ADSORPTION

When a solid surface is exposed to a fluid phase the molecules from the bulk of the fluid phase have tendency to accumulate or concentrate at the surface of a solid. The phenomenon of enrichment or chemical substances at the surface of a solid is called as adsorption. Adsorption involves the transfer of mass from either gas or liquid phase to the surface of a solid. To complete the separation the adsorbed constituent must then be removed from a solid. It is a fluid solid operation that involves selective collection and concentration of particular type of molecules contained in a fluid phase on the surface of a solid. So with this operation the components of gaseous or liquid solution can be separated from each other. Applications of Adsorption 1. Separation of gas from gaseous mixture: Removal of toxic gases from waste gases for air pollution control and de-colorisation of air Example: Activated charcoal is used in gas molecules in which all toxic gases and vapors are adsorbed by the charcoal while pure air passes through its pores particularly unchanged. 2. Separation of vapors from gases: Dehumidification of air and other gases recovery of valuable solvent vapors from solvent laden air and other gases. Example: Silica and alumina gel are used as adsorbents for removing moisture and for controlling humidity of room. 3. Separation of solutes from solutions:Removal of moisture in dissolved gasoline, decolorisation of sugar solution, vegetable oils and petroleum products, removal of taste and odour from water, removal of organic components from aqueous wastes for water pollution control. 4. Removal of ions from solutions: De-mineralisation of water. 5. A very good method of creating hish vacuum is to connect a bulk of charcoal cooled in liquid air to a vessel which has already been exhausted as far as possible by a vacuum

pump. Since the magnitude of adsorption at such low temperature is quite hish, the remaining traces of air, inspite of low pressure are adsorbed by like charcoal completely. 6. Adsorption also plays an important role in heterogeneous catalysis. Example: The role of finely divided iron in the presence of NH3 and that of finely divided nickel in the hydrogenation of oils. Free Energy change in Adsorption As a result of adsorption i.e. decrease in residue forces acting along the surface of adsorbent. Consequently there is a decrease of surface energy which appears as heat. Adsorption therefore is invariably accompanied by decrease in enthalpy of the system, i.e. H of the process is invariably negative. H = U+ PdV = -U- PdV H= negative Further since the adsorbate changes from the more random gaseous state to less random adsorbed state on the surface of the solid, adsorption is also accompanied by decrease in enthalpy of system, i.e. TdS of the process is also negative

dS= Tds= dq Adsorption is thus accompanied by decrease in enthalpy as well as decrease in entropy of the system. For spontaneous process, the free energy change given by the expression G=H- TdS G should be negative. Since H and S are both negative, it is evident that H should have a sufficiently high negative value. So that the net result of the expression on the right hand side of above equation is negative, i.e. the value of H-TdS should be negative. However we know from

the experiment that the heat of adsorption per mole of the adsorbate goes on decreasing, i.e. H becomes less and less negative as adsorption proceeds further and further. Ultimately, H becomes equal to TS and G becomes zero at this stage, equation is attained. G = H TdS = -H (-TdS) = -H + TdS G = negative G = 0 at equation,H = TdS Nature of Adsorbents 1. Adsorbent solids are usually used in granular form with size ranging from 12mm in dia to 50m 2. They must possess large surface per unit mass. 3. They should have preferential ability to take up the adsorbate (they should have sufficient specificity and adsorptive ability) 4. They are usually high porous materials. 5. They should be free flowing for easy handling. 6. They should offer low pressure drop for flow of fluid when used in fixed bed. 7. They should have adequate strength and hardness. 8. The adsorbent should be capable of being easily regenerated. 9. The adsorbent should not age rapidly, i.e. loose its adsorptive capacity through continual recycling. Adsorption Isotherms The equation data for adsorption are usually presented in the form of adsorption isotherms. The adsorption isotherm is the equilibrium relationship between the concentration of adsorbate held on the surface of the solid and the concentration of adsorbate in the fluid phase at a given temperature. The concentration of the adsorbate on the solid surface is expressed as the amount of substance adsorbed per unit mass of the adsorbent.

A Methane B Acetone C Benzene In case of gases, the concentration of adsorbate in the fluid phase is expressed in terms of partial pressure or mole % and in case of solutions; it is expressed as mass of adsorbate per unit volume of the solution or in mass unit such as ppm. The following figure shows several adsorption isotherms for particular activated carbon as adsorbent, where the concentration of adsorbed gas on the solid plotted against the equilibrium partial pressure of the vapor or gas at constant temperature. At 100 0C, pure acetone vapor at a partial pressure of 190 mmHg is in equilibrium with the adsorbate concentration of 0.2 kg adsorbed acetone/ kg carbon, as the raising curve indicates, and decreasing the pressure of the system at A will cause desorption from the carbon. While determined experimentally in this case, it is known that the 100 0C isotherm for acetone will continue to raise only to a pressure of 2790mmHg, the saturation vapor pressure of acetone at this temperature. At higher pressure, no

acetone can exist in the vapor state at this temperature but instead will condense entirely to a liquid. Different gases and vapors are adsorbed different extent under comparable conditions. Thus benzene is more readily adsorbed than acetone at the same temperature and gives a higher concentration for given equilibrium pressure. Theory of adsorption The Langmuir theory of adsorption Langmuir proposed his theory of adsorption of gas on the surface of the solid. He considered the surface of the solid to be made up of elementary sites each of which could adsorb one gas molecule. The following five assumptions are involved in the derivation of Langmuir adsorption isotherm. 1. The adsorbed gas behaves steadily in the vapor phase. 2. Only a mono layer is formed by the adsorbed gas. 3. The surface of the solid is homogenous so that each binding site has the same affinity for gas molecules. 4. There is no lateral interaction between the adsorbed molecules. 5. The adsorbed gas molecules are localized i.e. they do not move around the surface. 6. It is further assumed that a dynamic equilibrium exists between the adsorbed molecules and the free molecules. If A is the gas molecule and M is the surface sight then A(g) + M(surface)

AM

Where ka and kd are the rate constant for adsorption and desorption respectively. The rate of adsorption is proportional to the pressure of A i.e. PA and the number of vacant sites on the surface i.e. N (1-) Where

N = Total number of sites = Fraction of surface sites occupied by the gas molecules = Thus the rate of adsorption = ka PA N (1-) 1

The rate of desorption is proportional to the number of adsorbed molecules N Thus the rate of desorption = kdN 2

Since at the equation the rate of adsorption is equal to rate of desorption we can write the equation 1 and 2 Ka PA N (1-) = kdN PA (1-) = K PA (1-) = = 1/(K PA)

- 1 = 1/(K PA)

= 1 + 1/(K PA)

Equation 3 is called as Langmuirs adsorption isotherm.

The first assumption holds at low pressure the second braise down when the pressure of the gas is increased. The third adsorption is not strictly true because the real surface is quite heterogeneous so that affinity for gas molecules is different at different sites. Crystal imperfections and cracles lead to the creation of different sites on the surface the fourth and fifth are not strictly valid. Let us consider equation 3 At low pressure k<<1 so that = k PA I.e. the fraction of the surface covered is directly proportional to the partial pressure of the gas molecules. This behavior corresponds to first order reaction and is depicted by the initial stp rise of the isotherm. At high pressure KPA>> 1 so that equation 3 reduces to = 1

Thus at high pressure the value of trends to become unity i.e. the entire surface gets covered by a monolayer

The Freundlich Equation The Freundlich Equation is the empirical relationship that fits the equation of adsorption data (equation data for adsorption) in many cases. The Freundlich adsorption isotherm is represented by the equation C* = k (x/m)n (for solution) P* = k (x/m)n (for gases) Where C* is the equilibrium concentration of the adsorbate in the fluid phase and x/m is the mass of the substance adsorbed per unit mass of adsorbent. P* = equilibrium Partial pressure of the adsorbed gas (adsorbate) in the fluid phase (gas phase) x = Mass of the substance adsorbed m = Mass of the original adsorbent. K & n = Constant.

The Freundlich adsorption isotherm is a straight line for n=1, convex for n<1 and concave for n>1. In each case the solution is to be reduced from y0 to y1 in a single stage operation then three

operating line will radiate from the point P with slope proportional to the adsorbent to solution weight ratio. The values of n in the range 2 to 12 represent good, 1.2 moderately difficult and less than 1 poor adsorption characteristics. . Single stage adsorption

It may be batch or continuous. The following figure represents the all arrangement constituting one stage. Here the solution to be treated consists of adsorbable solute (c) in the solvent (A). It is contacted with adsorbent (B) either in batch or continuous manner. The amount of adsorbent used is very small in comparison with the solution. Only solute (C) is adsorbed and the adsorbent is insoluble in the solution. Let LS be the mass of solvent (batch) or mass of solvent/time (for continuous operation) in the solution to be treated. SS be the mass or mass/time of the adsorbent added to the stage. Yo is the adsorbable solution concentration in the solution to be treated expressed as mass of solute/mass of solvent Y1 is the adsorbable solute concentration in solution leaving the stage expressed as mass of solute/mass of solvent.

Xo is the solute concentration in adsorbent added, in mass solute/mass adsorbent. For fresh adsorbent Xo=0. X1 is the solute concentration in the adsorbent leaving the stage mass of solute/mass of adsorbent. Assume further the amount of solution mechanically retained with the solution phase separation (by filtration or settling) is negligible. This is quite satisfactory for most adsorption as the quantity of the adsorbent used is very small in comparison with the quantity of solution treated. So, with this, the material balance of solute is: Solute removed from the solution= solute picked up the solid LS(Yo-Y1) = SS(X1-Xo) (Yo-Y1)/(Xo-X1) = - SS/LS 1 This is a equation of operating line On X-Y co-ordinates equation 1 is a straight line of slope - SS/LS, passing through the point P(Xo, Yo) and Q(X1, Y1). For an equation or theoretical stage the effluent stream are in equation, so X1, Y1 are equation concentration of the respective stream and point Q(X1, Y1) lies on the equation adsorption isotherm. Graphically representation is shown in figure b. If the Ferundlich equation is applicable then Ferundlich adsorption isotherm in terms of concentration used here is Y* = m Xn So at final equation condition Y1 = m X1
n

X1 = [Y1/m]1/n Substituting in equation 1

(Yo Y1)/{Xo - [Y1/m]1/n} = - SS/LS Usually adsorption does not contain solute initially, Xo = 0 and with this we get (Yo Y1)/ [Y1/m]1/n = - SS/LS 2 With the half of equation 2 we can calculate the adsorption to solution ratio for a given change in solution concentration Yo to Y1.