A GENERALIZED PATEL-TEJA EQUATION OF STATE FOR POLAR AND NONPOLAR FLUIDS AND THEIR MIXTURES Key Words: Mixtures, Generalized EOS Introduction Patel and Teja! proposed a three-parameter cubic equation of state (EOS) which has proved to provide ‘good representation of vapor-liquid equilibrium (VLE) for several mixtures. The Patel-Teja (PT) equation contains two adjustable empirical parameters which can be calculated using vapor pressure data for pure ‘components. Patel and Teja”? reported values of these parameters for 34 substances. More recently, George ton ef al.® have recalculated these parameters and havealso provided the values for 29 more substances. Patel and Teja!) were able to correlate the two empirical parameters in terms of the acentrie factor. However, the correlations are valid for nonpolar fluids, only. Valderrama and Cisternas® correlated the = Raa ea, Sarone coming i dB VoL 23 No.1 1990 Jost O. VALDERRAMA Chemical Enginering Department King Fokd Univ of Petrolewn ‘and Minerals Dhahran 31261 Saudi Arabia Equation of States, Vapor-Liguid Equilibrium, Patel-Tega EOS, Cubic Equations of State parmeters in the PT equation in terms of the critical ‘compressibility factor. The correlations, however, are not of general applicability.” Therefore, the two parameters in the PT equations should, in principle, be calculated from vapor pressure data. Another problem with the PT equation is the introduction of an additional mathematical complexity which is not present in other common cubic EOS such as the Soave-Redlich-Kwong® or the Peng-Robinson”” equations, This problem is the solving of an additional cubic equation for one of the three parameters of the EOS. Table 1 gives details, In this note I propose new generalized correlations for the parameters in the PT equation. These correlations solve the problems mentioned above by transforming the equation into a generalized EOS and by eliminating the necessity of solving any additional equation. Therefore, the generalized proposed equa- tion of state regains the form of the standard w‘Table 1. Pate-Teja equation of sate Equation of sate PRT —1) aT VU +0) (V—8)] a= O,RT2IP, PORTS, en O.RTP, 7) =04 RJT? 27) 4 +13, 2, the smallest positive root of the cubic: M+ O31) +37, 2=0 F and y are adjustable empirical parameters Values of F and 7, for 63 substances are given by Georgoton eral? For nonpolar fuids only, the following correlations in terms of the acenri factor o can be sed F=0.45213+1 3098002959370" 112=0329032—-00767990+0.02119470 For mixtures two-parameter EOS (such as Soave or Peng- Robinson) with the advantage of having an extra generalizing parameter. 1, Development of Equations ‘The cubic equation under study is: RT agp) V—b ViV+b)+eV—6) ® where 4.=QR°T3P, b=Q,RT,{P. Q c= ORT JP, a(T,)= [1+ FV TP @) In the original PT equation, the coefficients 2,, 2, and Q, are calculated, using an empirical critical pa- rameter 7. as shown in Table 1, The coefficient F is the second adjustable parameter in the PT equation, Since the work of Georgeton et al.”, values of 7, (and therefore of @,, 2}, and Q) and F for 63 substances are available. Several pure-component properties were considered to generalize F and the @'s, The best correlations have bbeen found with the use of the critical compressibility factor for the ’s and with the product [acentric ig. 1. Conelation for the parameter ©, as 8 function of the critcal compressibility Iactor Fig. 2. Correlation forthe parameter 0 as a function of, the eitcal compressibility Factor Fig. 3. Correlation for the parameter Q, as a function of the ertcal compressibility factor factor] x{eritical compressibility factor] for the coefficient F. Figures 1 to 4 show the correlations. ‘These findings corroborate other results presented in the literature in which these two properties (acentric factor and critical compressibility factor) are used to JOURNAL OF CHEMICAL ENGINEERING OF JAPANFig. 4. Correlation forthe parameter Fas function ofthe grup [acentre factor] xertcal compressibility fctor} ‘Table 2 Proposed generalized PTV equation of state Equation of state PHRTIV—B)~aalT AVN +) +V—B), ATED, T9)=[14 I-VI ,=066121-0.76105.2, 0,-002207.020868.2, a 57165 1.87080.2, 046283 +3,58230(0-Z) +8.1981%0-2,)" For mistures| ae EE sys y= (0a)70— hy) bea Enb and cD) Expressions for the purecomponent fugacity and for the fugacity of a component in a mixture can be obtained from references (1) oF Q) generalize equations of state.**~" The advantages and disadvantages of using Z, as a generalizing parameter have been discussed elsewhere.'?" The proposed correlations are: 2, =0.66121 —0.76105-Z, 2, = 0.02207 + 0.20868-Z, “ 2,=0.57765—1.87080°2, 46283 + 3.58230(0Z,)+8.1941T(c7-Z,)? 6 Values of F and the Q's using these correlations are represented by the solid line in Figs. 1 to 4, The proposed generalized EOS is summarized in Table 2. VoL. 23 wo. 1 1890 \E cS Fig. S. Prediction of compressibility factor of several substances using the generalized Patel-Teia equation of state, Literature data (@) are from Schlunder'* Fig. 6. Predvction of vapor pressure of several substances ‘using the generalized Patel-Teja equation of state. Literature data (@) are from Sehlunder'® 2. Application of the Generalized EOS ‘Vapor pressure, liquid: and vapor-phase compres- sibility factors, and vapor-liquid equilibrium in mixtures have been predicted using the proposed correlations. Some results are shown in Figs. 5 to 8. ‘A more extensive study of the application of the proposed equation is in progress. Conclusions. ‘The empirical parameters of the Patel-Teja equation of state have been correlated in terms of the acentric factor and of the critical compressibility factor. The new PTV equation of state is a generalized equation in which no adjustable parameters are needed. TheFig. 7. Prediction and correlation of bubble pressure for the ‘COpsthyl acetate system at 313 K Experimental data are from Ongaki and Katayama'®? - 8 Equilibrium ratios at three temperatures for HS and nonane using the generalized Patl-Teja equation of state ‘The full lines are calculated values and the points are ‘experimental values from Eakin and de Vaney'® equation has given good results for pure polar and nonpolar fluid properties and VLE in mixtures containing polar and nonpolar substances. ‘Acknowledgement ‘The author thanks the King Fahd University of Petroteum & Minerals for its support, Mr. Ahmed A. Ibrahim for performing some of the calculations, and Me. Tasuddug Husain K. Rahman for the typing ofthe manuscript. Note ‘A computer program t0 perform VLE calculations using the ‘proposed EOS is availabe from the author, Hard printed copise (oF diskettes can be obtained upon request [Nomenclature a = force constant atthe critical point 44,4, = forceconstants for components and inthe misture a, = cross-foree constant in the mixture om force constant for the mixture be volume constants dye = volume constants for components é and jin the smisture besa = volume constants for the mixture FOS equation of state P = adjustable empirical parameter ky = binary interaction parameter Pp pressure PB = critical pressure Pr = Patel-Teja equation of state R ideal-gas constant Tr = temperature r, = critical temperature 1. = redoed temperature v ‘molar volume VLE = vapor-iguid equilbsium 5% mole actions of components and jin the mixture Zz = compressibility factor Zz = critical compressibility factor = temperature function adjustable critical parameter force constant coefficient = volume constant coeficients = cent factor Literature Cited 1) Teja, A.S. and N.C, Patel: Chem Brg. Comm. 13, 39-53, 098i), 2) Patel, N.C., and A. S. Teja: Chem. Bug. Sei 37 (3), 463-473, (4982), 3) Georgeton, G. K., RL. Smith, and A. S. Teja: pp. 434-451 in Chto and Robinson." 4) Valderrama, J.0., and L. A. Csternas: Fad Phase Egull, 29, 431-438 (1980), 5) Valderrama, J. 0 10th TUPAC Conferenoe om Chemical ‘Thermodynamics. Prague, Caschoslovakia (Aug. 2-Sep. 2, 1988). 6) Soave, G.: Chem. Eng. Sei, 7, 1197-1203 (1972), 1) Peng, D. ¥. and D. B. Robinson: Jad. Eng. Chom, Fundam, 1X(1, 59-64 (1976) 8) Lest, W. A., HEM, Lin and K. C. Chao: dnd. Eng. Chem. Fundam, 28, 85-701 (1986). 9) Tang HL! Int J. Chom. Eng., 27 (1), 148-184 (1987) 10) Watson, P., M. Casella, 8. Salemo, and D. Tassos: Fuld Phase Equil, 27, 35-52 (1986). 11) Valderrama, J.O-and A. A. Ibrahim: to be published in Fluid Phase Equi. 12) Leland, T. W. and P. S. Chappelear: Ind. Eng. Chem, 60, 15-43 (1968), JOURNAL OF CHEMICAL ENGINEERING OF JAPAN13), Valderrama, JO. and L, A. Cisternas: Chem, Eng. Sei, 42 16) Eakin, B. and W. de Vaney: AICHE Symp. Ser, 70, 0-90 (12) 2957-2961 (1987) 974), 14) Schlunder, E. U. (editor): “Heat Exchanger Design 17) Chao, K. C. and R. L. Robinson (editors: “Equations of Handbook, Vol. 5. Hemisphere Pub. Corp. USA (1983) ‘State, Theories and Applications" American Chemical Society 18) Ohgaki, K. and T. Katayama: J. Chem. Eng. Data, 20 3), ‘Symposium Seris No 300, Washington D. C. (1986) 264-267 (1975). VOL 23 wo. 1 1980 7