University of Anbar

Engineering College
Chemical and Petrochemical Engineering Department
Langmuir Isotherm
Prepared by:
Sufyan Hamd Hasn
Tiba Aziz Yas
Younis Khamees Mohamad
Hashim Mohamad Humady
Supervisor:
Sufyan Ahmed

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  Abstract

Langmuir adsorption isotherm equation is generally derived using the kinetics

approach and based on some assumptions. These assumptions are usually not
accompanied by an adequate explanation related with the mechanisms and the
determination techniques of its adsorption constants. Also, in this study, we will
discuss adsorption equilibria for multicomponent system, and by using the simplest
theory for describing multicomponent equilibria, the extended Langmuir isotherm
equation. And finally, modification of Langmuir isotherm.

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 1. Introduction

Adsorption arises as a result of the unsaturated and unbalanced molecular forces that
are present on every solid surface. Thus, when a solid surface is brought into contact
with a liquid or gas, there is an interaction between the fields of forces of the surface
and that of the liquid or the gas. The solid surface tends to satisfy these residual forces
by attracting and retaining on its surface the molecules, atoms, or ions of the gas or
liquid. This results in a greater concentration of the gas or liquid in the near vicinity of
the solid surface than in the bulk gas or vapor phase, despite the nature of the gas or
vapor. The process by which this surface excess is caused is called adsorption. The
adsorption involves two types of forces: physical forces that may be dipole moments,
polarization forces, dispersive forces, or shortrange repulsive interactions and chemical
forces that are valency forces arising out of the redistribution of electrons between the
solid surface and the adsorbed atoms [1].

Physical adsorption can be distinguished from chemisorption according to one or more

of the following criteria:

1-Physical adsorption does not involve the sharing or transfer of electrons and thus
always maintains the individuality of interacting species. The interactions are fully
reversible, enabling desorption to occur at the same temperature, although the process
may be slow because of diffusion effects. Chemisorption involves chemical bonding and
is irreversible.

2-Physical adsorption is not site specific; the adsorbed molecules are free to cover the
entire surface. This enables surface area measurements of solid adsorbents. In contrast,
chemisorption is site specific; chemisorbed molecules are fixed at specific sites.

3-The heat of physical adsorption is low compared to that of chemisorption; however,

heat of adsorption is not usually a definite criterion. The upper limit for physical
adsorption may be higher than 20 kcal/mol for adsorption on adsorbents with very
narrow pores. The heat of chemisorption ranges from over 100 kcal/mol to less than 20

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kcal/mol. Therefore, only very high or very low heats of adsorption can be used as a
criterion for this type of adsorption process [2].

2. Langmuir Adsorption Isotherm

The basic assumptions underlying Langmuir's model, which is also called the ideal
localized monolayer model, are:

1-The molecules are adsorbed on definite sites on the surface of the adsorbent.

2-Each site can accommodate only one molecule (monolayer).

3-The area of each site is a fixed quantity determined solely by the geometry of the
surface.

4-The adsorption energy is the same at all sites.

In addition, the adsorbed molecules cannot migrate across the surface or interact with
neighboring molecules. The Langmuir equation was originally derived from kinetic
considerations. Later, it was derived on the basis of statistical mechanics,
thermodynamics, the law of mass action, theory of absolute reaction rates, and the
Maxwell-Boltzmann distribution law.

The kinetic derivation considered the adsorbed layer to be in dynamic equilibrium with
the gas phase. A certain fraction of the molecules striking the bare sites will condense
and be held by the surface forces for a finite time and are regarded as adsorbed; the
remainder will be reflected. Those molecules striking sites that are already occupied
will immediately re-evaporate as if they had been reflected. If the fraction of the site
already filled isθ , then:

Rate of adsorption ¿ k a P ( 1−θ ) (2.1)

Rate of desorption ¿ k d θ (2.2)

Where k a= rate of adsorption, and k d= rate of desorption from a fully covered surface.

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At equilibrium the number of molecules in the adsorbed state at any instant is constant;
therefore:

k a P ( 1−θ )=k d θ (2.3)

θ ka
And = P (2.4)
1−θ k d

Taking k a /k d = b, which is the adsorption equilibrium constant, Equation (2.4) becomes:

θ
bP= (2.5)
1−θ

bP
Or θ= (2.6)
1+bP

Which is known as the Langmuir adsorption isotherm.

If V is the volume of gas adsorbed at pressure, P, andV m is the volume adsorbed at

infinite pressure—that is, when all the sites are occupied—then:

V
θ= (2.7)
Vm

And Equation (2.6) becomes:

V m bP
V= (2.8)
1+bP

This expression shows that V approaches V m asymptotically as Papproaches infinity. V m

is supposed to represent a fixed number of surface sites, and it should, therefore, be a
temperature-independent constant while the temperature dependence of the
equilibrium constant should follow a van't Hoff equation:

−∆ H
b=b° e RT (2.9)

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Since adsorption is exothermic (∆ H negative), b should decrease with increasing
temperature.

For adsorption from solution by solid adsorbents, the Langmuir adsorption isotherm is
expressed as:

X m b Ce
X= (2.10)
1+ b Ce

Where X = x/m, the amount of solute adsorbed, x, per unit weight of adsorbent, m; C e =
equilibrium concentration of the solute; X m= amount of solute adsorbed per unit weight
of adsorbent required for monolayer coverage of the surface also called monolayer
capacity; and b = a constant related to the heat of adsorption, [b ∝ ( e− ∆ H / RT ) ]

Equation (2.10) indicates that X approaches X masymptotically asC e approaches infinity.

For linearization of the data, Equation (2.10) can be written in the form:

Ce 1 C
= + e (2.11)
X b Xm Xm

When C e / X is plotted againstC e, a straight line, having a slope 1/ X m and an intercept

1/b X m , should result. Another linear form can be obtained by dividing Equation (2.11)

by C e:

1 1 1 1
= +( )( ) (2.12)
X Xm Ce b X m

Plotting 1/ X against 1/C e a straight line, having a slope 1/b X m and an intercept 1/ X m , is
obtained.

The monolayer capacity, X m, determined from the Langmuir isotherm, defines the total
capacity of the adsorbent for a specific adsorbate. Also, it may be used to determine the
specific surface area of the adsorbent by utilizing a solute of known molecular area.

It must be indicated that conformity to the algebraic form of Langmuir's equation does
not constitute conformity to the ideal localized monolayer model, even if reasonable

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values of b and X m are obtained. Therefore, a constant value of b may be a result of
cancellation of variations in∆ H [3].

3. Langmuirian Multicomponent Theory (Kinetic approach)

The treatment of the extended Langmuir isotherm of a binary system is due to

Markham and Benton (1931). Here, we present the general treatment for a
multicomponent gaseous system containing N species. The assumptions made by
Langmuir in the treatment of pure component systems are applicable to
multicomponent systems as well, that is each site occupying only one molecule, no
mobility on the surface, and constant heat of adsorption. We assume that the rate
constants for adsorption and desorption for all species are invariant.

The rate of adsorption of the species i onto the solid surface is

(
Ra ,i=k a ,i Pi 1−∑ θ j
j=1
) (3.1)

Where θ jis the fractional coverage of the species j and k a ,i is the rate constant for
adsorption and from the kinetic theory of gases it is given by

∝i
k a ,i = (3.2)
√2 π M i RT

In which we have assumed that the rate of adsorption is due to the rate of collision of
molecules towards the surface. Here ∝iis the sticking coefficient of the species (i). Here,
the rate of adsorption of the species (i) is proportional to the partial pressure of that
species and to the fraction of the vacant sites on the surface, namely

( 1−∑ θ j
j =1
) (3.3)

The rate of desorption of the species (i) is proportional to its fractional loading

Rd ,i=k d ,i θi (3.4)

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Here the rate of desorption of a species is unaffected by the presence of all other
species. In general, one would expect that the rate constant for desorption k d ,i is a
function of fractional loadings of all other species. However, it is treated as a constant in
this analysis because of the one molecule per site and the no lateral interaction
assumptions in the Langmuir mechanism.

At equilibrium, the rate of adsorption of the species (i) (eq. 3.1) is equal to the rate of
desorption of that species (eq. 3.4):

b i Pi ( 1−θT )=θi (3.5)

Where b iis the ratio of the rate constant for adsorption to that for desorption, and θT is
the sum of fractional loadings of all species:

k a ,i
b i= (3.6)
k d ,i

N
θT = ∑ θ j (3.7)
j=1

Summing (eq. 3.5) with respect to (i) over all species, we can solve for the total
fractional coverage in terms of the partial pressures of all components:

∑ b j Pj
j=1
θT = N (3.8)
1+ ∑ b j P j
j =1

And hence the fraction of the vacant sites is:

1
1−θ T = N
(3.9)
1+ ∑ b j P j
j=1

Knowing this total fractional coverage (eq. 3.7 & 3.8), the fractional coverage
contributed by the species (i) is then obtained from eq. (3.5), that is

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 bi P i
θi = N
(3.10)
1+ ∑ b j P j
j=1

or written in terms of molar concentration, we get

C μ ,i b i Pi
= N
C μs ,i (3.11)
1+ ∑ b j P j
j =1

This equation is known as the extended Langmuir isotherm equation, which gives the
adsorbed concentration of the species (i) in the multicomponent system. For a binary
system, Figure (3.1) shows plots of the fractional coverage of the component 1 versus
b 1 P1with the parameter b 2 P2as the varying parameter. We see that the presence of the

additional component 2 causes a decrease in the surface concentration of the

component 1 and vice versa due to the competition of the two species. The reduction in
the adsorbed concentration of the species 1 is

1+ b1 P1
1+ b1 P1 +b 2 P2

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 Figure (3.1): Plot of the fractional loading of the component 1 versus b 1 P1

The selectivity of species (i) in relation to the species (j) is defined as:

Si , j =¿ ¿ (3.12)

Which is equal to the ratio of the affinities of the corresponding two species.

(eq. 3.11) has assumed that each species maintains its own surface area (i.e. the area
covered by one species is not affected by the others). The thermodynamic consistency
of eq. (3.11) is only possible when the monolayer capacity is the same for all species,
that is C μs ,i=C μs , j

For binary systems where C μs ,1 ≠ C μs ,2 , the following formula might be used to calculate
the monolayer capacity:

1 x1 x2
= + (3.13)
C μs C μs ,1 C μs ,2

Where x 1and x 2are mole fractions of the adsorbed species, defined as

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 C μ ,1
x 1= (3.14)
C μ ,1 +C μ ,2

C μ ,2
x 2= (3.15)
C μ ,1+C μ ,2

It is reminded that the extended Langmuir isotherm is derived assuming the surface is
ideal and the adsorption is localised, and one molecule can adsorb onto one adsorption
site [4].

4. Modification of Langmuir isotherm

The Langmuir kinetic equation, which is commonly used to describe monolayer

adsorption on the energetically homogeneous solid surfaces, can be given as:

dθ
=k a C (1−θ )−k a θ (4.1)
dt

−1
Where θ is the fractional surface coverage that is a dimensionless constant;k a ( L mg−1 min
−1
) and k d(min) are the adsorption and desorption rate constants, respectively; and C (

mg L−1) is the concentration of solute at time t. The nonlinear form of the Langmuir
isotherm at equilibrium is expressed as:

q max K C
q e= L e
(4.2)
1+ K L C e

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Whereq max (mg g−1) is the maximum adsorption capacity; K L( L mg−1) is the Langmuir
constant ( K L=k a /k d); Ce (mg L−1) is the concentration of solute at equilibrium. In order
to facilitate the following analyses, another form of Eq. (4.2) is written as:

qe
C e= (4.3)
K L ( qmax −q e )

Inspired by the fractal-like concept, we argue that solute molecules can be freely
adsorbed on the bare solid surface (homogeneous or heterogeneous) in the initial
phase of adsorption. As time goes on, solute molecules adsorbed on the solid surface
may affect adsorption paths of the incoming solute molecules and thus adsorption of
the incoming solute molecules on the solid surface is suffered from the fractional
surface coverage. Consequently, the adsorption rate constant is a function of the
fractional surface coverage. In this study, we introduce the fractal-like concept or the
fractional surface coverage dependence of the adsorption rate constant to the Langmuir
kinetic equation, which is expressed as:

k a=k a , 0 θ−h (0 ≤h ≥ 1) (4.5)

Where k a , 0( L mg−1 min−1) is the fractal-like adsorption rate constant, h is a constant

parameter.

When adsorption process reaches equilibrium, substitution of Eq. (4.5) into Eq. (4.1)
leads to

q(he +1)
C e= (4.6)
b qhmax (qmax −q e )

Where b ( L mg−1) is the fractal-like isotherm constant (b=k a ,0 / k d ). It is worthy to note

that introducing the fractal-like concept into the Langmuir kinetic equation extends the
application scope of the Langmuir isotherm. The fractal-like Langmuir isotherm can
describe solute adsorption on the heterogeneous surfaces .

In addition, Eq. (4.6) includes the description of the equilibrium between the feed
concentration C 0 and the saturation levelq 0, which may occur in the fixed-bed

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adsorption column. Dimensionless concentrations, Y = (q e /q0) and X = (C e /C 0), are
introduced to Eq. (4.6), resulting in

q 0 −h
C e (1+ b C0 ( ) )
q e (h+1) q max
( ) = (4.7)
q0 q e −h
C 0 (1+b C e ( ) )
q max

Similarly, according to the procedure proposed by Hall et al. A dimensionless constant

R H (i.e. the separation factor or equilibrium parameter) can be used to reflect the

essential characteristics of the fractal-like Langmuir isotherm, which is defined as:

1
RH=
q0 −h (4.8)
1+ b C0 ( )
q max

Although the saturation level q 0is expediently obtained for the influent concentration C 0
in the fix-bed experiment, q 0is difficult to be determined in batch experiments.We note
that:

1
RH ≤ (4.9)
1+b C 0

Herein, the favorable adsorption process can be also determined when the right side of
inequality 1/(1+C 0 )<1 in batch experiments. Substitution of Eq. (4.8) to Eq. (4.7) leads to

X
Y (h+1)= (4.10)
R H +(1−R H )X

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 References

[1] Activated Carbon Adsorption, Roop Chand Bansal & Meenakshi Goyal.

[2] Lowell, S. Introduction to Powder Surface Area. John Wiley & Sons, New York
(1979).

[3] Adsorption processes for water treatment, Samuel D. Faust & Osman M. Aly.

[4] Adsorption analysis: equilibria and kinetics, Duong D. Do.

[5] https://www.sciencedirect.com/science/article/abs/pii/S0167732218326606

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