CHAPTER 2

CHEMICAL
KINETICS
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

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
Different reactions have different rates
- higher rate/faster reaction the reactant concentration
decreases quickly
- lower rate/slower reaction it decreases slowly
For reactants = -ve sign (conc. decreases)
For products = +ve sign (conc. increases)

Rate = [concentration]
time
Rate = [products] = - [reactants]
time
time

Reaction Rate and Stoichiometry

In most reactions, the coefficients of the
balanced equation are not all the same
H2 (g) + I2 (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 H2
used, 1 mole of I2 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

general, the differential rate law for the react

aA

bB

cC

dD

1 d A
1 d B 1 d C 1 d D
Rate

a dt
b dt
c dt
d dt
Reactants (decrease)

Products (increase)

e numerical value of the rate depends upon th

bstance that serves as the reference. The res
ative to the balanced chemical equation.
5

Example: For the reaction given, the [I] changes from1.000 M to

0.868 M in the first 10 s. Calculate the average rate in the first 10 s,
and [H+]/t.

H2O2

(aq)

+ 3 I(aq) + 2 H+(aq) I3(aq) + 2 H2O(l)

solve the rate

equation for the rate
(in terms of the
change in
concentration of the
given quantity)
solve the rate
equation (in terms of
the change in the
concentration for the
quantity to find) for
the unknown value
6

Example: Because it has a nonpolluting product (water vapor), hydrogen

gas is used for fuel aboard the space shuttle and may be used by
earthbound engines in the near future.
2H2(g) + O2(g)

2H2O(g)

(a) Express the rate in terms of changes in [H2], [O2], and [H2O] with
time.
(b) When [O2] is decreasing at 0.23 mol/L*s, at what rate is [H2O]
increasing?
SOLUTION:
(a) rate =

(b)

[O2]

[H2]

= -

[O2]

= - 0.23 mol/L*s
=+

t
[H2O]

=+ 1
2

[H2O]

[H2O]
t

= 0.46 mol/L*s

t
7

If 2.4 x 102 g of NOBr decomposes in a 2.0 x 102 mL

flask in 5.0 minutes, find the average rate of Br2 production
2 NOBr(g) 2 NO(g) + Br2(l)

Consider the reaction:

8A(g) + 5B(g) 8C(g) + 6D(g)
If [C] is increasing at the rate of 4.0 mol L1s1, at what rate is
[B] changing?
A.
B.
C.
D.
E.

-0.40 mol L1s1

-2.5 mol L1s1
-4.0 mol L1s1
-6.4 mol L1s1
None of these choices is correct,
since its rate of change must be positive.

at t = 0
[A] = 8
[B] = 8
[C] = 0

at t = 16
[A] = 4
[B] = 4
[C] = 4

A 2 A 1
Rate

t 2 t1
t

4 8
Rate
0.25
16 0

C C 2 C 1
Rate

t 2 t1
t

4 0
Rate
0.25
16 0

10

at t
[X]
[Y]
[Z]

=
=
=
=

0
8
8
0

at t = 16
[X] = 7
[Y] = 7
[Z] = 1

X
X 2 X 1
Rate

t 2 t1
t

7 8
Rate
0.0625
16 0

Z Z 2 Z 1
Rate

t 2 t1
t
Rate

1 0

16 0

0.0625
11

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

Average Rate
Change in measured concentrations in any
particular time period
linear approximation of a curve
12

average rate in a
given time period =
slope of the line
connecting the [H2]
points; and +slope
of the line for [HI]

the average rate for

the first 80 s is
0.0108 M/s
the average rate for
the first 40 s is
0.0150 M/s

the average rate for

the first 10 s is
0.0181 M/s
13

Instantaneous Rate
The instantaneous rate is the change in
concentration at any one particular time
Determined by taking the slope of a line
tangent to the concentartion vs time curve at
any particular point.

The initial rate is the reaction rate at the

beginning of a reaction
slope of a line tangent to the curve at time t
=0
No product formed yet, reversed rate = 0
14

H2 (g) + I2 (g) 2 HI (g)

Using [H2], the instantaneous
rate at 50 s is

Using [HI], the instantaneous

rate at 50 s is

15

2 NO2 2 NO O2
[ NO2 ]
Average Rate
t
d [ NO2 ]
Instantaneous Rate= dt

The instantaneous rate at the moment the reactants

are mixed (t = 0s) is called the initial rate.
16

C4H9Cl

(aq)

+ H2O

(l)

C4H9OH

(aq)

+ HCl

(aq)

In this reaction, the ratio of C4H9Cl to C4H9OH is 1:1

Thus, the rate of disappearance of C4H9Cl is the
same as the rate of appearance of C4H9OH
Rate =

-[C4H9Cl]
t

= [C H OH]
4 9
t

17

H2(g) + I2(g)
2HI
(g)
What if the ratio is NOT1:1?
[HI] increases twice as fast
as [H2] decreases.
Rate = -

[H2]
t

=-

[I2]
t

[HI]
1
=
t
2

[HI]
[H2]
[I2]
Rate =
= -2
= -2
t
t
t
The expression for the rate of a
reaction and its numerical value
depend on which substance serves as
the reference.
18

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 law must be determined experimentally!!
The rate of a reaction is directly proportional to the
concentration of each reactant raised to a power
aA + bB cC + dD
n and m = reactants orders
k = rate constant

Rate = k [A]n
m
[B]

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

Types of Rate Laws

Integrated Rate Law: how the
concentration of species in the
reaction depend on time
Differential Rate Law: how the rate of
a reaction depends on
concentrations
Determine the differential rate law
for a given reaction, the form of
integrated rate law can be
automatically known, and vice versa
21

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 overall order
2 NO(g) + O2(g) 2 NO2(g)
of the reaction
2
1
is: rate
Rate =
k[NO]
[O
]
The
law for the
reaction given:
2
The reaction is:
second order with respect to [NO],
first order with respect to [O2],
and third order overall.

22

 Reaction order is determined by

experiment only
Reaction order is an empirical quantity
(values range -2 to 3).
Can be fractional found mainly in gas
phase
n
Can be negative, m
k[ B ]
n

R k[ A] [ B ]

[ A]

A is an inhibitor
(decreases the
rate)

23

Units of the Rate Constant

k
Overall Reaction Order
0
1
2
3

Units of k (t in
seconds)
mol/L*s (or mol L-1 s1
)
1/s (or s1
)
L/mol*s (or L mol -1 s1
)
L2 / mol2 *s (or L2 mol-2 s1
)
24

Example: determine the reaction order with respect

to each reactant and the overall order from the
rate
law.
Look given
at the
rate
law and not the coefficients of the
chemical
reaction.
(a) 2NO(g)
+ O2(g)

2NO2(g)

rate = k[NO]2[O2]
2nd order in NO
1st order in O2

3rd order overall

(b) H2O2(aq) + 3I-(aq) + 2H+(aq)

2H2O(l)

I3-(aq) +

rate = k[H2O2][I-]
1st order in H2O2
2nd order overall
1st order in I0 order in H+
25

The rate equation for the reaction of NO with ozone is

Rate = k[NO][O3]. If the rate is 6.60 x 105 M/sec when [NO] = 1.00
x 106 M and [O3] = 3.00 x 106 M, calculate the rate constant k

26

What is the rate of the reaction when

[CH3CHO] = 1.75 x 103 M and
the rate constant 6.73 x 10 6 M1s1 is?

27

Finding the Rate Law:

1. Initial Rate Method
The rate law must be determined
experimentally
The rate law shows how the rate of a
reaction depends on the concentration of the
reactants
Changing the initial concentration of a
reactant will therefore affect the initial rate
of the reaction
28

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

29

Determining the Rate Law when

there are Multiple Reactants
Changing each reactant will effect the
overall rate of the reaction
By changing the initial concentration of
one reactant at a time, the effect of each
reactants concentration on the rate can
be determined
In examining results, we compare
differences in rate for reactions that only
differ in the concentration of one reactant
30

Reaction Order Tells How Changing

Reactant Concentration Affects Rate
0th Order; rate =k[A]0
double [A], rate same
1st Order; rate = k[A]1
double [A], double rate
2nd Order; rate =k[A]2
double [A]; quadruple rate
3rd Order; rate =k[A]3
double [A]; rate 8X

31

F2 (g) + 2ClO2 (g)

2FClO2 (g)

rate = k [F2]x[ClO2]y

Double [F2] with [ClO2] constant

Rate doubles
x=1
Quadruple [ClO2] with [F2] constant
Rate quadruples
y=1

rate = k [F2]1[ClO2]1

32

Plots of reactant concentration, [A], vs.

time for
first-, second-, and zero-order reactions.

33

Plots of rate vs. reactant concentration, [A],

for first-, second-, and zero-order reactions.

34

Effect of Concentration and Reaction Rate

In other reactions, different relationship between
reaction rate and reactant concentration
For example - reaction rate could be independent of
concentration, or it may depend on the reactant
concentration raised to some power [reactant]n
If reaction involved several reactants, the reaction
rate may depend on the concentrations of each of
them or only one of them.
If catalyst involved, its concentration may also
affect the rate of reaction.
35

Rate Equations
The relationship between reactant concentration
and reaction rate is expressed by an equation called
a rate equation or rate law.
Br2

(aq) + HCOOH

(aq)

2Br-

+
+
2H
(aq)

(aq) +

CO2

(g)

Consider, the above reaction, the rate is depend on

the concentration of Br2, but not concentration of
HCOOH.
So, the above reaction can be expressed as below.
Rate of reaction = k[Br2]
36

Rate Constant
Br2

(aq) + HCOOH

(aq)

2Br-

+
+
2H
(aq)

(aq) +

CO2

(g)

37

Rate Constant
Br2

(aq) +

HCOOH

(aq)

2Br-

(aq) +

2H+

(aq) +

CO2

(g)

rate [Br2]
rate = k [Br2]
rate
k=
[Br2]
k = rate
constant
= 3.50 x 10-3 s-1
Knowing the k allow you to calculate the rate at a particular
concentration. The units of k depends on the rate law or order of
reaction for a particular reaction- next slide will discussed further.

38

The Unit of Rate Constant

Reaction rates have units of mol/L.time
concentrations are given as moles per liter.

when

The time in rate constant can be seconds, minutes,

hours, days, year or whatever time unit is
appropriate.
Rate constants must have units consistent with the
order of a reaction
-1

0 order = Ms
1st order = s-1
2nd order = M-1 s-1

39

Experiment shows that the reaction is

first-order in Br2 and second-order in NO
2 NO

(g)

+ Br2

(g)

2 NOBr

(g)

a. Write the rate law for the reaction.

b. If the concentration of Br2 is tripled,
how will the reaction rate change?
c. What happens to the reaction rate
when the concentration of NO is

40

Determine the rate law and rate constant for the reaction
NO2(g) + CO(g) NO(g) + CO2(g)
1. Find value of n
Rate exp 4
:
Rate exp 2
k 0.40 0.10
0.033

n
m
0.0082
k 0.20 0.10
n

2n 4
n2
2. Find value of m
Rate exp 3
:
Rate exp 2
k 0.20 0.20
0.0083

n
m
0.0082
k 0.20 0.10
n

2m 1
m0

3. Rate k NO 2
k NO 2

CO m

Value k (from exp 1)

Rate k NO 2

0.0021 k 0.10
k 0.21 M -1s 1

2
41

Determine the rate law and rate constant

for the reaction NH4+ + NO2 N2 + 2 H2O

42

The rate of reaction between bromate ions and bromide

ions in acidic aqueous solution in terms of changes in concentration of
reactants and products is given below

Rate = - [BrO-3] = -1/5 [Br-] = -1/6[H+] = 1/3[Br2] =

1/3 [H2O]
t
t
t
Exp
[BrO
[Br-]
[H+]
Rate
t
t 3 ]
(L/mol.s
)

0.1

0.1

0.1

8.0 x 10-4

0.2

0.1

0.1

1.6 x 10-3

0.2

0.2

0.1

3.2 x 10-3

0.1

0.1

0.2

3.2 x 10-3

a) Write a balanced equation for the reaction

b) If the rate of the above reaction is first order with respect to BrO-3
and Br-, calculate the order of the reaction with respect to H + and
write the rate law of the reaction
c) Calculate the rate constant, k. What is the unit for k?
43

44

2. Integrated Rate Laws

For the reaction A Products, the rate law
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

45

Zero Order Reactions

Rate = k[A]0 = k
Integrated rate law:
[A]t = kt + [A]0
Graph of [A] vs. time is straight
line with slope = k and y
intercept = [A]initial
When Rate = M/sec, k = M/sec
46

y
[A]initial

[A]t =

-mx

kt + [A]0

slo
p

[A]

time

+ b

e=

47

First Order Reactions

Rate = k[A]1 = k[A]
ln[A]t = kt + ln[A]0
[A]0 = initial concentration of A
[A]t = concentration of A at some time, t
Graph ln[A] vs. time gives straight line
with slope = k and yintercept =
ln[A]initial
used to determine the rate constant
When Rate = M/sec, k = s1
48

ln [A]t =
[A]0

-mx

+ b

kt + ln

ln[A]initial

ln[A]

time

49

Second Order Reactions

Rate = k[A]2
1/[A]t = kt + 1/[A]0
Graph 1/[A] vs. time gives straight
line with slope = k and y
intercept = 1/[A]initial
used to determine the rate constant
When Rate = M/sec, k = M1s1

50

mx

+ b

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

1
[A]

p
o
l
s

k
=
e

1
[A]0

time
51

What can we conclude about RATE LAWS

versus
INTEGRATED RATE EXPRESSSIONS??

rate law can tell us the rate of a reaction,

nce the composition of the reaction mixture is known
integrated rate expression can give us the concentr
a species as a function of time. It can also give us t
te constant and order of the reaction by plotting the
propriate graph

52

3.

Half-Life
The half-life, t1/2, of a reaction is
the time it takes for the
concentration of the reactant to fall
to its initial value
The half-life of the reaction depends
on the order of the reaction

53

[A]t kt [A]0
Zero-order reactions
At time t = 0, [A] = [A]0
And when t = t, [A]t = [A]0/2
[ A]0
[ A]0 kt 1 / 2
2

[ A]0
[ A]0
2

kt1/ 2

[ A]0
kt1/ 2
2

[ A]0
t 1 / 2
2k

So t1/2 for 0 order reactions

depends on initial concentration

54

First-order reactions
ln[A]
At+
time
t = 0, [A]
0 = [A]

ln[A]t = - kt

Then at time t = t (half-life)

Substituting into above equation,

[ A]0
In[ A]0 kt1/ 2
2
[ A]0
In
In[ A] kt1 / 2
2
[ A]0 / 2
kt1/ 2
ln
[ A]0

In

1
ln
kt1 / 2
2
ln 1 ln 2 = -kt, where ln 1 =
0

55

Hence,

t1 / 2

ln 2

t1 / 2

or

0.693

What is/are the main point(s) to note from this expressio

For a 1st order reaction, the half-life is independent of reactant
concentration but dependent on k.
The half-life is constant for a 1st order reaction
[A]0

concentration
[A]0/2
[A]0/4
[A]0/8

Recall: [A]t = [A]0e-kt

t1/2
t1/2

t1/2

time

56

Second-order reactions

1
1
kt
[ A ]t
[A]0

At time t = 0, [A] = [A]0

And when t = t, [A]t = [A]0/2
1
1

kt1 / 2
[ A]0
[ A]0
2

2
1

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

1
t 1 / 2
k [ A]0

So t1/2 for 2nd order reactions

depends on initial concentration

57

Therefore, larger initial concentrations imply shorter half-lives

(so faster the reaction).

[A]0

concentration

[A]0/2 t1/2
[A]0/4

t1/2

[A]0/8

t1/2

time

58

The Half-Life of a First-Order

Reaction Is Constant

59

Rate Data for: C4H9Cl + H2O

C4H9OH + HCl

60

C4H9Cl + H2O C4H9OH + 2 HCl

slope = 2.01 x 103
k = 2.01 x 103 s-1

61

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
A i
t1
2
2k
For a first order reaction, the half-life is independent of
the concentration. (t1/2 = constant)
In 2
t1
2
k
For a second order reaction, the half-life is inversely
proportional to the initial concentration increasing
1
the initial
shortens the half-life
t 1 concentration

2
k A i

62

Example: Molecular iodine dissociates at 625 K with a

first-order rate constant of 0.271 s1. What is the half-life
of this reaction?
Given:
Find:

Conceptual
Plan:

k = 0.271 s1
t1/2
k

t1/2

Relationships:
Solution:

Check:

the new concentration is less than the original, as expected

63

The reaction Q 2 R is second order in Q.

If the initial [Q] = 0.010 M and the rate constant is
1.8 M1s1 find the length of time for [Q] = [Q]init

64

65

Example: Cyclopropane is the smallest cyclic

hydrocarbon. It is thermally unstable and
rearranges to propene at 1000oC via the
following first-order reaction:
CH2

H2 C

CH2 (g)

H3C CH

CH2 (g)

The rate constant is 9.2 s-1, (a) What is the half-life

of the reaction? (b) How long does it take for the
concentration of cyclopropane to reach onequarter of the initial value?
(a t1/2 = 0.693/9.2 s-1 =
)
0.075 s
(b) 2 t1/2 = 2(0.075 s) =
0.150 s
66

The reaction SO2Cl2(g) SO2(g) + Cl2(g) is first order with

a rate constant of 2.90 x 104 s1 at a given set of conditions. Find
the [SO2Cl2] at 865 s when [SO2Cl2]initial = 0.0225 M

67

The reaction Q 2 R is second order in Q.

If the initial [Q] = 0.010 M and after 5.0 x 102 seconds
the [Q] = 0.0010 M, find the rate constant

68

4.

Graphical Determination of

the Rate Law for A Product

Plots of [A] vs. time, ln[A] vs. time, and 1/[A]
vs. time allow determination of whether a
reaction is zero, first, or second order
Whichever plot gives a straight line
determines the order with respect to [A]
if linear is [A] vs. time, Rate = k[A]0
if linear is ln[A] vs. time, Rate = k[A]1
if linear is 1/[A] vs. time, Rate = k[A]2

69

Example: Determine the Rate Equation

for the Reaction A 2 Product

70

71

72

73

Conclusion for the determination of the rate

equation for the reaction A 2 Product
Because the graph 1/[A] vs. time is linear,
the reaction is second order,
Rate k[A]2
k slope of the line 0.10 M1 s 1

74

THEORIES OF CHEMICAL KINETICS

1.

Collision Theory

For most reactions, for a reaction to take place,

the reacting molecules must collide with each
other
on average about 109 collisions per second
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"; and
2. whether the reacting molecules collide in the
proper orientation for new bonds to form

75

2. 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
Any factor that can increase the
frequency of effective collisions would
increase the rate of a reaction

76

Kinetic Energy Factor

Molecules or atoms or ions
can only react if they
collide with each other.
In a chemical reaction,
bonds are broken and new
bonds are formed.
For a collision to be
effective, the reacting
molecules must have
sufficient kinetic energy to
overcome the energy
barrier.
77

Orientation Effect

78

BrNO collision

79

3. 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

80

Reaction Coordinate
Diagrams
It is helpful to
visualize energy
changes
throughout a
process on a
reaction
coordinate
diagram like this
one for the
rearrangement of
methyl isonitrile.
81

Reaction Coordinate
Diagrams
It shows the energy
of the reactants and
products (and,
therefore, E).
The high point on the
diagram is the
transition state.
The species present at the transition state
is called the activated complex.
The energy gap between the reactants
and the activated complex is the
activation energy barrier.
82

4. Activation Energy
The activation energy, Ea is a minimum
amount of energy required to initiate
reaction:
Molecules must possess a certain minimum
kinetic energy called the activation energy
for a reaction to occur
energy needed to break the bonds of the
reacting molecules
reaction with low activation energy is easier to
take place, and is faster
83

84

Activation Energy
The activation energy may be shown on diagrams
called energy profiles. The energy barrier, Ea is the
activation energy for forward reaction
E
n
e
r
g
y

Ea

reactants

H = -ve

E
n
e
r
g
y

products
Ea
H = +ve

products
reactants

Progress of reaction

(a) Energy profile for an

exothermic reaction

Progress of reaction

(b) Energy profile for an

endothermic reaction
85

Activated state

Activated state

E
n
e
r
g
y

Ea (forward)

Ea (reversed)

reactants

E
n
e
r
g
y

Ea (reversed)
Ea (forward)

products

products
reactants

Progress of reaction

Progress of reaction

H = Ea (forward) Ea (reversed)

H = Ea (forward) Ea (reversed)

H = -ve

H = +ve

A reversible reaction has two activation energies:The activation energy ,Ea (forward) , is the energy difference between
the activated state and the reactants
The activation energy ,Ea (reverse) is the energy difference between the
activated state and the products.
86

Drawing Reaction Energy Diagrams and

Transition
States
A key reaction in the upper atmosphere is
O3(g) + O(g)
2O2(g)
The Ea(fwd) is 19 kJ, and
the Hrxn for the reaction is -392 kJ. Draw
a reaction energy diagram for this reaction, postulate a
transition state, and calculate Ea(rev).
Exothermic reaction. The reactants are at a higher energy level
than the products and the transition state is slightly higher than
the reactants.

SOLUTION:

Potential Energy

PLAN:

Ea= 19
kJ
O3+O
Hrxn
kJ

transition
state
= -392
2O2
Reaction progress

Ea(rev)= (392 + 19) kJ

=
411kJ
breaking
O
bond
O
O
forming O
bond

87

NO (g) + F2 (g) NOF (g) + F (g) has an

overall enthalpy change of -60 kJ. The activation
energy the reaction is 16.3 kJ
a) Sketch the energy profile for the reaction and label
Ea, H and draw the activated complex.
b) What is the activation energy for reverse reaction?

88

The Transition State Theory

The transition state theory is concerned with what
actually happens during a collision.
This theory explains how the energy of collisions is
used to form a high-energy activated complex
when reactants particles collide with each other.
There exists an intermediate stage before reactant
molecules change into products.
The activated complex or transition state is a
chemical species with partially broken and partially
formed bonds
has highest energy and extremely unstable exists at instant
has more potential energy than either the reactants or the
products
the bonds in the reactant molecules are in the process of
breaking while the new bonds in the products molecules are start 89

Reaction energy diagrams and possible transition states.

90

5. Collision Frequency
The collision frequency is the number of
collisions that happen per unit time
The more collisions per second there are,
the more collisions can be effective and
lead to product formation

91

FACTORS CONTROLLING
RATES OF REACTIONS
1

CONCENTRATIONS OF REACTANTS

CHEMICAL NATURE OF REACTANTS

TEMPERATURE

THE USE OF A CATALYST

92

1. Reactant Concentration
Generally, the larger the concentration of
reactant molecules, the faster the reaction
increases the frequency of effective
collisions between reactant molecules
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)

93

2. Nature of the Reactants

Nature of the reactants means what kind of
reactant molecules and what physical conditions
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. potassium metal is more reactive than 94

3. Temperature
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 increase in frequancy of effective
collisions. Hence, increasing the rate of
reaction
The distribution of kinetic energy is shown by
the Boltzmann distribution curves

95

96

4. Catalyst
Catalysts are substances that affect
the rate of a reaction without being
consumed
Catalysts generally speed up a
reaction
They give the reactant molecules a
different path to follow with a lower
activation energy
97

98

99

The Arrhenius Equation

Changing the temperature changes the rate
constant, k, of the rate law
The Arrhenius Equation shows the
relationship between absolute temperature, T,
and rate constant, k :

where T is the temperature in kelvins

R is the gas constant in energy units, 8.314 J/(molK)
A is called the Arrhenius constant (which includes the frequency factor and
the orientation factor)
Ea is the activation energy, the minimum energy needed for the
molecules to react
100

The Arrhenius Equation:

The Exponential Factor

The exponential factor in the Arrhenius

equation is a number between 0 and 1

The larger the activation energy, Ea, 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

101

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
(R)(slope of the line) = Ea (in Joules), R = 8.314 J/(molK)
eyintercept = A (unit is the same as k)
102

Example: Determine the activation energy and frequency

factor for the reaction O3(g) O2(g) + O(g) given the
following data:

103

y = mx + c
104

slope, m = 1.12 x 104 K

yintercept, b = 26.8

105

Arrhenius Equation:
Two-Point Form
If you only have two (T,k) data points, the
following forms of the Arrhenius Equation
can be used:

106

Example: The reaction NO2(g) + CO(g) CO2(g) + NO(g) has a

rate constant of 2.57 M1s1 at 701 K and 567 M1s1 at
895 K. Find the activation energy in kJ/mol
Given: T1 = 701 K, k1 = 2.57 M1s1, T2 = 895 K, k2 = 567 M1s1
Find:

Conceptual
Plan:

Ea, kJ/mol
T1, k1, T2, k2

Ea

Relationships:
Solution:

Check:

most activation energies are tens to hundreds of kJ/mol so

the answer is reasonable
107

Find the activation energy in kJ/mol for

increasing the temperature 10 C doubling the
rate

108

Reaction Mechanisms
The sequence of events that describes the actual
process by which reactants become products is
called the reaction mechanism.
Reactions may occur all at once or through
several discrete steps.
Each of these processes is known as an
elementary reaction or elementary process.
In a multistep process, one of the steps will be
slower than all others.
The overall reaction cannot occur faster than this
slowest, rate-determining step.
109

An Example of a Reaction Mechanism

Overall reaction:
H2(g) + 2 ICl(g) 2 HCl(g) + I2(g)

Mechanism:
Step 1: H2(g) + ICl(g) HCl(g) + HI(g)
Step 2: HI(g) + ICl(g) HCl(g) + I2(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

110

Intermediates
Overall: H2(g) + 2 ICl(g) 2 HCl(g) + I2(g)
Step (1): H2(g) + ICl(g) HCl(g) + HI(g)
Step (2): HI(g) + ICl(g) HCl(g) + I2(g)

Notice that the HI is a product in Step 1, but

then a reactant in Step 2
Because HI is made but then consumed, HI
does not show up in the overall reaction
Materials that are products in an early
mechanism step, but then a reactant in a
later step, are called intermediates
Adding equations (1) and (2), removing
HI, will give the overall equation.

111

Molecularity
The number of reactant particles in an
elementary step is called its molecularity
A unimolecular step involves one particle
A bimolecular step involves two particles

though they may be the same kind of

particle
A termolecular step involves three particles

though these are exceedingly rare in

elementary steps

112

The molecularity of a reaction is the number of molecules

reacting in the rate determining (slowest) elementary step.

Unimolecular reaction elementary step with 1 molecule

Bimolecular reaction elementary step with 2 molecules

Termolecular reaction elementary step with 3 molecules

Slowest Elementary Reaction in Mechanism
Unimolecular reaction

products rate = k [A]

Bimolecular reaction

A+B

products rate = k [A][B]

Bimolecular reaction

A+A

products rate = k [A]2

113

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 directly from the equation of
the step
H2(g) + 2 ICl(g) 2 HCl(g) + I2(g)
1)

H2(g) + ICl(g) HCl(g) + HI(g) Rate = k1[H2][ICl]

2)

HI(g) + ICl(g) HCl(g) + I2(g)

Rate = k2[HI][ICl]
114

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.
NET EQUATION 2NO (g) + O2 (g)

2NO2 (g)

N2O2 is detected during the reaction!

N2O2 is an
REACTION MECHANISM
intermediate
1. Elementary step:
2. + Elementary step:

NO + NO

N2O2

N2O2 + O2

2NO2

Overall reaction:

2NO + O2

2NO2

115

Rate Laws of Elementary Steps

116

Rate Determining Step

In most mechanisms, one step occurs slower than
the other steps
The result is that product formation 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

117

A. Slow Initial Step

NO2 (g) + CO
CO2 (g)

(g)

NO

(g)

The rate law for this reaction is found

experimentally to be
Rate = k [NO2]2
CO is necessary for this reaction to occur, but the
rate of the reaction does not depend on its
concentration.
This suggests the reaction occurs in two steps.
118

 A proposed mechanism for this reaction is

Step 1: NO2 + NO2
NO3 + NO (slow)
Step 2: NO3 + CO

NO2 + CO2 (fast)

The NO3 intermediate is consumed in the second

step.
As CO is not involved in the slow, rate-determining
step, it does not appear in the rate law.
Rate = k1[NO2][NO2] = k1[NO2]2 and Rate = k2[NO3]
[CO]
K1 = k, the rate law for the rate-determining step
(slow) is identical to the experimental rate law

119

Another Reaction Mechanism

NO2(g) + CO(g) NO(g) + CO2(g)
Rateobs = k[NO2]2
1. NO2(g) + NO2(g) NO3(g) + NO(g) Rate = k1[NO2]2 Slow
2. NO3(g) + CO(g) NO2(g) + CO2(g) Rate = k2[NO3][CO] Fast
The first step is slower than the
second step because its
activation energy is larger.
The first step in this
mechanism is the rate
determining step.
The rate law of the first step is
the same as the rate law of the
overall reaction.

120

Validating a Mechanism

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

121

B. 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

122

k1 N O
1. 2 NO
(g)
2 2(g)

Fast

k1

2. H2(g) + N2O2(g) H2O(g) + N2O(g) Slow Rate = k2[H2][N2O2]

3. H2(g) + N2O(g) H2O(g) + N2(g)

Fast

2 H2(g) + 2 NO(g) 2 H2O(g) + N2(g) Rateobs = k [H2][NO]2

123

mechanism for the reaction 2 O3(g) 3

O2(g) matches the
observed rate
k
law Rate
= k[O3]2[O2]1
1

1.O3(g)k O2(g) + O(g) Fast

1

2.O3(g) + O(g) 2 O2(g) Slow

Rate = k2[O3][O]

124