Chapter 2

Chemical Kinetics
 SCOPE
• Reaction Rate Expression
• Factors affecting Reaction Rate
• Rate Law and Its Component
• Integrated Rate Laws:
- First and Second Order Reactions
• Effect of Temperature on Reaction Rate
• Catalysis
 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.
• Able to understand basic concepts in
catalysis.
 LEARNING OUTCOME
• 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
Chemical Kinetics
 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 L–1 s–1
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)
 2.1 Reaction Rate Expression
• Rate of reaction: the change in concentrations of
reactants or products per unit time
• Consider this reaction A  B
Δ 
Average rate =
Δt
 = delta = (final - initial) concentration of reactant/product
use [ ] to express concentration in moles/liter

• Average rate =  ΔA  = ΔB

Δt Δt
• The unit of reaction rate is: mol/L.s or M/s
2.1 Reaction Rate Expression
Consider the reaction A B
2.1 Reaction Rate Expression
Consider the reaction A B
 2.1 Reaction Rate Expression
Consider the reaction A B

• The concentration of the reactant, A, decreases with

time
conc of A at time t2 – conc of A at time t1 Δ[A]
rate (A) = =
t2 – t1 Δt

• The concentration of the reactant, B, increases with

time
conc of B at time t2 – conc of B at time t1 Δ[B]
rate (B) = =
t2 – t1 Δt
 2.1 Reaction Rate Expression
Consider the reaction A B
• Calculate the average rate at which [A]
changes in the first 50 seconds
Δ[A]
rate (A) =
Δt

([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 × 10-4 mol L-1 s-1

 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
-d[A]
rate = -(slope of tangent line) =
dt
= 2.3 × 10-4 mol L-1 s-1
 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 mol B.
Calculate average rate from t = 0 to t = 10 min.
Δ(moles B)
average rate 
Δt
(mol B at t  10 min) - (mol B at t  0)

10 min  0 min
0.26 mol - 0 mol
  0.026 mol/min
10 min - 0 min
 2.1 Reaction Rate Expression

Consider :

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

Butyl chloride Butyl alcohol

We can calculate the average rate in terms

of the disappearance of C4H9Cl.
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

 2.1 Reaction Rate Expression
C4H9Cl(aq)+ H2O(l)  C4H9OH(aq)+HCl (aq)

0.12 [C4H9Cl] vs time

0.1

0.08
[C4H9Cl]

0.06

0.04

0.02

0
0 100 200 300 400 500 600 700 800 900

time
 2.1 Reaction Rate Expression
C4H9Cl(aq)+ H2O(l)  C4H9OH(aq)+HCl (aq)

Average rate of disappearance of C4H9Cl

Δ (C4H9 Cl)

Δt
 C4H9 Clfinal time  C4H9 Clinitial time 
  
 final tim e   initial tim e  
2.1 Reaction Rate Expression
C4H9Cl(aq)+ H2O(l)  C4H9OH(aq)+HCl (aq)
Time (s) [ C4H9Cl ](M) Ave.rate (M/s)
0.0 0.1000
1.9 x 10-4
50.0 0.0905
1.7 x 10-4
100.0 0.0820
1.6 x10-4
150.0 0.0741
1.4x10-4
200.0 0.0671
1.22x10-4
300.0 0.0549
1.01 x10-4
400.0 0.0448
0.80x10-4
500.0 0.0360
0.56x10-4
800.0 0.0200
 Reaction Rates and Stoichiometry
Reaction : relationship one-to-one

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

1 mole of C4H9OH is produced for each mole of C4H9Cl

consumed. H2O is consumed and HCl is produced.

ΔH2O ΔHCl
Rate =  
Δt Δt
ΔC4H9 Cl ΔC4H9OH
 
Δt Δt
 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 ΔHI ΔH2  ΔI2 

rate =   
2 Δt Δt Δt

In general for: aA + bB  cC + dD
1 ΔA 1 ΔB 1 ΔC 1 ΔD
rate =    
a Δt b Δt c Δt d Δt
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)

24
 Reaction Rates and Stoichiometry

Solution:

1 ΔNH3  1 ΔO 2  1 ΔNO

rate    
4 Δt 5 Δt 4 Δt
1 ΔH 2O

6 Δt

25
 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 L–1 s–1, at what rate is the
oxygen concentration decreasing?

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

– Oxygen reacts at a rate of 1.3 mol L–1 s–1

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
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
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 
2.2 Factors Affecting Reaction Rate
• Surface area
– The area of contact between the phases
determines the reaction rate
A: nail (low surface area) B: Steel wool (high surface area)
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 
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!!
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
2.2 Factors Affecting Reaction Rate
• Presence of catalysts
 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
 2.3 Rate Laws
• The value of the rate constant depends
on the particular reaction being studied
and the temperature at which the reaction
occurs
• The order can be positive or negative, an
integer or a fraction
• The order cannot be deduced from the
balanced equation
 2.3 Rate Laws
• Types of rate laws:
– A differential rate law expresses the rate as a
function of concentration

– An integrated rate law expresses the

concentration as a function of time
 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
 2.3 Rate Laws
• Consider the following reaction:

  
H 2 SeO3  6I  4H  Se  2I  3H 2O
3

From experiment, the rate law (determined

from initial rates) is
 3  2
rate  k[ H 2 SeO3 ] [ I ] [ H ]
1

Rate law cannot be obtained from the balanced

equation !!!!!!!!
 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:
 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
m
rateexp 2 [A]exp 2 rateexp 2 0.40 mol L-1 s-1
= = =2
rateexp 1 [A]exp 1 rateexp 1 0.20 mol L-1 s-1

and
[A]exp 2 0.20 mol L-1
= =2
[A]exp 1 0.10 mol L-1
 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
 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
n
rateexp 4 [B]exp 4
=
rateexp 3 [B]exp 3

– For experiments 3 and 4, we have:

4.0 = 2.0n
– Therefore, n must equal 2
 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?

2.3 Rate Laws
 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:

d[A]
rate = – = k[A]
dt 49
 2.4 Integrated Rate Laws
• First-order reactions
Assume A  products is first order
The differential rate law has the form:
d[A]
rate = = 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
e = base of natural logarithms = 2.71828…
 2.4 Integrated Rate Laws
• First-order reactions
A   k t dt
A t d
rate = –
d[A]
= k[A]
A A
0
0
ln At  ln A0   k t
dt

ln At   k t  ln A0

[A]0
ln = kt or [A]t = [A]0e-kt
[A]t
 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

52
 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 N2O5 was
0.500 M ?
b. How much time required for 90% of N2O5 to
decompose ?
53
 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

54
 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
55
2.4 Integrated Rate Laws
• Second-order reactions
– Assume B  products is second order
– The differential rate law is:
d[B]
rate = = k[B]2
dt

– The integrated rate law would be:

1 1
= kt +
[B]t [B]0 56
 2.4 Integrated Rate Laws
• Second-order reactions
 A 
Rate    k A 
2
t
 A  A t dA  t

A 2
  k  t ,  
A 0 A 2
k 0 dt
1 1 1 1
  kt ,  kt 
At A0 At A0
 2.3 Integrated Rate Laws
– When a reaction is second order, a plot of 1/[B]t
versus t should yield a straight line with a slope k

58
2.4 Integrated Rate laws
• Zero-order rate laws
– 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

line of slope –k 59
2.4 Integrated Rate laws
Zero-order rate laws

60
 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 , substituting
2
[ A]0 ln 2
ln 1  kt1/ 2 or t1/ 2 
2
[ A]0 k 62
 Half life

First-order radioactive decay of iodine-131. The

initial concentration is represented by [I]0. 63
 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
1 = kt1/ 2
2 [ B]0
[B]0
1 l
= kt1/ 2 or t1/ 2 =
[B]0 k[B]0 64
SUMMARY

65
 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.

 Solution
0.693 0.693
t1  , k
2 k t1
2
0.693
k  1.21  10  4 yr 1
5.73  103 yr

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

 A 0 
ln 
 A  

 A 0   
ln A 0  kt  ln A t , kt  ln   t
t
 A  ,
 t  k
 A 0 
ln 
 0.10 A  
 0  ln 10 
t 1
 1
 1. 90  10 4
yr
1.21  10 yr
3
1.21  10 yr
3
2.5 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
2.4 Theory of chemical kinetics
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
 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-
 2.5 Theory of chemical kinetics
• Temperature effects
– The rate of a reaction increases with increasing
temperature
2.5 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
2.5 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

k2 –Ea 1 1
ln = –
k1 R T2 T1
 Example
An alteration in the structure of a certain virus follows first-
order 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
 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.

k1 Ea  1 1 
ln    
k2 R  T1 T2 
 4.28  10 -5 s -1  (587 kJ/mol)(1000 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
 Solution (cont.)

o
thus the half - life at 32 C:
t 1/2  0.693 / k 2
0.693

2.68  10 4 s-1
 2.58  10 s
3
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
 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
 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]
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

 2.5 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
 2.6 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]

 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
 2.7 Catalysts
• A catalyst is a substance that changes the
rate of a chemical reaction without being
used up
• The action caused by a catalyst is called
catalysis
• Positive catalysts speed up reactions
• Negative catalysts (inhibitors) slow
reactions down
 2.7 Catalysts
• The catalyst provides a path to the products that has a
rate-determining step with a lower activation energy
2.7 Catalysts
Catalyst : a substance that increases the rate
without being consumed in the reaction

Catalysts speed up reactions by altering the

mechanism to lower the activation energy
barrier. 90
 2.7 Catalysts
• Homogeneous catalysts
– Exist in the same phase as the reactants

• Heterogeneous catalysts
 Exist in different phase as the reactants
 They are commonly solids
 Usually functions by promoting a reaction
on its surface
 2.7 Catalysts
• Heterogeneous catalysts
Haber-Bosch process, 3H2 + N2  2NH3
The reaction takes place on the surface of an iron catalyst that
contains traces of aluminium and potassium oxides.
The End