r PRINCIPLES OF Ph SICAL CHEMISTRY the heat ofvetacation ofthe gs. Sine cis a content foc 2 iven 35 abd Yan ia constant for a gen sBssold sytem, th ptf pivaipy~P)aeint Py Shoal give a stiht ine Ts ts been checked inthe case ofadsopion ofa nur of gases on varios Salis sorbet. The reiulsoiined inthe ete of asortin of nope on lia gla -183°C ace shown in Fi. 3 4s canbe sen, he plot obisned isa good stag le. Fairy sattitry sight ines aeobtaed in mast cases 2 long as pressure p does nox exceed one-third ofthe Pa Sencaton pes ye per ere to condense th gas io the Tiga ae whe pevaling temperature At tiger pressures, However, devo ttn SUREACE CHeMstRY 1261 ® TABLE 2 j Ares of Cross-section of Some Caton Molecules z sia Dey ©) Mates ‘Temperature °C) aes ata? a a) 130 oi % = 86 sos oa o = 40 ou 2 - 18 0763 os ©o; 0 Ha om Fg, 5. BET plat fr te aon of cus = 40 ca oust isp 18°C, | Ny -36 os on \ The slope of the linear plot, evidently, gives the valve of (€~ 1)/Vaayt) While the intercept elds the value of (Yon). Thus, ftom the slope and the intercept, Bol Yun and € can be vase Determination of Surface Ares. Krowing vag, the surice area ofthe adsobent can be exis calculated, 28 stown in the following example: The assumption is that tbe molecules of the zas adsorbed in the first layer ae closely packed oa the surface. 4 i a Example 10, A YC and {peu the vale of nro gps rqurd to cover sn I, asmlng Langan nlaer ain fund fo be 130 ca othe ga Cale the race aa Fe pum of ag Cent ees eapel aepotee OS a Sation Yn ~ 15m? = C190 dg Vy = 2214? ma 6022 +108 mot" Aida ‘Are of eerstion of one ole = B12 (a Aa ever by 349% ales, sufi ara = OKI WPS p= 8 wt Determination of Area of Cross-Section of a Molecule: The area of érost-sectin a ofthe molec can be determined from the density ofthe quid or solidified adsorb. Thus if pis the ecsity and Mg i the molar mass ofthe adsorbate, ten the Volume v occaped by a single molecule, suming the aioe be closely packed wih no vod volume, is obaaed a follows © MglV = MIN») Nur of males catia Yon XO da? pt = 349310 12108 at v= Ma l(NgP) eee re | AB) ep 5 1,25 is oly apron for calling the area of cross-section of a molecule sic it does ‘ti int abc he nate of packing athe surface neaen. Also, the pescce of vid volume inthe cya lace hs been ignore. The ares of ersten of soe common meds ze given in Table 2. : es Derivation ofthe BET quation In 1938, Bronaver, Emmett and Teller proposed & mad known 23 (he BET ister, for muiayer adsorption. According to them, the fist stp ia adsopon i A@L+S. =A AS: ky = Gy0p ar) where A isthe gaseous adsorbate, 5 i8 4 vacamh site‘on the suctace, AS represents an adsorbed tooeculeof A or an occupied ite onthe surface, i the equilibrium constant Othe ation of Se sure sites covered by single rneculs, isthe fact of vacates and peptone of the a3, . ‘They further assumed tat abitonal molecules sit on top of one another to form a vasity of tllaers, This process was interpreted asa sequence of chemical reaction, each wit an appropriate sulci constant AG) +AS = A@+AS = AS; = 809 AO) + AS EAS: Ky = OyO.7 Jere the symbol A,Sincas a surface site that basa stick of A molecules pled pon it, The ‘us the ration of sts on which the stack of A iolecules i layers deep. The ieratiog between the fist A molecule andthe surface ste is unigue, depending othe mie ote paialar A ‘molecule and the surface. However, when the second A mmoles sits onthe first A mace, the {teraction cancot be very diferent from the interaction of two A molecules inthe liquid, The tame 4s true when’the third molecule sits on the second. All of these processes except the fist can be ‘Tega 23 being exsetially equivalent to liquefaction, Hence, they should have the sume equa constant, K. Thus; the BET teamest assumes that. AS: Ky = 03/0 Ky Re Keon Ke a Where K is the equiiium constant forthe reaction AY) =? Ala). Obviously, Ket 25) ‘where i the equiirium vapour pressure ofthe liquid ‘We can wse the equilibrium conditions to calculate the values ofthe various @, We have B= PKR Oy = tik 6 = Oke, a) Combining the fist wo, we have, 0; = 0,(kp)? Repeating the operation, we find thet 8 = adKpy 28)tase PRNOHLS OF SEAL ABMSTEY “Thee ofa tse ns mtb eg ay 128 13a <8, + Ace 09 re We ave wed E28 for at Kp 2 ten B,29 beeen Lege errr t et) ‘Assuming thatthe proess can go on infin, then n> and the series i simply the expansion ofa) el teee +... Ts, 10,4 60-9 0) Using the equilibrium condition forthe frst idsortion, we find that 8,~0)/Kip. Defiing anew constant, ¢ = Ky/K, we have 8, = 64/(x) and Eq, 30 becomes al-2) i = Tee=br ° at Xe te total nmber of miezles adworbe per unit mass of adsrbet and ¢ be het runber of sucess per wit mass. Tue oy i the numberof shes earying one ted, isthe number of sieseaying two molecules, and soon. Accord, N= 6,0) +205 +385 +.) » GSI, a From Et. 28, we have 6; = 8 0 hat Ne Zit = 68,1 42a e a ‘This series is the derivative of the ears ie. Ths, ra) N= c(t ~ xy 85) A the entire surface is covered with a inonolayer, then Nn ‘olesles would be adsorbed 50 that Nowy = C5 38d. N= Ng6 la? G8) Substnting te value of ; from Eq, 31; we have oo Rls ft fared tas.) = lamented oe Sere ) Using this ces, che expression for W becomes Ngee Vo (ase ‘The amount aéobed is usually reported as the volume of the gt adorbed measred at STP, The volume is, of courte, reportonal oS hat We Rave NIN = hs (=a +a Fig. 6 Mller pysiston where vg tans fo Yang an MASS ADSORBED——= o Veal = SURFACE OxEMSTRY 1269 Recalling that 6p and that K= Ifp*, we obtain the BET isotherm : Pps te DeIPN ‘Me voluce vg is measred as a fretion ofp. From the dats we,can obtain the value of Yaae and. Note tat ven p = pth equation ha 2 Singular and ¥ > eo, Ths acco fot ep Tie of the isotherm (Fig 6 a8 the pressure approaches p*. ‘To obtain the constants ¢ and vi, we multiply Both sides of En, 39 by (p* = pip: wep) tae 9 >” Tele=nipiy i Taking te reciprocal ott sides, we bave (e van a GIB) “ This is the wellknown BET equation, The lefthand side of this equation is experinietlly mesure, Te plot of pip) versus p Lud afin line. From the intercept, (I/¥qe) and.the slope, (¢-1)/(Ymcp°), we can calculate the Value Of Vp i.€., Yanao ° From teva of Yang at STP. Non cn be cleat Na%aone Ooms 14m mort Siace Naan i he sander of mele requted to cover unit mas of the ada! with 3 monolayer, thei if we Know the area, a, covered Dy a molecule, we can calculate the area of uit ‘mass of material 4) Aealunit mass = Npgg & 43) In this way the surface area of a finely divided solid canbe determined, ‘Tybes of Adsorption lotherms. A large tuber of adsorptioa lotr of gueson a variety adsorbents at itferent temperatures have now been determined It bas been possible to divide them ‘woadly fa five diferent types, at shown in Fig. 7. In each case, pp represents the tration resrre ofthe gas ‘Type I corres- ponds to: mono- ‘molecular aorpton as postulated by Langmuit. Tee volume of the gas adsorbed approaches 8 Timing value, just ‘enough fo complete © mono-molecular ‘ayer even when the Bas. pressure is rather low. Further increase in pressure hardly produces aay ay aa Fa Die tare