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Adsorption Isotherms
A relation between the amount of adsorbate adsorbed on a
given surface at
constant temperature and the equilibrium concentration of
the substrate in contact
with the adsorbent is known as Adsorption Isotherm. They
are generally classified
in the five main categories. In Figure 3.2, adsorbate partial
pressures (P) are
normalized by dividing by the saturation pressure at the
temperature in question
(P0)
Type I, referred to as Langmuir-type adsorption, is
characterized by a monotonic
approach to a limiting amount of adsorption, which
presumably corresponds to
formation of a monolayer. This type of behaviour is that
expected for
chemisorption. No other isotherms imply that one can
reach a saturation limit
corresponding to completion of a monolayer.
Type II is typical of the behaviour normally observed for
physical adsorption. At
values of P∕P0 approaching unity, capillary and pore
condensation phenomena
occur. The knee of the curve corresponds roughly to
completion of a monolayer. A
statistical monolayer is built up at relatively low values of
P∕P0 (0.1 to 0.3).
Type IV behaviour is similar to type II behaviour except that
a limited pore volume
is indicated by the horizontal approach to the right-hand
ordinate axis. This type of
curve is relatively common for porous structures of many
kinds. Hysteresis effects
associated with pore condensation are often, but not
always, encountered in this
type of system. They arise from the effects of surface
curvature on vapour pressure.
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Types III and V are relatively rare. They are typical of cases
in which the forces
giving rise to monolayer adsorption are relatively weak.
Type V differs from type III
in the same manner that type IV differs from type II.
Freundlich Adsorption Isotherm
It is an empirical relation between the amount of an
adsorbate adsorbed per unit
weight (x/m, mg/g) of adsorbent and the adsorbate
equilibrium concentration
(Ce,moles/l) in the fluid as follows:
Where, K and n are Freundlich coefficients
x = weight of adsorbate adsorbed on m unit weight of
adsorbent
Ce = equilibrium concentration of adsorbate
From equation (3.1), we get
(3.2)
The coefficients K and n can be determined from the
intercept and slope of a plot of
log(x/m) versus logCe.
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Langmuir Adsorption Isotherm
In the Langmuir model the adsorbent surface is considered
to possess a number of
active interaction sites for adsorption. Langmuir derived a
relation between
adsorbed material and its equilibrium concentration. His
assumptions are:
1. There are fixed adsorption sites on the surface of the
adsorbent. At a given
temperature and pressure some fraction of these sites are
occupied by
adsorbate molecules. Let this fraction be θ
2. Each site on the surface of the adsorbent can hold one
adsorbate molecule.
3. The heat of adsorption is the same for each site and is
independent of .
4. There is no interaction between molecules on different
sites.
Since the adsorption is limited to complete coverage by a
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monomolecular layer, the
surface may be divided into two parts: the fraction θ
covered by the adsorbed
molecules and the fraction 1 – θ, which is bare. Since only
those molecules striking
the uncovered part of the surface can be adsorbed, the rate
of adsorption per unit
of total surface will be proportional to 1 – θ; that is,
(3.3)
The rate of desorption will be proportional to the fraction of
covered surface
(3.4)
At equilibrium,
Rate of adsorption = Rate of desorption
Where,
K = k/k’ is adsorption equilibrium constant, expressed in
units of (pressure)
–1.
The concentration form of Eq. (3.5) can be obtained by
introducing the concept of
an adsorbed concentration , expressed in moles per gram
of catalyst. If
represents the concentration corresponding to a complete
monomolecular layer on
the catalyst, then the rate of adsorption, (moles/s. g
catalyst) is, by analogy with
Eq.(3.3),
(3.6)
Where is the rate constant for the catalyst and is the
concentration of
absorbable component in the gas. Similarly, Eq.3.4
becomes
(3.7)
At equilibrium the rates given by Eqs. (3.6) and (3.7) are
equal, so that
Slope of which will be and
Intercept as .
For chemisorptions Langmuir’s equation works very well
but fails for the cases where
multilayer formation takes place.
Multilayer Adsorption – BET Isotherm
Important assumption of Langmuir theory is the formation
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of monolayer. Because
of monolayer formation saturation in adsorption would
reach at higher equilibrium
concentration of the adsorbate. This type of adsorption
occurs due to short range
chemical forces which do not allow penetration through the
primary adsorbed
molecules. Multilayer formation has been observed when
molecules are adsorbed
through weak forces (long range forces normally under
physical adsorption) due to
cohesive forces exerted by the molecules of the adsorbate.
At high pressure multilayer adsorption takes place. The
theory of multimolecular
(multilayer) adsorption was developed by Stephen
Brunauer, Paul Emmet and
Edward Teller and is called BET isotherm. This isotherm
derived by them
successfully accounts for all types of adsorption.
It assumes that the surface possesses uniform, localized
sites and that adsorption
on one site does not affect adsorption on neighboring sites
just as in Langmuir
theory. Also, molecules can be adsorbed in second, third
and nth layers with the
surface available for layer equal to the coverage of the next
lower layer. The
development is briefly summarized as follows: Equation 3.5
can be rearranged to
the form
(3.10)
Brunauer, Emmet and Teller adapted this equation of
multilayer adsorption and
arrived at the result
(3.11)
Where p0 is the saturation or vapor pressure and c is a
constant for the particular
temperature and gas-solid system.
According to Eq.(3.11), a plot of
should give a straight line. The intercept and slope the
straight line can be given as,
(3.12)
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(3.13)
Solving these equations for the volume of adsorbed gas
corresponding to a
monomolecular layer gives
(3.14)
The volume can be readily converted to the number of
molecules adsorbed.
(3.15)
Where N0 is Avogadro's number, 6.02 × 1023
molecules/mole, and V is the volume
per mole of gas at conditions of vm· Since vm is recorded at
standard temperature
and pressure, V = 22,400 cm3/g mole.
Where N0 is Avogadro's number, 6.02 × 1023
molecules/mole, and V is the volume
per mole of gas at conditions of vm· Since vm is recorded at
standard temperature
and pressure, V = 22,400 cm3/g mole.
However, to determine the absolute surface area it is
necessary to select a value for
the area covered by one adsorbed molecule. If this is , the
total surface area is
given by
(3.16)
If vm is based on a 1 g sample, then Sg is the total surface
per gram of solid
adsorbent. Emmett and Brunauer proposed that is the
projected area of a
molecule on the surface when the molecules are arranged
in close two-dimensional
packing. This value is slightly larger than that obtained by
assuming that the
adsorbed molecules are spherical and their projected area
on the surface is
circular. The proposed equation is
Where M is molecular weight and is the density of the
adsorbed molecules. For N2
at –195.8°C, = 0.808 g/cm3, the area per molecule from is
16.2 × 10–16 cm2, or
"convert my exam preparation" and easy to understand
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To help with your exam preparation and make the concepts easier to understand, here's a
simplified breakdown of the key points:
Adsorption Isotherms
An adsorption isotherm shows the relationship between the amount of adsorbate (substance
being adsorbed) and its equilibrium concentration in contact with the adsorbent at a
constant temperature. Adsorption isotherms are classified into five types.
Types of Adsorption Isotherms:
1. Type I (Langmuir Adsorption):
Monolayer adsorption (one layer of adsorbate molecules on the surface).
The adsorption reaches a maximum limit.
Common in chemisorption (strong bonding between adsorbate and adsorbent).
2. Type II:
Physical adsorption (weaker forces between adsorbate and adsorbent).
Shows capillary condensation at high pressures.
Monolayer formation happens at low pressures.
3. Type IV:
Similar to Type II but with a limited pore volume.
Hysteresis effects (differences in adsorption and desorption curves due to pore
condensation).
4. Types III and V:
Less common.
Occur when the forces causing adsorption are weak.
Type V differs from Type III similarly to how Type IV differs from Type II.
Freundlich Adsorption Isotherm
This is an empirical relationship for adsorption, and it is expressed as:
x
= KCe1/n
m
Where:
x
m = amount of adsorbate adsorbed per unit weight of adsorbent (mg/g).
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Ce = equilibrium concentration of adsorbate (moles/l).
K and n are constants (coefficients for the system).
To find K and n, plot log(x/m) versus log(Ce ) and determine the slope and intercept.
Langmuir Adsorption Isotherm
Langmuir's model assumes:
1. Fixed adsorption sites on the adsorbent surface.
2. Each site can hold one adsorbate molecule.
3. Adsorption heat is constant and independent of coverage.
4. No interaction between adsorbate molecules on different sites.
The rate of adsorption is proportional to the uncovered sites (1 - θ), and the rate of
desorption is proportional to the covered sites (θ). At equilibrium, the rate of adsorption
equals the rate of desorption.
The Langmuir equation is:
θ
= KCe
1−θ
Where θ is the fraction of covered sites and K is the adsorption equilibrium constant.
BET (Brunauer-Emmet-Teller) Isotherm for Multilayer Adsorption
The BET isotherm is used for multilayer adsorption (more than one layer of adsorbate
molecules). It accounts for adsorption due to weak forces (like physical adsorption). This is
different from Langmuir, which assumes monolayer adsorption.
The BET equation is:
1 1 p 1
= ( )+
(V /Vm ) − 1
C p0 C
Where:
V = volume of adsorbed gas at pressure p.
Vm = volume corresponding to a monolayer.
p0 = saturation pressure.
p = equilibrium pressure.
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C = constant related to adsorption energy.
A plot of (V /V1 )−1 versus p gives a straight line, and from the slope and intercept, you can
p
m
0
calculate the surface area and other properties.
Key Equations for BET:
1. Monolayer Adsorption Volume:
V
Vm =
1 − (p/p0 )
2. Surface Area Calculation:
V m N0 A
Sg =
V
Where N0 is Avogadro's number and A is the area covered by one molecule.
Summary:
Langmuir: Assumes monolayer adsorption, suitable for chemisorption.
Freundlich: Empirical, describes adsorption at varying pressures.
BET: Accounts for multilayer adsorption, ideal for physical adsorption.
By understanding these models, you'll be able to predict and analyze adsorption behaviors
based on the type of interaction between the adsorbate and adsorbent.
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