., “Dynamics

( 1967).

of a Tubular Reactor with Re11. Nature of the Transient State,” ibid., 13, 519

Robertson, D C., and A. J. Engel, “Particle Separation by Controlled Cycling,” Ind. Eng. Chem. Process Design Develop.,
6,2 (1967).

Robinson, R. C., and A. J. Engel, “An Analysis of Controlled Cycling Mass Transfer Operations,” lnd. Eng. Chem., 59, 22

Root, R. B., “An Experimental Study of Steady State Multiplicity in a Loop Reactor,” Ph.D. thesis, Univ. Illinois, Urbana

., and R. A. Schmitz, “An Experimental Study of Steady State Multiplicity in a Loop Reactor,” AlChE J., 15, 607


Scale Study o Controlled CycIic Distillation,” Chem. Eng. f Sci., 22,766 ( 1967). Schmeal, W. R., and N. R. Amundson, “The Effect of Recycle on a Linear Reactor.” AlChE J., 12, 1202 (1966). Silverman, R. P., “Theoretical and Experimental Investigation of a Staged, Controlled-Cycling, Stirred Tank Reactor System,” M.S. thesis, Penn. State Univ., University Park (1969). Vejtasa, S. A., ‘‘Ah Experimental Study of Steady State Multiplicity in an Adiabatic Stirred Reactor,” Ph.D. thesis, Univ. Illinois, Urbana ( 1969). -, . R. A. Schmitz, “An Experimental Study o Steady f State Multiplicity in a Adiabatic Stirred Reactor,” AIChE J., 16,410 (1970).
Manuscript received June 14, 1973; revision received and accepted November 5, 1973.

Schrodt, V. W., J. T. Sommerfeld, and 0. R. Martin, “Plant

An Empirical Correlation of Second Vi riaI Coefficients
A new correlation of second virial coefficients of both polar and nonpolar systems is presented. It uses the Pitzer-Curl correlation for nonpolar compounds, but in a modified form. The second virial coefficient of nonhydrogen bonding compounds (ketones, acetaldehyde, acetonitrile, ethers) and weakly hydrogen bonding compounds (phenol) is fitted satisfactorily with only one additional parameter per compound, which is shown to be a strong function of the reduced dipole moment. Two parameters are needed for hydrogen bonding compounds (alcohols, water), but for alcohols, one parameter has been kept constant and the other expressed as a function of the reduced dipole moment. The extension of the correlation to mixtures is satisfactory, direct, and involves only one coefficient per binary.

Esso Reseach and Engineering Company
Florham Park, New Jersey 07932

Vapor-phase nonideality should properly be taken into account in the analysis and correlation of vapor-liquid equilibria, especially at superatmospheric pressures. For / reduced densities up to 14 (roughly speaking, up to pressures of 15 atmospheres), the effect of vapor-phase imperfection can be reliably calculated using only the second virial coefficient B of the pure components and crosscoefficients for each binary (for example, see Prausnitz, 1969). A very successful correlation of the B of nonpolar gases has been proposed by Pitzer and Curl (1957); see Equation (6). The soundness and reliability of the Pitzer-Curl correlation make its use as the basis of a correlation of the B of polar systems highly desirable. The objective of this study was to extend the Pitzer-Curl correlation to the following polar compounds of interest: ketones, aldehydes, acetonitrile, ethers, alcohols, phenol, and water. A similar approach has been taken by OConnell and Prausnitz (1967) and by Halm and Stiel (1971), but both

of these correlations are lacking in several respects, including reliability; they are fully discussed in the Appendix.” The OConnell-Prausnitz correlation has been used widely (for example, in two important monographs on computer calculations for vapor-liquid equilibria; Prausnitz et al., 1967; Renon et al., 1971); it is therefore used as the basis of comparison with the new correlation. Another correlation of the B of polar system which, while not using the Pitzer-Curl correlation, is based on a similar idea to ours is that proposed by Black (1958); it is discussed in the Appendix. Other correlations that are not based on the Pitzer-Curl correlation and are not considered here are those of Kreglewski (1969), Nothnagel et al. (1973), O’Connell(1971), and of Polak and Lu (1972).
The Appendix has been deposited as Document No. 02293 with the National Auxiliary Publications Service (NAPS), c/o Microfiche Publications, 305 E. 46 St., New York, N. Y. 10017 and may be obtained for $2.00 for microfiche or $5.00 for photocopies.

AlChE Journal (Vol. 20, No. 2)

March, 1974

Page 263

The polar contribution to B can be readily modified when new or better data become available-without invalidating the model. thus obviating the need of determining and using homomorphs (for example. When the equation is truncated after the second virial coefficient term. and critical pressure P c . and C is the third virial coefficient. 20. THE VlRlAL EQUATION OF STATE coefficient BM is given exactly by n n The virial equation is a power series in the reciprocal molar volume. ethane is methanol's homomorph). HB. The Pitzer-Curl correlation is the best available for second virial coefficients of nonpolar gases. For most chemicals applications.CONCLUSIONS A N D SIGNIFICANCE A modified form of the Pitzer-Curl correlation is used for nonpolar compounds. Hiza and Duncan.ij from the geometric mean. The third virial coefficient of polar gases. Pitzer and Curl (1957) had to use a third parameter for the correlation of B for nonpolar gases. Thus. etc. ethers). the mixture second virial Fluids with spherical molecules. these coefficients are functions only of temperature. In reduced form. or roughly up to 15 atm. it is reliable up to one fourth of the critical density.1445 .. This parameter is the acentric factor o defined as (Pitzer et al. 02 . and everything else has a positive O . 1955) For the evaluation of B from low-density P-V-Tdata. A strong correlation is shown to exist between this parameter and the compound's reduced dipole moment pR. No. roughly. B 5 limit [ u ( z . for example.75) but is also shown to have some advantage at high reduced temperatures. l / u (4) Bij ( i # j ) is the second virial cross-coefficient.) A great advantage of the virial equation is that it can be extended to mixtures without arbitrary assumptions. 1967. as it has already been done for nonpolar/nonpolar mixtures (Chueh and Prausnitz. have negative 0's. but all alcohol data are fitted with one parameter fixed. however. The actual acentric factor is used for all polar compounds. 2) . as it will incorporate the contribution of C. 15 atmospheres or below. Equation ( 1 ) predicts z accurately up to one half the critical density. have a zero acentric factor. NONPOLAR GASES z=- Pu B C =1+-+-+ RT 2.0 . Kr. for example. Equation ( 1 ) should be used. water) require two parameters for the polar term. He. the pressure is under 15 atm. inert gases and kydrocarbons. The second virial coefficient of the nonhydrogen bonding compounds investigated (ketones. however. the other has a weak dependence on p R . but the reverse is true at TR Page 264 March. are characterized by a zero dipole moment. 3 3 0 / T ~ for subcritical temperatures.. 1974 AlChE Journal (Vol. the quantum gases. The new correlation is especially superior to the other correlations in its extension to mixtures.. where z is the compressibility factor. A characteristic binary constant is introduced. that is. acetaldehyde. it is a function only of temperature like the pure-component coefficients (Bii and Bjj) . The principal significance of this work is that the new B correlation makes possible the reliable calculation of fugacity coefficients and therefore improves the fit and extends the useful pressure range of vapor-liquid equilibrium data obtained at pressures of. 1970). For a mixture of n components. 1957) where * This form is superior to the pressure-explicit form z= 1 + BP/RT > 1. then the apparent B calculated will have a density dependence. The modification mainly improves the fit at low reduced temperatures (TR < 0. for example. is satisfactorily fitted with only one additional parameter per compound. This application is the most sensitive as far as the second virial cross-coefficients are concerned. see Equation (18). if we know (1) the temperature dependence of the second virial coefficients and (2) how Bij is related to Bii and Bjj. the equation of state that will be used is z=l+- B v Nonpolar gases. is rarely known. For pure components. to account for the deviation of the characteristic critical temperature T. Hydrogen bonding compounds (alcohols. In addition to critical temperature T.. (Pa) f : (TR) = 0. Ar. B is the second virial coefficient. it is (Pitzer and Curl. The form of the polar term is such that its value drops to zero at high reduced temperatures in accordance with theoretical and experimental evidence. acetonitrile. and even of the weakly hydrogen bonding phenol. fugacities.l ) ] l/V+O (3) (If the limit to zero density is not taken. Equations (2) and ( 4 ) can be used to calculate vaporphase densities. and hence the second virial coefficient alone can account for vapor phase nonidealities. etc.

ethers. Second virial coefficient of gases with zero acentric factor.46/T~ (8) (0) . -'Yo0 v I D TR = 2 .211). 0 1 1 (1966) MacCormack .67 (Reamer et al. water. 2. ketones.53 have shown that fpc is unsatisfactory for T R the error is 10 percent. Second virial coefficient of carbon dioxide a t high temperatures. Recent measurements on Ar and Kr (Brewer.105) up to TR = 1. The spread in the experimental data (Baxendale and Enustun..008/T~' (10) 0 Vukalavlch & Masalov The differences between the Pitzer-Curl correlation and our modification are illustrated in Figure 2 for benzene (o = 0.398). 1944). which differ by 3 cc/gmol. These errors are rather small. The modified f"' fp: 1500 25 50 75 100 125 C 150 175 200 2? Fig. 1950. + < 0. 1967) down to T R = 0. 2) -". Kr. (1) J 75 100 12 5 T. while for n-octane we used the data of McGlashan and Potter (1962) and Connolly and Kandalic ( 1960). The comparison showed that f: predicted results that were too positive at low temperatures (6% error at TR = 0.200) and n-octane (o = 0. POLAR GASES f: ( T R ) = 0.C t : r l Corlclal8 > PlLrei-Ctlrl curreia:.0. 3. No. (0) Polar compounds are characterized by a nonzero dipole moment p which expresses the effect of electrostatic forces between molecules. Second virial coefficient of benzene. Polar compounds considered in this study are alcohols.. The tempei'ature range of the data used.55).0 ( 2 to 4% errors). 225 250 275 300 A slight modification to makes it possible to fit all these data to within 1% . bracket the experimental value.) . 1967.073 + 0. 1974 Page 265 . = 150 65°K) in Figure 2 have also been reported. this makes their behavior in the vapor different and more complex than that of nonhydrogen bonding compounds (ketones.5). Byrne et al. the modified f 0 ) is (9) The improvement in the fit is clearly shown in Figure 1. Connolly and Kandalic.-100 /I I -A T . [More negative and more positive data than those plotted AlChE Journal (Vol. Schneider 8 (19501 I t.0637 = + 0. aldehydes. 1960. Vukalovich and Masalov. Weir et al. Dymond and Smith (1969) have smoothed the data for n-butane.-- has one term less than f p c : (1) f"' (TR) 0. .. Bottomley and Spurling.8 6 T R 4 1. f ( l ) becomes progressively more negative than f p C . phenols. 20. OK 150 175 Fig. however. 1968. Zaalishvili and Belousova. I I ! I 300 400 500 600 T Fig. can be checked against reliable B data for compounds with large acentric factors. March. see Dymond and Smith ( 1969) ..0.O00607/T~* - 5 (D -1000 (0) /ijJ 9" . Crain and Sonntag. +20 1 .0073/T~' - Pitzer and Curl determined the coefficients of f p C by fitting the U data for Ar. 1966) and the modified correlation is clearly superior to the Pitzer-Curl correlation.225). where the most recent B data for Ar and Kr have been ~ plotted along with the calculated values. f"' and f p are virtually identical for TR > 0.87 (MacCormack and Schneider.331/T~~ . 5 0 / T ~ ~ 0 . whose quadrupole moment has an entirely negligible effect at supercritical temperatures. 1966. Hajjar et al. These two broad classes of compounds will be treated separately. was limited. 1951.53.75. and too negative at 0.o . and alkyl nitriles. Two such compounds are n-butane ( O = 0. 168°K for Kr) f'''( T R ) = jpc' ( TR). 1966.O. but they indicate the need for some adjustment.8 (120°K for Ar. The results from the two correlations. 1964) is larger than the difference between the two correlations. 1. which have zero acentric factor.] At high reduced temperature ( T R > 1. at T R = 0. The first three are hydrogen bonding compounds ( a bond forms between the hydrogen atom attached to oxygen in one molecule with the oxygen atom of another molecule). Knoebel and Edmister. 1968.-- 'Ullod f8ed P ~ l z e r . 1969. /' -. etc.423/TR3 .0 . A better example is offered by carbon dioxide ( w = 0. B data are available up to T R = 2. and Xe. Data are available for ethane ( o = 0. as shown in Figure 3. 0 9 7 / T ~ ~ 0.

Nickerson et al. which 0 C l m l q er ril .1211 and the root mean square deviation of B 156 cc/t?mol.8 ( 1 6 ) 151f (23) -0.5 it is only f'2' = . Nickerson et al. 2) . Chang et a1 (1965).95) is inherent in the correlation: at T R =TR' a The second virial coefficient of polar compounds is more negative than that of nonpolar compounds (for the same TR.282 112. acetonitrile.0. 0. (1961).02277 -0.4 56.4d ( 4 ) 66. but at T R = 1. l i l l ! b K o I y S k 3 !1960. Hajjar et al. 1974 AlChE Journal (Vol.sova (1964.29 0.__. (1949). or a < 0.34 0. and ethers were fitted very satisfactorily by adding a one-parameter term to the modified Pitzer-Curl correlation: -. The results of fitting Equations (11) to (12) to B data for five ketones. 'The 61.5 -0. Prausnitz and Carter ( 1960).3e (11) 25. f C 2 ) = .0. Tripp and Dnnlap (1962). Chevalier ( 1969).1198f 70. Chang et al. ( 1 9 6 8 ) .@ (4) = 10VPc/Tc2.21 0.34 14. 20.03090 Methyl ethyl ketone Methyl n-propyl ketone DiethyI ketone Methyl tert-butyl ketone Acetaldehyde Acetonitrile Methyl ether Ethyl ether 0.35 0. Kappallo e t al. TABLE NOSHYDROGEK 1.e. Hauthal and Sackmann (1969). which is clearly poor at low and high temperatures. Hofmann and Pfestorf ( 1968). (1963). and Zaalishvili et al.~ 50 100 150 200 2 50 '.8 cc/gmol for o = 0. (1967). BONDIXG POLAR CordPouPI'ns Root mean square deviation of B . Hales et al. Lambert et al.00246.-.4 81. Most of the deviation is due to three widely scattered points at 41. ( 1 9 6 3 ) .4 188 250.0. 4. Lainbert et a1 (1949).the units are Dehyes*-atm-'K-Z. 1 9 6 5 ) ~ -3000 D A b i -3 6 0 0 0 -.Nonhydrogen Bonding Compounds T h e second virial coefficients of ketones. f Including the 4 data points of Zaalishvili et al.i . i I K a w a I l o et al k1963: Z a a l # s .01873. Bottomley and Spurling (1962.02224 -0. acetaldehyde.0508 1 -0.5 to 60°C. the average deviation increases from 7.__--___A -L .4 to 64. without them.01065 -0. cc/gmol (no. 0 ) . (1971) makes a = -0. 1964) differ from the other data in their temperature dependence and were not used in determining the value of a ] T h e new correlation gives a good fit. (1941). A sensitive check of the new correlation is provided by the extensive data for acetone reported since 1960.7 cc/gmol for Q = -0. Knoebe1 and Edmister ( 1968).0 87. Prausnitz and Carter (1960).. no polar correction).0 90.0009. Russell and Maass (1931). Cawood and Patterson (1933).5 (10) 33. (1961). Dipole moment data taken from McClellan (1963).0 22. Kennedy et al.7"C point was discarded because i t is ahout 300 cc/gmol t o o negative.314 0. T h e root mean square deviations of B are small..6 -0. Osipiuk and Stryjek (1970).3 (36) Compound Acetone w PRa a Referencesb Abbott ( 1965). we have also plotted the results from the O'Connell-Prausnitz correlation ( 1967). (1965). acetonitrile. Hofmann and Pfestorf (1968).01686 -0. Chang et al. Knoebel and Edmister (1968). [The data of Anderson et al.0 (i. 1962).4 cc/ gmOl. T h e discontinuity at 210°C ( T R = 0. in agreement with observed behavior. acetaldehyde. For comparison. (1969). e T h r e e of Chang's (1965)data are clearly inconsistent with all the rest.39 ( 3 7 ) Isopropyl ether #R 0. PRernoving the questionable references identified in the text drops the root mean square deviation to 23. With it.00089 31. Haworth and Sutton (1971). I 1 Fig. Second virial coefficient of acetone. and three ethers are given in Table 1. f'2' < 0. &Root mean square deviation = 36. Page 266 March.00202 19.33 0. "C I A Aiidersoi el a1 '19681 Z n a l ~ s l i v i l b BeIo. Bottomley and Reeves ( 1958).. but the accuracy can be clearly illustrated only when B data for a given compound are available over a wide temperature range..01513 -0. Chevalier (1969).4c (19) 8. (1960.f c o ) ( T R ) BPc RTc + ofc1(T R ) ) + f"' (T R ) (11) where the polar term is given by f'2'(TR) are plotted in Figure 4. the root mean square deviation drops to 29.323 0. Aleunder and Lambert ( 1941) . Hauthal and Sackmann ( 1969). Only those used in the regression analysis are listed. Stryiek and Kreglewski ( 1965).31 147. points) 32. Riitzsch and Bittrich (1965).50. 1967).64 a t TR = 0. hence. The contribution of fC2) to B diminishes rapidly with increasing temperature.0 -0.2 ( 1 4 ) 50.4 cc/gmol for a = -0. Hauthal and Sackmann (1969). No. Zaalishvili and Kolysko (1960. For a = . Hauthal and Sackinann (1969).01.

the reduced dipole moment is a satisfactory correlating parameter only when each family of compounds is considered separately.00020483 ( p R ).63147 .6% ) and ethyl n-propyl ketone (average error of 19 cc/g-mol Rough but useful values for the a of CQf or 1. However.09681 In ( p ~ )ethers . in degrees Kelvin). This is especially true of alcohols. 1 4 0 ~ 0-4(~R)-4. that is. N ) tend to associate with each other by forming hydrogen bonds. -0.a ) = . 1974 Page 267 . The new correlation is again shown to be most satisfactory. At low temperatures the last term predominates. Figure 6 clearly demonstrates the diminishing importance of a. the fit of the B data for isopropyl ether is nearly equally good when a = 0. All available B data were used in determining the value of a. the results of Knoebel and Edmister (1968) and Ratzsch and Bittrich (1965) have too steep a temperature dependence. . but the limited available data (Osipiuk and Stryjek. No. The polar term of Equation (11) must now have two parameters : O'Connell and Prausnitz (1967) introduced the factor lo5 to make the pR values greater than unity (when P is given in Debyes". but less so for ethyl ether.0. they dimerize.= 0. (1949) are consistently too positive. therefore. Figure 5 is a plot of experimental and calculated B values for acetaldehyde and acetonitrile. that the polar contribution to B cannot be given for all polar compounds by a unique function of pR. ' t.95 the polar corrections (analogous to f ( 2 ) ) are set equal to zero. and T . Chevalier. An extensive compilation of dipole moments is given by McClellan (1963). 1 Debye = 10-18 esu-cm. P. 1969) lead to small positive values for a.1580 cc/ g-mol (Hauthal and Sackmann.05 - 0 100 2 00 300 REDUCED DIPOLE MOMENT. In the case of ketones. "C Fig. 1969). (15) CO 0 Ketoiies Acetaldehyde V Acetoliltrile D Ethers The value of . a is best expressed as a linear function of p R : Both a and b assume positive values. 2) March. while the O'Connell-Prausnitz correlation leads to serious errors. .0. -0. this reference treats the very strong dimerization of carboxylic acids). Eubank and Smith (1962) have shown that p~ by itself is inadequate as a correlating parameter since the location and direction of the dipole moment are also important. Dependence of o on reduced dipole moment for nonhydrogen bonding compounds.2) are.0. Second viriol coefficient of acetaldehyde ond acetonitrile.016. The effect of dimerization is to make more complex the temperature dependence of the polar contribution to the second virial coefficient of dimerizing compounds: it is steeper at very low T R (+ 0 5 ) .8. but their dimerization in the vapor ( u p to moderate densities) is much weaker than that of alcohols. It follows. while at high temperatures both terms become negligible. Listed in Table 1 are values for the reduced dipole moment PR defined by H y d r o g e n Banding Compounds Molecules containing hydrogen linked to an electronegative atom (for example.14 a = .. dimerization in water is limited (Tsonopoulos and Prausnitz.1590 cc/g-mol. aldehydes and alkyl nitriles can be estimated from Figure 6. Phenols associate in the liquid phase (Prausnitz. 6. With a values from Equation (14). it was possible to predict satisfactorily the B data of Hales et al.0052 and .ketones (14) The predicted value of a for methyl isobutyl ketone is . 1970. with which B at 120°C is calculated to be .The predicted a values for methyl ethyl ether ( p R = 33. but flatter at TR > 0. 1970. the experimental value is . 0. The B data for eight alcohols. a = .2 . More about this correlation can be found in the Appendix. There is good agreement (less than 30 cc/g-mol difference) between the new correlation and that of O'Connell and Prausnitz.308x10'21 1 -0.0.a ) and In ( p R ) for ethers: In (. There is an excellent linear relationship between In ( . 1969). phenol. and hence of f C 2 ) .1%). The new correlation is very satisfactory for methyl ether (maximum deviation is 42 cc/g-mol). Q pR Fig. (1967) for methyl isopropyl ketone (average error of 122 cc/g-mol or 6. in atmospheres. while those of Russell and Maass (1931) and Lambert e't al. -2 7 10 -100 r 50 100 I 150 I 200 210 -100 . Similarly. however.10 + 2. with decreasing PR.7) and ethyl n-propyl ether ( p R = 17. 5. 20. respectively.0 (see Table 1).0013.a drops very rapidly with decreasing PR.12. AlChE Journal (Vol. and water were t.

2 14. together with the results of an earlier careful investigation (Kretschmer and Wiebe.0006957 ( p R ) . Kretschmer and Wiebe (1954).635 0.00908 +0. Kudchadker and Eubank.0367 0. 1954)'. 1970) have been plotted.0447 0.0508 15.04Dl .586 0. See Table 1. ( 4 j Cox (1961). Figure 8 shows thaet the alcohols' b has a weak dependence on reduced dipole moment. 1968. (1960) were inconsistent with Opel's and were discarded. and hence their b less positive.5 cc/gmol off the calculated value.6 0. 0. respectively. ( 8 ) Ope1 (1969).0878 0.0560 28.572 87. points) (22) Reference8 0. The results are given in Table 2. Kudchadker and Eubank ( 1970).TABLE HYDRWEN 2. Kretschmer and Wiebe (1954). The new correlation provides an excellent fit of the data over the whole temperature range. 1969.1 (4) 19.0537 0. 0 Other alcohol data discarded were those of Hanks and Lambert (1951)for ethanol.0878 0.0229 16.06- 1 i I I I ! I Methanol Ethanol 2-Propanol tert-Butanol P 1-Propanal 0 05- 0. but it appears that the b of C2+ straight-chain 1-alkanols is given by h 0.2 52.70 0. 2) .) A two-parameter f"' may be needed to fit low-temperature ( T R < 0. All alcohols have p = 1.0878 0.95 is 80 cdg-mol.2 Ethanol I-Propanol 2-Propanol (isopropanol) I-Butanol 2-Butanol (sec-Butanol) 2-Methyl-1-Propanol ( isobutanol) 2-Methyl-2-Propanol ( tert-Butanol) Phenol Water 1 0. 0. d The 98'C point is inconsistent with the rest and has been discarded. The B data for ethanol and 2-propanol are adequate. b = 0. Dependence of b on reduced dipole moment for olcohols. The same value of a was used for all eight alcohols. (1954) for CI-Ca alcohols. Fi.0136 0. ( 4 ) Cox (1961). c This large deviation is misleading.0878 0. (1954)d. /JR ~ -~ 100 L J 25 50 75 125 150 175 200 225 "C Fig.6 172.0481 0.2 (13) 61.07 0. but those for 1-propanol and all C4 alcohols are limited in number and temperature range. ( 4 ) Cox ( 1961). Only the most recent data (Kell and McLaurin. A good example of the fit is illustrated in Figure 7 for methanol-for which we have the most extensive information.3c 0. The data for water are plotted in Figure 9.578 0.0006957 vR) 0.00908 * The data of Bottomley and Spurling (1967) have been discarded.0279 0. Only those used in the regression analysis are listed.6 23.666 0. Vukalovich et a1 ( 1967).625 0. The discontinuity in the correlation at TR = 0. (1967). the value for a would have been -0.2 24. Moreland et al.6 40.0878 0. or 40% of the B value.614 0. 20.the new correlation has provided a satisfactory fit (superior to that obtained with the OConnell-Prausnitz correlation).590 0. The O'Connell-Prausnitz correlation ( 1967) only fits the less precise data of Lambert et al.0878 0.0878) + Page 268 Moech.0878 -0. 1974 AlChE Journal (Vol.2 33. ( 6 ) Cox (1961).0101.7 41.1 Kell and McLaurin (1969). Reliable B data for C4+ alcohols are needed to clarify this.344 68. The data of Andon et al. In every case . but the reverse is shown in Figure 8. (If they had also been considered. analyzed with Equations (11) and (16). (22) Kell et a1 ( 1968). and of Foz et al.056. Opel's (1969) data for phenol were adequately fitted with only one parameter. ( 8 ) Knoebel and Edmister (1968).126.03- b = 0. The 0. (17) The branching in all other alcohols should make their B less negative. Cox (1961).8 44. 8. cc/gmol (no. 8 * .6)data. BONDING POLAR COMPOUNDS Compound Methanol W CLRa ( 1 b Root mean square deviation of B.9. Knoebel and Edmister. the experimental values at 60°C are + 109 and value is removed. 1963). No. If the too negative 0. Knoebel and Edmister ( 1968). Second virial coefficient of methanol.2 1. Foz et al. Their values at 125" and 150'C are 150 and_ 100 cc/g-mol.0572 71. Kretschmer and Wiebe (1954).01 -2800 o'021 REDUCED DIPOLE MOMENT.74 Cox (1961).0878 0.443 0.3 51.03 Debyes (McClellan.6 39.0487 0. straight-chain 1-alkanols ( a = 0. (1949)'.9 0. more negative than those plotted in Figure 7. 7.

07) (0. Ne. Tcij can be assumed to be the geometric mean of TCi and Tcj (kij = 0) only when i and i are very similar in size and chemical nature. Hemmaplardh and King ( 1972). 9. (An almost equally good fit can be obtained using only one parameter.5 7. kij can assume a negative value. etc.14) (0. Olds et al.9 6. The new correlation. Rigby and Prausnitz (1968). Tcij. the fit of Kell's data with the new correlation is excellent. O'ConnellPrausnitz "C (no. in gas j at elevated pressures. The O'Connell-Prausnitz correlation gives Bij's that are always much too negative (except for the CH30H/C02 binary).13) (0. ] The most sensitive bij = 0. Most of the BM da'ta are of unsatisfactory quality.8 7. (1942). For methane/n-heptane. Hz.35) (0. Rigby and Prausnitz ( 1968). and BM is given by Equation ( 4 ) . points) References Hemmaplardh and King ( 1972). The average deviation of the calculated Bij values for methanol/nonpolar and water/nonpolar binaries is given in Table 3.of Keyes et al.7 2.-. especially for t < 250°C.05) (0.kij) (18) oij = 0. CROSS-COEFFICIENTS FOR MIXTURES 50 100 150 200 1.8 (5) (5) (5) (5) (5) (5) (5) (4) (4) (9) 25-171. even over a range of 213°C (for H20/CH4).4 9. At higher temperatures (500" to 900°C) we used the values of Vukalovich et a]. (1936. the polar contribution to Bij is calculated by assuming that ~ i j (24) The suitability of the mixing rules.30) (0. (12). 1967). Bij is assumed to have no polar term: Uj = 0 i (21) bij = O (22) For polar/polar binaries. An extensive tabulation of characteristic binary constants for nonpolar systems is given by Chueh and Prausnitz ( 1967). with a temperature-independent k.13) (~. ( 1971).O'Connell-Pra"sn.9 3. MethanoVnitrogen MethanoVargon MethanoVmethane MethanoVethylene MethanoVethane MethanoVcarbon dioxide Methanol/nitrous oxide Water/nitrogen Water/argon Watedmethane Water/ethane Watedcarbon dioxide Water/nitrous oxide (0. Coan and King ( 1971). Only Kell's data (150 to 450°C) were used in the regression analysis.01) (0. which is clearly unsatisfactory.i for each binary. Hemmaplardh and King ( 1972 ) . = (TciTcj) ' ( 1 . 20. As shown in Figure 9.6 6. The mixing rules given below make it possible to relate these characteristic constanlts to pure-component parameters: Tcij .5 (bi + bj) = 0. (1968). For systems with polar components. For polar/nonpolar binaries. (1967). Reamer et al.4 16. If there is strong solvation (hydrogen bonding between molecules of digerent species). [The relationship between Bii.) The maximum deviation in B. Equations ( 18) to (20) suffice for nonpolar/nonpolar binaries. but it is also possible to determine Bij directly by measuring the solubility of liquid i. Hemmaplardh and King ( 1972).7 1.4 7.1 ( 7 ) 25-100 25-100 (4) (4) AlChE Journal (Vol. q. Coan and Kine. The uncertainty in Bij reflects the uncertainty in both the mixture and the pure-component data (which can be sub- 3.5 (% + ~ j ) (23) mixing rule is Equation (18). Hemmaplardh and King ( 1972 ) . Hemmaplardh and King ( 1972). VIRIAL CROSS-COEFFICIENTS TABLE SECOND Average deviation of i/i New 1. kij = 0. 2) March.10 (Chueh and Prausnitz.6 ( kij ) Bij. g: 250 300 350 400 450 -200 -300 - -400 - The second virial cross-coefficient Bij has the same temperature dependence that Bii and Bjj have.12) ( 0. and (16) are Pcij. will be indicated by the degree of success in fitting Bij. Bjj. Bij. Rigby and Prausnitz ( 1968). uij. cc/gmol t range. Hemmaplardh and Kinq ( 1972).and bij. Hiza and Duncan (1970) have presented both data and a correla'tion for the kij of nonpolar binaries of He. Coan nnd King (1971). The property usua!ly measured is BM. There are relatively few mixture data for polarhonpolar or polar/polar sys'tems. Equations (18) to ( 2 4 ) . This correlation uses Equation (18) with kij = 0 (see the Appendix).10) (0.34) (0.16) 15 19 40 39 54 22 55 41 49 52 117 41 45 15-60 15-60 15-60 15-60 15-60 15-60 15-60 25-100 25-100 25-237. The cross-coefficients have been directly determined from measurements of the solubility of liquid methanol or water in the compressed gas. Second virial coefficient of water. 1974 Page 269 .5 (mi + uj) (20) where kij is a characteristic constant for each binary. but the parameters to be used with Equations ( l l ) . g: Fig. (1943). kij can be even larger.37) (0. or BM data. Collins & Keves (1938)- t. up to 900°C ( T R = 1.81) is less than 4 cc/g-mol. provides an excellent fit of the data.n 0 D Correiallo" Kell e l a1 (19681 Kwes e l a1 (1936).5 1.New Correlation .2 3. 1938) are in serious disagreement with the recent measurements of Kell et al. No.

b Too negative. see Table 51. The average deviation of the calculated BM ( y = 0.2..12) (0. without this point.5) values for eleven polar/nonpolar and two polar/polar binaries is listed in Table 4. as shown in Table 5. Fox and Lambert (1952).j is needed to fit the BM ( y = 0. With such a constant. No.40) (0.7-158. The negative ki. probably formed by hydrogen bonding between nitrogen and the hydrogen attached to the carbonyl group. (1965): -1120 & 100.78 60-100 40-1OOc 60-100 175-250 (2) (2) (3) (4) (3) (6) =Their data are inconsistent with the more reliable results of Abbott (1965).1 100.12) ( -0. the optimum Icij is . VIRIAL COEFFICIENTS y = 0. 110°C).08) (0. (1969).15-47.85 45-90 75.20) (0.1069 -955 -920 -920 -857 -857 -800 -800 -747 -2081 .32) (-0. (0.1450b -860 1100 -855 (-960). are in agreement with Knoebel and Edmister at 80°C. 1968 (40. cc/gmol Calculated i/i t.1232 Acetone/benzene 40 60 75 80 80 90 90 100 100 110 . 1966) that benzene (electron donor) forms a complex with acetone (electron acceptor). Ope1 et al. 1969) have been fitted extremely well. 1960) is less satisfactory. (1965): -950 & 100.23) O'Connell-Prausnitz -1258 .a Bottomley and Spurling (1967). 1965 (80°C). Knoehel and Edmister.12) (0. "C Expenmentala New ( k i j ) -1384 -1060 -858 -824 -824 -761 -761 -706 -706 -657 -5854 -4209 -2553 -1856 (0.12) (0. Zaalishvili and Belousova.4 -5900 (-710)' -4180 -2540 . O'Connell and Prausnitz add a specific association constant for the dimer.51. 1974 AlChE Journal (Vol.5) data for acetone/benzene and acetaldehyde/ acetonitrile. (1963). -750 & 100 (-85O)C -710 ( -765)' Acetaldehyde/acetonitrile 40 60 80.90 53.76 53. Chang et al. the optimum ktj value is 0. Lambert et al. The recent phenol/water data (Ope1 et al. at 100°C. cc/gmol O'Connellt range. (When there is complex formation.32) (-0. Abbott ( 1985). Lambert et al.s for acetaldehyde/acetonitrile are a clear indication of the existence of a strong complex.5) 5.0. the complex becomes weaker.20) (0.00) (0.8 References Kappallo et al. It is therefore preferable to compare BM at y = 0.5.32. OF CROSS-DIMERIZING BINARIES BM ( y = 0.stantial.23. the agreement is even better with k. like the other mepsurements by Knoebel end Edmister (1968) at 40°C. Chang et al.10) (0. New (kij) Prausnitz "C (no.20) (0.05) (0.12 (which it assumes when there is no significant complex formation). 0 The BY data of Zaalishvili and Belousova (1964) have the wrong composition dependence.1060 . 1965 (75.1757 .76 51. Chang et al. SO. TABLE BM ( y = 0. The 40°C is most probably too negative ( B of methanol is 500 cdgmol too negative!).20).10) (0. The new correlation is again satisfactory and superior to the O'Connell-Prausnitz correlation. Page 270 March. Because of the strong chemical interaction between acetaldehyde and acetonitrile. Knoebel and Edmister ( 1968). Abbott (1965).25) (-0.0. it is .1810 a Acetone/benzene: Abbott.) The paucity of experimental B A data will make it neces~ sary to predict rough kij values in most cases. but the fit for acetone/ ethyl ether (Zaalishvili and Kolysko. 20.5).9 50-80 80 80 (4) (4) (2) (2) (5) (4) (1) (1) 53. Chang et al. The existence of this complex has been recognized by Prausnitz and Carter (1960). as already shown).14. 100.10) (0.12) (0. 90°C). Acetaldehyde/acetonitrile: Prausnitz and Carter (1960). GO. b0.12)b (0. rather than Bij. (0. A temperature-dependent lc. The avail- TABLE MIXTURESECOND 4. 2) . which weakens as the temperature is raised.j = 0.12)b (0.25.1477 . Zaalishvili and Kolysko ( 1960). and kij approaches its temperature-independent value of 0.13) (0. (1954). the O'Connell-Prausnitz correlation should provide a much better fit than that indicated in Table 5.15) 47 143 178 61 42 58 122 263 216 88 82 160 158 164 9. 90. Knoebel and Edmister ( 1968). In the case of acetone/ benzene. experimental error cannot be excluded [the data of Zaalishvili and Belousova (1964) should certainly be discarded. As temperature is raised. Knoebel and Edrnister ( 1968 ). 100°C).12 is the limiting k i j value for acetone/benzene (see Table 5).12) (0. points) Acetone/n-butane Acetone/n-hexane Acetone/c yclohexane Acetone/carbon disulfide Acetone/ethyl ether Methyl ethyl ketonehenzene Diethyl ketonehenzene Acetonitrile/cyclohexane Ethyl ether/n-hexane Ethyl etherhenzene Methanol/benzene E thanol/benzene PhenoVwater 11 19 23 118 5. 1964 (SO.07) (0. This is supported by the data: at 40°C.6 29 19 18 25 22 20 46 27 2.5 AT Average deviation of B M ( y = 0.12) (0. (1954). kij should be more negative at 40°C than it is at a higher temperature (compare acetone/benzene).12) (0. but the steep temperature dependence of B M has a physicochemical explanation: there is spectroscopic evidence ( Weimer and Prausnitz.

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