2.

2 Factors affecting rates of reaction

2.2.1 Collision Theory

This theory developed from kinetic theory to account for the effects of concentration
and temperature on reaction rates.

Molecules must possess a

certain minimum kinetic
energy, called activation
energy (Ea) to initiate a
chemical reaction

3 IDEAS OF
COLLOSION
THEORY
 TWO REQUIREMENTS

The reacting molecules must collide with energy

which must be equal or greater than activation
energy of the reaction
EFFECTIVE COLLISION
collision which involves reactants molecules
colliding successfully and lead to the
formation of products
The relative orientation of the reactants must allow
formation of any new bonds necessary to produce
products.
 Figure 2: Illustration of
Figure 1: Illustration of Effective Ineffective Collisions
Collisions

The nitrogen of NO3 and oxygen on NO

are in contact

The nitrogen on NO and oxygen on

NO3 must come in contact An oxygen on each molecule are in
contact
2.2.2 Transition State
minimum energy required by the reactant to form an activated
Activation energy, Ea
complex in the transition state

The activation energy is represented on a reaction profile

(reaction energy diagram) as the energy barrier
between reactants and products.
The height of the activation barrier influences the rate:

If Ea is large, then few molecules possess enough energy to get over the
barrier; few products are formed and the rate is slow.

If Ea is small, then many molecules possess enough energy to get over the
barrier; more products are formed and the rate is faster.

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Activated Complex (Transition State Theory)
The activated complex is a species intermediate between reactants and products with the
maximum potential energy.

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Factors affecting reaction rate
Any change in conditions which increase either frequency or the fraction of molecules with enough energy will
increase the reaction rate

Concentration
i. concentration increases, the frequency of collision also increases
ii. probability of collisions with sufficient energy for reaction to occur also increase
iii. rate of reaction increases.

Pressure (gases)
i. low pressure: the gas molecules are spread far apart, high pressure: the molecules are close together.
ii. increasing the pressure of the gas increase total collision frequency.
iii. probability of collisions with sufficient energy for reaction to occur also increase.
iv. rate of reaction increases
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Temperature
i. increase in temperature raises molecular velocity and so increases the frequency of collisions between molecules.
ii. higher the temperature, the faster the reaction.
iii. number of molecule which have kinetic energy equal or more with Ea increasing.
iv. will increase the frequency of effective collision.
v. rate of reaction increases
The Maxwell-Boltzmann distribution represents the distribution of the kinetic energy of collisions at a given temperature

• As the temperature increases, the curves flattens and

broadens, thus at higher temperature, higher population of
molecules has higher kinetics energy.
• As the temperature increases, the fraction of molecules
that can overcome the activation energy barrier also
increase.
• As a result, the reaction rate increases.

Maxwell-Boltzmann distribution graph at two different temperatures 8

Catalysts (substance that speed up reaction without itself
being chemically changed or consumed in the process)
i. provide an alternative pathway from reactants to
products
ii. lowers the activation energy of a reaction.
iii. catalyzed reaction has much lower activation
energy than uncatalyzed one
iv. reaction is faster with catalyst.

Size of particle
i. if a solid is broken down into smaller pieces, its surface area gets larger
ii. extra surfaces are exposed for other to attack, and total collision frequency will increase
iii. powdered solids reacts more quickly than larger lumps
2.3 Rate Law and Order of Reaction

Rate law : an expression for the reaction rate in terms of concentrations of chemical species involved in
the reaction. For example,
aA + bB → cC + dD

Rate = k [A]m [B]n

or Rate = -d[A] = -d[B] = k [A]m [B]n

dt dt
where : k is a rate constant,
m is reaction order with respect to A,
n is reaction order with respect to B,
m +n is the overall reaction order.
Order of reaction
For a general reaction aA + bB → cC + dD
1. Zero order rate = k[A]0[B]0 = k
2. 1st order rate = k[A] or =k[B]
3. 2nd order rate = k[A]2 or = k[B]2 or = k[A][B]
4. 3rd order rate =
5. Fractional order rate = k[A]½[B]
Overall order for each rate ??
 Rate and the Order of Reaction
aA + bB → cC + dD

Usually, the rate of a reaction is a function of the concentrations of reactants .

example :
Rate = k [A]m [B]n when [A] = doubles

If m = 0, the rate remains unchanged

m = 1, the rate doubles
m = 2, the rate quadruples, increase by a factor of 4 (22)
m = 3, the rate increase by a factor of 8 (23)

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Rate Constant
• The rate constant is independent of the concentrations of the chemical species
involved in the reaction.
• However, it depends on other factors such as temperature or ionic strength, e.g., k(T).

• The units of the rate constant depend on the overall reaction order.

• Magnitude of k indicates the speed of a reaction

Small k ( eg k = 10-5) = a slow reaction
Large k ( eg k = 105) = a fast reaction

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 Units of the rate constant
Example: second order
Assuming time in second(s).
Rate = k [A][B] or
Order Unit of rate constant
Zero moldm-3s-1( Ms-1)
First s-1
Second dm3mol-1s-1 (M-1s-1)
Third dm6mol-2s-1 (M-2s-1)

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Rates as Functions of Reactant Concentrations
In a general reaction,

a A + b B + → products
Rate = k[A]x[B]y

If concentrations of B is kept constant, you can measure the reaction rate of A at

various concentrations.

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