LECTURE 8

ADSORPTION

• When solids are allowed to remain in contact with a gas, a film of gas
molecules accumulates on the surface

– This creates unsaturated or residual forces

• Solid liquid interfaces have a tendency to satisfy their residual forces

by

– attracting onto and retaining on their surfaces molecules of

gases and other substances with which they come into contact

– This results in a higher concentration of molecules on the surface

of a solid or liquid than in the bulk of the media, a phenomenon
called adsorption

• Adsorption is the spontaneous accumulation of atoms or molecules at

an interface

• The substance on which adsorption occurs is called an adsorbent

• The substance which is adsorbed is called an adsorbate

• Applications of adsorption

– Manufacturing detergents

– GLC

– Homogeneous and heterogeneous catalysis

Adsorption of Gases on Solids

• To a measurable extent, all solids adsorb gases The magnitude of

adsorption of gases by solids depend on:

1. Nature of solid

– Solids which have the largest surface area are very good
adsorbing agents

• In practice the best adsorbents used are various kinds of

specially prepared carbon e.g. Wood, carbon obtained from
bone, blood; charcoals etc

• Other good adsorbing substances include silica gel,

alumina and alumino silicates

– The power of adsorption can be enhanced by activation forces

• The adsorbent is heated in steam or atmosphere (air) to

about 1500 °C

• Heating drives out impurities (which can be gasfied at that

temperature) from the pores and leads to a larger free
surface for adsorption. E.g. Activated charcoal at 24 °C can
adsorb 1.48 g of CCl4 per gram of charcoal but if this
charcoal is not activated, it can only adsorb 0.001g per
gram of charcoal.

– The gas being adsorbed

• Gases which condense more easily are much more strongly

adsorbed

– The state of subdivision (area) of contact between solid and gas

• It is difficult to determine the surface area of adsorbing

agents directly...therefore, the mass of the adsorbent is
taken as a measure of the surface available for adsorption
 • Adsorption is taken as the amount of substance adsorbed
per unit mass of adsorbing agent

– Temperature and pressure of the gas

• The amount of adsorbed gas decreases with temperature

at constant pressure and increases with a fall in
temperature

2. TYPES OF ADSORPTION
(i) Physical adsorption/ Vander Waals adsorption or physisorption
(ii) Chemisorption/chemical adsorption/ activated adsorption

Physisorption Chemisorption
DH ads < 40 – 42 KJ/mol and DH ads is 50 – 630 KJ/mol and
negative positive
Occurs at temp. Below the critical Can occur at any temperature
temperature (Tc) of the adsorbent
Amount of adsorbed increases Amount adsorbed decreases with
with each increment in pressure of each increment in pressure of the
the body adsorbent body adsorbent
Amount of gas adsorbed depends Amount of gas adsorbed depends
more on the nature of the gas on both the nature of the gas and
than the surface the surface
No activation energy is required Activation energy is required
Can be multilayer Can be multilayer
Forces involved are Vander Waals Formation of chemical bonds
– weak forces (ionic or covalent)
Reversible e.g. Nitrogen on silica Irreversible e.g. Oxygen on
gel charcoal

- When solids are allowed to remain in contact with a gas, a film of gas
molecules accumulates on the surface.
- It was pointed out under
-

NOTE:

1. In many cases, it has been observed that adsorption is neither physical

nor chemical but a combination of the two.
 2. Some systems show physical adsorption at low temperatures but as
the temperature is raised, physical adsorption changes into chemical
adsorption.

QUESTIONS

1. What do you understand by the colloidal state of matter? Bring out the
difference between a colloidal solution and a true solution
2. What are the different types of methods used for the preparation of
colloids? How would you prepare a colloidal solution of (a) Gold, (b)
arsenionssulphide (c) sulphur
3. Explain the use of (a) dialysis
(b) electro-dialysis
(c) ultrafiltration in the purification of colloidal
solutions

4. Distinguish between lyophobic and lyophilic colloidals. Describe

Bredig’s arc method for the preparation of lyphobic colloids.

5. What are emulsions? How are they classified? Give one method for their
preparation.

Measurement of Adsorption

• Experimental study of adsorption is explained in terms of adsorption

isotherms where you plot quantity adsorbed against pressure

• Equations are sought which fit these isotherms and these are known as
adsorption equations

• A simple experimental set up that can be used to measure adsorption

is the sorption balance
 • Procedure

– Evacuate A using a coil and cool

– Note the position of the bucket using a travelling microscope

– A desired quantity of gas is allowed in from the reservoir through

the doser

– The new position of the bucket is determined

– From previous calibration with a known weight, the mass of the

adsorbed gas is determined

– The equilibrium pressure for gas is measured by a manometer

– Repeat the process using different volume and get the isotherm

The B.E.T Equation

• The equation

is applied to multilayer adsorption

– where:
 • V = total volume adsorbed at STP

• Vm = Monolayer covering all available surface

• P = Pressure

• P0 = saturated vapour pressure (SVP)

• C = constant related to heat of adsorption

– This equation was proposed by Brunauer-Emmett and Teller

(BET)

– Using the same assumptions as of Langmuir but extended to

apply to multilayer assuming monolayer co exist

Validity/Application of B.E.T Equation

• Plotting P/V(P0 – P) Versus P/P0 gives a straight line of intercept 1/VmC

and slope/ gradient C-1/VmC

Application of the B.E.T Plot

 1. Determination of monolayer capacity (Vm)

2. Determination of specific surface area i.e. Area per unit mass of

adsorbent so that we can create more surface

– where:

• Am = cross sectional area of molecule in M 2

• L = Avogadro's number

• W – mass of adsorbent

• M – Molar mass of condensed vapour in Kgmol -1

3. Determination of roughness factor , r

• Actual area is obtained from BET

• Apparent area is obtained from the photomicrograph

– When r= 1, the surface is perfectly smooth ( may not be

practically unattainable)

4. It can be used in determining pore volumes

5. Can be used to determine the enthalpy of adsorption DH ads

• In practice the B.E.T plot is only straight between the limits of

P/Po of 0.05 – 0.35
Deviations

• Deviation from Langmuir and BET occurs as a consequence of

the short comings of the assumptions

i. One of the most doubtful assumptions is that of surface

uniformity

ii. You cant rule out lateral interaction thus

a. Deviation below 0.05 are due to active sites

(heterogeneity)

b. Above 0.35, lateral interaction exists

• In Principle, a minimum of three points is required and these

measurements should be made in relative pressure ranges of
0.05 – 0.35

• By good approximation when nitrogen is used as an adsorbent,

the straight line plot meets the ordinate at a point near the
origin such that b (1/VmC) can be ignored so that the equation
becomes
Pore volume and Pore Size Distribution

• The total pore volume Vp is given by Vp

– Wmax = mass of adsorbent

– rL = density of adsorbent liquid

• Usually the whole plot is not necessary. Measurement at relative

pressure of 0.95 can give valid information

Pore size distribution

• By using gases of various molecular cross sectional areas, it is possible

to determine the distribution of pore sizes

Question

– The adsorption of nitrogen on sphericabl copper particle of 0.01

mm in diameter was determined at 77K at the normal boiling
point of nitrogen. The volumes adsorbed per gram of powder at
various pressures was as follows
 V (Cm3) at 0.0155 0.0167 0.172 0.0184
STP
P(Torr) 44.8 69.2 82.8 118.6

– Show that the data obey the B.E.T equation (validity plot)

– Calculate the monolayer capacity VL and the specific surface

area (the molecular area of nitrogen = 0.162 nm 2)

Adsorption Isotherms

• Adsorption process is usually studied through graphs known as

adsorption isotherm.

– That is the amount of adsorbate on the adsorbent as a function if

its pressure or concentration at constant temperature .

– The quantity adsorbed is nearly always normalized by the mass

of the adsorbent to allow comparison of different materials.

Basic Adsorption Isotherm:

– From the above we can predict that after saturation pressure P s,

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

• The above graph depicts Monolayer adsorption.

• This graph can be easily explained using Langmuir Adsorption

Isotherm.

• If BET equation, when P/P0<<1 and c>>1, then it leads to monolayer

formation and Type I Adsorption Isotherm is obtained.

• Examples of Type-I adsorption are Adsorption of Nitrogen (N 2) or

Hydrogen (H) on charcoal at temperature near to -1800°C.

Type 2 Adsorption Isotherm

• Type II Adsorption Isotherm shows large deviation from Langmuir

model of adsorption.

• The intermediate flat region in the isotherm corresponds to monolayer

formation.

• In BET equation, value of C has to be very large in comparison to 1.

• Examples of Type-II adsorption are Nitrogen (N 2 (g)) adsorbed at -

1950°C on Iron (Fe) catalyst and Nitrogen (N2 (g)) adsorbed at -1950°C
on silica gel.

Type 3 Adsorption Isotherm

• Type III Adsorption Isotherm also shows large deviation from Langmuir
model.

• In BET equation value if C <<< 1 Type III Adsorption Isotherm

obtained.

• This isotherm explains the formation of multilayer.

• There is no flattish portion in the curve which indicates that monolayer

formation is missing.

• Examples of Type III Adsorption Isotherm are Bromine (Br 2) at 790°C on

silica gel or Iodine (I2) at 790°C on silica gel.

Type 4 Adsorption Isotherm

• 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.
Type 5 Adsorption Isotherm

• Explanation of 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.

TYPE IV & V

- Are irreversible unlike I and II and usually obtained if a gas is easily

liquefied.
- The isotherm obtained during desorption lies somewhat above the
adsorption curve
- The behavior is known as HYSTERESIS and is caused by liquefaction
in the pores spaces at pressure lower than the normal V.P of the
adsorbate as a result of the cohesive influence of the adsorption
forces.

NOTE: In case of chemisorption, only Type I curves are obtained while in

case of physical adsorption all the five isotherms are observed.