ENVE 206

Physico-chemical Principles of
Env. Eng
CHAPTER 4
Solid-Liquid (S-L) & Solid-Gas (S-G)
Interfaces –Part 1
2020– 2021 Spring
Filiz B. Dilek
 SOLID-GAS (S-G) AND SOLID-LIQUID(S-L) INTERFACES
Adsorption of gases or solutes on solids
When a gas or solute is brought into contact with a clean solid surface,
some of it will become attached to the surface in the form of an
adsorbed layer.
Adsorbed gas or solute is referred to as «adsorbate»
The solid is referred to as «adsorbent»
What is absorption? It is a process in which gas or solute molecules
interpenetrate throughly nearly uniformly among the molecules of
solid phase.
Adsorption and absorption can not always be distinguished
experimentally. Hence, the generic term «sorption» is used to
describe the general phenomenon of gas or solute uptake by solids
As in the case of L-L & L-G interface adsorption;

• It is a surface tension or surface free energy related phenomenon

• The main difference between solid and liquid surfaces: solid surfaces
are heterogeneous in respect of activity.
Adsorption at solid-liquid and solid-gas interfaces
is often divided into two classes:

• Chemisorption

• Physisorption
Chemisorption
• occurs as a result of chemical interaction between
adsorbent and adsorbate. (chemical bond formation or
electron exchange or charge interaction)
• May be slower than physisorption if the chemical
reaction is slow
• High energy of adsorption as compared to physisorption
• May involve an activation energy and may not be readily
reversible. It is possible e.g. to adsorb oxygen and
desorp CO or CO2.
Physisorption (ideal adsorption)
Adsorbent and adsorbate interact through Van der Waals forces

So, adsorption is relatively weak as comp. to chemisorption

- Low energy of adsorption (i.e. Adsorbate is not held strongly to the
adsorbent)
- Desorption can occur  adsorption is reversible for non-porous solids.
- Formation of multilayers on the adsorbent surface is possible
- Adsorbates are free to move on the surface
Factors affecting the degree of adsorption
• First driving force: The degree of solubility of a dissolved substance : The
more substance likes the solvent system, the less likely it is to move toward
the interface to be adsorbed.
• Second driving force: specific affinity of the solute for the solid i.e.
electrical attraction, Van der Waals attraction or chemical reactions.
Electrical attraction= exchange adsorption (ions concentrate at a surface as a
result of electrostatic attraction to charged sites at the surface. Charge on
the ion is imp factor: higher valency ions is attracted more strongly; for ions
of equal charge. Molecular size (hydrated radius) determines the order of
preference for adsorption; the smaller ions are more easily adsorbed (as they
can accomplish closer approach to the adsorption site)
Adsorption Equilibria and Adsorption Isotherm
• There is a dynamic equilibrium between the solute remaining in
solution and that at the surface, where there is a defined distribution
of solute between L & S phases. To depict this distribution, qe is
expressed as a function of Ce at fixed temperature. This expression is
termed as «adsorption isotherm».
Where: qe=amount of adsorbate/amount of adsorbent
qe at equilibrium
Ce= concentration of adsorbate remaining in solution
at equilibrium

The adsorption isotherm relates the amount of

solute adsorbed onto the solid and the equilibrium
Ce concentration of the solute in solution at a given
temperature.
 Isotherms are found by doing lab tests.

Add the same amount of solute (Co) but different dose of adsorbent (Csolid or X) to each tank volume (V)

adsorbent
Several Types of isothermal adsorption relations (Type I,
II, III, IV, V etc). We will see about Type I and II
Type I: most common and is valid for monolayer adsorption

Known as Langmuir Adsorption Model

Type II: is valid for multilayer adsorption of solute

Known as Brunauer, Emmett, Teller

(BET) Adsorption Model
Type I and II Isotherm Models

Type I (Langmuir) Type II (BET)

Both Models are limited by the assumptions of uniform energies of adsorption on the surface.
Langmuir Adsorption Isotherm

Assumptions:
(1)All adsorption sites are identical
(2)Fixed capacity for adsorption
(3)Monolayer adsorption
(4)Uniform energies of adsorption on the surface
 Langmuir Adsorption Isotherm
Imagine a dilute solution in which:
Solvent : component 1
Solute : component 2

Assumption: They occupy the same area when they are adsorbed on a surface.

Adsorption process:
Adsorbed solvent (𝑎1𝑠 ) + solute in solution (𝑎2𝑏 ) Adsorbed solute (𝑎2𝑠 ) + solvent in solution (𝑎1𝑏 )

where a = activity, s = surface of solid, b = bulk solution 𝑎2𝑠 𝑎1𝑏

K’= equilibrium constant K’=
𝑎1𝑠 𝑎2𝑏
Langmuir Adsorption Isotherm
Convert to mole fraction at the surface (X s ) (assume surface solution is ideal)
So, 𝑎 𝑠 ∝ 𝑋 𝑠 𝑋2𝑠 𝑎1𝑏
K’=
𝑋1𝑠 𝑎2𝑏
𝑋2𝑠 𝑎1𝑏
Since surface contains only two components : 𝑋1𝑠 + 𝑋2𝑠 = 1 K’=
(1−𝑋2𝑠 )𝑎2𝑏
K’𝑎 𝑏 /𝑎𝑏
Solving for 𝑋2𝑠 ; 𝑠
𝑋2 = 𝑏 𝑏 2 1
K’𝑎2 /𝑎1 + 1
In dilute solutions, activity of solvent is essentially constant, so the ratio K’/𝑎1𝑏
may be defined to equal to a new constant (K).
Langmuir Adsorption Isotherm

𝑠 K𝑎2𝑏
Then; 𝑋2 = Langmuir Equation
K 𝑎2𝑏 + 1
Or; in terms of area fractions (Ө) occupied by solvent and solute. We had assumed that both
the solvent and solute molecules occupy equal areas on the surface. Therefore, 𝑋𝑖𝑠 equals the
fraction of surface occupied by component 𝑖, Ө𝑖 .
Let 𝜎 𝑜 = 𝑎𝑟𝑒𝑎 𝑜𝑐𝑐𝑢𝑝𝑖𝑒𝑑 𝑝𝑒𝑟 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒
𝑁𝐴 𝜎 𝑜 = 𝑎𝑟𝑒𝑎 𝑜𝑐𝑐𝑢𝑝𝑖𝑒𝑑 𝑝𝑒𝑟 𝑚𝑜𝑙𝑒 ; 𝑁𝐴 𝜎 𝑜 𝑛 = 𝑡𝑜𝑡𝑎𝑙 𝑎𝑟𝑒𝑎 𝑜𝑐𝑐𝑢𝑝𝑖𝑒𝑑

𝜎2𝑜 𝑁𝐴 𝑛2𝑠 𝑜
Ө𝑖 = assumption was: 𝜎2 = 𝜎1𝑜 Then; Ө𝑖 = 𝑋2𝑠
𝜎2𝑜 𝑁𝐴 𝑛2𝑠 +𝜎1𝑜 𝑁𝐴 𝑛1𝑠
So;
K𝑎2𝑏
Ө2 = Another form of Langmuir Eqn
K𝑎2𝑏 + 1
Langmuir Adsorption Isotherm
drop b and 2 for simplicity
K𝑎
Ө=
K 𝑎+ 1
Two limiting cases:
1. 𝑎 0, θ = K 𝑎
2. K 𝑎 >> 1, θ = 1 (saturation of surface, i.e , 𝑎 is large)

Slope= K= Langmuir constant

Langmuir Adsorption
Another approach to derive the Langmuir eqn
Based on kinetic model of adsorption-desorption process:

A(g) + N (surface) ↔ AN
surface w/ N identical sites

Rate of adsorption: ka P (1- Ө) N

Rate of desorption: kd NӨ

where ka: adsorption rate constant, kd: desorption rate constant P: pressure of the adsorbate
N: total number of adsorption sites Ө : fraction of occupied sites.

𝐾𝑃
At equilibrium: ka P (1- Ө) N = kd NӨ Ө= where: K= ka/kd
1+𝐾 𝑃
For solute of solution:
𝐾𝑎 𝐾𝑐
Ө= a: activity of solute or Ө= c: concentration of solute
1+𝐾 𝑎 1+𝐾 𝑐

Experimentally, one does not measure the fraction of sites containing adsorbed
solute directly; instead, either:
𝒏𝒔𝟐
𝑾
= the number of moles of solute adsorbed per unit weight of adsorbent , or
𝒏𝒔𝟐
𝑨
= the number of moles of solute adsorbed per unit area of adsorbent
𝒏𝒔𝟐 𝒏𝒔𝟐
𝑨
Asp= 𝑾

Where: Asp= specific area of the adsorbent (total area/mass)

The fraction covered is related to these quantities:
𝒏𝒔𝟐 𝑜 𝒏𝒔𝟐 𝑁𝐴 𝜎𝑜
Ө= 𝑨
𝑁𝐴 𝜎 = 𝑾 Asp
The level at which saturation adsorption occurs may be identified with Ө=1
Therefore,
𝑛𝑠2 Asp 𝑛𝑠2 1
= 𝑜 or = 𝑜
𝑊 𝑠𝑎𝑡 𝑁𝐴 𝜎 𝐴 𝑠𝑎𝑡 𝑁𝐴 𝜎
We had:
𝑛2
𝑠 𝐾 𝑐
𝒏𝒔𝟐 𝑁𝐴 𝜎 𝑜 𝐾𝑐 𝒏𝒔𝟐 𝑊 𝑠𝑎𝑡
Ө= = Then; =
𝑾 Asp 1+𝐾 𝑐 𝑾 1+𝐾 𝑐

𝒏𝟐𝒔
=
𝑾 𝒔𝒂𝒕
In application:
𝒏𝒔𝟐
𝑾
= 𝑞𝑒 : number of moles of solute adsorbed per unit weight of adsorbent at conc. C at
equilibrium (i.e Ce )
𝒏𝟐𝒔
= 𝑄𝑜 = 𝑞𝑒𝑚𝑎𝑥 : number of moles of solute adsorbed per unit weight of adsorbent in forming
𝑾 𝒔𝒂𝒕
a complete monolayer on the surface
K=b : constant related to energy or net entalphy, ΔH, of adsorption. b is proportional to 𝑒 −ΔH/𝑅𝑇

So; Langmuir Eqn in practice: Linear Forms:

𝑸𝒐 𝒃𝒄 𝟏
=
𝟏 𝟏
+ 𝒐 or
𝒄
=
𝟏
+
𝒄
𝒒𝒆 = 𝒒𝒆 𝑸𝒐 𝒃𝒄 𝑸 𝒒𝒆 𝑸𝒐 𝒃 𝑸𝒐
𝟏+𝒃𝒄
 The Brunauer-Emmett-Teller (BET) Isotherm
Assumptions:
(1) multilayer adsorption;
(2) adsorption of first layer has a heat of adsorption, ΔHA;
(3) the subsequent layers are controlled by heat of condensation, ΔHL.
𝑆𝑖 : no of sites covered to a depth 𝑖
𝑛

𝑆 = 𝑆𝑜 + 𝑆1 + 𝑆2 + ⋯ + 𝑆𝑛 = 𝑆𝑖
𝑖=0

1st layer – similar description as for

Langmuir. e.g. for gas adsorption
𝓔
𝑘𝑑,1 = 𝒱 exp(− )
Rate of adsorption: 𝑘𝑎 P 𝑆𝑜 𝑘𝐵 𝑇
Where: P= gas pressure; 𝒱= frequency of collision; 𝓔=
Rate of desorption: 𝑘𝑑,1 𝑆1
energy for desorption ; 𝑘𝐵 = Boltzman constant; T= temp.

At equilibrium; 𝑘𝑎 P 𝑆𝑜 = 𝑘𝑑,1 𝑆1
 The Brunauer-Emmett-Teller (BET) Isotherm
For additional layers – 𝑆𝑖 𝑖>0 𝓔
𝑘𝑑,𝑖 = 𝒱 exp(− 𝑘 𝑣𝑇) where: 𝓔𝑣 = energy for vaporization
𝐵
𝑘𝑎 P 𝑆𝑖−1 = 𝑘𝑑,𝑖 𝑆𝑖
In the first layer, desorption involves detaching a molecule from the adsorbent while desorption from
the second layer involves detachment from another adsorbed molecule of the same kind. ∴ The
adsorption energy 𝓔 was used in the Boltzman factor in the first case; the energy of vaporization 𝓔𝑣
is a more appropriate value to use in the second case. (Heat of liquefactionof the vapor, Δ𝐻𝐿 , in the
second case; Heat of adsorption, Δ𝐻𝑎 , in the first case.) 𝒱 is assumed to be unchanged. 𝑘𝑎 is
assumed to be same for each layer.
Then;

𝑆𝑖 = (𝑘𝑎 P𝑆𝑖−1 )/𝑘𝑑,𝑖

Through repeated application of this equation, we can relate 𝑆𝑖 to 𝑆1 or 𝑆𝑜 . Then after some
arrangements and simplifications (not shown here), we obtain:
𝑘𝑎 𝑃 ℰ −ℰ𝑣
𝑖
𝑆𝑖 = 𝑋 𝐶 𝑆𝑜 where: 𝑋 = ; 𝐶 = exp
𝑘𝑑,𝑖 𝑘𝐵 𝑇
The Brunauer-Emmett-Teller (BET) Isotherm
Sustituting 𝑆𝑖 = 𝑋 𝑖 𝐶 𝑆𝑜 into 𝑆 = 𝑆𝑜 + 𝑆1 + 𝑆2 + ⋯ + 𝑆𝑛 = 𝑛
𝑖=0 𝑆𝑖 to give:

𝑆 = 𝑆𝑜 + 𝑋 𝑖 𝐶 𝑆𝑜
𝑖=1
Then, note:
𝑛
Total S (no. of sites) = 𝑖=0 𝑆𝑖
𝑛
Total adsorbed molecules = 𝑖=1 𝑖 𝑆𝑖

Also note that, as n →∞ , P → Po where Po : vapor pressure or saturation pressure.

The Brunauer-Emmett-Teller (BET) Isotherm
Then;
𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑎𝑑𝑠𝑜𝑟𝑏𝑒𝑑 (𝑉)
Ө= Ө > 1 for multilayer ads.
𝑣𝑜𝑙𝑢𝑚𝑒 𝑎𝑑𝑠𝑜𝑟𝑏𝑒𝑑 𝑎𝑡 𝑚𝑜𝑛𝑜𝑙𝑎𝑦𝑒𝑟 𝑐𝑜𝑣𝑒𝑟𝑎𝑔𝑒 (𝑉𝑚 )

𝑛
𝑛 𝑖=1 𝑖 𝑆𝑖 𝑉
𝑉 ∝ 𝑖=1 𝑖 𝑆𝑖 Then; we can write , Ө= 𝑛 𝑆 =
𝑉𝑚
𝑖=0 𝑖
𝑛
𝑉𝑚 ∝ 𝑖=0 𝑆𝑖
The rest is complex mathematics to evaluate the summations ! ( power series expansions, differentiation,
necessary substiutions and some simplifications).

𝑉 𝐶𝑋
𝑉𝑚 = BET Equation BET Profile
1−𝑋 [1+ 𝐶−1 𝑋]
The Brunauer-Emmett-Teller (BET) Isotherm

The condition that V →∞ is seen to correspond to X = 1 acc. to BET eqn. Recalling the definition
𝑘𝑎 𝑃
of X ( i.e. 𝑋 = ) and that V → ∞ as P → Po permits us to write:
𝑘𝑑,𝑖

𝑘𝑎 1 𝑘𝑎 𝑃
1=
𝑘𝑑,𝑖
Po then
Po
=
𝑘𝑑,𝑖
∴ we can write: 𝑋 = 𝑃𝑜

Thus, the independent variable in BET theory is the pressure relative to the saturation pressure.

∴ BET describes the volume of gas adsorbed at different 𝑃𝑃 in terms of 𝑉𝑚 and 𝐶.

𝑜
 The Brunauer-Emmett-Teller (BET) Isotherm
In case of solute adsorption from solution:
- Use ‘’c’’ (i.e conc) instead of ‘’P’’
- Use ‘’cs’’ instead of ‘’Po’’
ℰ −ℰ𝑠
- Use ‘’B’’ instead of ‘’C’’ where: 𝐵 = exp 𝓔𝑠 = energy for saturation
𝑘𝐵 𝑇
𝑐
𝐵 ( )
𝑞 cs
𝑞𝑚𝑎𝑥= 𝑐 𝑐 BET Equation
1− [1+ 𝐵−1 ] BET Profile
cs cs
The Brunauer-Emmett-Teller (BET) Isotherm

Linearized BET eqn

𝒄 𝟏 𝑩−𝟏 𝒄
= 𝒎𝒂𝒙
+
𝒒(𝒄𝒔 − 𝒄) 𝑩𝒒 𝑩𝒒𝒎𝒂𝒙 𝒄𝒔

This eqn is for solutions but similarly you can generate the one for gas adsorption
In Langmuir type, we saw how the saturation limit could be related to the Asp
(specific surface area) of the adsorbent.

In BET equation, qmax corresponds to the max capacity if the adsorption

were limited to a monolayer. ∴ qmax in the BET equation can be used
to calculate the Asp of adsorbent.

𝑛 Asp
∴ 𝑊 𝑠𝑎𝑡
=
𝑁𝐴 𝜎 𝑜
 Freundlich Adsorption Isotherm
One other equation for isothermal adsorption is Freundlich Isotherm.
This equation is a special case for heterogeneous surface energies in
which the energy term, b, in the Langmuir Eqn varies as a function of
surface coverage, qe, strictly due to variations in the heat of
adsorption.
1/𝑛
𝑞𝑒 = 𝐾𝐹 𝑐𝑒 Freundlich Eqn (emprical)

Where: 𝐾𝐹 and 𝑛 are constants. n>1 (usually)

Note: Freundlich eqn although emprical, may be derived by assuming a certain

distribution function for sites having different ΔG° value for the process and
assuming Langmuir adsorption at each type.
Freundlich Adsorption Isotherm
Linearized form:
1
log 𝑞𝑒 = log 𝐾𝐹 + log 𝑐𝑒
𝑛
Langmuir vs Freundlich
If n=1, Freundlich isotherm becomes 𝑞𝑒 = 𝐾𝐹 𝑐𝑒 which is
identical to the low-concentration limit of the Langmuir
isotherm (i.e. 𝒒𝒆 = 𝑸𝒐 𝒃 𝒄𝒆)

If n= ∞, Freundlich isotherm becomes 𝑞𝑒 = 𝐾𝐹 which is

identical to the high-concentration limit of the Langmuir
isotherm (i.e. 𝒒𝒆 = 𝑸𝒐 )
To be continued with subjects:

• Rate of Adsorption
• Factors affecting the adsorption
• Detergency