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In adsorption, the contact of solids with either liquids or gases is involved. The direction of
mass transfer is from fluid to solid. Certain solids have the characteristics to enable a higher
concentration of a specific substance from solution to be adsorbed onto their surfaces. This
ability is known as adsorption and it is used to separate the components in either gaseous or
liquid solution.
There are two types of adsorption known. In physical adsorption and chemical adsorption,
adsorbent and adsorbate are involved. However, both types of adsorption have very different
Physical Adsorption
Physical adsorption is a reversible phenomenon and also known as physisorption involve the
attraction by electrical charge difference between the adsorbent and adsorbate. It is formed
due to the intermolecular forces (van der Waals forces) of attraction between molecules of the
solids adsorbent and the adsorbed substance known as adsorbate. When the intermolecular
attractive forces between the solid and fluid molecules are greater than those existing
between the fluid molecules, the gaseous or liquid molecules will condense upon the solid
surface. The absorbed substance does not penetrate into the crystal lattice of the solid; it only
remains entirely upon the surface (Smith D and Adams NG 1974). At equilibrium, the partial
pressure of the adsorbed substance is equal to the contacting phase. If the pressure of the
phase is lowered or the temperature of the adsorbed substance is raised, the adsorbed
substance is readily removed in an unchanged form. This mechanism is better known as
desorption. It occurred in both gaseous and liquid phase. The physisorption capacity
decreased when temperature increased. Physical adsorptions always occur in low pH.
Chemical Adsorption
Chemical adsorptions involve the formation of chemical bond between the adsorbate and the
adsorbent. It can be referred to chemisorption or activated adsorption. It is highly directional,
as are all chemical bonds. After that, the adsorbate chemisorbed stick at the specific sites and
they exhibit a binding interaction that depends strongly on their exact position and orientation

with respect substrate. This adsorption is the result of chemical interaction between the solid
and the adsorbed substance (Clark A 1970). An identifiable chemical compound may not be
formed in the process, however with the presence of chemical bonding; the adhesive forces
appear to be much greater than that found in physical adsorption. Since this process is
irreversible, the initial substance found after desorption will have undergone a chemical
change. Chemisorption is particularly important in heterogeneous catalysis process.
Types of Adsorption
Types of Bonding
Enthalpy Change

Physical Adsorption
Chemical Adsorption
Weak van der Waals forces
Strong chemical bonding
Weak bindings generate Strong binding generate high

Other name

small enthalpy changes

enthalpy changes
Multilayer Adsorption
Monolayer Adsorption
Remain intact and can be May
freed easily due to the weak compounds if the molecules

Activation Energy

and short-range forces

Does not require

are removed
any Require activation energy

activation energy
Types of Reaction
Table 1: Comparison between physical and chemical adsorption
Adsorbent is a substance that adsorbs another, such as activated carbon. The absorbents are
solids in granular form and their sizes are varied from 50m to 10mm. The adsorbents must
possess certain engineering properties according to the application uses. For example, if they
are to be used in a fixed bed through which a liquid or gas has to flow, they must not offer too
great a pressure drop for flow, they must not be carried away by the flowing stream, they
must have sufficient strength and hardness so that they wont be reduced in size during
handling or get crushed in supporting their own weight in beds.
The adsorbents should have the specificity and adequate adsorptive capacity. For
example, Alumina (Al2O3) for decolourisation of petroleum products, bone charcoal for
refining of sugar, and silica gel for dehydration of air gases.
Since physical adsorption is a surface phenomenon, the larger the surface area, the
better the effectiveness of the absorbents. Their very large surface area is due to their highly
porous nature. Although the pores are very small in size, the extremely large number of the

pores provides a large surface area. The surface area of treated charcoals is of the order
1000m2g-1 (Gregg S.J. and Sing K.S.W., 1967).
Characteristics of an absorbent
Large surface area

Factors that affect adsorption capacity

Large surface area of the adsorbent will
provide more binding sites for the molecules
of the adsorbate onto the adsorbent, hence

Macroporous, Mesoporous, and Microporous

faster the adsorption rate.

Adsorbent with small pore size will provide
more binding sites for the molecules of the
adsorbate onto the adsorbent, hence faster the

adsorption rate.
Positive, Negative, and Neutral surface Positive charged




negative charged adsorbate

Negative charged adsorbent will attract
positive charged adsorbate
Neutral adsorbent will attract both positive

and negative charged adsorbate

Table 2: Characteristics of an adsorbent and the factors that affect the adsorption capacity


Adsorption process occurs in several stages. First, the adsorbate migrates towards adsorbent
surface. Then, the solute moves from the adsorbent surface towards its internal sites by
diffusion through pores. Finally, the solute is adsorbed onto the active sites inside the
adsorbent particles but long contact time is required. Figure 1 shows the mechanism of
adsorption process in a clearer view.

Figure 1: Mechanism of adsorption process

The rate of adsorption, Rads, of a molecule onto a surface can be expressed as any other
kinetic process. In terms of the partial pressure of the molecules in the gas phase above the
surface, the equation can be written as:
Rads = k' P x

x - kinetic order
k' - rate constant
P - partial pressure

When the quation is expressed in Arrhenium form, the kinetic equation is:
Rads = A exp( -Ea / RT ). P x

Ea - the activation energy for adsorption

A - pre-exponential (frequency) factor

Considering the factors that controlling this process at the molecular level, the rate of
adsorption is affected by:
1. The rate of molecules in contact with the surface of adsorbent
2. The proportion of incident molecules which undergo adsorption

The rate of adsorption per unit area of surface (m-2 s-1) can be expressed as a product of the
incident molecular flux, F, and the sticking probability, S.
Rads = S . F
The flux of incident molecules given by the Hertz-Knudsen equation:
Flux , F = P / (2mkT)1/2
P - gas pressure [ N m-2 ]


m - mass of one molecule [ kg ]

T - temperature [ K ]
The sticking probability of the adsorbate must lie between the range of 0 <S< 1. It may
depend upon various factors. The foremost amongst these factors are the existing coverage of
adsorbed species () and the presence of any activation barrier to adsorption. Therefore,
S = f () exp (-Ea / RT)

f() - function of the existing surface coverage of adsorbed species

By combining the equations for S and F gives the following expression for the rate of

1. The equation above shows that the rate of adsorption is expected to be in first order
with regard to the partial pressure of the gas molecules above the surface.
2. The activation energy for adsorption is dependent on the surface coverage.
3. The sticking probability is assumed to be directly proportional to the concentration of
vacant surface sites.


It is the equilibrium relationship between the concentration of the adsorbate in the fluid phase
and the concentration on the adsorbent at a given temperature. The word isotherm refers to
date being obtained at constant temperature. The concentration of gases is expressed in mol%
or partial pressure, the concentration of liquids is expressed in grams per litre or parts per
million, and the concentration of the adsorbate on the adsorbent is expressed as mass
adsorbed per unit mass of adsorbent.
Figure 2 shows the graph of adsorption isotherm. The graph shows the relationship of
mass of the adsorbate which adsorbed on the solid against concentration of the adsorbate in
the fluid phase. The linear isotherm that goes through the origin indicates that the amount
adsorbed is directly proportional to the concentration in the fluids. Isotherms that appear in
the shape of convex upwards are favourable because a relatively high solid loading can be
obtained at low concentration in the fluid. Isotherms that appear in the shape of concave
downwards are unfavourable because relatively low solid loadings are obtained and it leads
to mass transfer zones that are quite long.

Figure 2: Adsorption isotherm (source:


One of the most commonly used isotherms is known as the Langmuir equation by Irving
Langmuir. When applied to adsorption, the equation is written as:

K L qmC
1+ K L C


q adsorbed density (mg m-2 or mg g-1) on the surface

qm- maximum adsorbed density (mg m-2 or mg-1)
KL-adsorption equilibrium constant (L mg-1)
C equilibrium concentration in the solution (mg L-1)

However, application of the Langmuir equation is based on several assumptions, which is not
true in many examples of adsorption.
1. Adsorption occurs at adsorption sites, each of which has a specific surface area
associated with it.
2. Adsorption occurs up to formation of a single, uniform layer or monolayer on the
3. The energy of the adsorption is independent of how much is adsorbed, meaning that
adsorption at one site does not affect adsorption at another nearby site.
4. Differences in adsorption behaviour with loading are caused by differences in
adsorbate-solid interactions, and not by lateral interaction between neighbouring

When there is a poor fit to Langmuir equation, the Freundlich isotherm is used. The
Freundlich equation:
q = KfCn

q absorbate sorption density (mg m-2 or mg g-1)

C equilibrium concentration of sorptive ion or molecule remaining in
solution after sorption (mg L-1)

n constant expressing isotherm curvature

Kf Freundlich isotherm coefficient
When this equation is used, the log of the surface concentration of absorbate q is plotted
against the log of concentration of the adsorptive ion or molecule in solution, C.

Figure 3: A Comparison of a Linear and a Freundlich Isotherm (source: Appelo and Postma,

This isotherm can be used in multilayer adsorption. The initial adsorbed layer can act as a
substrate for further adsorption then, instead of the isotherm levelling off to some saturated
value at high pressure it can expect to rise indefinitely. The most widely used isotherm
dealing with multilayer adsorption was derived by the BET isotherm.

P and P0 are the equlibrium and the saturation pressure of adsorbates at the
temperature of adsorption

V is the adsorbed gas quantity (for example, in volume units), and Vm is

the monolayer adsorbed gas quantity. c is the BET constant,

El is the heat of adsorption for the first layer, and EL is that for the second and higher
layers and is equal to the heat of liquefaction


There are several important factors affecting the adsorption process. Besides, the adsorption
process is strongly influenced by a mixture of many compounds which are typically present
in water and wastewater. The compounds can mutually enhance adsorption, may act
relatively independently, or may interfere with one other.
The surface area of the adsorbent
Since adsorption is related to the sticking of the adsorbate into a surface of adsorbent, then
the extent of the adsorption is proportional to the specific surface area which defined as the
portion of the total surface area that is available for the adsorption process to take place.
The finely divided size of adsorbent has greater surface area which more porous
surface. Thus the rate and amount of adsorption accomplished per unit weight of a solid
adsorbent will increase. The adsorbent such as charcoal and silica gel is excellent adsorbents
due to their highly porous structures which also contribute to the large surface area. In
addition, smaller particle sizes of adsorbent reduce the internal diffusion and mass transfer
limitation to penetrate of the adsorbate inside the adsorbent. Hence smaller particle size and
larger surface area gives higher adsorption rates.
The contact time between the adsorbate and the adsorbent
The longer the contact time between the adsorbate and the adsorbent will lead to the complete
adsorption process. However, according to the research carried out by Kashayar Badii (2010)
on his article "Adsorption of Acid blue 25 Dye on diatomite in aqueous solution", the uptake
level of the dye (adsorbate) increases as the time increase from zero to 100 minutes.
These results indicate that, the adsorption process proceeds in two stages; an initial
rapid increase between zero and 10 minutes being very sharp, followed by a slower stage in
which the uptake rate gradually decreases with time indicating that the adsorption was rapid
and approached maximum at about 60-70 minutes for all the studied dyes. The time (70 min)
is used for the complete adsorption process on his research. Hence, the longer contact time,

more complete adsorption occurred and the shorter the contact time, the adsorption will be
partially completed.
The effect of temperature
The process of adsorption is an exothermic reaction. The magnitude of adsorption will be
increased with the decreased in temperature. This rule is obeying the Le-Chatelier's principle.
Le-Chatelier principle is applicable in the case of physical adsorption due to their van der
Waal's interaction. The forces of van der Waal's interaction are strong at low temperature. In
the case of Chemisorption adsorption, the adsorption rate first increases with the rise in
temperature and then starts decreasing.

Figure 4: Effect of temperature on physical and chemical adsorption

The initial increase indicates that the Chemisorption adsorption require an activation
energy. The curve obtained for physical adsorption shows a regular decrease in adsorption
with the rise in temperature. While for the chemisorption, initially it shows an increase in
adsorption rate and then shows regular decrease. This curve is known as 'Adsorption Isobar'.
The effect of pressure
At constant temperature, the adsorption of absorbates increases with the increases of pressure
and decrease in pressure causes desorption.


Figure 5: Relationship between extent of adsorption and pressure

The extent of adsorption is generally expressed as x/m where m is mass of adsorbent
and x is mass of adsorbate when equilibrium has attained. The graph between extent of
adsorption (x/m) and the pressure P of gas at constant temperature is called 'Adsorption
Isotherm'. This graph shows that at equilibrium pressure P s, maximum value reached and no
more adsorption takes place even if the pressure is further increased. This state is known
as 'SaturationState' and the corresponding pressure (Ps) is called 'Saturation Pressure'. These
states are obtained when adsorbing gases forms unimolecular layers on the surface of
adsorbent and adsorbing gas behaves ideally in vapour phase.
The activation of the solid adsorbent
The activation of the solid adsorbent means increasing the adsorbing power of an adsorbent.
This factor is related to the surface area of the adsorbent where the surface area of the
adsorbent need to be increased by several methods. The first method is through making the
surface of the adsorbent rough. This can be done by mechanical rubbing, chemical action or
by depositing finely metals on the surface of the adsorbent by electroplating.
Another method to activate the solid adsorbent is by substituting the adsorbent solid
into smaller pieces or grains but not too fine size to enable the penetration of the gas and
prevent the obstruction of adsorption process. The removal of the gases already adsorbed also
helps to increase the surface area thus activating the solid adsorbent which enhances the
adsorption process.
The solution pH
The degree of ionization of a species is affected by the pH, either weak acid or a weak basic.
The pH of a solution in turn affects the adsorption process. For example, the study on the
effect of the initial pH on the removal efficiency of Fe 3+ shows the precipitation of Fe3+ ions

occurred at pH greater than 4.5 which decrease the Fe 3+ ions removal capacity. At low pH, the
concentration of proton is high. Therefore, the positively charged of the Fe3+ ions and the
protons compete for binding on the adsorbent sites, this process decrease the uptake of iron
The concentration of proton in the solution decrease as pH gradually increases in the
ranges from 2 to 4.5. In this case, little protons have the chance to compete with Fe 3+ ions on
the adsorption sites of the adsorbent. Thus, higher pH in the acidic media is facilitated the
greater uptake of Fe3+ ions. Maximum removal efficiency is achieved in acidic solutions. The
adsorption efficiency decrease when we move to the neutral and basic media.
Nature and initial concentration or adsorbate
Both rate and capacity of adsorption are affected by the physicochemical nature of adsorbent.
The solubility of the solute greatly influences the adsorption equilibrium. Generally, extent of
adsorption of a solute and its solubility in the solvent where the adsorption takes place always
has an inverse relationship. The molecular size plays an important role in intraparticle
transport process, it can affect the rate of uptake of organic solutes trough a porous of the
adsorbent material. In this case the reaction will proceed faster with decrease of adsorbate

Column adsorption is the design of a column for adsorption starts with laboratory
testing to establish the breakthrough curve. At time intervals, the effluent from a column is
sampled. Time zero is when the solution is applied to the column. At first, the adsorbent
(usually activated carbon) is fresh with all its adsorption sites. Essentially none of the
material to be removed escapes from the column. As time passes, some of the adsorption sites
are used up, and concentration in the effluent rises. The shape of the graph may vary
considerably for different situations. Usually there is a long time before the effluent
concentration rises sharply and then levels off. If all the sites were occupied, we would expect
the inlet concentration and the outlet concentrations to become the same.


Figure 6: Graph of the effluent concentration

Based on the breakthrough curve shown in figure 6, noted the lines in blue. The
breakthrough concentration is determined by the process specifications. This is the allowable
concentration. If a pollutant is being removed, the breakthrough concentration might be the
government regulation for what your plant can discharge. For a commercial product where
the column is removing colour, the breakthrough concentration is determined by your
specification for product quality. The point is that breakthrough concentration is not some
fundamental number but depends on how you decide to operate your process.
A practical way to design an adsorption column is to experiment with a laboratory
column. If it is roughly the same length as the length of a full size column and of sufficient
diameter to minimize wall effects, scale up is merely a matter of increasing the area to match
the volume to be treated. Even if the dimensions of the production column are undecided,
operating the lab column until breakthrough shows how much solution has been passed
through so much carbon. This leads to a simple calculation of capacity of the carbon. A major
source of error is the effect of flow rate because this determines contact time, and the
approach to equilibrium takes time.
We have seen that columns in series are operated past the breakthrough point to the
exhaustion point. If the graph is steep, there will be little error in neglecting the volume that
passes after breakthrough. There is a method to account for this volume that will be presented
here. Note that a rate constant is needed for the main equation. It is more trouble to measure
this rate than to do experiments with a laboratory column for the scale up already mentioned.

Nevertheless, following the logic of the mathematical method improves understanding of

countercurrent adsorption.
There is another weakness in the theory which is shown in the shape of the
breakthrough curve relates to the adsorption isotherm. The time for the adsorption zone to
become defined and to move to the end of the column is:

- time as exhaustion zone exits


- volume applied to column, volume liquid/area


- flow rate to column, volume/time-area

The time for an established adsorption zone to move a distance corresponding to its own
thickness is:
t = ( Ve - Vb ) / Qt

- transit time


- volume, starts at conc. for breakthrough

The amount adsorbed in the adsorption zone is the integral from Vb to Ve of ( Co - C ) dV.
We next need to construct the shape of the adsorption zone from the adsorption isotherm.
This means that equilibrium is assumed. As is customary in the analysis of staged separations,
we consider a differential element in the column. The liquid and the solid adsorbent are
assumed to have velocities entering the element even though the solid is actually motionless.
A material balance for the entire column is:
Q t ( Co - 0 ) = Bt ( q - 0 )
A material balance for the section of the column containing the adsorption zone just as it is
exiting is:
Q t ( C - 0 ) = Bt ( q - 0 )
These material balances define an operating line shown in figure 7.


Figure 7: Material balances define an operating line

Each point on the operating line represents compositions of liquid and solid in contact at
some point in the column. For the differential element:
Q t dC = K (C - C* ) dZ

- a rate coefficient

- distance


- equilibrium solute concentration

The equation for the column = 1 / (C Ce )


C - concentration deemed the breakthrough

Ce - concentration at the other end of the element

The quantity (C - C*) is the horizontal distance between the operating line and the isotherm
line. It can be integrated graphically by taking the area under the function as in the following


There are two integrations, one from the top of the column to the end and one for the
adsorption zone.
The exhaustion concentration also depends on process considerations. If there are not
enough workers on the night shift, the column may have to be removed in time for
regeneration by the day shift so that it can ready in time the next day to become the t rail
column. Note that the column could still adsorb some more material. However, you get little
benefit by running for a longer time. You pay for labour, for electricity, for plant costs, etc.
When the benefits are not worth the costs, the column is considered exhausted.

Breakthrough curve also known as frontal chromatogram which represents the evolution of
the solution concentration in function of adsorption parameters such as contact time between
liquid and solid phase, solvent concentration and temperature. Besides, to evaluate the
parameter of the breakthrough curve, there are two different methods can be used which are
standard deviation method and direct method. For standard deviation method, the retention
volume of the analyte and breakthrough volume will be determined where direct method
using only relations comparison on the calculation of fundamental parameters.
Figure 8 shows the typical breakthrough curve and the fundamental chromatographic
parameters. It can provide important information regarding the cartridge and the solid phase
inside including the number of theoretical plates, the linear capacity or the recovery factor.


Figure 8: A typical breakthrough curve

In adsorption process, internal transport resistance and, in some cases, external
transport resistance are finite. Axial dispersion can also be significant, particularly at low
flow rates in shallow beds. These factors contribute to the development of broader
concentration fronts, as in Figure 9.

Figure 9: Solute wave fronts in a fixed-bed absorber with mass-transfer effects

(concentration-distance profiles)
The figure shows the typical solute concentration profiles for the fluid as a
function of distance through the bed at increasing time t1, t2, and tb from the start of flow
through the bed. At t1, no part of the bed is saturated. At t2, the bed is almost saturated for a

distance Ls. At Lf, the bed is almost clean. Beyond Lf, little mass transfer occurs at t2 and the
adsorbent is still unused. The region between Ls and Lf is the mass transfer zone, MTZ, where
adsorption takes place. Because it is difficult to determine where the MTZ zone begins and
ends, Lf can be taken where c/cF = 0.05, with Ls at c/cF = 0.95. From time t2 to time tb, the Sshaped front moves through the bed. At tb, the leading point of the MTZ just reaches the end
of the bed. This is the breakthrough point. Rather than using c/cF = 0.05, the breakthrough
concentration can be taken as the minimum detectable or maximum allowable solute
concentration in the effluent fluid.

Figure 10: Solute wave fronts in a fixed-bed absorber with mass-transfer effects
(breakthrough curve)
Figure 10 above shows a typical plot of the ratio of the outlet-to-inlet solute
concentration in the fluid as the function of time from the start of flow. The S-shaped curve is
called the breakthrough curve. Prior to tb, the outlet solute concentration is less than some
maximum permissible value, say cout/cF = 0.05. At tb, this value is reached, the adsorption step
is discontinued, and the regeneration part of the cycle is initiated or the spent adsorbent is
discarded. If the adsorption step were to be continued for t > tb, the outlet solute concentration
would be observed to rise rapidly, eventually approaching the inlet concentration as the outlet
end of the bed became saturated. The time to reach cout/cF = 0.95 is designated as te.
The steepness of the breakthrough curve determines the extent to which the
capacity of an adsorbent bed can be utilized. Thus, the shape of the curve is very important in
determining the length of an adsorption bed. For the ideal case, with a stoichiometric wave
front, all of the bed is utilized before breakthrough occurs. As the width of breakthrough
curve and the corresponding width of the MTZ for the concentration profiles increase, less

and less of the bed capacity can be utilized. The situation is further complicated by the fact
that the steepness of the concentration profiles shown in Figure 9 increases or decreases with
time, depending on the shape of adsorption isotherm.

Figure 11: Effect of shape of isotherm on sharpness of concentration wave front

(Isotherm shapes)

Figure 12: Effect of shape of isotherm on sharpness of concentration wave front

(Self-sharpening wave front caused by a favourable adsorption isotherm)
If the adsorption isotherm is curved, regions of the wave front at a higher
concentration move at a velocity different from regions at a lower concentration. Thus, for
linear isotherm (curve A in Figure 11), the width of the MTZ and the wave pattern remain
constant. For the favourable isotherm of the Freundlich or Langmuir type (curve B in Figure
11), high-concentration regions move faster than low-concentration regions, and the wave
front steepens with time until a constant pattern front (CPF) is developed (as shown in Figure
12). For the much less common unfavourable type of isotherm (curve C in Figure 11), lowconcentration regions travel faster and the wave front broadens with time. If the bed is
initially clean of adsorbate and a feed of constant solute concentration enters the bed starting
at t = 0, then wave front will be sharp, independent of the type of adsorption isotherm. For the
general case where external and internal mass-transfer resistances are finite and/or axial

dispersion is not negligible, methods for predicting concentration profiles and breakthrough
curves have been the subject of much study.

As a conclusion, adsorption is widely used in many different applications especially
industrial application such as activated charcoal, capturing and water purification. The design
of column adsorption starts with a laboratory test to establish breakthrough curve where the
graph provides the information regarding the relationship of concentration of analyte and
volume of effluent.


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