Chapter 14

Practice Exercises
14.1

Using the coefficients of the reaction, we find that the ratio of iodide production to sulfite disappearance in
1:3, and the ratio of sulfate production to sulfite disappearance is 3:3.
1 mol I
Rate of production of I = (2.4 104 mol L1 s1)
= 8.0 105 mol L1 s1
3 mol SO 2
3

3 mol SO 2
4
Rate of production of SO42 = (2.4 104 mol L1 s1)
= 2.4 104 mol L1 s1
3 mol SO 2
3

14.2

From the coefficients in the balanced equation we see that, for every two moles of SO2 that is produced, 2
moles of H2S are consumed, three moles of O2 are consumed, and two moles of H2O are produced.
3 mol O 2 0.30 mol
1 1
Rate of disappearance of O2 =

= 0.45 mol L s
2
mol
SO
L
s

14.3

14.4

2 mol H 2S 0.30 mol

1 1
Rate of disappearance of H2S =

= 0.30 mol L s
2
mol
SO
L
s

The rate of the reaction at 2.00 minutes (120 s) is equal to the slope of the tangent to the curve at 120 s.
After drawing the tangent, the slope can be estimated as follows:
1
1
[ HI ]

HI
final [ ]initial 0 mol L 0.075 mol L = 2.1 104 mol L1 s1
ratewith respect to HI =
=

t final t initail
360 s 0 s

The rate of the reaction after 250 seconds have elapsed is equal to the slope of the tangent to the curve at
250 seconds. First draw the tangent, and then estimate its slope as follows, where A is taken to represent
one point on the tangent, and B is taken to represent another point on the tangent:
A (mol/L) B (mol/L)
change in concentration
rate =
=
A
(s)

B
(s)
change in time

A value near 1 104 mol L1 s1 is correct.

14.5

14.6

(a)

Using the rate law:

Rate = k[NO]2[H2]
Substitute in the concentration and the rate and solve for the rate constant:
7.86 103 mol L1 s1 = k(2 106 mol L1)2(2 106 mol L1)
k = 9.8 1014 L2 mol2 s1
(b)
The units can be derived from the equation:
mol L1 s1 = k(mol L1)2(mol L1)
mol L1 s1 = k (mol3 L3)
mol L1 s 1
= L2 mol2 s1
k=
3 3
mol L
(a) First use the given data in the rate law:
Rate = k[HI]2
2.5 104 mol L1 s1 = k[5.58 102 mol/L]2
k = 8.0 102 L mol1 s1
(b) L mol1 s1

14.7

The order of the reaction with respect to a given substance is the exponent to which that substance is raised
in the rate law:
order of the reaction with respect to [BrO3] = 1
order of the reaction with respect to [SO32] = 1
287

Chapter 14
overall order of the reaction = 1 + 1 = 2
14.8

The rate law is second order with respect to Cl2 and first order with respect to NO. Therefore the exponent
for the Cl2 is two and the exponent for NO is one:
Rate = k[Cl2]2[NO]

14.9

Since the rate law is Rate = k[Br2] the order with respect to Br2 is 1 and the order with respect to HCO2H is
zero. The overall order of the reaction is 1.

14.10

In each case, k = rate/[A][B]2, and the units of k are L2 mol2 s1.

Each calculation is performed as follows, using the second data set as the example:
0.40 mol L1 s 1
k=
= 2.0 102 L2 mol2 s 1
2
0.20 mol L1 0.10 mol L1

)(

Each of the other data sets also gives the same value:
k = 2.0 102 L2 mol2 s1.
14.11

The rate law is: rate = k[A][B]2

(a)
If the concentration of B is tripled, then the rate will increase ninefold,
rate = k[A][3B]2
rate = 9k[A][B]2
(b)
If the concentration of A is tripled, then the rate will increase threefold,
rate = k[3A][B]2
rate = 3k[A][B]2
(c)
If the concentration of A is tripled, and the concentration of B is halved, then the rate will decrease
to three fourths, or seventy five percent
1
rate = k[3A][ B]2
2
3
rate = k[A][B]2
4

rate = k [ NO] [ H 2 ]
n

14.12
(a)

To find the rate law, take two reactions in which the concentration of one of the reactants is held
constant, compare the two reactions and solve for the exponent:
For NO, use the first two reactions:

k [ NO]1 [ H 2 ]1
n

k [ NO]2

[ H2 ]2

rate1
rate2

k 0.40 104 mol L1 0.30 104 mol L1

k 0.80 104 mol L1 0.30 104 mol L1

0.40 104 mol L1

8
1 1

= 1.0 10 mol L s
n
4.0 108 mol L1 s 1
0.80 104 mol L1

1
1
n=2
2 = 4

For H2, use the second two reactions:

288

1.0 108 mol L1 s 1

4.0 108 mol L1 s 1

Chapter 14

k [ NO]2

[ H2 ]2m
n
m
k [ NO]3 [ H 2 ]3
n

rate2
rate3

k 0.80 104 mol L1 0.30 104 mol L1

k 0.80 104 mol L1 0.60 104 mol L1

0.30 104 mol L1

0.60 104 mol L1

1
2

1
2

4.0 108 mol L1 s 1

8.0 108 mol L1 s 1

4.0 108 mol L1 s 1

8.0 108 mol L1 s 1

m=1

rate = k [ NO] [ H 2 ]
2

(b)

To find the value for the rate constant, choose one of the reactions and use the values for the
concentrations and rate and solve for the rate constant:

rate = k [ NO] [ H 2 ]
2

1
2

(c)

1.0 108 mol L1 s1 = k 0.40 104 mol L1 0.30 104 mol L1

k = 2.1 105 L2 mol2 s1

The units for the rate constant can be determined from the rate law and cancelling the units:
2

mol L1 s1 = k mol L1 mol L1

mol L1 s 1

= L2 mol2 s1
k=
2
1
mol L1 mol L1

14.13

(a)

The rate law will likely take the form rate = k[A]n, where n is the order of the reaction with respect
to A.
rate2 k [ A ]2
k(0.36) n 2.22x104
=
=
=
rate1 k [ A ] n k(0.10) n 6.17x105
1
n

3.6n = 3.6

Therefore, n = 1

rate3 k [ A ]3
k(0.58)n 3.58x104
=
=
=
rate1 k [ A ] n k(0.10)n 6.17x105
1
n

5.8n = 5.8

Therefore, n = 1

rate3 k [ A ]3
k(0.58)n 3.58x104
=
=
=
rate1 k [ A ] n k(0.36)n 2.22x104
2
n

1.6n = 1.6

Therefore, n = 1

289

Chapter 14

(b)

rate = k[sucrose]
(6.17 104 mol L1 s1) = k(0.10 mol L1)
k = 6.17 104 s1
The rate constant is 6.17 104 s1
The other two data sets give the same value for k.
This reaction is actually a pseudo-first order reaction. We cannot determine whether H+ or water
are part of the rate expression. The experiment did not vary the acid concentration so we do not
know how the rate might change with respect to acid and since it is an aqueous reaction we cannot
determine the effect changing waters concentration would have on the rate as the concentration of
water is so large that its concetration would not change significantly during the reaction.

14.14

(a)

The rate law will likely take the form rate = k[A]n[B]n', where n and n' are the order of the reaction
with respect to A and B, respectively.
rate1 k [ A ]2 [ B]2
k(0.40)n (0.30)m 1.00x104
x
=
=
=
rate2 k [ A ] n [ B] m k(0.60)n (0.30) m 2.25x104
3
3
n

0.6667n = 0.44444
n=2
On comparing the second and third lines of data, neither the concentration of A nor the
concentration of B are held constant, but we know that the reaction is secondorder with respect to
A and we can solve the two equations for the order with respect to B:
rate2 k [ A ]2 [ B]2
=
rate3 k [ A ] 2 [ B] m
3
3
2

2.25 104 mol L1 s 1

1.60 103 mol L1 s 1
2.25 104
1.60 103

( 0.30 M )m
=
2
m
k ( 0.80 M ) ( 0.60 M )
2

( 0.36 )( 0.30 M )m
( 0.64 )( 0.60 M )m

1
0.141 = 0.563
2
1
0.25 =
2

k ( 0.60 M )

1 1
=
4 2
m=2
Rate = k[A]2[B]2

(b)

For the rate constant, use one of the experiments and insert the values and solve for k
Rate = k[A]2[B]2
1.00 104 mol L1 s1 = k[0.40 mol L1]2[0.30 mol L1]2
k = 6.9 103 L3 mol3 s1

(c)

The units for the rate constant are

290

Chapter 14
mol L1 s 1

( mol L ) ( mol L )
2

(d)
14.15

= L3 mol3 s1

The overall order for this reaction is 2 + 2 = 4

Since this is a first order reaction, then we can use the integrated rate law for a first order reaction:
[ A ]0
ln
= kt
[ A ]t
If only 5% of the active ingredient can decompose in two years, then 95% must remain, therefore, [A]0 =
100, [A]t = 95, and t = 2 yr
[ A ]0
ln
= kt
[ A ]t
100
= k ( 2 yr )
95
k = 2.56 102 yr1
ln

14.16

(a)

In order to find the concentration at specific time for a first order reaction, we substitute into
equation 14.5, first converting the time to seconds:
t = 2 hr 3600 s/hr = 7200 s
ln

[ A]0
[ A ]t

= kt

[A ]
0
= antiln [ kt ]
antiln ln
[ A ]t
[ A]0
= antiln [ kt ]
[ A ]t

[ A]0
[ A ]t

= antiln 6.17 104 s 1 ( 7200 s )

0.40 M
= 84.98
[ A ]t

[ A ]t

0.40 M
84.98

= 4.71 x 10 3 M

(b) Again, we use equation 14.5, this time solving for time:
[ A]0
ln
= kt
[ A ]t

[ A ]0
1
1
0.40 M
=
= 466 s
ln
ln

4
1
k
0.30 M
[ A]t 6.17 10 s
4.66 102 s 1 min/60 s = 7.8 min
t=

291

Chapter 14
14.17

For a firstorder reaction:

0.693
0.693
t1/2 =
=
= 1.12 103 s
k
6.17 104 s 1

t1/2 = 1.12 103 s

1 min
60 s

= 18.7 min
If we refer to the chart given in the text in example 14.8, we see that two half lives will have passed if there
is to be only one quarter of the original amount of material remaining. This corresponds to:
18.7 min per halflife 2 half lives = 37.4 min
14.18

From practice exercise 14.15, the rate constant is: k = 2.56 102 yr1, and use the halflife of a first order
reaction equation:
ln 2
ln 2
= 27.1 yr
t 12 =
=
k
2.56 102 yr 1

14.19

Recall that for a first order process

0.693
k=
t1/ 2
So k =
ln

0.693
= 4.86 102/days. Also,
14.26 days

[A] 0
= kt
[A] t

Assume was start with 100 g of 32 P

ln [A]t = ln[A]0 kt = ln100 4.86x102 days x (60 days)

ln[A]0 = 1.689
[A]0 = 5.41 g or 5.41 %
Alternative method

1
2

t / t1/2

= [ 0.5]

60 days /14.26 days

= 0.0541g

Thus, 0.0541 grams would be left if you started with 1.00 grams, or 5.41 % was left.
14.20

Recall that for a first order process

0.693
k=
t1/ 2
So k =
ln

0.693
= 1.21 104/yr. Also,
5730 yr

[A] 0
= kt
[A] t

t =

[A] 0
1
1
ln
=
k
[A] t
1.21 10

/yr

ln

10
= 1.90 104 yrs
1

292

Chapter 14

14.21

Use the value of the rate constant for C14 from the previous practice exercise: 1.21 104 y1. To find the
upper and lower limits of dates before present, set the concentration of the C14 to 5% and 95%,
respectively, and then solve for the time:
For samples with less than 5% of the C14 remaining:
[A] 0
ln
= kt
[A] t
[A] 0
1
1
100
= 2.48 104 yr
ln
ln
=

4
1
k
[A] t
5
1.21 10 yr
Therefore the upper limit of dates is 24,800 years before present.
t =

For samples with more than 95% of the C14 remaining:

[A] 0
ln
= kt
[A] t
[A] 0
1
1
100
= 4.24 102 yr
ln
ln
=
4
1
k
[A] t
95
1.21 10 yr
Therefore the lower limit of dates is 424 years before present.
t =

14.22

This is a secondorder reaction, and we use equation 14.10:

1
1
= kt

[ NOCl]t [ NOCl]0
1

0.010
M]
[

1
= 0.020 L mol1 s 1 t
0.040
M
[
]

t = 3.8 103 s
t = 3.8 103 s 1 min/60 s = 63 min
14.23

This is the same reaction as in the previous practice exercise, so it is a secondorder reaction, and we use
equation 14.10 and k = 0.020 L mol1 s1:
1
1

= kt
[ NOCl]t [ NOCl]0
1

[0.00035 M ]

1
= 0.020 L mol1 s 1 t
[ x M]

We need to find the time in seconds:

From 10:35 to 3:15, 4 hours and 40 minutes has elapsed, or 280 minutes
60 s
4
s = (280 min)
= 1.68 10 s
1
min

1
1
= 0.020 L mol1 s 1 1.68 104 s

[0.00035 M ] [ x M ]

) (

) (

1
= 3.36 102 L mol1 2.86 103 L mol1
x
M
[ ]

4.0 104 M
14.24

Rate = k[NO2]2
To find the rate constant solve the rate law with the given data:
4.42 107 mol L1s1 = k(6.54 104 mol L1)2

293

Chapter 14

k=

4.42 10 7 mol L1 s 1

( 6.54 10

mol L

= 1.03 L mol1 s1

The half life of the system is found using the halflife equation for a secondorder reaction
1
t1/ 2 =
k ( initial concentration of reactant )
t1/ 2 =

(1.03 L mol

1 1

)( 6.54 10

mol L

= 1.48 103 s

14.25

The reaction is firstorder. A secondorder reaction should have a halflife that depends on the initial
concentration according to equation 14.11.

14.26

Use the equation 14.15:

Ea 1
k
1
ln 2 =

k1
R T2
T1
For the 5% decomposition over 2 years, or 104.4 weeks
1
1

=k t
[ B]t [ B]0 1
1
1
= k (104.4 weeks )

[95 M ] [100 M ] 1

k1 = 5.04 106 M1 weeks1

For the 5% decomposition over 1 week
1
1

=k t
B
B
[ ]t [ ]0 2
1
1
= k (1 week )

95
M
100
[
] [ M] 2

k2 = 5.26 104 M1 weeks1

Now use the values for k1, k2, T1 = 298 K, and Ea = 154 103 J mol1
Ea 1
k
1
ln 2 =

k1
R T2
T1

5.26 104 M 1 weeks1 154 103 J mol1 1

1

ln
=

6
1
1
1 1 T
298 K
5.04 10 M weeks 8.314 J mol K
2
1

ln(1.04 102) = (1.85 104 K)

3.36 103 K 1
T2

2.51 104 K1 =
3.36 103 K 1
T2

1
= 3.11 103 K1
T2
T2 = 322 K or 49 C

Alternatively,

294

Chapter 14

ln

104.4k 154 x 103 J mol1

=
k
8.314 J mol1 K 1

1
1
x

T2 298K

T2 = 322 K
14.27

(a) Use equation 14.15:

ln

Ea 1
k2
1

k1
R T2
T1

23 L mol1 s 1
E a
1
1

ln
=
1 1
1 1 678 K
628 K

3.2 L mol s 8.314 J mol K

Solving for Ea gives 1.4 105 J/mol = 1.4 102 kJ/mol

(b) We again use equation 14.12, substituting the values:
k1 = 3.2 L mol1 s1
at T1 = 628 K
k2 = ?
at T2 = 583 K
ln

Ea 1
k2
1

k1
R T2
T1

k2

1.4 105 J mol1 1

1

ln
=

1 1
1 1 583 K
628 K

8.314 J mol K
3.2 L mol s
k2

ln
=2.0697
1 1
3.2 L mol s

k2 = (e-2.0697) x 3.2
Solving for k2 gives 0.40 L mol1 s1.

14.28

Ea 1
k2
1

k1
R T2
T1
3.37x104 M 1 s 1
1
9.31 104 J mol1 1
ln

3
1 1
1 1
600 K
8.314 J mol K
T2
3.37x10 M s
ln

2.056 x 10-4 =

1
1
+
T2 600

T2 = 684 K
14.29

(a), (b), and (e) may be elementary processes.

Equations (c), (d), and (f) are not elementary processes because they have more than two molecules
colliding at one time, and this is very unlikely.

14.30

If the reaction occurs in a single step, one molecule of each reactant must be involved, according to the
balanced equation. Therefore, the rate law is expected to be: Rate = k[NO][O3].

14.31

The slow step (second step) of the mechanism determines the rate law:

295

Chapter 14
Rate = k[NO2Cl]1[Cl]1
However, Cl is an intermediate and cannot be part of the rate law expression. We need to solve for the
concentration of Cl by using the first step of the mechanism. Assuming that the first step is an equilibrium
step, the rates of the forward and reverse reactions are equal:
Rate = kforward[NO2Cl] = kreverse[Cl][NO2]
Solving for [Cl] we get
k [ NO Cl]
[Cl] = kf NO2
r [
2]
Substituting into the rate law expression for the second step yields:
k [ NO 2 Cl]

Rate =

[ NO2 ]

, where all the constants have been combined into one new constant.

Review Questions

14.1

Student responses will vary.

(a)
combustion of gasoline
(b)
cooking an egg in boiling water
(c)
curing of cement

14.2

A collision between only two molecules is much more probable than the simultaneous collision of three
molecules. We therefore conclude that a reaction involving a twobody collision is faster (i.e. will occur
more frequently) than one requiring a threebody collision.

14.3

The instantaneous rate of reaction is the rate of the reaction at a particular moment. The average rate of
reaction is the average rate for the reaction over the time of the whole reaction. This includes the very
rapid rates when the concentration of reactants is high and the very slow rates when the concentration of
reactants is low.

14.4

A tangent line to the curve of concentration as a function of time at time zero is drawn. The slope of this
line is determined which is the initial instantaneous rate of reaction.

14.5

A homogeneous reaction is one in which all reactants and products are in the same phase. An example
would be:
2H2(g) + O2(g) J 2H2O(g)
A heterogeneous reaction is one in which all reactants and products are not in the same phase. An example
would be:
25O2(g) + 2C8H18(l) J 16CO2(g) + 18H2O(g)

14.6

Chemical reactions that are carried out in solution take place smoothly because the reactants can mingle
effectively at the molecular level.

14.7

Heterogeneous reactions are most affected by the extent of surface contact between the reactant phases.

14.8

In a heterogeneous reaction, the smaller the particle size, the faster the rate. This is because decreasing the
particle size increases the surface area of the material, thereby increasing contact with another reactant
phase.

14.9

This illustrates the effect of concentration.

14.10

Reaction rate generally increases with increasing temperature.

14.11

In cool weather, the rates of metabolic reactions of coldblooded insects decrease, because of the effect of
temperature on rate.

296

Chapter 14
14.12

The low temperature causes the rate of metabolism to be very low.

14.13

Reaction rate has the units mol L1 s1, or molar per second (M s1). Reaction rates are reported as positive
values regardless of whether the species increases or decreases during the recaction.

14.14

The units are, in each case, whatever is required to give the units of rate (mol L1 s1) to the overall rate
law:
(b)
L mol1 s1
(c)
L2 mol2 s1
(a)
s1

14.15

A zeroorder reaction has no dependence on concentration while the firstorder reaction is linearly
dependent on concentration and the second-order reaction is inversely dependent on concentration.

14.16

No, the coefficients of a balanced chemical reaction do not predict with any certainty the exponents in a
rate law. These exponents must be determined through experiment.

14.17

This is the first case in Table 14.4 of the text, that is a zero-order reaction.

14.18

This is the fourth case Table 14.4 of the text, that is a first-order reaction.

14.19

This is the seventh case in Table 14.4, and the rate increases by a factor of 22 = 4.

14.20

This is the eleventh case in Table 14.4, and the order of the reaction with respect to the reactant is 3.

14.21

Since the substrate concentration does not influence rate, its concentration does not appear in the rate law,
and the order of the reaction with respect to substrate is zero.

14.22

The halflife of a firstorder reaction is unaffected by the initial concentration.

14.23

The halflife of a secondorder reaction is inversely proportional to the initial concentration, as expressed
in equation 14.11.

14.24

The half-life of a zeroth-order reaction is directly proportional to initial concentration.

14.25

First order
[ A]0
ln
= kt
[ A]t
Second order
1
1

= kt
[ A]t [ A]0

t1/2 =

[ A]t

1/2

1
1
[ A]0
2

1
[ A]0
2

ln

1
= kt
[ A]0 1/ 2

[ A]0
1
[ A]0
2

1
1
[ A]0
2

t1/ 2 =

= kt1/2

1
2
[ A]0
2

= kt1/ 2 =

ln 2 0.693
=
k
k

2
2
1

=
[ A]0 2 [ A]0 [ A]0

1
k [ A]0

Zeroth order

[ A]t = kt + [ A]0
14.26

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

kt1/ 2 = [ A]0

1
[ A]0
2

t1/ 2 =

For the zeroorder reaction, substitute half the value of [A]0 for the value of [A]t in the equation
[A]0 [A]t = kt
[A]0 1/2[A]0 = kt1/2
1/2[A]0 = kt1/2

297

[ A]0
2k

Chapter 14

t 12 =

14.27

[A]0
2k

To answer this question refer to the integrated equations for each order.
Graph (b) represents a kinetics plot for a first order reaction.
Graph (c) represents a kinetics plot for a second order reaction.
Graph (a) represents a kinetics plot for a zeroth order reaction.

14.28

According to collision theory, the rate is proportional to the number of collisions per second among the
reactants.

14.29

The effectiveness of collisions is influenced by the orientation of the reactants and by the activation energy.

14.30

This happens because a larger fraction of the reactant molecules possess the minimum energy necessary to
surpass Ea.

Potential Energy

14.31

Ea (forward)

Ea (reverse)

Products
Hreaction

Reactants
Reaction Coordinate

14.32

Potential Energy

Transition State

Reactants
H
Products
Reaction Coordinate

14.33

Breaking a strong bond requires a large input of energy, hence a large Ea.

298

Chapter 14
14.34

An elementary process is an actual collision event that occurs during the reaction. It is one of the key
events that moves the reaction along in the stepwise process that leads to the overall reaction that is
observed. It is thus one step in a potentially multistep mechanism.

14.35

The ratedetermining step in a mechanism is the slowest step.

14.36

The rate law for a reaction is based on the ratedetermining step.

14.37

Adding all of the steps gives:

2NO + 2H2 J N2 + 2H2O
The intermediates are N2O2 and N2O.

14.38

For such a mechanism, the rate law should be:

rate = k[NO2][CO]

14.39

Since this is not the same as the observed rate law, this is not a reasonable mechanism to propose.
Add all of the steps together:
CO + O2 + NO J CO2 + NO2

14.40

On adding together all of the steps in each separate mechanism, we get, in each case:
OCl + I J Cl + OI

14.41

The predicted rate law is based on the ratedetermining step:

rate = k[NO2]2

14.42

A catalyst changes the mechanism of a reaction, and provides a reaction path having a smaller activation
energy.

14.43

A homogeneous catalyst is one that is present in the same phase as the reactants. It is used in one step of a
cycle, but regenerated in a subsequent step, so that in a net sense, it is not consumed.

14.44

Adsorption is a clinging to a surface. Absorption involves a penetration below the surface, as in the action
of a sponge. Heterogeneous catalysis involves adsorption.

14.45

The catalytic converter promotes oxidation of unburned hydrocarbons, as well as the decomposition of
nitrogen oxide pollutants. Lead poisons the catalyst and renders it ineffective.

Review Problems

14.46

Since they are in a 1-to-1 mol ratio, the rate of formation of SO2 is equal and opposite to the rate of
consumption of SO2Cl2. This is equal to the slope of the curve at any point on the graph (see below). At
200 min, we obtain a value of about 1 104 M/min. At 600 minutes, this has decreased to about 7 105
M/min.

299

Chapter 14

14.47

The slope of the tangent to the curve at each time is the negative of the rate at each time:
Rate60 = 8.5 104 mol L1 s1
Rate120 = 4.0 104 mol L1 s1

14.48

This is determined by the coefficients of the balanced chemical equation. For every mole of N2 that reacts,
3 mol of H2 will react. Thus the rate of disappearance of hydrogen is three times the rate of disappearance
of nitrogen. Similarly, the rate of disappearance of N2 is half the rate of appearance of NH3, or NH3
appears twice as fast as N2 disappears.

14.49

From the coefficients in the balanced equation we see that, for every mole of B that reacts, 2 mol of A are
consumed, and three mol of C are produced. This means that A will be consumed twice as fast as B, and C
will be produced three times faster than B is consumed.
rate of disappearance of A = 2(0.25) = 0.50 mol L1 s1
rate of appearance of C = 3(0.25) = 0.75 mol L1 s1

14.50

(a)
(b)

rate for O2 = 1.35 mol L1 s1 19/2 = 12.8 mol L1 s1

By convention, this is reported as a positive number: 12.8 mol L1 s1
rate for CO2 = +1.35 mol L1 s1 12/2 = 8.10 mol L1 s1
300

Chapter 14
(c)

rate for H2O = +1.35 mol L1 s1 14/2 = 9.45 mol L1 s1

14.51

We rewrite the balanced chemical equation to make the problem easier to answer: N2O5 J 2NO2 + 1/2O2.
Thus, the rates of formation of NO2 and O2 will be, respectively, twice and one half the rate of
disappearance of N2O5.
rate of formation of NO2 = 2(4.2 106) = 8.4 106 mol L1 s1
rate of formation of O2 = 1/2(4.2 106) = 2.1 106 mol L1 s1

14.52

(a)

(b)

Rate =

(a)

(b)

Rate =

14.53

14.54

d [CH3Cl]
1 d [Cl2] d [CCl4] 1 d [HCl]
=
=
=
dt
3 dt
dt
3 dt

1
(0.029) M s 1 = 9.7 x 10-3 M s-1
3

1 d [PH3] d [P4] 1 d [H 2 ]
=
=
4 dt
dt
6 dt
1
(0.34) M s 1 = 0.085 M s-1
4

The rate can be found by simply inserting the given concentration values:
rate = (5.0 105 L5 mol5 s1)[H2SeO3][I]3[H+]2
rate = (5.0 105 L5 mol5 s1)(3.5 102 mol/L)(3.0 103 mol/L)3(1.5 103 mol/L)2
rate = 1.1 109 mol L1 s1

14.55

rate = (1.3 1011 L mol1 s1)(1.0 107 mol/L)(1.0 107 mol/L)

rate = 1.3 103 mol L1 s1

14.56

rate = (7.1 109 L2 mol2 s1)(2.5 103 mol/L)2(6.2 102 mol/L)

rate = 2.8 103 mol L1 s1

14.57

rate = (1.0 105 s1)(2.0 103 mol/L) = 2.0 108 mol L1 s1

14.58

For a zero order reaction the rate is independent of concentration so R = k

Therefore, the rate of the reaction is 6.4 x 102 M s-1.

14.59

Rate = k[Rn] = 0.0125 s-1 x 1.0 x 10-9 mol L-1 = 1.25 x 10-11 M s-1

14.60

On comparing the data of the first and second experiments, we find that, the concentration of N is
unchanged, and the concentration of M has been doubled, causing a doubling of the rate. This corresponds
to the fourth case in Table 14.4, and we conclude that the order of the reaction with respect to M is 1. In
the second and third experiments, we have a different result. When the concentration of M is held constant,
the concentration of N is tripled, causing an increase in the rate by a factor of nine. This constitutes the
eighth case in Table 14.4, and we conclude that the order of the reaction with respect to N is 2. This means
that the overall rate expression is: rate = k[M][N]2 and we can solve for the value of k by substituting the
appropriate data:
5.0 103 mol L1 s1 = k [0.020 mol/L][0.010 mol/L]2
k = 2.5 103 L2 mol2 s1

14.61

First, compare the first and second experiments: there has been an increase in concentration by a factor of
2. This has caused an increase in rate of:

301

Chapter 14
5.90 105 mol L1 s 1
2.95 10 5 mol L1 s 1

= 2.00 = 21

This is the fourth case in Table 14.4, and the order of the reaction is found to be 1. Similarly, on comparing
the first and third experiments, an increase in concentration by a factor of 3 has caused an increase in rate
by a factor of:
8.85 105 mol L1 s 1
= 3.00 = 31
2.95 105 mol L1 s 1
This is the fifth case in Table 14.4, and we again conclude that the order is 1.
rate = k[C3H6]
We can use any of the three sets of data to solve for k. Using the first data set gives:
2.95 105 mol L1 s1 = k(0.050 mol L1)
k = 5.9 104 s1
14.62

The reaction is firstorder in OCl, because an increase in concentration by a factor of 4.75, while holding
the concentration of I constant (compare the first and second experiments of the table), has caused an
increase in rate by a factor of 4.751 = 4.75. The order of reaction with respect to I is also 1, as is
demonstrated by a comparison of the first and third experiments.
rate = k[OCl][I]
Using the last data set:
1.05 105 mol L1 s1 = k[1.6 103 mol/L][9.6 103 mol/L]
k = 6.8 109 L mol1 s1

14.63

Compare the data of the first and second experiments, in which the concentration of NO is held constant
and the concentration of O2 is increased by a factor of 4. Since this caused a rate increase by a factor of
28.4/7.10 = 41, we conclude that the order of the reaction with respect to O2 is one (case number six in
Table 14.4). In the second and third experiments, an increase in the concentration of NO by a factor of 3
(while holding the concentration of O2 constant) caused a rate increase by a factor of 255.6/28.4 = 9. This
is the eighth case in Table 14.4, and the order is seen to be two.
rate = k[O2][NO]2
We can use any of the three sets of data to solve for k. Using the first data set gives:
7.10 mol L1 s1 = k[1.0 103 mol/L][1.0 103 mol/L]2
k = 7.10 109 L2 mol2 s1

14.64

Compare the first and second experiments. On increasing the ICl concentration by a factor of 6.5, the rate
is found to increase by a factor of 6.5 = 6.51, and the order of the reaction with respect to ICl is 1 (see
Tables 14.3 and 14.4). In the first and third experiments, the concentration of ICl is constant, whereas the
concentration of H2 in the first experiment is 1.35 times that in the third. This causes a change in the rate
by a factor of 1.36, and the rate law is found to be: rate = k[ICl][H2].
Using the data of the first experiment:
1.5 103 mol L1 s1 = k[0.12 mol L1][0.12 mol L1]
k = 1.04 101 L mol1 s1

14.65

In the first, fourth, and fifth experiments, the concentration of OH has been made to increase while the
[(CH3)3CBr] is left unchanged. In each of these experiments, there is no change in rate. This means that
the rate is independent of [OH], and the order of reaction with respect to OH is zero. The concentration
of (CH3)3CBr increases by a factor of 2.42 from the first to the second experiment, and by a factor of 3.84
from the first to the third experiment, as the OH concentration is held constant. There is a corresponding
2.4fold (i.e. 2.41) increase in rate from the first to the second experiment, and there is a 3.8fold (i.e. 3.81)
302

Chapter 14
increase in rate from the first to the third experiment. In both cases, we conclude that the order with respect
to (CH3)3CBr is one.
rate = k[(CH3)3CBr]
Using the third set of data gives:
3.8 103 mol L1 s1 = k[7.3 101 mol/L]
k = 5.2 103 s1
14.66

A graph of ln [SO2Cl2]t versus t will yield a straight line if the data obeys a firstorder rate law.

These data do yield a straight line when ln [SO2Cl2]t is plotted against the time, t. The slope of this line
equals k. Plotting the data provided and using linear regression to fit the data to a straight line yields a
value of 1.32 103 min1 for k.
14.67

Since it is the plot of 1/conc. that gives a straight line, the order of the reaction with respect to CH3CHO is
two. The rate constant is given by the slope directly:
k = 0.0771 M1 s1

14.68

(a)

The time involved must be converted to a value in seconds:

2 hr 3600 s/hr = 7.2 103 s, and then we make use of equation 14.5, where x is taken to
represent the desired SO2Cl2 concentration:
0.0065 M
ln
= (2.2 105 s 1 )(7.2 103 s)
x
x = 5.5 103 M

(b)

The time is converted to a value having the units seconds

24 hr 3600 s/hr = 8.64 104 s, and then we use equation 14.5, where x is taken to represent the
desired SO2Cl2 concentration:
0.0065 M
ln
= (2.2 105 s1 )(8.64 104 s)
x
x = 9.7 104 M
303

Chapter 14

14.69

1
1

= kt
[ A]t [ A]0
1
1
= kt +
[ A]t
[ A]0
(a)
1

= 0.0771 M 1 s 1 x 30 min x

= 142.1 M 1

= 0.0771 M 1 s 1 x 180 min x

= 836.0 M 1

[ A]30 min

60 s
1
+
min 0.300 M

[ A]30 min
[ A]30min = 7.0 x 103 M
(b)

[ A]180min

[ A]180min
[ A]180min =
14.70

60 s
1
+
min 0.300 M

1.2 x 103 M

Use equation 14.5 and assume the initial concentration is 100 and the final concentration is, therefore, 25.
The units are immaterial in this case since they will cancel out in the calculation:
[ A ]0
ln
= kt
[ A ]t
100
= k(85.0 min)
25
Solving for k we get 1.63 102 min1
ln

14.71

1
1

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

= k x18.7 min
0.075 M 1 M

14.72

k = 0.66 M 1 min 1
Any consistent set of units for expressing concentration may be used in equation 14.5, where we let A
represent the drug that is involved:
[ A ]0
ln
= kt
[ A ]t

ln

25.0 mg kg

= k(120 min)
15.0 mg kg
Solving for k we get 4.26 103 min1

304

Chapter 14

14.73

ln

ln

[ A]0
[ A]t

= kt

1.1 x 106 g L1
0.30 x 106 g L1

= k x 180 s

k = 7.2 x 103 s 1
14.74

We use the equation:

1
1
= kt

HI
HI
[ ]t [ ]0

1
1
= 1.6 103 L mol1 s 1 t

9.5 104 M
6.7 102 M

Solving for t gives:

t = 6.5 105 s or t = (6.5 105 s) 1 min/60 s = 1.1 104 min

14.75

1
1

= kt
A
A
[ ]t [ ]0

1
1

= 0.556 L mol1 s 1 x t
0.050 M 0.50 M
t = 32 s

14.76

Use the equation, taking time in minutes; 3 hr = 180 min.

x
ln
= 4.26 103 min 1 (180 min )
5.0 mg kg

x = 11 mg/kg
14.77

Use equation 14.10, where the time is: (2.5 103 min) 60 s/min = 1.5 105 s
1
1

= kt
[ B]t [ B]0
1
4

3.7 10 M

1
= 2.5 103 L mol1
HI
[ ]0

[ HI]0
14.78

)(

1
= 1.6 103 L mol1 s 1 1.5 105 s
[ HI]0

= 4.1 104 M

60 min 1 half life

half lives = (2.0 hrs)
= 6.0 half lives
1 hr 20 min
Six half lives correspond to the following fraction of original material remaining:

Fraction remaining
1/2
1/4
1/8
1/16
1/32
1/64

Number of half lives

1
2
3
4
5
6
305

Chapter 14

Alternatively, since 6 half-lives have occurred

0.56 = 0.0156

or 1/64

14.79

Since 1/2 of the Sr90 decays every halflife, it will take 5 halflives, or 5 28 yrs = 140 yrs, for the Sr90
to decay to 1/32 of its present amount.

14.80

It requires approximately 500 min (as determined from the graph) for the concentration of SO2Cl2 to
decrease from 0.100 M to 0.050 M, i.e., to decrease to half its initial concentration. Likewise, in another
500 minutes, the concentration decreases by half again, i.e. from 0.050 M to 0.025 M. This means that the
halflife of the reaction is independent of the initial concentration, and we conclude that the reaction is
firstorder in SO2Cl2.

14.81

From the graph, we see that the first halflife is achieved in about 65 seconds, because this is the amount of
time it requires for the concentration to decrease from its initial value (0.200 M) to half its initial value
(0.100 M). The second halflife period, i.e., the time required for the concentration to decrease from 0.100
M to 0.050 M, is longer, namely about 125 seconds (this is determined by estimating the time when the
concentration is 0.050 M and subtracting the time when the concentration is 0.100 M). Since the halflife
does depend on concentration; we conclude that the reaction is not firstorder. In fact, the data are
consistent with secondorder kinetics, because the value of the halflife decreases in proportion to the
inverse of the initial concentration. That is, as the initial concentration for any halflife period becomes
smaller, the halflife becomes larger.
t

14.82

1 t1/2
2 = 0.05
t

1 10 hrs
= 0.05
2
t
log 0.5 = log 0.05
10 hrs

t = 43.2 hrs
14.83

We can use the half-life to determine the value of k.

4.88 x 103 s = 0.693/k

[ A]0
ln
[ A]t
14.84

= kt

ln

k = 1.42 x 10-4 s-1

0.024 M
= 1.42 x 104 x t
0.0040 M

t = 1.3 x 104 s

In order to solve this problem, it must be assumed that all of the argon40 that is found in the rock must
have come from the potassium40, i.e., that the rock contains no other source of argon40. If the above
assumption is valid, then any argon40 that is found in the rock represents an equivalent amount of
potassium40, since the stoichiometry is 1:1. Since equal amounts of potassium40 and argon40 have
been found, this indicates that the amount of potassium40 that remains is exactly half the amount that was

306

Chapter 14
present originally. In other words, the potassium40 has undergone one halflife of decay by the time of
the analysis. The rock is thus seen to be 1.3 109 years old.
14.85

Using equation 14.9 we may determine how long it has been since the tree died.
r
ln o = 1.2 10 4 t where ro = 1.2 x 1012
rt

1.2 1012
ln
= 1.21 104 t
4.8 1014

Taking the natural log we determine:

1.2 1012
1
t=
ln
1.21 104 4.8 1014

14.86

= 2.7 104 yr

Use equation 14.8 and 14.9.

r
ln 0 = kt
rt
1.2 1012
ln
= 1.21 104 y 1 9.0 103 y

r
t

12
1.2 10

= exp 1.21 104 y1 9.0 103 y

r
t

1.2 1012

= rt = 4.0 1013

2.97

)(

)(

14.87

In a fashion similar to that outlined in the answer to Review Problem 14.84, we conclude that, in order for
the rock to be one halflife old (1.3 109 yr), there must be equal amounts of the two isotopes, one having
been formed by decay of the other. The answer is, thus, 1.16 107 mol of potassium40.

14.88

The graph is prepared exactly as in example 14.12 of the text. The slope is found using linear regression, to
be: 9.5 103 K. Thus 9.5 103 K = Ea/R
Ea = (9.5 103 K)(8.314 J K1 mol1) = 7.9 104 J/mol = 79 kJ/mol
Using the equation, we proceed as follows:
Ea 1
k
1
ln 2 =

k1
R T2
T1

1.94 103 L mol1 s 1

E a
1
1
ln

=
4
1 1
1 1 673 K
593 K

2.88 10 L mol s 8.314 J mol K

2.00 104 K 1

Ea
8.314 J mol1 K 1
Ea = 7.93 104 J/mol = 79.3 kJ/mol
1.907 =

14.89

The graph is prepared exactly as in example 14.15 of the text. The slope is found using linear regression, to
be:
1.67 104 K. Thus 1.67 104 K = Ea/R
307

Chapter 14
Ea = (1.67 104 K)(8.314 J K1 mol1) = 1.39 105 J/mol = 139 kJ/mol
Using equation 13.12 we have:
Ea 1
k2
1

k1
R T2
T1
1.08 101 L mol1 s 1
E a
1
1
ln

=
2
1 1
1 1 503 K
478 K

1.91 10 L mol s 8.314 J mol K

ln

1.732 =

1.04 104 K 1

Ea

8.314 J mol1 K 1

Ea = 1.38 105 J/mol = 138 kJ/mol

14.90

Using the equation we have:

Ea 1
k2
1
=

k1
R T2
T1
1.0 103 L mol1 s 1
Ea
1
1
ln

=
5
1 1
1 1 403 K
373 K

9.3 10 L mol s 8.314 J mol K

ln

2.37 =

2.00 104 K 1
8.314 J mol1 K 1

Ea

Ea = 9.89 104 J/mol = 99 kJ/mol

E
Equation states k = A exp a
RT
k
A=
E
exp a
RT

9.3 105 L mol1 s 1

9.89 104 J

mol
exp
8.314 J mol K ( 373 K )

= 6.6 10 L mol

s 1

9.89 104 J / mol

k = 6.6 109 L mol1 s 1 exp

8.314 J mol1 K 1 x 423 K

k = 4.0 103 L mol-1 s-1

308

Chapter 14
14.91

(a)

Substituting into the equation:

Ea 1
k
1

ln 2 =

k1
R T2
T1
1.1 105 L mol1
ln
6
1
1.3 10 L mol
6.34 105 K 1

Ea
8.314 J mol1 K 1
Ea = 2.8 105 J/mol = 2.8 102 kJ/mol
E
Equation states k = A exp a
RT
2.1 =

(b)

Ea
s1
1
1

=
1
1 1 703 K
673
K

s 8.314 J mol K

A=

k
E
exp a
RT

1.1 105 L mol1 s1

2.8 105 J

mol

exp
8.314 J mol K ( 703 K )

= 7.0 1015 L mol 1 s 1

(c)

The equation can be used directly now that the value of A is known:
E
k = A exp a
RT
2.8 105 J mol1

= 7.0 1015 L mol1 s 1

8.314 J mol K ( 598 K )

= 2.4 10 9 L mol 1 s 1

14.92

Use equation 14.13:

(a)

E
k = A exp a
RT
103 103 J mol1

= 4.3 1013 s 1 exp

8.314 J mol K ( 310 K )

= 1.9 10 4 s 1

(b)

E
k = A exp a
RT
103 103 J mol1

= 4.3 1013 s 1 exp

8.314 J mol K ( 390 K )

= 6.9 10 1 s 1

309

Chapter 14

14.93

Substitute into the equation:

Ea 1
k
1
ln 2 =

k1
R T2
T1
k2

108 103 J mol1 1

1

ln
=
5 1
1 1 328 K
308
K

8.314 J mol K
6.2 10 s
ln(k2/6.2 105 s1) = 2.57
k2 = 6.2 105 s1 exp(2.57) = 8.1 104 s1

14.94

If this reaction occurs in one step then the rate law is the product of the concentrations raised to the
appropriate powers.
Rate = k [AB][C]

14.95

See Review Question 14.41 for information about this mechanism. The know rate law is Rate = k[NO2]2.
The proposed mechanism is:
NO2 + NO2

NO3 + NO (slow)

NO3 + CO

CO2 + NO2

(fast)

From the slow, rate determining step, we can write a proposed rate law.
Rate = k[NO2]2
14.96

An intermediate is produced in one step and used up in another. The intermediate in this reaction is N2O2.
The overall reaction is the sum of the two steps
2NO(g) + O2(g)

'

2NO2(g)

The rate law is determined from the slow step.

Rate = k[N2O2][O2]
An intermediate cannot be part of the rate law expression. We can use the first step, which is an equilibrium
step to solve for the concentration of N2O2.
Rate =

k f [NO]2 = kr [N 2 O2 ]

Solve for [N2O2] to get

[N2O2] =

kf
kr

[NO]2

Rate = k[NO]2 [O 2 ] where all of the constants have been combined into a new constant
14.97

An intermediate is formed in one step of a mechanism and then used in another step.
Intermediates in this mechanism are Cl and CCl3
Sum the three steps to obtain the overall, balanced equation for the reaction.
310

Chapter 14

Cl2(g) + CHCl3(g)

HCl(g) + CCl4(g)

The rate law is obtained from the slow step.

Rate = k[Cl][CHCl3]
However, Cl is an intermediate and does not occur in the overall reaction. To obtain a rate equation in
terms of reactants or products we need to replace [Cl].
2
Cl]
[
K eq =
[Cl2 ]

From the first step,

[Cl] = {K eq [Cl2 ]}

1/ 2

1/ 2
} [CHCl3 ] = kK eq1/ 2 [Cl2 ]1/ 2 [CHCl3 ] = k ' [Cl2 ]1/ 2 [CHCl3 ]

Rate = k K eq [ Cl 2 ]

Additional Exercises

14.98

From the tangent lines we can obtain the instantaneous rate at 1000 s and 9000 s.
For the decomposition of cyclobutane:
At 1000 s the slope is 9.6 x 10-7 M s-1 which is the rate of decomposition.
At 9000 s the slope is 3.8 x 10-7 M s-1 which is the rate of decomposition
For the formation of ethylene:

311

Chapter 14
At 1000 s the slope is 1.9 x 10-6 M s-1 which is the rate of formation of.
At 9000 s the slope is 7.5 x 10-7 M s-1
The rate of formation of ethylene is twice the rate of decomposition of cyclobutane.
14.99

k = 0.693/12.5 y = 5.54 102 y1

ln

1
= 5.54 102 y 1 t
0.1

t = 41.6 y

14.100

Reaction is endothermic
14.101 From Section 14.4, the fraction remaining after n half-lives is 1/2n. Therefore, we have:
0.810 = 1/2n
Inverting both sides of the equation gives:
1.23 = 2n
We can solve this for now using trial and error: We know that 21 = 2, and that 20 = 1. Therefore n must be
between 0 and 1. We start by trying n = 0.50:
20.50 = 1.41
This is too high, so we might try 0.30:
20.30 = 1.23
This is just what we were looking for, therefore n = 0.30. Since one half life of C-14 is 5730 years, one
might estimate the age of the mummy as (0.30)(5730) = about 1,700 years old.
14.102 The chemical product is BaCl2.Recall that for a first order process k =
So k = 0.693/30 yr = 2.30 102/yr. Then,
[A] 0
ln
= kt
[A] t
[A] t = [A] 0 exp(- kt)
[A] 0
= exp[ (2.30 10 2 /yr)(120 yr)]
[A] t

312

0.693
t1 2

Chapter 14

[A] 0
= 6.33 10 2
[A] t
so 6.3% of the original sample remains.

14.103 (a) The reaction rate is first order so as the concentration of reactants doubles the rate will double.
(b) The reaction rate is second order so as the concentration of reactants doubles the rate will increase by a
factor of four.
(c) The reaction rate is zeroth order so the rate is independent of concentration. There is no change in the
rate.
(d) The reaction rate is second order so as the concentration of reactants double the rate increases by a
factor of four.
(e) The reaction rate is third order so as the concentration of reactants double the rate increases by a factor
of eight.
14.104 NO2 + O3 J NO3 + O2
NO3 + NO2 J N2O5

(slow)
(fast)

rate = k1[A]2
rate = k1[A2]1
rate = k2[A2]1[E]1
2A + E J B + C
The rates for the forward and reverse directions of step one are set equal to each other in order to
arrive at an expression for the intermediate [A2] in terms of the reactant [A]: k1[A]2 = k1[A2]
k
[A2] = 1 [A]2
k 1
This is substituted into the rate law for question (c) above, giving a rate expression that is written
k
using only observable reactants: rate = k2 1 [A]2[E]1
k 1

14.105 (a)
(b)
(c)
(d)
(e)

14.106 First, determine a value for Ea using the equation:

Ea 1
k2
1
=

k1
R T2
T1
2.25 105 min 1
Ea
1
1

ln
=
6
1
1 1 348 K
338
K

5.84 10 min 8.314 J mol K

ln

1.35 =

8.50 105 K 1
8.314 J mol1 K 1

Ea

Ea = 1.32 105 J/mol = 132 kJ/mol

Next, use this value of Ea and the data at 75 C to calculate a rate constant at 85 C:
ln

Ea 1
k2
1
=

k1
R T2
T1

313

Chapter 14
k2

1.32 105 J mol1 1

1
ln
=
358 K 348 K
5
1
1 1

8.314 J mol K
2.25 10 min
k2

ln
= 1.27
5
1
2.25 10 min

k2 = (2.25 105 min1) exp(1.27) = 8.02 105 min1.

Finally, use the firstorder rate expression to determine time:
ln

0.0025 M
= (8.02 105 min 1 ) t
0.0015 M

Solving for t we get 6.37 103 min.

14.107 Taking the log of both sides of this equation, we have:
log(rate) = log k + n log[A]
Thus, if we plot log(rate) vs. log[A], the slope should be equal to the value for n, and the intercept is equal
to log k.
A plot of the data is used to determine slopes of the tangents to the curve at time = 150, 300, 450, and 600
min. The negatives of these slopes are equal to the value of the rate constants at these particular times
during the reaction. (Notice that the rate decreases with time.)
The four rates are found to be approximately:
1.1 104 mol L1 min1, at t = 150 min
8.9 105 mol L1 min1, at t = 300 min
7.2 105 mol L1 min1, at t = 450 min
6.0 105 mol L1 min1, at t = 600 min
Suitable values for [SO2Cl2] at each of these times can be read from the graph of concentration vs. time.
Once each of these concentration values has been converted to log[SO2Cl2], the plot of log rate vs. log
[SO2Cl2] can be constructed:

The slope of this straight line has the value 1.0, which is the order of the reaction with respect to [SO2Cl2].

314

Chapter 14
14.108
Ea 1
k2
1
=

k1
R T2
T1
Ea
1
2
1
ln =

1
1

298 K
1 8.314 J mol K
308 K
5
(1.31 10 mol/J)(Ea) = 0.693
Ea = 5.29 104 J/mol = 52.9 kJ/mol
ln

14.109 The rate law for a first order reaction is given by,
Rate = k[A].
If the rate constant is doubled then the rate of the reaction will double.
14.110 The catalyzed reaction path is represented by the blue line. A catalyzed reaction path is lower in energy
than an un-catalyzed reaction path.
Since there are two activation energies shown for the catalyzed reaction there are two steps in the
mechanism. The slowest step would be the first step in the mechanism as that step has the highest
activation energy of the two steps in the mechanism.
14.111 To solve this problem, plot the data provided as 1/T vs 1/t where T is the absolute temperature and 1/t is
proportional to the rate constant.
t (min)
10
9
8
7
6

T (K)
291
293
294
295
297

1/T
0.003436
0.003412
0.003401
0.003389
0.003367

ln(1/t)
2.302585
2.197224
2.079441
1.945910
1.791759

13.6

288

0.003472

2.608

315

Chapter 14
The slope of the graph is equal to Ea/R, therefore:
7,704 = Ea/R
7,704R = Ea
7,704 K(8.314 J/molK) = Ea
Ea = 64,050 J/mol
Ea = 64 kJ/mol
From the straightline equation, we can determine the time needed to develop the film at 15 C is 14 min.
14.112 (a)

The number of chirps in eight seconds is simply the temperature minus 4. So, in order, there will
be 6, 11, 16 and 21 chirps at these temperatures.

The data are plotted below.

(b)
T
1/T
ln (chirps)
# of chirps
6
283 0.003534
1.791759
11
288 0.003472
2.397895
16
293 0.003413
2.772589
21
298 0.003356
3.044522

The slope of the line is equal to the Activation energy divided by R so Ea = 5.81 104 J/mol.
(c)

At 35 C the cricket would make 32 chirps.

14.113 Taking note of the inverse relationship between the reaction rate constant, k, and the cooking time, t, we set
up equation 14.15 in the following manner:
Ea 1
k
1
ln 2 =

k1
R T2
T1
1t
Ea 1
1
ln 2 =

1
R
T
T
t1
1
2

We are provided with some subtle but key information about the physical conditions. For instance, the 3
minute traditional egg provides a cooking time of 3 minutes at the normal boiling point of water, 100 C or
373 K. We are also given the atmospheric pressure (355 torr) on Mt. McKinley where the cooking is to be
carried out at a lower temperature. At 355 torr, H2O will boil when its vapor pressure equals 355 torr. The
temperature corresponding to this pressure is 80 C or 323 K (See Appendix). Thus, with the given value
of the activation energy, i.e., Ea = 418 kJ/mol, we can proceed with the calculation to obtain t2:

316

Chapter 14

1t
418 103 J/mol 1
1
2
=
ln

1
8.314 J/mol K
373 K
3 min
353 K
3 min
ln
= 7.64
t2
3 min
= exp( 7.64)
t2
t 2 = 3 min/exp( 7.64) = 6.2 103 min = 104 hrs
Thus, to get the same degree of protein denaturization, it would take roughly 4 days to cook the egg at an
atmospheric pressure of 355 torr as opposed to cooking the egg at normal atmospheric pressure.

14.114 (a)
(b)
(c)

The first step, in which a free radical is produced, is the initiation step.
Both the second and third steps are propagating steps since HBr, the desired product, and an
additional free radical are produced.
The final step in which two bromine free radicals recombine to give a bromine molecule is the
termination step.

The presence of the additional reaction step serves to decrease the concentration of HBr.
14.115 Consider a 1.00 g sample of radioactive material. After 10 half lives you would have (1/2)10 grams or 9.76
x 10-4 grams of material remaining.
Therefore, the percent of material remaining would be,
9.76 x 10 4 g
2

x 100 = 9.76 x 10 %
1.00
g

Multi-Concept Problems

14.116 The units on the rate constant tells us that this is a second order reaction.
Rate = k [C2H5OH]2
Since all chemicals are in the gaseous state the total pressure, at any given time, is given by,
PT = P(C2H5OH) + P(C2H4) + P(H2).
We can relate pressure to molar concentration using PV=nRT
P = (n/V)RT = [X]RT or [X] = P/(RT)
At time t the ethanol concentration we be reduced by x due to conversion to ethylene and hydrogen and
each of the products will increase in concentration by +x.
Now set up a table showing initial molar concentrations and concentrations at time t.

Initial

[C2H5OH]

[C2H4]

[H2]

0.020

+x

+x

Time t 0.020 x

Using our equation for total pressure, PT, we can write,

1.4 atm = (0.0200 x)RT + xRT + xRT
1.4/(RT) = 0.0200 + x
317

Chapter 14
x =1.4/(0.0821 L atm K-1 mol-1 x (327 + 273)K - 0.0200M
x=0.00842M

Thus, during the time necessary to achieve a pressure of 1.4 atm the reaction has converted 0.00842 moles
per liter to products.
[C2H5OH]0 = 0.0200M

[C2H5OH]t =0.0158M

1
1

= kt
[ A]t [ A]0

1
1

= 4.00 x 105 L mol1 s 1 t

[0.0158]t [0.0200]0

t = 3.32 x 105 s or 92 hrs

14.117 We can determine the temperature that the reaction mixture would achieve if all of the heat is supplied at
once by using the enthalpy of reaction and the heat capacity of the system.
q = CcalT

40 kJ mol-1 x 1000 J kJ-1 x 10,000 mol = 7.5 x 106 J oC-1 T

T = 53.3 oC
Thus, the final temperature of the mixture would be 78 oC or 351 K
ln

ln

ln

Ea 1
k2
1
=

k1
R T2
T1

1000 J
1
1
kJ
351 K 298 K
1
1

8.314 J K mol

50 kJ mol1 x

k2

k2

= 3.047

1x105 s1

1x105 s1

k2 = 2 x 10-4 s-1
If the temperature of the reaction mixture was 182 oC and all of the heat released at once the final
temperature would be:
182 oC + 53 oC = 235 oC so the reaction would indeed reach 199 oC.

318