Zero Order Reaction
A zero order reaction is a chemical reaction in which the rate is independent of the concentration
of the reactants, i.e. the rate does not change when the concentration of the reactants increases or
decreases.
Differential Form of the Zero Order Rate Law
Integrated Form of the Zero Order Rate Law
Rearranging we get,
Integrating both sides of the equation,
This provides the integrated form of the rate law:
Graphing Zero-order Reactions
(i) Rate vs time:
(ii) Concentration vs time
Half-Life of a Zero Order Reaction
A chemical reaction’s half-life can be defined as the amount of time required for the concentration
of the reactant to reach half of its initial concentration. It is represented by the symbol 𝑡1/2 and is
measured in seconds.
Therefore, when t = 𝑡1/2 ,
From the integrated rate law,
Substituting the value of [A], we get,
Therefore,
Notice that, for zero-order reactions, the half-life depends on the initial concentration of reactant
and the rate constant.
First Order Reaction
A first-order reaction can be defined as a chemical reaction in which the reaction rate is linearly
dependent on the concentration of only one reactant.
Differential Form of the First Order Rate Law
Integrated Form of the Zeroth Order Rate Law
Rearranging we get,
Integrating both sides of the equation,
This provides the integrated form of the rate law:
ln [A] – ln [A]o = −kt
Or, ln [A]o – ln [A] = kt
[𝐴]𝑜
Or, ln = kt
[𝐴]
Graphing First Order Reactions
(i) ln[A] vs time:
(ii) Concentration vs time:
(iii) Rate vs concentration:
Half-Life of a first Order Reaction
A chemical reaction’s half-life can be defined as the amount of time required for the concentration
of the reactant to reach half of its It is represented by the symbol 𝑡1/2 and is measured in seconds.
Therefore, when t = 𝑡1/2 ,
From the integrated rate law,
[𝐴]𝑜
ln = kt
[𝐴]
Substituting the value of [A], we get,
[𝐴]𝑜
ln = k 𝑡1/2
[𝐴]𝑜 /2
Therefore,
ln 2 = k 𝑡1/2
Or,
Notice that, for first-order reactions, the half-life does not depend on the initial concentration of
reactant.
Second Order Reaction
A second-order reaction is one whose rate is proportional to the square of the concentration of one
reactant or the product of the concentrations of two reactants.
Differential Form of the Second Order Rate Law
Integrated Form of the Zeroth Order Rate Law
Rearranging we get,
Integrating both sides of the equation,
This provides the integrated form of the rate law:
Graphing Second Order Reactions
(i) Rate vs concentration:
𝟏
(ii) vs time:
[𝑨]
(iii) Concentration vs time:
Comparison of concentration vs time plot between first and second order reactions
Half-Life of a Second Order Reaction
A chemical reaction’s half-life can be defined as the amount of time required for the concentration
of the reactant to reach half of its It is represented by the symbol 𝑡1/2 and is measured in seconds.
Therefore, when t = 𝑡1/2 ,
From the integrated rate law,
Substituting the value of [A], we get,
1 1
- = k 𝑡1/2
[𝐴]0 /2 [𝐴]0
2 1
Or, - = k 𝑡1/2
[𝐴]0 [𝐴]0
1
Or, = k 𝑡1/2
[𝐴]0
1
Or, 𝑡1/2 =
𝑘[𝐴]0
Notice that, for first-order reactions, the half-life depends on the initial concentration of reactant.
Sample Questions
1. Define half-life of a reaction.
2. Show that for a first order reaction, the half-life is independent of the initial concentration
of the reactant.
3. Derive the integrated rate equation for the zero-order reaction: A P and deduce the
expression of half-life for the reaction.
4. Derive the integrated rate equation for the first order reaction: A P.
5. The rate constant for a reaction is, k = 5.44 × 10–4 sec–1. Calculate the half-life of the
reaction. Also find the number of seconds required for the initial concentration of the
reactant to drop from 0.250 M to drop to 0.0250 M.
6. A first-order reaction has a half-life of 26.4 seconds. How long does it take for the
1
concentration of the reactant in the reaction to fall to 16 th of its initial reaction?
7. Compare between the concentration vs time plots of a first order and and a second order
reaction.
