1344 PRINCIPLES OF PHYSICAL, CHEMISTRY ‘momentum flux and J, the elect Aux (Le, the electric curren). The transport coefficients x; D, nd} depend upon the material properties of the spstem.K should be borne in mind iat Ex. 2, 3,4 Sd are aot igs In the tational usage of the term ; they are phenomenological iavs inecel 6 define the transport processes, : Phenomenological equations describe in a siple way how the system changes. Ohn's law and Pet's aw of ison ar some flit exaples of phencogcl equates. The phenomenological equations of irreversible thermodynamics ae sinilatw these equations but are mace general. Fak’ law of difsion, dmidr=D(deds), where dav ste rate of change of solute across unt surface area under the Influence ofthe concentration gralintdelds and is the diffusion cotfiient, may te adequate in a simple sytem. Suppose, however, that wile one solute diffses ‘ander is ova concentration gradient, anter soe aso dfising under is concentration gadie.. Can we Sssume that tbe movement of te second sole has no infvence on that of the fist? Asi, suppose that while one clues fusing, tere also simulancusly exits a temperate grad in he ‘stem resulting ina flow of heat. Wil te movement of he Slt sl be described by tt equation ven above ? The answer thse questions given by theory and also by ition i o We ean generalize the equation dnvar=D (df) fora one. dimension low a ftiows tim. «pM p 8 te py eB 6 were the second term incorporates the infeace of the gradient of the second solute on the movement ofthe fist slit. Silay, we ean we dowa another equation forthe movement of the ‘evond solute mp 1 4g a ae * Oa 2 where D, EF, G ate te corresponding ifixon cofciens, If there ate more Slues a tirmal zalents, oir terms wil have tobe wien. To simplify notation, we use a single symbol J for daft Symbols J, J a used forthe rates of movement of sferentenites (ne, heat et). Again, the multiplicity of cefiins D, ELF. G, can be replaced bya single symbol Z with appropiate subscripts. Accordingly, D tecomes Lis becomes Ly. Here te fis subset refers ote component tat moves (andi thus the same athe subscript ofthe cotespondng 1) while te second subscript refer othe componeat ‘whose gradient i being considered. The gratent or diving force is designated bythe symbol X. sf, and 39 of. This rlatn is ba convenient and easy to remember. given driving force in a system, there 1 associated with ita single iceveribie low wich can be dseribed by an approtie phenomenological relion, Likewite, wo simultaneous ireversle flows. provided they ate independent of each oer, can be described by appropriate phenomenological elation. In practice, however, te simultaneous ows arent independent ofeach titers gradem. Sich flows ere known as coupled flows. Onsager doveoped the inevesbe thermodynamics (or non-equilibrium thermodynanis) in 1931 for analyzing coupled irreversible fw. TF the gradients Xs are nt too great, he fess are linear functions ofthe driving fore. Ths, we ean wre + Lack © Jom LX, + bake + where 1= 1,23, 5 ‘The relations depicted by Eq. 8 ar called linear phenomenological relations. The coefficients Ly aze called the primary phenomenological coefficients while the coefficients Ly are called Gasager's phenomenological coefficients. tn the Onsager coefficients, the subscript # denotes the flux and the subscript j denotes the driving force, ‘The solution of Eq. 8 is extremely dificult: Soverat scientists including Kelvin had attempted its reverie Heroic ‘ tos soon in the 19th century. It was, however, Onsager who finaly solved it in 1931. The difficulty ia solving tis equation lies in the fact that the phenomenological coefficients have to be determined cexperimeatally. The peimary coefficients ca, of couse, be determined easily. The coupling coefcins (Onsager’s phezomenologcal coefficients, [,), however, presen-severe dificult. for thc experimen! reasiremet since they involve the control of many experimental parameters. Onsager theoretically sowed shat by = by ® aq, 9 gives Onsager’s reciprocal relations (ako called reciprocity relations). Let us duell further upon the reciprocal relations. Onsager showed that these relations exist for 4 properly selected pair of flows, called the conjugate flows. It i, however, not clear what ‘constitutes a propery selected pair. Suffice it to say that inthe case of a one-dimensional conducting rod or wire, If A is the potential difference and AT i the temperature difference between the ends, then wing AE and AT as the driving forces, the electric current f(s J,) and the entropy curren (ot ‘enttopy flux) J, form a pair of conjugate lows, though the electric curent andthe heat fax Ja do not do so. The expressions for F and J, are T= LyQE+ bait 10) Jp LAE + igh ny Using the definitions of electrical and thermal combutvitis, we can obtain two cquations relating the four phenomenological cofficiets Li, Liz, Farad Laz 0 measurable properties ofthe Syn, The fourth expresion is fmished by the Onsager reclroiy relation, vz, In = hy : 41% Ths, ll be coeticems can be determined In gener ly=la 8) In simple words this means thatthe coefficient which expresses the influence of foree jon the ‘fox Tis the same as the coefficient which expresses the effect of force {on the fuxj Consider, for instance, Ohm's law, E- (UR), where E isthe potential difference, [tbe cimrent,R the resistance and 1/R the conductance, Comparing this equation withthe equation : Jp = bX, + LiKe + LM oe ‘4 wwe see that Ly can be regarded a8 conductance coefficients. Like elevtrical conductance, theit ‘magnitude will depend upon the dimensions and the temperature of the system. Ifthe physical sizeof the syste is doubled, the values of L, will also be doubled. In biological systems the preseace of ‘enzymes will profoundly influence them. It may-be remarked here that while Onsagers relations ‘were originally proved only for small deviations from equllbrium, they have als been found applicable to considerable departures from equilibrium, Lars Onsager (1903-1976), the Norwegian- ‘American theoretical chemist, was awarded the 1968 Chemistry Nobel Prize forthe discovery of reclprocal relations in irreversible thermodynamic. Conservation of Mass and Energy tn Closed and Open Systems Consider a closed system ‘ containing ¢ components (y =1, +c) among which a chemical reaction may take place, [a euch a system, any variation of masses will result only from the chemical reaction, Thus, the change of mass m, of companenty during the time Interval dis given Fs 5 Aimy = WyMy ld ‘were My isthe mola mass of component y ad vi the solchlometrccoeficiet inthe cemieal reatton."By convetion, this sokkiomee coeficzat i taken ab postive forthe product and ‘epative forthe reactant; & isthe degree of advancement or extent of reaction intaduced by1348 PRINCIPLES OF PHYSICAL CHEMISTRY de Donder. sr example, forthe rection, N+ 3H, —> 2M, te A SS ge a, 15 gives Sa pacaies yeas ‘The tol mas ofthe system is gten by m =Fmy. Sumiag Eq, 15 over 1 the prinile of conservation of mass for 2 closed system is expressed by wpa lane ws The equation —EyyM, = 0, =) r is called the stoichlometrie equation ofthe chemical reaction, Instead ofthe mass ofthe component is convenient to we the mole UME My Myson My ‘Thus, we have : any = 4 48 9 4, 16 or Eq. 18 introduces §. The chemical reaction rate per unt time is defined as eit ll It is the ratio betwees the increment d& and the time interval dt. From Eqs.18 and 19, the increase inthe numberof moles my wil be given by ante = 49 Co) Eqs. 16 to 20 can be extended to r simultancous reactions designated by indices p (p=1, Te a ce of md Ben pom fh cages eng fm ‘reactions : an, = iy pe 7 2) a where vp deaotes the’ stoichiometric coefficient of y inthe pth reaction. The rate of the pth reaction is evidently given by vp = diglde A) Let ws illustrate the above discussion by considering ie following two simultancous reaction: 1c +0, —> 20 @=) Wehave Aico, = x We ext consider an open system. For this system the change in mass dm, of component 7s split into two terms : iy = bey + dy A) where he frst term is doe tthe mass extige wit the eneirsuragadings andthe second term {s de tothe internal changes inside the system. ees | 1 | } | | | wiosms netucoinundcs ea ae ital 29 ; = mtn Sint 5 pa Eq. 23 over y and taking into consideration the stoichiometric equation (Eq. 17), we = ann ee . 9 ‘This relation expresses the principle of conservation of mass in open syStcms ; it shows that the change inthe total mass is equal to the mass exchanged withthe exterior (surroundings). Some thermal energy associated with matter depends on the atare of matter and temperature. For an open system, the application of the principle of conservation of energy requires taking into account the thermal energy transfer which may occur independently of any mater transfer and also because of the mater transfer. Thus, in an open system, the flow of thermat energy transfer, dA, uring the time interval dt consists of the mastindependem energy trensfor as well asthe mass- pendent energy transfer. Since H = U + PY, we have df= dU + PAV + VaP @ ‘io from he Fist lw of thermodynamics, dpe ar, a ence, Eq: 27 can be writen a5 Ht = ag + EP ) ‘We now considera system consisting of two phases Wand I, herein bt: matter ac enccey are cachanged between phases T and TL altiough the ene syste isa closed system. Application of Eq, 29 each phase at constant P yields del = dig-+ Viet and atta dg 4 Var and V=V! + V7, thea the above two equations can be combined to give for the aot = ant + aul = alg + a4 + VaR 0) (Though the enthalpy is a state function and hence dH i an exact differential, andthe thermal egy is ota sate function and hence dg a neat leat, yet forthe sake of convenience we fave wed the same symbol dt show he infitesimal varias in both these quant) ‘Again, since ¢ is not characteristic of the two phases but pertains to them, we-have written the vatiatons in g in the two phases as d'g and lf rather than as dg" aad dg") Substituting the expression dq = aU + PaV in Eq. Z7, we set dH = dq + VaP GD Eq. 31 i applicable wo the closed system consiting ofthe two pass. From Eas, 30 and 31 we that y= dp +a ro) Since the system is closed, the term dif can be considered as made up of the energy flow from phase Tl to phase F and heat low from the exterior (surroundings) to phase T. Thus, we can write ais m dys dip at dlp = dig ed's 8) ee € and ar abbreviations fo exer ad inal, espe.