Simultaneous Heat and Mass

Transfer
Adsorption
 INTRODUCTION
• In adsorption, molecules distribute themselves between two phases, one of which is a solid
whilst the other may be a liquid or a gas.
• Unlike absorption, in which solute molecules diffuse from the bulk of a gas phase to the bulk
of a liquid phase, in adsorption, molecules diffuse from the bulk of the fluid to the surface of
the solid adsorbent forming a distinct adsorbed phase.
• Typically, gas adsorbers are used for removing trace components from gas mixtures. The
commonest example is the drying of gases in order to prevent corrosion, condensation or an
unwanted side reaction.
• For items as diverse as electronic instruments and biscuits, sachets of adsorbent may be
included in the packaging in order to keep the relative humidity low.
• In processes using volatile solvents, it is necessary to guard against the incidental loss of
solvent carried away with the ventilating air and recovery may be effected by passing the air
through a packed bed of adsorbent.
• Adsorption may be equally effective in removing trace components from a liquid phase and
may be used either to recover the component or simply to remove a noxious substance from
an industrial effluent.
• Any potential application of adsorption has to be considered along with alternatives such as
distillation, absorption and liquid extraction.
• Each separation process exploits a difference between a property of the components to be
separated. In distillation, it is volatility. In absorption, it is solubility. In extraction, it is a
distribution coefficient.
 INTRODUCTION
• Separation by adsorption depends on one component being more readily adsorbed than
another. The selection of a suitable process may also depend on the ease with which the
separated components can be recovered.
• When an adsorbent with pore size of 0.5 nm is exposed to a mixture of the gases, the
smaller molecules diffuse to the adsorbent surface and are retained whilst the larger
molecules are excluded. In another stage of the process, the retained molecules are
desorbed by reducing the total pressure or increasing the temperature.
• Most commercial processes for producing nitrogen and oxygen from air use the cryogenic
distillation of liquefied air. There is also interest in adsorptive methods, particularly for
moderate production rates. Some adsorbents take up nitrogen preferentially and can be
used to generate an oxygen-rich gas containing 95 mole per cent of oxygen. Regeneration of
the adsorbent yields a nitrogen-rich gas.
• It is also possible to separate the gases using an adsorbent with 0.3 nm pores. These allow
oxygen molecules of 0.28 nm in size to diffuse rapidly on to the adsorption surface, whereas
nitrogen molecules of 0.30 nm will diffuse more slowly. The resulting stream is a nitrogen-
rich gas of up to 99 per cent purity. An oxygen stream of somewhat lower purity is obtained
from the desorption stage.
• Adsorption occurs when molecules diffusing in the fluid phase are held for a period of time
by forces emanating from an adjacent surface. The surface represents a gross discontinuity
in the structure of the solid, and atoms at the surface have a residue of molecular forces
which are not satisfied by surrounding atoms such as those in the body of the structure.
 INTRODUCTION
• These residual or van der Waals forces are common to all surfaces and the only reason why
certain solids are designated “adsorbents” is that they can be manufactured in a highly
porous form, giving rise to a large internal surface.
• The adsorption which results from the influence of van der Waals forces is essentially
physical in nature. Because the forces are not strong, the adsorption may be easily reversed.
• In some systems, additional forces bind absorbed molecules to the solid surface. These are
chemical in nature involving the exchange or sharing of electrons, or possibly molecules
forming atoms or radicals. In such cases the term chemisorption is used to describe the
phenomenon.
• This is less easily reversed than physical adsorption, and regeneration may be a problem.
• Chemisorption is restricted to just one layer of molecules on the surface, although it may be
followed by additional layers of physically adsorbed molecules.
• It is often convenient to think of adsorption as occurring in three stages as the adsorbate
concentration increases. Firstly, a single layer of molecules builds up over the surface of the
solid. This monolayer may be chemisorbed and associated with a change in free energy
which is characteristic of the forces which hold it.
• As the fluid concentration is further increased, layers form by physical adsorption and the
number of layers which form may be limited by the size of the pores.
• Finally, for adsorption from the gas phase, capillary condensation may occur in which
capillaries become filled with condensed adsorbate, and its partial pressure reaches a critical
value relative to the size of the pore.
 ADSORPTION EQUILIBRIA
• Much of the early work on the nature of adsorbents sought to explain the equilibrium
capacity and the molecular forces involved.
• Adsorption equilibrium is a dynamic concept achieved when the rate at which molecules
adsorb on to a surface is equal to the rate at which they desorb.
• 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 gas–solid 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.
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.
 ADSORPTION EQUILIBRIA
• 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 = KaC (17.1)
• This expression is analogous to Henry’s Law for gas–liquid systems even to the extent that
the proportionality constant obeys the van’t Hoff equation and Ka = K0 e−ΔH/RT where ΔH 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.
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 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: k0a0C = k0(1 − a1)C = k1’a1
 ADSORPTION EQUILIBRIA
• where: a0 is the fraction of empty surface,
• a1 is the fraction of surface occupied by a monolayer of adsorbed molecules,
• B0 = k0/k’1
• k0 is the velocity constant for adsorption on to empty surface, and
• K’1 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:

• where: Cs is the concentration of the adsorbed phase,

• Csm is the concentration of the adsorbed phase when the monolayer is complete,
• B1 = B0/RT ,and P 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:
 ADSORPTION EQUILIBRIA
(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.
The BET isotherm
• In 1938, BRUNAUER, EMMETT and TELLER and EMMETT and DE WITT developed what is
now known as the BET theory.
• As in the case in Langmuir’s 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:
 ADSORPTION EQUILIBRIA
• The rate of adsorption on to empty surface = k0a0P, and
• the rate of desorption from a monolayer = k’1a1
• 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 e−E1/RT . Hence the rate of
desorption from a monolayer may be written as: A’1 e−E1/RT a1 where A’1 is the
frequency factor for monolayer desorption.
• The dynamic equilibrium of the monolayer is given by:

• where A’2 is the frequency factor for description from a bilayer, thus creating a monolayer.
• Applying similar arguments to the empty surface, then:

• From equations 17.5 and 17.6:

 ADSORPTION EQUILIBRIA
• 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:
• Hence it may be assumed that β is constant for layers after the first &:
• where B2 = α0/β, 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:

• The total volume of adsorbate associated with unit area of surface is given by:

• where v1s is the volume of adsorbate in a unit area of each layer.

• Since v1s 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:
 ADSORPTION EQUILIBRIA

• The numerator of equation 17.11 may be written as:

• and the denominator as:

• Substituting these values into equation 17.11 and rearranging gives:

• 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:
 ADSORPTION EQUILIBRIA
• 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/v1s approaches infinity.
• In equation 17.13, this condition corresponds to putting β = 1. It may be noted that putting β
= 1/(1 − B2) is not helpful. Hence from equation 17.8:

• where: λM is the molar latent heat and P0 is the saturated vapour pressure.
• Hence, from equation 17.8, β = P/P0.
• 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:

• where V 1s 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/P0)n approaches zero and equation 17.13 may be rearranged in a convenient
linear form to give:

• where V and V 1 are the equivalent gas phase volumes of Vs and V1s .
 ADSORPTION EQUILIBRIA
• where V and V 1 are the equivalent gas phase volumes of Vs and V 1s .
• If a plot of the left-hand term against P/P0 is linear, the experimental data may be said to fit
the infinite form of the BET equation. From the slope and the intercept, V1 and B2 may be
calculated.
• The advantage of equation 17.14 is that it may be fitted to all known shapes of adsorption
isotherm.
• Only gas–solid 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 alumina air- 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.
 ADSORPTION EQUILIBRIA
• The concave region that occurs at low gas concentrations is usually associated with the
formation of a single layer of adsorbate molecules over the 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.
 ADSORPTION EQUILIBRIA
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 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.

where P is the pressure of the sorbate and P0 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 ε, then: Number of particles = (1 − ε)/(π/6)(15 × 10−9)3
Surface area per unit volume = (1−ε)π(15×10−9)2/(π/6)(15×10−9)3 = 6(1 − ε)/(15 × 10−9) m2/m3
• 1 m3 of pellet contains 2290 (1 − ε) kg solid and hence:
specific surface = 6(1 − ε)/[15 × 10−9(1 − ε)2290] = 1.747 × 105 m2/kg
(a) Using the BET isotherm
• (P/P0)/[V(1−P/P0)] = 1/V’B + (B − 1)(P /P0)/V’B (equation 17.15)
where V and V’ are the liquid volumes of adsorbed nitrogen.
• From the adsorption data given:
 ADSORPTION EQUILIBRIA

• Plotting (P /P0)/[V (1 − P/P0)] against (P/P0), as shown in Figure 17.6, then:

• intercept, 1/V’B = 300, and slope, (B − 1)/V’B = 13,902 from which:
• B = (13,902/300) + 1 = 47.34 and:
• V = 1/(300 × 47.34) = 70.4 × 10−6 m3/kg.
• The total surface area =
• [(70.4×10−6×808×6.2×1026×0.162×10−18)]/28
• = 2.040 × 105 m2/kg .
(b) Using the Langmuir form of the isotherm:
• Assuming this applies at low concentrations then,
expressing pressure as the ratio P/P0, and the
amount adsorbed as a volume of liquid adsorbate,
equation 17.4 becomes:(P/P0)/V=(P/P0)/V’+1/(B2V’)
• Thus, a plot of (P /P 0)/V against (P/P0) will have
a slope of (1/V). Thus, from Figure 17.6:
1/V = 13,902 and: V=71.9×10−6m3/kg
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.
The Gibbs isotherm
ADSORPTION EQUILIBRIA
• 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:

• At constant temperature and pressure this becomes:

• where: μs is the free energy per mole or chemical potential of the film, and Γ is defined as a
two-dimensional or spreading pressure.
• The total Gibbs free energy may be written as:

• A comparison of equations 17.19 and 17.21 shows that:

•
ADSORPTION EQUILIBRIA
If the gas phase is ideal and equilibrium exists between it and the sorbed phase then, by
definition:
• where μg is the chemical potential of the gas.
• Substituting for dμs gives:
• Equation 17.23 has the form of an adsorption isotherm since it relates the amount adsorbed
to the corresponding pressure. This is known as the Gibbs Adsorption Isotherm.
• For it tobbe useful, an expression is required for Γ. Assuming an analogy between adsorbed
and liquid films:
• where α1, β1, are constants, am = As/Nns , the area per molecule of adsorbate and N is the
Avogadro number.
• Substituting for dΓ in equation 17.23 and integrating, at constant As, from some condition
P1, ns1 at which the adsorbed film becomes mobile, to an arbitrary coverage ns at pressure P,
gives:

• Equation 17.25 may be rewritten as:

• where V is the volume occupied in the gas phase by ns moles of sorbate at a temperature T
and pressure P.
•
ADSORPTION EQUILIBRIA
where ρg is the molar density of the gas phase. Equation 17.26 is the Harkins-Jura (H–J)
equation, which may be used to correlate adsorption data and to obtain an estimate of the
surface area of an adsorbent.
• The H–J model may be criticised because the comparison between an adsorbed film on a
solid surface and a liquid film on a liquid surface does not stand detailed examination.
• Although making fundamentally different assumptions about the static or mobile nature of
an adsorbed layer, the BET and H–J equations may often represent a set of experimental
data equally well.
 ADSORPTION EQUIPMENT
• The scale and complexity of an adsorption unit varies from a laboratory chromatographic
column a few millimeters in diameter, as used for analysis, to a fluidised bed several metres
in diameter, used for the recovery of solvent vapours, from a simple container in which an
adsorbent and a liquid to be clarified are mixed, to a highly-automated moving-bed of solids
in plug-flow.
• All such units have one feature in common in that in all cases the adsorbent becomes
saturated as the operation proceeds.
• For continuous operation, the spent adsorbent must be removed and replaced periodically
and, since it is usually an expensive commodity, it must be regenerated, and restored as far
as possible to its original condition.
• In most systems, regeneration is carried out by heating the spent adsorbent in a suitable
atmosphere. For some applications, regeneration at a reduced pressure without increasing
the temperature is becoming increasingly common.
• The precise way in which adsorption and regeneration are achieved depends on the phases
involved and the type of fluid–solid contacting employed. It is convenient to distinguish
three types of contacting:
(a) Those in which the adsorbent and containing vessel are fixed whilst the inlet and outlet
positions for process and regenerating streams are moved when the adsorbent becomes
saturated. The fixed bed adsorber is an example of this arrangement. If continuous
operation is required, the unit must consist of at least two beds, one of which is on-line
whilst the other is being regenerated.
 ADSORPTION EQUIPMENT
(b) Those in which the containing vessel is fixed, though the adsorbent moves with respect
to it. Fresh adsorbent is fed in and spent adsorbent removed for regeneration at such a rate
as to confine the adsorption within the vessel. This type of arrangement includes fluidised
beds and moving beds with solids in plug flow.
(c) Those in which the adsorbent is fixed relative to the containing vessel which moves
relative to fixed inlet and outlet positions for process and regenerating fluids. The rotary-bed
adsorber is an example of such a unit.