1-1

L.H. Sim
Chapter 1
Kinetics: Rates and Mechanisms
of Chemical Reactions
1-2
L.H. Sim
Kinetics: Rates and Mechanisms of Chemical Reactions
1.1 Expressing Reaction Rate: Differential rate law
Graphical representation of reaction rate
1.2 The Rate Law : Order of reaction, Initial rate method
Integrated rate law, rate constant, half -life
1.3 Collision Theory: Activation energy, effective collisions
1.6 Arrhenius Equation: Determination of rate constant and
activation energy
1.7 Reaction Mechanism: Intermediates, molecularity,
rate determining step
1.4 Factors affecting reaction rate: Concentration, temperature, catalyst,
nature of reactants
1.5 Transition State Theory: Activated complex
1-3
L.H. Sim
1.1 Chemical Kinetics
The speed of a chemical reaction is called its
reaction rate
The rate of a reaction is a measure of how fast
the reaction makes products, or how fast the
reactants are consumed.
Chemical kinetics is the study of the factors
that affect the rates of chemical reactions
Such as temperature, reactant
concentrations, addition of catalyst etc.

3
1-4
L.H. Sim
Figure 1.1
Reaction rate: the central focus of chemical kinetics
1-5
L.H. Sim
1.2 Expressing the Reaction Rate
Reaction rate is defined as the changes in the concentrations of
reactants or products per unit time
Reactant concentrations decrease while product concentrations
Increase. For the reaction
A B
Where [ ] denote the concentration in mol dm
-3
and , the change of
Unit for rate is mol dm
-3
s
-1
or

mol/L s
-1


or mol/dm
3
min
-1

Rate of reaction =
concentration
time
= -
[A
2
]

[A
1
]
t
2
-t
1

= -
[Reactant]
time
Or
A [product]
Rate of reaction = +
At
=
[B
2
]

[B
1
]
t
2
-t
1

1-6
L.H. Sim
Figure 1.2 The wide range of reaction rates.
1-7
L.H. Sim
| | | | | | ( )
( )
( )
( )
0625 0
0 6 1
8 7
Rate
t t
X X
t
X
Rate
1 2
1 2
. =

=
A
A
=
| | | | | | ( )
( )
( )
( )
25 0
0 6 1
8 4
Rate
t t
A A
t
A
Rate
1 2
1 2
. =

=
A
A
=
at t = 0
[A] = 8
[B] = 8
[C] = 0
at t = 0
[X] = 8
[Y] = 8
[Z] = 0
at t = 16
[A] = 4
[B] = 4
[C] = 4
at t = 16
[X] = 7
[Y] = 7
[Z] = 1
| | | | | | ( )
( )
( )
( )
25 0
0 6 1
0 4
Rate
t t
C C
t
C
Rate
1 2
1 2
. =

=
A
A
=
| | | | | | ( )
( )
( )
( )
0625 0
0 6 1
0 1
Rate
t t
Z Z
t
Z
Rate
1 2
1 2
. =

=
A
A
=
7
1-8
L.H. Sim
Initial rate is defined as the rate at the start of the reaction when an
infnitesimally small amount of the reactant has been used up and is
given by the gradient to the curve at time t = 0
Instantaneous rate is the rate at a particular time and is given by the
tangent to the curve at that time in the concentration-time graph.

Average rate is the rate given by the average change in concentration
of a reactant or product per unit time over a certain time interval.

For

Average rate = [ B ] at time t
2
[ B ] at time t
1
t
2
t
1

= [B]
t

t
2
= final time ; t
1
= initial time
1.3 Three different types of rates
A B
1-9
L.H. Sim
Table 1.1 Concentration of O
3
at Various Time in its
Reaction with C
2
H
4
at 303K
C
2
H
4
(g) + O
3
(g) C
2
H
4
O(g) + O
2
(g)
Time (s)
Concentration of O
3
(mol/L)
0.0
20.0
30.0
40.0
50.0
60.0
10.0
3.20x10
-5

2.42x10
-5

1.95x10
-5

1.63x10
-5

1.40x10
-5

1.23x10
-5

1.10x10
-5

A (conc O
3
)
-
At
1-10
L.H. Sim
Figure 1.3
The concentrations of O
3
vs. time during its reaction with C
2
H
4

-
A [C
2
H
4
]
At
rate =
A [O
2
]
At
or
(a) Initial rate, t = 0 s
(d) Instantaneous rate at t = 35 s
h
w
(b) Average rate from t = 10s to
t= 30s is concentration = h
time w
rate =
C
2
H
4
( g ) + O
3
( g ) C
2
H
4
O( g ) + O
2
(
g
)
1-11
L.H. Sim
Figure 1.4
Plots of [C
2
H
4
] and [O
2
] vs. time.
1-12
L.H. Sim
In general, for the reaction
aA + bB cC + dD
rate =
1
a
- = -
A[A]
At
1
b
A[B]
At
1
c
A[C]
At
= +
1
d
A[D]
At
= +
The numerical value of the rate depends upon the substance that
serves as the reference. The rest is relative to the balanced
chemical equation.
1.4 Reaction Rate and Stoichiometry
1-13
L.H. Sim
For the reaction below, the coefficients of the balanced equation
are not all the same
H
2 (g)
+ I
2 (g)
2 HI
(g)

Therefore, the change in the number of molecules of one
substance is a multiple of the change in the number of
molecules of another
for the above reaction, for every 1 mole of H
2
used, 1 mole of
I
2
will also be used and 2 moles of HI made
therefore the rate of change will be different
To be consistent, the change in the concentration of each
substance is multiplied by 1/coefficient
13
1-14
L.H. Sim
average rate in a given time
period = slope of the line
connecting the [H
2
] points; and
slope of the line for [HI]
the average rate for the
first 10 s is 0.0181 M/s
the average rate for the
first 40 s is 0.0150 M/s
the average rate for the
first 80 s is 0.0108 M/s
14
1-15
L.H. Sim
Sample Problem 1.1
PLAN:
SOLUTION:
Expressing Rate in Terms of Changes in
Concentration with Time
PROBLEM: Because it has a nonpolluting product (water vapor), hydrogen
gas is used for fuel aboard the space shuttle and may be used
by Earth-bound engines in the near future.
2H
2
(g) + O
2
(g) 2H
2
O(g)
(a) Express the rate in terms of changes in [H
2
], [O
2
], and [H
2
O] with time.
(b) When [O
2
] is decreasing at 0.23 mol/L*s, at what rate is [H
2
O] increasing?
Choose [O
2
] as a point of reference since its coefficient is 1. For every
molecule of O
2
which disappears, 2 molecules of H
2
disappear and 2
molecules of H
2
O appear, so [O
2
] is disappearing at half the rate of change
of H
2
and H
2
O.
-
1
2
A[H
2
]
At
A[O
2
]
At
= +
A[H
2
O]
At
1
2
0.23mol/L*s
= +
A[H
2
O]
At
1
2
; = 0.46mol/L*s
A[H
2
O]
At
rate =
(a)
A[O
2
]
At
-
= -
(b)
= -
A[O
2
]
At
1-16
L.H. Sim
Sample Problem 1.2
Determine Rate of reaction based on the
stoichiometry of a reaction
PROBLEM: Dinitrogen pentoxide, N
2
O
5
, decomposes to form nitrogen dioxide
and oxygen.
2 N
2
O
5
(g)

4NO
2
(g) + O
2
(g)
NO
2
is produced at a rate of 5.0 x 10
-6
Ms
-1
. What is the
corresponding rate of disappearance of N
2
O
5
and rate of
formation of O
2
?
(2.5 x 10
-6
, 1.25x 10
-6
M/s)
Sample Problem 1.3
PROBLEM: Ammonia,NH
3
, reacts with oxygen to form nitric oxide, NO and
water vapour.
4NH
3
(g)

+

5O
2
(g)

4NO(g) + 6H
2
O(g)
At a specific time in the reaction, NH
3
is disappearing at a rate of
0.068 Ms
-1
. What is the corresponding rate of disappearance ofO
2
and production of NO and H
2
O.
(0.085 , 0.068 , 0.102 M/s)
1-17
L.H. Sim
If 2.4 x 10
2
g of NOBr (MM 109.91 g) decomposes in a
2.0 x 10
2
mL flask in 5.0 minutes, find the average rate of
Br
2
production in M/s.

2 NOBr(g) 2 NO(g) + Br
2
(l)
Sample Problem 1.4
A M
A mole Br
2

Rate
A min
A s
}
0.018 M/s
1-18
L.H. Sim
1.5 Rate Laws and order of reaction
A. Differential rate law or rate law is an experimentally
determined equation that expresses how the rate of a reaction
depends on the concentrations of the reactants
Example: 2N
2
O
5
(g) 4NO
2
(g) + O
2
(g)

Rate [N
2
O
5
]
x

= k [N
2
O
5
]
x
where k = rate constant

x = order of reaction determined experimentally, not equivalent to the
stoichiometric coefficient of a balanced equation
1-19
L.H. Sim
B. The order of reaction is defined as the power to which the
concentration of a reactant is raised in the rate equation or rate law.
It must be determined experimentally.

Overall order of a reaction = sum of the powers of the concentration
terms in the rate law
The order of each reactant concentration explains how the rate of a
reaction varies with the concentration of a particular reactant. For
example
Rate = k [N
2
O
5
]
x
, when

[N
2
O
5
] is doubled,



If x = 0; the rate remains unchanged
If x = 1; the rate doubles
If x = 2; the rate quadruples / increase by a factor of 4
If x = 3; the rate increases eightfold / factor of 8

1-20
L.H. Sim
For the reaction
A product
The proposed rate law : Rate = k[A]
n

If a reaction is Zero Order, the rate of the reaction is
always the same
doubling [A] will have no effect on the reaction rate
If a reaction is First Order, the rate is directly
proportional to the reactant concentration
doubling [A] will double the rate of the reaction
If a reaction is Second Order, the rate is directly
proportional to the square of the reactant concentration
doubling [A] will quadruple the rate of the reaction
20
1-21
L.H. Sim
For a general reaction, A B
Order of
reaction
Differential rate law Units of rate constant (k)
(t in seconds)
zero Rate = k[A]
o
= k

k = mol dm
-3
s
-1
or mol L s
-1
The rate is independent of the
concentration of the reactant as
long as some is present.
First Rate = k[A]
k = rate/[A]
= mol dm
-3
s
-1
mol dm
-3

= s
-1

second Rate = k[A]
2

k = rate/[A]
2
=
mol dm
-3
time
-1
mol
2
dm
-6
= dm
3
mol
-1
s
-1
or L mol
-1
s
-1

Table 1.2: order of reaction and differential rate law
1-22
L.H. Sim
Sample Problem 1.5
SOLUTION:
Determining Reaction Order from Rate Laws
PROBLEM: For each of the following reactions, determine the reaction order
with respect to each reactant and the overall order from the
given rate law.
(a) 2NO(g) + O
2
(g) 2NO
2
(g); rate = k[NO]
2
[O
2
]
(b) CH
3
CHO(g) CH
4
(g) + CO(g); rate = k[CH
3
CHO]
3/2

(c) H
2
O
2
(aq) + 3I
-
(aq) + 2H
+
(aq) I
3
-
(aq) + 2H
2
O(l); rate = k[H
2
O
2
][I
-
]
PLAN: Look at the rate law and not the coefficients of the chemical reaction.
(a) The reaction is 2
nd
order in NO, 1
st
order in O
2
, and 3
rd
order overall.
(b) The reaction is 3/2 order in CH
3
CHO and 3/2 order overall.
(c) The reaction is 1st order in H
2
O
2
, 1
st
order in I
-
and zero order in H
+
,
while being 2
nd
order overall.
1-23
L.H. Sim
In order to determine the order of a reaction, an
experiment has to be carried out to measure the
reaction rates. The results obtained from these
experiments are used to determine the order of the
reaction.
The order of reaction and the rate constant can be
determined by
a) the initial rate method
b) the half-life method
c) Unit of the rate constant
d) linear plots based on the integrated rate law
1.6 To determine the order of a reaction
1-24
L.H. Sim
1.7 Experimental Determining of Reaction Orders
Initial rate method
Run a series of experiments, each of which starts with a different set
of reactant concentrations, and from each obtain an initial rate.
See Table 1.3 for data on the reaction
O
2
(g) + 2NO(g) 2NO
2
(g) rate = k [O
2
]
m
[NO]
n

Compare 2 experiments in which the concentration of one reactant varies
and the concentration of the other reactant(s) remains constant.
k [O
2
]
2
m
[NO]
2
n

k [O
2
]
1
m
[NO]
1
n

=
rate
2

rate
1

=
[O
2
]
2
m

[O
2
]
1
m

=
6.40x10
-3
mol/L*s
3.21x10
-3
mol/L*s
[O
2
]
2

[O
2
]
1

m
=
1.10x10
-2
mol/L
2.20x10
-2
mol/L
m
; 2 = 2
m
m = 1
Do a similar calculation for the other reactant(s).
1-25
L.H. Sim
Table 1.3 Initial Rates for a Series of Experiments in the
Reaction Between O
2
and NO
Experiment
Initial Reactant
Concentrations (mol/L)
Initial Rate
(mol/L*s)
1
2
3
4
5
O
2
NO
1.10x10
-2
1.30x10
-2
3.21x10
-3

1.10x10
-2
3.90x10
-2
28.8x10
-3

2.20x10
-2

1.10x10
-2

3.30x10
-2

1.30x10
-2

2.60x10
-2

1.30x10
-2

6.40x10
-3

12.8x10
-3

9.60x10
-3

2NO(g) + O
2
(g) 2NO
2
(g)
1-26
L.H. Sim
Sample Problem 1.6
PLAN:
SOLUTION:
Determining Reaction Order from Initial Rate Data
PROBLEM: Many gaseous reactions occur in a car engine and exhaust
system. One of these is
NO
2
(g) + CO(g) NO(g) + CO
2
(g) rate = k[NO
2
]
m
[CO]
n

Use the following data to determine the individual and overall reaction orders.
Experiment Initial Rate(mol/L*s) Initial [NO
2
] (mol/L) Initial [CO] (mol/L)
1
2
3
0.0050
0.080
0.0050
0.10
0.10
0.40
0.10
0.10
0.20
Solve for each reactant using the general rate law using the
method described previously.
rate = k [NO
2
]
m
[CO]
n

First, choose two experiments in which [CO] remains
constant and the [NO
2
] varies.
1-27
L.H. Sim
Sample Problem 1.6 Determining Reaction Order from Initial Rate Data
continued
0.080
0.0050
rate 2
rate 1
[NO
2
]

2

[NO
2
]

1
m
=
k [NO
2
]
m
2
[CO]
n
2

k [NO
2
]
m
1
[CO]
n
1
=
0.40
0.10
=
m
;
16 = 4
m
and m = 2
k [NO
2
]
m
3
[CO]
n
3

k [NO
2
]
m
1
[CO]
n
1
[CO]

3

[CO]

1
n
=
rate 3
rate 1
=
0.0050
0.0050
=
0.20
0.10
n
;
1 = 2
n
and n = 0
The reaction is 2
nd

order in NO
2
.
The reaction is
zero order in CO.
rate = k [NO
2
]
2
[CO]
0
= k [NO
2
]
2

1-28
L.H. Sim
Sample Problem 1.7
PROBLEM:
Consider the following reaction and the data given in the
table, determine the rate law for the reaction and also
calculate the rate constant, k.
NH
4
+
(aq) + NO
2
-
(aq) N
2
(g) + 2H
2
O(l)
Expt Initial [NH
4
+]
Initial [NO
2
-
] Initial rate (moldm
-3
s
-1)

1 0.10 0.005 1.35 x 10
-7

2 0.10 0.01 2.70 x 10
-7

3 0.20 0.01 5.40 x 10
-7

1-29
L.H. Sim
The following table shows the results for the reaction
BrO
3
-
(aq) + 5Br
-
(aq) + 6H
+
(aq) 3Br
2
(l) + 3H
2
O(l)
Sample Problem 1.8
PROBLEM:
Expt Initial [BrO
3
-
] Initial [Br
-
] Initial [H
+
] Initial rate (mol dm
-3
s
-1
)
1 0.10 0.10 0.10 8.00 x 10
-4

2 0.20 0.10 0.10 1.60 x 10
-3

3 0.20 0.20 0.10 3.20 x 10
-3

4 0.10 0.10 0.20 3.20 x 10
-3

Determine the order of the reaction with respect to each
reactant and the value of the rate constant.
1-30
L.H. Sim
1.8 Integrated Rate Laws
For the reaction A Products, the rate of the
reaction depends on the concentration of A
Applying calculus to integrate the rate law gives
another equation showing the relationship between
the concentration of A and the time of the reaction
this is called the Integrated Rate Law
30
The integrated Rate Law expresses how the
concentrations of the reactants depend on time. The
expression of an integrated rate law depends on the
order of a reaction.
1-31
L.H. Sim
Almost all experimental work in chemical kinetics deals
with integrated rate laws. The integrated rate laws
derived below are for simple reactions with only one
reactant.
(I) For zero-order reaction : A products

By the rate law (differential); Rate = - d[A] = k

dt

Integrating the differential rate law, we obtained the integrated
rate law
[A]
t
= -kt + [A ]
o

where [A]
o
= initial concentration of A

A plot of [A]
t
versus t gives a straight line, slope = -k and
y-intercept = [A]
o

1-32
L.H. Sim
The half- life of a reaction, t
1/2
is the time required for the concentration
of a reactant to decrease to half its original concentration

[A]
o

= -kt

+ [A]
o
kt

= [A]
o

t

= [A]
o
; ** the half life of a zero order reaction is
2k directly proportional to [A]
o


(II) For first- order reaction aA products

By the rate law , Rate = - d[A] = k[A]
dt
Integrated first-order rate law gives

ln[A]
t
= -kt + ln[A]
o



ln [A]
o
= kt
[A]
t
1-33
L.H. Sim
A plot of ln [A]
t
versus t will give a straight line. slope = k
and y-intercept = ln [A]
o
.
The half-life is derived by rewriting the integrated rate law as

ln{ [A]
o
/ [A]
t
} = kt

At t = t

, [A]
t
= [A]
o
; ln 2 = kt



0.693 = kt

and t

= 0.693/ k

** the half life of a first order reaction is independent of the initial
concentration of reactant. i.e 1
st
half-life (t

2
nd
half-life (t

(III) For second-order reaction aA products

By the rate law, Rate = -d[A] = k[A]
2

dt
Integration of the rate law will give the integrated second order rate
law as
1 = kt + 1
[A]
t
[A]
o
1-34
L.H. Sim
At half-life , t

, where [A]
t
= [A]
o

1 = kt

+ 1
[A]
o
[A]
o


kt

= 2 - 1 = 1
[A]
o
[A]
o
[A]
o

t

= 1
k[A]
o
A plot of 1/[A]
t
versus t give a straight line with a slope = k
and the y-intercept = 1/[A]
o
** The half life of a second order reaction is inversely proportional to
the initial concentration of the reactant
Thus , the second half-life (t

) = 2(t

1-35
L.H. Sim
Summary of Integrated Rate Laws
rate = -
A[A]
At
= k [A]
rate = -
A[A]
At
= k [A]
0

rate = -
A[A]
At
= k [A]
2

first order rate equation
second order rate equation
zero order rate equation
ln
[A]
0
[A]
t
= kt
ln [A]
0
= kt + ln [A]
t

1
[A]
t

1
[A]
0

- = kt
1
[A]
t

1
[A]
0

+ = kt
[A]
t
- [A]
0
= - kt
1-36
L.H. Sim
1.8.1 Relationship Between Order and Half-Life
For a zero order reaction, the half-life is directly
proportional to the initial concentration. The lower the
initial concentration of the reactants, the shorter the
half-life
t
1/2

= [A]
init
/2k
For a first order reaction, the half-life is independent of
the concentration. (t
1/2
= constant)
t
1/2
= ln(2)/k
For a second order reaction, the half-life is inversely
proportional to the initial concentration increasing the
initial concentration shortens the half-life
t
1/2
= 1/(k[A]
init
)
36
1-37
L.H. Sim
Table 1.4 An Overview of Zero-Order, First-Order, and
Simple Second-Order Reactions
Zero Order
First Order Second Order
Plot for straight line
Slope, y-intercept
Half-life
Rate law rate = k
rate = k [A] rate = k [A]
2

Units for k
mol/L*s
S
-1

L/mol*s
Integrated rate
law in straight-
line form
[A]
t
= -k t + [A]
0

ln[A]
t
=
-k t + ln[A]
0

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

[A]
t
vs. t
ln[A]
t
vs. t 1/[A]
t
vs t
-k, [A]
0

-k, ln[A]
0
k, 1/[A]
0

[A]
0
/2k
ln 2/k
1/k [A]
0

1-38
L.H. Sim
Figure 1.5
Integrated rate laws and reaction order
ln[A]
t
= -kt + ln[A]
0

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

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

1-39
L.H. Sim
Figure 1.6 A plot of [N
2
O
5
] vs. time for three half-lives.
For a first-order process, the half-life is a
constant and is independent of initial
concentration
ln 2 0.693
T

=
k k
=
1-40
L.H. Sim
Figure 1.7 Graphical determination of the reaction order for the
decomposition of N
2
O
5
.
The decomposition
reaction of N
2
O
5
is a
first order reaction,
only the plot of ln[N
2
O
5
]
vs t is linear. Plots of
[N
2
O
5
] vs t and
1/[N
2
O
5
] vs t not linear.
1-41
L.H. Sim
Sample Problem 1.9
PLAN:
SOLUTION:
Determining Reaction Concentration at a Given Time
apply integrated rate law
PROBLEM: At 1000
0
C, cyclobutane (C
4
H
8
) decomposes in a first-order
reaction, with the very high rate constant of 87s
-1
, to two
molecules of ethylene (C
2
H
4
).
(a) If the initial C
4
H
8
concentration is 2.00M, what is the
concentration after 0.010 s?
(b) What fraction of C
4
H
8
has decomposed in this time?
Find the [C
4
H
8
] at time, t, using the integrated rate law for a 1st order
reaction. Once that value is found, divide the amount decomposed by
the initial concentration.
; ln
2.00
[C
4
H
8
]
t

= (87s
-1
)(0.010s)
[C
4
H
8
]
t
= 0.83mol/L
ln
[C
4
H
8
]
0

[C
4
H
8
]
t

= kt
(a)
(b) [C
4
H
8
]
0
- [C
4
H
8
]
t
[C
4
H
8
]
0
=
2.00M - 0.87M
2.00M
= 0.58
1-42
L.H. Sim
Sample Problem 1.10
PROBLEM: The decomposition of N
2
O
5
is a first-order reaction with a rate
constant of 5.1 x 10
-4
s
-1
at 45
o
C.
2N
2
O
5
(g) 4NO

(g) + O
2
(g)
a) If the initial concentration of N
2
O
5
is 0.25 M, what is
the concentration after 3.2 min?
b) How long will it take for the concentration of N
2
O
5
to
decrease from 0.25M to 0.15M?
c) How long will it take to convert 62% of the starting
material?
d) Calculate the half-life of the reaction .
(0.25 M, 17 min, 32 min)
1-43
L.H. Sim
Sample Problem 1.11
PROBLEM:
Butadiene reacts to form its dimer according to the equation
2C
4
H
6
(g) C
8
H
12
(g)
The following data were collected for this reaction at a given
temperature
.


[C
4
H
6
(g) ] moldm
-3
Time (s) [C
4
H
6
(g) ] moldm
-3
Time (s)
0.01000 0.000 0.00313 3600
0.00625 1000 0.00270 4400
0.00476 1800 0.00241 5200
0.00370 2800 0.00208 6200
a) Is the reaction first order or second order?
b) What is the value of the rate constant for the reaction?
c) What is the half-life of the reaction?
1-44
L.H. Sim
Sample Problem 1.12
PLAN:
SOLUTION:
Determining the Half-Life of a First-Order Reaction
PROBLEM: Cyclopropane is the smallest cyclic hydrocarbon. Because its
60
0
bond angles allow poor orbital overlap, its bonds are weak.
As a result, it is thermally unstable and rearranges to propene at
1000
0
C via the following first-order reaction:
CH
2
H
2
C CH
2
(g)
A
H
3
C CH CH
2
(g)
The rate constant is 9.2s
-1
, (a) What is the half-life of the reaction? (b) How
long does it take for the concentration of cyclopropane to reach one-quarter of
the initial value?
Use the half-life equation, t

=
0.693
k
, to find the half-life.
One-quarter of the initial value means two half-lives have passed.
t

= 0.693/9.2s
-1
= 0.075s (a) 2 t

= 2(0.075s) = 0.150s (b)
1-45
L.H. Sim
The reaction Q 2 R is second order in Q. If the initial
[Q] = 0.010 M and after 5.0 x 10
2
seconds the [Q] =
0.0010 M,
(i) find the rate constant.
(ii) what is the length of time for [Q] = [Q]
initial

45
Sample Problem 1.13
1-46
L.H. Sim
(ii)
(i)
1-47
L.H. Sim
1.9 Collision Theory: Basis of the Rate Law
The Collision theory is developed from the kinetic theory to explain
the effects of concentration and temperature on reaction rates.
The basic concept of collision is that all chemical reactions occur as a
result of collisions between reacting molecules. However, for a
reaction between two particles to occur, an effective collision must
take place.
Two requirements must be satisfied for effective collisions between
two reacting molecules to take place.

1. The reacting molecules must collide with energy which must be
equal to or greater than the activation energy of the reaction (i.e.
the minimum amount of energy required to initiate a chemical
reaction). (Fig 1.8 & 1.9)

2. The molecules must approach each other in the right orientation
before a collision could lead to product formation. (Fig 1.11)
1-48
L.H. Sim
1.9.1 Activation Energy

The Activation Energy is defined as the minimum amount of kinetic
energy required for a chemical reaction to take place and form
products.
This energy is needed to break chemical bonds of the reactants and to
rearrange atoms and valence electrons to form the products as the
reaction proceeds.
Reaction with low activation energy is easier to take place, and is faster
A reaction profile or energy profile is a plot of energies (potential
energy) versus progress of reaction as shown in Fig 1.9 & 1.14. The
progress of reaction represents the extent of the reaction.
Fig 1.10 (a) and (b) shows the reaction profiles of an exothermic and
endothermic reactions, respectively.
Ea = Activation energy
H = Enthalpy of reaction or Heat of reaction
1-49
L.H. Sim
1.9.2 Effective Collisions depend on TWO Factors
For a collision to
be effective, the
reacting molecules
must have
sufficient kinetic
energy to
overcome the
energy barrier.
49
Figure 1.8
I. Kinetic Energy Factor
1-50
L.H. Sim
50
Figure 1.9
1-51
L.H. Sim
heat in
AH > 0
E
a

Figure 1.10
Reaction profiles of an exothermic and endothermic
reaction
AH < 0 AH < 0 AH < 0 AH < 0 AH < 0 AH < 0 AH < 0 AH < 0
heat out
AH < 0
E
a

(a) Exothermic reaction (b) Endothermic reaction
1-52
L.H. Sim
II. Orientation Factor
The proper orientation results when the atoms
are aligned in such a way that the old bonds can
break and the new bonds can form
The more complex the reactant molecules, the
less frequently they will collide with the proper
orientation
52
1-53
L.H. Sim
53
Figure 1.11
O
N
Cl
O
O
O
Cl
Cl
Cl
1-54
L.H. Sim
1.10 The Transition State Theory - Molecular nature
of the Activated complex
There is an energy barrier (activation energy) to almost all
reactions
There exists an intermediate stage when reactant molecules
change into products.
The activated complex or transition state is a chemical
species with partially broken and partially formed bonds
an intermediate formed between reactant and product
molecules
has highest energy and extremely unstable
54
E
a(forw)
= activation energy for the forward reaction
(from reactant to peak)
E
a(rev)
= activation energy for the reverse reaction
(from product to peak)
1-55
L.H. Sim
Figure 1.12 Energy-level diagram for a reaction
A reaction can occur in either direction, so the diagram shows two
activation energies. The forward reaction is exothermic because
the reactants have more energy than the products and the
E
a(forward)
< E
a(reverse)

C
o
l
l
i
s
i
o
n

E
n
e
r
g
y

ACTIVATED STATE
E
a
(reverse)

PRODUCTS
REACTANTS
E
a
(forward)

C
o
l
l
i
s
i
o
n

E
n
e
r
g
y

For molecules to
react, they must
collide with enough
energy to reach an
activated state. This
minimum collision
energy is the
activation energy,
E
a

1-56
L.H. Sim
Figure 1.13
An energy-level diagram of the fraction of collisions
exceeding E
a
.
1-57
L.H. Sim
Figure 1.14 Reaction energy profile for the reaction of CH
3
Br and OH
-
.
1 2 3 4 5
1-58
L.H. Sim
Refer to the reaction energy profile for the reaction between CH
3
Br
and OH
-
shown in Fig 1.14:
CH
3
Br + OH
-
CH
3
OH + Br
[1] Two molecules that are far apart but speeding toward each other
have high kinetic energy and low potential energy. As the
molecules get closer some kinetic energy is converted to potential
energy as the electron clouds repel each other.
[2] When the molecules collide, kinetic energy is changed into potential
energy because the molecules are distorted during collision to
break bonds and rearrange the atoms ready to form product
molecules. If this potential energy is less than the activation energy
the molecules bounce off without forming product.
[3] A fraction of the molecules which collide with sufficient kinetic
energy along the line of approach to carry them over the
activation barrier, the peak in the reaction profile, then reaction
occur. At the peak, the C-Br bond lengthen and weaken while the
C-OH bond began to form.
1-59
L.H. Sim
At this point during the transformation, the two reacting molecules are
highly distorted, forming the highly energetic and unstable species called
the transition state, or activated complex as shown in Fig 1.14 (3)
and Fig 1.15. The dotted line in the Fig represents bonds in the process
of breaking and making. C is surrounded by 5 atoms
This complex only forms if the molecules collide in an effective orientation
and with energy equal to or greater than the activation energy. Thus the
E
a
is the quantity needed to stretch and deform bonds in order to reach
the transition state
[4] The potential energy of the complex starts to decrease as the new
bond C-O bond in the product shorten and strengthen and the C-Br
bond in the reactant molecule weakens.
[5] At separations to the right of the maximum, the potential energy
rapidly falls to a low value as the product molecules separate .
1-60
L.H. Sim
Figure 1.15
Nature of the transition state in the reaction between CH
3
Br and OH
-
.
CH
3
Br + OH
-
CH
3
OH + Br
-

transition state or activated complex
1-61
L.H. Sim
Figure 1.16
Reaction energy diagrams and possible transition states.
1-62
L.H. Sim
Reaction progress
P
o
t
e
n
t
i
a
l

E
n
e
r
g
y
Sample Problem 1.14
SOLUTION:
Drawing Reaction Energy profile
PROBLEM: A key reaction in the upper atmosphere is
O
3
(g) + O(g) 2O
2
(g)
The E
a(fwd)
is 19 kJ, and the AH
rxn
for the reaction is -392 kJ. Draw a
reaction energy diagram for this reaction, postulate a transition state, and
calculate E
a(rev)
.
PLAN: Consider the relationships among the reactants, products and
transition state. The reactants are at a higher energy level than the
products and the transition state is slightly higher than the
reactants.
O
3
+O
2O
2
E
a
= 19kJ
AH
rxn
= -392kJ
E
a(rev)
= (392 + 19)kJ =
411kJ
O
O
O
O
breaking
bond
forming
bond
transition state
1-63
L.H. Sim

1.11 Factors Affecting Reaction Rate

Any factor that can increase the frequency of effective
collisions would increase the rate of a reaction
Under specific conditions, every reaction has its own
characteristic rate, which may be controlled by four factors:

1. Concentrations of reactants
2. Chemical nature and physical state of reactants
3. Temperature
4. The use of a catalyst
Tro: Chemistry: A Molecular Approach 63
1-64
L.H. Sim
(A) Concentration of reactants
Rate of reaction number of collision
Second
OR Rate of reaction frequency of collision
According to the collision theory, as the number of reacting
molecules in a given volume increase, the frequency of collisions
(the number of collisions that happen per unit time) will be increase
which then increase the amount of effective collisions (the
probability of collisions with sufficient energies for a reaction to
occur). This lead to an increase in the rate of a reaction. (Fig 1.17)
Concentration of gases depends on the partial pressure of the gas
higher pressure = higher concentration

Concentrations of solutions depend on the solute-to-solution ratio
(molarity)
1-65
L.H. Sim
Figure 1.17
The dependence of possible collisions on the product
of reactant concentrations.
A
A
B
B
A
A
B
B
A
4 collisions
Add another
molecule of A
6 collisions
Add another
molecule of B
A
A
B
B
A B
1-66
L.H. Sim
(B) Nature of the Reactants
Nature of the reactants means what kind of reactant molecules
and what physical state they are in
small molecules tend to react faster than large molecules
gases tend to react faster than liquids, which react faster than
solids
powdered solids are more reactive than blocks
more surface area for contact with other reactants leading to
higher frequency of collision. The probability of effective
collision will be increased. Surface area can be increased by
grinding the solids into fine powders. (Fig 1.18)

certain types of chemicals are more reactive than others
e.g. potassium metal is more reactive than sodium
ions react faster than molecules
no bonds need to be broken
66
1-67
L.H. Sim
Figure 1.18 The effect of surface area on reaction rate.
1-68
L.H. Sim
Increasing the temperature raises the average kinetic energy of the
reactant molecules.

Increasing the temperature increases the number of molecules with
sufficient kinetic energy to overcome the activation energy, leads to
an increase in the frequency of effective collisions between
molecules. (Fig 1.19)

The distribution of kinetic energy is shown by the Boltzmann
distribution curves shown in Fig 1.19
Fig 1.19 shows that at both temperatures T
1
and T
2
(T
2 .
> T
1
), a
relatively small fraction of collisions have sufficient kinetic energy
the activation energy to result in a reaction. Moreover, the
fraction of effective collisions

or collisions with the required
activation energy increases exponentially with an increase

in
temperature from T
1
to T
2
(see Fig 1.20).
(C) Temperature
1-69
L.H. Sim
Figure 1.19
The effect of temperature on the distribution of collision energies
1-70
L.H. Sim
1.12 The Arrhenius Equation

The Effect of Temperature
on Reaction Rate

k = Ae

Ea
RT
where k is the kinetic rate constant at T
E
a
is the activation energy
R is the gas constant = 8.314 J K
-1
mol
-1
T is the Kelvin temperature
A is the collision frequency factor
The exponential factor in the Arrhenius
equation is a number between 0 and 1
The larger the activation energy, E
a
, the fewer molecules that have
sufficient energy to overcome the energy barrier, the smaller the rate
constant k.
Increase in temperature, T, will gives a larger k value therefore
increasing the temperature will increase the reaction rate
1-71
L.H. Sim
71
This type of relationship is called an exponential relationship
which means that a small rise in temperature results in a large
increase in the fraction of molecules collide with energy equal to
or greater than the activation energy (Fig 1.19).
1.13 Arrhenius Plots
The Arrhenius Equation: The integrated form
This equation is in the linear form y = mx + b
where y = ln(k) and x = (1/T)
A graph of ln(k) vs. (1/T) is a straight line
e
yintercept
= A (unit is the same as k)
1-72
L.H. Sim
Figure 1.20 Dependence of the rate constant on temperature
1-73
L.H. Sim
Figure 1.21
Graphical determination of the activation energy
ln k = -E
a
/R (1/T) + ln A
1-74
L.H. Sim
Determine the activation energy and frequency factor for the reaction

O
3(g)
O
2(g)
+ O
(g)
given the following data:
74
Sample Problem 1.15
1-75
L.H. Sim
75
Plot the graph ln k versus 1/T. From the straight line curve,
slope = - E
a
/R
y-intercept = ln (frequency factor, A).
Figure 1.22
1-76
L.H. Sim
76
slope, m = -1.12 x 10
4
K
yintercept, b = 26.8
Or ln A = 26.8, anti ln (26.8) = 4.36 x 10
11
M
-1
.s
-1

1-77
L.H. Sim
Table 1.5 The Effect of E
a
and T on the Fraction (f) of Collisions
with Sufficient Energy to Allow Reaction
E
a
(kJ/mol) f (at T = 298 K)
50 1.70x10
-9

75 7.03x10
-14

100 2.90x10
-18

T f (at E
a
= 50 kJ/mol)
25
0
C(298K) 1.70x10
-9

35
0
C(308K) 3.29x10
-9

45
0
C(318K) 6.12x10
-9

1-78
L.H. Sim
1.14 Arrhenius Equation: Two-Point Form
If only two data points i.e two T and two k are
given, the following forms of the Arrhenius
Equation can be used:
78
1-79
L.H. Sim
Sample Problem 1.16
PLAN:
SOLUTION:
Determining the Energy of Activation
PROBLEM: The decomposition of hydrogen iodide,
2HI(g) H
2
(g) + I
2
(g)
has rate constants of 9.51x10
-9
L/mol*s at 500. K and 1.10x10
-5
L/mol*s at
600. K. Find E
a
.
Use the modification of the Arrhenius equation to find E
a
.
ln
k
2

k
1

=
E
a

R
1
T
1

1
T
2

-
R = - (8.314J/mol*K)
E
a
= 1.76x10
5
J/mol = 176 kJ/mol
ln
1
500K
1
600K
-
1.10x10
-5
L/mol*s
9..51x10
-9
L/mol*s
=
8.314 J/Mol*K
E
a

100
500 x 600
ln (0.11567 x 10
4
) =
8.314 J/Mol*K
E
a

7.0533 E
a
x 4.009 x 10
-5

=
1-80
L.H. Sim
Sample Problem 1.17
Determining Activation

Energy graphically
PROBLEM:
The 2
nd
order rate constant for the decomposition of N
2
O
into N
2
and O
2
has been measured at a series of
temperatures.






(a) Determine graphically the activation energy for the
reaction.
(b) Refer to the graph, predict the rate constant at 800K
k (1/M) 1.87x 10
-3
0.0113 0.0569 0.244
t (
oC)
600 650 700 750
1-81
L.H. Sim
Figure 1.23
Information sequence to determine the kinetic parameters of a reaction.
Series of plots
of concentra-
tion vs. time
Initial
rates
Reaction
orders
Rate constant
(k) and actual
rate law
Integrated
rate law
(half-life,
t
1/2
)
Rate constant
and reaction
order
Activation
energy, E
a

Plots of
concentration
vs. time
Find k at
varied T
Determine slope
of tangent at t
0
for
each plot
Compare initial
rates when [A]
changes and [B] is
held constant and
vice versa
Substitute initial rates,
orders, and concentrations
into general rate law:
rate = k [A]
m
[B]
n

Use direct, ln or
inverse plot to
find order
Rearrange to
linear form and
graph
Find k at
varied T
1-82
L.H. Sim
1.15 REACTION MECHANISMS
The reaction mechanism of a chemical reaction is the sequence of
reaction steps or elementary reactions that ultimately lead from the
initial reactants to the final products of a reaction.
An elementary reaction or elementary step represents a single
molecular event, such as dissociation or collision of molecules, in the
progress of the overall reaction.
An Example of a Reaction Mechanism
Overall reaction:
H
2(g)
+ 2 ICl
(g)
2 HCl
(g)
+ I
2(g)

Plausible Mechanism:
Step 1: H
2(g)
+ ICl
(g)
HCl
(g)
+ HI
(g)

Step 2: HI
(g)
+ ICl
(g)
HCl
(g)
+ I
2(g)

The reactions (1) and (2) in this mechanism are called the
elementary steps, meaning that they cannot be broken down
into simpler steps, and that the molecules actually interact directly
in this manner without any other steps
1-83
L.H. Sim
A catalyst does not appear in the net equation, it is consumed in the
first step and produced in the second or last step of the reaction
mechanism.
A reaction intermediate is a substance produced during a
elementary reaction that does not appear in the net equation because
it reacts in a subsequent step or elementary reaction in the
mechanism. In other words, Reaction intermediates are products in
an early mechanism step, but then a reactant in a later step
E.g: Overall reaction: 2H
2
O
2
(aq) 2H
2
O(l) + O
2
(g)

Plausible mechanism : H
2
O
2
+ I
-
H
2
O + OI
-

H
2
O
2
+ OI
-
H
2
O + O
2
+ I
-
OI
-
= intermediate; I
-
= catalyst
1-84
L.H. Sim
Each step in the mechanism is like its own little reaction
with its own activation energy and own rate law
The rate law for an overall reaction must be determined
experimentally
But the rate law of an elementary step can be deduced
directly from the equation of the step
Overall: H
2
(g) + 2 ICl(g) 2 HCl(g) + I
2
(g)
Elementary steps in the reaction mechanism:
1) H
2
(g) + ICl(g) HCl(g) + HI(g) Rate = k
1
[H
2
][ICl]
2) HI(g) + ICl(g) HCl(g) + I
2
(g) Rate = k
2
[HI][ICl]
84
1.15.1 Rate Laws for elementary steps
1-85
L.H. Sim
Molecularity refers to the number of species (free atoms, ions or
molecules) that must collide or dissociates to produce the reaction
indicated by a particular elementary step.
But the probability of more than 3 molecules colliding at the same
instant with the proper orientation and sufficient energy to overcome
the energy barrier is negligible. Most reactions occur in a series of
small reactions involving 1, 2, or at most 3 molecules
Molecularity
Table 1.6 Rate Laws for General Elementary Steps
Rate Law
A + B product
2A + B product
Unimolecular
Bimolecular
Bimolecular
Termolecular
Rate = k [A]
Rate = k [A]
2

Rate = k [A][B]
Rate = k [A]
2
[B]
A product
2A product
Elementary Step
1-86
L.H. Sim
1.15.2 The Rate-Determining Step of a Reaction Mechanism
The overall rate of a reaction is related to the rate of the
slowest, or rate-determining step. The slowest step or rate
determining step has the largest activation energy
The rate law of a reaction is determined by the rate of the rate -
determining step of the acceptable mechanism of the reaction.
The rate law of the rate determining step determines the rate
law of the overall reaction.
1.15.3 A plausible reaction Mechanism must satisfy two
requirements
a) The elementary steps must be physically reasonable and add
up to the overall equation.
b) The mechanism must correlated with the experimentally
determined rate law.
1-87
L.H. Sim
1.15.4 A mechanism with a slow step followed by a fast step
A mechanism can never be proved absolutely correct. We can only
say that a mechanism which satisfy the two requirements is
possibly correct or acceptable .
Example :
The balanced equation for the reaction of NO
2(g)
and F
2(g)
is
2NO
2(g)
+ F
2(g)
2NO
2
F
(g)
The experimentally rate law is Rate = k[NO
2
][F
2
]
A suggested mechanism for the reaction is
k
1
NO
2
+ F
2
NO
2
F + F slow
k
2
F + NO
2
NO
2
F fast
Is this an acceptable mechanism for the reaction?
1-88
L.H. Sim
Requirement 1: Add up the two elementary reactions
k
1
NO
2
+ F
2
NO
2
F + F slow
k
2
F + NO
2
NO
2
F fast
2NO
2(g)
+ F
2(g)
2NO
2
F
(g)
(same as the overall reaction
given)


Requirement 2: write the rate law based on the rate determining step
(i.e. the slow step)
Rate = k
1
[NO
2
][F
2
] (same as the experimentally determined
rate law given )
The mechanism is acceptable as it satisfies the 2 requirements.
1-89
L.H. Sim
Another Reaction Mechanism
The first step in this mechanism
is the rate determining step.
The first step is slower than the
second step because its
activation energy is larger.
The rate law of the first step is
the same as the rate law of the
overall reaction.
89
NO
2(g)
+ CO
(g)
NO
(g)
+ CO
2(g)
Rate
obs
= k[NO
2
]
2

1. NO
2(g)
+ NO
2(g)
NO
3(g)
+ NO
(g)
Rate = k
1
[NO
2
]
2
Slow
2. NO
3(g)
+ CO
(g)
NO
2(g)
+ CO
2(g)
Rate = k
2
[NO
3
][CO] Fast
1-90
L.H. Sim
Sample Problem 1.18
PLAN:
SOLUTION:
Determining Molecularity and Rate Laws for
Elementary Steps
PROBLEM: The following two reactions are proposed as elementary steps in
the mechanism of an overall reaction:
(1) NO
2
Cl(g) NO
2
(g) + Cl

(g)
(2) NO
2
Cl(g) + Cl

(g) NO
2
(g) + Cl
2
(g)
(a) Write the overall balanced equation.
(b) Determine the molecularity of each step.
(a) The overall equation is the sum of the steps.
(b) The molecularity is the sum of the reactant particles in the step.
2NO
2
Cl(g) 2NO
2
(g) + Cl
2
(g)
(c) Write the rate law for each step.
rate
2
= k
2
[NO
2
Cl][Cl]
(1) NO
2
Cl(g) NO
2
(g) + Cl

(g)
(2) NO
2
Cl(g) + Cl

(g) NO
2
(g) + Cl
2
(g)
(a)
Step(1) is unimolecular.
Step(2) is bimolecular.
(b)
rate
1
= k
1
[NO
2
Cl] (c)
1-91
L.H. Sim
Sample Problem 1.19
PROBLEM: (a) Consider the following two-step reaction mechanism for a
chemical reaction.
Step 1. NO
2
(g) + NO
2
(g) NO
3
(g) + NO(g) ..(slow)
Step 2. NO
3
(g) + CO(g) NO
2
(g) + CO
2
(g).(fast)
(i) Write the chemical equation for the overall reaction.
(ii) Identify the reaction intermediate
(iii) What is the order of the reaction?
(b) The decomposition of hydrogen iodide occurs via the action of the
following elementary steps
I. HI + HI H
2
I
2
.

Slow
II. H
2
I
2
H
2
+ 2I fast
III. 2I I
2
.fast

(i) Write the rate law of the reaction and state the order of the
reaction
(ii) What is the molecularity of each of the elementary step?
(iii) Write the stoichiometric equation for the overall reaction.
(iv) State the reaction intermediate.
1-92
L.H. Sim
1.15.5 Mechanism which involve a fast reversible step
Example: The reaction of Cl
2
with CHCl
3
is given by the equation
Cl
2(g)
+ CHCl
3(g)
HCl
(g)
+ CCl
4(g)
The rate law determined experimentally is Rate = k[Cl
2
]

[CHCl
3
]
A proposed mechanism for the reaction is
k
1
Cl
2
2Cl fast
k
-1

k
2
Cl + CHCl
3
HCl + CCl
3
slow
k
3

CCl
3
+ Cl CCl
4
fast
Is this an acceptable mechanism for the reaction?
I) Cl
2
2Cl
Cl + CHCl
3
HCl + CCl
3

CCl
3
+ Cl CCl
4

Cl
2(g)
+ CHCl
3(g)
HCl
(g)
+ CCl
4(g)
1-93
L.H. Sim
II) Rate = k
2
[Cl][CHCl
3
]
Cl is an intermediate which is allowed to be in the rate law. To substitute
the intermediate, we make use of the equilibrium of the fast step.
At equilibrium, rate of forward reaction=rate of reverse reaction
k
1
[Cl
2
] = k
-1
[Cl]
2

[Cl] = (k
1
/k
-1
)

[Cl
2
]

Substitute into the above rate law, Rate = k
2
(k
1
/k
-1
)

[Cl
2
]

[CHCl
3
]
= k[Cl
2
]

[CHCl
3
]
Since the mechanism satisfy the two requirements, it is acceptable

Sample Problem 1.20
PROBLEM: Consider the following reaction
2O
3(g)
3O
2(g)
The experimentally rate law is Rate = k [O
3
]
2
[O
2
]
The mechanism proposed for the reaction is


1-94
L.H. Sim
k
1
O
3
O
2
+ O ( fast equilibrium)
k
-1
k
2

O + O
3
2O
2
(slow)
Verify the acceptability of the proposed mechanism for the above reaction.
Sample Problem 1.21
The equation for the reaction is Tl
3+
+ Hg
2
2+
Tl
+
+ 2Hg
2+
The experimental determined rate law is : rate = k [Tl
3+
] [Hg
2
2+
]
[Hg
2+
]
Verify the acceptability of the proposed mechanisms below :
k
1
Hg
2
2+
Hg
o
+ Hg
2+
(fast)
k
-1

k
2

Tl
3+
+ Hg
o
Tl
+
+ Hg
2+
(slow)
1-95
L.H. Sim
1.16 CATALYSTS
A catalyst is a substance that increases the rate of a chemical
reaction without itself being consumed.
In general a catalyst lowers the activation energy, E
a
, of the reaction
by providing a different mechanism or energy pathway for the
reaction concerned. Lowering E
a
increases the rate constant, k, and
thereby increases the rate of the reaction
A catalyst increases the rate of the forward and the reverse
reactions to the same extent.
A catalyzed reaction yields the products more quickly, but does not
yield more product than the uncatalyzed reaction.
Two types of catalysis:
a) Homogenous catalyst is one that is present in the same phase
or physical state as the reactant molecules. Eg enzyme reaction
b) Heterogeneous catalyst is in a different phase from the
reacting molecules, usually in the solid phase .
1-96
L.H. Sim
Figure 1.24
Reaction energy profile of a catalyzed and an uncatalyzed process.
1-97
L.H. Sim
1. The depletion of ozone in the stratosphere by Cl atoms is an
example of homogeneous catalysis.
Cl(g) + O
3
(g) ClO(g) + O
2
(g)
ClO(g) + O(g) Cl(g) + O
2
(g)
O
3
(g) + O(g) 2O
2
(g) ( Cl catalyst)
The uncatalyzed reaction is O
3
+ O 2O
2
.
2. The decomposition of H
2
O
2
catalyzed by I
-
ion.
H
2
O
2
+ I
-
H
2
O + IO
-

H
2
O
2
+ IO
-
H
2
O + O
2
+ I
-
The uncatalyzed reaction is 2H
2
O
2
2H
2
O + O
2
.

3. The hydrolysis of an organic ester (RCOOR) to form a carboxylic
acid (RCOOH), the reaction is catalyzed by a strong acid (H
+
).


R C

O R + H
2
O R C OH + R OH

(uncatalyzed)
O
O
Examples of reactions catalyzed by homogeneous catalysts
1-98
L.H. Sim
Figure 1.25 The metal-catalyzed hydrogenation of ethylene-
heterogeneous catalysis
H
2
C CH
2
(g) + H
2
(g) H
3
C CH
3
(g)
Ni
1-99
L.H. Sim
CH
3
CH CH
2
+ H
2
CH
3
CH CH
2

H H
Ni
Example 2: Hydrogenation of an alkene catalyzed by Ni
propene
propane
1-100
L.H. Sim
Table 1.7