B.Sc.

Sem VI

Unit VII: Surface Chemistry

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Topic: Adsorption Isotherm

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By

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Souvik Garani

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Assistant Professor
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Department of Chemistry,
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Udai Pratap College
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Varanasi-221002
 Langmuir Adsorption Isotherm
Assumptions:

 The dominant force responsible for the adsorption is purely chemical,

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indicating complete chemisorption.

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 Each site on the adsorbent can accommodate a maximum of one molecule,

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implying the formation of only a monolayer.

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 The surface containing the adsorption sites is perfectly smooth & flat

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 All active sites are of the same nature and are equivalent.
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 There are no lateral interactions between adsorbate molecules on
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adjacent sites, resulting in the enthalpy of adsorption being independent

of surface coverage.
 A dynamic equilibrium exists between the free adsorbate molecules and the
adsorbed adsorbate molecules.
ka
A( g ) + S ( s ) 

kd

 AS ( s )

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𝑨𝑨 represents a gas-phase molecule

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𝑺𝑺 denotes an unoccupied surface site

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AS represents the molecule that has been adsorbed

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𝒌𝒌𝒂𝒂 and 𝒌𝒌𝒅𝒅 are the respective rate constants for the adsorption and desorption processes.

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KP Expression of Langmuir adsorption
θ=

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Isotherm
1 + KP
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𝑘𝑘𝑎𝑎
Where 𝐾𝐾 = , the equilibrium constant of the adsorption. P represents the Pressure
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𝑘𝑘𝑑𝑑

𝜃𝜃 is called the surface coverage. No. of sites occupied at equilibrium

θ=
Total no. of sites present on surface
 KP
θ=
1 + KP

In the limit KP<<1, when the

pressure is significantly low

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θ=KP

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Langmuir isotherm
In the limit KP>>1, when the

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pressure is significantly high

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KP
θ = 1
=

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KP

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Plot of 1/𝜃𝜃 versus 1/𝑃𝑃 for various

gases

1/P
 𝑣𝑣 𝐾𝐾𝐾𝐾
𝜃𝜃 = =
𝑣𝑣𝑚𝑚 1 + 𝐾𝐾𝐾𝐾
𝑣𝑣 represents the volume of gas adsorbed at a specific T and P when the surface coverage is 𝜃𝜃

𝑣𝑣𝑚𝑚 is the volume of gas adsorbed at the same T and P when 𝜃𝜃 equals 1, indicating the

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formation of a complete monolayer,

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𝑃𝑃 𝑃𝑃 1 Alternative form of

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= + Langmuir Adsorption

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𝑣𝑣 𝑣𝑣𝑚𝑚 𝑣𝑣𝑚𝑚 𝐾𝐾

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Isotherm

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𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 =
𝑣𝑣𝑚𝑚
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𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆
𝐾𝐾 =
𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼
1
𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼𝐼 =
𝑣𝑣𝑚𝑚 𝐾𝐾

verification of Langmuir adsorption isotherm

 Langmuir Adsorption Isotherm for a
dissociative adsorption

A A

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A2(g) + S S  S S

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 The adsorption rate remains directly proportional to the pressure 𝑃𝑃 of the overlying gas.

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 When two sites are necessary for adsorption, the rate becomes proportional to the square of

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the number of vacant sites per unit area i.e., 𝑁𝑁 2 1 − 𝜃𝜃 2

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the rate of adsorption: ep
𝑣𝑣𝑎𝑎 = 𝑘𝑘𝑎𝑎 𝑃𝑃𝑁𝑁 2 1 − 𝜃𝜃 2
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Similarly, two adsorption sites are required for desorption

and therefore, the rate of desorption:
𝑣𝑣𝑑𝑑 = 𝑘𝑘𝑑𝑑 𝑁𝑁 2 𝜃𝜃 2
At equilibrium,

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Similarly, when an n atomic molecule
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undergoes dissociation into atoms during
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adsorption, The final equation becomes

𝐾𝐾𝐾𝐾 1⁄𝑛𝑛
𝜃𝜃 =
1 + 𝐾𝐾𝐾𝐾 1⁄𝑛𝑛
 Limitations of Langmuir Adsorption Isotherm
 In the Langmuir adsorption isotherm, only chemisorption is considered, which can
elucidate just one of the five distinct types of adsorption isotherms observed in
experimental observations. However, both types of adsorptions occur simultaneously in
reality.

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 If the Langmuir adsorption isotherm holds true, the 𝑃𝑃 ∕ 𝑣𝑣 vs 𝑃𝑃 plot should form a linear

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relationship across the entire pressure range. However, experimental results indicate

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that this linearity is preserved only at low pressures, while deviations from linearity

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become evident in the high-pressure region.

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 At sufficiently high pressures, the fraction coverage should theoretically reach a value of
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1. However, experimental observations often reveal that in most cases, 𝜃𝜃 (the fraction
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coverage) ranges from 0.03 to 0.3.
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 While the Langmuir adsorption isotherm suggests no lateral interactions among adsorbed
molecules, experiments indicate that these molecules do interact laterally, affecting the
enthalpy of adsorption, which varies with surface coverage.
Brunauer–Emmett–Teller (BET) isotherm

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Different types of adsorption isotherm
The Brunauer, Emmett, and Teller (BET) theory is based on the following assumptions:

 The adsorbent surface is homogeneous and contains a specific number of equivalent

sites.

 The initial layer is formed through chemisorption, and subsequent layers can stack

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on top of each other. For instance, the second layer adsorbs on top of the first, the

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third on top of the second, and so on. This stacking is driven by physisorption,

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specifically Van der Waal forces of attraction.

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 A dynamic equilibrium exists between molecules in successive layers. In other

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words, the rate of evaporation from one layer is equal to the rate of adsorption on the

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preceding layer. ep
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 The heat of adsorption in the first layer, represented as 𝛥𝛥𝐻𝐻𝑎𝑎𝑎𝑎 , depends on the
specific adsorbate and adsorbent. In contrast, for subsequent layers (2nd, 3rd, 4th,
etc.), it remains constant and is equal to the heat of vapor condensation (𝐻𝐻𝑐𝑐 ).

 There are no lateral interactions among the adsorbed molecules.

 𝑝𝑝 1 𝑐𝑐 − 1 𝑝𝑝
= +

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𝑣𝑣 𝑝𝑝0 − 𝑝𝑝 𝑣𝑣𝑚𝑚 𝑐𝑐 𝑣𝑣𝑚𝑚 𝑐𝑐 𝑝𝑝0

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• Where 𝑣𝑣 represents the volume of gas adsorbed at the pressure 𝑝𝑝

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• 𝑣𝑣𝑚𝑚 is the volume of gas adsorbed, when the surface of the adsorbent is

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covered completely with a monolayer.

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• 𝑝𝑝0 is the saturated vapor pressure.
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• 𝑐𝑐 is a constant, approximately equal to 𝒆𝒆( 𝜟𝜟𝑯𝑯𝒂𝒂𝒂𝒂 −𝜟𝜟𝑯𝑯𝒄𝒄)/𝑹𝑹𝑹𝑹
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• 𝜟𝜟𝑯𝑯𝒂𝒂𝒂𝒂 is the heat evolved in the adsorption of the first layer of gas molecules
and 𝜟𝜟𝑯𝑯𝒄𝒄 is the heat of condensation of the gas to liquid which is also heat
evolved in the absorption of the second or subsequent layer of gas molecules.
 BET Adsorption Isotherm

𝑝𝑝 𝑝𝑝
vs  Straight line plot
𝑣𝑣 𝑝𝑝0 −𝑝𝑝 𝑝𝑝0

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𝑐𝑐 − 1 1

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Slope Intercept

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𝑣𝑣𝑚𝑚 𝑐𝑐 𝑣𝑣𝑚𝑚 𝑐𝑐

ol C
C f
From the slope and intercept,

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𝑣𝑣𝑚𝑚 → the volume required to form a complete monolayer can be calculated.

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 Determination of Surface Area

 𝑣𝑣𝑚𝑚 is the volume of the gas which is adsorbed when monolayer is fully occupied (𝜃𝜃 = 1).

 At STP, the volume occupied by 1 mol of gas is 22414 ml.

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 From the value of 𝑣𝑣𝑚𝑚 , the no. of molecules (𝑁𝑁) presents in 𝑣𝑣𝑚𝑚 volume of gas is

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𝑣𝑣𝑚𝑚 𝑖𝑖𝑖𝑖 𝑚𝑚𝑚𝑚
𝑁𝑁𝐴𝐴 is the Avogadro no.

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𝑁𝑁 = × 𝑁𝑁𝐴𝐴

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22414 𝑚𝑚𝑚𝑚 𝑚𝑚𝑚𝑚𝑚𝑚 −1

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If the cross-sectional area occupied by each molecule  𝐴𝐴, then the surface area of the adsorbent (𝑆𝑆)

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can be calculated from the following formula
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𝑆𝑆 = 𝑁𝑁 × 𝐴𝐴
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𝑣𝑣𝑚𝑚 𝑖𝑖𝑖𝑖 𝑚𝑚𝑚𝑚

𝑆𝑆 = × 𝑁𝑁𝐴𝐴 × 𝐴𝐴
22414 𝑚𝑚𝑚𝑚 𝑚𝑚𝑚𝑚𝑚𝑚 −1
 Brunauer–Emmett–Teller (BET) isotherm

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C f
C<1 and physisorption

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C<1 and indicates the
C>>1 and p<<po proceeds from beginning presence of capillary

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Different types of adsorption isotherm

C>1 and indicates the presence of

C>1 and multilayer formation takes place
capillary
 Limitations of BET Adsorption Isotherm

 Except in some ideal situations, a solid surface is usually inhomogeneous.

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 In BET adsorption isotherm theory, the interaction between the adsorbed molecules has

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been neglected. But there must be some lateral interaction.

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 In the derivation it has been assumed that the heat of adsorption from second layer

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onwards is equal, which is not true in real cases

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 BET theory is not valid in the entire pressure region. It gives a satisfactory result in the
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region 0.05 < p/p0 <0.3

 Gibbs Adsorption isotherm

 The concentration of a solute at the surface of a liquid might be more than

what is found in the overall solution.

 At a specific temperature 𝑇𝑇, this excess concentration depends on the surface

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tension of the solution.

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𝑐𝑐2 d𝛾𝛾
𝛤𝛤 = −

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𝑅𝑅𝑅𝑅 𝑑𝑑𝑐𝑐2

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 𝛤𝛤 is the excess concentration of the solute per unit area of the surface, as

C f
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compared with that in the bulk of the solution;

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 The term 𝑑𝑑𝛾𝛾/𝑑𝑑𝑐𝑐2 represents the rate at which the surface tension of the solution

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changes with the concentration of the solute 𝑐𝑐2
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 R is the universal gas constant

 T is the absolute temperature.

 Gibbs Adsorption isotherm

𝑐𝑐2 d𝛾𝛾
 Depending on the sign of the surface excess 𝛤𝛤 = −
𝑅𝑅𝑅𝑅 𝑑𝑑𝑐𝑐2
concentration (𝛤𝛤), the surface tension of a solvent
changes with the addition of a solute.

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 Based on the relationship between 𝛾𝛾 and 𝑐𝑐2 , solutes

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are generally classified into three categories.

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 Case I:

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 For solutes such as sucrose and salts like NaCl, KCl , the

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surface tension increases gradually with an increase in

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concentration. ep
 They have a strong affinity for polar solvents like water.
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 They tend to reside in the bulk rather than at the surface.

 As a result, the surface excess concentration (𝛤𝛤) is negative,
leading to an increase in surface tension with the addition of
solute.
 𝑐𝑐2 d𝛾𝛾
 Case II: 𝛤𝛤 = −
𝑅𝑅𝑅𝑅 𝑑𝑑𝑐𝑐2
 For solutes such as small organic compounds with polar groups like

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carboxylic acid group and sulphonic acid group

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 Feature both a polar group and a non-polar hydrophobic part.

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 The polar group exhibits a mild affinity for polar solvents like

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water, orienting towards the bulk

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 The non-polar hydrophobic part projects outward and occupies

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the solvent's surface.

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 As a result, the surface excess concentration (𝛤𝛤) is slightly

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positive, leading to a decrease in surface tension with the addition
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of solute.
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 Case III:
 For solutes consisting of medium-sized organic
molecules with an ionic head, such as Na+ or K+ salts of 𝑐𝑐2 d𝛾𝛾
carboxylic acids, sulfonic acids, and quaternary amine 𝛤𝛤 = −

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salts.
𝑅𝑅𝑅𝑅 𝑑𝑑𝑐𝑐2

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 In this case, the ionic head group exhibits a strong

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preferential affinity for polar solvents like water

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 The bulky non-polar hydrophobic part orients outward

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and predominantly occupies the liquid's surface.

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 As a result, the surface excess concentration (𝛤𝛤) is

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strongly positive, leading to a rapid decrease in surface

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tension with the addition of solute.
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 These solutes, which considerably decrease the surface
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tension by strongly adsorbing at the interface, are

called surface-active reagent or surfactants.
 Heterogeneous Catalysis

A heterogeneous catalyst is a catalyst that

operates in a phase distinct from that of the

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reactants and products.

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The metal furnishes a surface to which the

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reactants adhere, preparing them for reaction

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and facilitating their interactions.
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The reaction between gases on the solid surface is common, Majority of
catalytic processes falls into this category.

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The reactions are expected to proceed in five consecutive steps:

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C f
1. Diffusion of the reactant molecules towards the solid surface.

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2. Adsorption of the reactant molecules on the surface of catalyst.

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3. Reaction on the surface.

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4. Desorption of the product molecules from the surface.
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5. Diffusion of the desorbed products into the bulk of the gas/liquid phase.
 Rate expression for single reactant

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 The rate law can be expressed in terms of an adsorption

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isotherm if it is assumed that the adsorption equilibrium

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is left undisturbed by the slow reaction of the adsorbed

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reactant.

ol C
C f
 Then, the rate is proportional to the extent of surface

P to
coverage.

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𝑘𝑘2 𝐾𝐾𝐾𝐾

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 The fractional coverage θ is estimated by using the 𝑣𝑣 =
1 + 𝐾𝐾𝐾𝐾

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Langmuir isotherm ( 𝜃𝜃 = 𝐾𝐾𝐾𝐾/(1 + 𝐾𝐾𝐾𝐾)), the rate is 𝑣𝑣 = 𝑘𝑘2 𝜃𝜃
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When the pressure is sufficiently low, i.e., At extremely high pressure, when 𝐾𝐾𝐾𝐾 >>1
when 𝐾𝐾𝐾𝐾 << 1
𝑣𝑣 = 𝑘𝑘2
𝑣𝑣 = 𝑘𝑘2 𝐾𝐾𝐾𝐾