Chemical Kinetics

Chapter 13

1
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Method of Initial Rates

CHM023 CPMONTEROLA
 Learning Outcome
11. Express rate equation in terms of concentration of reactant or
product. (CO4)
 Chemical Kinetics

Thermodynamics – does a reaction take place?

Kinetics – how fast does a reaction proceed?

Reaction rate is the change in the concentration of a

reactant or a product with time (M/s).

A B
[A] [A] = change in concentration of A over
rate = -
t time period t
[B] [B] = change in concentration of B over
rate =
t time period t
Because [A] decreases with time, [A] is negative.
4
 A B

[A]
rate = -
t

[B]
rate =
t

5
 red-brown
Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)

time

t1 < t2 < t 3

393 nm Detector
light
[Br2]  Absorption
6
 Learning Outcome
12. Relate stoichiometry and rate equation.
(CO2, CO3, CO4)

7
 Reaction Rates and Stoichiometry

2A B

Two moles of A disappear for each mole of B that is formed.

1 [A] [B]
rate = - rate =
2 t t

aA + bB cC + dD

1 [A] 1 [B] 1 [C] 1 [D]

rate = - =- = =
a t b t c t d t

8
Example 13.1
Write the rate expressions for the following reactions in terms of
the disappearance of the reactants and the appearance of the
products:
Example 13.1
Strategy To express the rate of the reaction in terms of the
change in concentration of a reactant or product with time, we
need to use the proper sign (minus or plus) and the reciprocal
of the stoichiometric coefficient.

Solution
•Because each of the stoichiometric coefficients equals 1,

•Here the coefficients are 4, 5, 4, and 6, so

Example

For the hypothetical reaction A + 3B  2C, the rate of

appearance of C given by ([C]/t) may also be expressed
as
A) [C]/t = [A]/t
B) [C]/t = –(3/2) [B]/t
C) [C]/t = –(2/3) [B]/t
D) [C]/t = –(1/2) [A]/t

11
Example 13.2
Consider the reaction

Suppose that, at a particular moment during the reaction,

molecular oxygen is reacting at the rate of 0.024 M/s.

(a)At what rate is N2O5 being formed?

(b)At what rate is NO2 reacting?

Example 13.2
Strategy To calculate the rate of formation of N2O5 and
disappearance of NO2, we need to express the rate of the
reaction in terms of the stoichiometric coefficients as in
Example 13.1:

We are given

where the minus sign shows that the concentration of O2 is

decreasing with time.
Example 13.2
Solution
(a)From the preceding rate expression we have

Therefore
Example 13.2
(b) Here we have

so
Example

1. Chlorine dioxide reacts in basic water to form chlorite and chlorate according to the
following chemical equation:
2ClO2(aq) + 2OH–(aq)  ClO2–(aq) + ClO3–(aq) + H2O(l)
Under a certain set of conditions, the initial rate of disappearance of chlorine dioxide was
determined to be 2.30 x 10–1 M/s. What is the initial rate of appearance of chlorite ion
under those same conditions?
A) 5.75 x 10–2 M/s D) 4.60 x 10–1 M/s
B) 1.15 x 10–1 M/s E) 9.20 x 10–1 M/s
C) 2.30 x 10–1 M/s
Ans: B Category: Medium

16
Example

2. For the reaction BrO3– + 5Br–+ 6H+  3Br2 + 3H2O at a

particular time, –[BrO3–]/t = 1.5 × 10–2 M/s. What is
–[Br–]/t at the same instant?
A) 13 M/s D) 3.0 × 10–3 M/s
B) 7.5 × 10–2 M/s E) 330 M/s
C) 1.5 × 10–2 M/s
Ans:   Category:  Medium Section:  13.1

17
 Learning Outcome
13. Solve for the rate constant and order of
reaction using the method of initial rates
(CO4)
 The Rate Law
The rate law expresses the relationship of the rate of a reaction
to the rate constant and the concentrations of the reactants
raised to some powers.
aA + bB cC + dD

Rate = k [A]x[B]y

Reaction is xth order in A

Reaction is yth order in B
Reaction is (x +y)th order overall

19
 Rate Laws
• Rate laws are always determined experimentally.

• Reaction order is always defined in terms of reactant

(not product) concentrations.

• The order of a reactant is not related to the

stoichiometric coefficient of the reactant in the balanced
chemical equation.

F2 (g) + 2ClO2 (g) 2FClO2 (g)

rate = k [F2][ClO2] 1

20
Example 13.3
The reaction of nitric oxide with hydrogen at 1280°C is

From the following data collected at this temperature, determine

(a) the rate law
(b) the rate constant
(c) the rate of the reaction when [NO] = 12.0 × 10−3 M and
[H2] = 6.0 × 10 −3 M
Example 13.3
Strategy We are given a set of concentration and reaction rate
data and asked to determine the rate law and the rate constant.

We assume that the rate law takes the form

rate = k[NO]x [H2]y

How do we use the data to determine x and y?

Once the orders of the reactants are known, we can calculate k

from any set of rate and concentrations.

Finally, the rate law enables us to calculate the rate at any

concentrations of NO and H2.
Example 13.3
Solution (a) Experiments 1 and 2 show that when we double
the concentration of NO at constant concentration of H 2, the rate
quadruples. Taking the ratio of the rates from these two
experiments

Therefore,

or x = 2, that is, the reaction is second order in NO.

Example 13.3
Experiments 2 and 3 indicate that doubling [H2] at constant [NO]
doubles the rate. Here we write the ratio as

Therefore,

or y = 1, that is, the reaction is first order in H2. Hence the rate
law is given by

which shows that it is a (2 + 1) or third-order reaction overall.

Example 13.3
(b) The rate constant k can be calculated using the data from
any one of the experiments. Rearranging the rate law, we
get

The data from experiment 2 give us

Example 13.3
(c) Using the known rate constant and concentrations of NO
and H2, we write

Comment Note that the reaction is first order in H2, whereas

the stoichiometric coefficient for H2 in the balanced equation
is 2. The order of a reactant is not related to the
stoichiometric coefficient of the reactant in the overall
balanced equation.
Example
Seat work: F2 (g) + 2ClO2 (g) 2FClO2 (g)

From the following data collected at this temperature, determine

(a) the rate law
(b) the rate constant
(c) the rate of the reaction when [ClO2] = 0.03M and [F2]=0.15M
 First-Order Reactions
[A]
A product rate = - rate = k [A]
t
[A]
rate M/s - = k [A]
k= = = 1/s or s-1 t
[A] M
[A] is the concentration of A at any time t
[A]0 is the concentration of A at time t=0

[A] = [A]0e−kt ln[A] = ln[A]0 - kt

28
Example 13.4
The conversion of cyclopropane to propene in the gas phase is a
first-order reaction with a rate constant of 6.7 × 10 −4 s−1 at 500°C.

•If the initial concentration of cyclopropane was 0.25 M, what is

the concentration after 8.8 min?

•How long (in minutes) will it take for the concentration of

cyclopropane to decrease from 0.25 M to 0.15 M?

•How long (in minutes) will it take to convert 74 percent of the

starting material?
Example 13.4
Strategy The relationship between the concentrations of a
reactant at different times in a first-order reaction is given by
Equation (13.3) or (13.4).
In (a) we are given [A]0 = 0.25 M and asked for [A]t after 8.8
min.
In (b) we are asked to calculate the time it takes for
cyclopropane to decrease in concentration from 0.25 M to
0.15 M.
No concentration values are given for (c). However, if initially we
have 100 percent of the compound and 74 percent has reacted,
then what is left must be (100% − 74%), or 26%. Thus, the ratio
of the percentages will be equal to the ratio of the actual
concentrations; that is, [A]t/[A]0 = 26%/100%, or 0.26/1.00.
Example 13.4
Solution (a) In applying Equation (13.4), we note that because k
is given in units of s−1, we must first convert 8.8 min to seconds:

We write

Hence,

Note that in the ln [A]0 term, [A]0 is expressed as a dimensionless

quantity (0.25) because we cannot take the logarithm of units.
Example 13.4
(b) Using Equation (13.3),

(c) From Equation (13.3),

Example
Sample Problem
• The half life of carbon 14 is 5730 years.
In the 1988 cut piece samples of the
Shroud of Turin was subjected to
carbon dating. 92% of the original
carbon 14 is still present in the cloth.
Calculate the year the cloth is produced.

33
Example
Seat work

• The half life of strontium 90 is 28.78 years.

Strontium 90 is quiet similar to Calcium, it
found its way from grasses to milk and can
possibly cause cancer to humans. In 2011 a
9.0 magnitude earthquake hits Japan
causing nuclear waste leaking from
Fukushima Nuclear Plant. Calculate the
percent of strontium 90 from the Fukushima
nuclear plant that is still present in 2015.
34
Example

16. Appropriate units for a first-order rate constant are

A) M/s B) 1/M·s C) 1/s D) 1/M2·s

35
Example

36. A city's water supply is contaminated with a toxin at a

concentration of 0.63 mg/L. Fortunately, this toxin decomposes
to a safe mixture of products by first-order kinetics with a rate
constant of 0.27 day–1. How long will it take for half of the
toxin to decompose?
A) 0.17 days B) 0.27 days C) 0.38 days D) 2.3 days
E) 2.6 days

36
Example

25. The half life for a first order reaction is 45 min. What is the
rate constant in units of s-1?
A) 0.015 s-1 B) 65 s-1 C) 2.6 x 10-4 s-1 D) 3.9 x
103 s-1 E) 1.9 x 103 s-1

37
Example
22. At 25°C the rate constant for the first-order
decomposition of a pesticide solution is 6.40 × 10–3 min–
1
. If the starting concentration of pesticide is 0.0314 M,
what concentration will remain after 62.0 min at 25°C?
A) 1.14 × 10–1 M D) 2.11 × 10–2 M
B) 47.4 M E) 2.68 × 10–2 M
C) –8.72.0 M

38
Example

23. A certain first-order reaction A  B is 25%

complete in 42 min at 25°C. What is the half-life
of the reaction?
A) 21 min B) 42 min C) 84 min D) 20
min E) 101 min

39
Example

24. The half life for a first order reaction is 27 min. How
long will it take for 4 half lives to occur?
A) 53,000 min D) 260 min
B) 108 min E) Not enough information
given
C) 81 min

40
Graphical Determination of k

2N2O5 4NO2 (g) + O2 (g)

41
Example 13.5
The rate of decomposition of azomethane (C2H6N2) is studied by
monitoring the partial pressure of the reactant as a function of
time:

The data obtained at 300°C are shown in the following table:

Are these values consistent with first-order kinetics? If so,

determine the rate constant.
Example 13.5
Strategy To test for first-order kinetics, we consider the
integrated first-order rate law that has a linear form, which is
Equation (13.4)

If the reaction is first order, then a plot of ln [A]t versus t (y versus

x) will produce a straight line with a slope equal to 2k. Note that
the partial pressure of azomethane at any time is directly
proportional to its concentration in moles per liter (PV = nRT,
so P  n/V). Therefore, we substitute partial pressure for
concentration [Equation (13.5)]:

where P0 and Pt are the partial pressures of azomethane at t = 0

and t = t, respectively.
Example 13.5
Solution First we construct the following table of t versus ln Pt.

Figure 13.11, which is based on the data given in the table,

shows that a plot of ln Pt versus t yields a straight line, so the
reaction is indeed first order. The slope of the line is given by
Example 13.5
According to Equation (13.4), the slope is equal to −k, so
k = 2.55 × 10−3 s−1 .
 First-Order Reactions

The half-life, t½, is the time required for the concentration of a

reactant to decrease to half of its initial concentration.
t½ = t when [A] = [A]0/2

[A]0
ln
[A]0/2 ln 2 0.693
t½ = = =
k k k

46
First-order reaction
A product

# of
half-lives [A] = [A]0/n
1 2

2 4

3 8

4 16

47
Example 13.6
The decomposition of ethane (C2H6) to methyl radicals is a first-
order reaction with a rate constant of 5.36 × 10−4 s−1 at 700°C:

Calculate the half-life of the reaction in minutes.

Example 13.6
Strategy To calculate the half-life of a first-order reaction, we
use Equation (13.6). A conversion is needed to express the
half-life in minutes.

Solution For a first-order reaction, we only need the rate

constant to calculate the half-life of the reaction. From Equation
(13.6)
 Second-Order Reactions
[A]
A product rate = - rate = k [A]2
t

rate M/s [A]

k= = 2 = 1/M•s
- = k [A]2
[A] 2 M t

1 1 [A] is the concentration of A at any time t

= + kt
[A] [A]0 [A]0 is the concentration of A at time t=0

t½ = t when [A] = [A]0/2

1
t½ =
k[A]0

50
Example 13.7
Iodine atoms combine to form molecular iodine in the gas
phase

This reaction follows second-order kinetics and has the high

rate constant 7.0 × 109/M · s at 23°C.

•If the initial concentration of I was 0.086 M, calculate the

concentration after 2.0 min.

•Calculate the half-life of the reaction if the initial concentration

of I is 0.60 M and if it is 0.42 M.
Example 13.7
Strategy
(a)The relationship between the concentrations of a reactant at
different times is given by the integrated rate law. Because this
is a second-order reaction, we use Equation (13.7).

(b)We are asked to calculate the half-life. The half-life for a

second-order reaction is given by Equation (13.8).

Solution (a) To calculate the concentration of a species at a

later time of a second−order reaction, we need the initial
concentration and the rate constant. Applying Equation (13.7)
Example 13.7
where [A]t is the concentration at t = 2.0 min. Solving the
equation, we get

This is such a low concentration that it is virtually undetectable.

The very large rate constant for the reaction means that nearly
all the I atoms combine after only 2.0 min of reaction time.
(b) We need Equation (13.8) for this part.
For [I]0 = 0.60 M
Example 13.7
For [I]0 = 0.42 M

Check These results confirm that the half-life of a second-

order reaction, unlike that of a first-order reaction, is not a
constant but depends on the initial concentration of the
reactant(s).

Does it make sense that a larger initial concentration should

have a shorter half-life?
 Zero-Order Reactions
[A]
A product rate = - rate = k [A]0 = k
t

rate [A]
k= = M/s - =k
[A] 0
t

[A] is the concentration of A at any time t

[A] = [A]0 - kt
[A]0 is the concentration of A at time t = 0

t½ = t when [A] = [A]0/2

[A]0
t½ =
2k

55
13. Concerning the rate law, Rate = k[A]0, what are
appropriate units for the rate constant k?
A) s-1 B) M-1s-1 C) M-2s-1 D) M/s E) M2/s

56
53. For what order reaction does the half-life get longer as the
initial concentration increases?
A) zero order
B) first order
C) second order
D) none of them because half-life is always independent of
the initial concentration
Ans:  A Category:  Medium Section:  13.3

57
 
50. For the chemical reaction A  B + C, a plot of
[A]t versus time is found to give a straight line with a negative
slope. What is the order of reaction with respect to A?
A) zero
B) first
C) second
D) third
E) Such a plot cannot reveal the order of the
reaction.

58
Summary of the Kinetics of Zero-Order, First-Order
and Second-Order Reactions

Concentration-Time
Order Rate Law Equation Half-Life
[A]0
0 rate = k [A] = [A]0 - kt t½ =
2k

1 rate = k [A] ln[A] = ln[A]0 - kt t½ = ln 2

k
1 1 1
2 rate = k [A] 2 = + kt t½ =
[A] [A]0 k[A]0

59
 A+B AB++ C+D
Exothermic Reaction Endothermic Reaction

The activation energy (Ea ) is the minimum amount of

energy required to initiate a chemical reaction.
60
Temperature Dependence of the Rate Constant

k  A  e ( Ea / RT )
(Arrhenius equation)
Ea is the activation energy (J/mol)
R is the gas constant (8.314 J/K•mol)
T is the absolute temperature
A is the frequency factor

Alternate format:

Ea 1
ln k = - + lnA
R T
61
Example 13.8
The rate constants for the decomposition of acetaldehyde

were measured at five different temperatures. The data are

shown in the table. Plot ln k versus 1/T, and determine the
activation energy (in kJ/mol) for the reaction. Note that the
reaction is “3/2” order in CH3CHO, so k has the units of
1/M½ ·s.
Example 13.8
Strategy Consider the Arrhenius equation written as a linear
equation

A plot of ln k versus 1/T (y versus x) will produce a straight line

with a slope equal to −Ea/R. Thus, the activation energy can be
determined from the slope of the plot.
Example 13.8
Solution First we convert the data to the following table

A plot of these data yields the graph in Figure 13.18. The slope
of the line is calculated from two pairs of coordinates:
Example 13.8
From the linear form of Equation (13.13)

Check It is important to note that although the rate constant

itself has the units 1/M½ · s, the quantity ln k has no units (we
cannot take the logarithm of a unit).
 Alternate Form of the Arrhenius Equation

At two temperatures, T1 and T2

or

66
Example 13.9
The rate constant of a first-order reaction is 3.46 × 10−2 s−1 at
298 K.

What is the rate constant at 350 K if the activation energy for

the reaction is 50.2 kJ/mol?
Example 13.9
Strategy A modified form of the Arrhenius equation relates two
rate constants at two different temperatures [see Equation
(13.14)]. Make sure the units of R and Ea are consistent.

Solution The data are

Substituting in Equation (13.14),

Example 13.9
We convert Ea to units of J/mol to match the units of R. Solving
the equation gives

Check The rate constant is expected to be greater at a higher

temperature. Therefore, the answer is reasonable.
 Sample problem Arrhenius
• The frequency of sound produced by
chirping of tree crickets follows the
Arrhenius Equation. If the activation
energy, Ea is 51 kJ/mol and the pre-
exponential frequency factor, A is
1.55 X 1011. Calculate the frequency of sound
produced by tree cricket at 298 K.

70
 Seat work Arrhenius
Calculate the rate constant, k, of a reaction at
298 K if its activation energy is 50.2 kJ/mol
and A is 2.2 X 107 per s.

71
Importance of Molecular Orientation

effective collision

ineffective collision
72
 Reaction Mechanisms

The overall progress of a chemical reaction can be represented

at the molecular level by a series of simple elementary steps
or elementary reactions.

The sequence of elementary steps that leads to product

formation is the reaction mechanism.

2NO (g) + O2 (g) 2NO2 (g)

N2O2 is detected during the reaction!

Elementary step: NO + NO N 2 O2
+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2
73
 2NO (g) + O2 (g) 2NO2 (g)
Mechanism:

74
Intermediates are species that appear in a reaction
mechanism but not in the overall balanced equation.
An intermediate is always formed in an early elementary step
and consumed in a later elementary step.

Elementary step: NO + NO N 2 O2
+ Elementary step: N2O2 + O2 2NO2
Overall reaction: 2NO + O2 2NO2

The molecularity of a reaction is the number of molecules

reacting in an elementary step.
• Unimolecular reaction – elementary step with 1 molecule
• Bimolecular reaction – elementary step with 2 molecules
• Termolecular reaction – elementary step with 3 molecules
75
 Rate Laws and Elementary Steps

Unimolecular reaction A products rate = k [A]

Bimolecular reaction A+B products rate = k [A][B]

Bimolecular reaction A+A products rate = k [A]2

Writing plausible reaction mechanisms:

• The sum of the elementary steps must give the overall
balanced equation for the reaction.
• The rate-determining step should predict the same rate
law that is determined experimentally.
The rate-determining step is the slowest step in the
sequence of steps leading to product formation.
76
Sequence of Steps in Studying a Reaction Mechanism

77
Example 13.10
The gas-phase decomposition of nitrous oxide (N2O) is believed
to occur via two elementary steps:

Experimentally the rate law is found to be rate = k[N2O].

•Write the equation for the overall reaction.

•Identify the intermediate.

•What can you say about the relative rates of steps 1 and 2?
Example 13.10
Strategy
(a)Because the overall reaction can be broken down into
elementary steps, knowing the elementary steps would enable
us to write the overall reaction.

(b)What are the characteristics of an intermediate? Does it

appear in the overall reaction?

(c)What determines which elementary step is rate determining?

How does a knowledge of the rate-determining step help us
write the rate law of a reaction?
Example 13.10
Solution
(a)Adding the equations for steps 1 and 2 gives the overall
reaction

(b)Because the O atom is produced in the first elementary step

and it does not appear in the overall balanced equation, it is an
intermediate.

(c)If we assume that step 1 is the rate-determining step, then

the rate of the overall reaction is given by

and k = k1.
Example 13.10
Check There are two criteria that must be met for a proposed
reaction mechanism to be plausible.

•The individual steps (elementary steps) must sum to the

corrected overall reaction.

•The rate-determining step (the slow step) must have the same
rate law as the experimentally determined rate law.
A catalyst is a substance that increases the rate of a
chemical reaction without itself being consumed.
k  A  e ( Ea / RT ) Ea k
Uncatalyzed Catalyzed

ratecatalyzed > rateuncatalyzed

Ea′ < Ea 82
In heterogeneous catalysis, the reactants and the catalysts
are in different phases.
• Haber synthesis of ammonia
• Ostwald process for the production of nitric acid
• Catalytic converters

In homogeneous catalysis, the reactants and the catalysts

are dispersed in a single phase, usually liquid.

• Acid catalysis
• Base catalysis

83
 Haber Process

Fe/Al2O3/K2O
N2 (g) + 3H2 (g) 2NH3 (g)
catalyst

84
 Ostwald Process
Pt catalyst
4NH3 (g) + 5O2 (g) 4NO (g) + 6H2O (g)
2NO (g) + O2 (g) 2NO2 (g)

2NO2 (g) + H2O (l) HNO2 (aq) + HNO3 (aq)

Pt-Rh catalysts used

85
in Ostwald process
 Catalytic Converters

catalytic
CO + Unburned Hydrocarbons + O2 converter CO2 + H2O
catalytic
2NO + 2NO2 converter 2N2 + 3O2

86
Enzyme Catalysis

87
Binding of Glucose to Hexokinase

88
 Enzyme Kinetics

[P]
rate =
t

rate = k [ES]

89
6. For the overall chemical reaction shown below, which one of
the following statements can be rightly assumed?
2H2S(g) + O2(g)  2S(s) + 2H2O(l)
A) The reaction is third-order overall.
B) The reaction is second-order overall.
C) The rate law is, rate = k[H2S]2 [O2].
D) The rate law is, rate = k[H2S] [O2].
E) The rate law cannot be determined from the information
given.
Ans:   Category:  Medium Section:  13.2

90
7. The reaction A + 2B  products has been found to
have the rate law, rate = k[A] [B]2. While holding
the concentration of A constant, the concentration
of B is increased from x to 3x. Predict by what
factor the rate of reaction increases.
A) 3 B) 6 C) 9 D) 27 E) 30
Ans:   Category:  Medium Section:  13.2
 

91
12. Concerning the rate law, Rate = k[A][B], what are
appropriate units for the rate constant k?
A) s-1 B) M-1s-1 C) M-2s-1 D) M/s E) M2/s

13. Concerning the rate law, Rate = k[A]0, what are

appropriate units for the rate constant k?
A) s-1 B) M-1s-1 C) M-2s-1 D) M/s E) M2/s

92
31. Appropriate units for a second-order rate
constant are
A) M/s B) 1/M·s C) 1/s D) 1/M2·s

93
39. A reaction was experimentally determined to follow the rate
law, Rate = k[A]2 where k = 0.456 s-1M-1. Starting with [A]o
= 0.500 M, how many seconds will it take for [A]t = 0.250
M?
A) 2.85 x 10-2 s B) 1.14 x 10-1 s C) 1.52 s D)
4.39 s E) 5.48x10-1 s
Ans:   Category:  Medium Section:  13.3

94
45. At 25°C, the second-order reaction NOCl(g)  NO(g) +
1
/2Cl2(g) is 50% complete after 5.82 hours when the initial
concentration of NOCl is 4.46 mol/L. How long will it take
for the reaction to be 75% complete?
A) 8.22 hr B) 11.6 hr C) 15.5 hr D) 17.5 hr E)
23.0 hr
Ans:  D Category:  Medium Section:  13.3

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47. The reaction 2NO2(g)  2NO(g) + O2(g) is suspected to be
second order in NO2. Which of the following kinetic plots
would be the most useful to confirm whether or not the
reaction is second order?
A) a plot of [NO2]–1 vs. t D) a plot of ln [NO2]–1 vs. t
B) a plot of ln [NO2] vs. tE) a plot of [NO2]2 vs. t
C) a plot of [NO2] vs. t

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51. For the chemical reaction A  C, a plot of 1/[A]t versus
time was found to give a straight line with a positive
slope. What is the order of reaction?
A) zeroth
B) first
C) second
D) Such a plot cannot reveal the order of the reaction.
Ans:  C Category:  Medium Section:  13.3
 

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52. The graphs below all refer to the same reaction. What is the order of this reaction?

A) zero order B) first order C) second order D) unable to predict

Ans: A Category: Medium Section: 13.3

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60. Which one of the following changes would alter the
rate constant (k) for the reaction 2A + B  products?
A) increasing the concentration of A
B) increasing the concentration of B
C) increasing the temperature
D) measuring k again after the reaction has run for a
while
Ans:  C Category:  Medium Section:  13.4

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61.The Arrhenius equation is k = Ae–Ea/RT. The
slope of a plot of ln k vs. 1/T is equal to
A) –k B) k C) Ea D) –Ea /R E) A
Ans:  D Category:  Medium
Section:  13.4

100
63. The activation energy for the reaction CH3CO 
CH3 + CO is 71 kJ/mol. How many times greater is the
rate constant for this reaction at 170°C than at 150°C?
A) 0.40 B) 1.1 C) 2.5 D) 4.0 E) 5.0
Ans: C Category: Medium Section:
13.4

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66. At 30°C, by how much is a reaction's activation energy
decreased by the addition of a catalyst if the catalyst triples
the reaction rate?
A) 2.77 kJ/mol B) 274 J/mol C) 2.70 J/mol D) 119
J/mol E) 1.20 kJ/mol
Ans:  A Category:  Medium Section:  13.6
 

102
80.The following mechanism has been suggested for the reaction:
H2O2 + 2H+ + 2I –  I2 + 2H2O
H2O2 + I –  HOI + OH – Slow
OH – + H+  H2O Fast
HOI + H+ + I –  I2 + H2O Fast
Identify all intermediates included in this mechanism.
A) H+ and I – D) H+ only
B) H+ and HOI E) H2O and OH–
C) HOI and OH–
Ans: C Category: Medium Section: 13.5

103
81.The following mechanism has been suggested for the reaction:
H2O2 + 2H+ + 2I –  I2 + 2H2O
H2O2 + I –  HOI + OH – Slow
OH – + H+  H2O Fast
HOI + H+ + I –  I2 + H2O Fast
Identify the rate law that is consistent with this mechanism
A) Rate = k[H2O2][I-] D) Rate = k[HOI][H+][I-]
B) Rate = k[HOI][OH-] E) Rate = k[H2O2][[I-]2[H+]2
C) Rate = k[OH-][H+]
Ans: A Category: Medium Section: 13.5

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 82. The following mechanism has been suggested for the reaction:
H2O2 + 2H+ + 2I –  I2 + 2H2O
H2O2 + I –  HOI + OH – Slow
OH – + H+  H2O Fast
HOI + H+ + I –  I2 + H2O Fast
Identify the molecularity of the rate determining step
A) unimolecular D) unimolecular and bimolecular
B) bimolecular E) bimolecular and termolecular
C) termolecular
Ans: B Category: Easy Section: 13.5

105
84.The rate law for the reaction 2NO2 + O3  N2O5 + O2 is rate = k[NO2][O3]. Which one of
the following mechanisms is consistent with this rate law?
A) NO2 + NO2  N2O4 (fast)
N2O4 + O3  N2O5 + O2 (slow)
B) NO2 + O3  NO5 (fast)
NO5 + NO5  N2O5 + 5/2O2 (slow)
C) NO2 + O3  NO3 + O2 (slow)
NO3 + NO2  N2O5 (fast)
D) NO2 + NO2  N2O2 + O2 (slow)
N2O2 + O3  N2O5 (fast)
Ans: C Category: Medium Section: 13.5

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85. For the reaction X2 + Y + Z  XY + XZ, it is found that the rate equation is rate = k
[X2][Y]. Why does the concentration of Z have no effect on the rate?
A) The concentration of Z is very small and the others are very large.
B) Z must react in a step after the rate determining step.
C) Z is an intermediate.
D) The fraction of molecules of Z that have very high energies is zero.
E) The activation energy for Z to react is very high.
Ans: B Category: Medium Section: 13.5

107
87.Which of the following elementary steps is bimolecular?
A) 2A + B  A2B D) A2  2
B) 3B  B2 + B E) 2A  2
C) A + B + C  AB + C
Ans: E Category: Easy Section: 13.5

108
89.Which of the following statements is false?
A) A catalyst increases the rate of the forward reaction, but does not alter the reverse
rate.
B) A catalyst alters the mechanism of reaction.
C) A catalyst alters the activation energy.
D) A catalyst may be altered in the reaction, but is always regenerated.
E) A catalyst increases the rate of reaction, but is not consumed.
Ans: A Category: Medium Section: 13.6

109