The Langmuir isotherms – limiting cases

𝑲𝒑
𝜽=
𝑲𝒑 + 𝟏

• Where Kp or 𝐾[A]<< 1, when the pressure is low (concentration is low) or

when the K is small . 𝜃 = 𝐾𝑝 𝑜𝑟 𝜃 = 𝐾[A](low pressure region of the
adsorption curve, surface sparsely covered)

• Where Kp or 𝐾[A] >> 1, at high pressures (high concentrations) or

particularly strong adsorption at lower pressures,
 The Langmuir isotherms

• Surface coverage increases

with pressure/conc. and 𝑲𝒑
𝜽=
approaches 1 only at high 𝑲𝒑 + 𝟏
pressures or concentrations 1 K=10 atm-1
K=1.0 atm-1

• Different values of K are

K=0.1 atm-1
obtained at different θ
temperatures hence isotherms
K=0.01 atm-1

• K is an equilibrium constant
for the distribution of material 0 7 14
between the surface and the p (atm)
gas phase.
 The Langmuir isotherm
𝜕 ln 𝑃 ∆𝑯𝐨
=−
𝜕𝑇 θ
𝑅𝑇 2

𝜃
And 𝐾𝑝 =
1−𝜃
Therefore when θ is constant, InK + Inp = constant

𝜕 ln 𝑃 𝜕 ln 𝐾 ∆𝑯𝐨
=− =
𝜕𝑇 𝜕𝑇 𝑅𝑇 2
1 1
With 𝜕 𝜕𝑇 = − 𝑡ℎ𝑒 𝑒𝑥𝑝𝑟𝑒𝑠𝑠𝑖𝑜𝑛 𝑟𝑒𝑎𝑟𝑟𝑎𝑛𝑔𝑒𝑠 𝑡𝑜:
𝑇 𝑇2
𝜕 ln 𝑃 ∆𝑯𝐨
=
𝜕𝑇 𝑅𝑇
∆𝑯𝐨
And a plot of Inp vs 1/T has a straight line of slope = −
𝑅𝑇
4
Other isotherms
• Systems that obey the Langmuir type are often referred to as
showing ideal adsorption.

• Systems frequently deviate significantly from the Langmuir equation.

This may be because:

• the surface is not uniform,

• interactions between adsorbed molecules – a molecule

attached to a surface, may make it more difficult or less difficult,
for another molecule to become attached to a neighboring site
leading to deviation from ideal adsorption equation
 The BET equation

• Brunauer, Emmett and Teller extended the Langmuir isotherm to allow

for the physisorption of additional layers of adsorbed molecules.

• The basic assumption is that the Langmuir applies to each layer; first
layer heat of adsorption may have a special value and for the succeeding
layers heat of condensation applies.

• Another assumption is that evaporation and condensation can occur

only from or on exposed surfaces

• Involved the assumption that there is one enthalpy of adsorption for the
first layer, and that the enthalpy of liquefaction applies to the second and
subsequent layers.
5
6
The BET equation
• The BET equation has been written in various forms;

𝑥 1 𝑐−1 𝑃
= + 𝑥 ; 𝑥=
𝑣(1−𝑥) 𝑐𝑣𝑚 c𝑣𝑚 𝑃0

• v = volume of gas adsorbed at pressure P

• vm = volume of gas adsorbed when the surface of adsorbent is
covered with a monolayer
• c = constant of approximation equal to 𝒆(𝑸𝟏−𝑸𝑳 )Τ𝑹𝑻
Q1 = heat evolved in the adsorption of first layer of gases (ΔdesH ͦ)
QL = heat of condensation of gas to liquid (ΔvapH ͦ)
 The BET equation

• Straight line graph

• Slope c

• Intercept

• From the slope and intercept, the value of vm (volume of gas required to form a
monolayer) can be determined

• From known molecular diameter and assuming7

close packing in the
monolayer, surface area of adsorbent can be calculated
8
The BET equation
5

4
0.1
3
𝒗
1.0
𝒗𝒎 2
10.0

1 1000

0
0.2 0.4 0.6 0.8

𝑷
𝑷𝟎
The BET isotherms for various values of c

• When Q1 > QL – Type II isotherm, c > 1

• When Q1 < QL – Type III isotherm, c < 1

 The BET equation

𝑃𝑃0 1 𝑃
= +
𝑉(𝑃0 − 𝑃 ) 𝑉0 𝐾 𝑉0

• V = vol of gas at pressure P

• V0 = vol of monolayer
• P0 = saturation vapor pressure

9
10
Harkins – Jura adsorption isotherm
• Gives a thermodynamic approach to the problem of physical adsorption
(hysteresis).
𝑃 𝐴
𝑙𝑛 =𝐵− 2
𝑃0 𝑣

• v = quantity of gas adsorbed and A and B are constants

1
• A plot of ln 𝑃ൗ𝑃0 vs 𝑣 2 gives a straight line with a slope –A.

• Surface area of adsorbent is proportional to 𝐴 (proportionality dependent only

on the nature of adsorbate). SA = k 𝐴