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    File 346

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    1382 PRINCIPLES OF PHYSICAL CHEMISTRY (ie from a, 18, dn, = 28) a A> (6106p (oa i i te required elation been ad. (The net rae of fermion of given by =e 6 tee ye of he fal etn nf ro en asin. ow, typ rtd oh ale r,t Since = ky we have ve y-0m wo AAT @0) =A (@M w8(Qn = Aare 2 = (An f(A) a As own Ina. (, Entropy Production and Entropy Flow in Open Systems We consider a system consisting of two phases 1 and Ii. Each phase is open so that it can ‘exchange both matter and energy withthe ther phase. The ext system is, however, closed since it can exchange only energy withthe surroundings For an open system, we have from thermodyraics, au = ris pay + Ey dy mc) « Tas = au + Pav Ey dty : % 7 The mimber of components in ech pas isc (y=1, =~ yoy, Ba. 73 becomes Recalling that dU/=d ~ PV and (08) Shee A» Zipp #5 1 moms ; “ an 9 shes we a eng we a, em ie a ard yo vouheyteas eng tow Qs hai hd ee nate bse fly ft ore aft endl ete fa Sse We os nb seat ea cng: wenn Shan, 6), as=@ RREVERSBLE THERMODYNAMICS 1989 Tots, E, 75 can be wet as ; #6 yt oA om oot Thea fs Focte pes nd E977 sweat “ ach alle! asad, Me y(t mri ath Aas oy Bt Sar 7 at i i Here 4! aad A" are the antes of reactions occuring in phases 1 and Th, respectively ; dt sepreeais te number of moles of component y etterng phase I ftom phase Ii. Simlaly, forthe ‘aergy flow we can write - det , Ue (99) 7 ale a ot 0%) ‘Substituting for d'@/T! and d"\y/T" in Bq. 78, we get dq 4a, aft ) ye dag = 0. 81 ft 1) lie lat 4 Ae re pt * A SU rept ‘Tae fist wo ems in Bq 80 represent entropy flow de ihe fom the heat exchange between be Tose ant the extaalsurouodings. The id out, ff and sh terms repretetentpy sed The rd tem repens ey change de To ergy exhngeRetwen phe Ba the forth tere represents entop chage duet exchange of mater between phases 411 inthe tas two tes represent he enopy change resulung fom chenal reactors ing hes nce pane The ao aay pon he of 1) sft wl aah (4p) 20 9 Bart) x8 repeat) ae, Ine, 81, he coetficent ofeach at (low) term enclose in parentheses the force em. We cau tne capes th rte of estops, production as 4 sum of the products of generalized frcis (ats) denoted by Xj an be coresponding faxes (eave) deoted by J, Ths, SSX, >0 2) $- 4m ‘Transformation Properties of Fluxes and Foress. Fora chemical reaction, the rate of entropy production i given by 0 = dS/dt = IK (82) 83) a Bq, 83, the fux J, is identified with the rate v and the generalized force X is identified with the aii: X = A/T. ‘We consider a consecutive reaction of the type A — B 0 Bo Cc @ For reaction (2), the affinity is given by Ay == (9-8) = Ba BS 184) ‘Similarly, for reaction (i), the affinity is given by p= = (ic~ Ha) = HB-B 85) 1364 PRINCIPLES OF PHYSICAL CHEMISTRY ‘The change inthe mumber of moles of A per uit ime Is given by mdnylde = or dagldt = =, ‘The change inthe numberof moles of C per wit ime is given by ‘incldt =v ‘ . Hence, the change in the number of moles of B per unit ime is given by ngldt = ~ dny/dt ~ dngfdt=v, ~ %, ‘Hence, from Eq. 65, the rate of entropy production is represented as Ta Sidt= Ay + Amy (86) Consider now the’ reaction scheme writen as AC Boe ‘The corresponding affinities for reaction i) andi) are Ay = Ha te= Ai + Ay Ay = Wa tie Ap Hesce, dagidt =r, 5 dngldt =r; dnc/dt = ¥, 4 vy We find that yyy and mp = 9 + 94 Hence, the corresponding rate of entropy production is expressed as TA,Sidt = Ayr, + daha » Ai + A a) Notice thatthe new set of equtions are such tat the entropy production isthe same. The trasfcmation properties of the faxes Jp andthe generalized forces are such that We ean take 8 lear combination of the forces to give new set of foes XY and choose a ew set of Mixes J, such Dat Eq 88 holds. Thus, iF Principle of Miciascopic Reversibiliy and‘The Onsager Reeiprocal Relations ‘The principle of microscopic reversibility states ta! mechanical equations of motion of individual Particles of a system of particles are invariant with respect 10 the transformation t—>-t (he time reversal), The theory of fluctuations, which is an ingorant wpic in statistical mechanics, plays aa import role here. Detalsaboit the fucuation theory wil ot Be dealt with here. We consider the value ofthe fluctuation a ata tine instant ¢ and of fluctuation a after a time interval «and we form the produet of bot the quanties. The average value. of this product during a safely long lapse of tine is given by (88) aaT FS = fim Foun, trey 89) 3 According to the well known ergodic theorem, the rine-average (Eq. 89) is equal to the censenble-average, Tis i aooter result of the ensemble theory in statistical mechanics. ‘We next consider the average value of the product o{)a{¢+2) in which we consider the fuctations oft sud oft +0), the later curring after the ine interval ¢: The mean valve & (Dat + 1) difers ffom that given by Eq. 89 only by the temporal order ofthe two futons, or more briefly, bythe sbtuion => —1, Thus, we can expres the microscop by the relation Ga + 9) = alee) * (90) 1985 REVERSIBLE THERMODYNAMICS Subtracting the same quantity «(?) af) from both ses of Bq, 90, we Rave TOF : 61) einige? 9 al = a(R Now. 25 x=» 0, we have ea,(0) = a, i a Jing that the decay of fuctation dy where the ime-

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