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980

CHEMICAL ENGINEERING

of adsorption has been put forward which satisfactorily explains all systems. Fortunately
for the engineer, what is needed is an accurate representation of equilibrium, the theoretical
minutiae of which is not of concern. For this reason, some of the earliest theories of
adsorption are still the most useful, even though the assumptions on which they were
based were seen in later years to be not entirely valid. Most theories have been developed
for gassolid systems because the gaseous state is better understood than the liquid.
Statistical theories are being developed which should apply equally well to gassolid and
liquidsolid equilibria, though these are not yet at a stage when they can be applied easily
and confidently to the design of equipment.
The capacity of an adsorbent for a particular adsorbate involves the interaction of three
properties the concentration C of the adsorbate in the fluid phase, the concentration Cs
of the adsorbate in the solid phase and the temperature T of the system. If one of these
properties is kept constant, the other two may be graphed to represent the equilibrium.
The commonest practice is to keep the temperature constant and to plot C against Cs
to give an adsorption isotherm. When Cs is kept constant, the plot of C against T is
known as an adsorption isostere. In gassolid systems, it is often convenient to express
C as a pressure of adsorbate. Keeping the pressure constant and plotting Cs against T
gives adsorption isobars. The three plots are shown for the ammonia-charcoal system in
Figure 17.4 which is taken from the work of BRUNAUER(10) .

17.3.1. Single component adsorption


Most early theories were concerned with adsorption from the gas phase. Sufficient was
known about the behaviour of ideal gases for relatively simple mechanisms to be postulated, and for equations relating concentrations in gaseous and adsorbed phases to be
proposed. At very low concentrations the molecules adsorbed are widely spaced over the
adsorbent surface so that one molecule has no influence on another. For these limiting
conditions it is reasonable to assume that the concentration in one phase is proportional
to the concentration in the other, that is:
Cs = Ka C

(17.1)

This expression is analogous to Henrys Law for gasliquid systems even to the extent
that the proportionality constant obeys the vant Hoff equation and Ka = K0 e H /RT
where H is the enthalpy change per mole of adsorbate as it transfers from gaseous
to adsorbed phase. At constant temperature, equation 17.1 becomes the simplest form of
adsorption isotherm. Unfortunately, few systems are so simple.

17.3.2. The Langmuir isotherm


At higher gas phase concentrations, the number of molecules absorbed soon increases to
the point at which further adsorption is hindered by lack of space on the adsorbent surface.
The rate of adsorption then becomes proportional to the empty surface available, as well
as to the fluid concentration. At the same time as molecules are adsorbing, other molecules

ADSORPTION

Figure 17.4. Equilibrium data for the adsorption of ammonia on charcoal(10)


(a) Adsorption isotherm (b) Adsorption isobar (c) Adsorption isostere

981

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CHEMICAL ENGINEERING

will be desorbing if they have sufficient activation energy. At a fixed temperature, the rate
of desorption will be proportional to the surface area occupied by adsorbate. When the
rates of adsorption and desorption are equal, a dynamic equilibrium exists. For adsorption
which is confined to a mono-molecular layer, the equilibrium may be written as:
k0 a0 C = k0 (1 a1 )C = k1 a1
or:
a1 =
where: a0
a1
B0
k0
k1

B0 C
1 + B0 C

(17.2)

is the fraction of empty surface,


is the fraction of surface occupied by a monolayer of adsorbed molecules,
= k0 /k1 ,
is the velocity constant for adsorption on to empty surface, and
is the velocity constant for desorption from a monolayer.

Equation 17.2 has been developed for adsorption from the gas phase. It is convenient to
also express it in terms of partial pressures, which gives:
B1 P
Cs
=
Csm
1 + B1 P
where: Cs
Csm
B1
P

(17.3)

is the concentration of the adsorbed phase,


is the concentration of the adsorbed phase when the monolayer is complete,
= B0 /RT ,and
is the partial pressure of adsorbate in the gas phase
.

Equations 17.2 and 17.3 have the form of the LANGMUIR(11) equation, developed in 1916,
which describes the adsorption of gases on to plane surfaces of glass, mica and platinum.
A number of assumptions is implicit in this development. As well as being limited to
monolayer adsorption, the Langmuir equation assumes that:
(a) these are no interactions between adjacent molecules on the surface.
(b) the energy of adsorption is the same all over the surface.
(c) molecules adsorb at fixed sites and do not migrate over the surface.
When B1 P  1, equation 17.3 reverts to the form of Henrys Law, as given in
equation 17.1. Equation 17.3 can be rewritten in linear form to give:
P
P
1
=
+
Cs
Csm
B1 Csm

(17.4)

so that a plot of P /Cs against P will be a straight line when applied to a system that
behaves in accordance with the Langmuir isotherm.
It has been shown experimentally, however, that many systems do not follow this
isotherm and efforts continue to find an improved equation.

ADSORPTION

983

17.3.3. The BET isotherm


In 1938, BRUNAUER, EMMETT and TELLER(12) and EMMETT and DE WITT(13) developed what
is now known as the BET theory. As in the case in Langmuirs isotherm, the theory is
based on the concept of an adsorbed molecule which is not free to move over the surface,
and which exerts no lateral forces on adjacent molecules of adsorbate. The BET theory
does, however, allow different numbers of adsorbed layers to build up on different parts
of the surface, although it assumes that the net amount of surface which is empty or
which is associated with a monolayer, bilayer and so on is constant for any particular
equilibrium condition. Monolayers are created by adsorption on to empty surface and by
desorption from bilayers. Monolayers are lost both through desorption and through the
adsorption of additional layers. The rate of adsorption is proportional to the frequency
with which molecules strike the surface and the area of that surface. From the kinetic
theory of gases, the frequency is proportional to the pressure of the molecules and hence:
The rate of adsorption on to empty surface = k0 a0 P , and
the rate of desorption from a monolayer = k1 a1
Desorption is an activated process. If E1 is the excess energy required for one mole in the
monolayer to overcome the surface forces, the proportion of molecules possessing such
energy is eE1 /RT . Hence the rate of desorption from a monolayer may be written as:
A1 eE1 /RT a1
where A1 is the frequency factor for monolayer desorption.
The dynamic equilibrium of the monolayer is given by:
k0 a0 P + A2 eE2 /RT a2 = k1 a1 P + A1 eE1 /RT a1

(17.5)

where A2 is the frequency factor for description from a bilayer, thus creating a monolayer.
Applying similar arguments to the empty surface, then:
k0 a0 P = A1 eE1 /RT a1

(17.6)

From equations 17.5 and 17.6:


k1 a1 P = A2 eE2 /RT a2

and:

a1 =

k0 E1 /RT
e
a0 P = 0 a0
A1

(17.7)

a2 =

k1 E2 /RT
e
a1 P = a1
A2

(17.8)

The BET theory assumes that the reasoning used for one or two layers of molecules may
be extended to n layers. It argues that energies of activation after the first layer are all
equal to the latent heat of condensation, so that:
E2 = E3 = E4 = = En = M

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CHEMICAL ENGINEERING

Hence it may be assumed that is constant for layers after the first and:
ai = i1 a1 = B2 i a0
where B2 = 0 /, and ai is the fraction of the surface area containing i layers of adsorbate.
Since a0 , a1 , . . . are fractional areas, their summation over n layers will be unity and:
1 = a0 +

n


ai

i=1

= a0 +

n


B2 i a0

(17.9)

i=1

The total volume of adsorbate associated with unit area of surface is given by:
vs = vs1

n


iai = vs1

i=1

n


iB2 i a0

(17.10)

i=1

where vs1 is the volume of adsorbate in a unit area of each layer.


Since vs1 does not change with n, a geometrically plane surface is implied. Strictly,
equation 17.10 is not applicable to highly convex or concave surfaces. Equations 17.9
and 17.10 may be combined to give:
n


vs
=
vs1

iB2 i a0

i=1

a0 +

n


(17.11)
i

B2 a0

i=1

The numerator of equation 17.11 may be written as:


 n


 
d  i
d
1 n
= B2 a0

B2 a0
d i=1
d
1
and the denominator as:




1 n
a0 1 + B2
1

Substituting these values into equation 17.11 and rearranging gives:


B2 [1 (n + 1) n + n n+1 ]
vs
=
vs1
1 [1 + (B2 1) B2 n+1 ]

(17.12)

On a flat unrestricted surface, there is no theoretical limit to the number of layers that
can build up. When n = , equation 17.12 becomes:
B2
vs
=
1
vs
(1 )(1 + B2 )

(17.13)

ADSORPTION

985

When the pressure of the adsorbate in the gas phase is increased to the saturated vapour
pressure, condensation occurs on the solid surface and vs /vs1 approaches infinity. In
equation 17.13, this condition corresponds to putting = 1. It may be noted that putting
= 1/(1 B2 ) is not helpful.
Hence from equation 17.8:
k1
1 =  eM /RT P 0
A2
where: M is the molar latent heat and
P 0 is the saturated vapour pressure.
Hence, from equation 17.8, = P /P 0 .
Equation 17.12 may be rewritten for unit mass of adsorbent instead of unit surface.
This is known as the limited form of the BET equation which is:
Vs
P
[1 (n + 1)(P /P 0 )n + n(P /P 0 )n+1 ]
=
B
2 0
Vs1
P (1 P /P 0 )[1 + (B2 1)(P /P 0 ) B2 (P /P 0 )n+1 ]

(17.14)

where Vs1 is the volume of adsorbate contained in a monolayer spread over the surface
area present in unit mass of adsorbent.
When n = 1, adsorption is confined to a monolayer and equation 17.14 reduces to the
Langmuir equation.
When n = , (P /P 0 )n approaches zero and equation 17.13 may be rearranged in a
convenient linear form to give:
 
1
P /P0
B2 1 P
= 1 + 1
(17.15)
V (1 P /P0 )
V B2
V B2 P 0
where V and V 1 are the equivalent gas phase volumes of Vs and Vs1 .
If a plot of the left-hand term against P /P 0 is linear, the experimental data may be
said to fit the infinite form of the BET equation. From the slope and the intercept, V 1
and B2 may be calculated.
The advantage of equation 17.14 is that it may be fitted to all known shapes of
adsorption isotherm. In 1938, a classification of isotherms was proposed which consisted
of the five shapes shown in Figure 17.5 which is taken from the work of BRUNAUER
et al.(14) . Only gassolid systems provide examples of all the shapes, and not all occur
frequently. It is not possible to predict the shape of an isotherm for a given system,
although it has been observed that some shapes are often associated with a particular
adsorbent or adsorbate properties. Charcoal, with pores just a few molecules in diameter,
almost always gives a Type I isotherm. A non-porous solid is likely to give a Type II
isotherm. If the cohesive forces between adsorbate molecules are greater than the adhesive
forces between adsorbate and adsorbent, a Type V isotherm is likely to be obtained for a
porous adsorbent and a Type III isotherm for a non-porous one.
In some systems, three stages of adsorption may be discerned. In the activated aluminaair-water vapour system at normal temperature, the isotherm is found to be of Type IV.
This consists of two regions which are concave to the gas concentration axis separated
by a region which is convex. The concave region that occurs at low gas concentrations
is usually associated with the formation of a single layer of adsorbate molecules over the

986

Figure 17.5.

CHEMICAL ENGINEERING

Classification of isotherms into five types of BRUNAEUR, DEMING, DEMING and TELLER(14)

surface. The convex portion corresponds to the build-up of additional layers, whilst the
other concave region is the result of condensation of adsorbate in the pores so called
capillary condensation as discussed earlier in this Section.
At low gas concentrations, whilst the monolayer is still incomplete, the absorbed
molecules are relatively immobile. In the multilayer region, the adsorbed molecules behave
more like a liquid film. The amount of capillary condensation that occurs depends on the
pore sizes and their distribution, as well as on the concentration in the gas phase.
When n = 1, equation 17.14 represents a Type I isotherm.
When n = , equation 17.14 represents a Type II, and the rarer Type III isotherm by
choosing a suitable value for B2 . As B2 is increased, the point of inflexion or knee
of Type II becomes more prominent. This corresponds to an increasing tendency for the
monolayer to become complete before a second layer starts. In the extreme case of an
adsorbent whose surface is very uniform from an energy point of view, the adsorbate
builds up in well-defined layers. This gives rise to a stepped isotherm, in which each
step corresponds to another layer. When B2 is less than 2, there is no point of inflexion
and Type III isotherms are obtained. The condition 1 > B2 > 0 often corresponds to a
tendency for molecules to adsorb in clusters rather than in complete layers.
The success of the BET equation in representing experimental data should not be
regarded as a measure of the accuracy of the model on which it is based. Its capability
of modelling the mobile multilayers of a Type IV isotherm is entirely fortuitous because,
in the derivation of the equation, it is assumed that adsorbed molecules are immobile.

Example 17.1
Spherical particles of 15 nm diameter and density 2290 kg/m3 are pressed together to form a pellet.
The following equilibrium data were obtained for the sorption of nitrogen at 77 K. Obtain estimates

987

ADSORPTION

of the surface area of the pellet from the adsorption isotherm and compare the estimates with the
geometric surface. The density of liquid nitrogen at 77 K is 808 kg/m3 .
P /P 0
m3 liq N2 106 /kg solid

0.1
66.7

0.2
75.2

0.3
83.9

0.4
93.4

0.5
108.4

0.6
130.0

0.7
150.2

0.8
202.0

0.9
348.0

where P is the pressure of the sorbate and P 0 is its vapour pressure at 77 K.


Use the following data:
density of liquid nitrogen = 808 kg/m3
area occupied by one adsorbed molecule of nitrogen = 0.162 nm2
Avogadro Number = 6.02 1026 molecules/kmol

Solution
For 1 m3 of pellet with a voidage , then:
Number of particles = (1 )/(/6)(15 109 )3
Surface area per unit volume = (1 )(15 109 )2 /(/6)(15 109 )3
= 6(1 )/(15 109 ) m2 /m3
1 m3 of pellet contains 2290 (1 ) kg solid and hence:
specific surface = 6(1 )/[(15 109 (1 )2290]
= 1.747 105 m2 /kg
(a) Using the BET isotherm
(P /P 0 )/[V (1 P /P 0 )] = 1/V  B + (B 1)(P /P 0 )/V  B

(equation 17.15)

where V and V  are the liquid volumes of adsorbed nitrogen.


From the adsorption data given:
(P /P 0 )
V (m3 liquid N2 /kg solid 106 )
((P /P 0 )/V ) 106
(P /P 0 )/[V (1 P /P 0 )]

0.1
66.7
1500
1666

0.2
75.2
2660
3333

0.3
83.9
3576
5109

0.4
93.4
4283
7138

0.5
108.4
4613
9226

Plotting (P /P 0 )/[V (1 P /P 0 )] against (P /P 0 ), as shown in Figure 17.6, then:


intercept, 1/V  B = 300, and slope, (B 1)/V  B = 13,902

0.6
130.0
4615
11538

988

CHEMICAL ENGINEERING

12000

10000

(BET isotherm)

V (1 P /P 0)

P /P 0

or

P /P 0

8000

6000

(Langmuir isotherm)
4000

2000

0
0.2

0.4

0.6

0.8

P /P 0
Figure 17.6.

Adsorption isotherms for Example 17.1.

from which:
B = (13,902/300) + 1 = 47.34
and:
V  = 1/(300 47.34) = 70.4 106 m3 /kg.
The total surface area = [(70.4 106 808 6.2 1026 0.162 1018 )]/28
= 2.040 105 m2 /kg .

ADSORPTION

989

(b) Using the Langmuir form of the isotherm:


Assuming this applies at low concentrations then, expressing pressure as the ratio P /P 0 , and the
amount adsorbed as a volume of liquid adsorbate, equation 17.4 becomes:
(P /P 0 )/V = (P /P 0 )/V  + 1/(B2 V  )
Thus, a plot of (P /P 0 )/V against (P /P 0 ) will have a slope of (1/V  ).
Thus, from Figure 17.6:
1/V  = 13,902
V  = 71.9 106 m3 /kg

and:

which agrees with the value from the BET isotherm.


It may be noted that areas calculated from the isotherm are some 20 per cent greater than the
geometric surface, probably due to the existence of some internal surface within the particles.

17.3.4. The Gibbs isotherm


An entirely different approach to equilibrium adsorption is to assume that adsorbed layers
behave like liquid films, and that the adsorbed molecules are free to move over the surface.
It is then possible to apply the equations of classical thermodynamics. The properties which
determine the free energy of the film are pressure and temperature, the number of molecules
contained and the area available to the film. The Gibbs free energy G may be written as:
G = F (P , T , ns , As )

(17.16)

Hence:








G
G
G
G
dG =
; dP +
; dT +
; dns +
dAs
P T ,ns ,As
T P ,ns ,As
ns T ,P ,As
As T ,P ,ns
(17.17)
At constant temperature and pressure this becomes:




G
G
dG =
dns +
dAs
(17.18)
ns
As
= s dns % dAs

(17.19)

where: s is the free energy per mole or chemical potential of the film, and
% is defined as a two-dimensional or spreading pressure.
The total Gibbs free energy may be written as:
G = s ns %As
so that:

dG = s dns + ns ds % dAs As d%

A comparison of equations 17.19 and 17.21 shows that:


ns
d% =
ds
As

(17.20)
(17.21)