Surface chemistry

SSNCE Dr.S.L

As we approach smaller dimensions, surface effects become much
more dominant

small particle
Large particle High surface ratio
volume
Molecules (atoms) at a surface experience a net attractive force
towards the interior
-This unbalanced force manifests itself
as surface tension in liquids
Rain drops - spherical

Systems attempt to minimize Surface to

Volume ratio
The unbalanced force on the surface of a solid results in
ADSORPTION

This force on the surface has tendency to attract and retain

molecules of other species

Residual force on the surface decreases after

adsorption

Absorption : involves passing of the substances
through the surface into the solid /liquid substance
Adsorption is the first step in the viral infection cycle.
Why is Adsorption Useful?

Used in many industrial processes:
 dehumidification
 odour/colour/taste removal
 gas pollutant removal (H2S)
 water softening and deionisation
 hydrocarbon fractionation
 pharmaceutical purification
 Terms involved

Absorbate
A substance that becomes absorbed into another
material, or absorbent.

Absorbent
The substrate into which a substance is absorbed.

Absorption
The increase in quantity (transfer) of one material
into another or of material from one phase into another
phase.
 Adsorbate
A substance that becomes adsorbed at the interface or
into the interfacial layer of another material, or
adsorbent.

Adsorbent
The substrate material onto which a substance is

Sorption
 A process in which both of the processes of adsorption and
absorption takes place simultaneously
Desorption – release of adsorbed or absorbed substances into
surrounding medium

Sorbate
 A substance that becomes sorbed into an interface or another material
or both.

Sorbent
 The substrate into which or onto which a substance is sorbed or both.

Monolayer adsorption
 Adsorption in which a first or only a layer of molecules becomes
adsorbed at an interface.
 In monolayer adsorption, all of the adsorbed molecules will be in
contact with the surface of the adsorbent. The adsorbed layer is
termed a monolayer or monomolecular film

Difference between adsorption and
absorption

Adsorption is a surface phenomenon – due to surface tension
Absorption is a bulk phenomenon in which the substance
assimilated is uniformly distributed throughout the body of the solid
or liquid”- due to capillary action

Adsorption is a fast process as compared to absorption, which is a

slow process, because it involves the diffusion into the interior of
the matter

Adsorption - Equilibrium between adsorbate & adsorbent is attained

rapidly
Absorption – uniformly distributed throughout the body & occurs
slowly

Adsorption depends on the surface area of the adsorbent

Absorption – surface area independent
Adsorbent Materials

• Activated Carbon
• Activated Alumina
• Silica Gel
• Molecular Sieves (zeolite)
• Polar and Non-polar adsorbents
Characteristics of Adsorption

Spontaneous

Exothermic ∆H = negative

Decrease in entropy & free energy

∆S = negative, ∆ G = negative

Occurs on the surface, specific & selective.

Rate of adsorption is T dependent

How do molecules bond the surface?

Two principal modes of adsorption of molecules on

surfaces

- based on distinction in the nature of the bonding

between the molecule and the surface

Physical Adsorption ( Physisorption )

Chemical Adsorption ( Chemisorption )

 Physisorption

Bonding is by weak Van der Waals -

type forces / dipole forces.
There is no significant redistribution of
electron density in either the molecule
or at the substrate surface.

Less energy is released = enthalpy of

condensation

Physisorbed molecule retains identity

Reversible process

Eg Adsorption of Hydrogen/oxygen on
charcoal

Physisorption can be multilayer

 Chemisorption

Chemical bonding (using free valencies) occurs between

adsorbent(surface) & adsorbate (between ionic & covalent bond)

Results in formation of surface compound of single layer

Irreversible

Eg : Adsorption of hydrogen on nickel

High heat of adsorption : - 200 KJ/mol

Activation energy is involved

Adsorbed molecule loses identity

ADSORPTION OF GASES ON SOLIDS (OCCLUSION)

Factors
(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 higher the critical temperature (Tc), the more easily
the gas is liquefied - more readily it is adsorbed
Adsorption of various gases by 1 g of activated charcoal

Gas SO2 NH3 CO2 CH4 CO N2 H2

Tc (K) 430 406 304 190 134 126 33

mL of gas 380 180 48 16.2 9.3 8.0 4.5

adsorbed
Ease of liquefaction and adsorption decreases --------------->
Nature of adsorbent

Different materials possess different extent of adsorption

greater the surface area of the adsorbent, greater is its

adsorption capacity

activated charcoal and silica gel – excellent adsorbents –

high porosity & surface area

Surface activated to increase porosity

Methods of surface activation

Creation of rough surface by rubbing, by deposition

Dividing solid adsorbent to finer particles

By heating in superheated steam – opens pores

Heat of adsorption

Physical adsorption – heat evolved is low

Chemical adsorption – heat evolved is high

Reversible character

Physical adsorption – reversible – adsorbate desorbed when T

is increased
Chemical adsorption – irreversible – chemical compound is
formed at surface
Effect of Temperature

Adsorption isobar -
surface coverage θ

Temperature surface coverage θ

Temperature
Physisorption chemisorption
∆H -negative

Effect of T - Adsorption Isobar

T1
Vol. adsorbed

T2 >T1

T3 >T2

T4 >T3

T5 >T4

Pressure
 Effect of P

Extent of adsorption (x/m) dependent on P – Adsorption

isotherm
Adsorption of a gas on a solid in a
closed vessel – a reversible process

b Free gas ↔ gas adsorbed on solid

a Amount of gas adsorbed on a solid

x/m depends on equilibrium P

From the graph it is clear that the extent of

adsorption (x/m) increases with increasing
Ps pressure (P) and becomes maximum at Ps,
called the saturation pressure.
P
x/m = KP 1/n

At low pressure, the graph is almost straight line (point a), thereby
indicating

x/m α P or x/m = KP

• At high pressure, the graph (beyond b) becomes independent of P

(parallel to X-axis,) thereby indicating
x/m = constant or x/m α P0 or x/m = K ………….. (ii)
Point b –saturation state

• At intermediate pressure, x/m depends on 0 to 1 power of pressure

(i.e., fractional power of pressure).
x/m α P1/n or x/m = KP1/n Freundlich’s adsorption isotherm

Log x/m = log K + 1/n log P

log x/m is plotted against log P, a straight line would be obtained

Slope=1/n
log x/m

Deviates at high P
intercept+=log K

log P
Effect of P on adsorption – Adsorption Isotherm

P4>P3
P3>P2
Vol. adsorbed

P2>P1

P1

Temperature
Langmuir Adsorption Isotherm

Theoretical Explanation for

unimolecular layer formation
during physical & chemical
adsorption

Verifies Freundlich Isotherm

Limitations
Fails at very high P – owing to
multimolecular layer formation
& condensation of gas
molecules in the pores of the
adsorbate
-
Types of adsorption Isotherm

Ps refers to saturation
pressure of the gas

Type I : Langmuir Isotherm:

Monolayer formation
Eg: Adsorption of N2/ H2 on
charcoal at
– 180 C

Type II & III: Multi layer
Adsorption of N2 on Pt at -195 C
physical adsorption on
non porous materials

The amount of
adsorption increases with
increase in pressure.

Additional layer formation

due to the extension of
vander waals force.
Adsorption of Br2 on silica at 80 C
Type IV & V :
Formation of multimolecular
layer& also condensation
of gas molecules within
narrow capillary pores of
the adsorbent

Adsorption of H2O vapour

on activated Carbon at 100C

Adsorption of benzene
on silica gel at 50C
Adsorption of Solutes from solution

Solid substances adsorb dissolved substances

(solutes) from solutions
Activated animal charcoal adsorbs colouring matter
present in sugar solution making the latter colourless.
An adsorbent adsorbs certain solute from solution
in preference to other solutes.
Charcoal adsorbs non-electrolytes more readily
while Alumina adsorbs electrolytes preferentially from
solution
Types of adsorption of solutes from
solution

Positive adsorption

Negative adsorption
Applications of adsorption

In heterogenous catalysis : Contact Theory

Hydrogenation of Alkenes to Alkanes

Mechanism

Step 1. Hydrogen molecules react with the metal atoms at the

catalyst surface.

The relatively strong H-H sigma bond is broken and replaced

with two weak metal-H bonds.
Step 1 hydrogen first physisorbed
& then becomes chemisorbed)

Step 2

pi bond of the alkene
interacts with the metal
catalyst weakening the
bond.

A hydrogen atom is
transferred from the catalyst
surface to one of the
carbons of the double bond.

Step 3

The pi bond of the alkene

interacts with the metal
catalyst weakening the
bond.

A second hydrogen atom is

transferred from the catalyst
surface forming the alkane

Step 4

The alkane is released from
the catalyst's surface
allowing the catalyst to
accept additional hydrogen
and alkene molecules.

Finely divided catalyst
& Rough catalyst
surface possess high
Activity

Catalytic poisons &

inhibitors reduce the
activity of catalyst

Promoters increase the rate of the reaction
In Adsorption Chromatography

closely related substances

with almost similar and
physical and chemical
properties which cannot be
separated from one another
by ordinary means are
adsorbed to different
extents on the surface of
adsorbent.

This facilitates separation

and purification of
components in a mixture.
Method

Stationary phase : Some common adsorbents

used are : aluminium oxide, silica gel, MgO, MgCO3,
CaCO3, Charcoal, cellulose, Fuller’s earth.

Mobile Phase : Solvents used are: benzene,

cyclohexane, chloroform, ethylalcohol, water , CCl4,
pyridine etc.
Step 1 :Separation of mixture into
different components

A number of horizontal bands of different

colors are produced in the column.

Only a partial separation of various
constituents
Different stages of column
chromatography

Step 2 : Development of chromatogram

To improve the separation of constituents in a

mixture

Using either the original or some other
suitable solvent slowly through the column.

The solvent used is called Eluent

Step 3 : Isolation & Estimation of components

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.

Colored components are dissolved separately in suitable

solvents and estimated quantitatively
Applications of column chromatography:

Quantitative separation of two or more components

of a mixture (separation of metal ions, amino acids,
proteins)

Purification of substances from their contaminants

Concentration of solutes from dilute solutions

Identification of products.(eg : isomers of organic

compounds
Role of adsorption in softening of water

Demineralisation process

Electrical demineralisation process

Zeolite process
Deionisation of water
Electrical demineralisation of water

Ion exchange resins are supported on a paper or a

fibre

Used as membranes, ion-selective membranes

Cation selective membrane permits only cations not
anions

Anion selective membrane permits only anion

The rate of diffusion of ion is increased by passing
electric current through the electrode placed near
the membrane
Electrical demineralisation of water

Harde water +
-

+
-
-
-
+
-
+
-
+

+
-

anion exchange
Cation exchange Soft water membrane
membrane
Zeolite process (hydrated sodium alumino
silicates Na2O. Al2O3. xSiO2. yH2O)
h
Water softening process
Zeolite regeneration process

zeolite

Spent zeolite

Zeolites insoluble in water & are cation Exchangers

Ca(HCO3)2 + Na2 Z → 2NaHCO3 + CaZ

Regeneration

CaZ + NaCl → Na2Z + CaCl2

Disadvantages

Cannot be used for turbid water – clogs the bed

Cannot be used for highly acidic or alkaline water as it attacks the bed

Water should be free from iron / manganese salts. When adsorbed in
the bed , they cannot be regenerated

Hot water should not be used

Advantages

- removes hardness completely

- occupying small space
Summary

Adsorption – phenomenon of concentration of a gas/ liquid (adsorbate) at the
surface of a solid (adsorbent) with which it is in contact.

Adsorption on a surface can be through vanderwaals force(physisorption) or

through a chemical bond formation (chemisorption)

Increase in P upto saturation pressure increase the extent of adsorption on the

adsorbent.

Freundlich & Langmuir adsorption Isotherm explain the effect of P on

adsorption.

Adsorption of solutes from solution also obey Freundlich isotherm

Phenomenon of adsorption finds wide use in chromatography, in heterogenous

catalysis, in softening of water, in pollution abatement etc