LANGMUIR ADSORPTION

ISOTHERM
● In 1916 ,Irwing Langmuir published new model isotherm for gases adsorbed onto
solids,which retain his name.
● And he derived the mathematical equation for adsorption based on the kinetic theory
of gases
● The relation of amount of gas adsorbed to the pressure of the gas at constant
temperature is called Langmuir adsorption isotherm.

● He derived the equation based on the following assumption:

1. The adsorbed gas behaves ideally in the vapour phase.

2. Only a monolayer is formed by the adsorbed gas.
3. The surface of the solid is homogeneous .So that each binding site has same
affinity for the gas molecule.
4. There is no lateral interaction between the adsorbed molecule.
5. The adsorbed gas molecule are localised.ie ,they don't move around on the
surface.
● He suggested that adsorption takes place through this mechanism:

A(g) + B(s) ⇌↔ AB

Where,

A(g) = Unadsorbed gaseous molecule.

B(s) = Unoccupied metal surface.
AB = Adsorbed gaseous molecule.
Ka = Rate constant for adsorption.
Kb = Rate constant for desorption.
Unoccupied metal surface
Adsorbed gas molecule
Unadsorbed gas molecule
Monolayer formation
● The rate of Adsorption is proportional to the pressure of the gas p and the number of
vacant sites on the surface
Rate of Adsorption ∝ p
Rate of Adsorption ∝ Number of vacant sites ………………(1)
Let,
N = Total number of sites
θ = Fraction of the surface sites occupied by gas
molecules
ie,

θ = _Number of Adsorption sites occupied__

Number of Adsorption sites available

θ = _Number of Adsorption sites occupied__

N
Number of Adsorption sites occupied = Nθ
Therefore,
Number of vacant sites = ( Total number of - ( Number of Adsorption sites
sites ) occupied )
= N - Nθ
= N (1 - θ)
Substituting this in equation (1)
Rate of Adsorption ∝ N (1 - θ)
Therefore,
Rate of Adsorption ∝ p × N(1 - θ)
Rate of Adsorption = Ka×p× N(1 - θ)
Thus,
Rate of Adsorption = KapN(1-θ) ………………………........(2)

Where,
Ka = Rate constant for Adsorption.
● The rate of desorption is directly proportional to the Number of the adsorbed molecule

Rate of desorption ∝ Nθ
Rate of desorption = KdNθ …………………………………(3)
Where,
Kd = Rate constant for desorption
● At equilibrium,
Rate of adsorption = Rate of desorption
KapN(1-θ) = ΚdNθ
_Ka p(1-θ) = θ
Kd
bp(1-θ) = θ Where b = _Ka_
Kd
Therefore,
(1-θ) = __1__
θ bp
 _1_ - 1 = __1__
θ bp

_1_ = _1__ + 1
θ bp

_1_ = _1 + bp_
θ bp

Therefore, θ = _bp___ ……………………(4)

1 + bp

● If we were speaking about the adsorption of a substance from solution.Then p is

replaced by molar concentration C in the equation (5).
● Then the amount of substance adsorbed ,x/m ,will be proportional to θ for a
specified adsorbent .
 x_ = Kθ ( x/m = Mass of gas adsorbed per unit
m mass of adsorbent
Κ = A constant )

Then _x_ = __kbp__

m 1 + bp
or
_x_ = ___ab___ …...…….………………..(5)
m 1 + bp

Where the constant, a = kb

● Equation (5) relates the amount of gas adsorbed to the pressure of the gas at
constant temperature and is langmuir adsorption isotherm.
● The constants a and b depends on the nature of system and on the
temperature.
● In order to test this isotherm, equation (6) is rearranged as as to give:
_x_ = __ap___
m 1 + bp
__p__ = _1 + bp_
x/m a
__p__ = _1_ + _bp_
x/m a a

( similar to y = c + mx )
__p__ = _1_ + ( _b_ )p
x/m a a
….…………………(6)

● This equation is similar to that of the equation for a straight line.Hence if P/

(x/m) is plotted against p , a straight line should be obtained with a slope
equal to b/a and the intercept equal to 1/a as shown in the figure.
Two extreame cases of Langmuir isotherm

It was to be observed that in numerous cases that actual curves we're

straight lines then verifying Langmuir adsorption equation

CASE - 1 : When the gas pressure p is very small

● Under this condition,the factors bp is negligibly small as compared to unity in

the denominator of equation (4) .So Langmuir equation reduced to ,
θ = bp

● It means that at very low pressure the amount of gas adsorbed is directly
proportional to the pressure.
CASE - 2 : When the gas pressure p is very high

● At high pressure bp is also so large ,the factor (1 + bp) in the denominator can
be approximated as bp .So Langmuir equation reduced to,
θ = _bp_
bp
θ = 1

● It means that at very high pressure , the amount of gas adsorbed reaches a
constant limiting value.
Thank you