Mora, Roxan B.

BSChE-4

Adsorption is a process that occurs when a gas or liquid solute accumulates on

the surface of a solid or a liquid (adsorbent), forming a molecular or atomic film
(adsorbate). It is different from absorption, in which a substance diffuses into a liquid
or solid to form a solution.Adsorption is a well established and powerful technique
for treating domestic and industrial effluents. In water treatment, the most widely
method is “adsorption” onto the surface of activated carbon.

Figure 1 : Mechanism of Adsorption

The mass transfer and adsorption of molecule from a liquid or gas into solid
surface is an basic operation for carbon adsorption. The activated carbon will be
manufactured in order for the producing of extremely porous carbon particles whose
internal surface area at very large. The porous structure attracts and holds organic
molecules as well as certain metal and inorganic molecules, then, the adsorption will
be process.The reason why adsorption process is occur, because of (a) the
contaminant has low solubility in the waste, (b) The contaminant has greater affinity
for the carbon than for the waste or (c) combination of a and b.

Depending on the type of attractions between adsorbate and adsorbent, the

adsorption can be divided into two types. Forces of attraction exist between adsorbate
and adsorbent. These forces of attraction can be due to Vanderwaal forces of
attraction which are weak forces or due to chemical bond which are strong forces of
attraction.
 A. Physical Adsorption or Physisorption

When the force of attraction existing between adsorbate and adsorbent are weak
Vanderwaal forces of attraction. Physical Adsorption takes place with formation of
multilayer of adsorbate on adsorbent. It has low enthalpy of adsorption
( 20-40KJ/mol). Takes place at low temperature below boiling point of adsorbate. As
the temperature increases in, process of Physisorption decreases.

B. Chemical Adsorption or Chemisorption

When the force of attraction existing between adsorbate and adsorbent are
chemical forces of attraction or chemical bond. Takes place with formation of
unilayer of adsorbate on adsorbent. It has high enthalpy of adsorption. It can take
place at all temperature. With the increases in temperature, Chemisorption first
increases and then decreases.

Figure 2: Types of Adsorption

Adsorption process is usually studied through graphs known as adsorption

isotherm. The adsorption isotherm is the relationship between the amount of
adsorbate adsorbed on the surface of adsorbent and the pressure at constant
temperature.
 Figure 3: Adsorption Isotherm

At figure 3, it can predict that after saturation pressure Ps, adsorption does not
occur anymore, that is there are limited numbers of vacancies on the surface of the
adsorbent. At high pressure a stage is reached when all the sites are occupied and
further increase in pressure does not cause any difference in adsorption process. At
high pressure, adsorption is independent of pressure. This concept of adsorption
isotherm is found in freundlich adsorption isotherm

In 1909, Freundlich expressed an empirical equation for representing the

isothermal variation of adsorption of a quantity of gas adsorbed by unit mass of solid
adsorbent with pressure. This equation is known as Freundlich Adsorption Isotherm
or Freundlich Adsorption equation or simply Freundlich Isotherm.

1
x
 kP n
m
Where;
x = amount of adsorbate
m = weight of the adsorbent
P = Pressure,
k and n = are constants whose values depend upon adsorbent and gas at
particular temperature .

Though Freundlich Isotherm correctly established the relationship of adsorption

with pressure at lower values, it failed to predict value of adsorption at higher
pressure. This relation is called as the freundlich adsorption isotherm. As see the
following diagram. The value of x/m is increasing with increase in p but as n>1 it
does not increase suddenly. This curve is also called the freundlich isotherm curve.
Taking the log of the above equation, the following equation will be observed:

x/m is plotted on y axis and log p is on x axis. If straight line is observed than only
Freundlich isotherm is verified.

From this the value of slope equal to 1/n and the value of intercept equal to log k
can be obtained. Over and above, it the graph of log x/m against log p comes out to
be a straight line, it can be assured that the freundlich adsorption isotherm is satisfied
for this system.

Types of Adsorption Isotherm

A. Type I adsorption isotherm

 Figure 4: Type I

The above graph depicts Monolayer adsorption. This graph can be easily
explained using Langmuir Adsorption Isotherm. Examples of Type-I adsorption are
Adsorption of Nitrogen (N2) or Hydrogen (H) on charcoal at temperature near to
-1800°C.

B. Type II adsorption isotherm

Figure 5: Type II

It shows the large deviation from Langmuir model of adsorption. The

intermediate flat region in the isotherm corresponds to monolayer formation.
Examples of Type-II adsorption are Nitrogen (N2 (g)) adsorbed at -1950°C on Iron
(Fe) catalyst and Nitrogen (N2 (g)) adsorbed at - 1950°C on silica gel.

C. Type III adsorption isotherm

 Figure 6: Type III

At lower pressure region of graph is quite similar to Type II. This explains
formation of monolayer followed by multilayer. The intermediate flat region in the
isotherm corresponds to monolayer formation. The saturation level reaches at a
pressure below the saturation vapor pressure. This can be explained on the basis of a
possibility of gases getting condensed in the tiny capillary pores of adsorbent at
pressure below the saturation pressure (PS) of the gas. Examples of Type IV
Adsorption Isotherm are of adsorption of Benzene on Iron Oxide (Fe2O3) at 500°C
and adsorption of Benzene on silica gel at 500°C.

D. Type IV adsorption isotherm

Figure 7: Type IV

At lower pressure region of graph is quite similar to Type II. This explains
formation of monolayer followed by multilayer. The intermediate flat region in the
isotherm corresponds to monolayer formation. The saturation level reaches at a
pressure below the saturation pressure (Ps) of the gas. Example of Type IV
adsorption isotherm is adsorption of Benzene on Iron oxide at 500C and adsorption
of Benzene on Silica gel at 500C.

E. Type V adsorption isotherm

Figure 8: Type V

Type V graph is similar to Type IV. Example of Type V Adsorption Isotherm is

adsorption of Water (vapors) at 1000°C on charcoal. Type IV and V shows
phenomenon of capillary condensation of gas.

If the adsorption isotherm shape is Type I, II or IV, adsorption can be used to

separate the adsorbate from the carrier gas. If it is Type III or V, adsorption will
probably not be economical for the separation.

However in 1916, Irving Langmuir published a new model isotherm for gases
adsorbed to solids, which retained his name. It is a semi-empirical isotherm derived
from a proposed kinetic mechanism. This isotherm was based on different
assumptions one of which is that dynamic equilibrium exists between adsorbed
gaseous molecules and the free gaseous molecules. Langmuir suggested that
adsorption takes place through this mechanism:

Where;
 A(g)= unadsorbed gaseous molecule
B(s)= unoccupied metal surface
AB = Adsorbed gaseous molecule
Based on his theory, Langmuir derived an equation which explained the
relationship between the number of active sites of the surface undergoing adsorption
and pressure. This equation is called Langmuir Equation.

Where;

 = the number of sites of the surface which are covered with gaseous molecule,

P= pressure
K =is the equilibrium constant for distribution of adsorbate between the surface
and the gas phase
When at low pressure only, the KP is so small, that factor (1+KP) in denominator
can almost be ignored. So Langmuir equation reduces to:

When at high pressure, KP is so large, that factor (1+KP) in denominator is

nearly equal to KP. So Langmuir equation reduces to:

Adsorption kinetics (Rate of Absorption)

The rate of adsorption, (Rads) of a molecule onto a surface can be expressed in

the same manner as any kinetic process. For example, when it is expressed in terms
of the partial pressure of the molecule in the gas phase above the surface:

Rads = k' P x

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

If the rate constant is then expressed in an Arrhenius form, then :

Rads = A exp(-Ea/RT). Px

Where;

Ea – activation energy for adsorption

A-The pre-exponential (frequency) factor

The rate of adsorption is governed by the rate of arrival of molecules at the

surface and the proportion of incident molecules which undergo adsorption.

The rate of adsorption can be expressed as a product of the incident molecular flux, F,
and the sticking probability, S.

Rads = S.F (molecules. m2s2)

The flux of incident molecules is given by the Hertz-Knudsen equation

Flux,

F = P/(2)1/2 (molecules. m2s2)

Where;

P- gas pressure (N m2)

m- mass of one molecule (kg)

T- temperature (K)

The sticking probability is clearly a property of the adsorbate substrate system

under consideration but must lie in the range 0<S<; it may depend upon various
factors – foremost amongst these being the existing coverage of adsorbed species (ϴ)
and the presence of any activation barrier to adsorption. In general, therefore,

S = f (θ) . exp ( -Ea / RT )

Where, once again, Ea is the activation energy for adsorption and f(ϴ) is some,
as yet undetermined, function of the existing surface coverage of adsorbed species.

Combining the equations for S and F yields the following expression for the rate
of adsorption:

f ( ) P Ea
R exp( )
2mkT RT

Fixed bed Adsorption System

Fixed bed adsorption design is based upon the following considerations:

1. Absorbent bed profile and media loading capacity characteristics for the
specific application and adsorbent material used.
 Figure 9: Equilibrium Bed Profile

Equilibrium zone defines how much adsorbate media can hold under the process
conditions ( temperature, pressure and adsorbate concentration in the feed). This
adsorbate loading limits is refereed to as the equilibrium capacity, reported as the
weight percentage and use as the theoretical maximum 100% of the bed volume is
used to capacity. Th equilibrium zone is also measure of the absorbent volume (as the
percentage of the total olume) that use to full capacity before unacceptable adsorbate
breakthrough is suffered. The mass tansfer zone is defines that adsorbent volume
that is required to reduce adsorbate inlet concentration to that required effluent
specification in the portion of the bed where active absorption is taking place

Equilibrium capacities and mass transfer characteristics for a given adsorbate on

a given adsorbent are reflected in the adsorbent materials isotherm data and usually
graphically represented. Isotherm relates adsorbate loading capacity to adsorbate
concentration in the process stream at a given temperature. Concentration is typically
represented by partial pressure ore relative humidity in a vapor phase and weight per
volume for liquid applications.

2. Pressure drop characteristics across the adsorbent bed

In second major consideration in fixed bed adsorber design, it will set the
permissible operational limits for the adsorption bed. Insufficient pressure drop
will result in uneven distribution and channeling of the process liquid, resulting
in poor performance. Pressure drop guidelines for nominal 1/16” thru 1/4”
spherical, granular or extruded adsorbent media are follow:

For vapor phase service

<0.01 psi/ft : Un-even distribution and channeling

0.01-0.20 psi/ft : Upflow or Downflow operation

0.20-100 psi/ft : Downflow operation only (upflow will result in bed lifting)

>100 psi/ft : Bed compaction

For liquid phase

<0.001 psi/ft : Un-even distribution and channeling

0.001-0.20 psi/ft : Upflow or Downflow operation

0.20-10 psi/ft : Downflow operation only (upflow will result in bed lifting)

>10 psi/ft : Bed compaction

Fixed Bed pressure drop is being calculated by Ergun Equation

P kft Ct G 2

L DP

Where;

ΔP = pressure drop

L = length (depth) of adsorbent bed

 ft = friction factor

Ct = pressure drop coefficient

G = average fluid density

DP = average adsorbent particle

k = unit conversion constant

Pressure drop across fixed beds also reflected in bed operating parameters
such as linera velocity. Superficial mass velocity, modified Reynold’s number.

3. Reaction kinetics

The third one involves rate of interaction and reaction of the adsorbate with the
adsorbent. While most physical adsorption interaction occur readily, many chemical
adsorption mechanism do not. As the result, most adsorptive procsses base on the
physisorption can be designed solely upon absorbent capacities and pressure date
criteria. With chenisorption, reaction time between adsorbate and adsorbent can
become issue.