ADSORPTION

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 (the adsorbate" It is
different from absorption! in which a substance diffuses into a liquid or solid to form a
solution" The term sorption encompasses both processes! while desorption is the re#erse
process"

Adsorption is operati#e in most natural ph$sical! biological! and chemical s$stems! and is
widel$ used in industrial applications such as acti#ated charcoal! s$nthetic resins and
water
purification"

Similar to surface tension! adsorption is a consequence of surface energ$" In a bul%
material! all the bonding requirements (be the$ ionic! co#alent or metallic of the
constituent atoms of the material are filled" &ut atoms on the (clean surface e'perience a
bond deficienc$! because the$ are not wholl$ surrounded b$ other atoms" Thus it is
energeticall$ fa#ourable for them to bond with whate#er happens to be a#ailable" The
e'act
nature of the bonding depends on the details of the species in#ol#ed! but the adsorbed
material is generall$ classified as e'hibiting ph$sisorption or chemisorption"

Ph$sisorption or ph$sical adsorption is a t$pe of adsorption in which the adsorbate
adheres to the surface onl$ through (an der )aals (wea% intermolecular interactions!
which are also responsible for the non*ideal beha#iour of real gases"

+hemisorption is a t$pe of adsorption whereb$ a molecule adheres to a surface through
the formation of a chemical bond! as opposed to the (an der )aals forces which cause
ph$sisorption"
Adsorption is usuall$ described through isotherms! that is! functions which connect the
amount of adsorbate on the adsorbent! with its pressure (if gas or concentration (if
liquid"
One can find in literature se#eral models describing process of adsorption! namel$
,reundlich isotherm! -angmuir isotherm! &.T isotherm! etc" )e will deal with -angmuir
isotherm in more details/
Types of Adsorption
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. On the basis of type of forces of attraction existing between
adsorbate and adsorbent, adsorption can be classified into two types: Physical dsorption or
!hemical dsorption.
Physical Adsorption or Physisorption
"hen the force of attraction existing between adsorbate and adsorbent are weak Vanderwaal
forces of attraction, the process is called Physical dsorption or Physisorption. Physical
dsorption takes place with formation of multilayer of adsorbate on adsorbent. #t has low
enthalpy of adsorption i.e. $%adsorption is &'()'*+,mol.
#t takes place at low temperature below boiling point of adsorbate.s the temperature
increases in, process of Physisorption decreases.
Factors on which Adsorption Depends
Temperature
dsorption increases at low temperature conditions.
dsorption process is exothermic in nature. ccording to -e !hatleir principle, low temperature
conditions would fa.our the forward direction.
Pressure
s depicted by dsorption #sotherm, with the increases in pressure, adsorption increases up to
a certain extent till saturation le.el is achie.ed. fter saturation le.el is achie.ed no more
adsorption takes place no matter how high the pressure is applied.
Surface Area
dsorption is a surface phenomenon therefore it increases with increase in surface area.
Activation of Adsorbent
cti.ation of adsorbent surface is done so as to pro.ide more number of .acant sites on
surface of adsorbent. This can be done by breaking solid crystal in small pieces, heating
charcoal at high temperature, breaking lump of solid into powder or other methods suitable for
particular adsorbent.
T$pes of Adsorption
Depending on the nature of attracti#e forces e'isting between the adsorbate and
adsorbent! adsorption can be classified as/

i Ph$sical adsorption

ii +hemical adsorption

i Ph$sical adsorption (Ph$sisorption

In ph$sical adsorption! the forces of attraction between the molecules of the adsorbate
and the adsorbent are of the wea% #an der )aals0 t$pe" Since the forces of attraction are
wea%! the process of ph$sisorption can be easil$ re#ersed b$ heating or decreasing the
pressure of the adsorbate (as in the case of gases"

ii +hemical adsorption (+hemisorption

In chemisorption! the forces of attraction between the adsorbate and the adsorbent are
#er$ strong1 the molecules of adsorbate form chemical bonds with the molecules of the
adsorbent present in the surface"

Adsorption is generall$ accompanied b$ release of energ$! that is! most adsorption
processes are e'othermic in nature" Adsorption is a spontaneous process1 therefore its free
energ$ change is negati#e (D234" 5owe#er! the entrop$ change associated with
adsorption is generall$ negati#e because the adsorbate molecules lose their translation
freedom when the$ get attached to the surface of the adsorbent" Therefore! in order for
D2 to be negati#e! the enthalp$ change (D5 must be sufficientl$ negati#e! such that!
(D26D5*TDS34" This e'planation accounts for e'othermic adsorption processes" In
cases! where endothermic adsorption occurs as in the case of h$drogen adsorption on
glass! the entrop$ change DS is sufficientl$ positi#e such that D2 remains negati#e"
.nthalp$ of adsorption! which is the enthalp$ change for the adsorption of one mole of an
adsorbate on an adsorbent surface! is usuall$ in the range of 74 %89mole to :4%89mole
while for chemisorption! the #alues are an order of magnitude high! that is! 744 %89mole
to :44 %89mole"

The differences between ph$sisorption and chemisorption are summari;ed in the below
table"
dsorption Processes
(1) Adsorption involves the interphase accumulation of concentration of
substances at a surface or interface. The processes can occur at an
interface between any two phases, such as, liquid-liquid, gas-liquid, or
liquid-solid interfaces.
(6) Types of Adsorption
a. Exchange adsorption: Ions of one substance concentrate a surface as a result of
electrostatic attraction. The charge on the ion is the determining factor (trivalent ion
is attracted much more strongly toward a site of opposite charge).
b. Physical adsorption: It is a result of van der Waals force. The adsorbed molecule
is not afxed to a specifc site at the surface but is free the undergo translational
movement within the interface. It is predominant at low temperature, and is
characterized by a relatively low energy of adsorption.
c. Chemical adsorption: The adsorbate undergoes chemical interaction with the
adosrbent. (activated adsorption or chemisorption). It is favored by higher
temperature, because chemical reactions proceed more rapidly at elevated
temperatures. It exhibits high energy of adsorption.
Electrostatic adsorption involves the adsorption of ions through Coulombic forces, and is normally
referred to as ion exchange, which is addressed separately in the ion exchange modules.
In liquid adsorption, solutes concentrate at the surface of a sorbent, thereby reducing their
concentration in the bulk liquid phase.
+ommon Adsorbents
< Acti#ated carbon * a char*li%e material with high surface area"
< Silica gel * hard! granular! porous material made b$ precipitation from sodium silicate
solutions treated with an acid"
< Acti#ated alumina * aluminum o'ide acti#ated at high temperature and used primaril$
for moisture adsorption"
< Aluminosilicates (molecular sie#es = porous s$nthetic ;eolites used primaril$ in
separation processes"