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Chapter 13

Chemical
Kinetics
2008, Prentice Hall
Chemistry: A Molecular Approach, 1
st
Ed.
Nivaldo Tro
Roy Kennedy
Massachusetts Bay Community College
Wellesley Hills, MA
Tro, Chemistry: A Molecular Approach 2
kinetics is the study of the factors that affect
the speed of a reaction and the mechanism
by which a reaction proceeds.
experimentally it is shown that there are 4
factors that influence the speed of a
reaction:
nature of the reactants,
temperature,
catalysts,
concentration
Kinetics
Tro, Chemistry: A Molecular Approach 3
Defining Rate
rate is how much a quantity changes in a given
period of time
the speed you drive your car is a rate the distance
your car travels (miles) in a given period of time (1
hour)
so the rate of your car has units of mi/hr
time
distance
Speed
A
A
=
Tro, Chemistry: A Molecular Approach 4
Defining Reaction Rate
the rate of a chemical reaction is generally measured in
terms of how much the concentration of a reactant
decreases in a given period of time
or product concentration increases
for reactants, a negative sign is placed in front of the
definition
time
[reactant]
time
[product]
Rate
time
ion concentrat
Rate
A
A
=
A
A
=
A
A
=
Tro, Chemistry: A Molecular Approach 5
Reaction Rate Changes Over Time
as time goes on, the rate of a reaction generally
slows down
because the concentration of the reactants decreases.
at some time the reaction stops, either because the
reactants run out or because the system has
reached equilibrium.
Tro, Chemistry: A Molecular Approach 6
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
=
| | | | | | ( )
( )
( )
( )
25 . 0
0 6 1
8 4
Rate
t t
A A
t
A
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
=
| | | | | | ( )
( )
( )
( )
0625 . 0
0 6 1
8 7
Rate
t t
X X
t
X
Rate
1 2
1 2
=

=
A
A
=
Tro, Chemistry: A Molecular Approach 7
| | | | | | ( )
( )
( )
( )
125 . 0
0 6 1
4 6
Rate
t t
C C
t
C
Rate
1 2
1 2
=

=
A
A
=
| | | | | | ( )
( )
( )
( )
0625 . 0
0 6 1
7 6
Rate
t t
X X
t
X
Rate
1 2
1 2
=

=
A
A
=
| | | | | | ( )
( )
( )
( )
125 . 0
0 6 1
4 2
Rate
t t
A A
t
A
Rate
1 2
1 2
=

=
A
A
=
at t = 16
[A] = 4
[B] = 4
[C] = 4
at t = 16
[X] = 7
[Y] = 7
[Z] = 1
at t = 32
[A] = 2
[B] = 2
[C] = 6
at t = 32
[X] = 6
[Y] = 6
[Z] = 2
| | | | | | ( )
( )
( )
( )
0625 . 0
0 6 1
1 2
Rate
t t
Z Z
t
Z
Rate
1 2
1 2
=

=
A
A
=
Tro, Chemistry: A Molecular Approach 8
| | | | | | ( )
( )
( )
( )
0625 . 0
0 6 1
6 5
Rate
t t
X X
t
X
Rate
1 2
1 2
=

=
A
A
=
| | | | | | ( )
( )
( )
( )
125 . 0
0 6 1
2 0
Rate
t t
A A
t
A
Rate
1 2
1 2
=

=
A
A
=
at t = 32
[A] = 2
[B] = 2
[C] = 6
at t = 32
[X] = 6
[Y] = 6
[Z] = 2
at t = 48
[A] = 0
[B] = 0
[C] = 8
at t = 48
[X] = 5
[Y] = 5
[Z] = 3
| | | | | | ( )
( )
( )
( )
125 . 0
0 6 1
6 8
Rate
t t
C C
t
C
Rate
1 2
1 2
=

=
A
A
=
| | | | | | ( )
( )
( )
( )
0625 . 0
0 6 1
2 3
Rate
t t
Z Z
t
Z
Rate
1 2
1 2
=

=
A
A
=
9
Hypothetical Reaction
Red Blue
Time
(sec)
Number
Red
Number
Blue
0 100 0
5 84 16
10 71 29
15 59 41
20 50 50
25 42 58
30 35 65
35 30 70
40 25 75
45 21 79
50 18 82
in this reaction,
one molecule of Red turns
into one molecule of Blue
the number of molecules
will always total 100
the rate of the reaction can
be measured as the speed of
loss of Red molecules
over time, or the speed of
gain of Blue molecules
over time
Tro, Chemistry: A Molecular Approach 10
Hypothetical Reaction
Red Blue
Concentration vs Time for Red -> Blue
100
84
71
59
50
42
35
30
25
21
18
0
16
29
41
50
58
65
70
75
79
82
0
10
20
30
40
50
60
70
80
90
100
0 5 10 15 20 25 30 35 40 45 50
Time (sec)
N
u
m
b
e
r

o
f

M
o
l
e
c
u
l
e
s
Number Red
Number Blue
Tro, Chemistry: A Molecular Approach 11
Hypothetical Reaction
Red Blue
Rate of Reaction Red -> Blue
5, 3.2
10, 2.6
15, 2.4
20, 1.8
25, 1.6
30, 1.4
35, 1 40, 1
45, 0.8
50, 0.6
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
0 10 20 30 40 50
time, (sec)
R
a
t
e
,

A
[
B
l
u
e
]
/
A
t
Tro, Chemistry: A Molecular Approach 12
Reaction Rate and Stoichiometry
in most reactions, the coefficients of the balanced
equation are not all the same
H
2 (g)
+ I
2 (g)
2 HI
(g)
for these reactions, 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
in order to be consistent, the change in the concentration
of each substance is multiplied by 1/coefficient
t
HI] [
2
1
t
] I [
t
] H [
Rate
2 2
A
A
|
.
|

\
|
+ =
A
A
=
A
A
=
Tro, Chemistry: A Molecular Approach 13
Average Rate
the average rate is the change in measured
concentrations in any particular time period
linear approximation of a curve
the larger the time interval, the more the average
rate deviates from the instantaneous rate
14
Hypothetical Reaction Red Blue
Avg. Rate Avg. Rate Avg. Rate
Time
(sec)
Number
Red
Number
Blue
(5 sec
intervals)
(10 sec
intervals)
(25 sec
intervals)
0 100 0
5 84 16 3.2
10 71 29 2.6 2.9
15 59 41 2.4
20 50 50 1.8 2.1
25 42 58 1.6 2.3
30 35 65 1.4 1.5
35 30 70 1
40 25 75 1 1
45 21 79 0.8
50 18 82 0.6 0.7 1
15
H
2
I
2

HI
Avg. Rate, M/s Avg. Rate, M/s
Time (s) [H
2
], M [HI], M -
A
[H
2
]/
A
t 1/2
A
[HI]/
A
t
0.000 1.000
10.000 0.819
20.000 0.670
30.000 0.549
40.000 0.449
50.000 0.368
60.000 0.301
70.000 0.247
80.000 0.202
90.000 0.165
100.000 0.135
Avg. Rate, M/s Avg. Rate, M/s
Time (s) [H
2
], M [HI], M -
A
[H
2
]/
A
t 1/2
A
[HI]/
A
t
0.000 1.000 0.000
10.000 0.819 0.362
20.000 0.670 0.660
30.000 0.549 0.902
40.000 0.449 1.102
50.000 0.368 1.264
60.000 0.301 1.398
70.000 0.247 1.506
80.000 0.202 1.596
90.000 0.165 1.670
100.000 0.135 1.730
Stoichiometry tells us that for
every 1 mole/L of H
2
used,
2 moles/L of HI are made.
Assuming a 1 L container, at
10 s, we used 0.181 moles of
H
2
. Therefore the amount of
HI made is 2(0.181 moles) =
0.362 moles
At 60 s, we used 0.699 moles
of H
2
. Therefore the amount
of HI made is 2(0.699 moles)
= 1.398 moles
Avg. Rate, M/s
Time (s) [H
2
], M [HI], M -
A
[H
2
]/
A
t
0.000 1.000 0.000
10.000 0.819 0.362 0.0181
20.000 0.670 0.660 0.0149
30.000 0.549 0.902 0.0121
40.000 0.449 1.102 0.0100
50.000 0.368 1.264 0.0081
60.000 0.301 1.398 0.0067
70.000 0.247 1.506 0.0054
80.000 0.202 1.596 0.0045
90.000 0.165 1.670 0.0037
100.000 0.135 1.730 0.0030
The average rate is
the change in the
concentration in a
given time period.
In the first 10 s, the
A[H
2
] is -0.181 M,
so the rate is
s
M
0181 . 0
s 10.000
M 181 . 0
=

Avg. Rate, M/s Avg. Rate, M/s


Time (s) [H
2
], M [HI], M -
A
[H
2
]/
A
t 1/2
A
[HI]/
A
t
0.000 1.000 0.000
10.000 0.819 0.362 0.0181 0.0181
20.000 0.670 0.660 0.0149 0.0149
30.000 0.549 0.902 0.0121 0.0121
40.000 0.449 1.102 0.0100 0.0100
50.000 0.368 1.264 0.0081 0.0081
60.000 0.301 1.398 0.0067 0.0067
70.000 0.247 1.506 0.0054 0.0054
80.000 0.202 1.596 0.0045 0.0045
90.000 0.165 1.670 0.0037 0.0037
100.000 0.135 1.730 0.0030 0.0030
Tro, Chemistry: A Molecular Approach 16
Concentration vs. Time for H
2
+ I
2
--> 2HI
0.000
0.200
0.400
0.600
0.800
1.000
1.200
1.400
1.600
1.800
2.000
0.000 10.000 20.000 30.000 40.000 50.000 60.000 70.000 80.000 90.000 100.000
time, (s)
c
o
n
c
e
n
t
r
a
t
i
o
n
,

(
M
)
[H2], M
[HI], M
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
Tro, Chemistry: A Molecular Approach 17
Instantaneous Rate
the instantaneous rate is the change in
concentration at any one particular time
slope at one point of a curve
determined by taking the slope of a line tangent
to the curve at that particular point
first derivative of the function
for you calculus fans
18
H
2 (g)
+ I
2 (g)
2 HI
(g)

Using [H
2
], the
instantaneous rate at
50 s is:
s
M
0.0070 Rate
s 40
M 28 . 0
Rate
=

=
Using [HI], the
instantaneous rate at
50 s is:
s
M
0.0070 Rate
s 40
M 56 . 0
2
1
Rate
=
|
.
|

\
|
=
Ex 13.1 - For the reaction given, the [I

] changes from
1.000 M to 0.868 M in the first 10 s. Calculate the
average rate in the first 10 s and the A[H
+
].
H
2
O
2

(aq)
+ 3 I

(aq)
+ 2 H
+
(aq)
I
3

(aq)
+ 2 H
2
O
(l)

Solve the equation
for the Rate (in
terms of the change
in concentration of
the Given quantity)
Solve the equation
of the Rate (in terms
of the change in the
concentration for the
quantity to Find) for
the unknown value
( )
s
M
3 -
10 4.40 Rate
s 10
M 000 . 1 M 868 . 0
3
1
t
] I [
3
1
Rate
=

|
.
|

\
|
=
A
A
|
.
|

\
|
=

( )
( )
s
M
3 -
s
M
3 -
10 8.80 10 4.40 2
t
] H [
Rate 2
t
] H [
t
] H [
2
1
Rate
= =
A
A
=
A
A
A
A
|
.
|

\
|
=
+
+
+
Tro, Chemistry: A Molecular Approach 20
Measuring Reaction Rate
in order to measure the reaction rate you need to be
able to measure the concentration of at least one
component in the mixture at many points in time
there are two ways of approaching this problem (1) for
reactions that are complete in less than 1 hour, it is best
to use continuous monitoring of the concentration, or
(2) for reactions that happen over a very long time,
sampling of the mixture at various times can be used
when sampling is used, often the reaction in the sample is
stopped by a quenching technique
Tro, Chemistry: A Molecular Approach 21
Continuous Monitoring
polarimetry measuring the change in the degree of
rotation of plane-polarized light caused by one of the
components over time
spectrophotometry measuring the amount of light of
a particular wavelength absorbed by one component
over time
the component absorbs its complimentary color
total pressure the total pressure of a gas mixture is
stoichiometrically related to partial pressures of the
gases in the reaction
Tro, Chemistry: A Molecular Approach 22
Sampling
gas chromatography can measure the concentrations
of various components in a mixture
for samples that have volatile components
separates mixture by adherence to a surface
drawing off periodic aliquots from the mixture and
doing quantitative analysis
titration for one of the components
gravimetric analysis


Tro, Chemistry: A Molecular Approach 23
Factors Affecting Reaction Rate
Nature of the Reactants
nature of the reactants means what kind of reactant
molecules and what physical condition 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
certain types of chemicals are more reactive than others
e.g., the activity series of metals
ions react faster than molecules
no bonds need to be broken
Tro, Chemistry: A Molecular Approach 24
increasing temperature increases reaction rate
chemists rule of thumb - for each 10C rise in
temperature, the speed of the reaction doubles
for many reactions
there is a mathematical relationship between
the absolute temperature and the speed of a
reaction discovered by Svante Arrhenius
which will be examined later
Factors Affecting Reaction Rate
Temperature
Tro, Chemistry: A Molecular Approach 25
catalysts are substances which affect the speed of
a reaction without being consumed.
most catalysts are used to speed up a reaction,
these are called positive catalysts
catalysts used to slow a reaction are called negative
catalysts.
homogeneous = present in same phase
heterogeneous = present in different phase
how catalysts work will be examined later
Factors Affecting Reaction Rate
Catalysts
Tro, Chemistry: A Molecular Approach 26
generally, the larger the concentration of
reactant molecules, the faster the reaction
increases the frequency of reactant molecule
contact
concentration of gases depends on the partial
pressure of the gas
higher pressure = higher concentration
concentration of solutions depends on the
solute to solution ratio (molarity)
Factors Affecting Reaction Rate
Reactant Concentration
Tro, Chemistry: A Molecular Approach 27
The Rate Law
the Rate Law of a reaction is the mathematical relationship
between the rate of the reaction and the concentrations of
the reactants
and homogeneous catalysts as well
the rate of a reaction is directly proportional to the
concentration of each reactant raised to a power
for the reaction aA + bB products the rate law
would have the form given below
n and m are called the orders for each reactant
k is called the rate constant
m n
k [B] [A] Rate =
Tro, Chemistry: A Molecular Approach 28
Reaction Order
the exponent on each reactant in the rate law is
called the order with respect to that reactant
the sum of the exponents on the reactants is
called the order of the reaction
The rate law for the reaction:
2 NO(g) + O
2
(g) 2 NO
2
(g)
is Rate = k[NO]
2
[O
2
]
The reaction is
second order with respect to [NO],
first order with respect to [O
2
],
and third order overall

Tro, Chemistry: A Molecular Approach 29
Reaction Rate Law
CH
3
CN CH
3
NC
Rate = k[CH
3
CN]
CH
3
CHO CH
4
+ CO
Rate = k[CH
3
CHO]
3/2

2 N
2
O
5
4 NO
2
+ O
2

Rate = k[N
2
O
5
]
H
2
+ I
2
2 HI
Rate = k[H
2
][I
2
]
Tl
+3
+ Hg
2
+2
Tl
+1
+ 2 Hg
+2

Rate = k[Tl
+3
][Hg
2
+2
][Hg
+2
]
-1


Sample Rate Laws
The reaction is autocatalytic, because a product affects the rate.
Hg
2+
is a negative catalyst, increasing its concentration slows the reaction.
Tro, Chemistry: A Molecular Approach 30
Reactant Concentration vs. Time
A Products
Tro, Chemistry: A Molecular Approach 31
Half-Life
the half-life, t
1/2
, of a
reaction is the length
of time it takes for the
concentration of the
reactants to fall to its
initial value
the half-life of the
reaction depends on
the order of the
reaction
Tro, Chemistry: A Molecular Approach 32
Zero Order Reactions
Rate = k[A]
0
= k
constant rate reactions
[A] = -kt + [A]
0

graph of [A] vs. time is straight line with
slope = -k and y-intercept = [A]
0

t

= [A
0
]/2k
when Rate = M/sec, k = M/sec
[A]
0

[A]
time
Tro, Chemistry: A Molecular Approach 33
First Order Reactions
Rate = k[A]
ln[A] = -kt + ln[A]
0

graph ln[A] vs. time gives straight line with
slope = -k and y-intercept = ln[A]
0

used to determine the rate constant
t

= 0.693/k
the half-life of a first order reaction is
constant
the when Rate = M/sec, k = sec
-1
Tro, Chemistry: A Molecular Approach 34
ln[A]
0

ln[A]
time
Tro, Chemistry: A Molecular Approach 35
Half-Life of a First-Order Reaction
Is Constant
Tro, Chemistry: A Molecular Approach 36
Rate Data for
C
4
H
9
Cl + H
2
O C
4
H
9
OH + HCl
Time (sec) [C
4
H
9
Cl], M
0.0 0.1000
50.0 0.0905
100.0 0.0820
150.0 0.0741
200.0 0.0671
300.0 0.0549
400.0 0.0448
500.0 0.0368
800.0 0.0200
10000.0 0.0000
Tro, Chemistry: A Molecular Approach 37
C
4
H
9
Cl + H
2
O C
4
H
9
OH + 2 HCl
Concentration vs. Time for the Hydrolysis of C
4
H
9
Cl
0
0.02
0.04
0.06
0.08
0.1
0.12
0 200 400 600 800 1000
time, (s)
c
o
n
c
e
n
t
r
a
t
i
o
n
,

(
M
)
Tro, Chemistry: A Molecular Approach 38
C
4
H
9
Cl + H
2
O C
4
H
9
OH + 2 HCl
Rate vs. Time for Hydrolysis of C
4
H
9
Cl
0.0E+00
5.0E-05
1.0E-04
1.5E-04
2.0E-04
2.5E-04
0 100 200 300 400 500 600 700 800
time, (s)
R
a
t
e
,

(
M
/
s
)
Tro, Chemistry: A Molecular Approach 39
C
4
H
9
Cl + H
2
O C
4
H
9
OH + 2 HCl
LN([C
4
H
9
Cl]) vs. Time for Hydrolysis of C
4
H
9
Cl
y = -2.01E-03x - 2.30E+00
-4.5
-4
-3.5
-3
-2.5
-2
-1.5
-1
-0.5
0
0 100 200 300 400 500 600 700 800
time, (s)
L
N
(
c
o
n
c
e
n
t
r
a
t
i
o
n
)
slope =
-2.01 x 10
-3

k =
2.01 x 10
-3
s
-1
s 345
s 10 01 . 2
693 . 0
693 . 0
t
1 - 3
2
1
=

=
=

k
Tro, Chemistry: A Molecular Approach 40
Second Order Reactions
Rate = k[A]
2

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

graph 1/[A] vs. time gives straight line with
slope = k and y-intercept = 1/[A]
0
used to determine the rate constant
t

= 1/(k[A
0
])
when Rate = M/sec, k = M
-1
sec
-1
Tro, Chemistry: A Molecular Approach 41
l/[A]
0

1/[A]
time
42
Rate Data For
2 NO
2
2 NO + O
2
Time (hrs.)
Partial
Pressure
NO
2
, mmHg ln(P
NO2
) 1/(P
NO2
)
0 100.0 4.605 0.01000
30 62.5 4.135 0.01600
60 45.5 3.817 0.02200
90 35.7 3.576 0.02800
120 29.4 3.381 0.03400
150 25.0 3.219 0.04000
180 21.7 3.079 0.04600
210 19.2 2.957 0.05200
240 17.2 2.847 0.05800
Tro, Chemistry: A Molecular Approach 43
Rate Data Graphs For
2 NO
2
2 NO + O
2
Partial Pressure NO
2
, mmHg vs. Time
0.0
10.0
20.0
30.0
40.0
50.0
60.0
70.0
80.0
90.0
100.0
0 50 100 150 200 250
Time, (hr)
P
r
e
s
s
u
r
e
,

(
m
m
H
g
)
Tro, Chemistry: A Molecular Approach 44
Rate Data Graphs For
2 NO
2
2 NO + O
2
ln(P
NO2
) vs. Time
2.4
2.6
2.8
3
3.2
3.4
3.6
3.8
4
4.2
4.4
4.6
4.8
0 50 100 150 200 250
Time (hr)
l
n
(
p
r
e
s
s
u
r
e
)
Tro, Chemistry: A Molecular Approach 45
Rate Data Graphs For
2 NO
2
2 NO + O
2
1/(P
NO2
) vs Time
1/P
NO2
= 0.0002(time) + 0.01
0.00000
0.01000
0.02000
0.03000
0.04000
0.05000
0.06000
0.07000
0 50 100 150 200 250
Time, (hr)
I
n
v
e
r
s
e

P
r
e
s
s
u
r
e
,

(
m
m
H
g
-
1
)
Tro, Chemistry: A Molecular Approach 46
Determining the Rate Law
can only be determined experimentally
graphically
rate = slope of curve [A] vs. time
if graph [A] vs time is straight line, then exponent on A in rate
law is 0, rate constant = -slope
if graph ln[A] vs time is straight line, then exponent on A in rate
law is 1, rate constant = -slope
if graph 1/[A] vs time is straight line, exponent on A in rate law
is 2, rate constant = slope
initial rates
by comparing effect on the rate of changing the initial
concentration of reactants one at a time
Tro, Chemistry: A Molecular Approach 47
Tro, Chemistry: A Molecular Approach 48
Practice - Complete the Table and
Determine the Rate Equation for the
Reaction A 2 Prod
[A], (M) [Prod], (M) Time (sec) ln([A]) 1/[A]
0.100 0 0
0.067 50
0.050 100
0.040 150
0.033 200
0.029 250
Tro, Chemistry: A Molecular Approach 49
Practice - Complete the Table and
Determine the Rate Equation for the
Reaction A 2 Prod
[A], (M) [Prod], (M) Time (sec) ln([A]) 1/[A]
0.100 0 0 -2.3 10
0.067 0.066 50 -2.7 15
0.050 0.100 100 -3.0 20
0.040 0.120 150 -3.2 25
0.033 0.134 200 -3.4 30
0.029 0.142 250 -3.5 35
Tro, Chemistry: A Molecular Approach 50
[A] vs. Time
0
0.02
0.04
0.06
0.08
0.1
0.12
0 50 100 150 200 250
time, (s)
c
o
n
c
e
n
t
r
a
t
i
o
n
,

M
Tro, Chemistry: A Molecular Approach 51
LN([A]) vs. Time
-3.8
-3.6
-3.4
-3.2
-3
-2.8
-2.6
-2.4
-2.2
-2
0 50 100 150 200 250
time, (s)
L
n
(
c
o
n
c
e
n
t
r
a
t
i
o
n
)
Tro, Chemistry: A Molecular Approach 52
1/([A]) vs. Time
y = 0.1x + 10
0
5
10
15
20
25
30
35
40
0 50 100 150 200 250
time, (s)
i
n
v
e
r
s
e

c
o
n
c
e
n
t
r
a
t
i
o
n
,

M
-
1
Tro, Chemistry: A Molecular Approach 53
Practice - Complete the Table and
Determine the Rate Equation for the
Reaction A 2 Prod
the reaction is second order, Rate =
-A[A]
At
= 0.1 [A]
2
Ex. 13.4 The reaction SO
2
Cl
2(g)
SO
2(g)
+ Cl
2(g)
is first order
with a rate constant of 2.90 x 10
-4
s
-1
at a given set of conditions.
Find the [SO
2
Cl
2
] at 865 s when [SO
2
Cl
2
]
0
= 0.0225 M
the new concentration is less than the original, as
expected
[SO
2
Cl
2
]
0
= 0.0225 M, t = 865, k = 2.90 x 10
-4
s
-1

[SO
2
Cl
2
]

Check:
Solution:
Concept Plan:

Relationships:
Given:
Find:
[SO
2
Cl
2
] [SO
2
Cl
2
]
0
, t, k
0
ln[A] t ln[A] : process order 1st a for + = k
( )( ) ( )
M 0.0175 ] Cl [SO
4.04 3.79 0.251 ] Cl ln[SO
0.0225 ln s 865 s 10 2.90 ] Cl ln[SO
] Cl ln[SO t ] Cl ln[SO
(-4.04)
2 2
2 2
1 - 4 -
2 2
0 2 2 2 2
= =
= =
+ =
+ =
e
k
Tro, Chemistry: A Molecular Approach 55
Initial Rate Method
another method for determining the order of a
reactant is to see the effect on the initial rate of the
reaction when the initial concentration of that
reactant is changed
for multiple reactants, keep initial concentration of all
reactants constant except one
zero order = changing the concentration has no effect on
the rate
first order = the rate changes by the same factor as the
concentration
doubling the initial concentration will double the rate
second order = the rate changes by the square of the factor
the concentration changes
doubling the initial concentration will quadruple the rate
56
Ex 13.2 Determine the rate law and rate constant for the
reaction NO
2(g)
+ CO
(g)
NO
(g)
+ CO
2(g)

given the data below.
Expt.
Number
Initial
[NO
2
], (M)
Initial
[CO], (M)
Initial Rate
(M/s)
1. 0.10 0.10 0.0021
2. 0.20 0.10 0.0082
3. 0.20 0.20 0.0083
4. 0.40 0.10 0.033
Write a general
rate law
including all
reactants
Examine the
data and find
two experiments
in which the
concentration of
one reactant
changes, but the
other
concentrations
are the same
Expt.
Number
Initial
[NO
2
], (M)
Initial
[CO], (M)
Initial Rate
(M/s)
1. 0.10 0.10 0.0021
2. 0.20 0.10 0.0082
3. 0.20 0.20 0.0083
4. 0.40 0.10 0.033
Comparing Expt #1 and Expt #2, the
[NO
2
] changes but the [CO] does not
m n
k [CO] ] [NO Rate
2
=
Tro, Chemistry: A Molecular Approach 57
Ex 13.2 Determine the rate law and rate constant for the
reaction NO
2(g)
+ CO
(g)
NO
(g)
+ CO
2(g)

given the data below.
Determine by
what factor the
concentrations
and rates change
in these two
experiments.
Expt.
Number
Initial
[NO
2
], (M)
Initial
[CO], (M)
Initial Rate
(M/s)
1. 0.10 0.10 0.0021
2. 0.20 0.10 0.0082
3. 0.20 0.20 0.0083
4. 0.40 0.10 0.033
2
M 10 . 0
M 20 . 0
] [NO
] [NO
1 expt 2
2 expt 2
= = 4
0021 . 0
0082 . 0
Rate
Rate
s
M
s
M
1 expt
2 expt
~ =
Tro, Chemistry: A Molecular Approach 58
Ex 13.2 Determine the rate law and rate constant for the
reaction NO
2(g)
+ CO
(g)
NO
(g)
+ CO
2(g)

given the data below.
Determine to
what power the
concentration
factor must be
raised to equal
the rate factor.
Expt.
Number
Initial
[NO
2
], (M)
Initial
[CO], (M)
Initial Rate
(M/s)
1. 0.10 0.10 0.0021
2. 0.20 0.10 0.0082
3. 0.20 0.20 0.0083
4. 0.40 0.10 0.033
2
M 10 . 0
M 20 . 0
] [NO
] [NO
1 expt 2
2 expt 2
= =
4
0021 . 0
0082 . 0
Rate
Rate
s
M
s
M
1 expt
2 expt
~ =
2
4 2
Rate
Rate
] [NO
] [NO
1 expt
2 expt
1 expt 2
2 expt 2
=
=
=
|
|
.
|

\
|
n
n
n
Tro, Chemistry: A Molecular Approach 59
Ex 13.2 Determine the rate law and rate constant for the
reaction NO
2(g)
+ CO
(g)
NO
(g)
+ CO
2(g)

given the data below.
Repeat for the
other reactants
Expt.
Number
Initial
[NO
2
], (M)
Initial
[CO], (M)
Initial Rate
(M/s)
1. 0.10 0.10 0.0021
2. 0.20 0.10 0.0082
3. 0.20 0.20 0.0083
4. 0.40 0.10 0.033
2
M 10 . 0
M 20 . 0
[CO]
[CO]
2 expt
3 expt
= = 1
0082 . 0
0083 . 0
Rate
Rate
s
M
s
M
2 expt
3 expt
~ =
0
1 2
Rate
Rate
[CO]
[CO]
2 expt
3 expt
2 expt
3 expt
=
=
=
|
|
.
|

\
|
m
m
m
Expt.
Number
Initial
[NO
2
], (M)
Initial
[CO], (M)
Initial Rate
(M/s)
1. 0.10 0.10 0.0021
2. 0.20 0.10 0.0082
3. 0.20 0.20 0.0083
4. 0.40 0.10 0.033
Tro, Chemistry: A Molecular Approach 60
Ex 13.2 Determine the rate law and rate constant for the
reaction NO
2(g)
+ CO
(g)
NO
(g)
+ CO
2(g)

given the data below.
Substitute the
exponents into
the general rate
law to get the
rate law for the
reaction
Expt.
Number
Initial
[NO
2
], (M)
Initial
[CO], (M)
Initial Rate
(M/s)
1. 0.10 0.10 0.0021
2. 0.20 0.10 0.0082
3. 0.20 0.20 0.0083
4. 0.40 0.10 0.033
m n
k [CO] ] [NO Rate
2
=
n = 2, m = 0
2
2
0 2
2
] [NO Rate
[CO] ] [NO Rate
k
k
=
=
Tro, Chemistry: A Molecular Approach 61
Ex 13.2 Determine the rate law and rate constant for the
reaction NO
2(g)
+ CO
(g)
NO
(g)
+ CO
2(g)

given the data below.
Substitute the
concentrations
and rate for any
experiment into
the rate law and
solve for k
Expt.
Number
Initial
[NO
2
], (M)
Initial
[CO], (M)
Initial Rate
(M/s)
1. 0.10 0.10 0.0021
2. 0.20 0.10 0.0082
3. 0.20 0.20 0.0083
4. 0.40 0.10 0.033
( )
1 - 1 -
2
s
M
2
s
M
2
2
s M 21 . 0
M 01 . 0
0.0021
M 10 . 0 0.0021
1 expt for
] [NO Rate
- = =
=
=
k
k
k
Tro, Chemistry: A Molecular Approach 62
Practice - Determine the rate law and rate constant for the
reaction NH
4
+1
+ NO
2
-1
N
2
+ 2 H
2
O
given the data below.
Expt.
No.
Initial
[NH
4
+
], M
Initial
[NO
2
-
], M
Initial Rate,
(x 10
-7
), M/s
1 0.0200 0.200 10.8
2 0.0600 0.200 32.3
3 0.200 0.0202 10.8
4 0.200 0.0404 21.6
63
Practice - Determine the rate law and rate constant for the
reaction NH
4
+1
+ NO
2
-1
N
2
+ 2 H
2
O
given the data below.
Expt.
No.
Initial
[NH
4
+
], M
Initial
[NO
2
-
], M
Initial Rate,
(x 10
-7
), M/s
1 0.0200 0.200 10.8
2 0.0600 0.200 32.3
3 0.200 0.0202 10.8
4 0.200 0.0404 21.6
order first 1,
3 3 ] [NH Factor Rate
3
10 8 . 10
10 3 . 32
1 Expt
2 Expt
Rate,
3
0200 . 0
0600 . 0
1 Expt
2 Expt
], [NH For
4
4
7
7
=
= =
=

=
= =
+

+
n
n n
Rate = k[NH
4
+
]
n
[NO
2

]
m

order first 1,
2 2 ] [NO Factor Rate
2
10 8 . 10
10 6 . 21
3 Expt
4 Expt
Rate,
2
0202 . 0
0404 . 0
3 Expt
4 Expt
], [NO For
2
2
7
7
=
= =
=

=
= =

m
m m
( )( )
1 - 1 - 4
2 3 -
s
M
7 -
s
M
7 -
2 4
s M 10 70 . 2
M 10 00 . 4
10 10.8
M .200 0 M .0200 0 10 10.8
1 expt for
] [NO ] [NH Rate
- =

=
=
=

+
k
k
k
Tro, Chemistry: A Molecular Approach 64
The Effect of Temperature on Rate
changing the temperature changes the rate
constant of the rate law
Svante Arrhenius investigated this relationship
and showed that:
|
|
.
|

\
|
=

RT
E
a
e A k
R is the gas constant in energy units, 8.314 J/(molK)
where T is the temperature in kelvins
A is a factor called the frequency factor
E
a
is the activation energy, the extra energy needed to start
the molecules reacting
Tro, Chemistry: A Molecular Approach 65
Tro, Chemistry: A Molecular Approach 66
Activation Energy and the
Activated Complex
energy barrier to the reaction
amount of energy needed to convert reactants
into the activated complex
aka transition state
the activated complex is a chemical species with
partially broken and partially formed bonds
always very high in energy because partial bonds
Tro, Chemistry: A Molecular Approach 67
Isomerization of Methyl Isonitrile
methyl isonitrile rearranges to acetonitrile
in order for the reaction to occur,
the H
3
C-N bond must break; and
a new H
3
C-C bond form
68
Energy Profile for the
Isomerization of Methyl Isonitrile
As the reaction
begins, the C-N
bond weakens
enough for the
CN group to
start to rotate
the collision frequency
is the number of
molecules that
approach the peak in a
given period of time
the activation energy
is the difference in
energy between the
reactants and the
activated complex
the activated complex
is a chemical species
with partial bonds
Tro, Chemistry: A Molecular Approach 69
The Arrhenius Equation:
The Exponential Factor
the exponential factor in the Arrhenius equation is a number
between 0 and 1
it represents the fraction of reactant molecules with sufficient
energy so they can make it over the energy barrier
the higher the energy barrier (larger activation energy), the fewer
molecules that have sufficient energy to overcome it
that extra energy comes from converting the kinetic energy of
motion to potential energy in the molecule when the molecules
collide
increasing the temperature increases the average kinetic energy of the
molecules
therefore, increasing the temperature will increase the number of
molecules with sufficient energy to overcome the energy barrier
therefore increasing the temperature will increase the reaction rate
Tro, Chemistry: A Molecular Approach 70
Tro, Chemistry: A Molecular Approach 71
Arrhenius Plots
the Arrhenius Equation can be algebraically
solved to give the following form:
( ) A
R
E
k
a
ln
T
1
) ln( +
|
.
|

\
|

=
this equation is in the form y = mx + b
where y = ln(k) and x = (1/T)
a graph of ln(k) vs. (1/T) is a straight line
(-8.314 J/molK)(slope of the line) = E
a
, (in Joules)
e
y-intercept
= A, (unit is the same as k)
Tro, Chemistry: A Molecular Approach 72
Ex. 13.7 Determine the activation energy and frequency
factor for the reaction O
3(g)
O
2(g)
+ O
(g)
given the
following data:
Temp, K k, M
-1
s
-1
Temp, K k, M
-1
s
-1

600 3.37 x 10
3
1300 7.83 x 10
7

700 4.83 x 10
4
1400 1.45 x 10
8
800 3.58 x 10
5
1500 2.46 x 10
8
900 1.70 x 10
6
1600 3.93 x 10
8
1000 5.90 x 10
6
1700 5.93 x 10
8
1100 1.63 x 10
7
1800 8.55 x 10
8
1200 3.81 x 10
7
1900 1.19 x 10
9
Tro, Chemistry: A Molecular Approach 73
Ex. 13.7 Determine the activation energy and frequency
factor for the reaction O
3(g)
O
2(g)
+ O
(g)
given the
following data:
use a
spreadsheet
to graph
ln(k) vs.
(1/T)
Tro, Chemistry: A Molecular Approach 74
Ex. 13.7 Determine the activation energy and frequency
factor for the reaction O
3(g)
O
2(g)
+ O
(g)
given the
following data:
E
a
= m(-R)
solve for E
a

( )
mol
kJ
mol
J
4
K mol
J
4
1 . 93
10 31 . 9 314 . 8 K 10 12 . 1
=
=
|
.
|

\
|
=
-
a
a
E
E
A = e
y-intercept

solve for A
1 1 - 11
11 8 . 26
s M 10 36 . 4
10 36 . 4

- =
= =
A
e A
Tro, Chemistry: A Molecular Approach 75
Arrhenius Equation:
Two-Point Form
if you only have two (T,k) data points, the
following forms of the Arrhenius Equation can
be used:
( )
( ) T T
k
k
x T T R

T T
T T
k
k
R x

T T
k
k
R x
E
a
2 1
2
1
2 1
2 1
2 1
2
1
1 2
2
1
ln ln
1 1
ln

- -
=
-

=
|
|
.
|

\
|
=
|
|
.
|

\
|
2 1 1
2
T
1
T
1
ln
R
E
k
k
a
( )
a
a
a
E
E
E
= =
=
|
.
|

\
|
=
|
.
|

\
|

-
-

-
-
mol
kJ
mol
J 5
1 - 4
K
mol
J
K mol
J
s M
s M
145 10 45 . 1
K 10 2 9 0 . 3
314 . 8
5 6 39 . 5
K 895
1
K 701
1
314 . 8 57 . 2
567
ln
1
1 - 1 -
-1 -1
Ex. 13.8 The reaction NO
2(g)
+ CO
(g)
CO
2(g)
+ NO
(g)
has a rate
constant of 2.57 M
-1
s
-1
at 701 K and 567 M
-1
s
-1
at 895 K. Find
the activation energy in kJ/mol
most activation energies are tens to hundreds of
kJ/mol so the answer is reasonable
T
1
= 701 K, k
1
= 2.57 M
-1
s
-1
, T
2
= 895 K, k
2
= 567 M
-1
s
-1

E
a
, kJ/mol
Check:
Solution:
Concept Plan:

Relationships:
Given:
Find:
E
a
T
1
, k
1
, T
2
, k
2
|
|
.
|

\
|
=
|
|
.
|

\
|
2 1 1
2
T
1
T
1
ln
R
E
k
k
a
Tro, Chemistry: A Molecular Approach 77
Collision Theory of Kinetics
for most reactions, in order for a reaction to take
place, the reacting molecules must collide into
each other.
once molecules collide they may react together
or they may not, depending on two factors -
1. whether the collision has enough energy to
"break the bonds holding reactant molecules
together";
2. whether the reacting molecules collide in the
proper orientation for new bonds to form.
Tro, Chemistry: A Molecular Approach 78
Effective Collisions
collisions in which these two conditions are
met (and therefore lead to reaction) are called
effective collisions
the higher the frequency of effective
collisions, the faster the reaction rate
when two molecules have an effective
collision, a temporary, high energy (unstable)
chemical species is formed - called an
activated complex or transition state
Tro, Chemistry: A Molecular Approach 79
Effective Collisions
Kinetic Energy Factor
for a collision to lead
to overcoming the
energy barrier, the
reacting molecules
must have sufficient
kinetic energy so that
when they collide it
can form the
activated complex
Tro, Chemistry: A Molecular Approach 80
Effective Collisions
Orientation Effect
Tro, Chemistry: A Molecular Approach 81
Collision Theory and
the Arrhenius Equation
A is the factor called the frequency factor and
is the number of molecules that can approach
overcoming the energy barrier
there are two factors that make up the frequency
factor the orientation factor (p) and the
collision frequency factor (z)
RT
E
RT
E
a a
pze e A k

=
|
|
.
|

\
|
=
Tro, Chemistry: A Molecular Approach 82
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
reactions between atoms generally have p = 1
reactions where symmetry results in multiple orientations
leading to reaction have p slightly less than 1
for most reactions, the orientation factor is less than 1
for many, p << 1
there are some reactions that have p > 1 in which an electron
is transferred without direct collision
Tro, Chemistry: A Molecular Approach 83
Reaction Mechanisms
we generally describe chemical reactions with an
equation listing all the reactant molecules and product
molecules
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
describing the series of steps that occur to produce the
overall observed reaction is called a reaction
mechanism
knowing the rate law of the reaction helps us
understand the sequence of steps in the mechanism

Tro, Chemistry: A Molecular Approach 84
An Example of a Reaction Mechanism
Overall reaction:
H
2(g)
+ 2 ICl
(g)
2 HCl
(g)
+ I
2(g)

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

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

the steps in this mechanism are 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
Tro, Chemistry: A Molecular Approach 85
H
2
(g) + 2 ICl(g) 2 HCl(g) + I
2
(g)
1) H
2
(g) + ICl(g) HCl(g) + HI(g)
2) HI(g) + ICl(g) HCl(g) + I
2
(g)
Elements of a Mechanism
Intermediates
notice that the HI is a product in Step 1, but then a
reactant in Step 2
since HI is made but then consumed, HI does not
show up in the overall reaction
materials that are products in an early step, but then a
reactant in a later step are called intermediates
Tro, Chemistry: A Molecular Approach 86
Molecularity
the number of reactant particles in an elementary
step is called its molecularity
a unimolecular step involves 1 reactant particle
a bimolecular step involves 2 reactant particles
though they may be the same kind of particle
a termolecular step involves 3 reactant particles
though these are exceedingly rare in elementary steps
Tro, Chemistry: A Molecular Approach 87
Rate Laws for Elementary Steps
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 from the equation of the step
H
2
(g) + 2 ICl(g) 2 HCl(g) + I
2
(g)
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]
Tro, Chemistry: A Molecular Approach 88
Rate Laws of Elementary Steps
Tro, Chemistry: A Molecular Approach 89
Rate Determining Step
in most mechanisms, one step occurs slower than the
other steps
the result is that product production cannot occur any
faster than the slowest step the step determines the
rate of the overall reaction
we call the slowest step in the mechanism the rate
determining step
the slowest step has the largest activation energy
the rate law of the rate determining step determines the
rate law of the overall reaction
Tro, Chemistry: A Molecular Approach 90
Another Reaction Mechanism
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
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.
Tro, Chemistry: A Molecular Approach 91
Validating a Mechanism
in order to validate (not prove) a mechanism,
two conditions must be met:
1. the elementary steps must sum to the overall
reaction
2. the rate law predicted by the mechanism must
be consistent with the experimentally observed
rate law
Tro, Chemistry: A Molecular Approach 92
Mechanisms with a Fast Initial Step
when a mechanism contains a fast initial step, the rate
limiting step may contain intermediates
when a previous step is rapid and reaches equilibrium,
the forward and reverse reaction rates are equal so the
concentrations of reactants and products of the step are
related
and the product is an intermediate
substituting into the rate law of the RDS will produce a
rate law in terms of just reactants
Tro, Chemistry: A Molecular Approach 93
An Example
2 NO
(g)
N
2
O
2(g)
Fast

H
2(g)
+ N
2
O
2(g)
H
2
O
(g)
+ N
2
O
(g)
Slow Rate = k
2
[H
2
][N
2
O
2
]
H
2(g)
+ N
2
O
(g)
H
2
O
(g)
+ N
2(g)
Fast

k
1

k
-1

2 H
2(g)
+ 2 NO
(g)
2 H
2
O
(g)
+ N
2(g)
Rate
obs
= k [H
2
][NO]
2

for Step 1 Rate
forward
= Rate
reverse
2
1
1
2 2
2 2 1
2
1
[NO] ] O [N
] O [N [NO]

=
=
k
k
k k
2
2 2
1
1 2
2
2
1
1
2 2
2 2 2 2
] ][NO [H Rate
] [NO ] [H Rate
] O ][N [H Rate

=
=
=
k
k k
k
k
k
k
Tro, Chemistry: A Molecular Approach 94
Ex 13.9 Show that the proposed mechanism for the
reaction 2 O
3(g)
3 O
2(g)
matches the observed rate law
Rate = k[O
3
]
2
[O
2
]
-1

O
3(g)
O
2(g)
+ O
(g)
Fast

O
3(g)
+ O
(g)
2 O
2(g)
Slow Rate = k
2
[O
3
][O]
k
1

k
-1

for Step 1 Rate
forward
= Rate
reverse
1
2 3
1
1
2 1 3 1
] ][O [O [O]
][O] [O ] [O

=
=
k
k
k k
1 -
2
2
3
1
1 2
1 -
2 3
1
1
3 2
3 2
] [O ] [O Rate
] ][O [O ] [O Rate
][O] [O Rate

=
=
=
k
k k
k
k
k
k
Tro, Chemistry: A Molecular Approach 95
Catalysts
catalysts are substances that affect the rate of a reaction
without being consumed
catalysts work by providing an alternative mechanism
for the reaction
with a lower activation energy
catalysts are consumed in an early mechanism step,
then made in a later step
mechanism without catalyst
O
3(g)
+ O
(g)
2 O
2(g)
V. Slow
mechanism with catalyst
Cl
(g)
+ O
3(g)
O
2(g)
+ ClO
(g)
Fast

ClO
(g)
+ O
(g)
O
2(g)
+ Cl
(g)
Slow
Tro, Chemistry: A Molecular Approach 96
Ozone Depletion over the Antarctic
Tro, Chemistry: A Molecular Approach 97
Energy Profile of Catalyzed Reaction
polar stratospheric clouds
contain ice crystals that
catalyze reactions that
release Cl from
atmospheric chemicals
Tro, Chemistry: A Molecular Approach 98
Catalysts
homogeneous catalysts are in the same phase
as the reactant particles
Cl
(g)
in the destruction of O
3(g)

heterogeneous catalysts are in a different phase
than the reactant particles
solid catalytic converter in a cars exhaust system
Tro, Chemistry: A Molecular Approach 99
Types of Catalysts
Tro, Chemistry: A Molecular Approach 100
Catalytic Hydrogenation
H
2
C=CH
2
+ H
2
CH
3
CH
3

Tro, Chemistry: A Molecular Approach 101
Enzymes
because many of the molecules are large and
complex, most biological reactions require a
catalyst to proceed at a reasonable rate
protein molecules that catalyze biological
reactions are called enzymes
enzymes work by adsorbing the substrate
reactant onto an active site that orients it for
reaction
Tro, Chemistry: A Molecular Approach 102
Enzyme-Substrate Binding
Lock and Key Mechanism
Tro, Chemistry: A Molecular Approach 103
Enzymatic Hydrolysis of Sucrose