1348 PRINCIPLES OF PHYSICAL CHOMSTEY Eq, 32, therefore, becomes dg = dg + dips dlig + dig 0) 11d is the beat exchanged dever ie ete System aid the exo, das das dig G5) Thus, we se that deeds =o 5, Considering the hea fw fom phase Io phase I, lq + dlq=0 on) Eq, 37 represents the conservation of energy forthe entire system. Entropy Production due to Heat Flow. Though eneray is conserved as stated in the law of conéervation of energy, entipy isnot aconserved qanity. Naural or spontaneous proceses are accompanied by increase in entropy. We can ths say that cotopy is produced in such processes. The eatropy of a sfstem is an extensive propery. Ifa sytem consists of several parts, then the tla ‘entropy is equal to the sum of the entopies of ech part. The ehange in entropy, dl, can be sit into two pars. If we denote the low of entropy due to iatractions with the exterior by d,S and the contribuon due to changes inside the system by dS, then we have dS = d 5+ as 68) <4S=0 fora reversible proces and di > 0 for an crevesible proces; iti never negative. We may ‘etion thatthe spliting of entropy change jo two terms dS and dS permits an easy discussion of the difference between closed and open systems. Evident, this diference has to appear inthe term 4S which, for open systems, must contain terms duet the exchange of matter. Consider a closed system consisting of two phases | and II maintained respectively st uniform tenpertres Tan, Acorn tf Seon of eres, nso shat gen by 3 Telaton aS=dqT 9) where d isthe heat received from the surroundings and Tis te temperature, dS is postive and is an Imensve property. Applying Bq. 39 to each phase, we have forthe whole system a= ass ast ) ‘We now epi the heat received by each phase into two pars. Accordingly, dy = dig + dg; diq+ dig (al) (Because ofthe conservation of energy inthe syste, dle + aly =C), ‘The entropy change for the system of the two phases is given by ws(@2a) (42s) e858 THERVOONANS 00 Subting Et 2a no, ee 4 fa gf 1) r Gada 7) « ‘The first two terms in Eg, 43 correspond to dS of Eq. 38 and the third term of Ba. 43 gives dS, ‘wbich isthe entropy production arsiag from the ansfer of heat from phase I to phase Tas « result ofthe temperature difference (T= 7). Tas, rea a(t) From Eq. 44, we see that if 7" > T!, dS > 0 since dig > 0. Even if T! > 7", dS will still be > 0 though the quantity inside the parentheses in Eq.44 is < 0, since da will aso be < 0. #) as ‘The enropy production can only be zero when thermal equilibrium i established, dati, when Tart “5, Feo Eq 44 we can define entropy prodution per uni time, 0, by 248 diya 1), on = 4-0 8) Eq, 46 shows thatthe rate of entropy production, oi the product of two terms, viz thy sate of teat tansfer (dig/dt) anda difference of sate functions (/T"~ 1/78), ‘The later can be considered 1 the macroscapre cause ot the driving force forthe beat ransfer which can be considered as « ux ‘oF flow or & consequonce of the driving force [Entropy Production in Chenucal Reactions F ‘Let us consider a chemical reaction ogcuring a constant T and P. Let the surroundings absorb an infinitesimal quantity of enthalpy dF at weaperature 7. Then dS=dH/T, where dS is the infinitesimal entropy change ofthe external suroundlags. Further, let d be the infinitesimal entropy change arising from the chemical reaction. Then, since dS = 4, + dS, we have dS= HIT + ds an, o Tas = ait - Tas 48) Comparing this result withthe thermodynamic relation dG = a ~ Ta, we find to a= - dort A88) 0D) Ta ‘This can be expressed by saying thats is proportional to the decrease in the Gibbs free energy. According to Classis, the uncompensated heat dg, i given by dq TAS ~ deg si) ‘where dS is the entropy change of the system and dy isthe heat exchanged with the surroundings Since d5 = dS + 4, hence a= dgiT + dqiT BD) o Tés = deq + dig (53) 0, we “Treating the chemical reaction as an open sytem conning c components (Y=, have the el inown relation do - SAT + NOP + Sindy 59 71380 PRINCIPLES OF PHYSICAL CHEMISTRY where 1 isthe chemical potential ofthe th component and mis the mamber of moles ofthe yh component At constant Tand P, Eq, $4 becomes ~ (€G)rp = Zn dn, 69 7 . ‘From Eqs. 50 and $5, (56) Substining ford, rom Bq, 18, we have as . F 451) Following De Donde, we defie te trm afin, 4, ofa chemical ration as A= Doh si) 7 Thus from Bs. 57a $8, a8= Um &>0 9) « aside = (A/T) (ad > 0 0) The reaction rate, is defined in terms ofthe extet of reaction, &, a8 da, fa = 1 (6) 4 dt a ‘The moar concentration ofthe 78 cGmpone is defined as gan 0) ‘here ms the mune of moles ofthe tk component disor a volume V. & 255 1 er 3 a ave Va pa 6) Assuming that che volume remains conta during the reacon, we obtain Mw ade Var a aad ‘From Eqs. 60 and 61, we obtain 4s 4 oi Bet av>0 0 Tondv>0 4) Since Ts postive, we se that A and v must have the te sigh Catering Eqs. 46 and 65 we ‘Cocipacing fin that the afity A plays the cle ofthe driving force (UT! 1/F) ia Ea. 46. From Eq. 65, we sce tat the expression foro isthe profuct ofthe force (4) andthe flow (1). tis evidem froin Eq. 65 that when both A and v ae pst, the reaction occurs fom let 10 right. If, however, Both A and v are negative, the reaction wes place from right olf. If 4=0, the reaction isin 2 sale of equildrium. If ¥=0, does not necessarily follow that A is.also ze. If =O and A 0, we have the cas of false. epuiviam. Eq, 60'can be‘ extended to several reactions occuring simitaseously. Thus, for r reactions (© = 1, 9) curring simltncously, we gt 48 = 25 Aey > 0 (66) * 1351 WREVERSIBLE THERMODYNAMICS here dy is he afinty ofthe 9 eacton related to the chemical potentials by 4o= Dhol (sn) “ya the Sqn sa all affine ate aero, that i . Ape Apsene Ay 20 68) ‘The entropy production per unit time is now given by con H#elyay>o 0 ‘We sce thatthe entropy prodocton per unit time iste sum ofthe entropy productions due tothe ‘various reactions. must be emphasized tat th etopy production resting from al the simultaneous ‘eactons is postive. However, it may happen that a system undergoes two simaltancous reactions such that Ain <0, Ay > 0 c) frovided ta the fxm Am + A> 0 ™ Bodh the reactions ar then said to be coupled reactions, If folows from the above discussion that De Dooder’s definition of chemical afiity is closely related to ecropy prodetion, aap Deve th rltiosips betwen the recto afty and) he soit constan, the cue te cnr tnd (9 te rt te venton Hi)» KD) =e 2H, eso tat She pte bes Sain, HQ) + Ha) =? MH) (e Sice te system behaves Waly, the ties re ua ar raenaions of he ect a he rit sci Ths, by et, ee . aa-Eyh 0 For compu e henilpail ge by . wy=efekting, =e} Ing to, ect, fr ge acon, We ve 4 = ig“ 2) Tac 6%) =A + Tog a Sice AG* = ~ RF K, Eq i can be write 5 A= RTO, Ai) where Qs he mast tan ie eal conta. Eq, gives the dss ration exe and. (@ By denn, the chemi ptetil fy omni en by t= @Glr2y Sag Eg Loi 4B ), oo TNFa,