UNIT - 4.

SURFACE CHEMISTRY

ADSORPTION
Introduction
Adsorption: Concentration or assimilation of a gas (or liquid) at the surface
of a solid (or liquid)
Occlusion. The adsorption of gases on the surface of solids
Adsorbent: The material providing the surface upon which adsorption
occurs
Adsorbate: The substance get adsorbed or attached on the surface of
adsorbent
Ex: Charcoal, Silica gel, Alumina gel, Clay, etc.
Desorption: The removal of adsorbed substance from the surface
Positive adsorption: Concentration of the adsorbate is more on the surface
of the adsorbent than in the solution (bulk).
e.g., In the concentrated solution of KCl, charcoal adsorbs KCl rather than
water and this leads decrease in concentration of KCl in solution.
Negative adsorption: Concentration of the adsorbate is less on the surface
of the adsorbent than in the solution (bulk)
e.g. In the dilute solutions of KCl, charcoal adsorbs water, thereby the salt
concentration is increased.

Exothermic nature of adsorption

Occurs spontaneously as the unbalanced or residual forces acting along the
surface
The adsorbent has a tendency to attract and retain molecules of other
species
Results in decrease in the residual forces, thereby resulting decrease of
surface energy, which in turn appears in the form of heat.
The amount of heat evolved when 1 mole of any gas (or vapour) is adsorbed
on a solid adsorbent surface, is called “enthalpy (or heat) of
adsorption”.

Adsorption and Absorption:

Absorption: Substance distributed throughout the body of the solid or liquid

Adsorption Absorption
1. Concentration or assimilation of a 1. The substance assimilated is
gas (or a liquid) at the surface of a uniformly distributed throughout the
solid (or body of the solid
liquid) or liquid.
2. A surface phenomenon 2. A bulk phenomenon
3. A fast process 3. A slow process
4. Equilibrium is attained easily 4. Attainment of equilibrium takes
some time
CLASSIFICATION OF ADSORPTION
Based on the force of attraction
Physical adsorption (or physisorption) or van der Waals adsorption:
The adsorbed molecules are held to the surface of the adsorbent by weak
physical or van der Waal’s forces.
e.g: Adsorption of various gases by charcoal belongs to this type.
Chemical adsorption or chemisorption or activated adsorption:
The adsorbed molecules are held by chemical bonds.
e.g: Adsorption of oxygen on tungsten, and on charcoal.
Differences between Physical adsorption and Chemical adsorption
Physical adsorption Chemical adsorption
(Physisorption) (Chemisorption)
1. Heat of adsorption is about 20-40 Heat of adsorption is about 40-400
kcal/mol kcal/mol
2.Adsorption is completely Adsorption is irreversible, since
reversible, since the molecules are molecules are tightly retained by
not tightly retained by the adsorbent adsorbent
3. Adsorption is appreciable only at Adsorption can occur at high
temperature below the boiling point temperatures
of the adsorbate, and it decreases
with rise in temperature
4. Multilayer adsorption occurs, i.e., Adsorption leads to , utmost, a
adsorbed layer may be several monolayerForces
molecules thick, since the van der
Waal’s forces can extend from one
layer to another
5. Forces responsible for such responsible for such adsorption are
adsorption are very weak quite strong
6. The rate of adsorption increases The rate of adsorption decreases with
with the increase of pressure or the increase of pressure or
concentration of the adsorbate. Near concentration of the adsorbate. Near
saturation pressure, multilayers are saturation pressure, adsorption rate
formed decreases, since the adsorption is
confined only to upper surface layer
of adsorbent
7. The amount of adsorption on a The amount of adsorption is
surface is more function of the characteristicof both adsorbate and
adsorbate than the adsorbent adsorbent.
8. Such adsorption involves very Activation energy is involved in
small or little activation energy chemical bond formation

9. The equilibrium is established Establishment of equilibrium

rapidly requires time
10. No surface compound formation Actual surface compound formation
takesplace between the adsorbent and adsorbate
takes place.
11. It is not very specific in nature
Such adsorption, generally, involves It is highly specific in nature
appreciable activation energy
ADSORPTION OF GASES ON SOLIDS
Factors affecting the adsorption of gases on solid surfaces
(1) Nature of the gas:
Easily liquefiable gases (like HCl, NH3, Cl2, etc.) are adsorbed more easily
than the permanent gases (like H2, N2, O2, etc.).
The ease of liquefaction of a gas depends upon its critical temperature
The higher the critical temperature (Tc), the more easily the gas is liquefied
and consequently, more readily it is adsorbed.
The critical temperature increases the adsorption also increases
Adsorption of various gases on 1 g of activated carban
Gases SO2 NH3 CO2 N2 H2
C.T (K) 430 406 304 126 33
Amount of gas 380 180 48 8.0 4.5
adsorbed (ml)

(2) Nature of adsorbent:

Greater the surface area of the adsorbent, greater is its adsorption capacity.
Activated charcoal and silica gel are excellent adsorbents, since their
structure is highly porous and hence, possess large surface areas.
Activated charcoal and finely divide solid substances are better adsorbents.
Activation of adsorbent:
Activation leads to increase in the surface area i.e., adsorping power of the
adsorbent
i)Creation of roughness
Mechanical rubbing of metallic adsorbents,
Subjecting to some chemical reactions of metallic adsorbents
ii) Increasing effective area
Sub-dividing the solid adsorbents into finer particles and hence, increasing
surface area
Strong heating in superheated steam of some adsorbents, e.g., when charcoal
is subjected to the action of superheated steam, its pores are opened, thereby
adsorption increases.
(3) Effect of pressure:
The extent of adsorption (x/m) or (S) (where x is the mass of adsorbate, gas,
and m is the mass of the adsorbent) depends upon the pressure.
Adsorption isotherm is a graph plotted between magnitude of adsorption
and pressure, at constant temperature.
Graph: refer class notes
The extent of adsorption (x/m) increases with increasing pressure (P) and
becomes maximum at Ps, called the saturation pressure.

(4) Effect of temperature:

Adsorption isobar is a graph plotted between magnitude of adsorption and
temperature, at constant pressure.
Since adsorption is an exothermic reaction, so with an increase in
temperature, the amount adsorbed (x/m) should decrease.
However, in case of chemisorption, the amount adsorbed (x/m) initially
increases and then decreases, because chemisorption (like an ordinary
chemical reaction) requires some activation energy.
Adsorption isobars can be used to distinguish between physical and
chemical adsorptions.
Thus, in physical adsorption, there is a regular decrease in extent of
adsorption as temperature increases; whereas in chemisorption, there is
initial increase and then decrease in extent of adsorption as temperature
increases. (Ref. graph)

ADSORPTION OF SOLUTES FROM SOLUTIONS

Solid surfaces adsorb solutes from solutions in two ways
1) Solid substances adsorb dissolved substances (solutes) from solutions
Activated animal charcoal adsorbs Colouring matter present in sugar
solution, thereby making the latter colourless.
Activated charcoal adsorbs certain acids like acetic and oxalic present in
water, thereby acid concentration in water decreases.
Ammonia from solutions of NH4OH and phenolphthalein from solution of
acids or bases
2) An adsorbent adsorbs certain solute from solution in preference to
other solutes.
Charcoal adsorbs non-electrolytes more readily than electrolytes from a
solution.
Alumina adsorbs electrolytes in preference to non-electrolytes.
Factors influencing adsorption of solutes from solution
1) Effect of temperature and concentration
Adsorption from solution increases with rise of temperature and increase in
concentration of solution.
Freundlich adsorption equation is found applicable
Adsorption from solution decreases with rise of temperature and decrease in
concentration of solution.
Positive adsorption: when conc. Of the solution is high, the adsorption of
solute is high and the conc. of solute is more on adsorbent surface than in the
solution (bulk)
Nagative adsorption: when conc. Of the solution is low, the adsorption of
solute will be low and the conc. of solute is less on the adsorbent surface
than in the solution (bulk)

2) Effect of surface area

Adsorption increases with increase in surface area of the adsorbent
ADSORPTION ISOTHERMS
A graph plotted between the magnitude of adsorption and pressure at
constant temperature
Types of adsorption Isotherms
Type I: Monomolecular layer adsorption
Postulated by Langmuir
The rate of adsorption increases with the increase of pressure or
concentration of the adsorbate until it reaches the saturation pressure
Furthur increase in pressure will not increase the amt of adsorption
E.g., Adsorption of N2 or H2 on charcoal
Type II Multimolecular layer adsorption
Show large deviations from Langmuir model
The amt of adsorption increases with increase in pressure
Additional layer formation due to the extension of vander waals force
e.g., Adsorption of N2 on Pt at -195 C
e.g., Adsorption of Br2 on silica at 80C
Type III: Capillary condensation with multimolecular layer formation
Condensation of gases in the minute capillary pores of adsorbent
Multimolecular layer formation
e.g.: Adsorption of benzene on silica gel at 50o C
e.g.: Adsorption of H2O vapour on activated Carbon at 100o C
REFER THE GRAPHS FROM NOTES
FREEUNDLICH’S ADSORPTION ISOTHERM
The Freundlich equation or Freundlich adsorption isotherm is an
adsorption isotherm, which is a curve relating the concentration of a solute
on the surface of an adsorbent, to the concentration of the solute in the liquid
with which it is in contact.
For Adsorption of gases on solids
x/m = KP1/n
For Adsorption of solutes on solid in solutions
x/m = KC1/n
Where
x/m= extent of adsorption

where

x = mass of adsorbate
m = mass of adsorbent
p = Equilibrium pressure of adsorbate
c = Equilibrium concentration of adsorbate in solution.

K and 1/n are constants for a given adsorbate and adsorbent at a particular
temperature

From the adsorption isotherm, the following observations can easily be

made:
(i) At low pressure, the graph is almost straight line, 1/n = slop =
tan 45o = 1
Log x/m = log K + 1 log P
thereby indicating x/m ∞ P or x/m = KP
(ii) At high pressure, the graph becomes almost parallel to X-axis,
thereby indicating 1/n = slop= tan 0 = 0
Log x/m = log K + 0 log P
x/m = constant or x/m = K
(iii) At intermediate pressure, x/m depends on 0 to 1 power of pressure (i.e.,
fractional power of pressure). 1/n = 1 to 0
x/m ∞ P1/n
x/m = KP1/n
On taking the logarithm of both sides, the above expression assumes the
form:
Log x/m = log K + 1/n log P or
Log x/m = log K + 1/n log C
Thus, if log x/m is plotted against log P or log C, a straight line would be
obtained. The slope of the curve will give 1/n; while the intercepts on log
x/m axis at P = 0 or C=0 would give K
Limitations:
(i) Purely empirical basis
(ii) Valid upto certain pressure and invalid at high pressure
(iii) Fails when concentration of adsorbate is very high
(iv) K and n are temperature dependents, vary with temperature
LANGMUIR’S THEORY OF ADSORPTION
Assumptions or Postulates
1. Valencies at the surface of adsorbent atoms are not fully satisfied. Each
solid surface contains a fixed no. of active adsorption sites and each siter can
adsorb only one molecular or atomic species of the adsorbate
2. The residual valency force on the surface of adsorbent is effective only up
to a small distance (about 2 × 10-8 cm) and hence, the adsorbed gas layer is
only one molecule thick.
3. The phenomenon of adsorption consists of two opposing processes,
namely, condensation of the molecules of the adsorbate on the surface of the
adsorbent and evaporation or desorption of the adsorbed molecules from the
surface of the adsorbent.
4. A dynamic equilibrium is set up, when the rate of condensation becomes
equal to the rate of evaporation.
5. There is no interaction between the adjacent adsorbed molecules
6. The adsorbed gas molecule does not move around on the surface.
7. Each solid adsorbent surface has a fixed number of adsorption sites and
each site can adsorb only one atomic or molecular species
8. The heat of adsorption for all the adsorption sites are same irrespective of
the fraction of the surface covered with adsorbed molecule

Derivation Langmuir’s adsorption equation.

Refer notes
θ = aP/1+aP ……………… (1)
x= amt of the adsorbate per gm of adsorbent
P = Pressure
‘a’ is adsorption co-efficient
x∞θ
x =k ( aP/1+aP)
x = ka P/ 1+ aP
x = bP / 1+ aP
1/b + aP / b = P/x

The equation (1) may be re-written as:

P/x = aP /b +1/b

Thus, if we plot P/x against P, we should get a straight line.

Case I: At very low pressures, aP becomes negligible in comparison with 1,
hence, equation (1) reduces to:
1/b>> aP/b……………… (2)
P/x = 1/b
bP = x
x∞P
i.e., amount of adsorption per unit weight of adsorbent at a given
temperature is directly proportional to the pressure of the gas at low
pressures.
Case II: At high pressures, aP is very high as compared with 1 and,
therefore, (1) takes
the form
aP / b = P /x
x = (b/a) constant ……………… (3)
i.e., at high pressures, the extent of adsorption at a given temperature is
independent of
pressure of the gas, because the surface becomes completely covered. Case
III: At intermediate pressure, equation 3 becomes
x/m = KP1/n ……………… (4)
Where n lies between 0 and 1. Equation (4) is Freundlich’s adsorption
isotherm
Limitations
1. This equation is also not valid at high pressure
2. Apparent saturation of a surface is observed even only a small
fraction of the area of the adsorbent is covered
3. The adsorption maximum is also variable on temperature and
prussure, This equation does not explain the multimolecular layer
formation
APPLICATIONS OF ADSORPTION
(1) Activated charcoal
Gas masks in which all undesirable (toxic) gases are adsorbed selectively by
charcoal; while purified air passes through its pores.
Removing colouring matter of sugar solution and the decoloration of
vinegar.
Charcoal adsorption filters are used for removing organic matter from
drinking water and from industrial effleunts
Production of vacuum in Dewar’s flask.
(2) Silica and alumina gels
Removing moisture and for controlling humidity of room.
Silica gel has been employed for drying air, used in blast furnaces.
(3) Adsorption chromatography.
Selective adsorption by alumina, magnesia, etc., has been used for
separating different pigments
(4) Arsenic poisoning
Colloidal ferric hydroxide is administered which adsorbs the arsenic poison
and retains it and can thus be removed from the body by vomiting.
(5) Fuller’s earth
Refining petroleum and vegetable oils from unwanted materials, due to its
good adsorption capacity.
(6) Heterogeneous catalysis
Adsorption is the key process in catalysis
The adsorption of reactants on the catalyst surface provide close proximity
to the reactants and form products and products desorbed from the surface.
Contact process
Haber’s process
Hydrogenation of oils.
(8) Mordants (aldsorbent)
Dying cloth, Mordants adsorb the dye particles, which otherwise do not stick
to the cloth.
(9) Measurement of surface area
Surface area of powder and rough surface can be measured (BET method)
(10) Water Conservation
The adsorbed stearic acid on the surface of water minimizes evaporation of
water
(11) Ore Dressing
Froath floation process: Low grade sulphide ores are freed from earthy
impurities

Role in Activated carbon

Activated carbon has very high surface area and it adsorb odorous, gaseous,
and liquid contaminants forming a strong chemical bond or attraction. Its
adsorption property is put to use in following
1. In producing high vacua - For this partly evacuated apparatus is connected
to a vessel containing activated carbon, cooled in liquid air. At this
temperature, carbon adsorbs residual air very effectively.
2. In gas masks or respirators - it adsorbs poisonous or foul smelling and
other harmful gases and vapour more readily than it adsorbs air.. Thus the air
gets filtered on passing thro the gas mask before breathing.
3. Remove offensive odor from the air (deodorizer) in air-conditioning
process in large restaurants, auditoriums and in refrigerators, in shoe insole
4. In room air purifiers, the activated carbon is often combined with zeolite
and thus acts as a filter for odour control, toxin removal and as a chemical
sieve. In some units it is impregnated with potassium iodide or blended with
impregnated alumina to increase the adsorbent qualities. These home air
purifiers are particularly helpful to people with Multiple Chemical
Sensitivity (MCS) as well as for asthma patients
5. To remove impurities from gases such as hydrogen, nitrogen, Helium,
acetylene etc.
6. In cigarette filters – used either as granule or powder in filters to remove
some harmful elements of cigarette smoke, or taste and flavour control
7. During waste disposal containing domestic, clinical, chemical waste etc.
by high temperature incineration, the flue gas is made to pass carbon to
remove heavy metals, dioxins and other harmful substances prior to release
in the air.
ROLE OF ADSORPENTS
In Ion-Exchange Adsorption
The process of releasing the charged ion and adsorbing another ion with
similar charge by an adsorbent
Application: Water Softening
In Ion-Exchange Adsorption can be used in water softening process
1. Deionization or Demineralization
Demineralisation of water is done in an ion exchanger. In This process
anions and cations present in the hard water can be exchanged with the same
charged ions in the ion exchanger.

Ion Exchange resins are insoluble cross linked long chain macro polymer
with micro porous structure and the functional groups attached to the chains
are responsible for the ion exchanging properties.

The ion-exchanger commonly used is Styrene Divinyl Benzene Copolymer:

CH CH2 CH CH2 CH CH2

CH CH2 CH CH2 CH CH2

Cation Exchanger: Resins containing acidic functional group (▬ COOH,
▬SO3H) are capable of exchanging their H+ ions with other cations of hard
water. Cation exchange resin is represented as RH

CH CH2 CH CH2 CH CH2

- + - +
SO3 H SO3 H

CH CH2 CH CH2 CH CH2

- + -
SO3 H +
SO3 H
Capable of exchanging their cations with other cations
Polymers containing acidic functional gps like sulphonic (-SO3H) and
carboxylic(-COOH) acids
Sulphonated is more acidic because its pKa = 1, so completely ionized when
in contact with water
Generally represented as R-H+
Exchange H+ ions with other cations
2R-H++ Ca+===== R2Ca+ + 2H+
Cation exchange reaction is reversible, the original resin can be
regenerated on treatment with acid

Anion Exchanger: Resins containing basic functional groups (▬ NH2) or

quaternary ammonium groups are capable of exchanging their OH- ions with
other anions of hard water. Anion exchange resin is represented as ROH
 CH CH2 CH CH2 CH CH2

+ - + -
CH2 N(CH3)3 OH CH2 N(CH3)3 OH

CH CH2 CH CH2 CH CH2

+ - + -
CH2 N(CH3)3 OH CH2 N(CH3)3 OH

Capable of exchanging their anion OH- with other anions (Cl-, SO42-, etc,..).
Polymers containing basic functional gps like quaternary Ammonium
hydroxide and amino gps
Quaternary Ammonium hydroxide is more basic in nature, since its pKb =
14, so completely ionized when in contact with water
Generally represented as R+OH-
Exchange OH- ions with other anions
R+OH- + Cl- ===== R+Cl-+ OH-
Anion exchange reaction is reversible, the original resin can be
regenerated on treatment with base

Process:

The hard water is first passed through a cation exchange column, H+

ions can be exchanged with the cations like Calcium, Magnesium ions
in hard water.

RH+ + M+ ▬▬▬► RM+ + H+

CaCl2 + RH2 ▬▬▬► RCa + 2HCl

NaCl + RH2 ▬▬▬► RNa + HCl

The cation free water is then passed through an anion exchange

column, in which all the anions like chlorides, sulphates etc are
exchanged with OH- ions.

ROH- + X- ▬▬▬► RX- + OH-

H+ + OH- ▬▬▬► H2O

ROH + HCl ▬▬▬► RCl + H2O

The water coming out is completely free from cations and anions.
This water is known as DM water or deionised water.

Regeneration: when the cation exchange resin is exhausted, it can be

regenerated by passing a solution of dil. HCl or H2SO4.

RNa + HCl ▬▬▬► RH + NaCl

Similarly for the exhausted anion exchanger dil.NaOH can be used.

RCl + NaOH ▬▬▬► ROH + NaCl

Advantages
1. This process can be used to soften highly acidic or alkaline
waters
2. It produces water of very low hardness (2 ppm)

Disadvantages
1. This equipment is costly and more expensive chemicals are
needed.
2. Turbid water clogs the pores in the ion –exchange bed, so turbid
water cannot be used. Turbidity should be lower than 10 ppm
2. Zeolite process
REFER NOTES:
ZeNa2 + Ca2+

-
ZeCa + 2Na+
Adsorption Chromatography
Based on the differences in the adsorption coefficients of substances on
solid

An analytical technique for identification and separation of components of a

mixture based on their differences in their adsorption coefficients of
substances on solid.

Column chromatography that in which the various solutes of a solution

are allowed to travel down an absorptive column, the individual components
being absorbed by the stationary phase

The mobile phase is allowed pass through the stationary phase. The
stationary phase retains the components of mobile phase at different points
depends on their adsorption.

Stationary phase:
Adsorbent packed in the column. Ex: silica gel, alumina.

Mobile phase:
The mixture of components is allowed to flow slowly over the stationary
phase.

Process
StepI: Separation of various compounds

When the solution containing different solutes is poured down a column,

filled with finely divided adsorbent. partial separation takes place due to the
difference in adsorption coefficient.

The components with higher adsorption tend to be retained at the top, the
other components are adsorbed successively at various distance depends on
their adsorption.
A number of horizontal bands or zones or rings of different colours are
produced in the column. The colored zones or banded column of the
adsorbed substance is called as Chromatogram.
StepII: Identification of compounds

Colored compounds produce colored rings, zones or bands.

Colorless compounds are observed by either exposing UV light on the
column or by spraying suitable chemical reagent in order to make them
colored.
The chemical reagents are called as developers.
The process of visualization of a colorless chromatogram is called as
development of chromatogram.

StepIII: Separation and estimation

The separation is improved by passing suitable solvent (developer) slowly

through the column.

The various zones are dissolved separately in suitable solvents and estimated
The process of recovery of various substances is elution and the solvent is
called eluent.

*The adsorbate (solute) should possess sufficiently high solubility in the

solvent
*The competition between the solute and solvent molecules for the binding
sites (adsorption) in the adsorbent should also be considered.
*The solvent should not elute the solute more quickly and also should not
take a long time to elute, because leads to long retention time and band
broadening effects

*Some of the commonly employed solid adsorbents in the increasing order

of adsorptive power are,
powdered cellulose < starch < sucrose < CaCO3 < magnesia < silica gel <
alumina

• Some of the commonly employed solvents in the increasing order of

eluting power are
• ccl4 < toluene < benzene < chloroform< diethyl ether < ethyl acetone
<acetone< ethanol<methanol< water< Organic acids and bases
Examples for separable compounds by adsorption chromatograph:
1. Mixture of amino acids, proteins, lipids and pigments
2. separation of metal component from mixture of metals in alloys
3. separation of cis and trans isomers(cis and trans isomers of 1,4-
cyclohexane, olefins on activated alumina), keto and enol forms from
its mixture (Separation of keto and enol isomer of ethyl acetoacetate
and methylphenylketones)

Advantage
1. Separation of a mixture of molecules with similar chemical properties and
almost equal boiling points is possible only in adsorption chromatography
2. Large volume of samples can be separated.
Applications
1. Quantitative separation of two or more substances.
2. Purification of organic substances
ACTIVATED CARBON
Among the various adsorbents, in treatment of polluted water and air ,
the activated carbon is the most commonly used adsorbent because of
its porous structure with high surface area per unit mass
The S.A of A.C = 1000 m2 / g
It was first used as an adsorbent in gas masks in World War I.
Preparation
1. Preparation Char (carbon) form raw materials
The char is produced by heating (carbonizing) the raw materials like
coconut, wood, coal, petroleum residues, saw dust , lignite to red heat in
a retart to remove hydrocarbons in insufficient supply of air
2. Activation of carbon
1) Direct Process: Heating carbon at 850C in a current of superheated steam
2) Briquetting process: Powdered carbon is mixed with wood, tar and
caustic soda, compressed in small briquettes and then heated in steam at
800C.
3) Chemical Process: Wood is impregnated with the solution of zinc
chloride or phosphoric acid and then carbonized.
Classification of Activated Carbon
1)Granular Activated Carbon(GAC)
Diameter of greater than 0.1nm
Used for adsorption of gases, vapors and solute particles
Produced from coconut shells, fruit pits, charcoal and briquetted coal
2) Powder Activated Carbons(PAC)
Diameter of less than 200mesh
Used in purification of liquids
Saw dust and lignite are raw materials
Properties
Activated carbon has enormous surface area of the order of 1000 m2/ g.
Activated carbon is able to adsorb practically any volatile organic
compounds (VOC) at lower temperature (35oC) and can be released on
heating to a higher temperature (120o C).
II. In abatement of water or air pollution
The fresh water available on the earth is only 2%. Hence proper
maintenance, conservation and use of water resources are required to avoid
chances of water scarcity for future generation. It is therefore necessary to
treat water and reuse wastewater, so as to increase and improve the quality
of water and make it for use.
Activated carbon is used in water treatment process.
Theory:
*It is both hydrophobic and oleophilic (ie) it hates water but has affinity for
oil and other organic chemicals since A.C adsorbs preferably non-electrolyte
than electrolyte.
*When the flow condition is suitable, dissolved chemicals in water flowing
over the surface of carbon get adsorbed on the surface while the water passes
over.
*Activated carbons used in waste water treatment are Granular Activated
carbon (GAC) and powdered Activated carbon (PAC).
1. Using GAC
GAC is used because of its porous structure and high surface area. It is
cheaper, effective and can be reused.
Water treatment can be done by using two different type of fiixed bed
columns as follow,
1. Up flow fixed bed A.C contactors:
2. Down flow fixed bed A.C contactors
3. Advantages
4. Disadvantages
REFERBOOK
2. Using PAC
Biologically treated water --
mixed with PAC ---
allowed for adsorption
--
sedimentation with coagulants like poly electrolyte (Polyelectrolytes are
polymers whose repeating units bear an electrolyte group. These groups will
dissociate in aqueous solutions (water), making the polymers charged. Ex:
Poly(acrylic acid) PAA will lose their protons and acquire a negative charge
and poly(sodium styrene sulfonate). --
filteration using GAC bed and sand
filter --
pure water
Regeneration
Activated carbon is able to adsorb organic compounds (VOC) at lower
temperature (35oC) and can be released on heating to a higher temperature
(120o C).
GAC’s can be regenerated in a furnace by heating it in the presence of
limited amount of super heated steam, flue gas and oxygen. Some carbon (5
- 10%) is destroyed during regeneration process
ROLE OF ADSORPENTS
In Catalytic Reaction: Heterogeneous catalysis

Heterogeneous catalysis

This involves the use of a catalyst in a different phase from the reactants.
Typical examples involve a solid catalyst with the reactants as either liquids
or gases.

One or more of the reactants are adsorbed on to the surface of the catalyst at
active sites. An active site is a part of the surface which is particularly good
at adsorbing things and helping them to react.

There is some sort of interaction between the surface of the catalyst and the
reactant molecules which makes them more reactive.

This might involve an actual reaction with the surface, or some weakening
of the bonds in the attached molecules.

At this stage, both of the reactant molecules might be attached to the surface,
or one might be attached and hit by the other one moving freely in the gas or
liquid.

The product molecules are desorbed.

Desorption simply means that the product molecules break away. This
leaves the active site available for a new set of molecules to attach to and
react.

A good catalyst needs to adsorb the reactant molecules strongly enough for
them to react, but not so strongly that the product molecules stick more or
less permanently to the surface.

Silver, for example, isn't a good catalyst because it doesn't form strong
enough attachments with reactant molecules. Tungsten, on the other hand,
isn't a good catalyst because it adsorbs too strongly.

Metals like platinum and nickel make good catalysts because they adsorb
strongly enough to hold and activate the reactants, but not so strongly that
the products can't break away.
Examples of heterogeneous catalysis

The hydrogenation of a carbon-carbon double bond

The simplest example of this is the reaction between ethene and hydrogen in
the presence of a nickel catalyst.

In practice, this is a pointless reaction, because you are converting the

extremely useful ethene into the relatively useless ethane. However, the
same reaction will happen with any compound containing a carbon-carbon
double bond.

One important industrial use is in the hydrogenation of vegetable oils to

make margarine, which also involves reacting a carbon-carbon double bond
in the vegetable oil with hydrogen in the presence of a nickel catalyst.

Ethene molecules are adsorbed on the surface of the nickel. The double bond
between the carbon atoms breaks and the electrons are used to bond it to the
nickel surface.

Hydrogen molecules are also adsorbed on to the surface of the nickel. When this
happens, the hydrogen molecules are broken into atoms. These can move around
on the surface of the nickel.

If a hydrogen atom diffuses close to one of the bonded carbons, the bond
 between the carbon and the nickel is replaced by one between the carbon and
hydrogen.

That end of the original ethene now breaks free of the surface, and eventually
the same thing will happen at the other end.

As before, one of the hydrogen atoms forms a bond with the carbon, and that
end also breaks free. There is now space on the surface of the nickel for new
reactant molecules to go through the whole process again.

ACTUAL PROCESS IN REACTIONS

Step I : Diffusion of reactant molecules
Step II: Adsorption of reactant molecules
Step III: Formation of Activated complex
StepIV: Decomposition of Activated complex
StepV: Desorption of products
FACTORS AFFECTING THE CATALYTIC ACTIVITIES
1. Finely divided state of catalyst is more efficient
2. Rough surface enhances the activity
3. Catalysts are more specific towards adsorbate
4. Catalytic promoters increase the rate of the reaction
The interaction of promoters with catalysts may cause changes in
the electronic or crystal structures of the active solid component.
Commonly used promoters are metallic ions incorporated into
metals and metallic oxide catalysts
Ex; finely divided Fe is used as a catalyst to accelerate the reaction at
optimum temperature. The catalyst is mixed with small amounts of
promoter- molybdenum to enhance the efficiency of the catalyst
5. Catalytic poison destroys the activity of catalyst by preferably
adsorbing on catalyst surface.
Catalyst poison: the compound that bonds chemically (similar to an
inhibitor) but does not release, or chemically alters the catalyst.
Ex. As2S3 reduces the catalytic activity of Pt in contact process by the
formation of PtS2. It is a permanent poison of platinum.
N2 adsorption on zeolite during the fluid catalytic cracking of petroleum
fractions
Poisoning of palladium and platinum catalysts: Common poisons for these
two metals are sulfur and nitrogen-heterocycles like pyridine and quinoline
palladium poisoned with lead salts
6. Catalytic inhibitors
Inhibitors adsorb preferentially than adsorbate and slow the rate of reaction.
Sometimesthey even stop the reaction completely.

Inhibition should be distinguished from catalyst poisoning, in the former

case an inhibitor only hinders the working of a catalyst, while in the latter
case the catalyst is destroyed by an irreversible reaction with a chemical
substance (the active catalyst in the latter case may be regained by a separate
process).