REACTION KINETICS (AS)

1.Rate of reaction = change in concentration

of reactant or product over time
Rate of reaction = [reactant]/time OR
[product]/time

2.Concentration time graphs

Conc of

a reactant

Conc of reactant decreases

with time

time

Conc of
product

Conc of product
increases with
time
After certain time ,conc of
products becomes
constant

time

a. Rate of reaction at time , t :

(instantaneous rate)
draw a tangent to the concentration
vs time curve at time t
the gradient of tangent = rate of
reaction

Example

[reactant ]

Gradient = y/x =
rate of reaction
at time , t
Unit : mol dm-3 s-1 or
mol dm-3 min-1

y
x
t

time

Note :
i)Average rate : rate measured over a
period of time
Eg : rate = change in [reactant]/ t2 t1
ii)Initial rate : rate at almost t=0
b. Rate of rxn is proportional to
concentration of most reactants
Concentration increases, rate increases

Note : Rate is independent of

concentration of a reactant
Concentration changes but rate is constant
Zero order reaction
Conc of

Conc decreases with time

reactant

Constant gradient
Rate is constant

time

THEORIES OF REACTION
RATES
1. Collision theory :
a. reactions occur due to collision of
reactant particles
b. not all collisions results in reaction

effective collisions : collisions

between reacting particles that
results in a reaction

c.Characteristics of effective collisions

:
i) have favourable orientation
eg C C C C Br
+ OH C C C C OH + Brcollision of an OH- with the
bromoethane molecule is unlikely to
result in a reaction if it hits the end of
the molecule away from the Br

ii) possess a minimum energy = Ea

(1) Definition : Activation energy ,Ea,
is the minimum energy required for a
reaction to take place
High Ea slow reaction
(2) Ea is used to enable bonds in the
reactants to stretch and break as new
bonds form in the products

2. Transition state theory :

a. reactions takes place via transition
state in which reactants come together
b. bond making and breaking occur
continuously and simultaneously
In the transition state, bonds are in the
process of making and breaking.

A-B + C A + B-C

Bond breaking

transition state

Bond forming

c. reaction profile/enthalpy diagram :

Note :
(1) Transition state is the highest
point in the reaction profile
(2) Energy gap between reactants and
transition state = Ea
(3) Ea forward rxn Ea reverse rxn

Reaction profile or energy / enthalpy

diagram for uncatalysed reactions

exothermic reversible reaction

Transition state

Energy
Ea forward rxn
Ea reverse rxn

Reactants

Products
Extent of reaction

endothermic reversible reaction

Transition state
Energy
Ea forward rxn

Ea reverse rxn
Products

Reactants

Extent of rxn

d. Multi step reaction

Reaction that takes place via an
intermediate
Mechanism of rxn involves a multi
step reaction
The intermediate will occur at a
minimum on the graph
One minimum = one intermediate

Eg :
Step 1 : Reactants Intermediate ,
H = positive
Step 2 : Intermediate Products ,
H = negative
Overall : Reactants Products ,
H = negative

Transition state 1
Transition state 2
Energy
Ea(1)

Ea (2)
Intermediate

Reactants
Overall H
Products

Extent of rxn

e. Reacting particles must possess

energy greater than or equal to the Ea
before they can react

FACTORS AFFECTING
RATE OF REACTION

Concentration

Temperature

Catalyst

I. Concentration of reactants

1. conc increases , rate normally

increases
( exception : zero order )
2. as concentration increases :

frequency of collisions increases

no of effective collisions increases

rate of reaction increases

3. Expt to show effect of concentration on

rate of reaction :
Eg:
Na2S2O3(aq) + 2HCl(aq) 2 NaCl(aq) +
H2O(l) + SO2(g) + S(s)

a. Effect of [S2O32-] on rate of reaction

b. Sulphur appears as particles of solid
c. Measure time taken to block view of
cross/words under conical flask

Experiment to show effect of concentration

on rate of reaction :
Eg Na2S2O3 (aq) + 2HCl (aq)
2 NaCl(aq) + H2O(l) + SO2(g) + S(s)
a. Effect of conc of S2O32- on rate of rxn
b. Sulphur appears as small particles of
solid
c. Measure time taken for enough sulphur to
form to block view of the cross/words
under conical flask

d. Use different volumes of S2O32- but

keep volume of HCl constant
e. H2O used to keep total volume of all
mixtures constant
Hence volume of S2O32- used conc
S2O32eg : volume doubles , conc doubles

Mixture

Volume of Volume of
S2O32-/cm3 HCl/cm3

Volume of
H2O/cm3

10

20

30

20

20

20

40

20

Time/s

Rate of reaction 1/time

From expt ,
As volume of S2O32- increases,
[S2O32-] increases , time taken
decreases
Rate of reaction increases

Rate of reaction [S2O32-]

1 / time

[S2O32- ]

II.Temperature

1. When temperature increases :

average speed of reacting particles
increases
particles collide more frequently and
with greater energy
no of particles with energy Ea
increases
no of effective collisions increases
rate of reaction increases

2. Why does rate increase with

temperature?
Molecules in a gas does not all have the
same speed.
Their speeds and therefore their
energies are distributed according to the
Maxwell Boltzmann distribution curve

Maxwell Boltzmann distribution curve

Fraction or no of
molecules with
energy E

Most probable energy

Energy/speed

a. Shape : at a temp T , molecules in

a sample of gas have different
speed/energy
Most probable speed/energy
corresponds to the maximum of the
curve.
b. Area under the curve = total no of
molecules in the sample

c. As temp increases ,
curve flattens ( have a lower peak )
more spread out ( moves to the right )
however total no of molecules =
areas under the curves remains the
same

Effect on Maxwell Boltzmann distribution curve

No of molecules
with energy E

Lower T
Higher T

Ea

Energy/speed

d. Shaded area = no of molecules with

energy Ea
As temp increases ,
Size of shaded area increases
More molecules with energy Ea
No of effective collisions increases
Rate of reaction increases

Note : At temp T and ( T + 10 K ) ,

Size of shaded area doubles
No of molecules with energy Ea
doubles
Rate of reaction doubles

e. Reactions with larger Ea are slower

but rise in temp has more
significant increase on the rate of
reaction with a higher Ea

III.Effect of catalyst ( catalysis )

1.Catalysts are substances that affects the
rate of a chemical reaction without being
chemically changed themselves
They are not consumed and are
regenerated at the end of the reaction

Properties of catalyst:
increase the rate of reaction
amount of catalyst used affects the rate
which is proportional to the amount used
required in small amount
chemically unchanged after the reaction
do not affect H

2. Two types of catalyst :

a. positive catalyst : increases rate of
reaction
eg ferum in Haber process
b. negative catalyst / inhibitor : slows
down a reaction
eg glycerine or phosphoric acid
inhibits decomposition of hydrogen
peroxide

3. Action of positive catalyst

Provides alternative pathway with a
lower Ea
More molecules with energy Ea
No of effective collisions increases
Rate of reaction increases
Note : different catalyst can affect a
similar reaction differently

4. Diagrams :
a. Enthalpy diagram or energy profile :
eg exothermic rxn
Energy
Ea uncatalysed rxn
Ea catalysed rxn(lower)
Reactants
Products
Reaction pathway

b. Maxwell Boltzmann distribution curve

( at a certain temp T )

No of molecules
with energy E

Ea uncatalysed
Ea catalysed (lower)

Energy

For catalysed reaction :

Size of shaded area increases
No of molecules with energy Ea
increases
No of effective collisions increases
Rate of reaction increases
Note : another factor affecting rate is
surface area ( higher surface area ,
faster reaction )

5. Types of catalyst : 3 types

a. Heterogeneous catalyst : catalyst is in a different

phase compared to reactants .
Examples :
Reaction
Catalyst
N2(g) + 3H2(g) 2NH3(g)
ferum (s)
( Haber process )
2SO2(g) + O2(g) 2SO3(g)
V2O5 (s)
( Contact process )
C2H4(g) + H2(g) C2H6(g)
Ni (s)
( Hydrogenation of alkenes in
manufacture of margarine )

b. Homogeneous catalyst : catalyst is present in the

same phase as the reactants.
Examples:
Reaction
Catalyst
CH3COOH(aq) + C2H5OH(aq)
H+ (aq)
CH3COOC2H5(l) + H2O (l)
S2O82- (aq) + 2I- (aq)
2SO42- (aq) + I2 (aq)

Fe2+(aq)
or Fe3+ (aq)

c. Biological catalyst ( enzymes ):

Proteins which catalyses chemical reactions in living
systems
Are extremely specific , one enzyme normally
catalyses one reaction
Example: amylase found in saliva. It is used to break
carbohydrates into simpler molecules.

Autocatalysis

1. One of the product is a catalyst for the

reaction
2. Reaction proceeds slowly at first at
uncatalysed rate
until a significant amount of the product (
also the catalyst ) is established
3. Then reaction will speed up to catalysed
rate
Reaction will stop when reactants are
exhausted

Eg :
2 MnO4- + 16 H+ + 5 C2O42-
2 Mn2+ + 8 H2O + 10 CO2
catalyst

Slow decrease in conc

Slow reaction
[ MnO4- ]

Uncatalysed rate
Fast decrease in
conc
Faster reaction
Catalysed rate

time

rate

Fast
Catalysed rate

Slow
Uncatalysed
rate

time