ + Br (fast)
All species in this mechanism (HSO3, HBrO2, and HBrO) are known substances. This
mechanism also gives the correct experimentally determined rate law.
Rate = k2[BrO3] [HSO3]; assuming reaction one is a fast equilibrium step:
k1[SO32][H+] = k-1[HSO3], [HSO3] =
Rate =

65.

k1
[SO32][H+]
k 1

k 2 k1
[BrO3][SO32][H+] = k[BrO3][SO32][H+]
k 1

a. Rate =

[B*] =

d[E ]
d[B*]
= k2[B*]; assume
= 0, then k1[B]2 = k-1[B][B*] + k2[B*].
dt
dt

d[E ]
k1k 2 [B]2
k1[B]2
; the rate law is: Rate =
=
dt
k 1[B] k 2
k 1[B] k 2

b. When k2 << k-1[B], then Rate =

kk
d[E ]
k k [B]2
= 1 2
= 1 2 [B].
k 1
dt
k 1[B]

The reaction is first order when the rate of the second step is very slow (when k2 is very
small).
c. Collisions between B molecules only transfer energy from one B to another. This occurs
at a much faster rate than the decomposition of an energetic B molecule (B*).
66.

Rate =

d[O 3 ]
= k1[M][O3] + k2[O][O3] k-1[M][O2][O]; apply steady-state approx. to O:
dt

CHAPTER 15

CHEMICAL KINETICS

637

d[O]
= 0, so k1[M][O3] = k-1[M][O2][O] + k2[O][O3]
dt
k1[M][O3] k-1[M][O2][O] = k2[O][O3]
Substitute this expression into the rate law: Rate =

d[O 3 ]
= 2k2[O][O3]
dt

Rearranging the steady-state approximation for [O]: [O] =

Substituting into the rate law: Rate =

67.

k1[O3 ][M]
k 1[M][O 2 ] k 2 [O3 ]

d[O 3 ]
2 k 2 k 1[ O 3 ] 2 [ M ]
=
dt
k 1[M][O 2 ] k 2 [O3 ]

a. MoCl5

d[ NO 2 ]
b. Rate =
= k2[NO3][MoCl5]
dt

(Only the last step contains NO2.)

We use the steady-state assumption to substitute for the intermediate concentration in the
rate law. The steady-state approximation assumes that the concentration of an
intermediate remains constant; i.e., d[intermediate]/dt = 0. To apply the steady-state
assumption, we write rate laws for all steps where the intermediate is produced and
equate the sum of these rate laws to the sum of the rate laws where the intermediate is
consumed. Applying the steady-state approximation to MoCl5:

d[MoCl5 ]
= 0, so k1[MoCl62] = k-1[MoCl5][Cl] + k2[NO3][MoCl5]
dt

[MoCl5] =

k1[MoCl6 ]

k 1[Cl ] k 2 [ NO3 ]

; Rate =

k k [ NO ][MoCl6 ]
d[ NO 2 ]
= 1 2 3

dt
k 1[Cl ] k 2 [ NO3 ]

Temperature Dependence of Rate Constants and the Collision Model

68.

a. Thermodynamics is concerned with only the initial and final states of a reaction, and not
the pathway required to get from reactants to products. It is the kinetics of a reaction that
concentrates on the pathway and speed of a reaction. For these plots, the reaction with
the smallest activation energy will be fastest. The activation energy is the energy
reactants must have in order to overcome the energy barrier to convert to products. So
the fastest reaction is reaction 5 with the smallest activation. Reactions 1, 2, and 4 all
should have the same speed because they have the same activation energy. (This
assumes all other kinetic factors are the same.) Reaction 3 will be the slowest since it has
the largest activation energy.
b. If the products have lower energy than the reactants, then the reaction is exothermic.
Reaction 1, 2, 3, and 5 are exothermic. If the products have higher energy than the

638

CHAPTER 15

CHEMICAL KINETICS

reactants, then the reaction is endothermic. Only reaction 4 is endothermic. Note that it
is the thermodynamics of a reaction that dictates whether a reaction is exothermic or
endothermic. The kinetics plays no factor in these designations.
c. The thermodynamics of reaction determine potential energy change. In an exothermic
reaction, some of the potential energy stored in chemical bonds is converted to thermal
energy (heat is released as the potential energy decreases). The exothermic reaction with
the greatest loss of potential energy is the reaction with the largest energy difference ( E)
between reactants and products. Reactions 2 and 5 both have the same largest E values,
so reactions 2 and 5 have the greatest change in potential energy. Reactions 1 and 3 both
have the same smallest E values, so reactions 1 and 3 have the smallest change in
potential energy.
69.

Two reasons are:

1) The collision must involve enough energy to produce the reaction; i.e., the collision
energy must be equal to or exceed the activation energy.
2) The relative orientation of the reactants when they collide must allow formation of
any new bonds necessary to produce products.

70.

a. The larger the activation energy, the slower is the rate.

b. The higher the temperature, the more molecular collisions there are with sufficient energy
to convert to products, and the faster is the rate.
c. The greater the frequency of collisions, the greater are the opportunities for molecules to
react, and hence the greater is the rate.
b. For a reaction to occur, it is the reactive portion of each molecule that must be involved
in a collision. Only some of all the possible collisions have the correct orientation to
convert reactants to products.

71.

a. T2 > T1; as temperature increases, the distribution of collision energies shifts to the right.
That is, as temperature increases, there are fewer collision energies with small energies
and more collisions with large energies.
b. As temperature increases, more of the collisions have the required activation energy
necessary to convert reactants into products. Hence, the rate of the reaction increases
with increasing temperature.

72.

H3O+(aq) + OH(aq) 2 H2O(l) should have the faster rate. H3O+ and OH will be electrostatically attracted to each other; Ce4+ and Hg22+ will repel each other (so Ea is much larger).

73.

From the Arrhenius equation in logarithmic form (ln k = Ea/RT + ln A), a graph of ln k
versus. 1/T should yield a straight line with a slope equal to Ea/R and a y intercept equal to
ln A.
8.3145 J
a. Slope = Ea/R, Ea = 1.10 104 K
= 9.15 104 J/mol = 91.5 kJ/mol
K mol

CHAPTER 15

CHEMICAL KINETICS

639

b. The units for A are the same as the units for k (s1).
y intercept = ln A, A = e33.5 = 3.54 1014 s1
c. ln k = Ea/RT + ln A or k = A exp(Ea/RT)

9.15 104 J / mol

k = 3.54 1014 s1 exp
1
1
8.3145 J K mol 298 K

74.

k E 1
1
ln 2 a ; because the rate doubles, assume k2 = 2k1.
R T1 T2
k1
ln(2.00) =

75.

= 3.24 102 s1

1
Ea
1

, Ea = 5.3 104 J/mol = 53 kJ/mol

1
1
8.3145 J K mol 298 K 308 K

k = A exp(Ea/RT) or ln k =

Ea
+ ln A (the Arrhenius equation)
RT

k
E 1
1
(Assuming A is temperature independent.)
For two conditions: ln 2 a
R T1 T2
k1
Let k1 = 3.52 107 L mol1s1, T1 = 555 K; k2 = ?, T2 = 645 K; Ea = 186 103 J/mol

1.86 105 J / mol 1

k2
1

= 5.6
ln

7
1
1
3.52 10 8.3145 J K mol 555 K 645 K
k2
= e5.6 = 270, k2 = 270(3.52 10 7 ) = 9.5 105 L mol1 s1
3.52 107

76.

1.7 102 s 1
k E 1
1
Ea

ln 2 a ; ln
4 1
1
1
R T1 T2
k1
7.2 10 s 8.3145 J K mol

1
1

660. K 720. K

Ea = 2.1 105 J/mol

For k at 325oC (598 K):
5
1.7 102 s 1
2.1 10 J / mol
ln

8.3145 J K 1 mol1
k

1
1

, k = 1.3 105 s 1

598
K
720
.
K

For three half-lives, we go from 100% 50% 25% 12.5%. After three half-lives,
12.5% of the original amount of C2H5I remains. Partial pressures are directly related to gas
concentrations in mol/L:

PC2 H5I = 894 torr 0.125 = 112 torr after 3 half-lives

640

77.

CHAPTER 15
k E
ln 2 a
R
k1
ln(7.00) =

1
1
;
T1 T2

CHEMICAL KINETICS

k2
= 7.00, T1 = 295 K, Ea = 54.0 103 J/mol
k1

54.0 103 J / mol 1

1

,
1
1
8.3145 J K mol 295 K T2

1
1

= 3.00 104
295 K T2

1
= 3.09 103, T2 = 324 K = 51C
T2
78.

A graph of ln k versus 1/T should be linear with slope = Ea/R.

T (K)
338
318
298

Slope =

1/T (K1)

k (s1)

ln k

2.96 103
3.14 103
3.36 103

4.9 103
5.0 104
3.5 105

5.32
7.60
10.26

10.76 (5.85)
= 1.2 104 K = Ea/R
3
3
3.40 10 3.00 10

Ea = slope R = 1.2 104 K 8.3145 J K1 mol1, Ea = 1.0 105 J/mol = 1.0 102 kJ/mol
79.

The Arrhenius equation is k = Aexp(Ea/RT) or, in logarithmic form, ln k = Ea/RT + ln A.

Hence a graph of ln k versus 1/T should yield a straight line with a slope equal to Ea/R since
the logarithmic form of the Arrhenius equation is in the form of a straight-line equation, y =
mx + b. Note: We carried one extra significant figure in the following ln k values in order to
reduce round-off error.

CHAPTER 15

CHEMICAL KINETICS

641

T (K)

1/T (K1)

k (L mol1 s1)

195
230.
260.
298
369

5.13 103
4.35 103
3.85 103
3.36 103
2.71 103

1.08 109
2.95 109
5.42 109
12.0 109
35.5 109

ln k
20.80
21.81
22.41
23.21
24.29

Using a couple of points on the plot:

slope =

Ea
20.95 23.65
2.70

= 1.35 103 K =
3
3
3
R
5.00 10 3.00 10
2.00 10

Ea = 1.35 103 K 8.3145 J K1 mol1 = 1.12 104 J/mol = 11.2 kJ/mol

From the best straight line (by calculator): slope = 1.43 103 K and Ea = 11.9 kJ/mol
80.

When E is positive, the products are at a higher energy relative to reactants, and when E is
negative, the products are at a lower energy relative to reactants.

The reaction in part a will have the greatest rate because it has the smallest activation energy.

642
81.

CHAPTER 15

CHEMICAL KINETICS

In the following reaction profiles R = reactants, P = products, Ea = activation energy, E =

overall energy change for the reaction, and RC = reaction coordinate, which is the same as
reaction progress.

The second reaction profile represents a two-step reaction since an intermediate plateau
appears between the reactants and the products. This plateau (see I in plot) represents the
energy of the intermediate. The general reaction mechanism for this reaction is:
R I
I P
R P
In a mechanism, the rate of the slowest step determines the rate of the reaction. The
activation energy for the slowest step will be the largest energy barrier that the reaction must
overcome. Since the second hump in the diagram is at the highest energy, the second step
has the largest activation energy and will be the rate determining step (the slow step).
82.
125
kJ/mol

Ea, reverse

216
kJ/mol

P
RC

The activation energy for the reverse reaction is:

Ea,

reverse

= 216 kJ/mol + 125 kJ/mol = 341 kJ/mol

CHAPTER 15

CHEMICAL KINETICS

643

83.

The activation energy for the reverse reaction is ER in the diagram.

ER = 167 28 = 139 kJ/mol

Catalysis
84.

The slope of the ln k versus 1/T plot is equal to Ea/R. Because Ea for the catalyzed reaction
will be smaller than Ea for the uncatalyzed reaction, the slope of the catalyzed plot should be
less negative.

85.

a. W because it has a lower activation energy than the Os catalyst.

b. kw = Aw exp[Ea(W)/RT]; kuncat = Auncat exp[Ea(uncat)/RT]; assume Aw = Auncat.
kw
E a ( W) E a (uncat)
exp

k uncat
RT
RT

163,000 J / mol 335,000 J / mol

kw
= 1.41 1030
exp
1
1

k uncat
8.3145 J K mol 298 K

The W-catalyzed reaction is approximately 1030 times faster than the uncatalyzed
reaction.
c. Because [H2] is in the denominator of the rate law, the presence of H2 decreases the rate
of the reaction. For the decomposition to occur, NH3 molecules must be adsorbed on the
surface of the catalyst. If H2 is also adsorbed on the catalyst surface, then there are fewer
sites for NH3 molecules to be adsorbed, and the rate decreases.
86.

A catalyst increases the rate of a reaction by providing reactants with an alternate pathway
(mechanism) to convert to products. This alternate pathway has a lower activation energy,
thus increasing the rate of the reaction.
A heterogeneous catalyst is in a different phase from the reactants. The catalyst is usually a
solid, although a catalyst in a liquid phase can act as a heterogeneous catalyst for some gas-

644

CHAPTER 15

CHEMICAL KINETICS

phase reactions. Since the catalyzed reaction has a different mechanism than the uncatalyzed
reaction, the catalyzed reaction most likely will have a different rate law.
87.

a. The blue plot is the catalyzed pathway. The catalyzed pathway has the lower activation.
This is why the catalyzed pathway is faster.
b. E1 represents the activation energy for the uncatalyzed pathway.
c. E2 represents the energy difference between the reactants and products. Note that E2 is
the same for both the catalyzed and the uncatalyzed pathways. It is the activation energy
that is different for a catalyzed pathway versus an uncatalyzed pathway.
d. Because the products have a higher total energy as compared to reactants, this is an
endothermic reaction.

88.

a. NO is the catalyst. NO is present in the first step of the mechanism on the reactant side,
but it is not a reactant since it is regenerated in the second step and does not appear in the
overall balanced equation.
b. NO2 is an intermediate. Intermediates also never appear in the overall balanced equation.
In a mechanism, intermediates always appear first on the product side, whereas catalysts
always appear first on the reactant side.
c. k = A exp(Ea/RT);

k cat
A exp[E a (cat)/RT ]
E (un) E a (cat)

exp a

k un
A exp[E a (un)/RT ]
RT

0.85
k cat
2100 J / mol
= e = 2.3
exp
1
1

k un
8
.
3145
J
K
mol

298
K

The catalyzed reaction is approximately 2.3 times faster than the uncatalyzed reaction at
25C.
89.

The mechanism for the chlorine catalyzed destruction of ozone is:

O3 + Cl O2 + ClO (slow)
ClO + O O2 + Cl
(fast)
_________________________
O3 + O 2 O2
Because the chlorine atom-catalyzed reaction has a lower activation energy, the Cl-catalyzed
rate is faster. Hence Cl is a more effective catalyst. Using the activation energy, we can
estimate the efficiency that Cl atoms destroy ozone compared to NO molecules (see Exercise
15.88c).
(2100 11,900) J / mol
k Cl
E (Cl ) E a ( NO)
3.96
exp a

exp
At 25C:
= e = 52

k NO
RT
RT
(
8
.
3145

298
)
J
/
mol

At 25C, the Cl catalyzed reaction is roughly 52 times faster than the NO-catalyzed reaction,
assuming the frequency factor A is the same for each reaction.

CHAPTER 15
90.

CHEMICAL KINETICS

645

Assuming the catalyzed and uncatalyzed reactions have the same form and orders, and because concentrations are assumed equal, the rates will be equal when the k values are equal.
k = A exp(Ea/RT), kcat = kun when Ea,cat/RTcat = Ea,un/RTun
4.20 104 J / mol
7.00 104 J / mol
o

, Tun = 488 K = 215 C

1
1
1
1
8.3145 J K mol 293 K
8.3145 J K mol Tun

91.

Rate =

d[A]
k[A]x
dt

Assuming the catalyzed and uncatalyzed reaction have the same form and orders and because
concentrations are assumed equal, rate 1/t, where t = time.

Ratecat
ratecat
k
t
2400 yr
un
cat
and
Rateun
rateun
k un
t cat
t cat

A exp [E (cat)/RT ]
Ratecat
k
E a (cat) E a (un)
a
cat
= exp

RT
A exp [E (un)/RT ]
Rateun
k un

a
5.90 104 J / mol 1.84 105 J / mol
k cat
= 7.62 1010
exp
1
1

k un
8
.
3145
J
K
mol

600
.
K

t un
ratecat
k

cat ,
t cat
rateun
k un
92.

2400 yr
= 7.62 1010, tcat = 3.15 108 yr 1 s
t cat

The reaction at the surface of the catalyst follows the steps:

H H
D

C C

DCH2
H

CH2

D D

CH2DCH2D(g)

metal surface

Thus CH2DCH2D should be the product.

93.

At high [S], the enzyme is completely saturated with substrate. Once the enzyme is completely saturated, the rate of decomposition of ES can no longer increase, and the overall rate
remains constant.

646

CHAPTER 15

CHEMICAL KINETICS

Additional Exercises
94.

One experimental method to determine rate laws is the method of initial rates. Several
experiments are carried out using different initial concentrations of reactants, and the initial
rate is determined for each experiment. The results are then compared to see how the initial
rate depends on the initial concentrations. This allows the orders in the rate law to be
determined. The value of the rate constant is determined from the experiments once the
orders are known.
The second experimental method utilizes the fact that the integrated rate laws can be put in
the form of a straight-line equation. Concentration versus time data are collected for a
reactant as a reaction is run. This data are then manipulated and plotted to see which
manipulation gives a straight line. From the straight-line plot we get the order of the reactant,
and the slope of the line is mathematically related to k, the rate constant.

95.

The most common method to experimentally determine the differential rate law is the method
of initial rates. Once the differential rate law is determined experimentally, the integrated rate
law can be derived. However, sometimes it is more convenient and more accurate to collect
concentration versus time data for a reactant. When this is the case, then we do proof plots
to determine the integrated rate law. Once the integrated rate law is determined, the
differential rate law can be determined. Either experimental procedure allows determination
of both the integrated and the differential rate law; and which rate law is determined by
experiment and which is derived is usually decided by which data are easiest and most
accurately collected.

96.

Rate =

d[ES]
d[ P]
= k2[ES]; apply the steady-state approximation to ES,
= 0.
dt
dt

k1[E][S] = k-1[ES] + k2[ES]; [E]T = [E] + [ES], so [E] = [E]T [ES]

Substituting: k1[S]([E]T [ES]) = (k-1 + k2)[ES], k1[E]T[S] = (k-1 + k2 + k1[S]) [ES]
[ES] =

k1[E]T [S]
; substituting into the rate equation, Rate = k2[ES]:
k 1 k 2 k1[S]

Rate =

97.

Rate =

k1k 2 [E]T [S]

d[ P]
=
k 1 k 2 k1[S]
dt

d[Cl 2 ]
d[Cl ]
= k2[NO2Cl][Cl]; Assume
= 0, then:
dt
dt

k1[NO2Cl] = k-1[NO2][Cl] + k2[NO2Cl][Cl], [Cl] =

Rate =

98.

k1[ NO 2 Cl ]
k 1[ NO 2 ] k 2 [ NO 2 Cl ]

d[Cl 2 ]
k1k 2 [ NO 2 Cl ]2
=
dt
k 1[ NO 2 ] k 2 [ NO 2 Cl ]

k E 1
1
We need the value of k at 500. K; ln 2 a
R T1 T2
k1

CHAPTER 15

CHEMICAL KINETICS

k2
ln
12
1 1
2.3 10 L mol s

647

1.11 105 J / mol 1

1

8.3145 J K 1 mol1 273 K 500 K = 22.2

k2
= e22.2, k2 = 1.0 102 L mol1 s1
12
2.3 10
Because the decomposition reaction is an elementary reaction, the rate law can be written
using the coefficients in the balanced equation. For this reaction, Rate = k[NO 2]2. To solve
for the time, we must use the integrated rate law for second-order kinetics. The major
problem now is converting units so they match. Rearranging the ideal gas law gives n/V =
P/RT. Substituting P/RT for concentration units in the second-order integrated rate equation:

1
1
1
1
RT RT
RT P0 P

kt
,
kt
,

kt, t
[ NO 2 ]
[ NO 2 ]0 P / RT
P0 / RT
P
P0
k P P0
t=

99.

a.

(0.08206L atm K 1 mol1 )(500. K) 2.5 atm 1.5 atm

= 1.1 103 s

2
1 1
1.0 10 L mol s
1.5 atm 2.5 atm
T (K)
298.2
293.5
290.5

1/T (K1)

k (min1)

3.353 10
3.407 103
3.442 103

178
126
100.

ln k
5.182
4.836
4.605

A plot of ln k versus 1/T gives a straight line (plot not included). The equation for the
straight line is:
ln k = -6.48 103(1/T) + 26.9
For the ln k versus 1/T plot, slope = Ea/R = 6.48 103 K.
6.48 103 K = Ea/8.3145 J K1 mol1, Ea = 5.39 104 J/mol = 53.9 kJ/mol
b. ln k = 6.48 103(1/288.2) + 26.9 = 4.42, k = e4.42 = 83 min1
About 83 chirps per minute per insect. Note: We carried extra significant figures.
c. k gives the number of chirps per minute. The number or chirps in 15 s is k/4.
T (C)

T (F)

25.0
20.3
17.3
15.0

77.0
68.5
63.1
59.0

k (min1)
178
126
100.
83

42 + 0.80(k/4)
78 F
67F
62F
59F

The rule of thumb appears to be fairly accurate, almost 1F.

648
100.

CHAPTER 15

CHEMICAL KINETICS

a. If the interval between flashes is 16.3 s, then the rate is:

1 flash/16.3 s = 6.13 102 s1 = k
Interval

T
2

16.3 s
13.0 s

b.

k
1

6.13 10 s
7.69 102 s1

21.0C (294.2 K)
27.8C (301.0 K)

k E 1
1
ln 2 a ; solving: Ea = 2.5 104 J/mol = 25 kJ/mol
R T1 T2
k1

k
2.5 104 J / mol
1
1

= 0.30
ln

2
1
1
6.13 10 8.3145 J K mol 294.2 K 303.2 K
k = e0.30 6.13 102 = 8.3 102 s1; interval = 1/k = 12 seconds.

c.

Interval

21.0 C
27.8 C
30.0 C

16.3 s
13.0 s
12 s

54-2(Intervals)
21 C
28 C
30. C

This rule of thumb gives excellent agreement to two significant figures.

101.

k = A exp(Ea/RT);

A cat exp (E a , cat / RT )

E a , uncat
E
k cat

exp a , cat
k uncat
A uncat exp (E a , uncat / RT )
RT

E a , cat 5.00 104 J / mol

k cat

2.50 10 =
exp
8.3145 J K 1 mol1 310. K
k uncat

ln(2.50 103) 2.58 103 J/mol = Ea, cat + 5.00 104 J/mol

E a , cat = 5.00 104 J/mol 2.02 104 J/mol = 2.98 104 J/mol = 29.8 kJ/mol
102.

From 338 K data, a plot of ln[N2O5] versus t is linear (plot not included). The integrated rate
law is:
ln[N2O5] = (4.86 103)t 2.30; k = 4.86 103 s1 at 338 K
From 318 K data: ln[N2O5] = (4.98 104)t 2.30; k = 4.98 104 s1 at 318 K
4.86 103
k E 1
1
Ea
1
1

ln 2 a , ln

4
1
1
R T1 T2
k1
4.98 10 8.3145 J K mol 318 K 338 K

Ea = 1.0 105 J/mol = 1.0 102 kJ/mol

CHAPTER 15
103.

CHEMICAL KINETICS

649

Rate = k[DNA]x[CH3I]y; comparing the second and third experiments:

1.28 103
4

6.40 10

k (0.200) x (0.200) y
x

k (0.100) (0.200)

, 2.00 2.00x , x 1

Comparing the first and second experiments:

6.40 104
3.20 104

k (0.100)(0.200) y
k (0.100)(0.100) y

, 2.00 2.00 y , y 1

The rate law is Rate = k[DNA][CH3I].

Mechanism I is possible because the derived rate law from the mechanism (Rate =
k[DNA][CH3I]) agrees with the experimentally determined rate law. The derived rate law for
Mechanism II will equal the rate of the slowest step. This is step 1 in the mechanism giving a
derived rate law that is Rate = k[CH3I]. Because this rate law does not agree with experiment, Mechanism II would not be a possible mechanism for the reaction.
104.

a. From the plot, the activation energy for the reverse reaction = Ea, forward + (G) =
Ea, forward G (G is a negative number as shown in the diagram).

Ea
A exp

(E a G )
kf
Ea
RT
,

kf = A exp
and
k
=
A
exp

r
RT
(E a G o )
RT

k r
A exp

RT

If the A factors are equal:

E
G o
(E G o )
kf

exp a a
= exp

kr
RT
RT

RT

G o
k
; because K and f are both equal to the
From G = RT ln K, K = exp

kr
RT
same expression, K = kf/kr.

b. A catalyst will lower the activation energy for both the forward and reverse reactions (but
not change G). Therefore, a catalyst must increase the rate of both the forward and
reverse reactions.
105.

Carbon cannot form the fifth bond necessary for the transition state because of the small
atomic size of carbon and because carbon doesnt have low-energy d orbitals available to
expand the octet.

106.

The pressure of a gas is directly proportional to concentration. Therefore, we can use the
pressure data to solve the problem because d[SO2Cl2]/dt is proportional to dPSO2Cl2 /dt.
SO2Cl2(g) SO2(g) + Cl2(g); let P0 = initial partial pressure of SO2Cl2.

650

CHAPTER 15

CHEMICAL KINETICS

If x = PSO2 at some time, then x = PSO2 PCl2 and PSO2Cl2 P0 x.

Ptotal = PSO2Cl2 PSO2 PCl2 = P0 x + x + x, Ptotal = P0 + x, Ptotal P0 = x
At time = 0 hour, Ptotal = P0 = 4.93 atm. The data for other times are:
Time (hour)

0.00

1.00

2.00

4.00

8.00

16.00

Ptotal (atm)

4.93

5.60

6.34

7.33

8.56

9.52

PSO2Cl2 (atm)

4.93

4.26

3.52

2.53

1.30

0.34

ln PSO2Cl2

1.595

1.449

1.258

0.928

0.262 1.08

Because pressure of a gas is proportional to concentration, and because the ln PSO2Cl2

versus time plot is linear, the reaction is first order in SO2Cl2.
a. Slope of ln(P) versus t plot is 0.168 h1 = k, k = 0.168 h1 = 4.67 105 s1; because
concentration units dont appear in first-order rate constants, this value of k determined from
pressure data will be the same as if concentration data in molarity units were used.
b. t1/2 =

ln 2
0.6931
0.6931

= 4.13 h
k
k
0.168 h 1

c. After 0.500 h: ln PSO2Cl2 = kt + ln P0 = (0.168 h1)(0.500 h) + ln 4.93

ln PSO2Cl2 = 0.0840 + 1.595 = 1.511, PSO2Cl2 = e1.511 = 4.53 atm
PCl2 PSO2 = 4.93 atm 4.53 atm = 0.40 atm

CHAPTER 15

CHEMICAL KINETICS

651

Ptotal = PSO2Cl2 + PCl2 PSO2 = 4.53 + 0.40 + 0.40 = 5.33 atm

After 12.0 hours: ln PSO2Cl2 = (0.168 h1)(12.0 h) + ln(4.93) = 0.42

PSO2Cl2 = e0.42 = 0.66 atm, PSO2 = 4.93 0.66 = 4.27 atm, PCl2 = 4.27 atm
Ptotal = 0.66 + 4.27 + 4.27 = 9.20 atm

d.

PSO 2Cl2
ln
P0

= 0.168 h1(20.0 h) = 3.36,

PSO 2Cl2

P
0

3.36
= e
= 3.47 102

Fraction left = 0.0347 = 3.47%

107.

a.

t (s)
0
1000.
2000.
3000.

[C4H6] (M)

ln[C4H6]

1/[C4H6] (M 1)

0.01000
0.00629
0.00459
0.00361

4.6052
5.069
5.384
5.624

1.000 102
1.59 102
2.18 102
2.77 102

The plot of 1/[C4H6] versus t is linear, thus the reaction is second order in butadiene.
From the plot (not included), the integrated rate law is:

1
= (5.90 102 L mol1 s1)t + 100.0 M 1
[C 4 H 6 ]
b. When dimerization is 1.0% complete, 99.0% of C4H6 is left.
[C4H6] = 0.990(0.01000) = 0.00990 M;

1
= (5.90 102)t + 100.0
0.00990

t = 17.1 s 20 s
c. 2.0% complete, [C4H6] = 0.00980 M;

1
= (5.90 102)t + 100.0,
0.00980

t = 34.6 s 30 s
d.

1
1
= kt +
; [C4H6]0 = 0.0200 M; at t = t1/2, [C4H6] = 0.0100 M.
[C 4 H 6 ]
[C 4 H 6 ]0
1
1
= (5.90 102)t1/2 +
, t1/2 = 847 s = 850 s
0.0100
0.0200
Or: t1/2 =

1
1
=
= 847 s
2
1 1
k[A]0
(5.90 10 L mol s )(2.00 102 M )

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CHEMICAL KINETICS

c. From Exercise 15.32, k = 1.4 102 L mol1 s1 at 500. K. From this problem, k = 5.90
102 L mol1 s1 at 620. K.
5.90 102
k E 1
1
Ea
1
1

ln 2 a , ln

2
1
1
R T1 T2
k1
1.4 10 8.3145 J K mol 500. K 620. K

12 = Ea(3.9 104), Ea = 3.1 104 J/mol = 31 kJ/mol

108.

For second order kinetics:

1
1

= kt
[A] [A]0

1
1
1
1
,
= (0.250 L mol1 s1)t +
= (0.250)(180. s) +
[A]0 [A]
[A]
1.00 10 2 M

a.

1
= 145 M 1, [A] = 6.90 103 M
[A]

Amount of A that reacted = 0.0100 0.00690 = 0.0031 M

[A2] =

1
(3.1 103 M) = 1.6 103 M
2

b. After 3 minutes (180. s): [A] = 3.00[B], 6.90 103 M = 3.00[B], [B] = 2.30 103 M

1
1
1
1
1
1
= k2t +
;
= k2(180. s) +
, k2 = 2.19 L mol s
3
[ B]
[ B]0 2.30 10 M
2.50 10 2 M
c. [A]0 = 1.00 102 M; at t = t1/2, [A] = 5.00 103 M.

1
1
= (0.250)t +
, t1/2 = 4.00 102 s
3
5.00 10 M
1.00 10 2 M
Or we could have used the equation t1/2 = 1/k[A]0.
109.

Heating Time
(days)
0.00
1.00
2.00
3.00
6.00

Untreated

Deacidifying

Antioxidant

ln s

ln s

ln s

100.0
67.9
38.9
16.1
6.8

4.605
4.218
3.661
2.779
1.92

100.1
60.8
26.8

4.606
4.108
3.288

114.6
65.2
28.1
11.3

4.741
4.177
3.336
2.425

CHAPTER 15

CHEMICAL KINETICS

653

a. We used a calculator to fit the data by least squares. The results follow.
Untreated: ln s = (0.465)t + 4.55, k = 0.465 d1
Deacidifying agent: ln s = (0.659)t + 4.66, k = 0.659 d1
Antioxidant: ln s = (0.779)t + 4.84, k = 0.779 d1
b. No, the silk degrades more rapidly with the additives since k increases.
c. t1/2 = (ln 2)/k; untreated: t1/2 = 1.49 day; deacidifying agent: t1/2 = 1.05 day;
antioxidant: t1/2 = 0.890 day.
110.

a. Let P0 = initial partial pressure of C2H5OH = 250. torr. If x torr of C2H5OH reacts, then at
anytime:
PC2 H5OH = 250. x, PC2 H 4 = PH 2O = x; Ptotal = 250. x + x + x = 250. + x

Therefore, PC2 H5OH at any time can be calculated from the data by determining x (= Ptotal
250.) and then subtracting from 250. torr. Using the PC2 H5OH data, a plot of PC2 H5OH
versus t is linear (plot not included). The reaction is zero order in PC2 H5OH . One could
also use the Ptotal versus t data since Ptotal increases at the same rate that PC2 H5OH
decreases. Note: The ln P versus t plot is also linear. The reaction hasn't been followed
for enough time for curvature to be seen. However, since PC2 H5OH decreases at steady
increments of 15 torr for every 10. s of reaction, then we can conclude that the reaction is
zero order in C2H5OH.
15
From the data, the integrated rate equation involving Ptotal is Ptotal =
t + 250.
10
15
At t = 80. s: Ptotal =
(80.) + 250. = 370 torr
10

654

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CHEMICAL KINETICS

b. Slope = k = 15 torr/10. s = 1.5 torr/s (from PC2 H5OH versus t plot), k = 1.5 torr/s; the
Ptotal versus t plot would give the same rate constant since Ptotal increases at the same rate
that PC2 H5OH decreases.
c. Zero order
d. Ptotal =

15
(300.) + 250. = 7.0 102 torr; this is an impossible answer!
10

Because only 250. torr of C2H5OH are present initially, the maximum pressure can only
be 500. torr when all of the C2H5OH is consumed, i.e., Ptotal PC2H4 PH2O = 250. + 250.
= 500. torr. Therefore, at 300. s, Ptotal = 500. torr.

Challenge Problems
111.

a. Rate = (k1 + k2[H+])[I]m[H2O2]n

In all the experiments the concentration of H2O2 is small compared to the concentrations
of I and H+. Therefore, the concentrations of I and H+ are effectively constant, and the
rate law reduces to:
Rate = kobs[H2O2]n, where kobs = (k1 + k2[H+])[I]m
Because all plots of ln[H2O2] versus time are linear, the reaction is first order with respect
to H2O2 (n = 1). The slopes of the ln[H2O2] versus time plots equal kobs, which equals
(k1 + k2[H+])[I]m. To determine the order of I, compare the slopes of two experiments
in which I changes and H+ is constant. Comparing the first two experiments:
slope (exp. 2)
0.360 [k1 k 2 (0.0400 M )] (0.3000 M ) m

slope (exp. 1)
0.120 [k1 k 2 (0.0400 M )] (0.1000 M ) m

0.3000 M
3.00 =
0.1000 M

= (3.000)m, m = 1

The reaction is also first order with respect to I-.

b. The slope equation has two unknowns, k1 and k2. To solve for k1 and k2, we must have
two equations. We need to take one of the first set of three experiments and one of the
second set of three experiments to generate the two equations in k1 and k2.
Experiment 1: slope = (k1 + k2[H+])[I]
0.120 min1 = [k1 + k2(0.0400 M)](0.1000 M) or 1.20 = k1 + k2(0.0400)
Experiment 4:
0.0760 min-1 = [k1 + k2(0.0200 M)](0.0750 M) or 1.01 = k1 + k2(0.0200)

CHAPTER 15

CHEMICAL KINETICS

655

Subtracting 4 from 1:
1.20 = k1 + k2(0.0400)
1.01 = k1 k2(0.0200)
____________________
0.19 =
k2(0.0200), k2 = 9.5 L2 mol2 min1
1.20 = k1 + 9.5(0.0400), k1 = 0.82 L mol1 min1
c. There are two pathways, one involving H+ with rate = k2[H+][I][H2O2] and another not
involving H+ with rate = k1[I][H2O2]. The overall rate of reaction depends on which of
these two pathways dominates, and this depends on the H+ concentration.
112.

a. Rate = k2[A][M]; assuming a fast equilibrium first step:

k1[A][B] = k-1[M], [M] =
Rate =

k1[A][B]
k 1

k 2 k1
[A]2 [B]
k 1

b. Rate = k2[A][M]; applying the steady-state approximation to M:

k1[A][B] = k-1[M] + k2[A][M], [M] =

Rate =

k1[A][B]
k 1 k 2 [A]

k 2 k1[A]2 [B]
k 1 k 2 [A]

c. If [A] << [B], the rate law from part b reduces to

as in part a.
113.

k 2 k1
[A]2[B]. This is the same rate law
k 1

a. Rate = k[CH3X]x[Y]y; for experiment 1, [Y] is in large excess, so its concentration will
be constant. Rate = k[CH3X]x, where k = k(3.0 M)y.
A plot (not included) of ln[CH3X] versus t is linear (x = 1). The integrated rate law is:
ln[CH3X] = (0.93)t 3.99; k = 0.93 h1
For experiment 2, [Y] is again constant, with Rate = k [CH3X]x, where k = k(4.5 M)y.
The natural log plot is linear again with an integrated rate law:
ln[CH3X] = (0.93)t 5.40; k = 0.93 h1
Dividing the rate-constant values:

k'
0.93 k (3.0) y
, 1.0 = (0.67)y, y = 0

k" 0.93 k (4.5) y

656

CHAPTER 15

CHEMICAL KINETICS

Reaction is first order in CH3X and zero order in Y. The overall rate law is:
Rate = k[CH3X], where k = 0.93 h1 at 25C
b. t1/2 = (ln 2)/k = 0.6931/(7.88 108 h1) = 8.80 1010 hour
c.

7.88 108
k E 1
1
1
Ea
1

ln 2 a , ln

1
1

R T1 T2
k1
0.93 8.3145 J K mol 298 K 358 K

Ea = 3.0 105 J/mol = 3.0 102 kJ/mol

d. From part a, the reaction is first order in CH3X and zero order in Y. From part c, the activation energy is close to the C-X bond energy. A plausible mechanism that explains the
results in parts a and c is:
CH3X CH3 + X

(slow)

CH3 + Y CH3Y

(fast)

Note: This is a possible mechanism because the derived rate law is the same as the
experimental rate law (and the sum of the steps gives the overall balanced equation).
114.

k E 1
rate2
k
1
2 40.0 :
ln 2 a ; assuming
k
R
T
T
rate
k1
2
1
1
1
ln(40.0) =

1
Ea
1

, Ea = 1.55 105 J/mol = 155 kJ/mol

1
1
8.3145 J K mol 308 K 328 K
(carrying an extra sig. fig.)

Note that the activation energy is close to the F2 bond energy. Therefore, the ratedetermining step probably involves breaking the F2 bond.
H2(g) + F2(g) 2 HF(g); for every two moles of HF produced, only one mole of the
reactant is used up. Therefore, to convert the data to Preactant versus time, Preactant = 1.00 atm
(1/2)PHF.
Preactant

Time

1.000 atm
0.850 atm
0.700 atm
0.550 atm
0.400 atm
0.250 atm

0 min
30.0 min
65.8 min
110.4 min
169.1 min
255.9 min

CHAPTER 15

CHEMICAL KINETICS

657

The plot of ln Preactant versus time (plot not included) is linear with negative slope, so the
reaction is first order with respect to the limiting reagent.
For the reactant in excess, because the values of the rate constant are the same for both
experiments, one can conclude that the reaction is zero order in the excess reactant.
a. For a three-step reaction with the first step limiting, the energy-level diagram could be:

E
R
P
Reaction coordinate

Note that the heights of the second and third humps must be lower than the first step activation energy. However, the height of the third hump could be higher than the second
hump. One cannot determine this absolutely from the information in the problem.
b. We know the reaction has a slow first step, and the calculated activation energy indicates
that the rate-determining step involves breaking the F2 bond. The reaction is also first
order in one of the reactants and zero order in the other reactant. All this points to F2
being the limiting reagent. The reaction is first order in F2, and the rate-determining step
in the mechanism is F2 2 F. Possible second and third steps to complete the
mechanism follow.
F2 2 F
F + H2 HF + H
H + F HF

slow
fast
fast

_____________________________________

F2 + H2 2 HF
c. F2 was the limiting reactant.
115.

d[A]
= k[A]3,
dt
n
x dx

[ A ]t

[ A ]0

d[A]
k dt
[A]3
0

1
xn 1
; so:
n 1
2[A]2

[ A ]t
[ A ]0

kt,

1
1

kt
2
2[A]t
2[A]02

658

CHAPTER 15

CHEMICAL KINETICS

For the half-life equation, [A]t = 1/2[A]0:

1
1

2 [A]0
2

3
2[A]02

4
1
1

kt1/ 2
kt1/ 2 ,
2
2
2[A]0
2[A]02
2[A]0

kt1/ 2 , t1/2 =

3
2[A]02 k

The first half-life is t1/2 = 40. s and corresponds to going from [A]0 to 1/2[A]0. The second
half-life corresponds to going from 1/2 [A]0 to 1/4 [A]0 .

6
3
3
; second half-life =
=
2
2
[A]02 k
2[A]0 k
1

2 [A]0 k
2

3
2[A]02 k
First half life

= 3/12 = 1/4
6
Second half life
[A]02 k

First half-life =

Because the first half-life is 40. s, the second half-life will be four times this, or 160 s.
116.

a. [B] >> [A], so [B] can be considered constant over the experiments. This gives us a
pseudo-order rate-law equation.
b. Note that in each case the half-life doubles as time increases (in experiment 1, the first
half-life is 40. s, the second half-life is 80. s; in experiment 2, the first half- life is 20. s,
the second half-life is 40. s). This occurs only for a second-order reaction, so the reaction
is second order in [A]. Between expt. 1 and expt. 2, we double [B] and the reaction rate
doubles, thus it is first order in [B]. The overall rate-law equation is rate = k[A]2[B].
Using t1/2 =

1
1
, we get k =
= 0.25 L mol1 s1; but this is actually
2
k[A]0
(40.)(10.0 10 )

k where Rate = k[A]2 and k = k[B].

k=
c. i.

k
0.25
= 0.050 L2 mol2 s1

[B]
5.0

This mechanism gives the wrong stoichiometry, so it cant be correct.

CHAPTER 15

CHEMICAL KINETICS

659

ii. Rate = k[E][A]

k 1 [A][B]

k k1

[A]2 [B]
k 1
k 1
This mechanism gives the correct stoichiometry and gives the correct rate law when
it is derived from the mechanism. This is a possible mechanism for this reaction.

k1[A][B] = k-1[E]; [E] =

; Rate =

iii. Rate = k[A]2

This mechanism gives the wrong derived rate law, so it cant be correct. Only
mechanism ii is possible.
117.

Rate = k[A]x[B]y[C]z; during the course of experiment 1, [A] and [C] are essentially constant,
and Rate = k[B]y , where k = k[A]0x [C]0z .
[B] (M)
1.0 103
2.7 104
1.6 104
1.1 104
8.5 105
6.9 105
5.8 105

time (s)

ln[B]

1/[B] (M 1)

0
1.0 105
2.0 105
3.0 105
4.0 105
5.0 105
6.0 105

6.91
8.22
8.74
9.12
9.37
9.58
9.76

1.0 103
3.7 103
6.3 103
9.1 103
12 103
14 103
17 103

A plot of 1/[B] versus t is linear (plot not included). The reaction is second order in B, and
the integrated rate equation is:
1/[B] = (2.7 102 L mol 1 s1)t + 1.0 103 M 1; k = 2.7 102 L mol1 s1
For experiment 2, [B] and [C] are essentially constant, and Rate = k[A]x, where k =
k[B]0y [C]0z k[B]02 [C]0z .
[A] (M)

time (s)

ln[A]

1/[A] (M 1)

1.0 102
8.9 103
7.1 103
5.5 103
3.8 103
2.9 103
2.0 103

0
1.0
3.0
5.0
8.0
10.0
13.0

4.61
4.72
4.95
5.20
5.57
5.84
6.21

1.0 102
110
140
180
260
340
5.0 102

A plot of ln[A] versus t is linear. The reaction is first order in A, and the integrated rate law
is:
ln[A] = (0.123 s1)t 4.61; k = 0.123 s1

660

CHAPTER 15

CHEMICAL KINETICS

Note: We will carry an extra significant figure in k.

Experiment 3: [A] and [B] are constant; Rate = k[C]z
The plot of [C] versus t is linear. Thus z = 0.
The overall rate law is Rate = k[A][B]2.
From experiment 1 (to determine k):
k = 2.7 102 L mol1 s1 = k[A]0x [C]0z = k[A]o = k(2.0 M), k = 1.4 102 L2 mol2 s1
From experiment 2: k = 0.123 s1 = k[B]02 , k =

0.123 s 1
= 1.4 102 L2 mol2 s1
2
(3.0 M )

Thus Rate = k[A][B]2 and k = 1.4 102 L2 mol2 s1.

118.

First, we need to convert the data from total pressure versus time to pressure of O2 versus
time.

3 O2(g)
Before
Change
After

1.000 atm
3x
1.000 3x

2 O3(g)
0
+2x
2x

Ptotal = 1.000 3x + 2x = 1.000 x ; we use this equation to convert the data.

For example, at t = 46.89 s, where Ptotal = 0.9500 atm, 1.000 x = 0.9500
x = 0.0500 (carrying extra sig. fig.)
So PO 2 = 1.000 3(0.0500) = 0.850 atm. The following table contains the other values.
Time
0s
46.89 s
98.82 s
137.9 s
200.0 s
286.9 s
337.9 s
511.3 s

PO 2

1.000 atm
0.850 atm
0.710 atm
0.620 atm
0.500 atm
0.370 atm
0.310 atm
0.170 atm

A graph of ln PO 2 versus time gives a straight line (plot not included) with a slope of
0.00347.

CHAPTER 15

CHEMICAL KINETICS

a. Rate = k[O2] or Rate = k(PO 2 )

661
b. k = 0.00347 s1

c. When Ptotal = 0.7133 atm: 1.000 x = 0.7133, x = 0.2867 atm (extra sig. fig.)
PO 2 = 1.000 atm 3(0.2867 atm) = 0.140 atm

ln(P/P0) = kt, ln(0.140/1.000) = (0.00347 s1)t, t = 567 s

119.

Rate =

d[ N 2 O5 ]
= k1[M][N2O5] k-1[NO3][NO2][M]
dt

Assume d[NO3]/dt = 0, so k1[N2O5][M] = k-1[NO3][NO2][M] + k2[NO3][NO2] +

k3[NO3][NO].
[NO3] =

k1[ N 2 O5 ][M]
k 1[ NO 2 ][M] k 2 [ NO 2 ] k 3 [ NO]

Assume

k
d[ NO]
= 0, so k2[NO3][NO2] = k3[NO3][NO], [NO] = 2 [NO2].
k3
dt
k1[ N 2 O5 ][M]

Substituting: [NO3] =

k 1[ NO 2 ][M] k 2 [ NO 2 ]

k 2k3
[ NO 2 ]
k3

k1[ N 2 O5 ][M]
[ NO 2 ](k 1[M] 2k 2 )

Solving for the rate law:

Rate =

d[ N 2 O5 ]
k k [ NO 2 ][N 2 O5 ][M]2
= k1[N2O5][M] 1 1
= k1[N2O5][M]
dt
[ NO 2 ](k 1[M] 2k 2 )

Rate =

d[ N 2 O5 ]
k 1k1[M]
[N2O5][M]; simplifying:
= k1
k 1[M] 2k 2
dt

Rate =

2k1k 2 [M][N 2 O5 ]
d[ N 2 O5 ]
=
k 1[M] 2k 2
dt

k 1k1[M]2 [ N 2 O5 ]
k 1[M] 2k 2

662

CHAPTER 15

CHEMICAL KINETICS

Marathon Problem
120.

a. Rate = k[A]x[B]y; looking at the data in experiment 2, notice that the concentration of
A is cut in half every 10. s. Only first-order reactions have a half-life that is independent
of concentration. The reaction is first order in A. In the data for experiment 1, notice that
the half-life is 40. s. This indicates that in going from experiment 1 to experiment 2,
where the B concentration doubled, the rate of reaction increased by a factor of four. This
tells us that the reaction is second order in B.
Rate = k[A][B]2
b. This reaction is pseudo-first order in [A], because the concentration of B is so large, it is
basically constant.
Rate = k[B]2[A] = k[A], where k = k[B]2.
For a first-order reaction, the integrated rate law is:

[A]
ln
[A]0

= kt

Use any set of data you want to calculate k. For example, in experiment 1 from 0 to 20.
s, the concentration of A decreased from 0.010 M to 0.0071 M.

0.0071
ln
= k(20. s), k = 1.7 102 s 1
0.010
k = k[B]2, 1.7 102 s 1 = k(10.0 mol/L)2
k = 1.7 104 L2 mol2 s 1
We get similar values for k using other data from either experiment 1 or experiment 2.
c.

[A]
ln
0.010 M

= kt = (1.7 102 L2 mol2 s 1 ) 30. s, [A] = 6.0 103 M

d. All the mechanisms add up to give the correct overall balanced reaction. Now we need to
derive the rate law for each mechanism to see if the derived rate law agrees with the
experimentally determined rate late (Rate = k[A][B]2).

CHAPTER 15

CHEMICAL KINETICS

663

Mechanism i
Rate = k2[B2][A]; from the fast equilibrium first step:
k1[B]2 = k1[B2], [B2] =
Rate =

k1
[B]2
k 1

k 2 k1
[B]2 [A]; this agrees with experiment.
k 1

Mechanism ii
Rate = k1[A][B]; mechanism ii is not a possible mechanism for this reaction because
the derived rate law does not agree with experiment.
Mechanism iii
Rate = k2[A][B]2; this agrees with experiment.
Both mechanisms i and iii are possible mechanisms for this reaction. However, mechanism iii depends on a termolecular step in order to occur, and termolecular steps are very
rare. Therefore, mechanism i would be the best (most likely) mechanism of the three
mechanisms listed.