Centre for Foundation Studies, UTAR

Scopes

Chemical Kinetics
Chapter 6

Chemical Kinetics

Study of the rates of chemical reaction

Macroscopic level (rates of reactions)
determination of a reaction rate
factors that influence rates
Particulate level (chemical reaction)
reaction mechanism

D[A]
rate =
Dt

D[A] = change in concentration of

A over time period Dt

D[B]
Dt

D[B] = change in concentration of

B over time period Dt

rate =

[A] decreases with time, D[A] is negative

[B] increases with time, D[B] is positive

FHSC1114 Physical Chemistry

Rate of reactions
Rate constant, half-life of a reaction
Rate determining step
Collision frequency
Zero,1st & 2nd order of reactions
Factors affecting rate of reaction:
concentration, temperature, catalyst and
surface area
Concept of activation energy
Arrhenius equation

Reaction Rate
The change in the concentration of a
reactant or a product with time

Rate of reaction change in concentration

change in time

Methods for Expressing

Reaction Rates
1) Initial rate
rate of the reaction when the reactants are
pure (precisely known)
2) Instantaneous rate (tangent rate)
rate of change in concentration at any
particular instant during a reaction
3) Average reaction rate
A measure of the change in concentration
over a defined period
The differences in concentrations of a reactant
between 2 points in time are divided by the
time elapsed

Centre for Foundation Studies, UTAR

Reaction Rates and Stoichiometry

2A

Two moles of A disappear for each mole of B that

is formed.
rate =

rate =

aA + bB
Slope of
tangent

cC + dD

rate =

Write the rate expression for the following

reaction:
N2 (g) + 3H2 (g)
2NH3 (g)

Rate Law
Expresses the relationship of the a reaction rate
to the rate constant and the concentrations of
the reactants raised to some powers.
aA + bB

rate =

cC + dD

Rate = k [A]x[B]y
The exponents x and y
are the reaction order
can be 0, 1, 2 or fraction
must be determined by experiment
total reaction order = (x + y)

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)

Interpreting Rate Law: Rate = k [A]x

2FClO2 (g)
1

rate = k [F2][ClO2]

FHSC1114 Physical Chemistry

a) If x = 1, reaction is 1st order in A

Rate = k [A]1
If [A] doubles, then rate goes up by factor of
__
b) If x = 2, reaction is 2nd order in A.
Rate = k [A]2
Doubling [A] increases rate by __
c) If x = 0, reaction is zero order in A.
Rate = k [A]0
If [A] doubles, rate ________________

Centre for Foundation Studies, UTAR

Determining a Rate Equation

F2 (g) + 2 ClO2 (g)

No
change

2 FClO2 (g)

x4

x4

Quadruple [ClO2] with [F2] constant,

Rate quadruples
Rate Experiment 2 k[F2]x [ClO2] y

Rate Experiment 1 k[F2]x [ClO2] y

Rate k F2 ClO2
x

The reaction is ___ order in [ClO2]

Determining a Rate Constant, k

No
change

x2

x2

Double [F2] with [ClO2] constant,

Rate doubles

Rate = k [F2][ClO2]
Using Exp. 1:
Rate = 1.2 x 10-3 M s-1 = k [0.10 M][0.010 M]
k = 1.2 M-1 s-1 = 1.2 L mol-1 s-1

Rate Experiment 3 k[F2]x [ClO 2] y

Rate Experiment 1 k[F2]x [ClO 2] y

x= ,y=
rate =

or
Using Exp. 2:

The reaction is ___ order in [F2]

Zero-Order Reactions
A
D[A]
rate = - Dt

First-Order Reactions

product
rate = k [A]0 = k

A
D[A]
Dt = k

rate = -

D[A]
Dt

[A] is the concentration of A at any time t

[A] = [A]0 - kt

[A]0 is the concentration of A at time t = 0

FHSC1114 Physical Chemistry

ln[A] = ln[A]0 - kt

product

rate = k [A]

D[A]
= k [A]
Dt

[A] is the concentration of A at any time t

[A]0 is the concentration of A at time t = 0

Centre for Foundation Studies, UTAR

The reaction 2A
B is first order in A
with a rate constant of 2.8 x 10-2 s-1 at
800C. How long will it take for A to
decrease from 0.88 M to 0.14 M ?

Half-Life, t1/2
The time required
for a reactant to
decrease to half of
its initial
concentration /
amount

Half-Life & First-order Process

Problem :
At a given temperature, hydrogen peroxide
(H2O2) decomposes to water and oxygen with
the rate law as below:
Rate = k[peroxide], k = 1.06 x 10-3 min-1

Solution:
After 15% of the H2O2 has decomposed,
85% remains.
fraction remaining is 0.85

What amount of time is required for 15% of the

sample of to H2O2 decompose?
Fraction remaining = [A]t
[A]0

FHSC1114 Physical Chemistry

Centre for Foundation Studies, UTAR

Problem:
Radioactive decay is a first order process.
Tritium electron + helium
3H
0 e
3He
-1
If you have 1.50 mg of tritium, how much is
left after 49.2 years? Given t1/2 = 12.3 years

Solution:
ln [A]/[A]0 = -kt
[A] = ?
[A]0 = 1.50 mg,

t = 49.2 years

Need k, so we calc. k from:

k = 0.693 / t1/2 k =
Now ln [A]/[A]0 = -kt =
=
Take antilog: [A]/[A]0 =
__________ = fraction remaining
Because [A]0 = 1.50 mg, [A] = __________ mg

Second-Order Reactions
A
rate = -

D[A]
Dt

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

product

rate = k [A]2

D[A]
= k [A]2
Dt

Summary of the Kinetics of Zero-Order,

First-Order and Second-Order For The
Reaction Type A Products

[A] is the concentration of A at any time t

[A]0 is the concentration of A at time t=0

- D[A]/Dt = k [A]0
- D[A]/Dt = k [A]1
- D[A]/Dt = k [A]2

Factors Affecting Rates

Concentration & Rates

Mg(s) + 2 HCl(aq) MgCl2(aq) + H2(g)

Concentrations
Temperature
Physical state of reactants
(surface area)
Catalysts
Rate concentration

FHSC1114 Physical Chemistry

Centre for Foundation Studies, UTAR

Physical State of Reactants

(Surface Area)

Temperature & Rates

Rate Temperature

Reactions generally
occur slower at lower
T.

Catalyst & Rates

A substance that increases the rate of a

chemical reaction without itself being
consumed.

Speed up reaction by altering the

mechanism to lower the activation energy
barrier

If the reactants are in the same state, all

molecules can be fully exposed to 1
another
If the reactants are in different phases
(e.g. 1 is solid, 1 is gas), reaction rate is
inhibited by the inability of the molecules
to approach 1 another
Depend on the exposed surface area of
the reactants (the greater the surface
area, the faster the reaction)

Catalysts: catalyzed decomposition of H 2O2

2H2O2 2H2O + O2

Ea (catalyzed) < Ea (uncatalyzed)

ratecatalyzed > rateuncatalyzed

Activation Energy, Ea
The minimum amount of energy required
to initiate a chemical reaction.
A+ B

AB

+
+

Exothermic Reaction

FHSC1114 Physical Chemistry

Activation Energy, Ea

C+D
Endothermic Reaction

Ea the energy required to surmount the

barrier
If the barrier is low, Ea is low, the energy
required is low, high proportion of the
reactant molecules may have sufficient
energy to react, the reaction will be fast

Centre for Foundation Studies, UTAR

Arrhenius Equation

Collision Theory

k = A exp( -Ea / RT ) = Ae-Ea/RT

Reaction happens if the reacting molecules:

a) must collide with sufficient energy
b) must come together in the correct
orientation
affect the rate constant, k
determine the reaction rate

e-Ea/RT = fraction of molecules having the

minimum E required for reaction
k = rate constant
A = frequency factor (L mol-1 s-1)
R = 8.31 x 10-3 (kJ K-1 mol-1)
Ea = activation energy
T = temperature (K)

ln k = -

Ea 1
+ lnA
R T

Plot ln k vs. 1/T

Example:

Slope = -Ea/ R

The variation in the rate constant, k at two different temperatures

for the reaction is given in the following table.
2HI (g) H2 (g) +I2 (g)

Calculate the activation energy, Ea

-Ea/ R
40

Catalysis

Solution:

Heterogeneous catalysis reactants and

catalysts are in different phases.
Haber synthesis of ammonia
Ostwald process production of nitric acid
Catalytic converters
Homogeneous catalysis reactants and
catalysts are dispersed in a single phase,
usually liquid.
Acid catalysis
Base catalysis
41

FHSC1114 Physical Chemistry

Centre for Foundation Studies, UTAR

Summary

Determination of reaction rates &

stoichiometry
Write the rate law & determination of:
rate equation
rate constant
Orders of reactions zero, first, second
orders
Half life
Factors affecting reaction
Activation energy & Arrhenius Equation
Types of Catalysis

FHSC1114 Physical Chemistry