Chemical Kinetics

Chemical kinetics is the study of reaction rates and how it is influenced by certain conditions. It
further helps to gather and analyze the information about the mechanism of the reaction and define the
characteristics of a chemical reaction.
Reaction rate
The reaction rate is the speed at which a chemical reaction takes place. Let us consider a simple reaction
A→B
As the reaction proceeds, the concentration of the reactant A decreases and that of B increases with time.
“The rate of reactions is defined as the change in concentration of any of reactant or product per unit
time”. For the given reaction, the rate of reaction may be equal to the rate of disappearance of A which is
equal to the rate of appearance of B.
Thus, rate of reaction = rate of disappearance of A = rate of appearance of B
𝑑[𝐴] 𝑑[𝐵]
Rate = − =+
𝑑𝑡 𝑑𝑡

Here [ ] represents the concentration in moles per litre; „d‟ represents infinitesimally small change in
concentration. Negative sign shows the concentration of the reactant A decreases, whereas the positive
sign indicates the increase in concentration of the product B.
Units of Rate
Reactions rate has the units of concentration divided by time. We express concentrations in M or
[Link]–1 or [Link]–3; time may be given in second (s). So, the unit is M s–1 or mol lit–1 s–1or mol dm–3s–1
Rate Laws
The rate of a reaction is directly proportional to the reactant concentrations, each concentration
being raised to some power.
For a substance A undergoing reaction, A → B
rate ∝[A]n
or rate = k [A]n
For a reaction, 2A + B → products
rate = k [A]m [B]n
An expression which shows how the reaction rate is related to concentrations is called the rate
law or rate [Link] power (exponent) of concentration n or m in the rate law is usually a small whole
number integer (1, 2, 3) or fractional. The proportionality constant k is called the rate constant for the
reaction.
Examples of rate law:
Reaction Rate law (experimentally determined)
1) 2NO2→2NO+O2 rate=k[NO2]2
2) H2+I2→2HI rate=k[H2]1[I2]1
3) 2N2O5 →4NO2+O2 rate = k[N2O5]1

1
Order and Molecularity of a reaction
Molecularity of a reaction is the number of reactant molecules appearing in the stochiometric equation of
the reaction.
For a reaction, A + B → products
Molecularity is + 
Order of a reaction is the sum of the powers of concentration terms in the experimentally determined rate
law of the reaction.
For a reaction, A + B → products
Rate=k[A]x[B]y
order = x + y; both x&y are obtained from the experiment, which cannot be judged from the
stochiometric equation
For e.g.,
Reaction Rate equation Molecularity order
1) 2NO2→2NO+O2 rate=k[NO2]2 2 2
2) H2+I2→2HI rate=k[H2]1[I2]1 2 1+1= 2
3)H2+Br2→2HBr rate=k[H2]1[Br2]1/2 2 1+0.5= 1.5
4)2N2O5 →4NO2 +O2 rate = k[N2O5]1 2 1
5) H2(g)+Cl2 (g) h2HCl rate=k[H2]0[Cl2]0 2 0

A zero order reaction is the one whose rate is independent of reactant concentration.
Integrated rate law
The integrated rate law of a chemical reaction shows how the concentrations of reactants change
with time. The integrated rate law depends on the reaction order and is derived by taking the integral of
the corresponding differential rate law.
First order reaction
In a first order reaction, rate is proportional to concentration of a single reactant.
𝑑𝑥
𝑅𝑎𝑡𝑒 = 𝑑𝑡
𝑑𝑥
𝑑𝑡
∝ [𝐴]1

2
 𝑑𝑥
= 𝑘1 [𝐴]
𝑑𝑡
𝑀. 𝑠 −1
Rate constant k1 unit is 𝑀 , which becomes s–1. (Remember M= mol dm–3)
Rate equation for a first order reaction
Let us consider a first order reaction
A product
At the initial time (t = 0) the concentration of reactant A is a and the product is 0. After a certain time „t’,
x moles of A have converted into product, so the concentration of A is a – x.
We know that for a first orderreaction, the rate of reaction, dx/dt, is directly proportional to the
concentration of the reactant. Thus,
𝑑𝑥
𝑟𝑎𝑡𝑒 = − = 𝑘1 [𝑎 − 𝑥]1
𝑑𝑡
𝑑𝑥
(𝑎−𝑥)
= −𝑘1 𝑑𝑡 …………….. (1)
Integration of the above expression with interval gives
𝑥 𝑡
𝑑𝑥
= −𝑘1 𝑑𝑡
(𝑎 − 𝑥)
0 0
(Initial conditions are 0 inboth cases, whereas x refers to the concentration after a time 𝑡 has passed)
𝑑𝑥
Recall from calculus that 𝑥
= 𝑙𝑛𝑥 ; 𝑑𝑥 = 𝑥
Using the above calculus, we get, ln(𝑎 − 𝑥) 0𝑥 = −𝑘1 𝑡 𝑡0
After evaluating over the limits, which means upper limit minus lower limit
ln(𝑎 − 𝑥) − ln⁡ (𝑎 − 0) = −𝑘1 𝑡 − 0
ln(𝑎 − 𝑥) − ln𝑎 = −𝑘1 𝑡 …………….. (2)
On rearranging, ln 𝑎 − ln(𝑎 − 𝑥) = 𝑘1 𝑡
𝑎
𝑙𝑛 𝑎−𝑥 = 𝑘1 𝑡
On rearrangingand changing into common logarithms
1 𝑎
𝑘1 = 𝑡 2.303 𝑙𝑜𝑔 …………….. (3)
𝑎−𝑥
This is the integrated rate equation for a first order [Link] value of k1 can be found by substituting
the values of a and (a – x) determined experimentallyat time interval t during the course of the reaction.
Linearity plot
On rearranging equation 2, ln(𝑎 − 𝑥) = −𝑘1 𝑡 + ln 𝑎
This equation looks like y= mx + c. Here y= ln(a-x), m=–k1, x= t and c= ln a.
This means that if we plot ln(a-x )𝑣𝑠 𝑡, we get a line with a slope that is the negative of the rate constant.

3
Half-life of a reaction
Reaction rates can also be expressed in terms of half-life or half-life period. It is defined as: the
time required for the concentration of a reactant to decrease to half its initial value. It is represented by the
symbol t1/2.
At half-time, t = t1/2, concentration of the reactant will be x= a/2. Substitute this in rate equation 3

1 𝑎
𝑘1 = 2.303 𝑙𝑜𝑔 𝑎
𝑡1 𝑎−2
2

On rearranging,
1 𝑎
𝑡1 = 2.303 𝑙𝑜𝑔 𝑎
2 𝑘1
2
2.303
𝑡1 = 𝑙𝑜𝑔 2
2 𝑘1
0.693
𝑡1 =
2 𝑘1
From the half-lifeperiod equation, it is clear that:
(1) half-life for a first order reaction is independent of the initial reactant concentration.
(2) it is inversely proportional to the rate constantk1.
Examples of First order reactions
Some common reactions which follow first order kinetics are:
1. Decomposition of H2O2 in aqueous solution.
2. Radioactive decay
Second order reaction
In a second order reaction, rate is determined by the variation of two concentration terms. It may be
2A products
or A+B products
Here we will see rate equation when both reactants have same initial concentration
𝑑𝑥
𝑅𝑎𝑡𝑒 = 𝑑𝑡
𝑑𝑥 2
𝑑𝑡
∝ [𝐴]
𝑑𝑥
= 𝑘2 [𝐴]2
𝑑𝑡
𝑀. 𝑠 −1
Rate constant k2 unit is 𝑀2
, which becomes M–1s–1. (Remember M= mol dm-3)
Rate equation for a second order reaction
Let us consider a second order reaction
2A products

4
At the initial time (t = 0) the concentration of reactant A is a and the product is 0. After a certain time „t’,
x moles of A have converted into product, so the concentration of A is a – x.
We know that for a second orderreaction, the rate of reaction, dx/dt, is directly proportional to the
concentration of two reactants. Thus,
𝑑𝑥
𝑟𝑎𝑡𝑒 = − = 𝑘2 [𝑎 − 𝑥]2
𝑑𝑡
𝑑𝑥
− (𝑎−𝑥)2 = 𝑘2 𝑑𝑡 …………….. (1)
Integration of the above expression with interval gives
𝑥 𝑑𝑥 𝑡
− 0 (𝑎−𝑥)2
= −𝑘2 0
𝑑𝑡 …………….. (2)
(Initial conditions are 0 inboth cases, whereas x refers to the concentration after a time 𝑡 has passed)
𝑥 𝑛 +1
Recall from calculus that 𝑥 𝑛 𝑑𝑥 =
𝑛+1
−2 𝑎−𝑥 −2+1 1
Here, 𝑥 = 𝑎 − 𝑥 ; 𝑛 = −2; 𝑠𝑜 , which will be −
−2+1 𝑎−𝑥
1 𝑥
𝑡
Using the above calculus, equation 2 becomes, = 𝑘2 𝑡 0
𝑎−𝑥 0
After evaluating over the limits, which means upper limit minus lower limit
1 1
− = 𝑘2 𝑡 − 0
𝑎−𝑥 𝑎−0
1 1
− = 𝑘2 𝑡 …………….. (3)
𝑎−𝑥 𝑎
Further simplification leads to,
𝑎 − (𝑎 − 𝑥)
= 𝑘2 𝑡
𝑎(𝑎 − 𝑥)
𝑥
= 𝑘2 𝑡
𝑎(𝑎 − 𝑥)
1 𝑥
𝑘2 = …………….. (4)
𝑡 𝑎(𝑎−𝑥)
This is the integrated rate equation for a second order [Link] value of k2 can be found by
substituting the values of a and (a – x) determined experimentallyat time interval t during the course of
the reaction.
Linearity plot
1 1
On rearranging equation 3, = 𝑘2 𝑡 +
𝑎−𝑥 𝑎
This equation looks like y= mx + c. Here y= 1/(a-x), m= k2, x= t and c= 1/ a.
This means that if we plot1/(a-x) vs.𝑡, we get a line with a slope that is the rate constant.

5
Half-life of a reaction
At half-time, t = t1/2, concentration of the reactant will be x= a/2. Substitute this in rate equation 4
1 𝑥
𝑘2 =
𝑡 𝑎(𝑎 − 𝑥)
𝑎
1 2
𝑘2 =
𝑡1 𝑎(𝑎 − 𝑎 )
2 2
𝑎
1 2
On rearranging,𝑡1 = 𝑎
2 𝑘 2 𝑎( )
2
1
𝑡1 =
2 𝑘2 𝑎
As in case of the first order reaction, half-life for a second order reaction is inversely proportional
to rate constant k2. While half-life of a first order reaction is independent of initial concentration, half-life
of the second order reaction depends on initial concentration. This fact can be used to distinguish between
a first order and a second order reaction.
Examples of second order reaction
Hydrolysis of an Ester by NaOH.
CH3COOC2H5 + NaOH → CH3COONa + C2H5OH
ethyl acetate ethyl alcohol