Rate of reaction

The rate of reaction is defined as the decrease in molar concentration of the reactant or increase
in molar concentration of the product per unit time.

As the reaction proceed, concentration of A decreases whereas, concentration of B increases.

So the rate of reaction is equal to the rate of disappearance of A, which is equal to the rate of
appearance of B.
A B

conc.
(mol L-1)

Fig: concentration of [A] and

[B] at different time
Write down the rate of reaction for the following equation?

Rate of reaction =
Problem: 2A —> 3B
If the concentration of reactant A, in a reaction is 0.20 mol L-1 at time 15 seconds after the start of
the reaction and the concentration is 0.12 mol L-1 after 75 seconds from the start, then calculate the
rate of the reaction and the rate of consumption of A.

How can we determine the rate of a reaction?

Ans: In order to determine the rate we have to determine the concentration as a function of time.
Concentration can not be directly measured. That’s why we measure a parameter (e.g: absorbance
etc.) which is proportional to the concentration.

Color change

Pressure change

Conductivity change
Types of rate of reaction
1. Initial rate
2. Average rate
3. Instantaneous rate

Initial rate
Initial rate is the rate at the beginning of the reaction which can’t be determined experimentally

Average rate
If we measure the change in concentration over a period of time, then the
rate determined is called the average rate of reaction. Average rate
means the rate between two points in conc. vs time curve.

Instantaneous rate
The rate at particular instance or particular
point is called instantaneous rate.
the slope of the line joining two
points along the
curve=Average Rate

Slope of a tangent line =

Instantaneous rate
Factors affecting rate of reaction

• Concentration

• Pressure (in case of gases)

• Temperature of reaction

• Catalyst

• Light (in some cases)

• Surface area of solid reactant or

catalyst)
Concentration
⮚ Often the rate of reaction increases when the concentration of a reactant is increased.

⮚ As the concentration increases the number of molecules increases. As a result,

collisions are more likely to occur and give the higher rate.
 Pressure (in case of gases)
When pressure applies the volume of a gas is reduced. So in unit volume higher numbers of
molecules are present at higher pressure. Therefore, the concentration is increased with the
increase of pressure. As a result, the collisions between the molecules are increased which
enhance the reaction rate. Example: production of ammonia from N2 and H2.
Temperature
Effect of temperature on the rate of a reaction is two fold.

Increase in temperature increases the kinetic energy of the reactant species bringing about an
increase in frequency of collision.

At higher temperature more reactant species have the required energy of activation. That why
the reactants become more successful to convert into product.

Both of the above factor increase rate when temperature increases.

Light
• Light activates some of the reactant molecules producing free radicals.
• Since free radicals are very excited, therefore, they react immediately with other
molecules to form products.
• We know that light consists of photon. When photons strike the reactant
molecule, they provide necessary activation energy to the reactant molecules.
Catalyst
❑ A catalyst is a substance that increases the rate of reaction without being
consumed in the overall reaction.
❑ Catalysts are of enormous importance to the chemical industry, because they
allow a reaction to occur with a reasonable rate at a much lower temperature
than otherwise; lower temperatures translate into lower energy costs.
❑ The catalyst must participate in at least one step of a reaction and be
regenerated in a later step.
Surface area of a solid reactant or catalyst
❑ If a reaction involves a solid with a gas or liquid, the surface area of the solid affects the
reaction rate.
❑ Because the reaction occurs at the surface of the solid, the rate increases with increasing the
surface area.
❑ A wood fire burns faster if the logs are chopped into smaller pieces.
❑ Similarly, the surface area of a solid catalyst is important to the rate of reaction. The greater the
surface area per unit volume, the faster the reaction.
Rate Laws

► At a fixed temperature the rate of a given reaction depends on concentration of reactants.

► By a study of numerous reactions it is shown that : the rate of a reaction is directly
proportional to the reactant concentrations, each concentration being raised to some
power.

The exponents m and n, called the reaction orders, define how the rate is affected by reactant
concentration. Two key points to remember are
• The balancing coefficients a and b in the reaction equation are not necessarily related in any
way to the reaction orders m and n.
• The components of the rate law—rate, reaction orders, and rate constant—must be found by
experiment.
Rate constant, k
The rate constant, k is defined as the proportionality constant between the rate and the concentration term
(concentration with its power). Units of rate constant varies with values of ‘n’ (order of the reaction)

Order of a reaction (n)

The order of a reaction can be defined as the power to which the concentration is to be raised in order to make
the concentration term proportional to the rate.
So it may be defined as the sum of power of concentration in the rate law.
 Order of a reaction (n)
Order of a reaction can be 0,1,2,3, fraction value or negative. It is experimentally determined. It cannot be
guessed by looking at the reaction.

In a general reaction, A + B product

rate = k [A]m [B]n or k CAm CBn

Where, m = order with respect to A

n = order with respect to B
k = rate constant
CA or [A] is concentration of A e.g. 2NO2(g) + F2(g) → 2NO2F(g)
CB or [B] is concentration with respect to B
Rate = k[NO2][F2] (experimentally determined)
Overall order of the reaction = m + n
The reaction is first order with respect to the NO2.
m + n = 1; 1st order reaction
m + n = 2; 2nd order reaction Similarly, the reaction is first order with respect to F2.
m + n = 3; 3rd order reaction Overall order = 1+1 = 2
 Order of a reaction (n)
The order of a reaction can be defined as the power to which the concentration is to
be raised in order to make the concentration term proportional to the rate.
So it may be defined as the sum of power of concentration in the rate law.
In a general reaction, A + B product

rate = k [A]m [B]n or k CAm CBn where, m = order with respect to A

n = order with respect to B
k = rate constant
CA or [A] is concentration of A
Overall order of the reaction = m + n CB or [B] is concentration with respect to B

e.g. 2NO2(g) + F2(g) → 2NO2F(g)

Rate = k[NO2][F2] (experimentally determined)

The reaction is first order with respect to the NO2.

Similarly, the reaction is first order with respect to F2.
Overall order = 1+1 = 2

Possible values of n: 0,1,2,3, 3/2, ½

Order of a reaction VS Rate

m + n = 1; 1st order reaction; rate is proportional to concentration

m + n = 2; 2nd order reaction; rate is proportional to (concentration)2
m + n = 3; 3rd order reaction; rate is proportional to (concentration)3
❑ Most of the reactions are1st order reaction
❑ 0 and 3rd order reactions (A+A+A > Product)
are very rare
Rate constant, k

The rate constant, k is defined as the proportionality constant between

the rate and the concentration term (concentration with its power).

Units of rate constant varies with values of ‘n’ (order of the reaction)
Difference between order and molecularity
Order Molecularity
1. It is the sum of the powers of the 1. It is the number of reacting
concentration terms in the rate law species undergoing simultaneous
expression collision in the elementary or simple
reaction

2. It is an experimentally determined 2. It is a theoretical value

value
3. It can have fractional value 3. It is always a whole number
4. It can assume zero value 4. It can not have zero value
5. Order of the reaction can change 5. Molecularity is invariant for a
with collisions such as pressure, chemical equation
temperature, concentration etc
 Collision theory of reaction rate

According to collision theory there are three pre-conditions to take

place a reaction. They are:

1st condition: In order for a chemical reaction to take place, the

reactants molecules must collide.

2nd condition: Collision between the molecules must be occurred in

such a way so that they can achieve minimum amount of energy to
occur the reaction.

3rd condition: The molecules must also collide in the right

orientation.