Unit 111 - Lesson Schedule SURFACE CHEMISTRY Objective To make the student conversant with the fundamentals of surface

chemistry and its industrial applications

Lecture

Topics to be covered

Introduction Terms involved in surface chemistry Adsorption Vs Absorption Types and Mechanism of Adsorption Physisorption and Chemisorption Positive and Negative adsorption Factors influencing adsorption Adsorption isotherms Definition Type I Type V with examples Freundlich adsorption isotherm Langmuir adsorption isotherm Adsorption of solute from solution Principles and application of column chromatography Role of adsorbents in catalysis Chambers process Contact process Applications of adsorption Ion exchange adsorption Pollution abatement
Page 1 20th September 2008

2 and 3

4 and 5

8 and 9

Dr.V.S.Gayathri And Dr.K.Yamuna

ADSORPTION In solids and liquids, the molecules are in close contact. Hence a molecule in the depth of a liquid is pulled equally in all directions while a molecule at the surface is pulled sideways and towards interior only. This leads to residual forces or unbalanced force which acts along the surface of a liquid giving rise to surface tension. Such forces exist on the surface of a solid also. Due to these forces the solid has a tendency to attract and retain molecules with which it comes in contact. However in gaseous molecules the intermolecular attraction is negligible and hence the space between gaseous molecules is large. Due to the unbalanced force on the surface of solid , it has a tendency to attract and assimilate liquid , gaseous molecules which are in close contact . The phenomenon of assimilation of a gas ( or liquid) at the surface of a solid (or liquid) with which it is in close proximity (contact) is called Adsorption. Adsorption is always accompanied with a decrease in residual surface forces.

Dr.V.S.Gayathri And Dr.K.Yamuna

Page 2

20th September 2008

Absorption: It involves passing of the substances through the surface into bulk of the solid /liquid substance

Dr.V.S.Gayathri And Dr.K.Yamuna

Page 3

20th September 2008

Terms involved Adsorbate A substance which gets adsorbed on the surface of a solid or liquid is called adsorbate. Example : Carbon di oxide, oxygen, sulphur di oxide, moisture etc., Adsorbent The surface (substance/material) which adsorbs a liquid or a gas is called adsorbent. Example: Charcoal, Silica gel, Alumina gel, Clay etc., Adsorption The process of assimilation of a gas (or a liquid) on the surface of a solid (or a liquid) with which it is in close contact is called adsorption. Absorption The process of uniform distribution of a substance in the bulk of the material is called absorption. The substance is absorbate The material is absorbent Sorption Sorption is the process in which both adsorption and absorption occurs simultaneously.

Dr.V.S.Gayathri And Dr.K.Yamuna

Page 4

20th September 2008

Example: When ammonia is added to a beaker containing water and charcoal, ammonia is adsorbed on charcoal and absorbed by water. Desorption Desorption is the reverse of adsorption, in other words evaporation is desorption. Desorption is defined as the process by which adsorbed or absorbed substances is released into the surrounding medium Monolayer adsorption If only a layer of molecules gets adsorbed on the adsorbent, it is called monolayer adsorption. 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 Differences between adsorption and absorption

Adsorption

Absorption

Accumulation of adsorbate at the surface of the adsorbent

Uniform distribution of the absorbate throughout the absorbent

Surface Phenomenon

Bulk phenomenon

Dr.V.S.Gayathri And Dr.K.Yamuna

Page 5

20th September 2008

Occurs due to surface tension

Occurs due to Capillary action

Fast process

Slow process

Equilibrium is attained easily

Takes time to attain equilibrium

Extent of adsorption is dependent on applied pressure Proportional to surface area

No such effect

No relation between absorption and surface area

Dr.V.S.Gayathri And Dr.K.Yamuna

Page 6

20th September 2008

Enthalpy of adsorption or Heat of adsorption The amount of heat given out when 1 mole of any gas or vapour gets adsorbed on a solid surface is termed as enthalpy of adsorption Types Of adsorption Based on the nature of adsorbent and adsorbate adsorption can be of various types Occlusion: adsorption of Gas on Solid surface. It can be further classified into Physical and Chemical adsorption This principle finds application in Gas masks To remove odour from polluted water In industries to carry out chemical reactions (Habers process and Contact process) Physisorption or Vander Waals adsorption If the adsorbate forms a physical bond ( Van der Waals / Hydrogen bonding ) with the adsorbent, it is called as physisorption Example: Adsorption of various gases by charcoal Adsorption of H2 on Platinum surface
Dr.V.S.Gayathri And Dr.K.Yamuna Page 7 20th September 2008

Characteristics of physisorption: Between the adsorbent and adsorbate there is no chemical attraction, only a weak Van der Waals attraction / hydrogen bond binds the adsorbate to the adsorbent surface. The adsorbent should be inactive or inert. Characterized by a comparatively low heat of adsorption Desorption and adsorption occurs at same temperature ie. Reversible Attainment of equilibrium is fast Chemisorption or activated adsorption If the adsorbate forms a chemical bond (ionic / covalent) with the adsorbent, it is called as chemisorption Examples: Adsorption of oxygen on tungsten or charcoal Adsorption of hydrogen on Cu or Ni Characteristics of chemisorption: The force of attraction between adsorbent and adsorbate is of chemical nature viz., ionic / covalent The adsorbent should be chemically active. Characterized by a high heat of adsorption ( ten fold greater than physisorption) Desorption and adsorption does not occur at same temperature. Hence considered as irreversible. Attainment of equilibrium is slow
Dr.V.S.Gayathri And Dr.K.Yamuna Page 8 20th September 2008

For mechanism of physical and chemical adsorption refer class notes

Differences between Physisorption and Chemisorption Physisorption Chemisorption

Type of bond

Vander Waal / Hydrogen bonding Multi

Ionic / covalent

No. of adsorbed layers

Mono

Adsorption heat

Low (10-40 kJ/mol)

High ( 40 - 400 kJ/mol)

Selectivity

low

high

Activation Energy

low

high

Nature

Reversible

Irreversible

Effect Of pressure

Adsorption is directly proportional to pressure

Page 9

No appreciable effect

Dr.V.S.Gayathri And Dr.K.Yamuna

20th September 2008

Surface compound

Not formed

Compound formed between adsorbate and adsorbent

Bond length

~5A

1-2A

Factors influencing adsorption (1) Nature of the Adsorbate / 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 and hence more readily it is adsorbed Adsorption of various gases by 1 g of activated charcoal Gas Tc (K) SO2 430 NH3 406 CO2 304 CH4 CO 190 134 N2 126 H2 33

Vol of 380 Gas adsorbed

180

48

16.2

9.3

8.0

4.5

------Ease of liquefaction and adsorption decreases --------

Dr.V.S.Gayathri And Dr.K.Yamuna Page 10 20th September 2008

(2) Nature of adsorbent Different materials possess different affinity for adsorption due to the difference in surface energy Hence the two factors which influences adsorption are surface area and pore size surface area of the adsorbent is directly proportional to its adsorption capacity Greater the pore size easier the adsorption Activated charcoal and silica gel are excellent adsorbents due to high porosity & surface area Adsorption capacity of adsorbents can be increased by activating the surface Methods of surface activation Increasing the roughness of adsorbent surface by mechanical methods such as rubbing, filing etc The pore size can be increased by adopting chemical cleaning methods and / by passing superheated steam through the pores to widen it.

Sub -dividing solid adsorbent to finer particles results in increasing the surface area and number of pores

Dr.V.S.Gayathri And Dr.K.Yamuna

Page 11

20th September 2008

(5) Effect of Temperature Adsorption isobar is a graph plotted between magnitude of adsorption (x/m) and temperature, at constant pressure. Physisorption decreases with increase in temperature as the inter molecular distance increases with temperature

x/m

Temperature Chemisorption initially increases till a maxima is attained and then on increasing the temperature further , adsorption decreases due to the dissociation of metal adsorbate bond.

x /m

Temperature Adsorption isobars can be used to distinguish between physical and chemical adsorptions.
Dr.V.S.Gayathri And Dr.K.Yamuna Page 12 20th September 2008

Adsorption of solute from solution When a salt solution is kept in contact with charcoal, either water or the ions (salt) can get adsorbed on the surface of charcoal. Based on this adsorption of solute from solution can be positive or negative Positive adsorption: If the concentration of the adsorbate is more at the interface than in the bulk, it is positive adsorption. e.g., when concentrated KCl solution is shaken with charcoal, the solute is adsorbed preferentially. As a result the concentration of the solution decreases. However the concentration of KCl at the interface is much greater than the concentration of KCl in the bulk of the solution. Hence it is positive adsorption. Negative adsorption: If the concentration of the adsorbate is less at the interface than in the bulk, it is negative adsorption. e.g., when dilute KCl solution is shaken with charcoal, the solvent (water) is adsorbed preferentially. As a result the concentration of the solution increases. However the concentration of KCl at the interface is much less than the concentration of KCl in the bulk of the solution. Hence it is negative adsorption
Dr.V.S.Gayathri And Dr.K.Yamuna Page 13 20th September 2008

This principle finds application in Separation of chemical identical in property such as amino acids - column chromatography To remove dyes and other soluble impurities from polluted water ion exchange chromatography (demineralization and zeolite process) Adsorption isotherm is a graph which gives the relationship between the extent of adsorption (x/m) and pressure, at constant temperature. Types of Adsorption Isotherms Refer notes dictated in class Freundlichs Isotherm Freundlich found that the extent of adsorption was directly proportion to the fraction of pressure applied for physisorption. He expressed this in the form of a mathematical expression x/m = P1/n

Where x is the amount of adsorbate, m is the area on which adsorption had taken place and p is the pressure applied. x/m = K P1/n where K is proportionality constant. Freundlich plotted a graph with his experimental data

Dr.V.S.Gayathri And Dr.K.Yamuna

Page 14

20th September 2008

a
x/m

Ps
Pressure

Case (i): At low pressure At the initial stages, the number of vacant sites is more hence as the pressure increases, the extent of adsorption increases. (i.e.) extent of adsorption is directly dependent on pressure. x/m P x/m = KP Case (ii): At high pressure At high pressure adsorption is almost constant as the number of vacant sites is almost nil and equilibrium sets in and rate of adsorption = rate of desorption. x / m P0 x / m = K P0
Dr.V.S.Gayathri And Dr.K.Yamuna

( P0 = 1)
Page 15 20th September 2008

x/m = K Point b saturation state Case (iii) At intermediate pressure: As the pressure keeps on increasing from 0 to 1, the number of vacant adsorbent site decreases. Hence the extent of adsorption was found to be x / m P1/n x/m = KP1/n Where n is a whole number, whose value depends on the nature of adsorbate and adsorbent this is Freundlichs adsorption isotherm. taking logarithm on both sides, Log x/m = log K + 1/n log P If log x/m is plotted against log P, a straight line is obtained, the slope gives the value of 1/n , while the intercept gives log K value.

Dr.V.S.Gayathri And Dr.K.Yamuna

Page 16

20th September 2008

log x/m

Slope=1/n

Intercept = log K

log P

Limitations: Does not account for adsorption at high pressure Fails if the concentration of adsorbate is high Langmuir Adsorption Isotherm

Langmuir isotherm is based on the following assumptions

The adsorbent surface is homogenous (i.e.) uniform energy. Hence all binding sites have the same affinity for adsorbate molecules. The adsorbate behaves ideally in vapour phase. Only a monolayer is adsorbed. The adsorbed layer is uniformly spread over the adsorbent

Dr.V.S.Gayathri And Dr.K.Yamuna

Page 17

20th September 2008

 The adsorbed gas molecules do not move around on the adsorbent surface ( they are localized) There is no lateral interaction between the adjacent adsorbed molecules The phenomenon of adsorption is characterized by two opposing processes viz. condensation (adsorption) and evaporation (desorption). During the beginning of the process, the entire adsorbent surface is free; hence adsorption is predominant and fast. As time passes, the number of free adsorbent sites decreases. However, once desorption sets in, the number of free sites increases. When the rate of desorption becomes equal to the rate of adsorption, a dynamic equilibrium sets in. At this stage G = 0. Though pressure is an important factor in adsorption, its influence can be seen only till the saturation point. After Ps increase in pressure does not increase adsorption. Derivation of Langmuir adsorption isotherm Refer class notes

Dr.V.S.Gayathri And Dr.K.Yamuna

Page 18

20th September 2008