1284 PRNOPLES OF PHYSICA CHEMISTRY farter rise in the amonct of wforping. The examples are furnished by adsorption of nitrogen oF lnydogea on charcoal at temperatures close to -180°C, ‘Types Hand WF show large deviation from Langmuir model, The amount of adsorption keeps 0 rising in each case wit increase in pressure, This is atriuted to the formation of addtional layers of physically adsorbed gas molecules. It is postulated that the gas molecules adsorbed inthe first layer may hold by van der Waals forces a second layer of gas molecules whic, in tr, may bold a third layer and so 00. The examples of Type Il isoterms are furnished by sfsorption of alrogen on ‘am iron or a platinum catalyst at 195°C and those of Type Wt by adsorption of bromine on silica oF alumina gel at 89°C. ‘Types IV and V have been observed in those cases in which there is a posibiltyofcondessaton of gases in the minut capillary pores of te adsorbent at presses even below the stan pressure ‘of the gs. An example of Type IV is furnished by adsorption of Benzene on sila gel at 30°C and that of Type V by adsorption of water vapour on activated earbon at 100°C. I may again be noted that nthe eae of adsorption isthe of Types WV and V, thre isnot oly formation of muimoleculat adsorbed layers of the gas molecules but also condensation of some of the gas meleeles win the ‘arrow capillary pores of the adsobeat. This latter ptenomenon is knowa as capillary condensation of the gas. ADSORPTION FROM ‘SOLUTION Adsorption ofa solute from 3 soliton onta said adsorbent is more dificult to tet theoretically than the corresponding adsorjtion of gases on Solids. It appeats, howese, sha ia tit ease, 100, like ‘he gas—solid adsorption, a monomolecular layer is formed. ‘The slvating power of the solvent inhibi the formation ofa multilayer. For adsorption from solutions, a commonly used isotherm isthe Freundlich adsorption isotherm, Wx isthe mss of the solute adsorbed on mass m of adsorbent and is the concentration of the Solute in the solution, then the Frew adsorption isotherm is expresed as aim = a= ket a) where and ae empirical constants, Taking logs, We=ink+nie 48) “his garde form i convenient to us. we plot Ina Vers Inc, the pt would be a Stag ine with lope equal 0 an mere emul 0 Ink ‘The Gibbs Adsorption isotherm for Adsorption From Solutions ‘To concentration of » solute atthe sutfae ofa solution is, in general, asked differeatfeém that in the bulk. If the surface tension of the solute is lower han that of the liguid, it tends to accomeate at the surface ofthe liquid thereby decreasing the surface tension (r the surface free energy pet uit aca) of the liquid. A quantstive treatment ofthe thermodynanics of adsorption of 2 Selote atthe surface of a liquid’ was given in 1878 by J.W. Gibbs, (1839-1903), the greatest 19th century American mathematical physicist, For a system conning wo components, the Gibbs free energy canbe writen 38 C= my + Hn 46) ‘where mand my are the amounts (numberof moles) and yy ands ae the chemical poteials (i... patil molar Gibb fre energies) of the two componens, respective. Since we ae dealing with the ‘sorption of one ofthe components onthe surface whieh resus in changing the sufce fre energy, Eq. 45 is madifed to G= my + mn +10 “ SUREACE CHEMISTRY 1265 * where is the surface energy which is numerically he Sie as he srfice tension and it the surface ae, ‘The compe tifereaal ot Eq, 47 is writen as 4G = rudy + pda, + tad + pda yds + ray 8) We see that fee energy G now depends upon five independent variables, vic. T, P. my, mand 6. Ths, GF P.m m0) 9) «FL (FE. EL Bhan” 0) According to thermodynamics, the partial derivatives, FS. (Hy hg a8 Hen, 4G = SET + VAP yd + yada + yd (31) ‘At constant temperature, d7=0 and at constant pressure, dP=0. Hence, Eq, St reduces to (aGhr,» = wy + pony + yd 452) From Eqs. 48 and 49, id # mn + oy = 0 63) ‘The corcesponding expesion for the bulk ofthe liquid is Medi, + Aid = 0 8) Where mand nar ie amounts (number of moles} of the ligand the solu, respectively, in the ‘ul pe Siac the system isin equilibrium, the chemical potenai of eich component in the bulk and the Surfiee phase must be the sim. The system; on being distacbed, ata & new equilibrium so th the changes in the chemical potentials must be identical in both.the phases, i.e. dy; and diy in qe, 53 and 54 must be identical, Elimination of diy from these equations gives mle (ini )dig) + ma + dy = 0 (59) or ( — mth In la + ody = 0 o aL = m= tong i) 6) iy 7 ‘The quantity within parenthesis of Eq. $6 gives the amount yf of solute 2 associated withthe mount nf quid | inthe bulk phase. On te other Yaad, ni the amount ofthe solute associated withthe amount n ofthe guid atthe surface. Tus, the numerator onthe right hase of B4. 56 ives the excess amour of the solute present in the surface of the liquid, Evidently, te right band |1266 PRINCIPLES OF PHYSICAL CHOMSTRY side of. 36 gives the surface excess, i.e, the excess concentration ofthe sole pr ust are of the suc, designated aT, Le, fm ~ (Rm Vo = > Thus, from Ba. 56, ~ tld, : ‘sn The chemical potenal of solue 2 is given by =) + eTIng, 488) here 13 () isthe chemical pol of the pure solute inthe liquid phase, Hence, y= REd in ay Co dig = 0) 9) Sbstittng fr dyin Ba. S7, we otin balsa) 2 ‘When the solution is very dilute, it behaves ideally so thet the activity ay of the solve cin be replaced by its concentration cy. Thus, (a2) =A ry Ec. 61 is called the Gibbs adsorption isotherm. Knowing the concentation-dependence of y Fy can be eaeulted, Fe 2 solute tat lowers the surface tension, the surfce exces concenaton Tis postive and fora sole that raises the surface tension, Tis nepaive. Soaps have a higesconseataton io the ‘eighbotiond of tte surface thin in the Buk aqueous phase whereas iorgane als hve lower concentrations inthe neighbourhood ofthe surface than in the balk agieous phate Solues are clasied as eapillary"active or capillary-iaaeive on the basis of thir effect on surfasé tension. For the aqueous solton—air interface, capillary-sctive solutes are orpale acids, ateobols, ethers, esters, amiaes, ketones, ‘te. and eapillary-inactve solutes ae iowgaak eeecolytes, salts of organic acids and bases of lower moar mass and certain nonvolatile compounds such as sigat and glycerol ‘The surface tension of water is quite high, vic, 0-072:8 N am at room temperate ad mis of the solutes tend to reduoe this value. Therefore, most of the solutes are positively adsorbed. from ‘agueous solutions by adsorbent such as charcoal and slic gel. The surface tension of ethanol (00223 'N ar} fs considerably lower than tht of water. Hence, most of the solutes dcréase the surface tension of ethanol oa much smuller magnitude than they do in the case of water. It leads to the Conclusion that 2 given solute would be more readily adsorbed from aqueous solatioa than from ‘leobolc solution. This has ben ally supported by experiment in majority of case, h Example 11, The sucface tension of dilute solations of solute vaces linearly wlth the spate concetration 6 88 ‘ip where is the surface tenson ofthe stent and ai acon. Sto’ Lat Fr= by Dine Salon: T= wean ier) ao 3 (dey = 0 « Fits, fom Ba. 61, Fy wo | | SURFACE CHeWSTRY a Frm 64 ore Suing teva fay. be Th (= WRT Example 12, An 14°C, the sacice tno of an aque soltion of butyric acid is repeated by the TS Nm ad i the eatin 7 p= +I) here jy the surface eas of wat r ution 7" tg - 298 log (U6 + 1) her ee bulk coocateaton ofthe sole. Call, wing the Gibbs adsorption uaber, da concentrating G81 sa da. Satan 1 = 19 298 lg (964 g + Given S413 se, oar At g)= 0601 mal dx = 0010003 at a 296194,0.01417 nla AOKI aa | NEST ax BIR = 8990107 mat wt heat (ais tio) Soin za stern = L010" nota"? 2) ga wt TE oa haHRD = 32.006 al The avenge ee lie fr eh cle pee Eee ee GIF mol VCO xT) * SAKIC? wP Trample 16. 6106 mg of stare a (My = 284g mst) i fond to cove SO cn? of wal ei wie tess pre Join srl at he conceal sre sear sid lea and thine, he suTace film of set ai on waters Given # deny f Sail= 68S gone Solin 0:16 «107g 284 gn (6.02102 mal'}a = 500 ea? @= x10 ea? Asin, ($00 en! = 010610" gf0 geen? f= 25x10 on = Insoluble Surface Films on Liquids ‘The long-chain, water-insoluble compounds like stearic acid, CH(CH)4«COOH, lauryl aleobol, (CH,(CH} OH and ety! palmitate, CHs(CH,),4COOCyHs spread spontaneoesy onthe water surface lving rise to surjece lms. These films are found to be one molecule thick and are clled spread ‘monolayers. Bat sls an! tgs can fora spread monolayers bat the fate of spreading of ls is ‘more thn tat of solids. These surface films can be studied by a surface balance in which a floating 2 um = 2500 pe