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# International Journal of Thermophysics, Vol. 9, No.

6, 1988

**Selected Equation of State in the Acentric Factor System I
**

D o n a l d R. Schreiber 2 and Kenneth S. Pitzer 2

A new equation of state in the acentric factor system is developed on the basis of high-precision data. The region in Tr, Pr space where there is good agreement is identified, as well as the regions of significant departures. The equation fits very well in the critical region.

KEY WORDS: acentric factor; corresponding states; equation of state; virial

coefficient. 1. I N T R O D U C T I O N The acentric factor has proven to be very useful in the representation or estimation of fluid properties. In comparison with earlier three-parameter systems extending corresponding states, there were two important advances. The first was the use of theory [1] to indicate the characteristics of molecules which could be expected to follow accurately a pattern of behavior defined by To, Pc, and a third parameter. The second was the choice of an easily and accurately measurable quantity, the slope of the vapor pressure curve, as the basis for the third parameter [2]. Initially, the P-V-T and other properties were given in the form of tables [2, 3], although an analytical equation was soon developed for the second virial coefficient [4]. At the time of the original work, the best analytical equation of state failed to represent the experimental P V T behavior within experimental uncertainty [5]. Advances in electronic computers soon made it feasible, however, to use more complex equations, and various investigators have presented equations of state using the acentric factor. Some of these 1Paper presented at the Tenth Symposium on Thermophysical Properties, June 20-23, 1988, Gaithersburg, Maryland, U.S.A. 2 Department of Chemistry and Lawrence Berkeley Laboratory, University of California, Berkeley, California 94720, U.S.A.

965 0195-928X/88/1100-0965$06.00/0 1988 Plenum Publishing Corporation 9

e. 2. we included Ar. But others do provide analytical equations of good accuracy and wide applicability. and all of the normal paraffins through octane together with a selection of other fluids of different molecular types within the criteria given above for which there were data of high precision. original literature values were used. and of these we take that of Yamada [6] as the best example for comparison. Excluded are strongly polar or hydrogen bonding molecules such as H20. acids. The primary results and the selected equation are given below. of Rabinovich et al 1-8] for Ar. Also. and of Younglove and Ely [9] for the paraffins through butane. Table I lists the critical constants and acentric factors. In 1955. however. It is our purpose to revisit this subject with recognition of recent investigations of high precision. etc. it was shown that most nonpolar molecules of various shapes and sizes conformed to three-parameter system. the apparent discrepancies were within the experimental uncertainties for most. if their dipole or quadrupole moments are small.g. and Xe. DATA SELECTION From the theoretical analysis for the second virial coefficients [1 ]. Xe.. He. if not all. Wherever there were recent critical compilations. Molecules interacting primarily by dispersion (London) forces can be included. Dipolar effects follow a somewhat different pattern. Full details and references exceed the limit for this report and will be given elsewhere in a full account.000 (1) . The acentric factor definition is ~o= . Kr. The very light gases H2. It is now possible to determine the accuracy of conformity to the acentric factor theory. For the present research.7) .l o g Pr(at Tr = 0. an equation can be selected which represents fluid behavior to the accuracy to which various individual fluids conform to the three-parameter acentric factor system.1. It was never pretended that an acentric factor equation would express the true equation of state of a particular fluid exactly. the recommended values were adopted. those of Dymond and Smith [7] for second virial coefficients. and Ne had to be excluded because of quantum effects on their translational motion. alcohols. of those fluids expected to conform. Kr. since the discrepancies exceed the uncertainties of recent measurements. For several other fluids.966 Schreiber and Pitzer equations have limited ranges of validity or were intentionally simplified for convenience. however.

031 o) .3086 5.4766 37. where Pr is the r e d u c e d v a p o r pressure at Tr = 0.64 30.0 .40 45. dm 3) 13.41 10.215 2.76 Pc (bar) 48.74 190.21 469.59 3.85 540.9797 34.75 425.527 433.646 42.590 73.214 3. 1.002 0.20 282.011 0.004 .87 8.0.3452 305. (2) are s h o w n in Fig.100 0.398 Used only for the second virial coefficient calculation.86 209. and References for the Fluids Included in this Research 967 Fluid Argon Krypton Xenon Methane Nitrogen Ethylene Ethane Propylene Propane Tetrafluoromethane Neopentane Butane Sulfur hexafluoride a Carbon dioxide Pentane Hexane Heptane Octane Tc (K) 150. Also n e e d e d was a "best" expression for the c o m p r e s s i b i l i t y factor as a function of the acentric factor.087 0.153 0. The i n d i v i d u a l values of the critical c o m p r e s s i b i l i t y factor a n d the line for Eq.7105 2.979 54.39 289.70 304.0.53 126.87 Pc (mol.58 27.16 318. Thus. 0 7 8 7 c o (2) T h e asterisk is a d d e d to r e m i n d one t h a t this is the value from the e q u a t i o n r a t h e r t h a n the value c a l c u l a t e d from the r e p o r t e d critical p a r a m e t e r s of the p a r t i c u l a r fluid.57 369.303 0. b u t co can be e v a l u a t e d from a n y v a p o r pressure d a t u m well r e m o v e d from the critical point. C H O I C E O F F O R M F O R R E D U C E D DENSITY W h i l e the usual definition of r e d u c e d density is the simple ratio to the e x p e r i m e n t a l critical d e n s i t y pr=p/po.36 24.7.875 5.96 58.177 0.197 0.7143 46.370 10.208 0. Acentric Factors.037 0.1096 3.963 37.85 227.34 365.252 0.350 0.825 33.920 5.403 48.067 10.2905 .634 6.223 0.45 31.15 568.15 11.21 7. Critical Properties. A linear expression sufficed: z~ = 0.000 7.96 37.00 50. there is a significant a d v a n t a g e in the use of a r e d u c e d density .Equation of State in the Acentric Factor System Table I.69 507.200 0. the latter q u a n t i t y is n o t directly m e a s u r e d a n d is subject to c o n s i d e r a b l y greater u n c e r t a i n t y t h a n either T c of P~.141 0. 3.002 0.345 2.

1. We then fitted the complete equation and eliminated terms that were not significant. E Q U A T I O N O F STATE An extended Benedict-Webb-Rubin ( e B W R ) e q u a t i o n as developed by Jacobsen [10] was selected as the complete equation of state. instead of the one here defined.28 zC 0.24 I 0 ID[I I 012 01. (3) 4. and Pr which avoided the use of p. We considered the alternative forms p. The second form has the advantage of giving values approximately equal to those obtained from p . In the latter. 0 7 8 7 ~ 0. = p(RTc/P~) and p~ = p(z*RTc/Pc).. z* is the "standard" value of the compressibility factor for the acentric factor of the particular fluid from Eq. and the resulting terms were held fixed thereafter (Fig. = p / p c .3 0. In each case. we first fit the simple fluids. 2 9 0 8 . The original presentation of the acentric factor system was in terms of the compressibility factor as a function of T.4 Fig. (2). Since wide-ranging PVT data of numerous substances had been previously fit to this particular eBWR.30 A Kr C(CH3)4 9 •215 eCleCl ~ / 0. The line is the linear fit of the data [Ed. .0 .968 i i ~ i Schreiber and Pitzer J-- zc : 0 . Hence. But we now wish to use Pr along with Tr as independent variables in our equation.26 CF4 C3 C4 COz C6 & C I . The second virial coefficient was first fitted. (2)]. based on T c and Pc instead Pc. 2). we adopt the definition p* = p(z* RTclPr and the asterisk can be added to distinguish this quantity from P/Pc. Individual critical compressibility factors as a function of acentric factor. no gross error will arise if one uses the ordinary p.C 8 = normGI poreffin$ 0. Thus. we felt that it was flexible enough for our purposes.

with krypton and methane intermediate.t T r = 1. Xe. (4)] from the Ar. 0 5 ~ A ~ && AAA v vv vv vvv n ~ 2 Pr 3 OI 0 I Fig. and CH 4 data for two reduced-temperature isotherms. . A careful review of the data on a corresponding-states basis for the simple fluids Ar. Kr. Deviations of our calculated pressures [Eq. In that region argon showed the highest reduced pressures and xenon the lowest.5. especially at low reduced temperatures. and CH4 showed excellent conformity at low densities but significant deviations at reduced densities above 1.0 i A Ar u • 77 Kr 0 CH4 ? 'c~ a-~ 0 0 0. 3. Kr. Xe. (4a)]. Second virial coefficient data as a function of temperature for several sustances. l O.C4HIo -200 7 E -400 ~E o m -600 -800 -I000 200 300 400 5 0 T. The lines represent our calculated values [Eq.02 0 zx .O5 ~ Tr ~ 2. 2.q.K 600 r 700 q Fig.Equation of State in the Acentric Factor System 969 I I CF4 j .

Kr.. we chose methane as a model simple fluid.:. The final values of the parameters of the resulting equation are listed in Table II. 6 % for argon and about + 1.0 % for xenon. 1(D -1.Ci.970 Schreiber and Pitzer After exploring various methods for the derivation of a specific numerical equation. o -~. Xe.... = (c..Ci. significant deviations from the fit appear in the dense fluid region.2 (D2 (5) Figure 3 shows deviations of the data from our calculated values for two isotherms for Ar.o terms were those for methane. they are only about . Increased uncertainties were assigned to the pressure values at high reduced densities.p ~ ) Dr = c9 + Clo/Tr + ell/T~ E r = Cl2/T2r + C l 3 / T 3 (4c) (4d) F. and CH 4. Although these deviations seem large. The simple fluid equation was used in the overall fit without further refinement. removing the quadratic acentric factor-dependent terms first./Tr (c~7/T~+c~s/T~r)eXp(_pD H.1 . This resolved fitting problems in the dense fluid region. As was the case with simple fluids. Those for the paraffins (Fig. and the overall equation was developed by the addition of acentric factor-dependent terms. The deviations from the near-critical isotherm become significant above a reduced density of 1.5. Thus. if one considers deviations in Pr at given Pr. 4) start at approximately the same reduced density as for the simple fluids and are the . it should be noted that the 0 in Pr/O In Pr is about 6 in this region. while the rest were evaluated from a fit of the entire data base. The resulting equation after elimination of unnecessary terms was Z = 1 + B r p r + C r f l 2 + D r p 3 + Erp~ + Frp7r + Grpgr + H rPr + I r P r12 ~1o (4) (4a) (4b) B r = c 1 + c2/T r + c3/T 2 + c4/T 6 C r = c 5 + c6/T r + c7/T 3 + (cs/T4r) e x p ( .. as seemed appropriate for these incompressible regions. Terms that were not significant were then eliminated from the equation..p2) I. Thus.1/T~ + c22/T4~ ) exp(--pr2) with Pr = P* throughout and Ci = Ci. = (c19/T3r + c2o/T~) e x p ( . = c14/T~ + c~5/T~ (4e) (4f) (4g) (4h) Gr--cl. the ei.

262028 0.904622 8.687471 0.204099 8.02 i Pr Fig.102699 -0.4158241 0.398844 -1.005896265 0.8842722 0.24976 -0.2432806 1. as in Fig. I A n-Pentane o Neopentane r7 n-Heptane o O ~ ~ n o~ ~A V u O.3266766 -3.2191255 ---10.7812220 1.306706 4. a n d n-heptane.0004665477 -0.01945101 0.442259 -0. 2 cI c2 c3 ca c5 c6 c7 c8 c9 c~o cll q2 c]3 c14 ca5 q6 q7 c18 c19 C2o c21 c22 0.872169 -6.5515101 -2.04541961 -0.04083643 -0.180988 0.04382625 1. 3.725650 0.190046 ---- i i O.1375109 -0.002877955 0.0910596 -1.6361056 0.696068 3.002338 -14.2104505 0.00419959 0.14146 -9.41174 15.005969554 0.76854 -0. o Ci.00515624 0. for n-pentane.1786378 -2.521409 2.15 ~ ~ z ~ V ~V T r -~ 1.456041 --0.02450537 -0.3412103 -0.1513654 -0.129384 0.7914067 -0.03546917 -0.1443457 -0. .Equation of State in the Acentric Factor System 971 Table II.218714 -1.40386 11. v oo T r ~ 1.286932 0. (4) Ci. Coefficients for Eq.189187 2. 4. neopentane.980970 -0.826772 4.611142 -0. 1 Ci. r Deviations.008759626 0.

l ~ Pr I 2 3 Fig.205 3.648 0.274 0.969 .378 0.396 2. Deviations.355 0.699 0.983 2.152 0. and C3H8.I Tr ~ 1.406 0.827 0.02 ~7L~ 0 oo a~ L~ ao~ ~ - O o .647 0.573 1.711 0.647 1. in pressure (%) Fluid Argon Krypton Xenon Methane Ethylene Ethane Propane Carbon tetrafluoride Neopentane Butane Carbon dioxide Pentane Hexane Heptane Propylene Total Number of data 260 149 233 208 231 281 178 139 306 223 273 140 51 54 99 2825 This work 0.833 0. for CO2. I V Propane Z~ Propylene Tr = [ . 5. x O.342 0.783 0.291 0.364 0.972 Schreiber and Pitzer J o CO 2 O. abs.609 0. ~ o Io. 3 0 v ~ ~-O.456 0. C3H6. 3.007 1.353 0. Table IlL Comparison of Equations of State with the Data Base Avg.109 2. as m Fig.588 0.527 I.547 0. dev. 133 0.336 0.584 Yamada [6] 0.

Equation of State in the Acentric Factor System 973 opposite sign for the two pentane isomers.0.mol . In general. Our equation. as well as including some near critical data. but guided by his data base.dm -3 Fig. It is interesting to note that the agreement for propylene (Fig. D I S C U S S I O N A comparison of our fit with that for the 44-parameter equation of Yamada [6] is shown in Table III for a number of fluids using our data base. Our equation showed a significant improvement over Yamada's for fluids where our data covered a much larger temperature range. 6. does better for our data base over this range. That Yamada's equation does slightly better for a few fluids with data of limited temperature ranges is not disturbing. Yamada does not give a temperature limit. We adopted Yamada's reduced density limit of 1.8 for the comparison. since our intent was to develop an equation that could be used over a wide range of reduced temperature and density. is within the range seen for other substances. in general. 5. Comparison of Eq. (4) with the experimental C(CH3) 4 pressure data for the critical isotherm. we have limited the comparison to reduced temperatures less than 3.. 5). i i i i 35 Neopentone 9 = 34 j 33 P~bar 32 31 50 29 I 2 I 3 1 q [ 5 p . which was not used in the fit. we include a wider temperature and density range in our data base than did Yamada. .

T. Chem. Eng.974 Schreiber and Pitzer The other area in which we hoped to improve a generalized equation of state was in the critical region. of the U. 77:3433 (1955). 1980). Oxford. The Second Virial Coefficients of Gases: A Critical Compilation (Clarendon. Thermophysical Properties of Neon. thesis (Washington State University. Curl. V. B. AIChE J. C. 3. F. B. Ind. J. Office of Energy Research. 5. S. 9. Ind. Chem. Z. Ref Data 16:577 (1987). Sage.. and K. and K. Soc. A. K. 77:3427 (1955). B. Chem. C. Chem. K. Lippmann. REFERENCES 1. Yamada. 50:265 (1958. Rabinovich. Jr. J. this is shown for neopentane in Fig. Dymond and E. Am. B. Pitzer. Phys. H. Division of Chemical Sciences. D. F. S. Am. This aspect will be discussed fully in an expanded paper to be published soon. and D. Veksler. Am. J. 1988). Office of Basic Energy Sciences. Washington. . F. Soc. Smith. R. 7. Petersen. F. Pitzer. J.. Younglove and J. S. 6. Pitzer. 19:286 (1973). 1972). Pitzer and R. A. Curl.C. 3.D. A. Our use of many near-critical data enabled us to obtain a good fit in the critical region. J. B. ACKNOWLEDGMENTS This work was supported by the Director. Huggins. K. D. Ely.) 4. and L. 48:2069 (1956). 2. Ph. Argon. Chem. 8. and Xenon (English translation) (Hemisphere. Jacobsen. Nedostup. Jr. S. 10. Eng. R.. 79:2369 (1957). V. Opfell. S. Department of Energy under Contract DE-AC03-76SF00098. Curl. 6. S. Pullman. R. Soc. Krypton. E. Chem. Pitzer. Vasserman.. A. I.S. Jr. M.