5. M. Blinder! University of Michigon ‘Aan Arbor Thermodynamics is the study of the laws which govern transformations of matter and energy during physical and chemical changes. ‘These laws have their most rigorous and concise formulation in terms of certain specialized mathematical constructs, inchiding partial derivatives, linear differential forms, and line integrals. This paper contains a condensed treatment of some of the mathematical techniques relevant to the study of thermodynamies. It has been the writer’s experience in teaching physical chemistry and thermodynamics courses that prior familiarity with this mathematics greatly facilitates the student's subsequent progress. For then he should be able to concentrate more on physieal principles, unencumbered by irrelevant mathematical difficulties. In. addition, the student will hecome more aware of the distinction between physical inference and mathematical manipuls- tion in various steps of a derivation. Mathematies provides a compact language for con- veying quantitative ideas. A mathematical symbol ean express something which would take many pages to say in words. By use of mathematics, a train of ab- stract thought ean be broken down into a series of short manegeable steps. Otherwice, a complex logical sequence might be beyond comprehension ‘The stress in our approach i on intuitive conceptual- ization rather than on mathematical rigor. The reader is referred elsewhere for more rigorous treatment of the topies eovered Partial Derivatives ‘Thermodynamic systems are characterized by certain quantitative physical variables, such as pressur Volume, temperature, internal energy, and entrop: Experience has shown that it is not always possible to vary such quantities at will, but that specification, ‘of some results in definite values for others, Mathe- matically, such a situation is expressed by saying tl functional relations exist among the variables, The methods of partial differentiation then become es- pecially appropriate. In this first section we shall re- ‘Adapted from Chapter 1 of « physical chemistry textbook to be Published by Macmillan Co, New York §" Guggenheim Fellow, 1805-06, at University College, Lordon «#80, for example, Wioven,’D. V., “Advanced Caleulusy” Prentice-Hall Ine, Englewood Clif, N’ J, 1947 * See any’ book on elemnontary calculus, fo example, Grasviae, ‘A, Sutra, P-E,, ano Loxauny, W.R,, "Elements of Dilfer: prlentntcer Cte” Gm ands, etn, Ma ——____ Mathematical Methods in Elementary Thermodynamics view some of the more useful results from the theory of functions of several independent variables Consider first single-valued function 2 of two in- dependent variables z and y. ‘The functional relation, written 2 = f(z) or 2 = 2(a,), expresses the fact that for & pair of numbers 2, y (perhape within a restricted range) there exists a unique value for z. Geometri- cally, the functional relation may be represented by a surface in three-dimensional space.t If one of the it dependent variables is constrained to a constant value, ¢ can be considered a function of the other variable alone. Partial derivatives can then be defined: ae Ha 4+ asy) = sey) @),=.5, ar and ay ae as + ay) = sa) ().= 2, ay ‘The subscripts x or y ean be omitted, but only if there is no ambiguity in what is being kept constant. A par- tial derivative, like an ordinary derivative, ean be interpreted geometrically as the instantaneous slope of ervotie. The carved 1 The hevionly and Figyre 1. Grophicelrepreenttion of {htloce repre x ~ fay) he rs Yerteoly toolehed planes ore y= esmtont, end x = cater Texpecieys one intersection cover, (S/o, When 1 (Oe/Oyle equal 0 he Slope af ed. curve (Fig.1). Thus (@e/02), represents the slope of the curve cut from the surface z = f(z,y) by a plane constant; similarly (2:/2y), represents the slope in a plane 2 = constant. Partial derivatives are evaluated by the rules for “For example, = ax + by is represented by a plane and ¢ = Gt + PM by a sphere. Volume 43, Number 2, February 1966 / 85ordinary differentiation, treating the appropriate vari= ables as constants, For examples, the pressure P of one mole of an ideal gus is given by Peary where Vis the volume, 7'is the absolute temperature, and R is a universal’ constant. Treating P as the dependent variable, we have (@P/evyr = -RTIVE a (OP/eT Ir = RIV w Since the partial derivatives are also functions of the independent variables, they may themselves be differ entiated to yield second (and higher) derivatives. These are written mau) « ().), ata () & [5(&),]«° \When the function and its derivative are singlo-vslued and continuous, the order of differentiation in the mixed desvativesis material and Be a7 ‘This is always the ease in thermodynamie applications. For the above example. rar ® o i) Products of partial derivatives ean be manipulated in the same way a produets of ordinary derivatives, pro- vided that the same variables are held fixed. ‘Two ti ful identities are (2),G), - GD. aa) GOG).-1 & G), aa, 2 ‘Thus far we have considered changes in 2(2,y) brought bout by changing only one of the independent varia bles at a time. The more general cace involves simul- tancous variation of z and y. This could be represented by the slope of the surface z = j(z,y) along a direction not, in general, parallel to either coordinate axis. For a function of a single independent variable y = f(z), the inerement in y brought about by sn infinitesimal change in zis given by dy = (fy/dz)dz. When z = f(cy), the inerement in 2 wrought by simultaneous infinitesimal ‘changes in z and y is given by the total differential” "This can be shown as follows, Lat ar = dz + az, y + Sy) ~ ae, y) Adding and subtracting the quantity s(2, y + ay) and inserting the factors 42/2 and ay/y, we have ae [ee tertan lz Passing tothe limit Az ~ 0,24y +0, the two bracketed quantities ‘become partial derivatives. by ean. (1), while the increments 8, Sy, Sa become dierentals ds, dy, and 2) aes (%), a aay Extension of the above theory 16 functions of more than tio variubles is straightforward. For a funetion wof r variables, = f (iy 7... %), there are r first partial derivatives Ou/O7, Qu/dre,..., 0u/dr,. The total differential is given by @+& ) tee +(e Ger wo Other properties have obvious analogies and need not be remarked upon further. Several useful relationships among partial derivatives can be obtained from (12). Suppose, for example, that 2(z.y) = constant. ‘Then de = Oand. ),e+ i). Rearranging we find dy _ (2/02), ae” ~ (@e/Ovie ay But the ratio of dy to dz means, in this instance, (2y/~ nee 2 is constrained to a constant value, | Thus ‘arrive at the important identity BY), = = Re (az), > ~ ron. This relationship often enables us to evaluate physical quantities not divectly obtainable. To ith as) Wt 7 LP Peeve which agrees with (0T/01))» caleulated direct solving the ideal gas equation for 7. Making use of eqn. (11), eqn. (15) ean be rearranged to (52).(85).(68), = ~* a In the preceding discussion, the relationship among, che three variables x, y, 2 has been given in explicit form, ie, 2 = f(ey). Solving for x or y, one could alternatively write 2 = g(y.2) or y = h(z,t). Thus the ideal gas equation could be written in any of three Be ieee Tg eB us Pe r= " In many applications it is more desirable to express, he fimetional relationship among +, y, and z in a more symmetrieal fashion, We accordingly write F(z,y,2) = 0 (for example, PV — RT = 0). In this way, the choice of dependent and independent variables is left free. One might choose 2 as the dependent variable in one application and y in another, without needing to reformulate the functional relationship. One would then say, for example, that 2 is an implicit function of = and y through the relation F(z,y,2) = 0. Implicit funetions ean be applied to the evaluation of derivatives. Consider the total differential of F(a, 2) using eqn. (13), ae (2), a+ (2), art (Z), te 9 09‘This vanishes since F is a constant (= 0), thus dF = Suppose now that we require (Qy/2z),.. Sine zis being held constant, we may drop the term in dz, ‘Thus ae oF at Dut + Grad = ” and Dv) _ OF oz), 2) az), * ~ QF ou ).e “ This method is useful when it is impossible or in- convenient to solve the implicit relation for y or x. To illustrate, suppose we wish to evaluate (0/07) for a gas obeying Dieterici’s equation of state PO = beret = RE @ where a and b are two additional empirical constants, Eqn. (22) cannot be solved in closed form for either For 7. But defining ehavet rare MM ome an orate = Pfr EY] em ey Whence by (21), after simplification using (22), QV) _ (oF OT mr fa at), > ~ (eaves ~ (+ a7)/ (a Hy : 2) In most thermodynamic applications, there are alter~ native choices of the independent variables even if the dependent variable is fixed. We next consider some formulas arising from transformation of variables. Suppose 2 = f(xy) but x = x(u,t) and y = ylu). If eqn, (12) is divided by du and coustant v is speci- fed, we obtain the “chain rule” for two independent ©. @O.2Q.@W. Similarly, CE). + H).GD, ee For a function of r independent variables u(rs, 2, 2), the chain rule generalizes to 2 en where the ty j = 1... 7, are an alternative set of in- dependent variables. It is seen that = could equally wel be regarded asa function of the new variables w and 4 namely z = g(ue). The total differential can be ex- Pres as a= (2) av (2), 0) ater wing the ttl dirt de and dy i ems of du and dy, and liinating among eqns (12), 7, and (28). are an' This method of evaluating derivatives is entirely equivalent, {in this instance, to diferentising eqn. (23) with respect to 7 at constant P, then solving for (OV /00)p. ‘This, in fect, re- ‘races the steps in the derivation of ean, (21) a ‘The following relations among the altern LQ). AQ.-2 en OOOO & Another useful formula involves a “mixed” pair of independent variables, wherein we take 2 = h(zu). Dividing eqn. (12) by dz at constant 1, we obtain? sily proved @).-@),*G).G), 9 ot applying ean. (15) ).- @),- Gi). cia ‘Thus if the internal energy Fis given as a funetion of and V, (QE/27)¢ can easily be evaluated from ar), Gi)e* (BP), Gr), We conclude this section with a brief discussion of homogeneous functions. A funetion f(r, ..., %) is said to be “homogeneous of degree N” if $255) 82) = 8M oy 20) (30) where Aisan arbitrary number. ‘Thus (x,y) Slay) = (e+ y')", and f(z,y) = y/z are homogeneous, ‘of degrees 2, 1, and 0, respectively. Euler's theorem ‘on homogeneous functions states that = NMG on) wn xs, when f(ey, «.., 22) is a homogeneous funetion of degree NV. To prove (87), we define a new set of independent variables Next wwe differentiate each side of (36) with respect to A. The left-hand side becomes, using the chain rule 9, LL aon ax 7 2 dui ax ce while the right-hand side gives simply am ae Equating (38) and (39), noting that u/X = setting A= 1, we obtain Euler’s theorem, eqn, (37). Homogeneous functions of degree 0 and L are impor- tant in thermodynamics, especially in the study of multicomponent systems. Corresponding to the vari- ables 2, are usually the component mole numbers 7. Thermodynamic quantities homogeneous of degree 0 are Known as intensive variables. These do not change in value when the mole numbers are inereased in proportion, i.e, fom, oy A) fly oy med 0) Examples of intensive variables are temperature, pres- sure, density, viscosity, and index of refraction. AY one) an) Note the importance ofthe subscripts here. Volume 43, Number 2, February 1966 / 87.‘Thermodynamic quantities homogeneous of degree 1 are known as extensive variables. These have values proportional to the amount of matter in the system, 0h myo .5 BM) = Ray a Examples of extensive variables are mass, volume, ternal energy, entropy, and, of course, the mole num- bers themselves. The ratio of two extensive variables is again intensive, for if om) Kinyo a =) no me) (48) ‘Thus density (mass/volume) is intensive, as are various molar quantities, eg., molar volume (volume/number of moles), Euler's theorem is useful in relating extensive thermodynamic variables to the corresponding partial molal properties. To illustrate, the volume of @ mix ture of two liquids at a fixed temperature and pressure depends on the mole numbers nm and 2, V = V (ns) By Buler’s theorem, eqn. (37), with V = 1, ar on, ‘The quantities OV/Om and OV/On (more precisely QV /Om)r.p.¢ and (OV /2re)z.0.4) ate known as partial molal volumes (usually abbreviated Py and Y). The first of these represents, for example, the change in volume per mole when a small smount of component 1 is added to a mixture of m; moles of component 1 plus ne males of component 2. Other extensive variables like- wise have partial molal analogs, the partial molal free energy 0; being especially important in the derivation of thermodynamic principles, a Differential Expressions Differential quantities of the type difay) = Xtzyis + Yau «sy known as Pfaff differential expressions, are of central importance in thermodynamics. Two eases are to be distinguished: (2) in which there exists some function Fay) for which eqn. (43) is the total differential, and (2) in which there exists no funetion of z and y which yields (43) upon differentiation, In case (1), dis said to be an exact differential (or eomplete differential or perfect differential) and we ean write dla) = Mawhée + Vauhdy 0) In case (2), dg is called an inexact (incomplete, im- perfect) differential.* ‘A differential expression can be tested for exactness without explicit reference to the function F(z). Con- sider frst the case in which eqn. (45) is exact and F(z») isknown. We ean then write the total differential 4Some authors use the notation dy or Dg when the diferential i inexact but we sball not reake this distinction 8 /- Journal of Chemical Education a ),«+@).# co But sioe tis diferent) ecpanion is uniqu, os (46) and @) mut be ual and we ean deny ren = (2), re = (6), ao Furthermore, ay _ DF, Oy 7 dyae! dx ~ Bry U9) but as discussed earlier, mixed second derivatives of well-behaved functions sre independent of the order of, differentiation [egn. (6)]. This leads to Euler's reciprocity relation aN) _ (2¥" - GS). @), wo ‘as a necessary condition for exactness. It is also a suffi- cient condition and ean thus be used as a test for exact ness. That is to say, if eqn. (50) applies to X(z,y) and ¥ (xy), then eqn. (45) is an exact differential and there exists come function F(z,y)* which satisfies eon. (46). Note however that the reciprocity criterion neither requires nor identifies the function F(z,y). ‘To illustrate, let us test the differential expression yer body o for exactness, Here X(x,y) = y and ¥(z,y) = z, and aX/oy = d¥/2r = 1. Thus by eqn. (50), (1) must represent the total differential of some function of z and y. ‘The latter is easily identified by inspection as Fee) = zy since d(ry) = y dz + x dy. Again, con- sider the differential (RT/P HAP + (R/PMT (3) ‘The reciprocity condition is again fulfilled since (ie (-#)], «Lo G@)], and eg, (52 fund to represen te total deivasive of V(P,T) = RT/P. ‘Two diferent expression for whieh the reciprocity tet flea -R/PY (33) yd — edy ai and (Rr/pyap ~ Rat (33) These are consequently inexact differentials. ‘There exist no funetions whieh have total differentials (54) or (58) ‘An inexact differential expression X dx + Y dy (@X/dy + D¥/2z) can be converted into an exact one bby means of an integrating fuctor M(e,y). In that ease A(X dz + ¥ dy) becomes exact, ie, auasx _ aur) a Co) For example, (54) can be converted into an exact differ- ential by choosing M(z,y) = 1/24. It is easily verified * Ast proof of sufficiency, thé function Flay) = SXealds + SVewldy — SS22/eyleody satisfies eqn. (48) provided that eqn. (50) holds.that dz ody | ay = HES Mae dav satisfies (50) and that it is the ‘total differential of flzy) = —y/2, Alternatively, the integrating factor 1/y! eonveris (64) to d(2/y). Likewise, multiplication by —P tums (55) into the exact differential (52). Au integrating factor can always be found for an inexact differential expression in two independent variables. Evidently, the choice of M(z,y) is not unique. _ In fact, ‘M(zqy) times any funetion of P(e,y) is also an integrat ing factor. The concept of exaet differential is especially impor tant in the formulation of the first. and second laws of thermodynamics. Thus, the first law postulates that GE = dQ + dIV is an exact differential even though dQ, the increment of heat gained by a system, and dW, the increment of work done on a system, are individually in- exact. This constitutes « definition of the internal energy E. The second law postulates that 1/7, the re- ciprocal of the absolute temperature, is an integrating factor for dQ. Thus, dS = dQ/T is exact, which de- fines the entropy S. ‘Many of the cheniieal applications of thermodynamics involve more than two independent variables. The linear differential expression in r independent variables is written tia, 42) = EL Nay os zehdes (38) where each of the r functions X depends on some or all of the x Recalling that the total differential of a funetion F(z, ..., 2°) of these r independent. variables is given by, ar = yan co) we obtain, when (58) is exact, + 0) From (60) we obtain, in analogy with (50), r(r ~ 1)/2 reciprocity relations (one for each pair i,j) BW yess wo Conversely, the reciprocity conditions (61) eoustitute a testforexaciness : As in the case of two independent variables, an tegrating factor M(n, ..., 1.) can convert an inexact differential expression into an exact one. In contrast, to the former ease, however, an integrating factor does ot always exist. "A criterion for the existence of an integrating factor for eqn. (58) forms the basis of Carathéodory's formulation of the second law of thermo- dynamics. Before stating this important. principle, Ne observe that the first order partial differential equa- tion a= EXd 0 (2) (known as a Pfaff differential equation) possesses a family of solutions of the forra Sle - 1 =) = constant (3) po eeeemee ee The solutions (63) are here expressed as implicit fune tional relations among the. Exch solution ean be rep- resented by a surface in r-dimensional space. Car théodory's prineiple is now stated without proof: Let fin, 127) = cwistaut be ove ofa family of sulutioms to the dierent guation D> Nley = Oand let each solution be faces If there exist points Pla’, «5 21°) “r") i reinissuna pace hie aod he co te une ofthese surfaces, ten ‘he diferent expres YD Neda, possesses an integrating factor see mag In the thermodynamic application of Carathéodory's principle, dQ represents an jnerement of heat gained by a thermodynamie system, each point P', P*, ete., repre sents a possible state of the system, and each suriace represents a manifold of states accessible one from another by adiabatic proeesses (those in which no heat is transferred). ‘The experimental fact that there exist, thermodynamie states inaccessible by adiabatic means from s given state thus implies the existence of an integrating factor for dQ. This leads to a definition of, entropy and to # compact statement of the second law, To conclude this section, we describe a method for ‘modifying a differential expression in order to change its independent variables. Such transformations are of considerable importance in chemical thermodynamics. Consider a differential aiizy) = Mews = Veewdy cr) and define a function =s-Xe (65) The differential of g is given by ly = of ~ Naz ~ 24 66) Substituting (64) for df we obtain fg = Nas + Yady ~ Nae ~ 6X ww The first and third terms eaneel to give ay = Yay — 2X «s) ‘The differential (68) is appropriate for a funetion g = g (y.X) dependent upon y and X as independent variables. Analogously one could define faty @) and obi ah = Naz — yt¥ oo showing that hk = hG@Y). It is also possible to carey ‘out « transformation in whieh both independent vari- ables are changed, for « ay has a total differential dy = dX — yl ro) showing that « = u(X,¥)._ The above are examples of Legendre transformations, in which one or more of the funetions X; in eqn. (62) replace the corresponding 2. Fora proof, see Manon Hand Muspay, G. ML 'Math- ematies of Physics and Chemistry," D. Van Nostrand & Co, Tne, Prineaton, N. J, 1943, sect. 218. Volume 43, Number 2, February 1966 /. 89as independent variables." The prescription for these transformations, as exemplified by (65), (69), and (72), is to define a new funetion g by subtracting from the original function f produets of the original and the new pendent variables. ie most important thermodynamic application of Legendre transformations is based upon Clausius's dif ferential relation, a = Ts ~ Pav @) which is actually a compact statement of the coi bined first and second laws of thermodynamics. ‘The internal energy E is evidently a natural function of 8 and V. Ifa natural funetion of 8 and P were required, ‘one would define the enthalpy H=E+ Dv cy for then aH = ab 4 Pav + vap ras + Vee On the other hand, transformation to a funetion of and V would be accomplished by defining the Helmholtz, funetion ~1s giving ag ~ Tas ~ sar = ‘The remaining choice of independent variables, 7 leads to the Gibbs function or free energy E+ PV -TS=H-TS= A+ PV sat Pay 77) and P, ) with total differential ag = —ser + vaP rc) ‘The four functions, B, H, A, and G are known eollec- tively as thermodynamic potentials. General condi- tions for chemical equilibrium ean be formulated in terms, of them, Line Integrals Finite quantities known as_ fine integrals (or curvilinear integrals) derive from differential expressions hy integration along curves in space, Before taking up The student familiar with analytical mechanics will recognize that the Lagrangian and the Hamiltonian functions are connected bya Legensie transformation. ‘The Lagrangian depends upon coordinates and velocities, and the Hamnftonian on coordinates snd momenta © integral J.P Made equ the shaded rea. 90 / Journal of Chemical Edveaton line integrals we shall review briefly the theory of ordinary (Riemnann) integration for functions of a single independent variable. Fhe defipite integral of ae tinuous funetion f(z) is defined by the limit: fiiteraees fin lip, Eteaee cy where Ate=2 tj ~ 24-1, 20 = a and 2, = b. The geo metrical interpretation of (80), of an integral as an area, is illustrated in Figure 2. Another fundamental property of the definite i tegral, connecting the differential and integral caleulus isgiven by flavts = Fb) ~ Fle) wy where ate) de «© ‘This follows easily when the definition of the derivative lin, = Pas) fa) ws is eubstituted into (80). We have then ~ Ferses)t = FU) = Fla) 1) which establishes (81). Alko, using (82) in (81). fierce which expresses the definite integral entirely in terms of, the boundary values of a function. An extension of the concept of integration to the ease of a funetion of more than one independent variable involves continuous summation of a differential ex- pression dg(z,y) along a specified curve. For the case of two independent variables, we define « line integral as follows (Fig. 3) Fb) — Fla) (sa) Tin fim gli _g 3 |Mewndase + ¥ sdsut (SO) where all the points 2, y, lie on a continuous curve C connecting 2’, y'(toys) with 2", y"(tny). Possibly the best known example of a line integral oceurs in me- chanies, where the work done on a particle is defined as Figue 2. The te Wlegrok defined in equotion (86).the line integral of force along 2 trajectory Me = fod = file + Pulp $ Fats} 82) A Line integral, like a Riemann integeal, depends on the sense (direction) of integration. From the defn tion (86) i¢ follows that It should however be noted that, in contrast to a Riemann integral, a line integral is not represented in any obvious way by an ares Tt is readily verified that ($6) reduces to a Riemann integral (80) when the path of integration is parallel to either coordinate axis. For example, along the linear path y = ye = eonstant, ($6) becomes see = [ Xiewode (69) (Gince dy = 0). In general, when the curve C repre- sents a functional relationship wade) con) y can be eliminated between (86) and (90) to yield a Riemann integral seen J Iatonen + rinten Bh en The limits on y are automatically fulfilled since y' = g(a’) and y" = g(z"}, Alternatively one could elim- inate z between (86) and (90) to obtain a Riemann integral over y. Three possible peths between the stotes Tay ond Tui of @ thermody Hye As an illustration, we integrate the differential ex- pression (53) along the three paths shown in Figure 4. ‘These line integrals aa fan nar on represent the work done on one mole of an ideal gas in reversible expansion or compression. Along path A, (G2) reduces to the sum of two Riemann integrals: aire = ff ap — nar RT ap _ part = ar, [# — Sunt jaan fre far = ariel — mtr 19) (09) Along path B we obtain analogously, Wg = Ten BE = eM = 7 on aluate SIV’, we climinate 7’ using the equation of path C (05) whence ) (96) and wy Thus _ RTP = TP), Ps Rah Comparing (98), (01), and (08) we se that Wa als # ale, ™ ‘Thus the Tine integral depends in general on the path of integration. If, on the other hand, we integrate the differential expression (52) ae [Oar ark cw along the same three paths, we find Hs sVp w are = BD r Wy a a¥ sw ae = = Ms coy [using T’ from the ideal gas law (2)]._ In fact, eqn. (100) evaluated along any path between T,,Peand TP gives the same result, ‘The independence of path stems from the fact that we are integrating an exact differential 2) {whereas (82) contains the inexact differential (55)} To prove the above statement, let din (86) be the toial differential ofa funetion Fy). Then using (48) we can write Flea = Xanwoas + Vewydawe (102) where A F(e,y) means Ferg) — Plemaues) Sub- stituting (102) in (86) we find rev ides tthe path, Note th corn want ns han Vac Rar Ue oy i nd i seat as etl as hoe egal independent of path, the differential must be exact. Fatal nfrtoe se ne tpl sow dosed paths, in which ease the initial and final points ty te hugh teste’ For ele, it integral sign is usually written ¥. The closed curve EAE ante laa ht cites 3D aresud ea'y') (108) Volume 43, Number 2, Fobrucry 1966 / 9%Figure 6, Representation of work ot rent Figure 5. Line etagral around cored patho defined in equations (105) fond (08 sense. If dg(z,y) is an exuet differential, then cf alos) = of 1Stenie + Yewyt = 0 coh for an arbitrary closed path C. This is easily proved, for dividing @ into two segments " and C connecting xy! with 2" y" (Fig. 8), we have due fr Pr a Both since both integrals on the right hand side are independent of path by eqn. (103), and sinee one is the negative of the other by eqn. ($8), wo obtain eqn. (104). When dg(z,y) is inexact, however, the cyclic integral is, in general, different irom zero. ‘A final connection between differential expressions and line integrals is provided by Green's theorem? of (Saws + Yoo) = SL IC,- des where the right hand side represonts a double Riemann integral over the area S$ enclosed by the curve C. If Euler's reciprocity condition (50) holds for dg(x,y), ‘then the right hand side of (208) vanishes and (104) follows. Conversely if the left hand side of (108) vanishes for arbitrary C, then the integrand of the right hand side must vanish and (50) follows. By Green’s theorem, certain eyelic line integrals ean be represented by ares. To illustrate, a differenti element of work done on a system in a reversible proc cess is given by aw = ~ Pav aa using eqn, (106) with P and Vas independent vari (noting that the coefficient of dP is 0), we find, for the work done in a cyclic reversible process fear ff arav aos, ‘The right hand side is clearly equal to the negative of the area S enclosed by the path C... Note that the non- vanishing of (108) shows d¥V to be an inexact differ- ential, “Actually, sinee the dP term is lacking in eqn (107), AWW can be represented by an area even for a non- ayelic process. ‘Thus we may write We For proot seo, for example, Kaptan, Wo “Advanced Co ulus,” Addison-Wesley Publishing Co, Inc, Resding, Mass, 1952, p. 230. stew =f" ear “pay ow: Srv where the path C determines P as a function of V. Since the right hand side is a Riemann integeal it ean be represented by an area (Fig. 6). To summarize several of the interrelationships dealt with in this section, for a Pfaff differential expression giz) = NGxyyis + Yawn elo any of the following statements implies the other ve: (1) There exists a function F(2,y) whose total derivative is dg(z.y) (dg is an exact differential); (2) @X/2y) (Y/dx), (Euler's reciprocity relation): and Bef do(2;y) = O for an arbitrary closed Many of the mathematical abstractions encountered in this paper have obvious analogs in thermody! terms. A point in the zy plane ean represent the state of, a thermodynamie system having two degrees of freedom. ‘The independent variables ean be chosen from among P, V, 7, E, S, ete. A function F(e.y) corresponds to another thermodynamic variable. It is called a fune= tion of state since it is uniquely the state of the system. An exact differential represents an inerement in a function of state whercas an inexact Aiffereatial represents an inerement in a thermodynamic quantity nol a function of state. A curve on the zy plane can represent an equilibrium proc sequence of states between some initial and final stares, A line integral represents the change in a thermo quantity is a function of state, the line dependent of path. ‘This is entirely reasonable the change in a function of state is simply the differ- cence between its initial and fal values. A line integral around a closed path represents a eyelie process, one which returns the system to its initial state, Clearly, such a process leaves a function of state unchanged ® The work done in traversing the path C’ from Py Voto Pils is equal to the negative of the ares under C”. aio = = f Pav ‘The work done in returming to the original state via path C™ is equal to the area under C™ ff. Pav fo ar Pa edn by Wee ‘The net work done in the eydie proves i gv We = aWer + alWer and is equal to the area enclosed by the cyclic path. ‘The last alana eat ah