Unit III ADSORPTION Introduction 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.

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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

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Adsorption is always accompanied with a decrease in residual surface forces. Absorption: It involves passing of the substances through the surface into bulk of the solid /liquid substance 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

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Sorption Sorption is the process in which both adsorption and absorption occurs simultaneously. 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 sorption, 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

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Surface Phenomenon

Bulk phenomenon

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

No such effect

Proportional to surface area

No relation between absorption and surface area

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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 Definition: Adsorption of Gas on Solid surface. Adsorbent: Solid Adsorbate: Gas 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) Based on Mechanism adsorption can be classified as Physisorption and Chemisorption Mechanism of Adsorption 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

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Example: Adsorption of various gases by charcoal Adsorption of H2 on Platinum surface 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 and adsorbate 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/ adsorbate should be chemically active. Characterized by a high heat of adsorption ( ten fold greater than physisorption)

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Desorption and adsorption does not occur at same temperature. Hence considered as irreversible. Attainment of equilibrium is slow

For mechanism of physical and chemical adsorption refer class notes

Differences between Physisorption and Chemisorption

Physisorption

Chemisorption

Type of bond

Vander Waal / Hydrogen bonding

Ionic / covalent

Attainment of equilibrium

Fast

Slow

Enthalpy of Adsorption

Low (10-40 kJ/mol)

High ( 40 - 400 kJ/mol)

Reaction of adsorbate

Adsorbate does not undergo dissociation

Adsorbate undergoes dissociation

Activation Energy

low

high

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Nature

Reversible at the same temperature

Irreversible at the same temperature

Effect Of pressure

Adsorption is directly proportional to pressure

No appreciable effect

Effect of Temperature

Adsorption is inversely proportional to temperature

Directly proportional to temperature initially ( till a maxima is reached) then inversely proportional due to desorption

Surface compound

Surface compound not formed

Surface Compound formed between adsorbate and adsorbent

Bond length

~5A

1-2A

No. of adsorbed layers Selectivity

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More than one

single

low
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Factors influencing adsorption (1) Nature of the Adsorbate / gas Easily liquefiable gases (like SO2 , HCl, NH3, Cl2, moisture 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 SO2 NH3 CO2 CH4 CO N2 H2

Tc (K) Vol of Gas adsorbed

430

406

304

190

134

126

33

380

180

48

16.2

9.3

8.0

4.5

---Ease of liquefaction and adsorption decreases ----- Temporary gases Permanent gases

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(2) Nature of adsorbent Different materials possess different affinity for adsorption due to the difference in surface energy Hence the three factors which influences adsorption are surface area, surface roughness and pore size Surface area surface area of the adsorbent is directly proportional to its adsorption capacity Surface area can be increased by pulverizing the adsorbent Surface Roughness Greater the roughness greater will be the unbalanced forces hence greater will be the adsorption Roughness of the surface can be increased by mechanical methods such as rubbing, filing etc. Pore Size 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

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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 (3) 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 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.
Adsorption iso bars Effect of temperature on extent of adsorption at constant pressure

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Adsorption isobars can be used to distinguish between physical and chemical adsorptions. 5. Effect of pressure As pressure increases adsorption increases till a maxima is reached, there after adsorption becomes constant. The pressure at which maximum adsorption occurs is termed as Saturation pressure or Saturation point (Ps).

x /m Or

Ps ------- Pressure--------

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:

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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. This principle is utilized in removing poisonous substance present in any solution 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) 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.

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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 Adsorption isotherm The rate of adsorption at a given temperature can be altered by applying pressure on the adsorbate molecules (more so for physi sorption). The relation between the extent of adsorption (x/m) or fractional coverage () and pressure at constant temperature is called adsorption isotherm. X/m= Mass of adsorbate Area of adsorbent

Number of adsorbed sites Total no. of sites on adsorbent

Many experiments have been performed to study the effect of pressure on the adsorption behavior of various systems at different temperatures. The data showed repeated occurrence of certain types of adsorption isotherms. It was found that five types adsorption isotherm recurred frequently. The shapes of these five types along with examples are given below.

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Type I Adsorption Isotherm

The above graph depicts Monolayer adsorption. This graph can be easily explained using Langmuir Adsorption Isotherm. Examples of Type-I adsorption are \ i. Adsorption of Nitrogen (N2) on charcoal at temperature near to -180oC ii. Hydrogen (H2) on charcoal at temperature near to 180oC. Type II Adsorption Isotherm

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Type II Adsorption Isotherm shows large deviation from Langmuir model of adsorption. The intermediate flat region in the isotherm corresponds to monolayer formation.

Examples of Type-II adsorption are i. Nitrogen (N2 (g)) adsorbed at -195oC on Iron (Fe) catalyst ii. Nitrogen (N2 (g)) adsorbed at -195oC on silica gel.

Type III Adsorption Isotherm

Type III Adsorption Isotherm also shows large deviation from Langmuir model. 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 i. Bromine (Br2) at 79oC on silica gel ii. Iodine (I2) at 79oC on silica gel.

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Type IV Adsorption Isotherm

At lower pressure region of graph is quite similar to Type II. This explains formation of monolayer followed by multilayer. 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 i. adsorption of Benzene on Iron Oxide (Fe2O3) at 50oC ii. adsorption of Benzene on silica gel at 50oC. Type V Adsorption Isotherm

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Explanation of Type V graph is similar to Type IV. Example of Type V Adsorption Isotherm is i. adsorption of Water (vapors) at 100oC on charcoal.

Type IV and V shows phenomenon of capillary condensation of gas

Freundlichs Adsorption Isotherm: It is an empirical equation 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

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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 x/m = K Point b saturation state

( P0 = 1)

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.
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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.

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 Langmuirs 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.
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 The adsorbate behaves ideally in vapour phase. Only a monolayer is adsorbed. The adsorbed layer is uniformly spread over the adsorbent 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.

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Where A (g) is un adsorbed gaseous molecule, B(s) is unoccupied metal surface and AB is occluded surface.

Derivations of the Langmuir Adsorption Equation Calculation of Equilibrium Constant Langmuir proposed that dynamic equilibrium exists between adsorbed gaseous molecules and the free gaseous molecules. Using the equilibrium equation, equilibrium constant can be calculated.

Where Ka represents equilibrium constant for forward reaction and Kd represents equilibrium constant for backward direction. According to Kinetic theory, Rate of forward reaction = Ka [A] [B] Rate of backward reaction = Kd [AB] At equilibrium, Rate of forward reaction is equal to Rate of backward reaction

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The above equation represents the equilibrium constant for distribution of adsorbate between the surface and the gas phase. Derivation Langmuir Equation which depicts a relationship between the number of active sites of the surface undergoing adsorption (i.e. extent of adsorption) and pressure. To derive Langmuir Equation and new parameter is introduced. Let the number of sites of the surface which are covered with gaseous molecules. Therefore, the fraction of surface which vacant is Total Occupied = (1 ). Now, Rate of forward direction depends upon two factors: (i) (ii) Number of vacant adsorbent, (1 ) Pressure, P. sites available on the surface of

Therefore rate of forward reaction is directly proportional to both mentioned factors.

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Similarly, Rate of backward reaction or Rate of De sorption depends upon number of occluded sites. ie. Sites occupied by the gaseous molecules on the surface of adsorbent.

At equilibrium, rate of adsorption is equal to rate of desorption. Ka P (1 ) = Kd We can solve the above equation to write it in terms of . KaP KaP = Kd KaP = KaP + Kd KaP = (Kd + KaP)

Divide numerator and denominator on RHS by Kd, we get

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Equilibrium constant K = Ka / Kd

Now putting

in above equation we get

Langmuir Adsorption Equation This is known as Langmuir Adsorption Equation. In the above equation P is applied pressure and K is equilibrium constant and both are experimentally determinable. Hence can be calculated.

Case (i) : when pressure assumes a lower value, The expression 1 + KP 1, So

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 = KP is directly proportional to P1

Case (ii) : when pressure assumes a higher value, The expression 1 + KP KP, So = KP / KP =1 ( a constant) is directly proportional to P0

In general it can be written as is directly proportional to Pn (where n assumes values between 0 and 1)

If a is the amount of adsorbate adsorbed per unit mass of adsorbent, then a is proportional to Hence

a = K1
= KPn

a = K1KPn
K1 K is substituted as KL , Langmuirs constant

a = KLPn
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hence

Pn

This expression is called Langmuirs Adsorption Isotherm We know that

a = K1
Hence

and

a = K1KP / 1 + KP a = KLP / 1 + KP
therefore

( K1K = KL)

P/a = 1 + KP / KL P/a = 1 KL + K P KL

If P/a is plotted Vs P , then the intercept gives 1 / KL and the slope is K / KL

P/a

P
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Limitations of Langmuir Adsorption Equation 1. The adsorbed gas has to behave ideally in the vapor phase. This condition can be fulfilled at low pressure conditions only. Thus Langmuir Equation is valid under low pressure only. 2. Langmuir Equation assumes that adsorption is monolayer. But, monolayer formation is possible only under low pressure condition. Under high pressure condition the assumption breaks down as gas molecules attract more and more molecules towards each other. ( BET theory proposed by Brunauer, Emmett and Teller explained more realistic multilayer adsorption process.) 3. Another assumption was that all the sites on the solid surface are equal in size and shape and have equal affinity for adsorbate molecules i.e. the surface of solid is homogeneous. But in real solid surfaces are heterogeneous. 4. Langmuir Equation assumed that molecules do not interact with each other. This is impossible as weak force of attraction exists even between molecules of same type. 5. The adsorbed molecules has to be localized i.e. decrease in randomness is zero (S = 0).This is not possible because on adsorption liquefaction of gases taking place, which results into decrease in randomness but the value is not zero. From above facts we can conclude that, Langmuir equation is valid under low pressure conditions.

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