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elsevier. E-mail addresses: polishuk@ariel. 0378-3812/$ – see front matter © 2010 Elsevier B. Koak et al. Theory The SAFT EOS models treat the compressibility factor as a combination of terms representing different inter-molecular interactions: Z = Z repulsive + Z attractive + Z associative (1) ∗ Tel.fluid. the SAFT EOS models are expected to be robust and reliable in the entire thermodynamic phase space. while the VLE matching the experimental data might be in fact metastable. The comprehensive reviews of different SAFT EOS models are available elsewhere [1–5]. which makes their general analytical investigation relatively easy. In addition. 2. However the reasons of this behavior have not been investigated with great details. It has been concluded that this behavior appears to be inconsistent with the intention of the original theories and it needs to be resolved (see also [9]). Based on the advanced molecular approaches. The associative term includes logarithmical expressions for the volume.13] have demonstrated that the predictions of PC-SAFT [14] are affected by crossing of isotherms. It is demonstrated that the unrealistic phase splits might present the globally stable states established by the models. [12.com/locate/fluid About the numerical pitfalls characteristic for SAFT EOS models Ilya Polishuk ∗ Department of Chemical Engineering & Biotechnology.ac.07.Author's personal copy Fluid Phase Equilibria 298 (2010) 67–74 Contents lists available at ScienceDirect Fluid Phase Equilibria journal homepage: www. namely the multiple critical points for pure compounds. thus far several studies have reported some worrying results. while the smallest practically unrealistic root is more stable than the realistic ones. However. All rights reserved. The first factor is responsible for predicting the negative values of the heat capacities at very high pressures and the intersections of isotherms at high densities. The undesired predictions discussed in the present study arise queries regarding the robustness and the over-all physical validity of the models under consideration in their present forms. The predictions of the excessive phase equilibria for large variety of pure compounds exhibited by PC-SAFT have been recently discussed in great details by Privat et al. namely the temperature dependencies of a segment packing fraction and the very high-polynomial orders by volume. attributed to the polynomial expression of the dispersion term. All rights reserved. Israel a r t i c l e i n f o a b s t r a c t This study demonstrates that SAFT EOS models might exhibit the practically unrealistic and even nonphysical predictions due to the two factors. This study discusses the ways of removing the numerical pitfalls. [6] have investigated the effect of the Chen–Kreglewski (CK) [7] dispersion term on the pressure–volume behavior of two non-associating pure components predicted by the CK-SAFT of Huang and Radosz [8]. doi:10.2010. which substantially hinders its analytical investigation. © 2010 Elsevier B.il.: +972 3 9066346. Article history: Received 30 May 2010 Received in revised form 3 July 2010 Accepted 5 July 2010 Available online 13 July 2010 Keywords: Equation of state Statistical association fluid theory Phase equilibria Global stability 1.ac.il. The very high-polynomial orders of several SAFT EOS models result in prediction of the additional stable unrealistic critical points and the pertinent fictive phase equilibria. fax: +972 3 9066323. [15].V. Hence the question of an over-all consistence of this term has been left outside the scope of the present study and it . It has been demonstrated the P–v isotherms exhibit multiple volume roots at low temperatures and volumes. In particular. The comprehensive studies of Yelash et al.V. 40700 Ariel. In the paper discussing the numerical pitfalls introduced by the Soave-type -functions in Cubic Equations of State [10] it has been demonstrated that the theoretically based models such as the SAFT version of Huang and Radosz [8] and Johnson–Zollweg–Gubbins approach for the Lennard–Jones fluids [11] exhibit the practically unrealistic predictions.1016/j. the excessive complexity of certain SAFT models might result in wrong prediction of auxiliary thermodynamic properties of the experimentally available fluid phases. polishyk@bgumail.003 In most of the cases the first two terms are the polynomial expressions by volume. and by appearance of practically unrealistic phase equilibria. The aim of the present study was detection and investigation of the numerical pitfalls exhibited by several popular SAFT EOS models necessary for further development of their consistent versions.bgu. It has been concluded that the unrealistic phase behavior can be a problem when the model is applied to polymer solutions and polymer blends. attributed to the temperature dependence of hardsphere diameter. Ariel University Center of Samaria. Introduction The EOS models based on the Statistical Association Fluid Theory (SAFT) are among the most important approaches for modeling thermodynamic properties of pure substances and their mixtures.

(2) results in decrease of covolume with temperature. (2) is the model’s covolume. 4. experimental data [20]. at high-pressures volume will decrease with temperature and the isotherms will Fig. 5.12. Lines of zero CV predicted by several versions of SAFT for ethane. 3. dashed line. Fig. experimental data [20]. = 0. It can be seen that Eq. In other words. As a result. exponential expression Non-applicable. 2. . should be considered in future studies. Polishuk / Fluid Phase Equilibria 298 (2010) 67–74 Table 1 Phenomena of the multiple critical points generated by the non-associative SAFT EOS models considered in the present study. [21] for ethane. For example. 9000 bar. 1. The numerator of Eq. the infinite pressure is approached at the smaller values of volume. after formulating the appropriate approaches for its general analysis. The numerical pitfalls of the repulsive term are generated by the temperature dependence of the reduced density Á. solid line. .74048 and C = 0. CV of ethane predicted by SSAFT [19]: 100 bar. and . Fig. . . as the temperature rises. Intersection of isotherms predicted by SAFT of Chapman et al. experimental data [20]. exponential expression Appearance of the phenomena No No No No Yes Yes Yes Yes Yes Soft-SAFT [25] m = 1 / Yes Fig. where uo /k and Voo are the positive compound-specific parameters.Author's personal copy 68 I. Intersection of isotherms predicted by SSAFT [19] for ethane. or the volume at the infinite pressure. and . according to CK-SAFT of Huang and Radosz [8] it is given as: Á= V oo (1 − C exp[−3(uo /k)/T ]) V 3 (2) Fig. and . The 120 K isotherm of nitrogen predicted by CK-SAFT [8]. Model SSAFT [19] m = 1 SSAFT [19] m = 1 / Original SAFT [21] m = 1 Original SAFT [21] m = 1 / CK-SAFT [8] m = 1 CK-SAFT [8] m = 1 / Simplified PC-SAFT [24] m = 1 Simplified PC-SAFT [24] m = 1 / Soft-SAFT [25] m = 1 Polynomial order by volume 5 6 8 9 13 14 19 24 Non-applicable. .

33 50.9 46646. Fig.04 151.15 39. experi- Fig.20 682.4 32643. The latter phenomena might affect different models with the different degree of extend.71 725. . [16].24 92. Departure Gibbs energy – pressure projection of nitrogen generated by CK-SAFT [8] at 150 K. The same effect is characteristic for other expressions of covolume exhibiting similar behavior.85 146. Another serious drawback of the temperature-dependent covolumes is the description of the caloric properties at high pressures. This is because the mechanical limit represents a response of higher-order than the thermal limit [17.Author's personal copy I.74 242.56 192.18]. experimental data [23].59 311.16 60. In particular. mental data [21]. since the mechanical stability limit will be violated before the thermal limit.95 191.1 34125. While some models. such as the CKSAFT of Huang and Radosz [8]. Compound Nitrogen Argon Methane Carbon monoxide Ethane Carbon dioxide Water Tc1 (K) 127. 7. Polishuk / Fluid Phase Equilibria 298 (2010) 67–74 Table 2 Critical points predicted by CK-SAFT [8] for several pure compounds.28 48.45 320. it has been proven that any temperature dependency of the covolume necessarily results in infinite negative value of the isochoric heat capacity at the infinite pressure. 6. exhibit the negative isochoric heat capacities at the extremely high pressures (the reason will be dis- Fig. Two-phase envelopes of pure nitrogen predicted by CK-SAFT [8].75 254. The 120 K isotherm of nitrogen predicted by CK-SAFT [8] at high densities. . Fig. 8. The 150 K isotherm of nitrogen predicted by CK-SAFT [8].7 63525. it cannot actually occur.8 69 Fig.7 26131.88 Tc2 (K) 159. Considering a fact that the models with the temperature-dependent covolumes exhibit the negative CV under conditions of mechanical stability. 10.38 Pc2 (bar) 23870. such predictions should be considered as non-physical. It should be pointed out that although CV < 0 is mathematically possible. 9.61 320. . intersect in contradiction with experimental facts. as recently demonstrated by Kalikhman et al.7 166350.95 Pc1 (bar) 35.17 136. Two vapor pressure curves of pure nitrogen predicted by CK-SAFT [8].50 422.

In what follows let us consider the particular models.5 144762. 2 presents the zero values of CV predicted by several versions of SAFT for ethane.27 59. Two vapor pressure curves of pure ethane predicted by CK-SAFT [8]. Polishuk / Fluid Phase Equilibria 298 (2010) 67–74 Table 3 Critical points predicted by CK-SAFT [8] with D29 = 0. . experi- . However the model is still affected by the temperature-dependent covolume. the number of the solutions increases. Fig. 3. Fig.3 45041. At the volumes lower that C the isotherm should approach the infinite pressure.29 319. 4 depicts the intersection of isotherms predicted for ethane and Fig. experimental data [20]. However. The points A. the other ones might yield the non-physical predictions at much lower pressures [16].26 47. which are still very high (14. if the polynomial order and. 3.18 Tc2 (K) 16. 13. 3. B and C represent the realistic phase envelope matching the experimental data (A is the vapor and C is the liquid solution). then it must fire in the last act” [22]). and the extrema ˛ and ˇ represent the spinodal. Fig. Table 1 lists several popular SAFT EOS models. consequently.87 135. As the polynomial order becomes higher. 1 depicts the intersection of isotherms predicted by SSAFT [19] for ethane.2 43542. [21] Although this model has a relatively high-polynomial order (see Table 1).1 22. Fig.02 29. Fig. mental data [20].88 Pc2 (bar) 36477. In particular.97 91.53 16.1.4 86343. cussed below). 2 presents the zero values of CV .87 60.0 260270. The minus departure Gibbs energy – pressure projection of nitrogen generated by CK-SAFT [8] at 120 K. The complex solutions and the solutions smaller than the covolume should be considered as the “numerical noise” having no impact on the performance of the model. CK-SAFT of Huang and Radosz [8] The polynomial order of this model is higher than in the previously considered cases (see Table 1) and analysis shows that it may exhibit up to five real solutions for molar volume bigger than the covolume. Compound Nitrogen Argon Methane Carbon monoxide Ethane Carbon dioxide Water Tc1 (K) 125.06 Pc1 (bar) 33. irrelevant for most practical implementations. the additional practically improbable real solutions bigger than the covolume appear. as Fig.3. . 3 demonstrates that SSAFT substantially underestimates the experimental CV data at 9000 bar.1 Fig. 12. but might also be dangerous like the famous Chekhov’s gun (“If in Act I you have a pistol hanging on the wall.15 45. their polynomial order (when applicable) and appearance of unrealistic volume solutions.32 38. Two-phase envelopes of pure ethane predicted by CK-SAFT [8]. However the temperature dependence attached to its covolume still affects its robustness.2. 11.78 320. the EOS models yield more solutions for the volume.Author's personal copy 70 I. SAFT of Chapman et al. However. whose analytical calculation is not always possible.31 409. It can be seen that SSAFT starts to predict the non-physical negative values at the lowest pressures.32 45.900 bars and above). However it would not be surprising that these undesired phenomena have an impact on modeling the experimentally available caloric data. These multiple real solutions are not only excessive on the thermodynamic phase scene. the additional practically unrealistic solutions for the volume have not been detected.54 149. which should be explained by the behavior of the model at higher pressures.87 721.54 17. Fig. 5 depicts the isotherm predicted by the Huang and Radosz’s version of CK-SAFT [8] for nitrogen at 120 K. Simplified SAFT (SSAFT) of Fu and Sandler [19] This model has the lowest polynomial order among the SAFT models (see Table 1) and it does not exhibit the additional practically unrealistic solutions for the volume. The attractive terms of SAFT EOS models typically present polynomials adjusted to the theoretical expressions.74 189.2 44798. Results 3.

It can be seen that the two excessive solutions (E and D) deform the thermodynamic phase space established by the model. 9 depicts the isotherm at 150 K of nitrogen. Departure Gibbs energy – pressure projection of ethane generated by CKSAFT [8]. Table 2 lists these critical points for certain pure compounds. 11 is not trivial because the practically unrealistic phase behavior generated by the model under consideration cannot be explained by experimental facts. Thus. SAFT exhibits five real solutions bigger than its covolume. 14. 2. However at the coexisting of two-phase equilibria the picture becomes complicated (see Fig. It can be seen that the stable. pure compounds. Polishuk / Fluid Phase Equilibria 298 (2010) 67–74 71 Fig. The interpretation of Fig. There are no phase equilibria between the liquid phases. 3. As discussed previously [10]. therefore.Author's personal copy I. two spinodal loci and two-phase equilibria are generated simultaneously: the saturation pressure 1 in the vicinity of experimental datum and the unrealistic saturation pressure 2 located at the deep vacuum. It can be seen that this time it takes a conventional form (three solutions and two extrema). 11. the metastable (A = E − and A = E − ı) and the unstable (ı − D − ) parts exhibit a robust behavior characteristic for phase equilibria in pure compounds. Fig. As a result. Fig. two practically unrealistic extrema and ı appear (additional details are shown in Fig. experimental data [26]. Thus. noticed. Globally stable phase diagram of methane predicted by SOFT-SAFT [25]. Three facts can be observed: 1. although in total disagreement with experimental facts. − G is used for creating the logarithmic scale). 7 and 8 depict two vapor pressure lines and two-phase envelopes predicted by the CK-SAFT [8] for nitrogen. at such conditions the liquid-2 (solution E) presents the most stable phase. there are no doubts regarding the stability of VLE-2 above the critical point 1. at the GE closer to zero than the VLE-1. Fig. Let us consider nitrogen at some point along VLE-1. 6). . 10 presents the excess Gibbs energy – pressure projection for this isotherm. As noticed. The VLE-2 take place at the conditions closer to the ideal gas state and. 15. the model exhibits at least two critical points for . Figs. The liquid-2 (solution E) is more stable than the liquid-1 (solution C) and the VLE-1 at the pertinent pressure.

100 bar. 5000 bar. 16. Thus. and therefore both are globally stable. 200 bar. Yet vapor has lower G than LLE and liquid-2 has lower G than VLE-1. . Thus. . 5 and 6) until appearance of VLE-2 at the deep vacuum. at T < TLLVE the situation gets different. Thus. However it should be noticed that in the present case the numerical pitfalls significantly affect the accuracy of the model. Table 2 shows that for some compounds CK-SAFT [8] generates the realistic critical points at the temperatures higher than the unrealistic ones. similar behavior has been described by Privat et al. 12 and 13 depict the globally stable parts of the ethane’s phase diagram as predicted by CK-SAFT [8]. Thermodynamic properties of methane [26] at high pressures as predicted by SOFT-SAFT [25]. Polishuk / Fluid Phase Equilibria 298 (2010) 67–74 Fig. the realistic VLE-1 is actually metastable and the unrealistic VLE-2 represents the globally stable phase diagram established by CK-SAFT [8]. [15] for PC-SAFT. In particular. it can be seen that at the T > TLLVE both VLE-1 and LLE do not face other phases with lower G at the pertinent pressures. An explanation is provided in Fig. 10. . Figs.Author's personal copy 72 I. only the unrealistic VLE2 is now globally stable. . .000 bar. at the conditions of VLE-1 and in the varying-volume vessel nitrogen is supposed to shrink into this highly compressed liquid. Remarkably. 2000 bar. . 1000 bar. However. 14. It can be seen that yet at least some part of the realistic phase equilibria (VLE-1 above LLVE) is globally stable. . However even the microscopic increase of the vessel’s volume should result in a drastic fall of pressure (see Figs. . according to CK-SAFT [8]. 500 bar.

The latter ones are supposed to be robust and reliable in the entire thermodynamic phase space. Thermodynamic Models for Industrial Applications. Ind. Investigation of the maximal equation orders free of the numerical pitfalls is essential for further progress of SAFT. In addition. It would be tempting to find a relation these two facts [17. A total disagreement with the experimental facts is evident. 4. Folas. For example. 16 demonstrates that Soft-SAFT [25] could be an incredibly accurate model for describing the high-pressure densities. Fig.8 bar.97 bar. it should be pointed out that CK-SAFT [8] unavoidably exhibits the numerical pitfalls characteristic for the previously considered simpler versions of SAFT.W. Chem. Thus. H.13. 3. CK-SAFT [8] generates the negative isochoric heat capacities at much higher pressures (see Fig. the excessive complexity of certain SAFT models might result in nonphysical prediction of auxiliary thermodynamic properties of the experimentally available fluid phases. Res. Polishuk / Fluid Phase Equilibria 298 (2010) 67–74 73 An artificial attempt of decreasing the polynomial order of CKSAFT [8] by considering the zero value for D29 might improve the situation (see Table 3). The same could be concluded regarding the Soft-SAFT [25]. E. Grant No. Res. R. Sadus. M. de Loos.64 K and Pc2 = 24371. List of symbols C integration constant of CK-SAFT [8] CV isochoric heat capacity k Boltzmann’s constant P pressure R universal gas constant T temperature uo /k temperature-independent dispersion energy of interaction between segments V molar volume Voo temperature-independent segment volume of CK-SAFT [8] W speed of sound Z compressibility factor Greek letters Á reduced density segment molar volume in a closed-packed arrangement Subscripts c critical state r reduced property Abbreviations EOS equation of state SAFT statistical association fluid theory Acknowledgment Acknowledgment is made to the Donors of the American Chemical Society Petroleum Research Fund for support of this research. K. It should only be noticed that the rescaled simplified PC-SAFT [24] does not exhibit an improvement in comparison with the original version. AIChE J. the unrealistic phase equilibria could interrupt the high-pressure LLE in asymmetric mixtures at high pressures. Hence. Th.A. Kontogeorgis.13]. Chem. G. However it can be seen that the significant part of the Soft-SAFT’s [25] fluid phase diagram is actually metastable because the artificial high-pressure phase split takes place above the compound’s solidification temperatures. G. the undesired predictions yielded by PC-SAFT [14] are not expected to affect most of its practical implementations. Remarkably. However since approaching the infinity pressure at low temperatures is yet hindered by the unusual forms of its isotherms. typically generates the unrealistic phase equilibria at relatively low temperatures [15] should not be neglected. 47 (2008) 8063–8082. Wei.G.5. Fig. 46 (2000) 169–196. John Wiley & Sons Ltd. Ind. it seems highly recommendable to make the segment packing fraction of SAFT models temperature-independent.E. the probability of numerical problems might increase with increasing the number of compounds in a mixture. some SAFT EOS models should be re-evaluated while using fewer coefficients. PC-SAFT [14] The case of PC-SAFT [14] has been already investigated with great details in the previous studies [12.S. From Classical and Advanced Mixing Rules to Association Theories. 3. . Res. Eng. Ind. Tc2 = 320. Pc1 = 50. in spite of its very high-polynomial order. However it can be seen (Fig. it results in negative values of the heat capacities at extremely high pressures. it predicts the negative values for the heat capacities and. Heidemann. Müller. Moreover. In addition. 41 (2002) 953–962. PRF#47338-B6. Soft-SAFT [25] The Soft-SAFT [25] EOS is based on the Johnson–Zollweg–Gubbins approach for the Lennard–Jones fluids [11].15]. 40 (2001) 2193–2211. Radosz. However the very concept of the model’s applicability is characteristic for empirical correlations rather than theoretically based approaches.18]. In addition. In addition. Conclusions This study demonstrates that the SAFT EOS models might exhibit the practically unrealistic and even non-physical predictions due to the two factors. Moreover. Nevertheless the fact that PC-SAFT.A.. 2). the current non-physical results could rather be explained again by the excessive complexity of the model under consideration. I. namely the temperature dependencies of a segment packing fraction (covolume) and the very high-polynomial orders by volume. 38 (2001) 1718–1722. heat capacities and sound velocities. wrong results for the sound velocities below 100 K. It could be argued that the temperature-dependent covolumes result in numerical pitfalls outside the range of the model’s applicability (extremely high pressures). New York.Author's personal copy I. Gubbins. Eng. Chem. 15 depicts the globally stable phase equilibria yielded by Soft-SAFT [25] for methane. Thus. Eng. Economou. while the VLE matching the experimental data might be in fact metastable.K. Finally. In addition. this practice does not affect the CK dispersion term radically.J.4. [6] N. One might anticipate for problems just in certain cases [12. as a consequence. In particular. Tan. for methane it predicts: Tc1 = 193.27 K. S. which however might affect the predictions of the experimentally available data as well. References [1] [2] [3] [4] [5] Y. the first factor is responsible for predicting the intersections of isotherms at high densities. it does not seem possible to cancel the numerical contribution of the repulsive term to the residual isochoric heat capacity at high pressures by other model’s terms. Koak. Res. Adidharma. The latter approach typically exhibits the additional artificial phase equilibria at the temperatures higher than CK-SAFT [8] (see for example [10]). Chem. Ind. R. It is demonstrated that the unrealistic phase splits might present the globally stable states established by the models. Eng. The very high-polynomial orders of several SAFT EOS models result in prediction of the additional stable unrealistic critical points and the pertinent fictive phase equilibria. 16a) that Soft-SAFT’s [25] still predicts the mechanical stability at the experimentally available fluid range.P.M. 2010.

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