Models for Adsorption Isotherms

(1) Langmuir Adsorption Isotherm

Assumptions:
(a) Surface is (energetically) homogeneous
(b) Each site adsorb only one atom/molecule
(c) No interactions between adsorbed atoms/molecules
Limitations:
(a) Energetic heterogeneity cannot be handled
(b) Only monolayer coverage can be handled; multi-layer adsorption not allowed
(1)

Temperature dependency is incorporated into the affinity parameter b through

(2)

Q is the activation energy for desorption.

The isosteric (isoster means curves with constant loading i.e. fractional occupancy) is
defined as
ln
1

ln
(3)

Note that the derivative in Eq. (3) can also be taken at constant fractional loading , if
the saturation loading Cmax (or Nmax) is constant.

Although according to the original development, the saturation loading is fixed the
Langmuir development was later modified for better description of the experimental
data by incorporating a temperature dependency to the parameter Nmax also through the
following equation (exponentially decreases with temperature).

(4)

The isosteric heat of adsorption incorporating the temperature dependency for both the
affinity parameter b and the saturation loading Nmax is given by
(5)

If (as in the usual case) the saturation loading is invariant with temperature, then
0 and Eq. (5) reduces to
(6)

Note that this is a measure of the strength of interactions.

At the Henrys law limit (P 0) Eq. (1) reduces to
lim

(7)

The Henrys constant is

lim

(8)

At the saturation limit,

lim

(2) Freundlich Adsorption Isotherm

Advantages:
(a) Can handle heterogeneous surfaces (through the parameter n)

(9)

Limitations:
(a) Not applicable at very low pressures (Henrys law limit)
(b) Not applicable at high loading (saturation limit)
The isotherm is given by
/

(10)

The temperature dependency of the parameters K and n is incorporated through

(11)

1
where , K0 and A0 are the temperature dependency parameters.
(3) Sips Adsorption Isotherm

/
/

(12)

The temperature dependency is incorporated through,

1
1

1
,

where

and

(13)
1

are the values at the reference temperature T0. Q,

the parameters that describe the temperature dependency.

Advantages:
(a) Can handle heterogeneous surfaces (through the parameter n)
(b) Has well defined saturation limit.

and

are

lim

Limitations:
(c) Not applicable at very low pressures (Henrys law limit)

(4) Toth Adsorption Isotherm

(14)

The temperature dependency is incorporated through,

1
1
,

where

and

(15)
1

are the values at the reference temperature T0. Q,

and

the parameters that describe the temperature dependency.

Advantages:
(a) Can handle heterogeneous surfaces (through the parameter n)
(b) Has well defined saturation limit.
lim

(c) Has well defined Henrys law limit. The Henrys constant is
lim

lim

(16)

are

Problem 1:

Consider the following data for adsorption of propane on activated carbon taken from Cheripally
et al. Journal of Chemical & Engineering Data 58(6):16061612 (2013).
T=293.15 K
P

0
2.560E-04
7.053E-04
2.084E-03
4.976E-03
1.029E-02
1.160E-02
6.925E-02
0.106
0.138
0.197
0.372
0.400
0.705
1.020
1.050
1.533
1.929
2.564
3.145
3.799
4.648

T=318.15 K

0
0.156
0.305
0.543
0.840
1.168
1.267
2.321
2.662
2.850
3.107
3.549
3.593
3.958
4.195
4.215
4.438
4.563
4.699
4.782
4.851
4.922

0
4.266E-04
1.572E-03
4.031E-03
5.677E-03
8.090E-03
9.581E-03
1.333E-02
1.381E-02
2.532E-02
5.728E-02
9.454E-02
0.113
0.189
0.379
0.713
1.052
1.060
1.571
1.933
2.565
3.203
3.841
4.724

T=358.15 K

0
0.108
0.266
0.459
0.503
0.657
0.683
0.866
0.844
1.128
1.587
1.923
2.041
2.407
2.903
3.337
3.599
3.606
3.863
3.994
4.166
4.293
4.390
4.487

0
1.028E-03
3.797E-03
9.512E-03
1.600E-02
3.332E-02
5.596E-02
8.792E-02
0.107
0.190
0.369
0.696
1.050
1.117
1.593
1.974
2.598
3.256
3.958
4.886

0
0.067
0.176
0.315
0.443
0.637
0.840
1.045
1.141
1.469
1.910
2.383
2.696
2.745
3.003
3.156
3.353
3.508
3.638
3.777

Perform the following isotherm model fits and obtain the parameters. For each case, compare
the experimental data with the calculated value from the fits.

(a) Langmuir, Freundlich, Sips and Toth isotherm for each temperature individually
(b) Langmuir isotherm including temperature dependency for parameter b (consider Nmax to
be constant)
(c) Langmuir isotherm including temperature dependency for parameter b as well as Nmax
(d) Freundlich isotherm with temperature dependency for both K and n.
(e) Toth isotherm with temperature dependency for b and Nmax, consider t to be a constant
and independent of temperature.
Use Matlab or any suitable software for obtaining the results.