The Calculus of Thermodynamics = 5 Inthis chapter we develop functional property relationships for simple systems, These. relationships are completely general and are a direct consequence of applying the postulates and laws of thermodynamics discussed in Chapters 2-4. They also reflect behavior consistent with the calculus of multivariable functions. ‘These functional propery relationships are fundamentally different than physical property models, such as PVTN equations of state, which represent practical constitutive ‘equations specific for each pure substance or mixture composition. In order to obtain working physical property equations, experiments are performed and data correlated or suitable estimation methods are utilized to predict property values (see Chapters 8 and 13), Altematively, molecular models using statistical thermodynamics may be used, albeit with some approximations (see Chapter 10) ‘A major objective of this chapter is to introduce techniques for recasting derived properties and their derivatives into forms that can be directly evaluated in terms of primitive properties which are measurable. Our starting point is to introduce a fundamental operating equation for simple systems that establishes the functional dependence of internal energy U on the variables entropy $, volume V, and moles (or masses) of all components present Nj,.., Ny, This Fundamental Equation has its origin from the combined first and second laws for open simple systems that was derived in Section 4.7. The 5, ¥; Nis Ny Coordinates of that equation were used extensively by J.W. Gibbs in his classic work on thermodynamics inthe late 1800's, and asa result they ‘are commonly referred to as Gibbs coordinates, They represent a set of n +2 natural or canonical variables that provide the necessary and sufficient information required to describe the thermodynamic state of a simple system. By employing methods from calculus and geometry, Gibbs was able to sbow, in a completely rigorous mathematical manner, how various thermodynamic properties were related, He clearly laid the groundwork for understanding the functional inter- relationships that exist among the so-called potential functions, U, HA, and G, Without the computational power and graphical display methods that we have today, Gibbs had to conceptualize the structure ofthese property inter-relationships in his mind without ‘being able to illustrate them graphically. He used only narratives with equations in his ‘writings to describe his findings. In part, tis restriction has limited how fast we have been able to understand the details of Gibbs’ work. Ithas taken over a century of study to fully appreciate the significance of his contributions. Interested readers should consult Section 5.1 The Fundamental Equation in Gbibs Coordinates 125 the papers by K. Jolls and his co-workers listed at the end of the chapter for a ‘comprehensive discussion of Gibbs’ contributions inthis area. Inthe sections that follow, we will employ graphical methods to illustrate some of the geometric aspects of the Fundamental Equation and its transformations. In addition, several methods of manipulating functions and partial derivatives will be described and applied to problems frequently encountered in classical thermodynamics. 5.1 The Fundamental Equation in Gibbs Coordinates ‘As will be seen presently, the relationship U= FS, VN My) G1) completely describes all of the stable equilibrium states of a simple system containing n components. By solving Eq, (5-1) explicitly for S, an altemative form is obtained: f5(Us Ys Novos Ny) 5-2) Either relationship is called the Fundamental Equation: Eq. (5-1) is termed the energy representation and Ea, (5-2) the entropy representation, ‘The Fundamental Equation is represented by a (hyper) surface in (n + 3) dimensional space, The points on this surface represent stable equilibrium states of the simple system. Quasi-static processes can be represented by a curve on this surface. Processes that are rot quasi-static are not identified with points on this surface. (Recall that derived properties such as U and $ are not defined for non-equilibrium states.) ‘The n + 2 first-order partial derivatives of the Fundamental Equation correspond to traces in the respective coordinate walls of planes tangent t0 the thermodynamic surface'. The significance of these tangent plane traces can be seen by expressing the Fundamental Equation in differential form. For the energy representation, Eq. (5-1), “(a w-(28| where subscript Afi] indicates that all N; except j=i are held constant in the differentiation, If we compare Eq. (5-3) to the combined law for a simple system (see Section 4.7), namely HL 2G 6% win 6-4) itis clear that 1 The ter plane is used inthe generic sense her. Even fora pure Mui there ate tree independent vanabies ‘and three patil denvatives. Thus the tangent plane is really 2 Uhee-dimensional hyperplane128 The Calculus of Thermodynamics Chapter § = T= BAS MN MD co) ale = = 8S Va Nps Np) 6-6) <= eS u and is ( ) hema where the functions gs gp, and g, could be obtained directly ftom the Fundamental Equation ifit were available, Equations (5-5) through (5-7) representa particular set of ‘equations of sate expressed in Gibbs S VN coordinates. As shown late in Sections 5.2 and 53, only two of these three equations of state for a pure substance are independent "The second-order partial derivatives of the Fundamental Equation are also related to quantities that can be measured experimentally. For example, fora pure material, there are four second-order partial derivatives at constant mass or moles: ‘au Le 9) = BIS YN yo Ny) on (5-10) (11) Of these four derivatives, only three are independent because the last two are related by the reciprocity theorem of Maxwell (See Section 5.3, part 4). For an n-component mixture there are n+ | first-order and (n +2)(n + J)/2 second order independent partial derivatives of the Fundamental Equation given by Bq. (5-1) for Eq, (5-2). These derivatives are particularly important because they form a basis for all other partial derivatives involving thermodynamic properties. That is, any partial derivative can be expressed in terms of an independent set of first-order and second-order derivatives of any forra of the Fundamental Equation. Proof of this statement for a pure ‘material is given in Section 5.3. ‘Ac this point, interesting to consider what the shape ofthe intemal energy surface ‘would fook like in $ VN coordinates. Since even fora pure material this would entail a Seaton 5.4 The Fundamental Equation in Gibbs Coordinates 27 four-diraensional plot, one is forced to reduce the dimensionality ofthe eystem in order to visualize the surface in three dimensions. For a pure system, one can propose a 3-D plot of intensive U as a function of $ and V. In fact, James Clerk Maxwell in the (ate 1800's was so intrigued with Gibbs’ work that he actually made a 3-D mode! ofthe USV surface for water. He senta plaster replica of bi model to Gibbs at Yale, where itremains on display today. Figure 5.13 is photograph of a more recent 3-D USV surface for water constructed by Clark and Katz (1939) while Figure 5. Ibis a2-D projection ofthe surface showing several important features. Note for example, the point of triple tangeney that corresponds to the three-phase, solid-liquid-gas, triple point equilibrium for water. We will have much more to say about such geomnetrical aspects and their relationship to the characterization and limits of stable equilibrium states in Section 5.7. With more accurate thermodynamic data available and computational tools for covrelating and ‘manipulating these data itis possible to generate USV surfaces as computer-generated, 3-D plots for a wide range of pure materia. Jalls (1990), Coy (1993) and coworkers (1981, 1992) at Iowa State have done just this for a number of pure compounds using a well-tested PVIN equation of state developed by Peng and Robinson (see Section 8.4) and a temperature-dependent correlation for the heat capacity in an ideal gas state. The actual methods for generating values of U for specified values of S and V are straightforward and described in detail in Sections 8.1 and 8:2 {see also Coy (1993)]. Figure 5.2 shows two fundamental USV surfaces—one for an ideal gas and the other generated by Jolls and co-workers for ethylene using the Peng-Robinson equation of state as # made It is important to keep ‘n mind thatthe values of S, Vand U are not absolute, they depend on the specification of reference state conditions, S” and U°. Example 5.1 actually derives the governing equation for U for a monatomic ideal gas that is plotted in Figure 5.2a. The USV surface is convex with respect to variations in S as the second derivative is always positive for the exponential dependence of U on $ shown in Figure 5.2a. Later we will invoke even stronger arguments that this convexity rust be true in general. Although the actual functional dependence of U on V will vary from substance to substance, the general power Iaw decrease depicted in Figure 5.2a will be followed for all fuids in the dilute gas region where nearly ideal behavior is expected, ‘The important thing fo remember is that the graphical representation of the USV surface encodes all the thermodyitamic information about a pure substance as itis equivalent to the Fundamental Equation itself. The geometry of the surface represents all single phase stable equilibrium states, all two-phase coexistence points, and all triple points; it lso can be used to identify limits of stability such as critical and spinodal points (see Chapter 7). A major difficulty, of course, is that a significant arsount of physical property information is required to construct the Gibbs USV surface fora pure substance, eg, the steam tables for water, or a robust PVT equation of state that models the behavior of a compound adequately in afl states of aggregation.18 The Calculus of Thermodynamics Chapter 5 face for pare wate from Figure la Three-dimensional model ofthe USV surface for ps CChrk and Katz (1938), with permission ofthe Royal Society of Canada. HE Metastable region 5 Unstable region [ES subleregion Figure S.1b A two-dimensional projection of the USV surface for pure water shown in Figure 5.18 Section 5.1 The Fundamental Equation in Gibbs Coordinates. 129 Figure 52 The USV surface from the Fuodarvental Equation for pure monatomic ideal gas referenced to US, and V* (see Example 5.) Figure S.2b A predicted USV surface for the fluid phases of pure ethylene. ‘Voluenetric PVT properties from the Peng-Robinson equation of state and beat capacities from a fied ideal gas stale equation. (V,,4,= 15 V,) [adapted from Jolls and Coy (1992)]. It should be clear that Fundamental Equations would be of great use if they were ‘generally available, The problem is that the complete form of the Fundamental Equation is not specified by classical thermodynamics; each substance has its own peculiarities130 ‘The Caleulus of Thermodynamics Chapter § hat are elected in ferent neonates ofthe Fundamental Equation Thos, there a le Fundamental Equation goveming te ropes ofall materi Ta eta css themmodyrames les some rescns onthe form of the Patten Egon Lat ve examine the diferente frm ofthe Fundamental ‘Equation in the energy representation, Eq. (5-3). Since U must be first order in mass or ae tan cat apy Euler's ote ce Appendix © tain he inepated form of Bq, (5-3). In dffereatial form, dU is given by w-{), as {| a3 a, G2) AS Ie As ON nea or as we demonstrated earlier ay= as Pav +S wan, 19 a which can be directly integrated using Euler's theorem recognizing, of course, that T, , and ji are intensive properties and kept constant. The result is U=TS-PV+ Dun, (5-14) ‘Equation (5-12) is a linear partial differential equation of the first order. Therefore, the solution must be of the form vat 5 | G15) Basle 2 where x9, 24.» €an be S, Vs Noe Ny OF any permutation of these variables. For a one-component system, itis often convenient o choose x= N, ind 2 = V; we then obtain 6-16) or, since U= NU, U=a5,)) 6-17) ‘The only other requirements our prior developments placed on the form of the Fondamental Equation are that UU should be a single-valued function of S, V, and N (see Postulate I), and that, (3fy/AS)yv=T should be nonnegative. 5.2 Intensive and Extensive Properties ‘Atthis point, let us digress to a special case of Postulate J. In Eg. (5-17), we see that for a one-component system, only two properties, $ and V, are required to obtain the specific energy of a system. This is in no way a violation of Postulate I; by delineating. Section 5.2 Intensive and Extensive Properties 131 the specific properties (expressed in terms of unit mass or mole number), we have determined the intensity” of the system but not the “‘extent’” of the systern. To specify the system completely c.g. so that it can be reproduced by others), we must specify the mass of the system in addition to $ and V. ‘The variables that express intensity ofthe system are zero orderin mass and are called intensive variables. Variables that relate to extent ofthe system are first order in mass and are called extensive variables. ‘We now prove that fora single-phase system of n components, any intensive property can be defined by the values of m + 1 other intensive properties.” Let us call B.C1s Cope pe intensive properties of a single-phase simple system containing n components. In general, we can express b as a function of n + 2 other properties ‘according to Postulate I. Let us choose these n + 2.88 yy Cys Gq and the total moles (or mass) N. Thus, = (2 eof) + (2 a2] mene] te eQ] ow om jin th a Integrating Eq, (5-18) by using Euler's theorem (see Appendix C), we have » (3) Ne 19) ‘Since Ncan be nonzero, (9b/@N),,.. <_, mustbe zero. Therefore, Eq. (5-18) reduces toa function of n + 1 intensive variables. OF course, these n + 1 intensive variables must be independent, so that we clearly cannot use al ofthe n mole fractions x}... 2. We could, however, use n 1 mole fractions in addition to two other intensive variables to ‘obtain the required n + 1. [Note that this result is valid beeause we limited the original set of n + 2 variables to include only one extensive variable; if we had included two extensive variables in the original n + 2 set, no partial derivative would have tobe 2er0, Thus, we could state as a corollary to Postulate I: Forasingle-phase simple system, the change of any intensive variable can be exprested ‘asa function of any n + other independent intensive variables. We shall use this corollary frequently in Chapter 9 in dealing withthe properties of mixtures. AL this point, a word of caution is in order when dealing with intensive and ‘extensive variables in partial derivatives. For example, if fora pure material we express Uas a fnction of Sand V, then using Eqs. (5-18) and (5-19), we find (@U/AN)s, y= 0. But (QU/@N)¢ vis not zero; from Bq. (5-7) applied to a pure material, 2 The proof i reset toa single phase system to allow us to choose any n + 2 variables as an independent se. The prof canbe extended to speifc cases of composite simple systems provided thatthe n+ 2 variables chosen form an independently variable se192 The Calculus of Thermodynamics Chapter § &] . 6-20) aL ‘Since U= NU, we also have al Gi, ven) =n 6.21) Since U is not equal to 1, (@U/2N)sy is not equal to zet0. Thus, each of the three derivatives, (BU/2N)s y, (QU/2N)sy, and (QU/2N)g.y bave different connotations. The first represents the change in the specific energy as we add more material while maintaining Constant specific entropy and specific volume. Since we are holding two intensive variables constant during the process, all other intensive variables (eg. 7, P, ‘atc forthe pure material must remain unchanged, The only way to conduct the process is to enlarge the system in direct proportion to the added mass. The second and third ceases, however, represent changes in the (otal and specific energy during a process in ‘which we maintain constant total entropy and total voluree. Since we are adding mass to the system, the only way to keep total entopy and total volume constants to change the specific entropy and specific volume (e.g., by varying T and P during the addition ‘of mass). Thus, the specific energy changes as the state of the system is varied. Tbe total energy changes because both the specific energy and mass vary Example 51 In the entropy representation, the Fundamental Equation for a monatomic ideal gas (uch as He, Ne, Kr, or Ar at low pressure) is soa|sene (2) z| 6.2) where S°, 0°, and ¥” are constanis representing values ina reference or base state, From she energy representation in the form of Ea (5-1), determine te three equations of state in te form of Eqs. (5-5) through (5-7) Solution Solving Eq, (5-22) explicitly for U yields 5-23) and, thus, (5-24) ‘Seaton 5.3 Methods for Transfonning Derivatives 1m Using Bq. (5-24), U= U/N was plotted in Figure 5.2a as a function of $ and V, The ‘equations of state can be found direcy by partial differentiation of Bq (5-23) or (5-24); ele essvE 625 aus woe a ~Girl, (i) Popes HP GESVR) (5.26) iL abet?) ee, AG oof 26-38 } 2 ‘The results given in Eqs. (5-25) through (5-27) may be simplified if Bq (5-22) is used to evaluate the exponential terms Wf this is done, then (5-28) Infect, the assumptions behind the development of Eq. (S-22) are thee U = RT and Pv: 5.3 Mathods for Transforming Derivatives Often one is faced with the problem of evaluating the magnitude ofa particular partial derivative or integral involving non-measurable, derived thermodynamic properties. For example, suppose we needed a specific value for the entropy change AS of a pure fluid between two well-defined states (7), Py) and (7, P;). The calculus of continuous functions in two variables works to specify the intensive state for a pure component system with n+ 1 = 2 degrees of freedom. Thus, (= ool ar (5-28) oP or “The second integral involves (@5/27)p which equals C,/T. Presumably, values of Cy may be tabulated for the substance of interest at particular emperatures and pressures. ‘But what about the first integral that requires evaluation of (35/8P)z which is not readily available? We need some convenient way to express this partial derivative io terms of measured of tabulated properties ‘Again, by adhering to the calculus of continuous functions, we have several tls for ‘manipulating these derivatives. Some of the more important ones for applications in thermodynamics ae listed below. For a general function F(x, )) of two variables:138 The Cats of Themodynamies Chape 5 1, Derivative inversion (ar) 1 : Sl om, 5-30) For example, as, 1 = l-ats; a0 ee OL! eee: 4. Chain re expansion to add another independent variable © ar) _@F/®), (ap) (30) oa (sae (1) Foresample st =7 (3s) _@S@D» _ G/T (i) Han, CT (5-32) For example, (5-33) 6-35) 4. Maxwell reciprocity relationship ‘Maxwell's reciprocity theorem states thatthe value of 2nd or higher order derivatives i independent of the order of the differentiation fora smootlly varying, continuous function FG,» (a@rer,) _(20F/ay), 6:36) { ay co representing these 2nd order derivatives in abbreviated for Fy Fy, 631) “The relationships cited above in (1) ~ @) can easily be extended to larger functionalities, for example where n +2 variables exist such as in the Fundamental Equation ‘Our original problem of evaluating the integral containing (@S/8P)r can be made tractable using a Maxwell relation in the appropriate thermodynamic variables, Later in this chapter we will establish methods to select the appropriate variables for these transformations, but for now, let's employ the Gibbs free energy Function, G. Fora pure system, G is wtten in intensive form as a function of Tand P, G=fT,P). and dG=~SaT + VaP 6-38) Seaton $3 Methods for Transloming Derivatives 195 where 6) a) “s (#) ona v=(38) hs, G/N») _(8(@G/AP), Sins PS =| =e a0) fs * s0 we can use PVT properties ora fitted PVT equation of state to determine (2S/@P), and then evaluate the integral directly. Earlier in Section 5.1, we stated thatthe 2nd derivatives of U with respect to $ and V [see Eqs. (5-10) and (5-11)] were related by Maxwell's reciprocity theorem, Now we ean show that these 2nd derivatives re indeed equal to one another Sav § (5-41) ‘where we have used the abbreviations introduced earlier forthe 2nd derivative. By taking. the reciprocal of Eq. (5-40), we immediately see that, (5-42) recognizing, of course, that we have retumed to an extensive form for U. In addition to the derivative manipulations characterized above, itis also useful to illustrate some of the different properties of intensive and extensive variables. A partial derivative may involve intensive and extensive variables, For a pure material, only n+ 1 =2 intensive variables are independent; hence, a partial derivative involving only intensive variables b,c, and d can be expressed as (26/8c)4, where itis implied that NV is constant. Thats, (2) (20 lec alee (6-43) ‘We now show that for a pore material, any partial derivative involving extensive variables can always be reduced to expressions involving paral derivatives of entirely intensive variables. [Now consider the derivative (98/8), , where one ofthe four variables is extensive. 1G). Treisextensive, then ° (5-44)138 ‘The Calculus of Thermodynamics Chapter S “The proof follows from applying Euler's theorem to b=/1Gs 42 (ab a 1G) Heb isextensiv, then aby ae |, (e708), ($45) ai). If d (or @) is extensive, then e-e os ah, 2 Since dP), Ad/ANy, LON/O,e 2 Cd/Ab),,¢ Qd/AN), (ON/Ab),,- wt then a) __ ON. (ab) _ (2 (&, --avanet a by [a “Ths, if only one variables extensive, the partial derivative is finite and nonzero only iffd ore is extensive. The extensive variable may be deleted to yield a partial involving iy neni wales i ice essin which two ofthe four vibes extensive 2), Ifband eae extensive, then | = (5-47) wich follows direc by applying Buler's theorem to b=f(E; ds ¢: ab 2c and ben c=Ne bof) cant bent Gi) IF and d (ore) are extensive, then (5-48) Since, expanding b Section 6.4 Jacobian Transformations 137 Ob fan (5-49) o@ eR), oo By (546) may be we to rode (BA), The ls term i rece as ellows fat) =n0e00n, NOU, he CHAM. « 2Gii). If d aod ¢ are extensive, then (2) (5-5) a ( “The numerator and denominator cn cach be reduced by applying the resuls of cate 2. ‘Any partial derivative involving three extensive variables can now be reduced to partials involving two extensive variables by using Ea. (5-49) followed by one or more ofthe steps illustrated above. Similarly, partials invalving four extensive variables can be reduced to three, ete, The net result that any partial derivative for a pure material can be expressed in terms of partials involving only three intensive variables 5.4 Jacobian Transformations ‘A seful technique for manipulating thermodynamic propetics and their derivatives involvesa transformation using Jacobians or functional detertinans.Forthe derivatives of functions of 2 variables. f(t) and x,y), the Jacobian is defined as: ee reel ee) Os ay)" |(22) (2e" ar} [ay y 4 Certain properties of Jacobians make them particularly useful for transforming derivatives of thermodynamic variables. These include: 1. Transposition Sh. Hed (5-52) Ax, y) ~~ x, y) 2. Inversion Oe) 1 (5-53) 3x») “aD 659) ag) 3. Chain rule expansion Aha). Aha) Hew) 5 Gx, ») ~ B(e, w) O06»)138 The Caleuus of Thommodynamics Chapter where z and w are two additional variables, Another important propery is the Simpliation tat occurs to Eq (551) i we are ony interested in evaluating the fist partial derivative of a function fiz, g) with respect to z at constant g: (ar) - 2d (55) & Aza) ‘By applying the chain rule expansion and inversion property (Eqs. (5-54) and (5-53)], Bq, (688) becomes otha) (af) _ Xe. y) (5-57) ach IG) a(x, ») ‘The properties of two-variable Jacobians are easily extended to functions in m variables x41, i fit, Zpnen y)- The Jacobian is Mefonte (5-58) Beep kant) rin determinant form RH HI a ay “ (5-59) te ey dy dy bk where each partial derivative holds all x; constant except the one involved in the differentiation, Let's consider a few examples to illustrate how Jacobians are used in thermodynamics, Example 52 Consider the isenhalpie oule-Thompeon) expansion ofa Nuid across well-insulated valve. Here, the derivative {= ‘= Joutie~Thompson coefficient =a, ap |, ms =Oy is of interest, Express ay in terms of measurable properties, Solution For a pure fluid, the specific enthalpy, H'=/(T, P),s0 we ean use Bq, (5-57) with f= 7, = H,and z= P. Thus, Section 5.4 Jacobian Transformations 138 OT, A) ar) _ ae (@)-38 oo x, y) ‘Now we need toselectxandy. Although we have many choices, fequendy, asin this case, ‘we want to obtain expression in tenns of measurable properties like 7, PV, le. A good frst guess for x and y would bo to se Tand P since they ar in the derivative of interes. ‘Thus, (TH) & = DP) 6-6 oP oP, H) XT, P) Using the transposition property (EQ, (5-52) and Eq, (5-55), Eq, (5.61) is quickly simplified o an) (an sen Ge) ) f) 2, P H a (5-62) ‘3H. P) oe ‘aT, Py Tn this instance, We could have used the triple product directly (Ba, (5-38) to obtain Eq. (6-62). However, such direct unasformation ie not always posible. For example, in Section 59 we will emonsieatehow Jacobien transformations are of considerable us in ‘manipulating complex parial derivatives of multivariable functions. Before we ty to evaluate (H/0P)rin Eq (5-62) n terms of measurable properties, let's consider another example. Buample 5; “The isentropic (reversible, adiabatic) expansion ofa pure Mud involves the derivative: @T/AP),= isentropic coefficient = os [Express the isentropic coefficient in terms of measurable properties, Solution ‘The a, derivative can algo be reconstructed using Jscobiens @- (=, aP L” OP.) ~ “fas oe) OT, P) lar0 ‘The Calculus of Thermodynamics. Chapter § In order to express ols (or &y) i terms of measurable properties we must convert (@S/APy, [or (OH/AP}_] to another form. To start with, consider the closed system ‘combined Law equation which is equivalent to the intensive form of the Fundamental Equation in differential form aU = Tas ~ Pav (5-64) By rearranging, and differentiating with respect to P at constant , we get as) _1(au) , P/av (| iG: irl ee ‘Again, we end up with a cumbersnine derivative (3U/@P}p. Some readers may recognize that we need (o introduce an auxiliary potential function that has as its nanural variables P and T. Ths is the Gibbs fre energy G = f(T, P) which is defined as G=U+PV-TS So by chain rule expansion ofthe differentials: dG= dU + Pav + vaP - (TaS + Sd1) (5-66) “Thus, by substituting the expression for dU given in Eq, (5-64), 4G becomes dG=~ Sar + VAP 5-67) ‘And, by usiog Maxwell's reeiprociy theorem, we obtain ‘as av ele oe Now we can revise Bq. (5-63) fora to or - Let's see if we can use this result to help us evaluate the derivative (QH/@Pyp in the cy expression (Eq. (5-62)]. Here we begin with tho definition of H= Li» PY, differentiate, ‘and use the closed system combined law as we did before to obtain d= Tas + VaP (5-70) ‘Thus, by dierentiating with respoct to P at constant T. we get 6-69) 6-7) Because we already have an expression for (Q5/9P)7 in terms of measurable PVT properties (Bq, (5-68), we ean express the Joule Thompson coeicient oy as TAVANy + ¥ a,=(2 t wane 2) 0 [ap G where only PVT properties and Cp values are needed to evaluate cy. Section §§ Reconstruction af the Fundamental Equation on Most vapor compression reftigeration systems in domestic use employ Joule-Thompson expansions to cool the circulating refrigerant. Thus, in these practical situations, dy must be > 0 to obtain cooling as the pressure is lowered across the valve. ‘What happens if the fluid being expanded is an ideal gas? In this case, oy = 0; thus, fluids whose PVT properties closely approximate ideal gas behavior would not be good choices for reftigerants when Joule-Thompson expansions are used. An altemative isto use an adiabatic turbine to expand the fluidto# lower pressure. Here, csis the appropriate scaling parameter as it provides the maxinaum cooling effect forthe limiting case of a reversible, adiabatic or isentropic expansion. Now, even an ideal gas will cool upon expansion 5.5 Reconstruction of the Fundamental Equation ‘The Gibbs Fundamental Equation where U=f(S,V,Njvu»Nq) provides the necessary and sufficient information needed to describe all the stable equilibrium states of any simple system, Unfortunately, § VN coordinates are nat completely arnenable to direct measurement-—for example, no direct-teading entropy meters exist! Thu a formal transformation is required that preserves the encoded information content of the Fandamentaf Equation while expressing the functional dependence in variables other than S, V, and N, (éI,....n)- Once we have this procedure, we can be sure that all other information of interest to us in classical thermodynamics can be obtained from the transforroed equation. The Legendre transformation provides a rigorous mathematical route to achieve the desired reconstruction ofthe Fundamental Equation. ‘As shown in Section 5.1, if the Fundamental Equation were known, the properties 7, and Ui, could be determined by partial differentiation as expressed in the equations of state in Eqs. (5-5) through (5-7). Alternatively, the Fundamental Equation can be recovered, if all the equations of state are known, by substituting these equations into Eq, (5-13) or the common integrated form (Eq, (5-14)] TS-P¥+ DUN, 6-73) a ‘As shown in Section 5.2, the n + 2 intensive variables, 7, P, and Hy (iL), which ase expressed explicitly by the equations of stat, are not all independently variable, Any fone of these variables can be expressed in differential form in terms ofthe other n+ 1 variables and, upon integration, an expression coriecting the n + 2 variables can be determined to within an arbitrary constant. It thus follows that only n + 1 equations of state are necessary to determine the Fandamental Equation to withinan arbitrary constant (equivalent to specifying one or more reference state conditions). In Example 5.1, if Bq, (5-28) is combined with Eq. (5-22) to eliminate S, 1 can be expressed in terms of reference state constants U°, V’ and $°; and variables T, V. ‘As an example, let us considera pire material. The intensive Gibbs free energy oF ‘chemical potential, G = u, can be expressed as a function of T and P:142 The Calelus of Temodynamics Chapter S ar In Section 5.4 [see Eq. (5-61) it was shown that (4/87) Eqs. (5-5) and (5-6) were known, we could solve these simpltaneously to obtain S=a,P) 75) a-@)aBle sm and vas?) (5-16) “These equations are usually available, although not necessarily in analytical form, but she entropy is known only to within an arbitrary constant. Let us assume that we have available Bag. (5-76) ané (5-77). Sasser?) om here isan arbitrary constant or reference state condition Substitution into Bq. (5-78) wad ‘integration from an arbitrary reference state for which T=7°, P . Vv’, and B=! leads to pep eso--Leanarel einer 678) which isthe desired lationship for yas a fnction of Tand P. Although this equation contains two arbitrary constants (5° and u°), when Eqs, 5-5), (5-6) and (5-78) are Substituted into Eq, (5-73) in order to obtain the Fundamental Equation, these two trbirary constants appear asa sum; in particular, we would find U= ff, + (PS - PV +4") (5-79) War's - PV +! (5-80) ‘Of the three arbitrary constants in Eq, (5-80)(i.,U", ©, and pits clear that only ‘wo canbe chosen independently. Thus, wecan set base values of U and Satthe reference State for which T=, P= PP, V= V?, buthaving dane so, the base value fortis uniquely specified by Eq. (580). 5.6 Legendre Transformations Th the energy representation ofthe Fundamental Equation, Ba (Sth properties Peer wented a ndependevaabes, This is ot always an appropiate See sant parameters, For example, since temperature canbe eased mich moreconnicy fan ensop, weit tose 7, Nw Nya te independent ann aaverr ange phase simple sstem, we can always xpress a property uct a as eee hae popes such a6 7. Nyro TRUS, 8e EnOw tha & Fnedon feiss such hat UPD Nyon yd 81) Secon $6 Legendre Transformations 10 and a = (a au # ary & asd, (& a, (5-4) be SM ban Given the Fundamental Equation, te function of Eq, (5-1) ean be found by Ssferentating Eq (5-1) to obain Ba. 5-5), T= aS VN yoo N) and then solving Eqs. (5-1) and (5-5) simultaneously in order to eliminate $, The result isan equation of the form, UaATY.N »-4(%) “YAN "] oe by Although Bq. (5-83) i ofthe form desired (ic., Eq (S-81)), the information content of Bq, (5-83) is less than that of the Fundamental Equation. Equation (5-83) isa partial f and thus one may generalize the result as ai as) 9 oy mB G0) The partial derivatives in Eg (5-96) were expressed without indicating the set of variables to beheld constant. However, itis clear from the discussion above thatthe degree of the transform determines the set, and the oly exception would be that variable sed inthe actaldifereniation, For example, the retaints on the ter 23!" oy, ‘would be that Ey,..-5 4, pt» yp Would be held constant. To illustrate the application of these relations, let y® be the total internal energy of a simple system U: then the Funsaronal Baton would be given n Eq, (5-1). Suppose that we desired the transform y”. Using the ordering of variables given in Eq, (5-1), we can onganiae te transformation sig the table below yeu Prag a 1 os |r 2 ov | a mom | oy with this ordering of variables: =f En ba Me 97) with (5-98) 5-99)48 The Calls of Thermodynamics Chapter S ‘Then, with Eq. (5-91), = U-TS-(- PYRG 100) ‘where G is the total Gibbs energy. The analogs of Eqs. (5-92) and (5-93) are Eqs. (5-4) and (5101). dy = dG=—SaT+VdP+ Yu, aN, (s-101) a where the chemical potential jean be defined in several ways as m= sim (hoe. or equivalently as w-(an (5-108) PAIN ool JooN, The significance of the Legendre transform is thus evident. The important thermodynamic property G is simply a partial Legendre transform ofthe energy U from (VMN) space 10 (T.P.Nye Ny) space. Equation (5-101) is also. a Fundamental Equation and no loss in information content has resulted in going from the Ut the G representation ‘We could have started our transformation in reverse. Referring othe table of x, and & given above, we could have defined a new basis function as G=)=y" and transformed back to U = y" = y, that is to the old basis function. Again, there would be no loss of information content. ‘The total Legendre transforn of Bq, (S-1)'s y= U-TS+PY- SKN, =0 [by Ba. (5-73) (5-104) “Ths, Bq. (5-83) becomes an = aT + VaP— YN, dy, 6-105) Equation (5-105) is known as the Gibbs-Duhem equation, Later in Chapter 9 on mixtures and in those chapters thet follow, we wil utilize the Gibbs-Duhem relationship extensively. Ttisimportantto point out certain generates in the nse of Legends transformations, We introduced a general functional equation (Eq, (5-87)} with arbitrary ordering of “jus Zqe We noted that for each there was a conjugate coordinate variable, &; (Eq (5-88), We then illustrated that one could readily derive a functional relation with the same information content wherein we replaced independent variables xyw.n.% DY ‘Section 5.7 Graphicel Representations of Thamedymamic Funeons and Ther Tensions 149 Etsnu Eq This was the lab Legendre transform defined in Eq. (5-91) and shown in Gifferential form in Eq, (5-93). ‘As we demonstrated in the example above, one may als redefine this kth Legendre transform as a new y" basis function if care is taken in defining the cormect independent variable and conjugate coordinates. For example, we have shown that beginning with En, (51), we obtained the Gibbs energy potential function by a Legendte transform of Uitho 7, P, Nyy. Ny Space. We could now use the Gibbs energy function as our basis function y®, but the independent variable set (x4... %_) Would be (P, P, Ny... N,) with arbitrary ordering, The conjugate coordinate variables E,,..., Eq would still be defined by Eq. (5-88); for example, for the variable 7, E; =(OG/E7)py =—S: for P, Ep = V, and or 4, &)= Hy. In fact, we may select any Legendre transform as the y basis function by redefining the independent variable sex, Examples illustrating the use of Legendre transform for raanipulating paral derivatives ae found atthe end of Section 5.8, Tf we had started the mathematical transform development with the entropy form of| the Fundamental Equation $=/(U,V,Njyuy Ne We would have produced an equivalent set of tansforms that are called Massieu-Planck functions, which are sometimes easier to use than Legendre transformations, e.g. when working in 7 coordinates (see Debenedetti (1986)]. Additional treatments of Legendre transform- ations are given by Callen (1985), Alberty (1994), Aris and Amundson (1973), and Tisza (1966). 5.7 Graphical Representations of Thermodynamic Functions and Their Transforms ‘Beginning with the Fundamental Equation for U (Eq. (5-!)], we can now transform ‘one ofall ofthe independent variable setS, V. Ny... Ny-Letus choose only the variable Vand reorder so that ¥ cepresents xy. Then yay 8x, = U- (CPV =U + PV =H (5-106) “where this particular Legendre transform is called the enthalpy. We note that H=S(PS.MyoN) (5-107) ‘We cal! Eg, (5:107) a Fundameatal Equation in the same way that we refer to Eq (5-1); then P is x, $ is x, ete, and E = (GH/2P) = V. We can recover Eq. (5-1) by caying outa Legendre wansform assutaing that Eq, (5-107) is the y® function; that is, =9 by =H WP. (5-108) “This transform can be readily shown in Figure 5.5 for « common pressure-enthalpy diagram, Ifa curve of constant entropy is considered, the slope is V. The intercept of this tangent of the enthalpy axis is, s shown, equal to the internal energy U.¥ — 180 Te Cas of Temodynanes Chapers | Ssoion 7 Guphicl Represents of Themodyrai Funclonsané Ther Tenses 151 Table §.2 Thermodynamic Potential Functions and the Gibbs-Dubem Relation for Simple Systems Canonical Type Functional Equation” ‘Symbol, Funetion' — Coordinates" Eee ee ‘mero Baergy — U=7§- PUSH y PP SYM Mitoum) Enthalpy “me PSN Gloom) Pema 2 EM Oibbe Fise PP TPN tou) Gibbs-Dubern e 1a > ep pnd ee PP TP (tem) igure 55 With intemal energy as the basis function, there are n + 2 permutations of first ‘Tye ‘Total Differential Legendre transforms: the two common potential functions, H(P. S,Mjv.N,) and ———__—____ ‘A(T, V, NjyuNq)» abd nother functions for the independent variable set of * SY, Nyon Ney By Nits Nr: Since the ordering of components is arbitrary, we shal] Aeterna Bessy Pas Dual, to the n functions as U'(S, V.yty, Nj N,). In a similar manner, there are a (n+2)(n + D2 second Legendre transforms: one is another potential function, the Ena e Gibbs free energy G(T, P, Nj... N,) there are n of the form A(T, Ly, V, Np,.., N,) and ey hm TAS + Va +S wean, n of the form H’'(P.Hy,S,Nou.No, and (an — W/2 of the form Hetmbok ” Uy Hy SV Ng Ny). Third Legendre transforms would involve G’, A”, #”, and —e ae-ser~pav ‘U"" potential functions. Tabie 5.2 lists the important potential functions used in chemical An nSat~ Pay +S yan, thermodynamics. ‘Again itis instructive to ce-examine tbe plots of the Fundamental Equation to show Ghia Fes dGu-sarsvars> how various Legendre Transforms are geometrically related to the USV surface. eee ‘Gaga war + Swan, Fundamental equations are plotted in Figures 5.1 and 5.2 for pure water and ethylene, Maltiple phase equilibrium conditions, such as the triple point of pure water and the bette i"? =-$ars vp particular substance. At first glance, one might expect that the thermodynamic potential rd that involves the natural variables of temperature T and pressure P would yield useful 1 (= ass anton selationsbips. This function is, ofcourse, the Gibbs free energy G which is the second 3 =Firt Legendre aston, y= Second Legendre ransorn, ‘Legendre transform of U and can be visualized geometrically as the intersection point Obiained by Euler integration ‘of a tangent plane tothe U $ V surface withthe U axis. 5 Ream cna ts theo nara vt tt eres enon152 The Caluls of Themmodynamics. Chapter § For a pure component system, the intensive form of the Fundamental Equation can be used as we did with Figures 5.1 and $2 where Us plosed asa function of Sand V. Tnthis case, = Vand y= G = and points of multiple tangeney with a plane rolling over the USV surface will have the same intersection poiat on the U axis and thus will have identical valves of y® = G==j. Laterin Chapter 6 we will show that this geometric condition rigorously describes the mathematical criteria for phase equilibrium. Thus, i is no accident that the triangular piane in Figute 5.1b corresponds to the triple point ‘here solid ice, liquid water, and water vapor or steam coexist in equlibeium. The triple point is equivalent toa unique condition where triple planar tangency exists on the USV sutface of Figure 5.1a, Similar common points for double tangency on the USV surface ccan be used to characterize two-phase equilibria, such as the liquid-vapor coexistence region for a pure substance. 5.8 Modifications to the Fundamental Equation for Non-simple Systems Additional variables given in the original expression for the Pundamental Equation [Eq (S-1)] may be needed to describe the bebavior of systems in many practical situations in chemical thermodynamics. Some of these cases have already been introduced in Chapters 3 and 4. For example, there is frequently a need to account for savitational or inertial forces—potential and kinetic energy contributions to the total energy E, Systems with these effects, of course, are not simple systems as we have defined them in this text; butnonetheless, their behavior canbe represented by modifying he Pundamental Equation given in Eqs. (5-1) of (5-2), A common approach is to introduce additional generalized work terms, such that 6-109} ‘where the last suramation involving terms F, «cx, represents all non-PaV work effects that may be important. A number of these are listed in Table 3.1 in Chapter 3. These effects typically include: + Surface deformation work - oda ‘+ Bleetric charge transport -€ dy + Blecitic or magnetic polarization - EdD or HuB Linear elastic deformation - Fy dae ‘The addition of these other work or energy effects does not violate the four postulates that we have set forth to develop the iaws of thermodynamics. In particular, Postulate 1 still holds in that two independently variable properties plus the masses of all ‘components present are sufficient to specify the equilibrium states of a simple system. Non-simple systems with these non-PdV work effects, with potential or kinetic energy effects, or with other constraints (such as semni-permeable boundaries) can be treated. a Secton 5.8 Modifications lo the Fundamental Equafon for Non simple Stans 183 With sufficient information we can speci path of a particular quasistatic process. ‘Assuming that Eq. (5-109) can be integrated using Euler's theorem, we can write: wc hous Bor U=$ SVs Nyro Ny Epos By) 110) Which should be a well-behaved continuous function. ‘Then all of the tel Seveloped erie in ths copter canbe tized for manpulting pata ene nog the Tike. For example, Maxwell reciprocity relationships can be applied: “ & al oan as a " © owas OR va) Legendre transformations can also be ceveloped to interrelate thermodynamic properties: The following example problem illustrates the use of Legendre Teonaferms in manipulating partial derivatives, Seeenie ans ify the equilibrium state of these systems or the Example 5 S.A(@) Express (85/@P)p,n in terms of PTY properties and/or their derivatives Solution ‘The variables held constant (7, N) and variable involved i ie yl eld constant (7, and variable involved ine difereniaion ()sugest (S112) aGrn 546 ees] SE] sms Leget nom rN, ~ Solution Because Gy is involved with tsnatural cordinaes of P, TN fst yt simplify ie inate Nia first Nfs try to simplify by expanding the derivative, recognizing that Gp=(3G/2T}p,y =~ and tha G=yP=U~TS+PY= HTS a(G/T) ‘AG Ee 6 rf O/T) |p y 2 GHIS=H-TS+TS=4 (5-113) G11 ithe famous Gib Hehe lation enka which wl wed fequeny show the temperature dependencies of various derived properties ‘ecveniyto154 ‘The Calcul of Thermodynamics Chapter § 5.(o) Express (8C,/@V)pin terms of PVT properties andlor their derivatives Solution We start by usiog the definition of C, and the basis function of y= U in intensive form, Ge G) and. dU= Tas ~ Pav = corel av ‘Tere ith @U/2VIp=TAS/AYy Panda eel eatin fee av ac, , av or | C,) _(as) , ,(8@S/Mm)\ _ (ap) [av -G f or | With the V, T variable set, use to s0e if a suitable Maxwell relation can be developed to express (85/3V)y differently — ihestr-rt wt nf) {2 ne Expanding, and we can simplify the equation for @C/2V)j 10 (ac, PP Pa 5-114) [fee en 5.4(4) For systems where surface frees are important, the Fundamental Equation canbe redefined by adding aterm +6 to account forthe reversible work due to surface deformation, where O=surfae tendon in Jn? and = arcain ra, Develop an expression for @S/2e)r,y, in terms of properties that ean be measured experimentally Solution ‘The modifies Fundamental Equation in diferotial and integrated form is d= Tas - Pav + 0d +, AN, and U=TS-PV+0a+> 1, ‘Section §.9 Relationships Between Partial Derivatives of Legendre Transforms 155, ‘Again by inspecting the variable set 6, 7, V, and N; involved in the derivative, a y® transform is suggested that yields that set, 60 two transformations from § to T and (0.6 coordinates are needed: 40) — Sa ~ dds - Pav-+ Su, dN, [A Maxwel relation on he firs cwo erms gives the desired result ® 6-115) 5.9 Relationships Between Partial Derivatives of Legendre Transforms Although not obvious at this stage of our theoretical development, it is extremely helpful to be able to express derivatives of Legendre transforms. For example, later in Chapter 7 we will introduce criteria that will determine the limits of phase stability for single and multicomponent systems. Often the functional forms of various PVTN equations of state and other models of non-ideal behavior, such as activity coefficient models, require that certain variables be used to facilitate calculation of the phase stability criteria, This situation leads directly to the manipulation of partial derivatives of Legendre transformations ‘The presentation below follows earlier work by Beegle, Modell, and Reid (1974) which has been updated by Kumar and Reid (1986) who applied Jacobian transformations to calculate partial derivatives of Legendre transforms. Single variable transforms. Starting with Ea, (5-87), we wish to investigate the relations between derivatives of y® and the first transform y°", where IPF] aq) (5-116) ("| em) ary ‘There are several ways to obtain the desired results, but the most expeditious involves the use of the derivative operators fH, (Gori> 1) and (2 Beet "h, oy [BBL > om158 ‘The Cakealus of Thermodynamics Chapter 5 a 1 fa fe], “ ‘The terms y(? and y{? are second-order derivatives: 02 oy 5-120) W353, (5-120) ayo fy (8-121) eB Equations (5-118) and (5-119) are of litle value to obtain first derivatives since, in view of Eqs. (5-94) and (5-95), & (5-122) Gi However, to relate, for exarople, yf t0 second-order derivatives of y, one can employ the operator equation (Eq. (5-119)] on yf”. Thus for él: (a? ) ° we E = =m 123 (ae, a oo (a - ‘where Eq, (5-96) was used to simplify the third step. In 2 similar manner, other second- and third-order derivatives may be readily transformed. A list of these is presented in Table 5.3, Example 55 ‘Assume that the basis function is: U= derivatives of this basis function. WN ova). Determine 9 in terme of Solution With y!9 =f (1, ¥, Noy Ny) and ¥ =; (9-124) Section 59 Relationships Between Partel Derivatives of Legend Transforms 187 mae of oi “where the underbars have been omitted for simplicity. Now we ean write ors (PT/AS), fOT/AV) sy @TAS), » (@T/S3,y (125) ‘Table 5.3 Second- and Third-Order Derivatives of y in Terms of Dirt uty ‘my persed Bguat =| e a) x x 6119) ® 2 ou an me G19) mt ” 6-19) # garry e ex mo 3a te Se ey tg Me Ya)159 The Calculus of Thermodynamics Chapter 5 Multiple Variable Transforms. The development shown above was limited to the case where only a single variable was transformed. Should one wish to transform more than a single variable, itis always possible to proceed astep ata time and transformeach separately as was shown above. ICs also possible to develop a more general technique to allow one to express the partial derivatives of a Legendre transform Gon Bp Hpnnn Sy) in terms ofthe basis funtion y® or, in general, some other Legendre transform 3", where q= 1,2, j. The equations to obtain these second- order derivatives ae shown in Table 5.4 for the basis function and in Table 5.5 for other functions. In Table 5.4 there are three cases for y{f’: that is, j> i, ki k2j> i; andj i,k. Various cases are illustrated in Examples 5.6 and 5.7. Note that we can make use of Maxwells reciprocity elation yf? = 92 to simplify the calculations. ‘Table 5.4 Relations Between Second-Order Derivatives ofthe jth Legendre Transform and the Basis Funetion D Dele r AT) ji we DP isk isi jek 8, Kronecker dst, A, Jers each witha vale of Sy) where m= 1, 2d B: j terms; each with a value of (5), where m= I, 2,.. Cj thers cach ih eva oF 5, whem Ds G1) tems each with a valve of(1~ 8,9, where m= 12-40 D E F a One term; (1 ~8,)9!9 ~ 5. (One term; (1 - 5) — Be 1-891 By? and pir oy 0) pet © p= pr | ‘Seaton 5.9 Relationships Between Paral Dervatives of Legendre Trancforms 189 Table $$ Relationships Between Second-Order Derivatives of thejth Legendre Transform and the ¢~ 9) Transform and i 2 oo penn ethndeay Hy te 2 pio Phrae nn Pe 9 -0) ) foen i * Ze=0 ifrss itros AL (g- 1) terns; cach with a value of (2y-gety EBs —By-pyd where p= (4-1) (oun AY Zjngsnah BY (q~ 1) terms, each with # value of [Zg-getye MH — By-ptd where p= (9-1), Dray 1 BY: Zyasn) B Dig i-ayt? Dr (ge temas een witha av of ~ Bp 6 Ba where p= (1) Fi (1-5 -§ Tr (1-802 -een0 Fi (g- 1) terms, cach witha valve of (1 ~ 5d9-Bh where p= (1) (Q-Bon R: (1 Boy - 8; 2: 0-80 8oskk? Brample 56 Relate the derivative yf to second-order derivative of y forfour eases: (@) j=3i= k=!160 The Caleulus of Themodynamics Chapter § © j=2, @ jn3, Solution Table 5.4 is employed. The results are: inn S19] oo 32] peo 2] 99 ol Su Sa Al 0 pe *I oP Dp 28,99 (yb (1-899 = 35 (-B,e pir 2 ot —|(1 8,991 - By, ys? Pye ~Bal(1- 3,11 - 8,9 st @. ee = we @ j= 8 Eeample 57 Using Tobe 5.5, expres: (2) 989 in terms of derivatives of (©) y§9) in terms of derivatives of y™. Seation 59 Relationships Between Parial Derivatives of Legendre Transforms 181 Solution (2) In this case j= 4, '= 2, k=3, q=3. We will use the case where j> i,k. Notice that Zy-uiyy~ Zee-soay Zar Since 2 ~ i, then Zy,=0. Also, Zy. gee 0. pe =D? where D2 oP oft 0 oO pS of p92 ofl Then us| nS op fs} pe w of | pw » one oP () Here pi ick F=54=2,8=6,953, — Zyoguyy=Zp= @ a ae 2 9 9 ol [BoB 9 yl ma oO ya ye vee BI] po VB 2 ) 2 sp PB VG] pp oO 2) ae D2 of 2 sl PB 8 VG 38 a a Dy DP Letus now consider derivatives in intensive variables only and show that they can be reduced to expressions involving only S, T, P, V. In general, a partial derivative of intensive variables may involve U, H, A, G, S, TP, V. We have excluded N because it is extensive; Lis also excluded because [1 is equal to G fora pure material ‘The first step in reducing the general derivative (Ob/2c), is to eliminate any of the four potential functions U, HA, or G, which may appear as b, c, or d. The three possibilities are treated as follows: 1. UDis U,H.A, oF G, eliminate it by using the diferente form of the wansform, For example, with Eq, 5-101), fora closed, non-reacting sytem,182 The Cakulus of Thermodynamics Chapter ° flag +422) as | as.” “Las. (5-126) 2. Ifeis U, H,A,0FG, invert the derivative using Bg (5-30) (de) ___ S127) ab | 7a, snd then proceed by step 3. Ifdis U,1,A, oF G, bring the potential function into the brackets by using the triple product relation of fg. (5-32) (ab) __ @d/Ae), (128) lac” aa, and then proceed by step 1 Using these three steps, we can reduce any partial derivative invalving only S, V, 7, and Pto second-order derivative of one of he four forms ofthe Fundamental Equation ‘This is illustrated in Example 5.8 below. Example 58 For a pure material there are 24 partial derivatives involving S, 7, P, and V. Suggest 2 technique to refate any such derivative to second-order derivatives of the Gibbs energy and, therefore, to Cy. Ks and O Where Satution Of the 24 derivatives, 12 are simply inverses. The others are as follows: (1) (@S/87),, (2) (85/2), (3) (85/APYp (4) (AS/AP)y, (5) (AS/PVp, (6) (BS/2V),, (7) (V/AP)y (8) (BV/BP}g, 8) @V/ANp (10) GV/ANg (11) P/ANg (12) @P/SDy. Number (3) is ‘equal to the negative of (9) fom the Maxwell reciprocity theorem; similry fr (4) and (10). Number (5) is equal ta (12) and (6) to (11). Thus, there remain (1) through (8). Three ofthese ze second-order derivatives of the Gibbs enerey () @S/N,=-G= O/T 8) QSAP)_=-Grp Gp, (QV/BN),= Va, O) OVP), = Cy =-Ve, In addition, derivatives (2), (5) and (10) arerelated by the X-¥-2-1 rule, as ae (4, (6) and (8). The ets (1), 9), (11) and (7), (@), (12) ae also 50 related, but these derivatives have already been eliminated } Thus, itis ooly necessary to relate (2), (4), and (6) to derivatives ‘Section 68 Relationships Between Parte Derivative of Legendre Transforms 183 in Go low al derivatives tobe so expressed, The reduction of) has heen introduced Fol 3.12 For) and (we eo outa nen GC TUT-PN, ) where the x-£ values are shown below. For (6), we define y= fy = ‘Jandt JE vales are also shown below Y= HFS, P. Ny) andtic , a so o8 ee Lg a oy a M Hy ete. But, by Table 5.3, and QS p= G/a, V7. For derivative), using the same basis faction, we need tase adobe transorm Pe CHGS VN) with ime ro a Y $ r 2 yo 2M and QS/AP Wy y= NOS/AP)y-= NGL since P Reragelt ig, =o ADP -OBY ” Orr Opp Gp 9?) From Table 3.4,164 The Callus of Memodymamics Chaptor § Although the procedure described above is always valid and unequivocal, there are shorteut methods such as those introduced earlier in Sections 5.3 and 5.4 which, when applicable, are usually less tedious. Example 5.9 Evaloate the folowing partial derivative as funetions of P, V, 7, their partial derivatives, and Gy: (8) @S/@P gi (0) @A/3G)p Solution (@) Using Bas. (5-126) and (5-128), we find thet (s CGAP) -SCTAP s+ ¥ ex) lar |, e679," ser/as), Using Ba. (5-128) wo eiminate @7/2P)o, (ar) __@S/P)r_@V/AD» (6-130) [ar |""@s7an, C/T as) ¥G_jav eis OP. TS (a, “The enepy, Sn a, (6131 can be expesied fonction of he ened variables, as demonseated in Secon 8. Ge Bg 625) (8) Tis paral derivative can be rede by he following shores pocedze (aA) _ QAM P 0G | @G/V),_— VOP/OV)> inwhicha, (538) wasemplojed. The inseion of Vis convenient bu ntanasiary ee Atmoogh Pcouldeve een ved in place of Vth neal spl, S woul bare ‘been less convenient. The choice was guided by the fact that A = f(T, V)and G= f(T, P); since T was the constant in the differentiation, ether 7, Vor T, P would be a convenient fet of independent variables. As an alternative, Jacobian transforms could be used. so that Section 5.10 Summary 165 5.10 Summary Starting with che Fundamental Equation U=f(S, VN) as & basis function, this chapter introduces a mummber of mathematical techniques for manipulating variables. The Jmportant methods discussed were: 1. Baler integration ofthe Fundamental Equation 2. Maxwells reciprocity theorem for relating 2nd and higher order derivatives 3. Derivative inversion, tiple product, and chain role expansion for manipulating variables Jacobian transformations for derivative manipulation 5. Legendre transformations to express the U=(S, , N) Fundamental Equation in terms of different variables without lsiog any information content 6. Modifications tothe Fundamental Equation to account for non-PV work effets 7. Derivation of relationships involving partial derivatives of Legendre transforms In addition, graphical techniques were used to illustrate the geometric relationships ofthe USV surface and various Legendre transformed functions References and Suggested Readings Alberty, R.A. (1994), “Legendre transforms in chemical thermodynamics," Chemical Reviews, 94(6),p 1457-1482 [Chemist's perspective on Legendre transforms} ‘Aris, R. and N.R, Amundson, (1973), Mathematica? Methods in Chemical Engineering, Prentice Hall, Englewood Cliffs, NJ, Vol 2, p 197-201, (Jaroduction to Legendre transformations) Beegle, B.L., M. Modell, and R.C. Reid (1974), “Legendre transforms and thie application in ‘hermodynamics," AICAE J. 20 2), p 1194-1200, Callen, HB. (1985), Thermodynamics an an Introduction to Thermostatsics, 2nd ed, Wiley, New York. (Legendre transformations} Clark, A.L, and L, Katz (1939), "Thermodynamic surfaces of 10," Trans Reyal Soc. Canada, Sed series, Section 1, 33, p. $9-72 [Figure 5.1a taken from p 72). Coy, DC. (1993), "Visualizing thermodynamic stability and phase equilibrium through ‘computer graphics, PRD dissertation, Dept. of Chem. Eng. Jowa State Univ., Ames, Iowa [G-D images of variws!y cansformed and sealed fundamental euefaces of pure, binary, and ternary systems} Dehenedeti, P.G. (1986), “Generalized Massiew-Planck functions: Geometric representation extrema and uniqueness propetis,* J. Chem. Phys. 85(4), p 2131-2139. Gyftopoulos, .P. and G.P. Bereta (1991), Thermodynamics: Foundations and Applications, ‘MacMillan, New York, (Meclsnical engineering perspective)The Calculus of Thermodynamics Chapter § Jolls, KR. (1990), "Gibbs and the art of thermadynemics", Praceedlngs ofthe Gibbs ‘Shmposium, published in G.D. Mostow and DG. Caldi (eds.) Amer. Math. Soc. and presented at Yale University, New Haven, CT (May 15-17, 1989) p 293-321. [computer ‘onerated fundamental surfaces fora pure fluid) Jolls, KR, MC. Schmitz, and D.C. Coy (1991), "A new look at an old subject,” The Chemical Engineer, institution of Engineers (UK), No. 497, May 30, p 42 Jolls, KR. and D.C. Coy (1992), “Gibbs's models visualized,” Physics Today, March, p96, Kumar, S-K. and R.C. Reid, (1986), "Derivation ofthe relationships between partial derivatives of Legendte transforms", AICKE J. 32 (7), p 1224-1226, Tisza, L. (1966), Generalized Thermodynamics, MET Press, Cambridge, MA, Ch, 2 in general and specifically, p61, 136, 236, [Transformation methods] Problems. Demonstrate the utility of Ba (5.96) for a system with six components and Where i= 4, Order the Fundamental Bquation 3s. DHFS Nyon No) (©) WFone were to write the Fundamental Equation as S=F QM Mor Nd 51 @ ‘What would the derivative ofthe total Legendre transform bo? (©) Suppose that one were write the Fundamental Equation as ” TPN yoo Ny) Prepare a able showing the varons conjugate coordinates , x, Next, write the third ‘Legendre transform of the basis function y® shown above. Prepare a, x, table for this transform. What generalization can you infer from this exercise? (@) Choose the basis function for the Fundamental Equation to be = FU Nyro Nqw D CObian an expression for yin terms of derivatives y®. 52. Given =/(S, VN Nyy. N,)oblsi the Legendre transform ands differential fone ‘wished ta work in the following coordinate systems @ FTV end) ©) FEAT), VN Nave Nal 5.3, Express the following patil derivatives in an equivalent form using the Pundameital Equation ys uw UE. YM Naya) Problems 187 5A, 55. 56. and Maxwell's relations. Indicate, if possible, how they might be measured experimentally @) ® |5n, © @ | (ihn (eh, OZ. al, Cary cute flowing wansfomatons (@) Express (@S/AVp. yy, 852 fonction of P, VT and thee devivatives. (©) Express (AH/AP), yy, a a function of G and is derivatives and show how these say be given in ens of. V, TN. and C, (©) Bxpress [A/T /A1/My n,.9, 2 # function of U and is derivatives. (©) Express @H/2V)r 9,9, 8 function of Gand its derivatives and show haw these may be given im terais oP, ¥,7,N, and Gy. (©) Express @7/2Na)y 5»... 88 8 funtion of U and its independent derivatives. © 8 a funetion of U and is independent derivatives. ‘The following discussion i limited to one-dimensional motion along the x coordinate and for a constant-mass system. Newtonian mechanics relates the force on a particle tothe rags and acceleration; that is, P= emi (eat) (ae Another way in which o td the dyna of moons wth Lagrangian esha, this case, a function L is defined as L=S - ©, where 3 ~ the kinetic energy = ma/2 ‘and @ is the potential energy = f(x). Newton's Lavi in Lagrangian mechanics is given as LEE Lestni) i= B= velocity Another branch of mechanics uses a function (-H), which is a function of x and the momentum ofa particle, p: that is, “H=f@.2) swith168 8. 58. 59. The Caleuos of Themmedymamics Chaptor 5 8 (a) Using the concepts of Legendre wansforms, define -H io terms of Lp, and x @) Inthe ter branch of mechanics, H is called the Hamiltonian; with your definition ‘of H complete the following equations: ee [Express the following in terms of Gy PV, Tand desivatives of these variables. @) Q/Den ©) CAG Prove that for an mcomponent mixture there are (n+ 2)(n + 1/2 independent second-order derivatives ofthe Fundamental Equation, AA spherical tank contains 1 mot of helium gas at 10 bar and 300 K (see Figure P5.9). We ‘would ike fo carry out ay experiment in which helium is released to dhe atmosphere, but atthe same Gime, the remaining contents of the sphere maintain a constant total energy, U, Heating of cooling evs may be used 1 keep U constant during venting. Helium behaves a5 ideal gas with a constant value af C, = 12.6 Jmol K. Choase a base state where te specifi enthalpy is zero at 300 K. (9) When one half ofthe elim hasbeen Veoted, what is the temperature and pressure ofthe cesidval helium? What sth beat interaction? (©) Determine (@F/4P)y yatibe instant when venting begins. (©) Repeat pars 2) and () ifthe base state were chosen so tat the specific imernal nergy, U, were 2270 3t 300 K (4) Forpart (a), what would be the residual helium temperature when 60% of the gas had been eomoved? Problems 169 5.10. san. s.2, saa, S14. 58, 5.16 Choose a a basis fonction = f(S,Ny Ny Ny P) and obtain yin terms of derivatives ofthe basi function. Discuss how experiments ould be designed and condoced wo ablan ates vale ofthe J daivatves Using your result, consider the following problem. We have a system containing, initially, 1N, moles of a material. We wish to remove Nj/2 moles under conditions were the total ‘entropy and the pressure remain constant. Ifthe intial temperature is 400 K, what isthe final temperature? Assume thatthe base sate for entropy is such that st 400 K and the system pressure, che specific eatropy i [0 S/mol K. Also assume thatthe heet capacity is 10 simol K, independent of temperate. 1 he bass fein is hasen a P= VHS. YN Nd Uw Uy UUs, UssUsy| Usy Ur} by performing two single-step transforms from y to y") and then toy Assume thatthe basis generator sy) =f(P.T. N,N.) Exoress incre of derivatives of y!” and interpret the results on a physical basis. Express yf interns f derivatives of "fora temary mixtare when the bass function y= U=F(SVANy Np No) show that » Expres in tems of eaves of he tsi funtion Show that fg Legendre iransorm ofa basis function J, where If =F Oy Xp. Sq) YP =f Er Barn baa Sn)im san, 5.18. 5.19. 5.20, ‘The Calculus of Thermodynamics Chapt S Deve general equation expres he derivative Rp tem of desvaives of PEapende uanform y, where O 210K, the function depicted in ‘he figure i adequately described by the equation «= 7/200, with Tin K and tin ‘MPa, What conclusion can you draw about entropic contributions (0 the elastic response? Rocky and Rochelle Jones, while backpacking near the Presidential Range ofthe Whit Mountains of New Hampshire, were tapped ina severe thunderstorm. Rocky was very woried that they would be struck by lightning. As thunder and lightning bots crashed slong the mountain ridges, he remembered that one aught ro be able to estate the distance oa lighting strike by counting the seconds betwoen when you fstse the tke and when you first hear the thunder Rochelle recalled her 1040 waning and remembered thatthe speed of sound coud be elated to certain thermodynamic propories: Dep in her photographic meraory ste recalled tht: = @P/AP). Figure P5.20 ‘where vc isthe sound speed, P isthe pressure, pis the fluid density, and isthe entropy. ‘But neither Rochelle nor Rocky can quite figure out how to evaluate the isentropic derivative @P/2p)q in terms of measurable properties. Please help them out! Rocky just timed the las strike and it was only 2 seconds away. State and justify all assumpions in ‘your analysis. NB. Rocky's portable solid-state weather computer which fits int his backpack has provided some valuable meteorological data air temperature = 0°C 32°F) relative humidity = 80% barometric pressure = 0.99 bar and falling eapidly* wind speed = 50 mph (80 xaph) from the SE In addition, Rochelle had a copy of Perry's Handbook with her which provided some other (hopefully useful) thermophysical parameters fr air.522, 523. ‘The Calculus of Themodynamies Chapter § ¢,= 293 simol K molecular wt = 29 g/mol “407°C 372bar = 1/V, = 350 kelm? 2 p= LIT ker . Joule Thompson coat Cicient = Oy = (87/AP)y = 0.23°C/bar ‘viscosity = 0,19 x 10° Pas Prandtl number=Pr=070 thermal conductivity = A= 2.6x 10 Wimo K (a). Soaring withthe following alternative definition of C, and Cy: G,=T@S/2P)p C,=TOS/ANy show that Gy ~ C, can be expressed asa fustion of PT properties only, Using he result of pat (8) show that C,~ C, = for an ideal gas the ratio Given that C,~ C,=f(P, Ys) fom past (a) is it possible to express # © PE Esastn explicit nein PVT poperies nd ter derivatives? Explain your nse. ‘Abas funetion is defined as follows: =f (T.VsN,NoZ) ‘ity conjugate coordinate variable pir given at a & TS vo Mo Na we a OF Je in mas) and Fy 2 tere 8a generac exesvedslacemen at order in ms) and Fy wer ace oc (ez eret i Das) an the ther rms ave thei sa ae i capes for be following @ 4 3° © G8) BFY/A ny npg in tons of @ derivative of Ny : (© 98= Him ets of © and its derivatives, ‘Yoo may want to use Table 53. Probloms m 524, Ly PVPS V, Nye Ne ace and dj alvays equal to 280? Answer yes 528, 5.36. corno and explain briely Uy =f hy, Py T, Nyy Nyro N,), wha are Y and dy? ‘What derived thermodynamic property does y correspond to? Give one example of f= yf for any kth Legendre rvstorm of y= 0 and any $60 independent variables i andj: Express your answer as an equality of partial derivauves involving derived properties (U, 3, H, G,4) andor primitive variables (7,P, VN). ‘A basis function for a modified Fundamental Equation that includes reversible Cleetromagnetic work effects in a two-component system is given 95: y FS, Vs Nye Noy B)=f Cys Kaye X3) here the conjugate pair of variables added for electromagnetic work sects is fis6}=WB. and magnetic field strength (amp/mn) ¥= toxal volume subject tothe magnetic field, includes the system volume and any fret space outside the Boundaries ofthe system (m°) agnetic induction (Volt-s/m) For all cases of interest, you can assume that the volumetric magnetic permeability is constant, () Whatare y and dy? (©) Derive an expression fOr @hy/2B)r vs. (©) AtcorstantT, P, and B could you caleulae yas a function of mote frsson of ‘component (x) from knowledge of how jy varies with x,?If 0, explain your answer ‘According oarecentanicit nthe March, 1989 issue of Sciemific American harbor seas are believed to have sophisticated acoustic transmission ard deection eyStems that are similar to Sonar. For exaznple, mothe seals locate their pups by measuring tha difference in reflected acoustic wave arial times in air and in water Given tha the speed of sound (¥,) can be related to an isentropic derivative of pressure with respect to density: v2= @P/0p)s174 527, 5.28, 5.28. The Galeuus of Thammedynamics Chapter 5 estimate about how fara mother seal is from her pup ifthe time difference is 3 seconds. Air ean be assumed to bebave as an ideal gas with C,=$/2R. The properties of liquid ‘water can be obtained from the steam tables, The aif and water tempersnures are about 2c. A norvideal gas of constant heat capacity C,~= 12.56 Jmol K undergo a reversible ‘adiabatic expansion. The gas is described by the van des Waals equation of state P+a/PV—b)=RT where a= 0.1362 1 m?/mol? and b = 3.215 x 10° m?/mel, Derive an expression for the temperature variation of th gas internal energy, and calculate is Value when the {285 volume of 400 moles is 0.1 mand its temperature is 294 K. “The basic thermodynamic reitionships for an axially stressed bar can be written as: dQ y_y> TAS, dWroy=—tde, & fe where € is the stress and € is the strain, Devive the Fundamental Equation for 3 ‘one-component bar and show that @L- Gl. {A very useful property isthe partial malar volume of one component in a mixture. It is defined for an n-component case a5, = @Mrony Ate have abasis function y®, YS FS VN gy Nooo) we can se that, if we deste Vp, then Vere where re However, o evaluate V, we aacmally only have property relations which express P as 8 flanction ofthe independent variable set V, 7, Ny. Navn Ny FPN g Nyro) Use this variable st to define a new basis function Y, and express 69 in terms of LV, T.Ng. Nps Nq using the following equation of state Problems 6 530. where bg, Bp by re constants and N= EN with (=a, Bou ‘The extensive variable that characterizes magnetic behavior is the magnetic dipole ‘moment 7. In ths situation, the fundamental equation i rewrite at U=UEVLN) with Ge added conjugate variable set (x1 (LH) where His the magnetic field strength, Fora pure component system develop expressions for: @ yu @) and df © CSADy yy