1356 FRINCILE OF PHYSICAL CHEMISTRY Whe rate ofthe chemical reaction vi designated at J, Eq. 97 can be writen es Jas = HG + 04) ~ Rc + 05) 2) Since heh = Kyef and ay = ~ ap, we have Jas = 04 +3) = a4 (14.178) 8) ‘Let ws nw study the thermodynan ; i ; ic aspects of he rescton. The aftity (i.e. he genta fore is even by A'= ha = by Se the Boe, te tof e chemical econ arg 1 te Onsager theorem, proportional othe genlcd face, Le he ang, See en Ja= 1A = Lita ~ 1) ro) Je kaw that for an ideal sytem at cont steric walt ema cnt Tai Pe tenia pot of ss we WP + RT ing, (105) ‘Substnutng for ¢ from Eq, 99 and writing e+ a as -+a/et), we have Hae He + RTInch + RTI + (aye) 005) Ha = ip + RT inch + RT taf + (ap/ch)] 008) Ths, A= Ung + RTInch + TING + ayle§) Ene + RTIncg] ~ RTInC + ople) C17) Since at eqiibeum yf. = yf, the tems ic brackets of Eq 17 cancel ving A= RTUn( + oleh) ~ tl + aple6)) (108) WOE) <1, them Ind + lef = oy lef), 80 that A RTL 1e)~ 9/61 (005) = RTM aa IG) + Cu /G)) & = Rag McA + RIG = er2a{iet) algae Substituting for A from Eq. 110 in Eq 104, we obin ERP aR, tanta He a J au 10) x Eq. 111 is derived by assuming that the reaction is close to equilibrium so that af /ef << Comparing Eqs. 103 and 111, we find that ae can Le (RT = vp /RT «112, where vj is the rate of the fo : Ys the rate Of the forward reaction at equilib : ¥f= cf. Eq. 112 shows thatthe etoetnogia coef epeats onthe ql comexiao of & cts agen empeaue, veseverso THe woornaniés 1387 production de tthe transfer ofthe constituents fom vesel Ito vessel Il is given by ds = LD Aydt = -2A dnb cu) aay Ln here j, isthe electochesca tft coresponting to he transfer of the component fom phase to past IL is defined as dy = A, + FG = Gh + FA) Gl 4 FFD 9, Here zis the charge number (clectrovalence) ofthe ion component whichis being transfered and F is Faraday (1F=96,485 C mot). For convenicace we assume thatthe system a8 a whole is closed and the degree of advancezent of phase change is given by war = a =, ee eae 1 ape gd-dd+grd -#) (11s) : = byt Fag (016) Since the teerature and composition are the same in both the vessels, we have *” ny = WAP ae an where isthe specific molar volume of component 1. We can write Bq, 113 as as 19) where I isthe electrical current due tothe transfer of charges ftom vessel I to vessel Il and J is the resulting flow of matter, ‘Thus, te eniopy production (Eq, 113) becomes as 4s ro) tnd the phenomenological equations ate given by nee noe eee 1 yt + at? ta oP Jo bytts int mm here the Onsager relation Lyy = Lay holds goo. In the above discussion we have deat with two ireversible effects, viz, the transfer of matter under the combined influence of a difference of pressure and flow of- electrical current due to the difference of electrical potential, Also, we have a cross effect related by the coefficient Z2=La1, Which is due tothe interference of the two ireversble processes. We shall now define the four elerokinetic effets, ealid the streaming potential (SP), the elestro- cemness (EO), the electro-asmotie pressure (EOP) andthe streaming current (SC), as follows. La 1103)1380 PRINCES OF PHYSICAL CHOUSTY J (2) «4 ro-(),.° it ceed Se zor -(4?) = Lan (Sao it 8 D) -n S0-(fapo =H (26) From Eq. 123, SP is defined as the potential difference per unit pressure difference in the state wis Ie ete ea rs ame re ae SALT seat Poa Be aa ot tl oe seem itr ema BOE ie ae the ol ea street mS e165 en ae ae are Sse te ( (48), 6 =-Bang ten BOP = se ti Eqs. 127 and 128 relate an domotic effet toa st effect. is town as Saxen's eat seaming effect. Eq, 127 is known as Saxen’ Thermomolecular Pressure Diferenct (TPD) and Thermomechanial (or Mechanocaloric) Efect. We shall next consider a one-component sjiem (hid) contained in two vessels I and It which are connected by means ofa gapilary, a stall hole, a membrane or 2 porous wall. If temperature difference is maintained Between the two vesels, 2 mater fx J results. We have already caleulated the cate of entrpy prodcton for such a system (Eq 81). Modifying this equation suitably and assuming tat no reaction is ang place, we have Le, SP=- £0" A127) as _ doris ul at wae 4) -(3-4) ss 9) 11). ft) Pot. ar sdk EM (€a7 is small T= T= 7) Sap (cane vPtedtand a=) 30 Here» is specific lar volume ands specific molar enzopy. ‘he thermal energy ux Jy and the mater fx Jae ge by Jy = digidt and Ina (132) ‘The ettopy production becomes seers , Hata star 89) and the phenomenological law now becomes at me Jal a) Jn ~~ 439 - fs expressed in terms of the phenomenological coefiients (Eqs. 134 and 135) as follows IRREVERSIBLE THERMODYNAMICS 1359 We have again the Onsager relation by = Li 126 We salt dy two phenomena; viz; thrmomlecular pressure diference (TP) a thermomechaical cffect. The thermomolecular pressure diference is defined asthe difference of pressure which arses between the two phases ia the stationary state Jq=O when a temperatre diffeeuce is maintained From Eq, 135, this pressure is given by ap 4 (0° Tar as ‘us cross penomenon is dv tthe inevecace ofthe ineversle process of fansport of cag) ta mer The TPD ts ale Kaalen eft i be sytem consis of go and the esl Sse Routed by arow copies or smal penigs. When the samc effect ous in ges o iwi eran eprting he wo pase, scaled hermo-osmsis. Tet ws sow sy the oer phenomenon, We del with ke sane sytem defined above, if ne asizin's pro fierce between he fv vec and# orf temperature troglowt te ‘Stoker ows fom one vse he ober and. an sled energy Ho, propos fhe ater tow, b bserved. Tis energy fw canbe meaned by determining te est neces 1 ai afm omperate ine sytem. Tus eet faba as theremechanical effect (2), < BE emt te = ‘The quatty Lysis called the heat of transfer defined as energy transfor per unit transfer of @ = Lille 39) ‘From Eqs. 137 and 138, using the Onsager relation (Eq, 136), we obtain the following relationship beween TPD and the thermomechanical effect: h : (2B oo HI) i wo ‘Thus, both effets will appear inthe same system. ‘Staionary Nou-Equilibrium States ‘We have earlier dealt with atypical stationary non-equilibrium state in discussing thermomolecular ‘potential difference. In this ease the transport of mater Jy is 20; yet the transport of energy between the two phases a differet temperatures as well asthe entropy production are diferent from zero. By ‘contrast the slate variables are independent of time, so that we may describe this state a8 stationary ‘nowequirium state or simply as stalonary state. There should not be any confusion between such staes and equilibrium states which are characterized by zero entropy production. A stationary state arises when the concentrations of the intermediate components no longer vary with tine. Consider a one-component system in which bot the temperature gradient (Xu) as well a tbe erence i) ene. he vy fea, eee ‘production per unit time Sw Igy + Inka > 0 e189 (ttt tad he linear phenomenological laws ae (Eqs. 134 and 135) Jos = Lat Xn + Lin Xn sto Ig = Lat Xe + Lea Xe eee Here Ly and Lay are the coefficient of thermal conductivity and diffusion coefficient, respectively. {Ly represents the coefficient of heat flow associated with a concentration gradient and Lay represents