1256 PRINCIPLES OF PHYSICAL CHEMISTRY T= exp (eR 4.5) Present fcor, ty = xem (= EJRD) trea |= tose Gait TT al \0300 ‘The Langmuir Theory of Adsorption |i 1916 Langmuir proposed his theory of adsorption of a gas on the surface of a solid, He considered the surface ofthe solid to be made up of elementary sites each of which could adsorb one as caolecule, Is assumed tat all adsorption sites are equivalent and the ably ofthe gas molecule {o get bound to any one ste is independent of whether or not the neighbouring ses are occupied. It 's further assumed that « dynamic equilibrium exists between the adsorved molecules and the free molecules. IFA isthe gas molecule and M isthe surface site, thea be Aig) + Mlsutice) = AML where and fy are the rate constants for adsorption and desorption, respectively. The rate of sorption is proportional to the presire of A, vic.,"py and the auimber of ica sites of the surface, vie, NC1~6) where WV is the total number of sites and 6 is the fraction of surface sites ‘occupied by te gas molecules, ., Number of adsorption sites occupied Number of adsarption sites available ‘Tus, the rate of adsorption = key ML = 6) 8) ‘The rate of desorption is proportional to the mmber of adsorbed molecules, NB. Thus, the rate of desorption= ky N 6* o Since at equilibrium, the rate of adsorption is equal tothe rate of desorption, we can write from Bes. 8 and 9, bp" 9) » by NO (10) o Kpa(l-®) =0 uy Where K = fly Eq, 11 may, ths, be writen as -8 4 fe « Key a 1 « eye at baa a9 bet os aE » Koy ; tne ioe 5 a 0 = kB a9 Big, 15 scaled the Langrouir adsorption isotherm. SURFACE CHOMISTRY sr ‘The following assumptions are involved in the derivation ofthe Langmuir anptioe‘soherm : 1, The adsorbed gas behaves ideally in the vapour phase. 2. Only a monolayer le formed by the adsorbed gas. 3, The surface of the solid is homogeneous so that each binding site kas the Same alfnity forthe gas molecules. 4. There i ao lateral interaction between the adsorbate mcecules, 5. ‘The adsorbed gas moleeles are jocalize,.-e, they donot move around of the afar. ‘The first assumption holds at low presse; the second assumption breaks down when the pressure Of the gas is inereaed. The third assumption isnot strictly true because the real surfaces are quite beterogencous so that affinity for gas molecules is diferent at diferem sites. Crystal imperfections and ercks lead to the creation of cifferent sites on the surface. The fourth and fifth assumptions, too, ae not sretly valid Now, let us consider Eq. 15, At low preseutes, Kpx << | so hat 0 = Kp, «19, 09. ie, the fraction of te sue covered is tet proportions ecb 1 the pain presue ofthe gas molecules. This tehaviour | 08 corresponds to fs-onct reaction and is depicted by the | 07 pasa) ina sep tise of te soberm (Fig. 4) i Athigh press, Kp4>> 1 so tha Eq, 15 reuées io | | Oy e= | Bq ‘Thus, at high pressures, the value Of @ tends to become unity, te en sis pcre ty smn ie ‘of the gas thereby making the reaction rate independent oa. ‘of the pressure. Thus, the reaction is of the zero order |! 91 ea) Combining the results of Eqs. 16 and 17, it is evident PRESSURE —e x sg i ery. mage of arpa | Teanga @ given temperature should first increase in proportion to es = — irene of pes ad aly tnd oan een ange, This is ath a ened Oy sep bots ge aie a Sue stow pests, arto rope ops, on ko! foe o-oo) and, at high presures, = 1 = (pa)? (tom Bg 1, it follows that, at intermediate pressures, the following expression should bold good : 8 = Kipg)* where 1 lies between O and 1 8) Since, according to Langmuir’s theory, only a single layer of molecules is adsorbed ot the surface ofthe acsorbent, the fraction @ gives the amount ofthe gas adsorbed per uit mass of the Adsorbent, that is, a0" or a = £0 where i i another constant. Thus, 2 = AO = ARIA = Ra) 9) Ea, 19 isthe sae asthe Freundlich empivial equation (1). This agreement was taken a a proof for the theory of monomolecslar adsorption advanced by Langmuir. Irving Langruit(1881-1957), the American chemist, was awarded the 1932 Chemistry Nobel Prize for his eontibtions to surface emistry, Research in surface science has now acquired ttemendous importance and a research Journal called Langmuir is exclusively devoted to contributions in all areas of surface sien. Exar S. Show that whea a datomic gas adsorbs at atoms oa the surace of xsl, the Langmuir ssorton later becomes © = (Kp) (Rp)!4] where the gms have thar stl meals1258 PRINCIPLES OF PHYSICAL CHEMISTRY Here 8 is he fan of see covered by eg 7s re of Seon prow tere of ears fe ans on tea a i, a, pipe fas Ament of ech. Sis is umunt NB, the eof desertion i EANENAE) = RAGE Ac ep ee ‘te of spn is el te eof depo. Hence, KaBNAL = OF = by N29? e Kol =P wee k= bly ime? 1 Cat +a ean rer bebe ete Soten? 8 err! key” oe T+ Beams 6 If the volume of ga (creed t STP) adored om the tice of 2 il he show {ins is ves, whee ps he gt preset Langu snp ete Best are "Al sow that or all sat coverage, 2 lat ofa ip teams Sse ee es Selina + Rearangg e Laretiravetion tern, 8 «Kp + Kp) we pe oI ep o 12. Ham Wit to evolu conepoatig to cape evens, Le, volte eed fr se forma o alee re Te, Yom, Mtoe pt Ht We gt ok oa Ths lo) vers wil give a srg ie with slope eq © rac tego ‘i Fe he meson cf he ae aa thee, Ye nd Ka deb Apia fm B68 = Kt ~ 9 0h ip © KC = 8) Taking gs (0p) = MK 4 nh =. IF Aten maeatily, = 6) 8 son ip) = in 8 Heme pa of a eee st ie «a ae Wipe el 2 ramps 7. The flowing dla wes shied forthe sores of earoa lac af 0°C and 1 at prea. Very that the sh he Cee ‘Abo dermis the consent Kad the lame arson econ marr so Po) 1m a0 50a sete roe) Was ass. kane onion The Laggan iter hu convert to prope bm ing hen ‘Th sb ee at uae we Oe soup a AE Plea A Ne ea cm ieee t Fen wo = SURFACE CHEMISTRY 1258 ‘Ths, we can cece filowiag bie : Ic © a ETI = a a] Senter) | s0 [ ow [us | nw | ne oe} angi 8 Yet a8 Ht OF ane esp vs & nig wih spe = 0 td inset = 90. gm = 0008 hee Yap = Sth em? UR pee = $0 whence a ite x9 Oar aay ree ater Mas of alae adsorbed per gram of slid adsorbent I get bythe Franch Steen ltherm as x= te, where and are OG) and O01, rexpetenly: Castano ene esac y= 005 gma) at 1h of charcoal onl aor foe DENT NY vince eh = (O16) (837 per gam of charcoal = G18 pact wt) G charcoa* = (48 aati seit (ey cay! 109 er creating te sve i, ve Od at As = ~ 252 AF mat? BET Theory af Malilayer Adsorption lees ml ear of sic s restricted othe formation ofa monomolea aye of the Sey pace ence al suc and depts he possibly tht mullaye adsorp nay le BET teary EO of adsorntion proposed in 1938 by Brasaer, Exet and Teles Qos oe BET theory, afer the initials of these i i siai@bouring ses, as was assumed ia the Langmuir theory. Its further assumed tet see fring coc eg So: i... an mh Layer, the surface area avalate fo te nly Send oy SOME ofthe (r~ I tye, The eneey of adsorption inte fen yee Ze See ee Comsat a0d the erergy of adsorption in succeeding layers assed he oe & Fi, the energy of liguefacation ofthe gas. Based oa the above ns, Brunaner, Emmett and ‘Teller derived the folowing equation, known aftr them as the BET eqeaion Yat P=) i Tercera Yoame of he gas adsorbed at the pressure p, Yous isthe volume aarted when wai tthe si covered comply wid a mower of tr adsbed tea ene te peennan peng won the ase ofthe gas, Is mumercl value it evesaporicy {9 te exreson cmexpE-E,VAT nich Ei the heat of adsorption in efit Mee or Be