Adsorption & Catalysis _Thephenomenon of concentration of a gas (ora liquil) on the surface of a solid (or liquid) with which “ontact is known as adsorption. Adsorption is a term coined.to denote the taking up (Latin- Sorber guid by a surface of interface. It is a property of a liquid or solid to retain On, or concentrate at its ace, one or more components (atoms, molccilcs or ions) from another solid, liquid or gas in contact the surface. Adsorption is a charactcristic surface or interface phenomenon, » The adsorption of a gas on a solid is sometimes called ‘occlusion, © Why does Adsorption occur ? We know that the surface of a liquid is in a state of strain or pluration due to the unbalanced or residual forces which act along the sutface of a liquid. Similar to he surface of a solid may also have residu; ces or valencies, Thus, the outer surface of a solid has dency to attract and to retain molecules of other Species (gas or liquid) with which such surface come pntact, This process of saturating these fréevalencics resulisin adsorption. The adsorption is therefore, Pmpanicd by decrease in residual surface forces, « The removal of the adsorbed substance is called desorption. _, The material providing the surface upon which adsorption occurs is known as the adsorbent and the lance absorbed is known as adsorbate: i . _ Adsorption is a surface phenomenon and is quite different from absorption. Absorption is a bulk lomenon in which a substance is. uniformly distributed throughout the body of the solid or. liquid, while Bsorption the substance is only retained ‘on the siuface, but does not go into the bulk or interior: of the solid to suck up) of gas, vapour, (Surface concentration) (Uniform-penetiation) x Sorption ‘Adsorbate Molecule Absorbed Molecule (Adsorption and absorption) O00g000 “OOO0O00000 ‘Adsorbent + Adsorption / Absorption 4 Sorption Fig 1-1. Mlustration of adsorption, absorption and sorption 1dAdsonprion & Catalysis 1.2 is or liquid. Thus, when a blotting paper iformly into the absorbent, the blotting paper, On beriginchy charcoal the surface of th bat carte some : litmus i trated at the surface of adsorbent, g 4 oe en dh biciton the equilibrium ts easily ‘attained, whereas in absorption the equilibrium t oo Peoiallasd the word sorption is used to include both adsorption and absorption. Dilference between Adsorption and Absorption, 2.5. Absorption ‘Absorption is, a. bulk. phenomenon. In. which substance gets uniformly distributed throughout of the solid or liquid, : It takes place at a uniform rate, i ith ink, the latter is.adsorbed and penetra, Tein con i ia dilute solution of litmus i hake i ‘of the litmus, In this practically at ‘Adsorption “The adsorbing 1,,,| Adsorption is a surface phenomenon, abatanee (adsorbate) is reiained on the surface of the adsorbent, " 2,. |The rate of adsorption is rapid initially but decreases slowly with time, Free molecules at constant temperature Surface occupied’ by molecules (8) Base surface (1-6 Types of Adsojption ) sion ag Sialhege az ai ol Physical and chemical adsorptions. Depending upon the nature of the forces holding th fecules to the solid surface adsorption can be of the following-wo types : (D) Physical adsorption or van der Waals adsorption, (ii) Chemical adsorption or activated adsorption or chemisorption, In Physical or van der Waals adsorption, the adsorbed molecules arc held to the surface'al adsorbent by weak physical or van der Waals forces similar s form a ligqlid, Such adsorption s characterised Bya comparatively ‘type of adsorption is completely r eversible, Adsorptionaf various as In case of chemical adsorption or chemis rption or activated adsorption th ] ci 1c. forge whi the adsorbed molecules is of valence typo, TI ween the adsorbent and adsorbate & Ee the product appears to be a surface compound, This type of adsorption involves interact ‘Yalencies at the surface molecules of the adsorbent and the adsorbed all available valencies on the surface of the adsorbent would produ at evolved is entire surface, In chemisorption the he: adsorption, Such, an adsorption is irre ‘ype. Other important cxamples are oxygenosorption; For example, adsorp! tion of H, on a mixture of manganese oxide and chromifuin sea ido is ‘adsorption type at high temperature (715K and higher) jorption, The ‘main’ distinguishing physical type » Di at low temperature and ch inction between’ Physical Ads laracteristics of the two kinds of adsorptior jorption and. chemis n aro summarised in the following table Characteristic Physteal adsorption Heat of adsorption and binding forces Reversibiliy. Effect of teinperature Effect of pressure, and. concentration poe Sirucuire of the adsorbed =| layer Formation of compound. fe Chemisorption ent of adsorption (heat evolved) is comparatively law (20 ~ 40 kJ mal!) duo to weak ‘binding, van, der Waals type, sis ‘Adsorption is completely reversible, ‘Adsorption is ‘appreciable at tow temperature” (only ‘at “temperature, below. tho pis. of the: adsorbate), Desorption occurs on increasing the temperature, ‘The rate of adsorption increases with the increase of pressure or concentration of the adsorbaic ‘Amount of adsorption on yAurface is, ‘more a function of she adsorbate than Such adsorption involves very amall or litle activation energy. ‘The equilibrium is established rapidly. ‘Multilayer adsorption, No surface compound formation takes place, m4 _|,#PPreciable activation energy, Heat, of adsorption. (heat evolved) is ‘considerably higher than that in case of, physica! adsorption (80... to 400 kI mol!) due to... chemical compound type binding, 7 Ttis irreversible. ‘Adsorption “can occur’ “at” high ‘omperatures, ‘There’ may’ be an ‘optimum temperature, ab ct Dut “if ‘The rate of adsorption decreases with the Increase. of pressure or concentration of the adsorbate, Amount of adsorption is characteristic of, both the, adsorbate...and . the adsorbent (specific). Such - adsorption generally involves Establishment of equilibrium requires Hime. Monolayer adsorption: ‘Actual surface compound formation between adsorbent and adsorbate takes place: s i, Adsorption of Gases by Solids — ‘All solids adsorb ga he following fuctors, ( Nature of the adsorbate (gas absorb ict the do noi iguely easily, This is because the eal i or cohesive forces, Ecular forces of att ent of adsorption in any combination, That s 6 Hatiire of the adsorbent and | the gas (adsorbate) which is.ta.be-adsorbed. Gases like SO,, NHSTHG! and fi asily are adsorbed more readily than the permanent gases like Hy,.N,-and.O, efiable gases have greater van det Waals or the ses lo some measurable extent, The amount of gascous adsorption depends 2 ed) and adsorbent, Th ive and specific, Thus, to what cxtent a certail ga i cous substance will snds upon the physical and chemical nature of bot adsorbent and adsorbate and itis not possible to is the amount of the gas adsorbed depends upon' phenomenon_of adsorption is 1¢_adsorbed by an adsorbentof the easly iquefiable gases are more than the, permanetit gases, ure of the gas (adsorbate), the grater isthe extent oF adsorption, , ns. When nickel and aluminium surface are brought in contact with hydrog er identi ions, i is seen'that hydrogen is strongly adsorbed on the nickel surface but not so on aluminium surface. : : : 5 Surface uren of the adsorbent. Since udsorption is the surface phenomenon, itis evident that sorption of gases by solids depends upon the exposed surface aréa ofthe adsorbent. ItisW known that larger the surface arca of the adsorbent larger will be the extent of adsorption under given conditions of temperature and pressure. It is for this reason that silica gel and charcoal obtained from different animal and vegetable sources arc excellent adsorbents since they possess porous structures ai have larger surface arcas: The adsorbing power of these substances can further be enhanced by met! which help to incr surface arca,)For cxample; wood charcoal can be activated by heating iti yacuum or some inert gas at temperatures between 660 K to 1270 K. This treatment remoyes hydrocarb Ont ‘and other gases making larger surface available for adsorption. Ang For thc same reason, fincly divided substances have larger adsorbing power than when they are divided. i : Since it is difficult to determine the surface.arca of the adsorbing agents directly, the 1 i taken asia orption. 4 for the same pressure, this can be explained as under. Adsorption of.a gas by a solid is accompanied by evolution of heat (exothermic pi ¢ heat of adsorption. The amount of heat evolved when one mole of a gas or vapou on a solid is called molar heat of adsorption. The. pro adsorption) of equilibrium, The pro may thus be shown as Condensation ‘ (adsorption) Gas (adsorbate) + solid (adsorbent) ——* Gas adsorbed on solid + heat Evaporation (desorption)Adsorption & Catalysis Fig. 1.3. shows qualitatively the variation in the extent, f adsorption with pressure at different temperatures, The Kdsorption isotherms ‘shown in Fig. 13. can be casily I derstood onthe basis that athe suzfacs, of adsorpt Variation in the extent of adsorption with © pressures. at different + lemperatures. cfs thcwattiane of the amount of gas adsorbed per unit mass of adsorbent, with pressure pastapt {emperattirc Freundlich suggested an empinicalequalion. me x m Vn Kip (1) wherc.xis the mass of gas adsorbed, m is the mass of adsorbent, p isthe equilibrium Pressure and and 7 are constants which depend on the,nature of the adsorbate and adsorbent and on the pressure, his equation is known as Freundlich Adsorption Isotherm.-This is an empirical expression representing fe isothermal variation of extent of adsorplion with pressure as suggested by Freundlich, _ Taking logarithms on both sides, the equation treat ba = logk He fe logp * (2) Thus, a plot of los * aga h'slopé equal to 4, and intercept ual tok. twat eater swore sraightlines only low pe ssures and showed a slight curvature Amount adsorbed xim fog xm Seger i ers Pressure log p ened (A) A plot between wm and p +o) AIBLA plat between log xm und log P13 ig. 14. Freundlich Adsorption isothermAdsorption'& Caralyals 1.6 - at higher pressure, specially atlow temperature. Thisit be regarded as an equation of gencral applicabili 1.4, Types of Adsorption Isotherms indicates that equation ( (2) isapproximate and can, a explain adsorpti ses by solids, ‘i it the adsorbent and ihe idsorbed per unit mass of aie £ the amount of stibstarice a “ sate ihe Ciba eh then ‘of agas) orcovicentration (in case of solition) at cor "perature isknown ‘as the adsorption Isotherm. Five different types of adsorpti These are’shown in Fig. 1.5, ‘on istherms have been observed in the ad: of gases on solids, Amount adsorbed ‘Amount adsorbed = pressure required to condense the gas to liquid Fig. 1.8, Five types of adsorption isotherms ‘Type I. Adsorption of nitrogen on charcoal at 90 K, ‘Type IL. Adsorption of nitrogen on iron or silica gel at 78 K, ‘Type Ill. Adsorption of bromine or iodine on silica gel at 356 K, ‘Type IV. Adsorption of benzene vapours.on ferric oxide gel at 323K, ‘Type V. Adsorption of water vapours at 373 K, i 4 In case of chemisorption, Only Type 1 curves are obtained while in case of physical adsor the five isothcrms are observed, * 2 Further it is of interest to note that ‘Type Lis u typical Langmuir isotherm when the ad: ’ sorption is monolayer i.e., the adsorption 0¢ on the surface of the solid till the whole of its surface is o ie ‘overed by'a unlinolecular layer of gas molecu!sorption & Catalysis ‘Type II represents a case of multilayer physical adsorption on non porous materials, ‘Type III represents a case of multilayer physical adsorption of porous materials, Both type Il and type II] isotherms are explained on the basis of BET multilayer theory. Type IV and V represent case of multilayer physical adsorption om porous materials accompanicd ndensation of the gas in the pores and capillaries of the adsorbent, ‘Adsorption Theorles o Since the earlier adsorption theories of Langmuir and of Polanyi, important advances have been fe in the study of solid surfaces. Langmuir interpreted in terms of the kinetics of monolayer adsorption. inauer, Emmett and Teller derived an isotherm equation for the multimolecular adsorption of gases, inaucr, Deming and Teller have cxtended isotherm equation for van der Waals adsorption. The modynamic consequences of adsorption of the frec interfacial energy were quantitatively formulated ibs. These theories are discussed bricfly in the following sections. |. Langmuir Adsorption Isotherm—Langmuir Adsorption Equation ~ bi ts first quantitative theory of adsorption was given by Langmuir in 1916. The various assumptions le theory are? he solid surface is hbriogenedustand has a fixed number of adsorption sites. {Ui Each site can adsorb only one gaseous molecuile, .&, the adsorplion of molecules is confined to jomolecular layer. 7 (iii) The adsorbed gas behaves ideally in the vapour state. ¢ (iv) Adsorption is considered as an equilibrium betweeh condensation of the adsorbate molecules ori idsorbent and their desorption from it i.e, the rates of condensation (adsorption) and ‘desorption tially become equal at equilibrium. 7 2 () The gascous molecules of adsorption at different sites.do not interact with each other, (vi) Heat of adsorption is the same for all the sites and is independent of the fraction of the adsorbent pe.cover i i ©’ These postulates may be formulated mathematically as under : . Let @ be the fraction of the total surface arca covered by gas molecules at,any.instant, The rate of desorption (ie., evaporation) of molecules from the surface is proportional-to the fon of the surface, @ occupied by the molecules i.e, i a The rate of evaporation « 8... Takia) Waste = kyo ve is the rate constant for the desorption\process. ‘i SheeThe rate of condensation or adsorption « (1'48) & P. : we where P is the pressure of gas which is proportional to the rate ‘at which the molécules strike the face: i : Rate of adsorption = K, (1 — 6) P “Where K, is the rate constint for the adsorptiok process, i ” ® he. equilibrium, the rate of adsorption (condensation) equals, the rate of desorption aporation). , j : K)0=K, (1-6) P“Adsorpi 1.8 N OK Nan GK) PS Pe OR DP OORT ER /KDP 1+ OP. Ky + K,P. K, ‘where b = a ‘and ‘is called the adsorption coefficient. a The ma sorbed per unit area or per unit mass of the adsorbent; will obviously propbrtional to t 7 PS Sratia tae KbP) 2 @P AE Sb, KOT bP 1+bP mt where the constant 5, a=Kb This equation which gives the relationship of the amount of gas adsorbed to.the. pressure of the gas constant temperature is known as the Langmuir isotherm or Langmuir equatio The constants @ and b dépend on the nature of the system and on the temperature. liv Order fo test this isotherm, equation (2) is rearranged by first dividing it by P on both sides af then taking the reciprocals. i b My Pat Fi aa i ce she Fig. 1.6. Ply equal to? and intercept shown in Fig. 1.6. It was observed-in_numierous cases that actual’ ‘curves Were straight lines thus verilying Langmuir adsorption équation, This'shows superiority to the Froundlich isotherm. This confirms that adso is covered only by a monomolecular layer of gas molecules. Let us consider the two limiti isotherm, te Case 1. When the gas pressure P is very small: Under these conditions; 2s compared to unity in the denominator.of equation (2). The equation th wv or yep ‘which means that at very low pressures, ‘the amount of gas adsorbed is directly proporti Pressure, the factor bP is negligibly’ ercfore, becomes y = ¥ SrtA Under these: conditions, unity can be neglected , and this equation becomes ji Case II. When the gas pressure P is very high, comparison to bP in the denominator of equation (2), a in b * ( ~ 3] : m Hl which means that at very high pressure \This situation arises when the su ° pressures so change in pressui Howeyer,-in.the intermediAdsorption & Catalysis is than Freundlich Adsorption isotherm cause therm are in better agreement with the obseryed Langmuir adsorption Isotherm is better than > \(i) The results obtained in case of Langrm values. Gi) It is applicable over a wide range Of pressuré Whe¥¢as Freundlich isotherin is, applicable only cas¢ of intermediate range of pressure. ) Limitation of Langmuir Isotherm. Langmuir equation is-applicable forsmooth, ingh-csend faces, which are not good adsorbents, and for low values of pressure. If the surface is a very good adsorbent and pressurc.is very high, there arc.chances.of multi- layer formati Brunauer Emmet and Teller (Bet) Equation Theory —Brunauer, Emmet and Teller—~ T) Equation (Isotherm) : muir isotherm failed to explain all the five types of adsorption Sate 15.) exces iecpt nperature (1). ¥,, = volume of the gas’(reduced to STP) adsorbed when: the “surface is fully covered wi a ¢ = constant at a given temperature the value of which i given by 6 = when E, = heat of adsorption of the'gas in the first layer. and E = heat of liquefaction of the gas. ay sitet The equation (1) may also be written in the following form... 4.19 ik, 1 V(P =P) pet ‘To Test the validity of the BET equation {arin salon yf { ; fe 3 lowed agains, (698.2) P oy ———> against P/P® (cqn. 3). as yea ACAdsorption & Caralys| cland the intercept equal tos The plot'should be a straight linc with'slope equal to (¢ —1)/%yn ‘(Fig 17,. ; -., «From the values of the slope and the intercept %p, “* Explanation of Isotherm (i) In Fig:1.5.adsor ption isotherm type His obtained whe when E, > Ej. as-is considerably greater than 1. “Tsotherm type IIT is obtained when Ey < Ey, (i) Ifthe adsorption is supposed to be unimolecular layer ¢ equation reduces to the langmuir isotherm Fi Type | isotherm). This equation is then able to explain the Ct lsrpion other of pe (ii) Isotherms of type IV and V, in Fig. 1.5. can. be explained when jt is assumed thal in addition to. multilayer y adsorption, the pores and capillaries of the adsorbent are filled ig 1.7, tsotherm plot according ta satioit-at pressures much lower than, saturation ‘equation and ¢ cari be calculated, fe RY Beier daa entice - Determination of Surface area of the adsorbents by BET. equation — We have already sven that the plot of P/v (P? =P) against P/P? (ie,//v (1. = if) against f) vee a Atraight line with slope equal to (c = 1)/v,, ¢ and the intercept = 1/vp, c. ae the slope and the intercept. of the curve, values Of Yy_ and ¢.¥, is the volume of the Its known that 22400 ml ofthe gas at STP contain oné mole é., Nmolecules (N = 6-023 molecules) of the gas adsorbed, ‘The nuinber of moles layer present in volunie'¥,, of the adsorbed gas'at STR.” RTy when Py = Standard pressure (je., 1 atm) and Tp = Standard temperature (i. 273 K) and RS the gas constant. RT Where N = Avogadro's number = 6:023 x! 10%: aby ee Ain the above equation is the surfuce area of the gi given mass of the solid adsorbent, sorbent, Pov, Hence, the number of molecules present in =°" moles = [i P by all N molecules of the gas, AsjORPTION. & Catalysis : ya c= | N XD, where M is the molecular mass and D is the density, of the liquefied gas. tively, the surface area of the adsorbent by a simpler method from ¥,, directly as detailed x ;. §, the surface arca covered by single molecul 400 cm? of the gas at STP. contain 6;023 x 10% molecules f : .6E 23, <. ¥,,, cm? of the gas contain eae If Sis the area of a single molecule the area A occupied by ‘neu 6-023 x 103 x v,, XS X vp», molecules = 5575 X¥, molecules 6-023 x 107 22400 cord 3, 6.023. 107 3 x 30 XM XS A, the total surface area of the adsorbent Value of »,, can be directly obtaincd from the isotherm for adsorption isotherms I, II and IV. For m type I it is obtained from limiting adsorption and for isotherms II‘and IV it is obtained by jolating the middle linear flat portion (marked X) to zero pressure. The gas which is most commonly used for finding out the surface area is Ny at its normal boiling = 195-8°C or at liquification temperature, ~ 183°C. when the area of a single molecule of N, is to be 16:2 (A)? or 16-2 x 10720 m?