First Order Reaction

The Chemical reaction that depends on the concentration of only one reactant is called
First order reaction. First order reaction is directly proportional to the concentration of
reactant raised to power one.

Let consider a chemical reaction which is first order

A  Product

When t = 0 a 0
When t = t a-x x

Rate law:

Rate of reaction ∝ [ A ]1
ⅆ𝑥
= 𝑘(𝑎 − 𝑥 )…………..(1)
ⅆ𝑡

This is differential rate equation for first order, Where K is rate constant.

Separation and Integration:

Separating the variables in above equation (1).
ⅆ𝑥
(𝑎−𝑥)
= 𝑘 ⅆ𝑡

Integrating this equation

ⅆ𝑥
∫ (𝑎−𝑥)
= 𝑘∫ ⅆ𝑡

According to rule of integration

− 𝑙𝑛(𝑎 − 𝑥 ) = 𝑘𝑡 + 𝐶……. (2)

Value of C:
To find the value C, putting initial condition

Where t=0 , x= 0
 − 𝑙𝑛(𝑎 − 0) = 𝑘(0) + 𝐶

− 𝑙𝑛 𝑎 = 𝐶 ……….. (3)
Now put the value of “C” in equation 2

− 𝑙𝑛(𝑎 − 𝑥 ) = 𝑘𝑡 − 𝑙𝑛 𝑎 ………. (4)

Multiply with negative

𝑙𝑛(𝑎 − 𝑥 ) = −𝑘𝑡 + 𝑙𝑛 𝑎 …….. (5)

This equation 5 is straight line equation. It has two variables. i.e. ln(a-x) and ‘t’.
When a graph is plotted between independent variable ‘t’ on X-axis and ln(a-x) on Y-
axis, then a straight line is obtained with negative slope

The slope of Straight line is equal to rate constant ‘k’ in equation 5

Equation 5 can be rearranged to get another form of first order equation.

Taking 𝑙𝑛 𝑎 on L.H.S − ln 𝑎 + 𝑙𝑛(𝑎 − 𝑥 ) = −𝑘𝑡
Rearrange it 𝑙𝑛 𝑎 − 𝑙𝑛(𝑎 − 𝑥 ) = 𝑘𝑡
𝑎
𝑙𝑛 = 𝑘𝑡………… (6)
𝑎−𝑥

This is the rate integrated equation for a first Order reaction. This is equation of
𝒂
straight line. When a graph is plotted between time on x-axis and 𝐥𝐧 on Y-axis,
𝒂−𝒙
then a straight line with positive slope is obtained passing through origin. Slope is
equal to rate constant.

Exponential form of First order:

The equation 6 can be converted to exponential form by taking the antilog on both
sides.
𝑎
Since, ln = 𝑘𝑡 …….(6)
𝑎−𝑥
𝑎
So, = ⅇ 𝑘𝑡
𝑎−𝑥
𝑎−𝑥
Inverting, = ⅇ −𝑘𝑡
𝑎
Or 𝑎 − 𝑥 = 𝑎ⅇ −𝑘𝑡 ………. (7)
Half life of First Order reaction:

Half life of chemical reaction is time which is required to convert half of reactants
into products. It depends upon nature of reactant and condition of reaction.

To find half life of first order,

By using equation 5 which s as follow:

𝑙𝑛(𝑎 − 𝑥 ) = −𝑘𝑡 + 𝑙𝑛 𝑎
𝑎
When t=t½ x=
2

𝑎
So, 𝑙𝑛 (𝑎 − ) = −𝑘𝑡1⁄ + 𝑙𝑛 𝑎
2 2

2𝑎−𝑎
𝑙𝑛 ( ) = −𝑘𝑡1⁄ + 𝑙𝑛 𝑎
2 2

𝑎
𝑙𝑛 ( ) = −𝑘𝑡1⁄ + 𝑙𝑛 𝑎
2 2
𝑎
𝑙𝑛 + 𝑘𝑡1⁄ = 𝑙𝑛 𝑎
2 2
𝑎
𝑘𝑡1⁄ = ln 𝑎 − ln
2 2
𝑎
𝐾𝑡1⁄ = 𝑙𝑛 𝑎
2 2

2𝑎
𝑘𝑡1⁄ = 𝑙𝑛
2 𝑎

𝑘𝑡1⁄ = 𝑙𝑛 2
2
𝑙𝑛 2 0.693
𝑡1⁄ = = ……. (8)
2 𝑘 𝑘
This is the expression for the half life of a first order. According to this equation 8 ,
half life period of first order reaction is inversely proportional to the rate constant and
is independent of initial concentration.

Unit of First order:

The equation (6) of first order is
𝑎
𝑘𝑡 = 𝑙𝑛
𝑎−𝑥
1 𝑎
𝑘 = 𝑙𝑛 (𝑎−𝑥)
𝑡

1 𝑚𝑜𝑙 ⅆ𝑚−3
𝑘= 𝑙𝑛
𝑠𝑒𝑐 𝑚𝑜𝑙 ⅆ𝑚−3
1
𝑘=
𝑠𝑒𝑐

Unit of k = sec-1

Examples of First order:

Different examples of first order reaction are as follow:

*Inversion of Cane Sugar

The inversion of cane sugar (sucrose) in the presence of dilute HCl as a catalyst has
been found to be a first order reaction.
C12H22O11 + H2O → C6H12O6 +C6H12O6

Sucrose glucose fructose

Such a reaction involving two products, one of which (glucose) is dextrorotatory and
the other (fructose) is levorotatory, proceeds with change in optical rotation. The
progress of this reaction is followed by noting the optical rotation of mixture.

*Decomposition of H2O2 in aqueous solution

H2O2 → H2O + O

The progress of this reaction is followed by volumetric analysis. H2O2 is titrated with
standard solution of KMnO4
*Hydrolysis of an ester
CH3COOH + H2O CH3COOH + C2H5OH

This reaction is first order with respect to ester. Because this reaction does not depend
upon water.
Rate = k [ester]1 [H2O]0

Rate = k [ester]

The progress of this reaction is followed by volumetric analysis.

*Reaction of aryldiazonium ion

In the reaction of aryldiazonium ions with nucleophiles in aqueous solution

ArN2+ + X− → ArX + N2

The rate equation is r = k[ArN2+] , where Ar indicates an aryl group.

So this reaction is first order.

Applications of First Order

Some Applications are as follow:

Mathematical description of coal devolatilization:

The first-order single-reaction model offers a simple but effective mathematical

description of coal devolatilization. Under conditions where the effects of physical
transport processes and secondary reactions are relatively small but not negligible, the
model approximates the complex chemical decomposition and any transport effects by
a single global first-order decomposition reaction occurring uniformly throughout the
particle.

Pharmaceuticals Reaction:
The most common pharmaceutical reactions such as drug absorption and drug
degradation follow first order reaction. The rate of reaction is directly proportional to
the drug concentration.