SEPARATION PROCESSES (CHE432)

ADSORPTION AND ION

EXCHANGE
 Adsorption Equilibria
• The adsorption isotherm is the equilibrium relationship between
the concentration in the fluid phase and the concentration in the
adsorbent particles at a given temperature.

• For gases, the concentration is usually given in mole present or as

a partial pressure. For liquids, the concentration is often
expressed in mass units, such as mg/L (ppm) or μg/L (ppb).

• The concentration of adsorbate on the solid is given as mass

adsorbed per unit mass of original adsorbent.
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• Most of the experimental data pertaining to adsorption
represents equilibrium measurements.

• Many of them were gathered to provide correlation for one

or another of the many theories which have been advanced
in an attempt to explain the adsorption phenomena.

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 Types of adsorption isotherms
• Figure 4 shows some typical isotherms shapes on arithmetic graphs.
• Notice that the quantities plotted on the axes determine the
shapes of the graphs. Here, the ordinate is the mass adsorbed/g
solid while concentration is plotted on the abscissa.
• Linear isotherm: Amount adsorbed is proportional to the
concentration in the fluid.
• Isotherms that are convex upward** are called favourable, because
a relatively high solid loading can be obtained at low concentration
in the fluid.
• The limiting case of a very favourable isotherm is irreversible
adsorption, where the amount adsorbed is independent of
concentration down to very low values.
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Figure 4: Adsorption Isotherms Engr. A.T. Ogunbiyi CHE432 Nov. 2021 5
An isotherm that is concave that is concave upward is called
unfavourable because relatively low solid loadings are obtained and
because it leads to quite long mass-transfer zones in the bed.

Studying isotherms of this rare shape helps understand the

regeneration process of the desired, strongly adsorbed adsorption
cases. Why?

Effect of temperature
All systems show a decrease in the amount adsorbed with an increase
in temperature, and of course, adsorbate can be desorbed by raising
the temperature even for cases labelled irreversible.

Discussion:
Compare the temperature requirements of the desorption of a strongly
favourable/irreversible systems with that of less favourable one.
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 Single gases and vapours
Fig. 5 shows several equilibrium adsorption isotherms for a particular
activated carbon as adsorbent, where the concentration of adsorbed gas
(the adsorbate) on the solid is plotted against the equilibrium partial
pressure 𝑝*ҧ of the vapour or gas at constant temperature.

At 100oC, for example, pure acetone vapor at a pressure of 190 mm Hg is

in equilibrium with an adsorbate concentration of 0.2 kg adsorbed
acetone/kg carbon, point A.

Increasing the pressure of the acetone will cause more to be adsorbed, as

the rising curve indicates, and decreasing the pressure of the system at A
will cause acetone to be desorbed from the carbon.
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 Figure 5: Equilibrium adsorption of vapours
on activated carbon
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• From theory, it is known that the 100oC isotherm for acetone will
continue to rise only to a pressure of 2790 mmHg, the saturation vapour
pressure of acetone at this temperature.
• At higher pressure than the saturation pressure, no acetone can exist in
the vapour state at this temperature but instead will condense entirely to
a liquid.
At higher pressure than the
vapour pressure, (as at point B
in Fig. 6), large concentration
of the substance will be
obtained on the solid, which
does not necessarily indicate
adsorption of the vapour but
Engr. A.T. Ogunbiyi CHE432
liquefaction.
Nov. 2021
How about gases above
9
Figure 6: Typical complete vapour-adsorption isotherm their critical temperature?
• Different gases and vapours are adsorbed to different extents
under comparative conditions. Thus benzene (Fig. 5) is more
readily adsorbed than acetone at the same temperature and
gives a higher adsorbate concentration for a given equilibrium
pressure.
• As a general rule for vapour and gases, the higher their molecular
weight and the lower their critical temperature, the more readily
adsorbed they are, although chemical differences such as the
extent of unsaturation in the molecule also influences the extent
of adsorption.
• The so-called permanent gases are usually adsorbed only to a
relatively small extent, e.g. the methane isotherm of Fig. 5.

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 Adsorption isotherms are not
always concave to the pressure
axis. The shapes shown in Fig. 7
have all been observed for various
systems. Here, the ordinate is the
relative saturation in order to place
all the curves on a comparable
basis.

Figure 7: Equilibrium adsorption of vapours on activated carbon

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• The adsorption characteristics of the same substance on
different adsorbents are different. The equilibrium curves for
acetone, benzene, and methane on silica gel would be totally
different from those of Fig. 5 (See Fig. 8, pages 13 & 14).

• Differences in the origin and method of preparation of an

adsorbent will result in significant differences in the equilibrium
adsorption as well. So what happens to old adsorption data?

• Repeated adsorption and desorption will also frequently alter

the characteristics of a particular adsorbent, probably due to
the progressive changes in the pore structure within the solid.
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Figure 8: Adsorption isotherms for water inEngr.
air A.T.
at Ogunbiyi
20 to 50oC CHE432 Nov. 2021 13
• To show the variety of isotherm shapes for a single adsorbate,
data for water adsorbed from air on three dessicants are given
in Fig. 8.
• Silica gel has a nearly linear isotherm up to 50 percent relative
humidity, and the ultimate capacity is about twice those for the
other solids.
• At high humidity, the small pores become filled with liquid by
capillary condensation, and the total amount adsorbed depends
on the volume of the small pores and not just the surface area.
• Water is held most strongly by molecular sieves, and the
adsorption is almost irreversible, but the pore volume is not a
great as for silica gel.
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 Types adsorption equilibria models
There are three commonly use mathematical expressions to describe vapour
adsorption equilibria: (1) the Langmuir (2) the Brunauer-Emmett-Teller (BET),
and (3) the Freundlich isotherms. You can read up about these three in the
Literature.

• The first two were derived with a theory in mind while the last one is from
empirical observation.
• None of them is applicable universally, nor can it be predicted which will
apply to a particular case.
• Since, we shall make no application of them, they are not detailed here.

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 Langmuir Isotherm
𝐾𝑐
𝑊 = 𝑊𝑚𝑎𝑥 ×
1 + 𝐾𝑐
Where, 𝑊= adsorbate loading; 𝑐 = concentration in fluid, and K =
adsorption constant
• The isotherm is of the favourable type. When 𝐾 is large and 𝐾𝑐 ≫ 1,
the isotherm is very favourable.
• When 𝐾𝑐 < 1, the isotherm is nearly linear.
• The assumption upon which the Langmuir isotherm is based is that of
a uniform surface. Although the assumption is not valid, the relation
works fairly well for gases that are weakly adsorbed.
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Freundlich isotherm
• For strongly favourable isotherm, the empirical Freundlich equation

𝑊 = 𝑏𝑐 𝑚

Where 𝑏 and 𝑚 are constants, and 𝑚 < 1, is often a better fit,

particularly for adsorption from liquids.

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Adsorption Hysteresis
Since the curves on Fig. 5 are true
equilibrium curves; it therefore
follows that they represent
completely reversible phenomena.

Point A on Fig. 5 can be obtained in

two ways: adsorption onto fresh
carbon or by desorption of a
sample with an initially higher
adsorbate concentration.

Figure 8: Adsorption isotherm showing hysteresis

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Occassionally, however, different equilibria result, at least over a
part of an isotherm, depending upon whether the vapour is
adsorbed or desorbed, and this gives rise to the hysteresis
phenomenon indicated in Fig. 8.

Hysteresis may be the result of the shape of the openings to the

capillaries and pores of the solid or of complex phenomena of
wetting of the solid by the adsorbate. In any case, when
hysteresis is observed, the desorption equilibrium pressure is
always lower than that obtained by adsorption.

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