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Chapter 2

Chemical
Kinetics
1

SCOPE

Reaction Rate Expression


Factors affecting Reaction Rate
Rate Law and Its Component
Integrated Rate Laws:
- Zeroth, First and Second Order
Reactions

Effect of Temperature on Reaction Rate


2

LEARNING
OUTCOME

Able to determine simple reaction orders.


Able to apply the Arrhenius equation and rate
law in calculations.

Able to identify reaction mechanism and rate


determine step for a given reaction.

LEARNING
OUTCOMES

Determine reaction orders


Calculate rate constants
Write expression for integrated rate laws
Determine half life

LEARNING
OUTCOME

Apply Arrhenius equation to calculate rate


constant or activation energy.

Express rate law based on elementary


reactions

Derive rate law using rate-determining step


5

2.1 Reaction Rate


Expression

Chemical kinetics is the study of the rate


of a reaction

The reaction rate is the speed with which


reactants disappear and products form

Reaction rates are always reported as


positive values

The unit is mol L1 s1


6

Average, Instantaneous and Initial


Rates

Instantaneous rate:
slope of a line tangent
to the curve at a
particular point (e)

Initial rate:
the instantaneous rate
at the moment
reactants are mixed (a)

Average rate:
slope of line joining
any two points (b, c, d)
7

2.1 Reaction Rate


Expression

Rate of reaction: the change in concentrations


of reactants or products per unit time

Consider this reaction

A B


Average rate =
t
= delta = (final - initial) concentration of
reactant/product
use [ ] to express concentration in moles/liter

A
B
Average rate = t = t
8

2.1 Reaction Rate


Expression
Consider the reaction

A B

2.1 Reaction Rate


Expression
Consider the reaction

A B

10

2.1 Reaction Rate


Expression
Consider the reaction

A B

The concentration of the reactant, A, decreases with


time

rate (A) =

[conc of A at time t2 conc of A at time t1]


t2 t 1

[A]
t

The concentration of the product, B, increases with


time

rate (B) =

conc of B at time t2 conc of B at time t1


t2 t 1

11

[B]
t

2.1 Reaction Rate


Expression
Consider the reaction

A B

Calculate the average rate at which [A]


changes in the first 50 seconds
rate (A) =

[A]
t
([A]t=50 [A]t=0)
50 s 0 s
(0.0629 mol L-1 0.0750 mol L-1)
50 s

-(-2.4 10-4 mol L-1 s-1)

2.4 10 mol L s
-4

-1

-1

12

2.1 Reaction Rate


Expression
Consider the reaction

A B

The rate at a particular time is called the

instantaneous rate
This can be determined from the slope of a
tangent to the curve
For example, from plotting of [A] against time,
at t = 50 s
rate = -(slope of tangent line) =
= 2.3 10-4 mol L-1 s-1

13

-d[A]
dt

2.1 Reaction Rate


Expression

Reaction:

A B

Supposed the reaction begins with 1.00 mol


A.
At t =0 there is 1.00 mol A, no B present.
At t =10 min, there is 0.74 mol A and 0.26
mol B
At t =40 min, there is 0.30 mol A and 0.70
(moles B)
mol B.

t
Calculate average rate from t = 0 to t = 10
(mol B at t 10 min) - (mol B at t 0)
min.

10 min 0 min
average rate 0.26 mol - 0 mol
14

0.026
mol/min
10 min - 0 min

2.1 Reaction Rate


Expression
Consider :
C4H9Cl(aq)+H2O(l)
Butyl chloride

C4H9OH(aq)+HCl (aq)

Butyl alcohol

We can calculate the average rate in terms


of the disappearance of C4H9Cl.
15

2.1 Reaction Rate


Expression

C4H9Cl(aq)+ H2O(l) C4H9OH(aq)+HCl (aq)


Time (s) [ C4H9Cl ] (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
0.0360
800.0
0.0200

Plot [ C4H9Cl ] versus time

16

C4H9Cl(aq)

2.1 Reaction Rate


Expression
+ H O C H OH +HCl
2

(l)

(aq)

(aq)

17

2.1 Reaction Rate


Expression

C4H9Cl(aq)+ H2O(l) C4H9OH(aq)+HCl (aq)

Average rate of disappearance of C 4H9Cl


(C4H9Cl)

t
C4H9Cl finaltime C4H9Cl initialtime

final
time

initial
time

18

2.1 Reaction Rate


C4H9Cl(aq)+ H2O(l)Expression
C4H9OH(aq)+HCl (aq)
Time (s)
0.0
50.0
100.0
150.0
200.0
300.0
400.0
500.0
800.0

[ C4H9Cl ](M) Ave.rate (M/s)


0.1000
1.9 x 10-4
0.0905
1.7 x 10-4
0.0820
1.6 x10-4
0.0741
1.4x10-4
0.0671
1.22x10-4
0.0549
1.01 x10-4
0.0448
0.80x10-4
0.0360
0.56x10-4
0.0200
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Reaction Rates and


Stoichiometry
Reaction : relationship one-to-one
C4H9Cl (aq) + H2O (l)
(aq)

C4H9OH (aq) + HCl

1 mole of C4H9OH is produced for each mole of


C4H9Cl consumed. H2O is consumed and HCl is

H2O
HCl

t
t
C4H9Cl
C4H9OH

Rate =
t
t 20

produced.

Reaction Rates and


Stoichiometry
Reaction : relationship is not one-to one
2HI (g)

H2 (g) + I2(g)

The rate of disappearance of HI is twice the rate of


appearance of H2 and I2 .

1 HI H2 I2

rate =
2 t
t
t
In general for: aA + bB
rate =

cC + dD

1 A
1 B 1 C 1 D

a t
b t
c t
d 21t

Reaction Rates and


Stoichiometry
Example:
Write the rate expressions for the following
reactions in terms of the disappearance of
the reactants and the appearance of the
products.
4NH3 (g) + 5O2 (g)

4NO (g) + 6H2O (g)

22

Reaction Rates and


Stoichiometry
Solution:

1 NH3
1 O 2 1 NO
rate

4 t
5 t
4 t
1 H 2 O

6 t
23

Reaction Rates and


Stoichiometry

Example :

2C4H10(g) + 13O2(g) 8CO2(g) + 10H2O(g)


If the butane concentration is decreasing at a
rate of 0.20 mol L1 s1, at what rate is the
oxygen concentration decreasing?

Solution:
0.20 mol C4H10
13 mol O2
rate (O2) =
x
Ls
2 mol C4H10

1.3 mol O2
Ls

Oxygen reacts at a rate of 1.3 mol 24L1 s1

2.2 Factors Affecting Reaction


Rate
Principal factors influence reaction rates:

1. Chemical nature of the reactants


2. Ability of the reactants to come in contact with
each others
3. Concentrations of the reactants
4. Temperature
5. Availability of rate-accelerating agents called
catalysts

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2.2 Factors Affecting Reaction


Rate
Chemical nature of the reactants
During reactions, bonds break and new
bonds form
Some reactions are fast by nature and
others are slow

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2.2 Factors Affecting Reaction


Rate

Ability of the reactants to meet


Most reactions involve two or more reactants
whose particles (atoms, ions or molecules)
must collide for the reaction to occur
In a homogeneous reaction, all of the reactants
are in the same phase
In a heterogeneous reaction, the reactants are
present in different phases
Surface area , Rate

27

2.2 Factors Affecting Reaction


Rate

Surface area

The area of contact between the phases


determines the reaction rate

28

A: nail (low surface area)

B: Steel wool (high


surface area)
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2.2 Factors Affecting Reaction


Rate
Concentration of the reactants
The rates of both homogeneous and
heterogeneous reactions are affected by the
concentrations of the reactants
For example, red-hot steel wool bursts into flame
when thrust into pure oxygen

Rate collision frequency concentration


Concn , Rate
30

2.2 Factors Affecting Reaction


Rate

Temperature of the system


Almost all chemical reactions occur
faster at higher temperatures

Rate collision energy temperature

Temperature , rate
a: energetic collision - lead to
product
b,c,d: molecules just bounce off!!
31

2.2 Factors Affecting Reaction


Rate

Presence of catalysts
Catalysts are substances that increase
the rate of chemical reactions without
being used up
For example, enzymes that direct our
body chemistry are all catalysts
32

2.2 Factors Affecting Reaction


Rate

Presence of catalysts

33

2.3 Rate Laws


A rate law is an equation in which the rate is
given as a function of reactant concentrations
for example, rate = k[HI]n
k is the rate constant of the reaction
n is the order of the reactant
Both rate constant and order must be
experimentally determined
34

2.3 Rate Laws


The value of the rate constant, k depends
on the particular reaction being studied
and the temperature at which the
reaction occurs

The order, n can be positive or negative,


an integer or a fraction

The order cannot be deduced from the


balanced equation
35

2.3 Rate Laws


Types of rate laws:
A differential rate law expresses the rate as a
function of concentration
d[A]
rate =
= k[A]
dt
An integrated rate law expresses the
concentration as a function of time

[ A]0
ln
kt or [ A]t [ A]0 e kt
[ A]t
36

2.3 Rate Laws


Consider the hypothetical reaction:
A + B products
The rate law for the reaction is:
rate = k[A]m[B]n
The values of m and n can be discovered by
looking for patterns in the rate data (experimental
data)
Order cannot be deduced from the balanced
equation
37

2.3 Rate Laws

Consider the following reaction:

H 2 SeO3 6 I 4 H

Se 2 I 3H 2O

From experiment, the rate law


(determined from initial rates) is
3

rate k[ H 2 SeO3 ] [ I ] [ H ]
1

Rate law cannot be obtained from the balanced


equation !!!!!!!!
38

2.3 Rate Laws


A + B product (C)
Suppose that the data in the table below has
been obtained in a series of five experiments:

39

2.3 Rate Laws


A + B product (C)
For experiments 1, 2 and 3 [B] is held constant. Any
changes in the rate must be due to the change in [A]
The rate law says that at constant [B] the rate must
be proportional to [A]m
rateexp 2
rateexp 1

[A]exp 2

[A]exp 1

rateexp 2
rateexp 1

0.40 mol L-1 s-1


0.20 mol L s
-1

-1

=2

and
[A]exp 2
[A]exp 1

0.20 mol L-1


0.10 mol
L
40

-1

=2

2.3 Rate Laws


A + B product (C)
So doubling [A] from experiment 1 to experiment 2
doubles the rate
The relationship reduces to:
2.0 = 2.0m
The only value of n that makes this equation true is
m=1
The reaction must be first order with respect to A
41

2.3 Rate laws


A + B product (C)
In the final three experiments, the concentration
of B changes while the concentration of A is held
constant
This time it is [B] that affects the rate
rateexp 4
rateexp 3

[B]exp 4

[B]exp 3

For experiments 3 and 4, we have:


4.0 = 2.0n
Therefore, n must equal 2

42

2.3 Rate Laws


A + B product (C)
We now know that the rate law for the
reaction must be:
rate = k[A]1[B]2
The overall order is the sum of the orders for
each reactant in the rate law = 3
What is the value of k?
43

2.4 Integrated Rate


Laws

The integrated rate laws

Integrated rate laws express concentration as a


function of time
Consider the hypothetical reaction:
A products
The (differential) rate law has the form:
rate =

d[A]
dt

= k[A]n
44

2.4 Integrated Rate


laws
Zero-order rate laws, n=0
The differential rate law is:
rate = k[C]0 = k(1) = k
The integrated rate law is:
[C]t = kt + [C]0
A plot of [C] versus time gives a straight
45
line of slope k

2.4 Integrated Rate


laws
Zero-order rate laws

46

2.4 Integrated Rate Laws

First-order reactions
Assume A products is first order, n=1
The differential rate law has the form:

rate = d[A] = k[A]


dt
The integrated rate law would be:

[ A]0
kt
ln
kt or [ A]t [ A]0 e
[ A]t
[A]0 is [A] at t (time) = 0
[A]t is [A] at t = t
47
e = base of natural logarithms = 2.71828

2.4 Integrated Rate Laws

First-order reactions
rate =

d[A]
dt

= k[A]

A k t dt
A A
0
ln A t ln A 0 k t
At d
0

ln A t k t ln A 0
ln

[A]0
[A]t

= kt

or

[A]t = [A]0e-kt
48

2.4 Integrated Rate


Laws
For first order reactions a plot of the natural
logarithm of concentration versus reaction time
always gives a straight line

49

2.4 Integrated Rate


Laws

Example

The specific rate constant for the first-order


decomposition of N2O5 in CCl4 at 45oC is 6.32 10-4 s-1
2N2O5 4NO2 + O2
a. What is the concentration of N2O5 remaining after
2.00 hr if the initial concentration of N 2O5 was
0.500 M ?
b. How much time required for 90% of N2O5 to
50
decompose ?

2.4 Integrated Rate


Laws

Solution

a. need a relationship between time and concentration


ln [ A ]t = -kt + ln [ A ]o , ln [N2O5]t = -kt + ln [N2O5]o
ln [N2O5]t = -( 6.32 10-4 s-1) x
(2.00 hr 3600 s/1 hr) + ln (0.500)
ln [N2O5]t = -4.55 + ( -0.693) = -5.24
[N2O5]t = exp (-5.24) = 5.3 10-3 M

51

2.4 Integrated Rate


Laws

Solution

b. assume the final concentration is 10% of the initial


concentration.
90% of N2O5 has decomposed, so only 10% remains
[N2O5] = (0.1)(0.500 M N2O5)= 0.0500 M N2O5
ln [ 0.0500 ] = - (6.32 10-4 s-1) t + ln [ 0.500 ]
- 2.996 = - ( 6.93 10-4 s-1) t + (-0.693)
t = 3.64 103 s
The time it takes for 90% of N2O5 to disappear is
3604 s or 1.01 hrs
52

2.4 Integrated Rate


Laws
Second-order reactions, n=2
Assume B products is second order
The differential rate law is:
rate =

d[B]
dt

= k[B]2

The integrated rate law would be:


1
[B]t

= kt +

1
[B]0

53

2.4 Integrated Rate


Laws
Second-order reactions

B
2
Rate
k B
t
At d B
t
B
k t ,
k dt
2
2
A 0 B
0
B
1
1
1
1

kt ,
kt
B t B 0
Bt
B 0
54

2.4 Integrated Rate


Laws
When a reaction is second order, a plot of 1/[B]

versus t should yield a straight line with a slope k

55

Half life
The amount of time required for half of a
reactant to disappear is called the half-life, t1/2
The half-life of a first-order reaction is not
affected by the initial concentration
[ A]0
First - order rate law : ln
kt
[ A]t
1
at t t1/ 2 , [ A]t [ A]0 , substituti ng
2
[ A]0
ln 2
ln 1
kt1/ 2 or t1/ 2
k
[ A]0
56
2

Half life

First-order radioactive decay of iodine-131. The


initial concentration is represented by [I]
570.

Half life
The half-life of a second-order reactions
does depend on the initial concentration
1
1
Second - order integrated rate law :
kt
[ B ]t [ B ]0
1
at t t1/ 2 , [ B]t [ B ]0 , substituting
2
1
1
kt1/ 2
1
[ B]0 [ B]0
2
1
l
kt1/ 2 or t1/ 2
[ B ]0
k[ B ]0

58

SUMMARY

59

Example
Carbon-14 (14C) is a radioactive isotope
with a half-life of 5.73 x 103 years. It
decays following the first order reaction.
The amount of 14C present in an object can
be used to determined its age. Calculate
the rate constant for decay of 14C and
determine how long is required for 90% of
the 14C in a sample to decompose.
60

Solution
t1

0.693
,
k
0.693

5.73 103 yr

0.693
t1
2

1.21 10 4 yr 1

When 90% has decayed, 10% remains, or [A ] t = 0.10[A ] 0

ln A 0 kt ln A t ,

ln

A 0
0.10 A 0

kt ln

A 0
A t

ln

A 0
A t
k

ln 10

1
.
90

10
yr
3
1
3
1
1.21 10 yr
1.21 10 yr
61

2.5 Theory of chemical


kinetics
Collision theory
One of the simplest models to explain
reaction rates is collision theory
Collision theory says that the rate of a
reaction is proportional to the number of
effective collisions per second among the
reactant molecules
An effective collision is one that actually
gives product molecules

2.5 Theory of chemical


kinetics
Concentration can influence the number of
effective collisions per second
As reactant concentrations increase, the
number of effective collisions increases
Not every collision between reactant
molecules actually results in a chemical
change
Only a very small fraction of all the collisions
can really lead to a net change
Why is this so?

2.5 Theory of chemical


kinetics
Molecular orientation
When two reactant molecules collide they must
be oriented correctly for a reaction to occur
(see next slide)

2.4 Theory of chemical


kinetics

2.5 Theory of chemical


kinetics

Activation energy
The activation energy (Ea) is the minimum
energy required for a reaction to occur
The activation energy determines the rate of
a reaction
At a given temperature, only a certain fraction
of the collisions possess enough energy to be
effective and form products
66

2.5 Theory of chemical


kinetics

67

2.5 Theory of chemical


kinetics
The arrangement found on the top of the
potential energy hill is called the activated
complex or transition state
Once the transition state is reached, the
reaction proceeds to give products, with the
release of energy
A reaction intermediate corresponds to an
energy minimum between two transition
states
68

Transition State
Theory
The activated complex is unstable species and what exists
is neither reactant nor product but a transitional species
with partial bonds. Consider reaction between:
CH3Br + OH- CH3OH + Br-

69

2.4 Theory of chemical


kinetics

Temperature effects

The rate of a reaction increases with increasing


temperature

70

2.4 Theory of chemical


kinetics
The activation energy is related to the rate
constant by the Arrhenius equation

k = Ae

-Ea/RT

k = rate constant
Ea = activation energy
R = universal gas constant
T = temperature (in Kelvin)
A = pre-exponential or frequency factor
71

2.4 Theory of chemical


kinetics
The activation energy can also be obtained
from two rate components measured at
different temperatures
Most reactions obey the Arrhenius equation
to a good approximation
ln

k2
k1

Ea

T2

1
T1
72

Example
An alteration in the structure of a certain virus follows firstorder kinetics with Ea = 587 kJ/mol .The half-life at 29.6oC is
1.62 104 s ( 1 yr = 3.154 107 s ). What are the rate
constants at 29.6oC and the half-life at 32oC for the alteration
of the virus ?

Solution
For a first order rxn: k1 = 0.693 / t1/2
Rate constant at 29.6oC = 0.693 / (1.62 104 s)
= 4.28 10-5 s-1
73

Solution (cont.)
Ea is given, so k2 can be calculated using the Arrhenius
equation.The t 1/2 at 32.0oC can be obtained from k2.

Ea
k1
ln

k2
R

1
1

T1 T2

4.28 10 -5 s -1
(587
kJ/mol)(10
00
J/kJ)

ln

k
8.314 J/mol.K
2

1
1

305.0 K 302.6 K
k 2 2.68 10 - 4 s -1

74

Solution (cont.)
o

thus thehalf - life at 32 C :


t1/2 0.693/ k2
0.693

2.68 10 4 s-1
2.58 103 s

75

2.6 Reaction
mechanisms
Most reactions do not occur in a single
step

The net overall reaction is the result of a


series of simple reactions

Each of these is called an elementary


process

The entire set of elementary processes is


the reaction mechanism
76

2.6 Reaction
mechanisms
The rate law of an elementary process can
be written from its chemical equation

This rule only applies to elementary


processes

The overall rate law derived from the


mechanism must agree with the
observed rate law for the overall
reaction
77

Example
The following two reactions are proposed as elementary steps in the
mechanism for an overall reaction:
(1) NO2Cl (g) NO2 (g) + Cl (g)
(2) NO2Cl(g) + Cl (g) NO2(g) + Cl2(g)
Overall reaction: (1) + (2)
Overall rxn: 2NO2Cl(g) 2NO2 (g) + Cl2
Reaction intermediate is a substance that is formed and used up in
the overall reaction, does not appear in the overall reaction: Cl (g)
Rxn(1) : Unimolecular, Rate = k1[NO2Cl]
Rxn(2): Bimolecular, Rate = k2[NO2Cl][Cl]

78

2.6 Reaction
mechanisms
The rate-determining step
Consider the gaseous reaction:
2NO2Cl 2NO2 + Cl2

The actual mechanism of the reaction is the


following two-step sequence of elementary
processes:
NO2Cl NO2 + Cl

(slow)

NO2Cl + Cl NO2 + Cl2

(fast)

The Cl radical formed is an intermediate


79

2.6 Reaction
mechanisms
In any multistep mechanism, one step is
usually much slower than the others

The slow step in a mechanism is called


the rate-determining step

The rate law for the rate-determining


step is directly related to the rate law
for the overall reaction
80

2.5 Reaction
mechanisms
Rate laws for elementary
steps

The rate limiting step will dominate the


expression of rate laws.
Eg:
Step 1: NO (g) + Br2 (g) NOBr2

(fast)

Step 2: NOBr2 (g) + NO (g) 2NOBr (g) (slow)


Rate law

: Rate=k[NOBr2] [NO]

81

Example
NO catalyzes the decomposition of N2O possibly
through the following mechanism:
NO(g) + N2O(g) N2(g) + NO2(g)
2NO2(g) 2NO(g) + O2(g)
What is the overall reaction?
(1) 2 2NO (g) + 2N2O (g) 2N2 (g) + 2NO2
(g)
(2)
2NO2(g) 2NO(g) + O2(g)
_________________________________
2N2O (g) 2N2 (g) +O2(g)
NO = catalyst;
NO2=intermediate 82

The End
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