Lo ‘PRINCIPLES OF PHYSICAL CHEMISTRY he coefficient of mass flow associated with temperature gradient. We shall see below that stationary states may be characterized by an extremum principle which states that in the stationary sate, the enteopy production has its minimum value compatible with some auxiliary conditions to be specified ii each case. Thus, we shal derive a equti (Eq: 146) which would specify the condition that the entropy production is a minimum fora given value of Xp. Using Ege. 141 and 142 and the ‘Onsager reciprocal relation L1pL, the estropy production becomes Bo iyXh + 2p KaXy + In¥ > 0 Al) Taking te derivative of Eq, 41 with expt to Xq at cot Xy , we have 2 (as) ie (28) = 2 ciate take) = Mn 49) In the steady ste, Jy=0, which means hat te feof eazopy production bas an extemsm ia the state. This extreaum Is a minimum as can be shown by taking the second derivative. Sine inthe steady state, (B/0Kq) (dSldt)=0 (as shown above), we have Beg (He) (a conta X3) 2a (aka + Lake 0) =n 49) Since Uy is postive, the second derivative is aso positive so thatthe extremum is minimum. ‘This statement furnisies the mathematical statement of Priggine’s principle of minimum entropy production according to which, atthe steady state, all the flows corresponding to restricted forces vanish, Iya Prigogine (1917-2003), the Belgian theoretical chemist, was awarded the 1977 Chemistry [Nobel Prize for his conteibutions to non-equiibeium thermodynamics. ‘The above argument can be generalized tothe case ofm independent ants X, ... Xp of Which acertaia number k, Xi... Xj ae kept coastant. in that ase, we have forthe sationary state, Jest eh=0 + Ast) “These conions ae equivalent othe mina conto fo entopy produton as la) <9 Yeti -«t) Prigogine proved thatthe time variation ofthe rite of entropy production, vi. (dt (dS) can be split up into two terms : () du tothe irreversible processes occuring inside the system and (i) due tothe flow of entropy from the system to the surroundings. The itevecsible processes ocurring lnside the system deereate the rte of entropy production ul this rte becomes rinimum, When the system is in this nonequilibrium steady state, it cannot by itself come out of it despite being a Spontaneous ireversible state. If some fluctuations occur which disturb the syste from the steady state, the internal changes will our so as to bring it back to the steady stat Application of Irreversible Thermodynamics to Biological Systems Biological systems are open systems which exchange both mater and energy withthe environment. ‘Tee growth of a living organism or cell is characterized by transitions resulting in greater order and thus decrease of entropy from the intial sate, Recall that for an isolated system, spontaneous change results in an increase of entropy and heave of disorder. Thus, if we treat a biological system as an ated system, rather than as an open system, then it appears to violate the basic principles of ‘hermoxfynamic. The theory of stationary non-equilibrium states leads to a beter understanding ofthe ‘slobal behavior of tving organisms, IRREVERSIBLE THERMODYNAMIES , 1361 ‘The evolution ofthe living organism upo the saoary sate may be considered as taking pice under a numberof constraints determine by the ouse word, constsns such ate concentrations of some subsances inthe ous word whieh ae trasfrmed inside the ving ergansms Regards ofthe nau of the constant parameters, th atoary Sate may be regarded se ste of minima etry production per unit tine. In ages atte, the mata con butce to ay Producto, $f arses from the process of metabolism wiry te assimilated food ls degrade 2 simple substances toch as 0, acrmpacied by an energy cles. As the orzmism owe, ‘Sigh dirs postive, Sis negate ad grec tan dS. “Ths, tei sum dS bene hive, This eduction in etopy implies a reat oder (or organiza) in the organi, Darag 148 growth ofthe organism, 1 sbjeted 1 several fed consi, as sid above exerted bythe ‘ste wl, so that the maturation of he oganism is ccompaied by dee fa cary. Wher ae steady sate, or the satinary sae ofthe loi system, is retched, dSi-=d.E 50tat en athe steady state he sytem emaine Sale exe pete. cndinear Thermodynamics of Irreversible Processes ‘The irreversible thermodynamics in the linear regime, we may recall, assumes (@) laeat plsomenlogical laws (6) validity of the Onsager reciprocal rations and (c eating the phenomenaogicsh coe‘Tciens a5 constanis However, inthe case of chemical reactions, linear phenomenological laws ‘may not be a sufficiently good approximation. Als inthe transport processes it becomes necessary to take into account the variation of the phenomenclogical.coeficients (for instance, the varation‘6f the coeficient of thermal conductivity with temperature). Sucheffets, which may be considered to be ‘o0-tnar, introduce complications in the general weatmedt of the hetmodynamics of irreversible proces since they desitoy the lear phenomenological equations or transform the macroscopic ‘equals of change into non-linear equations. Prigogine and Gtansdorf consider the rate of entropy ‘rodxion tobe given by : on Sua 0 08) and spe time change de into two parts. One is related tothe change of forces and the other to the cbang. of flows. Thus, de Hot do = THAN + DX Asay t t The flowing theorems have been proved by Gnedrf zd Priggine (Unter he resticive condions, da = dy5.= Yao disp The catbution of te time change of he forest the etopy production i equa otha of he time change flows, In fat, iyo = J) Jelly = Yih 4150) r Using the Onsager reciprocal relations and treating the phenomenological coefficients Ly as constants, we lve dyo = DXi(lydX) = DX = dye A133) i T ©) Sice in the hermodynanics of ineversible process the conibuion ofthe te change of forest the ent>py production is negative or ze, we have dea <0 059 ‘This inequait' holds whenever the boundary conditions wsed are time-independent. It isthe most ener result in thermodynamics of irreversible process. The discussion of the general proof of1362 PRINCIPLES OF PHYSICAL CHEMISTRY the pecan, AES Brved for chenicalreacons by Glas and Pigoize, i beyond the sope of tensttclading Remarks. Exciting things ae happening inimeversible thermodynamics. Irreversible ‘miodynamics i the creation of one scientist, Onsager, wha has been called the greatest themed fatemtical physicists and mathematician sch a8 Bekof, von Neon, IF. Nash Hot, Beanie Lanta, Ketmagry, patty, Maroy, Lypum, Pina, Lape, Nase Sot Eat iS. Chandrasekbar, Terns sich as ireversiliy,expy as dsorder,entopy ‘tne ee ‘Scene of complesy, chemical chaos, qunnm choc, facta eaves a aca, strange atuceon, trenton reactions, Auctions in eesembl theory, fucatnedspaton there, bifurcations Host bitrcation, Lyapunov exponent, bute efet,ete, have end ths facinating sje leis pertinent to conclude this chapter by three quotas. ington (1882 iss ean! 0 Conclude this chapter by hee quoains AS. Edington (1882194), te get “The law that entopy always increases—the Second law of thermodynati reasesthe Second law jynamies ~holds, 1 think, the {upreme postion among the laws of Nature. I someone points out to you tht your pet thcry ofthe ‘The other quotation of great historical interes is that de to Einstein: A theory is mote impresive he reer te sialic of penis i, he ice deren kins Of hings relates and he more extended ts ac of spplkabliy. Tee, pet tape sce slau termodynanics made yon ine. I ise eny phys tery of caver sane cee ish am sopvned tha, wine tamevort of he aplebliy of ts be" "septs & ae je ot ow a ay appear othe wor bo mys en oe bene ay pl so eto i pee te ike hy plying on he sash, Stain rel row and te ga anh pee rere an ran whee Pes sein oe fron tue! Uae Nevo rly fo bis deta 1727 ory flesh event ofl te sess frm hance past ta the presen : {: Review Questions P——____ ‘et nso psa ee mp tn, Die ener pn ey cd cen ee f Drive epi fc) pin he os De snes ey pr eles, i Deira expen cy oes ary wep sm. Dis emi pepi cel es Beit: One ie ins om pin pe mei ‘sty he nage ei lions ese etree, 9. Ons’ eens wat eo ces / 10 Dees es he cease, 8, BP a. 1. Dis essen any oan ai ria gl sn ex pain {#4 Textbooks on Physic! Chemisty and Related Subj ‘Abad, ALA AS, Siboy, snd M0. Bais, Pséal Chas. edn, Wie 005 ‘dan, AW. A Toto of Piya) Gnamty, eaten Prin, 13. tis, PW. 084 9 Pel, Pye! Crom tha, Ocloe erty Pease, 2006, aon, Gi, Phys! Comisy. sh eon, Maw, TS Bey, RS, 8.4 fico, and) Rots Pryic Cros ded, Wey, 2000, {Gaslan, GV, Pryeal Camis edn, aden ese. 16 Enya cand BR, Pst Oras. Parson eon 28. Kain Hand H.0 Facieing Preis o Physica Cems Wy, 200, asso. §, A Textbook of Prac! Cremtry, Mactan in), New Dah 1976. Eg. 0. Henaerson, and W. oat fade}, Piysel Chonty * An Ahantod Treo (2 mul-wume Pete fee ae roe veo din.BVS. and Jee Sys! Chemis ad Pdions, Tata Mora 108 Doga, Sk, and Desa SPs! Gremisty Twaugh Petons Wey Enter Ut. 00, apt, Ki, Physi Chemisty, ob and Marian ede) Lis: New Ost, 1380-4. Ko, a lan 8, Poy Chants Ort and Ca Now shi 100% Love, is Physical Chemisty, 8h adn, ara Meu, DA. ad J.D. Sino, Pysca!Chemsty. Univ Score Book, 1996. Moor, Wi. Pry! Chemis, saan, Pree al 172 Veruigpait Gi, Pye! Chomsty Prt ona, 102 fer A Concepts of Meco Pyles adn sri, 208, ten, J, Supramelacuar Choy, Vor, Wenhen To Neo. and Pigogne, ExrnyConpleny Feonan New, 19 Hal hin ed), ho Rew Gremsry, canoe Unvosy Pcs, 20, (©) Toxtooots and Monographs ‘quawrus wecHancs tn, PM, and FS. Pesan, Moteur Quantum Mécranos 48 edn, On, 2005, ‘cs: PM, Quanta & Hanabock of Cares, Oxon Uae Pest, 1991 Sat, A, Quantum hechanes»Fourdaton ana Aptcton te edn, Speer, 194, Bathe, Hh, and LH. Jeo, ornette Quantom Mootonta, ra ed Bastin Ceriogs, 985 Gehes-Teniou. C8. Du, ana Lalo, Quanta Maan, Vo. 8, Wey, 1077 tania. AK, Inieducion Quanta Chart, hoa, Tala Meeew Nev Oe, 1294 Cntstfersn, Re. Bast Pungpes and Tectguas of iteauar Guana Mechanics, Spoaet (88, Engel T, Quan Chamsty and Spactocopy. Pearson Edsaton, 2008 Disa, CE, Inosuoton o Quanisn Chemisty, Pentel 1884. faye, MD, Elements of Quatum Mochans, Oxor, 2001 Ft, 0.0. Pines of Quanium Mecranes 2 Apes to Gham and Chemie Physics, Canby, 1938 Gifs, 6, nteduton to Qvartum Nachric nd ed, Paran Ebvo, 200 Ghatak, A: and 8 Lxarathan, Qurtum Ngo, Sh én, Macnilen, New Doi, 200, ot, Wa, Rago, P Slee, and. A. Pop, Abo Mtr rst! Theo, iy. 1968, anda, 6, and © isha, Quanta Masta, Pergamon, 184 {vig Quart Chas, th edn. Pearson Easton, fo, 250, eQuari,0.A, Quantum Chemisty 2nd ed. Unversity Ss Boks, 2008 Peres. Quariom Teor; Conese and Meads, Kamer hese, 1S, Pl, Elementary Quantam Charis, 2nd edn McGraw fa 1280, Paltaia M8. Quantum Chemisty ard Spoctossn, rd edn, Vahl Pueaton, Jasna a), 188 Pauing Land E- 8 Wison, J, lnsoduoton fo Guan Meche, Maran Hl, 1306 “Pr asad, Ri, Quantum Choris, Wey Eater Lid, New Del 1880 PE. Quartrs Machaies, Penton Unietey Pree, 1 ‘Aoanva, 8, ane a Prakash, Quantum Macha, Protes Half ina, New Deli, 1997. ‘Simons and J Ncels, Quantum Mactrace i Cherasy, Ox, 1997 ‘Swati F., Quatur Meohane, SpingerVtag. Bein, 169 Thantappan, VK, Quantum Mechanics, Kew Age taratna New Dei, 197. dha. 6. Qvantum Mechanics, Pree a fa, New Ut, 202, Sakura J: Meda Quant ocrancs, Person Eccaton, 184.” ‘Salm, The Moteur Orbe Theoyaf Conga Macca, Bei, 1968. Soha, GC, and MLA. Rater, Cuantan Mecnaves hn Chemsty, Ee Horod, 292. ‘Sons, J, 3nd J Nehols, Quantum Mcancs h Choy. Oxo, 28 Saab Asa N: Osan Medam Quantum Chamty, Netw i 1988. owe, 1.0, 29d KA. Paeson, Quantum Gnensty, 21 wn, season: Press, 2006, Mordaches, Quantum Mochi, sean. Whe, 968 1363