Latin American Applied Research GENERAL EXPRESSIONS FOR 19: 99-109 (1989) MULTICOMPONENT FUGACITY COEFFICIENTS AND RESIDUAL PROPERTIES FROM CUBIC EQUATIONS OF STATE ERICH A. MULLER*, CLAUDIO OLIVERA-FUENTES Universidad Simén Bolivar, Departamento de Termodinémica y Fendmenos de Transferencia, Apartado Postal 89000 Caracas 108¢ L ANTON 364A, Venezuela 110 ESTEVEZ University of Puerto Rico, Department of Chemical Engineering, Mayagiiez, PR 00709-5000, Puerto Rico Keywords: thermodynamic properties, fugacity coefficient, equation of state. Abstract Starting with a generalized four parameter cut ‘bic equation of state, exact expressions are presented for the fugacity coefficient of a component in a mixture, and for the residual properties of the mixture. ‘The expressions are general in regard to the equati ‘examples the particular expressions for the Peng an anes ‘The equation of state (EOS) approach has evolved into a standard tool in the solution of multicompo- rent phase equilibrium problems. In particular, cubic EOS have become popular due to the their com- putational simplicity and predictive accuracy, espe- cially at high pressures where other models, eg. those based on activity coefficients may fail In the prediction of phase equilibria the EOS is not used directly. Rather, the criterion most com- monly employed is that a derived property, the fugacity of each component must be the same in all phases. An expression for the fugacity can be found in terms of the system pressure (or volume), tempera- ‘ture and composition, but it must be derived speci- fically for each EOS’ and for the particular set of ‘mixing rules that has been established for the EOS parameters ‘As a general rule, authors who develop new EOS also report the related fugacity expressions. Never- theless, there are certain EOS for which these have not been provided, eg. Schmidt and Wenzel", Harmens and Knapp?. Aiso, the continual publication of new cubic EOS makes it desirable to have available * Autor to whom correspondence should be addressed, ‘ion and to the mixing and combination rules used. As \d Robinson (1976) equation of state are shown. a general relation from which the fugacity function can readily be synthesized. A fully generalized treatment does not seem to have been published in the open literature; the equation presented by Vera et ul.> is limited to pure components only, while the multicomponent treatments by Mollerup* and Wilezek-Vera and Vera’ are restricted to cubic EOS with three real pressure asymptotes (A > 0 in the present notation) therefore excluding the Clausius family and part of the Schmidt Wenzel family of EOS. It is the purpose of this work to present a more general analytical expression for the calculation of multicomponent fugacities, valid for most cubic EOS and mixing rules. The derivation is based on a residual Helmholtz energy approach; this makes it possible also to derive and present general expressions for other residual properties, including enthalpy and entropy, which should be useful in process calcu- lations by EOS methods. Residual Helmholtz energy Our starting point is the general four-parameter cubic EOS originally proposed by Schmidt and Wenzel", as this proves to be the simplest form that 99Latin American Applied Research incorporates most cubic EOS in current use. In Table 1 we present examples of some popular cubic EOS expressed in this form. A more general five-pa- rameter form has been presented by Abbott®, but in general five-parameter EOS are still rare. We thus take the EOS to be P NRT Nea V— (Nb) V? Fu(NByV + w(NB)™ 7) In the present case the parameters a, b, u and w refer to the mixture. Apert from varying with tem- erature, they may all be composition dependent according to specific mixing rules. The final form of the derived property functions for each particular EOS will change with this functional dependence. ‘Table 1.— Values of u and w for some common cuble EOS Equation u w ‘van der Waals 0 ausius? 2elb Redlich and Kwong * 1 Peng and Robinson " 2 Usdin and McAuliffe afb Harmens'® 3 ‘Schmidt and Wenzel! 1+3u Harmens and Knapp? e Patel and Teja (bse Adachi etal." (ALS) (03—b2)/6 —(0362)/0* Adachiet al"* (3VL) 2clb ~(c/b)* ‘Toghiani and Viswansth"” +e xe Yoand Lu” 34/0) eld ‘Yu and Lu'* (TPR) 2-A(c/b) 2c/b)? -1 ‘Trebble and Bishnoi"” 14 eh) =6(be~a*) We determine first the general expression for the residual Helmholtz energy, A’ of the fluid mixture. This is @ natural function of the independent variable set {T, V, Nj... Np}; hence it is most easily estab- lished fora pressure-explicit EOS, and in turn provides @ convenient generating function for other residual Properties. From the definition of residual properties, AUT, V,Na,-- Nn) Q) For the cubic EOS, Eq (1), we get v AT=NRT+In————+(N2a)ly (3) V— (ND) where ly is the integral (4) 19: 99.109 (1989) &, being the quadratic polynomial BCT. V.Nu, 1, Ny) = V2 + u(NB)V + (NB)? (5) The integral, ly has different analytical expres- sions depending on the discriminant b= —4w © which indicates whether the isotherms of the cubic EOS will have three (A > 0), two (A = 0) or only ‘one (A <0) vertical asymptote in the P — y plane. Accordingly, we get 1 fe enenw Wve Ng eee oS 2V + u(Nb) ed ia pete] ® HVE [onsyv-a J 2 if4<0 (7) Partial derivatives of ly with respect to tempera- ‘ture and composition will also be required in the development that follows. A general procedure for generating these derivatives is presented in Appendix a Fugacity coefficients Multicomponent fugacity coefficients for pres- sure-explicit EOS are frequently obtained from the exact thermodynamic relation presented by Beattie”: PV ¥{RT [ap =-h— al a av NRT RTE BNilrv,Nyy @) Comparison with Eq. (2) shows that this formula is equivalent to iw & ‘The derivative of A” will include terms containing composition derivatives of the EOS parameters. We introduce the notation NO) any for 2=a, b,u,w (10) ON; ITNE. A. MULLER, C, OLIVERA-FUENTES, L, ANTONIO ESTEVEZ and differentiate Eq (3) with respect to Nj to obtain L [oar ; RT Nv Nu in V-Nb- V-Nb Nidffaly eat Rt|Lanjr,v, +1} an The corresponding derivative of ly. taken from Appendix A, is br . PNT vNtiy 1 Vit gvly = — | (sia — 2rw)b ~ (iu 251) wh v bl? if4=0 (12) where 4 Ratu tu (3) b si = (yi - w) +20 «ay ’ Equations (9) through (14) give the multicom- ponent fugacity coefficients for the general cubic EOS. The equations may be combined into a more ‘compact expression, which will be presented after the next section. Other residual properties In considering the remaining residual properties, it is convenient to make use of the dimensionless molar residual Helmholtz function, ar NRT © from which other dimensionless residual properties may be derived as (16) (7) 1- (13) r 19 NRT ey From Eq (3) we obtain: vw Arein +o (20) V— (Nd) ” NRT which is differentiated with respect to temperature to give be N [ab], (N%a) | aly] py o(a/7)] V—(No)[aT|n; NRT [aT|vy, RL aT |. i (2y) ‘The corresponding derivative of ly, taken from Appendix A, is & es aT] vin 1 V +Evly [loe-2rmmp ~ (rqu—257) eae wh N 1 = preth? ifa=0 (22) where ae fe 23) reat] yy LT, aw], wan w=s{G3, Carl J as Equations (16) through (22) give the residual properties for the general cubic EOS. A more compact formulation and the simplifications that ensue when only the cohesion parameter a isa function of tempe- rature are considered in the following section. Tt must be noted that the above results correspond to the {T. V, Nys....Nq} representation, which is most practical for the pressure-explicit cubic EOS. 101Latin American Applied Research In the {T, P, Ni,...,Ng} representation, Eqs (16) and (18) are still valid, since ideal gas enthalpies and internal energies depend only on temperature, but Eqs(17) and (19) should be modified to: SR(T,P,Ny, Nn) = pv = S(T, VANuy. Nn) + In —— (25) if in) ner ) GR(T,P.Ni, -. Na) = Pv = GT. V,Nay. Na) — In — (26) ¢ ) arr Results in terms of the compressibility factor The thermodynamic properties defined by Eqs (9) and (15){19) are both intensive and dimen- sionless, therefore the corresponding final equations may be conveniently reexpressed in terms of the compressibility factor Z and appropriate dimen- sionless EOS parameters. Equation (1) may be written as ‘eae te Z-B g ay or, in cubic polynomial form, as 2 + [(u~ 1)B~1]2? + [—w)B —uB + A]Z— (B? + B*) + AB]=0 (28) where Sa (29) (RT)? RT and g=Z? + uBZ + wB? (30) Rearrangement of Eqs. (7), (11) and (12) in dimensionless form, and combination with Eq. (27) now yields for the fugacity coefficients (Z—1)-n(Z-B)FAQ (31) 19: 99-109 (1989) 1 [by If gj fen A- (7-25) ] ifA#0 [2 (2 Hi ) W=+(—z+oB i] ifA=0 (32) a b 2 with 1 [22+ Bw vB) [eg eee ave “lz+aurya | *4>° eo ifa= 22 +uB oD) 7 2 tan 2Z +uBi 2 fA. 33) aaa ahd paso and 7, s; given by Eqs. (13) and (14). Equation (31) can be shown to reduce to the case of a pure component when the EOS parameters 4, , wand w are not functions of composition. The equation presented by Vera er al? for Eq. (1) is then regained, Ing=(Z~1)-InZ-B) +Al G4) Of the residual properties, enthalpy and entropy are possibly the most important, because of their occurrence in first and second law calculations. We introduce the notation a ‘ainQ] er aint] yy Rearrangement of Eqs. (17), (18) and (20){22) in dimensionless terms, plus introduction of the EOS Eq. (27), now yields the expressions: for=a,b,u,w (38) ~ Bor - AQr (36) z-B Hr =Z~1~ Bby ~AQz—-1) G7) 102E, A, MULLER, C. OLIVERA-FUENTES, L. ANTONIO ESTEVEZ 1 T T Or = Zap Br + loru—2raw)B — (rr er) (38) 1171) Nar Hor +57) Bly a= Here, I is given by Eq. (33) and rr, sp may be taken from Eqs. (23) and (24), or the following may be used: Tr srruer tap (9) Tsp reer + 2b) 40) The temperature variation of the EOS parameters is in most cases limited to the cohesion parameter a, with b, w and w taken as independent of temperature. In such cases, simpler forms of Eqs. (36) and (37) apply as (41) ) Application to particular cubic EOS In order to specialize the general results to any specific cubic EOS, the EOS parameters 4, b, u, w must be identified (e.g. as in Table 1), and their ‘composition and temperature derivatives must be obtained from the particular functional relations ‘employed in the OS development. These relations are seldom unique for a given EOS, because successive researchers usually seek to improve the EOS perform- ance by modifying the mixing rules, temperature dependencies, or both. The Redlich-Kwong EOS is possibly the most notable example of this variations- ‘on-a-theme approach. For greater flexibility of application of the pres- ‘ent general results, we have therefore collected in Tables 2 and 3 the composition and temperature derivatives corresponding to a number of functional relations that have been proposed in the literature for one or more cubic EOS. In addition, we have indi- cated in Table 4 which of these relations should be employed with several popular cubic EOS developed or modified by different authors. It should be noted that even if some of the EOS listed in Table 4 were developed for application to pure components only in the original references, they can always be com- bined with any of the mixing and combination rules given in Table 2 to generate corresponding multi- component versions in a straightforward manner. ‘AS an example of the application of our results, consider the cubic EOS proposed by Peng and Ro- binson". From Table 1, u = 2 and w = — 1, there- fore the discriminant, A is always positive, 2 h=u? -4w=8>0 (43) ‘Also, Eq. (28) becomes 2 — (1 ~ B)Z? +(A ~ 3B? — 2BYZ —(AB-B?-B*)=0 (44) To obtain the fugacity coefficient we must first develop the derivatives in Eq. (10). We search in Ta- bles 4 and 2 to obtain, for parameter a: Ba g=—2+ slat + BENET Nu (12.4) 0 (12.10) Since ay = aj, these reduce to aya 2Exay (45) i For parameters b, u and w we have, also from Table 4, 49) a7) (48) It Follows that 4 n= (y-w) tu co) b bb — w) + 2w. ? oe (50) Qs es nu — 25) = 8 si (ra - 25) = 85 GD 103Latin American Appliod Research 19: 99.109 (1989) Table 2.~ Composition derivatives of EOS parameters Mixing rile, & 8) = [ANDANT. Nyy = constant, a 121) 2x My 2% (7221 fxn! 2194499"? - (723) Dix Bex ty HAs Ea(N5+ N+ EEN — ima) NTN tip seamen] > Bony? 3M!” fern ra eee ims) Brit) Say Ex Bi i alts | 1261 ee BeBimy Eh ayy avn pean oa by lan 271 ON fain ) + Ey pa (m2 % 2, af taf cx, ima & ou B alt sali A =) (72.9) a Sub Combination rule, Raq Monn ANGIE. Sun = constant ° imo} (—xmkma~*nk mmm an) 2m imk ma + inom! Mmm tan? (T2.41)* iar (Bt erate tga = Va (1 Simkmn + Siakam Saka “eho ) Xmkmn+¥okom * Signs Bin = Kronecker deltas (5iu — 2rw) = 0 (52) For the residual enthalpy, given that only the cohesion parameter a is a function of temperature, With A positive and the above, Eq. (32) gives La. (42) applies and may be written as [bee “ 1 3) Hera 1) - ( ) (5) a = ~ 1) (aay ~ Chiao cS) oRp te Finally, the Fugacity expression is On recognizing that ing Téa ‘aint © “a OT VB aay by 2424148 =} inf-———__] (54) a Z~- 0.4148 we obtain 104 (56)E. A, MULLER, C. OLIVERA-FUENTES, L. ANTONIO ESTEVEZ Table 3.— Temperature derivatives of EOS paramerers Mixing le, & “By = Ginn/ain De 1 dint Ean 2x04 — m3. on ae rma) ag)" ancy iia Eu) 11321 a! “Gar 1 [= 2Expy = saxo] ——| m1 a a I dino, ExMiny"” Ee Mu)"”] * \ 173.4) Bap"? Exo)" ay} 3 b ay f2anny andy a, emia ee las oy 2 my a) [3 aint ant o My fain; indy ‘ag’ seo, wai aig lant amt Td val ney andy Pe Expy Bf ant aint +B aft] -_—— 13.1 all sxe, EP Combination rule, GnayeADN dinny aly +25 — aot ant TY ae oe 13.81 waa y+ 1 ar ain ain ay kyg + 1-9, et dkny —— + Tyo —p 3 ue A ater Maar ae si dino, a4 VORP (3.10) aint Haina; ney (xy) Vp -|— 4h may Saar aint ki 1 fain, ana, _ a d 173.121 ay 2laint * ant 105Latin American Applied Research 19: 99-109 (1989) TABLA 3.~ Continuacion, @) = if iderveat alndigidint = dina /aint, 1 0 173.13], 1 =n (73.14) Acw(-BT) -81, 173.15) om—79 . [ro-m a Tanto (13.61 A+ Bexpim(l ~ Tp) = ma AN(Tyfa) (73.7) f+ ma-Te")p ~m(T,fa)""* (73.18) 1+ m(L—T) + n¢T,-* =) = n+ aT-*)(Tfa) (73.19) 1+ X(T,- 1) + YY? - 2 (1X + (Y/20T "7 Tyla) 173.20} U1 mC Ty") — pL=T NOT Ty —fm + 4pT,— 0.85)T,!"2 | (Tyfa* m2 1 +Ad—T4)~ BUT bP 1A 4 28,779) (Tyfay"?? 173.22) 1+q0-T,-tr) = (1, + Dialay 173.23) (1 = CinT, — D(inT,)?} [C+ 2D In Tyla 173.24) UF AU TH) 4 BUTT, DP — {A+ BICT,— DICT, ~D=4CU TT," 1K Ty/e)"* (73.25) A+BT, + rCyT (B~ EKCT F(T la) (73.26) ECuCTy — Dy FERC R(T, ~ Dy" yf) (73.27) Tr. PI In particular, for a pure fluid we obtain Were pt aT . Z2+2414B 6 T, anes N 2b Z~0.414B ar=- n(2) (58) Eqs. (44), (54) and (57) are exactly the same equations given in the original reference for the compressibility factor, fugacity coefficient and resi- dual enthalpy. Our formulation further enables us to obtain a more explicit form of Eq. (57). As suggested by Table 4 we have from Table 3: (133) i TE. ont (73.10) =) Tk ~kiyat ain For temperature-independent binary interaction parameters (ky), the last term in the right hand side Vanishes. From Tables 4 and 3, Blnag x aint) > (73.18) and finally: (Zeyh o(2)"] (9) Appendix A The coefficients of the volume polynomial gy defined by Eq. (5) may in general depend on the system tempeyature and composition. Partial deriva- tives of gy with respect to either T or Nj have the common structure DV + sNb? a (Al) where differentiation is denoted by a prime, and we define 106E, A. MULLER, C, OLIVERA-FUENTES, L. ANTONIO ESTEVEZ pono aouarayou ut oqydxe You Suottoung ammyesedtO (4) Henan abuareyos ur pasodowd sojnu Tupxiut ON (6) ) (iad OTK = = o= a Te oO & © 5 ep oe 02 $= ore @=at =e =a T= eo as (srw) o= et es Oo w © (a) Glas) 29 HORPY eb t= o= o= ar o o 8 (GAB fe preoy = = = 3 3 Guo ppey & o= o= o= Hi o Oo Gone ees ous a1 01 soa erup o= o= o- Wek z z z“OLy woman, tergtoy arb o= o= 02 Ore G=at=m6 C=aT=96 toot Corse a o- o- o= sore GO Col =D 2 Oly oeuagapranes @ o= o> o= wz @ on a) ()—duyestouny @ o= o= o= i z= =O o sual 12 1.419 pea vRNES uo o- o= woe I= z= zoo satpuns-nx n wero o= o= o= “won't Les ze z «pur renaotans uD o= o= o= more i a Pacis reuse osu 054 «ez o= o- o= a o= I= @ 10 9 snsepuns ip) o= o= o> or‘or'e o= t= 2 oD o= o= aore |= ert o= I= on eo o= o> os Ore o= t=O rey neous 6 o= o= fa o= i= rp wus uo o= os wo o= t= z e worpneN oD o= o= oe o= te i og wo o= o= o- o= I= z wos e=or op o- o= o= " o- t= z € Suow AbD (put pur ut Wo orez=, =a = L a @ © © © “we pvosiem wD o= o= oF GD @=az=6 Hat = U5 7 3 ates (9c eget 9) 9 (@) @=az=0L eget o= sce =a'2-6 =a =96 zoe aan ray o= = Ore « o= oe = o= o= too wusuo ste 20 uA a am a ay im " 5 woRIe/S08 = onea 10 EL “€ a8, WF SHORES = ongea 10 521, IG, WF suopENbg |s031 29n9 wowi09 awwos Jo} saapoayap eamjozodwes puo uoptBoduon —"p IACI, 107Latin American Applied Research refenwy=n[u 1 252). poe Rather than obtaining the corresponding deriva- tives of Iy directly from the appropriate form of Eq. (7), it is preferable to work these out from Eq. (4) by interchanging the differential and integral opera- tors. Vet fae = By a \° vav | oy (a4) The last two integrals have analytical expressions that depend on whether the discriminant A of Eq. (6) is zero or nonzero: ifa%0 ifa=0 (As) Vvav 1 [uv +2wNb f= Ee a] rao 'e By? NbA &y ly? (uNbly +3] ha = (a6) Combination of Eqs. (A4) - (A6) finally gives ly = ppl PND Cre 29K as] / ira4o rh (AT) ifA=0 In obtaining the last equation, we have taken advantage of the fact that the combination of terms (ru~2s) vanishes identically when A = 0 In the main text, rj, sj have been used for the auxiliary variables 7, s when the differentiation implied in Eqs. (A2) and (A3) is performed with respect to Nj. Similarly, rp and sy have been used in the case of temperature derivatives, 19: 99.109 (1989) ‘Symbols a EOS parameter A dimensionless EOS parameter, aP/(RT)? A total Helmholtz energy A dimensionless Helmholtz energy, A/(NRT) b EOS parameter B dimensionless EOS parameter, bP/(RT) g ‘quadratic polynomial in Z,Eq (30) & quadratic polynomial in V, Eq (5) G total Gibbs energy G dimensionless Gibbs energy, G/(NRT) H total enthalpy H dimensionless enthalpy, H/(NRT) 1 auxiliary variable, Eq. (33) Ty EOS integral, Eq. (7) k binary interaction parameter N total amount, moles P pressure Q auxiliary variable (Eq. (32): Qj; Eq. (37): Qn) r auxiliary variable Eq. (A2) (Eq. (13); 13 Eq. (23): rp) al gas constant auxiliary variable, Eq. (A3) (Eq. (14): Eq. (24): sr) s total entropy s dimensionless entropy, $/(NRT) 1 temperature u EOS parameter U total internal energy U dimensionless internal energy, U/(NRT) V total volume w EOS parameter x mole fraction Zz compressibility factor, PV/(NRT) Greek alphabet 4 BOS discriminant, Eq. (6) 6 fugacity coefficient © acentric factor 2 generalized EOS parameter Subscripts i ‘of component i in a mixture ii of pure component i ij of component pair i,j [i] all components except i “i generalized composition derivative, Eq. (10) -T generalized temperature derivative, Eq. (35) Superscripts r residual property at (T, V. N} Residual property at {T,P, N} composition or temperature derivative 108E, A. MULLER, C, OLIVERA-FUENTES, L. ANTONIO ESTEVEZ References 1. G. Schmidt and H. Wenzel, Chem. Eng, Sei, 35, 1503 1980). 2. A. Harmens and H. Knapp, Ind. fing. Chem. Fundam., 19,291 (1981). LH. Vera, MJ, Huron and J. Vidal, Ghem. Eng. Comm, 26,311 (1984. J. Mollerup, “Thermodynamic properties from a cubic ‘equation of state", SEP 8601, Instiuttet for Kemitek- rk, Lyngby, Denmark (1986). G, Wilezek-Vein and J.H. Vera, Fluid Phase Equil, 37, 241 (1987). M.M. Abbott, in “Equations of state in engineering and research” edited by K.C. Chao and R.L. 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