10/17/2022

Chapter 4-2
Adsorption from Solution

Equilibrium Models (Batch Adsorption)

Adsorption Equilibria
1. Linear
2. Langmuir
3. Freundlich

The most commonly used isotherms for the application of activated carbon in water and
wastewater treatment are the Freundlich and Langmuir isotherms. Freundlich
isotherm is an empirical equation.
Langmuir isotherm has a rational basis.

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1. Linear Adsorption

qe is the amount of solute adsorbed at equilibrium (mg/g or g/g or mmol/g or mol/g)

Ce is the concentration left in solution at equilibrium (Equilibrium Concentration)

This type of constant partition is rare to find on solid surface

2. Langmuir Isotherm Model

1. Monolayer coverage, qe
(mg/g)
2. Equilibrium model,
3. All adsorption sites are equally probable,
4. Active sites are homogenous
5. No interaction between neighbor adsorbates
Ce (mg/L)
𝑞.𝑏.𝐶𝑒
qe =
1+𝑏.𝐶𝑒
qe is the amount of solute adsorbed (mg) per unit mass of adsorbent (g) at equilibrium,
Ce is the equilibrium concentration of the molecule (mg/L),
q is the amount of solute adsorbed per unit weight of adsorbent required for monolayer saturation of the surface, or monolayer
capacity;
b (L/mg) is Langmuir constant.

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Langmuir Constant b
b (L/mg) is the adsorption equilibrium constant that is related to the heat
of adsorption following equation  H

b  bo e RT
where bo (L/mg) is a constant, ΔH is the relative energy of adsorption and R is the gas constant.

Linearized Langmuir equation

qe
(mg/g)
𝐶𝑒 1 𝐶𝑒
= +
𝑞𝑒 𝑏. 𝑞 𝑞
Ce/qe
Slope = 1/q

Intercept = 1/b.q Ce (mg/L)

S = 1/q

Ce (mg/L)

Another linearized form

1
1 1 1 1 𝑞𝑒
= + .
𝑞𝑒 𝑞 𝑏.𝑞 𝐶𝑒
1
S=
1 𝑏.𝑞
Slope =
𝑏.𝑞 1
𝑞
1
Intercept =
𝑞 1
𝐶𝑒
q = maximum adsorption or monolayer capacity (mg/g)
b = Langmuir constant

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Separation factor, Rs & Adsorption favorability

The isotherm shape may be assumed with a view to predict if an

adsorption system is “favorable” or “unfavorable”.
Hall et al. Equation (1966)
1
Rs 
(1  bCo )
Rs value Isotherm Type
Rs = Separation Factor (dimentionless factor) Rs>1 Unfavorable
b = Langmuir constant (L/mg) Rs= 1 Linear
Co = Initial Concentration (mg/L)
0<Rs<1 Favorable
Rs= 0 Irreversible

0< Rs < 1 Favorable Adsorption

Adsorption isotherm shape ( 0<Rs<1) Application of Langmuir Equation

90 0.7
80 0.6
70
qe (adsorbed (mg/g)

0.5
60
Ce/qe (mg/l)

0.4
50
40 0.3
30 0.2
20 0.1
10
0
0
0 20 40 60
0 20 40 60 Ce (mg/L)
Ce (mg/L)

b is intermediate value (not large or very small)

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Rs = 0, Irreversible adsorption
Adsorption isotherm shape ( 0<Rs<1) Application of Langmuir Equation

0.7
90
80 0.6
70 0.5
60 0.4

Ce/qe (g/L)
50
Qe (mg/g)

0.3
40
30 0.2
20 0.1
10 0
0 0 20 40 60
0 20 40 60 Ce (mg/L)
Ce (mg/L)

b is large value

Rs = 1, Linear
Adsorption isotherm shape ( 0<Rs<1) Application of Langmuir Equation

120 1.2

100 1
Ce/qe (g/L)
qe (mg/g)

80 0.8

0.6
60
0.4
40
0.2
20
0
0 50 100 150
0
0 50 100 150 Ce (mg/L)
Ce, mg/L

b is very small

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Rs > 1 Unfavorable

9
8
80
70 7
60 6
50 5

Ce/qe
40 4
qe (mg/g)

30 3
20 2
10 1
0 0
0 20 40 60 0 20 40 60
Ce (mg/L) Ce (mg/L)

b has a negative value

3. Freundlich Isotherm qe
(mg/g)
Empirical Equation and very widely used
/𝑛
𝑞𝑒 = 𝐾𝐶𝑒1

K is Freundlich constant Ce (mg/L)

K is an indicator of adsorption capacity.
The higher the maximum capacity, higher the K.

1/n is a measure of the intensity of adsorption.

The Higher the 1/n value (the smaller n),
The more favorable is the adsorption

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Linearized form of Freundlich Equation

1
Log Ce = log K + log Ce Log qe
𝑛

Slope = 1/n

Intercept = log K

Log
How to investigate the fitting of Model Ce
Check the linear form and calculate R2

Higher R2 means better fitting to the model.

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Training

Thermodynamics of Adsorption From Solution

Thermodynamic parameters are calculated from the change of equilibrium
constant Kc, at two different temperatures

Kc is given in Eq. 4.5.

Kc = CAe/ Ce
Kc = CAe/ Ce

where CAe is the amount sorbed on a sorbent at equilibrium (mg/L),

Ce is the equilibrium concentration (mg/L).
Kc is estimated from the initial part of the adsorption isotherm in which qe
versus Ce is linear.

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Gibbs Free Energy Change (ΔG°) can be measured from Kc

ΔGo = -RTlnKc
Equation 4.4

R universal gas constant in terms of energy

= 8.314 Joule per Kelvin per mole

The enthalpy (ΔHo) can be calculated from Van’t Hoff equation for two
temperatures

Kc2 H o 1 1 where Kc1 and Kc2 are the equilibrium constants at

ln( ) (  )
K c1 R T1 T2 T1 and T2 (absolute temperature), respectively.

Enthalpy Change using 3 temperature points or higher

van’t Hoff equation
S o H o
ln Kc  
R RT
Plotting ln Kc versus 1/T for the wet and dry carbons for both metals shows straight lines

ln Kc ln Kc

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Knowing both ΔGo and H o, the entropy change ΔSo, can be calculated
from the following equation (Eq. 4.8).

Go = H o- TSo

If Go is positive non-spontaneous (unfoavorable)

If Go is negative spontaneous (favourable)
If H o is positive Endothermic process
If H o is negative Exothermic process

So is usually negative but for adsorption from solution , it could be

positive due to changes in solutions like ion exchange,...

BET Equation for Adsorption from Solution

For the BET isotherm wType equation here.e can arrange the isotherm
equation to get
𝐶𝑒 𝐾𝐵𝐸𝑇 −1 𝐶𝑒 1
𝐶𝑜−𝐶𝑒 𝑞𝑒
= .
𝐾𝐵𝐸𝑇.𝑞 𝐶𝑜
+ 𝐾𝐵𝐸𝑇.𝑞
1
Intercept = 𝐾
𝐵𝐸𝑇.𝑞 𝑲𝑩𝑬𝑻 − 𝟏
𝟏 𝑲𝑩𝑬𝑻. 𝒒. 𝑪𝒐
𝐾𝐵𝐸𝑇 −1
Slope = 𝑲𝑩𝑬𝑻. 𝒒
𝐾𝐵𝐸𝑇.𝑞.𝐶𝑜

1 𝑆𝑙𝑜𝑝𝑒
𝑞= 𝐾𝐵𝐸𝑇 = 1 +
𝑆𝑙𝑜𝑝𝑒 + 𝐼𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 𝐼𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡

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Problem
• For the adsorption of Cu(II) from solution at 25 and 35 oC, Kc1 = 1.7,
Kc2 = 2.1, respectively.
Calculate thermodynamic parameters and comment on the results.

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