287
J. Chem. Eng. Data 1980, 25,267-271
T
degrees Celsius, OC
Literature Cited
(14) Vargaltik, N. B., Os'minin, Yu. P., Teploenergetiks (Moscow), 3, 11 (1956). (15) 14a7m Chernyshev, A. K., rr. GIAP, No. 41, 65 (1976); Chem. Abstr., 91, 500
,,",-,.
Lyon, R. N., Kolstad, G. A,, Eds., "A Recommended Research Program in Geothermal Chemistry", WASE-1344, Department of Energy, Washlngton, DC, 1974. Sllvester, L. F., Pitzer, K. S., J. Phys. Chem., 81, 1822 (1977). Fabuss, 6.M., Korosi, A,, "Properties of Sea Water and Solutions Containing Sodlum Chloride, Potassium Chloride, Sodium Sulphate and Magnesium Sulfate", Offlce of Saline Water Research and Development Progress Report, No. 384, Washington, DC, 1968. Korosi, A.. Fabuss, B. M., "Thermophysical Properties of Saline Water", Offlce of Saline Water Research and Development Progress Report, No. 363, Washington, DC, 1968. Yusufova, V. D., Pepinov, R. I., Nikoiaev, V. A,, Guseinov, G. M., Inzh.-Fiz. Zh.,29, 600 (1975). Rowe, A. M., Chou, J. C. S., J. Chem. Eng. Date, 15, 61 (1970). Haywood, R. W., J. Eng. Power, 88, 63 (1966). Kestln, J., WhBelaw, J. H., J. Eng. Power, 88, 82 (1966). Touloukian, Y. S., Liley, P. E., Saxena, S. C., "Thermal Conductivity", Vol. 3. IFIlPlenum Data Cow.. New York. 1970. Rledel; L., chem.-mng.-rech'., 23, 59 (1951).,, Jarnieson, D. T., Itvlng, J. B., Tudhope, J. S., Liquid Thermal Conductivity: a Data Survey to 1973", HMSO, Edinburgh, 1975. Jamieson, D. T., Tudhope, J. S., Desalination, 8, 393 (1970). Washburn, E. W., Ed., "International Critical Tables", Vol. V, McGraw-Hill, New York, 1929.
(16) Unterberg, W., "Thermophysical Propertis of Aqueous Sodium Chloride Solutions", Report No. 64-21, May 1964, Department of Engineerlng, University of California, Los Angeles, Los Angeies, CA. (17) Chernen'kaya, E. I., Vernlgora, 0. A., Zh. frikl. K h h . (Lenlngrad),45, 1704 (1972). (18) Tufeu, R., LeNdndre, B., Johannin, P., C.R . Hebd. Seances Acad. Sci., Ser. 6 , 282, 229 (1966). (19) Chiquillo, A,, "A Measurement of the Relative Thermal Conductivlties of Aqueous Salt Solutions by a Non-Steady State Hot-Wire Method", Thesis No. 3955, Edg. Technische Hochschule, Zurich, Switzerland, 1967. (20) Kaputinski, A. F., Ruzavin, I. I., Zh. Fiz. Khlm., 29, 2222 (1955). (21) Predvoditelev, A. S., Zh. Fiz. Khim., 22, 339 (1948). (22) Fatullaev, F. G., Kerimov, A. M., Russ. J. fhys. Chem. (Engl. Trans/.), 47, 913 (1973). (23) Jamieson, D. T., J. Chem. Eng. Data, 24, 244 (1979). (24) Verba, 0. I., Gruzdev, V. A,, Genrikh, V. N., Zakharenko, L. G., Lawov, V. A., Psakhis, B. I., Issled. Tepbfk. Svoistv. Zhidk. Rastvorov Splevov, 40-59 (1977).
Received for review October 15, 1979. Accepted February 19, 1980. Supported by the U. S. Department of Energy, Office of Basic Energy Science, Dlvislon of Engineering, Mathematical and Geosciences under Contract W7405ING48.
Review of Density Estimation of Saturated
Mixtures
Doddlpatla Veeranna and Devinder N. Rihani' Engineers India Ltd., New Delhi 110 00 1, India
Various correlations with regard to the density model and mlxlng rules needed for this purpose have been reviewed. I t has been found that the modlfled Rackett equation with the Chueh-Prausnitr mixing rule, which predicts the denslty within 3 % , should be acceptable from an englneering design standpoint. A total of 3600 data points from 88 systems (contalnlng polar and nonpolar constltuents) were tested. The data extended well into the critlcal region for systems with nonpolar components. Whenever polar compounds were present, this was generally in the T, range of 0.4-0.7 and to that extent the validity of this exercise would be limiting. 1. Introductlon Density is a parameter affecting directly or indirectly every stage of the process design activity. For pure components a large volume of liquid density data has been reported in standard handbooks ( 1 - 4 ) , etc. However, such is not the case with mixtures where, besides temperature and pressure, composition is also one of the variables. For mixtures the required data are seldom available; it is necessary to reduce and correlate the data for meaningful interpolations. The u t i l i of having a reliable estimation tool can be easily realized if we consider that for an actual system the number of components to be handled may be more than 1O s a y for the case of a CBaromatics separation train this could be close to 20, with some of them being superciritical. This paper presents the results of a study undertaken to review the estimation procedures for mixtures containing nonpolar and polar components. Attention was given to criteria like (i)accuracy, (ii) range of application, (iii) ease of use, and (iv) availability of input parameters. For use with a computerized thermophysical property package, it would be advantageous to have a method based on common input parameters, i.e., critical 0021-956818011725-0267$01 .OO/O
properties, acentric factor, etc., which are normally available
or can be estimated with a high degree of reliability. 2. Avallable Correlations The estimation method may utilize either an equation of state like Redlich-Kwong, BWR, etc., or the corresponding states approach. The latter is preferred because of wider applicability and lesser computational efforts. This paper is also restricted to the corresponding states approach. 2.1 Nonpolar Systems. On the basis of the work of many authors (5-12)it was decided to limit this investigation to testing with the following correlations. ( a ) Harmens Equation ( 9 ) . Originally Harmens tabulated F( T,) as a function of reduced temperature in the range 0.3 I T, I 0.96. Spencer and Danner (5)enhanced its usage by converting it into an analytical form. ( b ) Modified Rackeft Equatlon ( 5 ) . The original equation by Rackett ( 13) has been modified ( 14, 23)and extended to mixtures. It employs critical temperature, pressure, and an adjustable parameter called the Rackett parameter, Z R A , as shown.
(4) T,, pseudocritical temperature for mixtures, was obtained through one of the mixing rules mentioned later on.
0 1980 American
Chemical Society
266
Journal of Chemical and Engineering Data, Vol. 25, No. 3, 1980
( c ) Generalized Guggenheim Equation ( 6 ) . The original Guggenheim equation has been generalized by correlating the two constants a and b a s functions of acentric factor by Chiu et al. I t uses the concept of scaling volume as the correlating parameter in preference to the critical volume. Essentially, all these equations were originally developed for pure components and later on extended to mixtures. The mixing rules used for evaluating various parameters are likely to play a significant role. The important parameter in the present case is pseudocritical temperature. A reference to the literature indicated the suitability of the following mixture rules. ( 7) Hannens(9). It uses a mean of mole fraction and weight fraction for averaging purposes. ( 2 ) Chlu et a/. ( 6 ) . Weighting factors based on critical temperatures and acentric factors were recommended for use with the Guggenheim equation. ( 3 ) Chueh-PrausnRz ( 75). This was originally proposed for use with the modified Redlich-Kwong equation for prediction of phase behavior. Spencer and Danner ( 5 )adopted this, for use with the modified Rackett equation. The interaction parameter, ky,has been reported for some pairs while for others this may be estimated. The equations for this are as follows: n
n
(5)
3 . Data Sources. Table I gives the details of the various systems for which the experimental data have been tested. Pure component data needed for this purpose were obtained as follows: (i) Critical temperature, pressure, volume, compressibility, and acentric factor were taken from ref 3 and 19. (ii) Constant C for use in the Harmens equation was estimated through the recommended correlation, whenever it was not available in the original reference. Modifications advocated by Harmens for the presence of methane and nitrogen were not found to be necessary. (iii) Z , was taken from ref 14, wherever available; otherwise this was estimated from the experimental density data by using either a nonlinear optimization program or a single point estimation through eq 1. The estimated values are given in Table 11. Recently, Spencer and Adler (23) reported data for a large number of compounds. However, this could not be adopted for the present purpose since it was published after the completion of this work. In general the Z,,,values are quite comparable. (iv) V,, was obtained from the work of Gunn and Yamada (22). When not available, it was estimated through pure component density data. (v) To account for the presence of quantum gases the various parameters were adjusted as recommended by Chueh and Prausnitz (75).(vi) The Xparameter for using the Halm and Stiel equation has been tabulated in ref 20; for others it was estimated. 4. Results
CqVGj j=l
(7)
( 4 ) Barner and Oulnlan ( 76). I n an attempt toward more reliable pseudocritical constants for enthalpy and density predictions, a new binary interaction parameter k; was introduced. For the systems where k',, is unity, the correlation reduces to the well-known Kay's mixing rule. ( 5 ) Lee and Kesler ( 77). This method utilizes individual component properties without binary parameters, for estimation of pseudocritical properties. ( 6 ) Ll( IS). This involves averaging critical temperature on critical volume fraction basis. It was originally proposed for estimating the true critical temperature. 2.2 polar Systems. Not much information has been published about mixtures containing these compounds. Reid et al. ( 79) recommend the use of the Yen and Woods correlation (8). Halm and Stiel (20) advocate the use of a fourth parameter for correlation of pure component data. The Joffe and Zudkevitch (27)method uses two fitted constants. For evaluation purposes the method of Yen and Woods was not considered since it was basically developed for nonpolar substances and Spencer and Danner ( 74) have reported large errors with this correlation even for pure hydrocarbons. The Joffe and Zudkevitch method was also dropped because it (i) requires two arbitrary constants for each of the components involved in the mixture and (ii) uses critical volumes, which can be in large errors for polar substances. Correlation of Halm and Stiel has been tested in the present work by extending it to mixtures. Constants V(O)to V(5)were fitted as a function of T, for use with machine computations. On the basis of earlier experience with nonpoar systems it was decided to use only the Chueh-Prausnitz mixing rule for estimation of pseudocritical temperature and the modified Prausnitz and Gunn mixing rule ( 79) for pseudocritical pressure. From the application point of view it would be desirable to have a single correlation which is valid for mixtures of all components irrespective of the polarity. It was thus considered worthwhile to explore the possibility of using the three earlier models as well (section 2.1).
4 . I Nonpolar Systems. A preliminary analysis of the data indicated consistently larger errors with the Barner-Quinlan and Lee-Kesler mixing rules, when used in conjunction with various density models. Table 111 shows deviations for some of the systems chosen at random. These mixing rules were thus dropped from further analysis. Out of a total of 2796 data points tested, the number of points that could be handled by various mixing rules is shown in Table IV. The Li mixing rule which was originally proposed for estimation of true critical temperature was applicable for a maximum number of points (2741) while the mixing rule of &mer and Quinlan accepted the lowest numer of points (2497). In an actual case this could sometimes become a limitation when one is working in the critical range. Use of one or the other mixing rule for pseudocritical temperature may decide the phase of the system and also the validity of the density model. For hydrogen- and helium-bearing systems the quantum correction approach showed lower deviations and is recommended for use. However this observation is based on limited published data and should be used with caution. Percentage average and maximum deviation for various density models were determined. In an attempt to analyze these as a function of T,, as shown in Table IV, the following observations could be made. (i) Region I: T, I0.4. The number of points in this region were negligible to draw any meaningful conclusion. These are not included in the table. (ii) Region 11: 0.4 < T, I 0.95. The maximum number of points (approximately 80%) were found to lie in this region. The lowest deviation (2.28%) was observed for the modified Rackett equation using the mixing rule of Chueh-Prausnitz. The Harmens equation with the same mixing rule was the second lowest (2.34%). Even though this temperature range is far removed from the critical, maximum deviations are noticed to be quite large. No partiiuhr trend in maximum deviation could be noticed, except that it occurred generally at higher T, values. Most of the systems, including inorganics like COBand H2S, showed maximum deviations to be less than 10%. The C0,-eicosane system showed consistently high deviations for all the cases. It could be an indication of the data error. (iii) Region 111: 0.95 < T, < 1.00, The generalized Guggenheim equation in conjunction with the Chueh-Prausnitz mixlng
Journal of Chemical and Engineering Data, Vol. 25, No. 3, 1980 269
Table I. Data Sources system
system no. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
61 62 63 64 65 66 67 68 69 70 71 72 73 74
system methane-ethane -propane +-butane -isobutane -n -pentane -n-octane -n-nonane n-decane -e thane-propane -propane+-decane -ethane-propane+-butane+-pentane -ethane-propane+-pentane+-hexane et hene-n -hep t ane et hane-pro pene -propane -%butane -isobutane -n -pentane -cyclohexane +-heptane -n -oct ane +-decane propene-propane propene-1-butene propane-n-butane +-butane -isobutane +-pentane -isopentane -n - hexane
acetic acid-acetone -methyl isobutyl ketone -toluene ace tone-benzene -ethanol -methanol -1-propanol -toluene -water -water benzene-chloro form 2-methylpropanol-carbon tetrachloride 1-butanol-carbon tetrachloride 1-butanol-methyl isobutyl ketone
ref
system
no.
(a) Nonpolar Systems propane-benzene 31 -n-octane b 32 -n -decane i 33 n-butane-isobutane c 34 -n-octane d 35 +-decane e 36 carbon dioxide-ethane 37 f -propane 38 g -n -b u t ane a 39 -isobutane h 40 -n-pentane bbb 41 -n-decane bbb 42 -n-eicosane 43 i -hydrogen sulfide k 44 hydrogen sulfide-methane 1 45 -ethane m 46 n -propane 47 -isobutane 0 48 +-pentane 49 P +-decane 50 4 ' -nitrogen r 51 nitrogen-methane S 52 t -me thane-ethane 53 U -met hane-propane 54 V -methaneethane-propane 55 -methane-ethane-propane-n-butane-n-pentane+-hexane 1 56 -helium-methane-ethane-propane 1 57 V -helium-methane-ethane-propane+-butane 58 -helium-methane-ethane-propane-n-butane-n-pentaneW 59 X n-hexane+-heptane hydrogen-n-hexane 60 a
(b) SIMeins with Polar Compounds 75 2-butanol-carbon tetrachloride PP 76 carbon tetrachloride-1-heptanol 44 aaa 77 -methanol 78 -1-octanol PP aaa 79 -3-methylbutanol 80 -1-pentanol aaa aaa 81 -2-methyl-2-butanol 82 -2-propanol 44 83 -1-propanol YY ZZ 84 chlorofonn-ethene it 85 ethane-methanol ww 86 methanol-water ww rnonoethanolarnine-water 87 ss 88 1-propanol-water
ref
Y Z
aa
1 Z
bb cc t t
dd ee
ff gg hh t
ii
ii
kk 11 t
mm a a a
nn nn nn nn nn 00
ww ww
ww ww ww ww ww ww ww
rr vv zz xx uu
Huang, E. T. S., Swift, G. W., Kurata, F., ibid., 13, 846 (1967). Olds, R. Rodosevich, J. B., Miller, R. C.,AZChEJ., 19, 729 (1973). Sage, B. H., Reamer, H. H., Olds, R. H., Lacey, W. N.,ibid., 34, 1108 H., Sage, B. H., Lacey, W. N.,Znd. Eng. Chem., 34, 1008 (1942). Sage, B. H., (1942). e Kohn, J. P., Bradish, W. F.,J. Chem. Eng. Data, 9, 5 (1964). Shipman, L. M., Kohn, J. P., ibid., 11, 176 (1966). Lavender,, H. M., Lacey, W. N.,Znd. Eng. Chem., 32,743 (1940). Wiese, H. C., Reamer, H.H., Sage, B. H., J. Chem. Eng. Data, 15,75 (1970). Sage, B. H., Budenholzer, R. A., Lacey W. N.,Znd. Eng. Chem 32, 1262 (1940). Kay, W. B., ibid., 40, 1459 (1948). McKay, Kay,W. B., R. A., Reamer, H. H., Sage,B. H., Lacey, W. N.,ibid., 43, 2112 (1951). "'Kahre, L. C.,J. Chem. Eng. Data, 18,267 (1973). Znd. Eng. Chem., 32, 353 (1940). Reamer, H. H., Sage, B. H., Besserer, G. J., Robinson, D. B.,J. Chem. Eng. Data, 18, 301 (1973). Lacey, W. N., ibid., 5, 44 (1960). Kay, W. B., Albert, R. E.,Znd. Eng. Chem., 48,422 (1956). a Kay, W. B., ibid., 30, 459 (1938). Rodrigues, A. B. J . , McCaffrey, D. S., Jr., Kohn, J . P.,J. Chem. Eng. Data, 13, 164 (1968). ' Reamer, H. H., Sage, B. H., ibid., 7, 161 (1962). Sage, B. H., Lacey, W. N., Monograph for API Research Project No. 37, "Some Properties of Lighter Hydrocarbons, Hydrogen Goff, G. H., Farrington, P. S., Sage, B. H.,Ind. Eng. Sulfide and Carbon Dioxide", American Petroleum Institute, Washington, D.C., 1955. Chem., 42,735 (1950). Kay, W. B.,J. Chem. Eng. Data, 15,46 (1970). Vaughan, W. E., Collins, F. C.,Znd. Eng. Chem., 34,885 (1942). Kay, W. B., J. Chem. Eng. Data, 16, 137 (197 1). Glanville, J . W., Sage, B. H., Lacey, W. N.,Znd. Eng. Chem., 42,508 (1950). Kay, W. B., Genco, J . , Fichtner, D. A.,J. Chem. Eng. Data, 19, 275 (1974). Reamer, H. H., Sage, B. H., ibid., 11, 17 (1966). bb Reamer, H. H., Sage, B. H., ibid., 9, 24 (1964). cc Gugnoni, R. J . , Eldridge, J. W., Okay, V. C., Lee, T. J.,AZChEJ., 20, 357 (1974). dd Besserer G. J., Robinson, D. B.,J. Chem. Eng. Data, 18,298 (1973). ee Besserer, G. J., Robinson, D. B., ibid., 18 416 (1973). If Reamer, H. H., Sage, B. H., ibid., 8, 508. (1963). Kay, W. B., Bierlein, Huie, N. C., Luks, K. D., Kohn, J . P.,jbid., 18, 3 11 (1973). Kay, W. B., Rambosek, G. M., ibid., 45, 221 J. A . , Znd. Eng. Chem., 45, 618 (1953). I' Kay, W. B., Brice, D. B., ibid., 45, 615 (1953). (1953). k k Besserer, G. J . , Robinson,D. B.,J. Chem. Eng. Jpn., 8, 11 (1975). " Reamer, H. H., Sage, B. H., Lacey, W. N.,Znd. Eng. Ctzem., 45, 1805 (1953). m m Besserer, G. J., Robinson, D. B.,J. Chem Eng. Data, 20, 157 (1975). n n Gonzalez, M. H., Lee, A. L.,ibid., 13, 172 (1968). O 0 Nichols, W. B., Reamer, H. H., Sage,B. H.,AZChEJ., 3, 262 (1957). p p Howard, K. S., Pike, F. P.,J. Chem. Ens. Data, 4, 331 (1959). Hafez, M., Hartlands, S., ibid., 21, 179 (1976). "Shim, J . , Kohn, J. P., ibid., 9, 1 (1964). '* Murty, P. D., Rao, K. V., Rao, P. V., Chiranjivi, C., ibid., 18, 39 (1973). tt Sanni, S. A., Hutchison, P., ibid., 18, 317 (1973). uu Mikhail, S. J., Kimal, W. R., ibid., 8, 323 (1963). " Ma, Y. H., Kohn, J. P., ibid., 9, 3 (1964). w w Gold, P. I., Perrine. R. L.. ibid.. 12, 5 (1967). x x Tseng, Y. M., Thompson, A. R., Yegrovich, T. W., Swift, G. W., J. Chem. Eng. Data, 9, 264 (1964). y y Thomas, K. T., McAllister, K. A.,AIChEJ., 3. 161 (1957). Kurata, F.,J. Chem. Eng. Datu, 16, 222 (1971). aaa Hellwege, K. H., "Landolt-Bomstein, Numerical Data and Functional Relationships in Science and Technology, Group IV", Vol. 1, Densities of Liquid Systems Part a, Springer Verlag, Berlin, 1974. b b b Hanson, G. H., Kuist, B. B., Brown, G. G.,Znd. Eng. Chern, 36, 1161 (1944). J
'
'
''
270
Journal of Chemical and Engineering Data, Vol. 25, No. 3, 1980
Table 11. Z R Values ~ for Compounds Estimated in the Present Work compd eicosane hydrogen helium ethanol 2-propanol 1-butanol 2-methylpropanol 2-but an01 1-pentanol
ZRA
compd 3-methylbutanol 2-methyl-2-butanol 1h e p t anol 1-octanol water methyl isobutyl ketone monoethanolamine chloroform carbon tetrachloride
0.2266 0.2835' 0.2854' 0.2504 0.2514 0.2585 0.2619 0.2553 0.2582
rule gave the lowest error (6.14%), followed closely by the modified Rackett equation (6.18%) using the same mixing rule. The Harmens model which was found to be good for region I1 showed large deviations. This could be due to the extrapolation of the model which was originally developed for the 0.3 IT, I0.96 range. For the development of a computerized estimation package it would be desirable to have a single correlation over the entire temperature range, if possible, without sacrificing much of the accuracy. With this objective the data were analyzed, over the entire temperature range. For the 2600 points common to the various mixing rules, the information in Table V was obtained: predictions from the two density correlations, modified Rackett and generalized Guggenheim, using the Chueh-Prausnitz and Li mixing rule, respectively, are quite acceptable for engineering design purposes. 4.2 Polar System. On the basis of the analysis for nonpolar systems under 4.1 above, the Barner-Quinlan and Lee-Kessler mixing rules were omitted from this data testing. The Li mixing rule, which has been developed for the critical region, was also not tested as a majority of the experimental data were found to be within the T, range of 0.4-0.7. Table V I summarizes the results of this analysis. An attempt at extending the Halm and Stiel correlation to mixtures was not successful, due to large errors. The modified Rackett equation in conjunction with the Chueh-Prausnitz mixing rule gave an error of 1.55 % for common 824 points which is quite acceptable for engineering design purposes.
ZRA 0.2619 0.2692 0.2554 0.2858 0.2377 0.2573 0.2000 0.2748 0.2721
'Optimized values with quantum correction. Table 111. Results of Preliminary Testing for Various Mixing Rules for T,, syst no. points'
7
10
131
81
% av dev pointsb Harmens MRC GGd
mixingrule i Harmens ii Chiu et al. iii Chueh-Prausnitz iv Barner-Quinlan v Lee-Kesler vi Li i ii iii iv
130 131 130 124 123 131 77 87 83 77 74 87 4 4 4 4 4 4 61 65 61 59 57 65 73 78 78 74 75 78
V
vi
12
4
i ii iii iv V
22
69
vi i ii iii iv V
42
78
vi i ii iii iv V
vi Number of total points. MR = modified Rackett.
.,.,
2 QQ
1.41 4.65 7.75 1.73 3.06 2.06 4.40 7.79 5.1 1 1.81
2.90 5.88 9.28 5.00 3.04
6.44 9.92 13.81 3.42
3.42 6.83 6.07 11.96 11.17 16.69 6.45 3.29 2.78
2.19 9.30 9.20 7.96 1.75
2.34 14.44 14.19 4.97
3.69 2.73 14.93 10.61 4.11
2.12
2.65 6.69 8.02 2.34
2.39 3.26 7.26 2.40 3.04
1.76 5.89 1.27 2.84
2.62 6.04 4.86 3.95
2.15 2.54 6.06 3.03
5. Summary For the purpose of this investigation about 3600 experimental data points from 88 systems were analyzed for prediction purposes. It has been found that the modified Rackett equation with the Chueh-Prausnitz mixing rule is suitable for estimation of density of saturated liquid mixtures. The accuracy of the predicted data should be acceptable from an engineering design standpoint. After submission of this paper a new correlation following the form of Gunn and Yamada equation has been published by Hankinson and Thomson (24).
2.77 4.69 2.08 2.24 6.96
Glossary Chueh and Prausnitz binary interaction parameter Dressure. atm gas constant, 82.057 atm cm3/(g-mol K) temperature, K
k,/ P R
Number of points accepted. GG = generalized Guggenheim.
r
Table IV. Summary of Deviations generalized Guggenheim
Harmens
III~
11'
IIIb
(i) no. of points (ii) % av dev (ii)% max dev
2155 2.94 -21.30
475 6.14 -50.16
(a) Chueh-Pnusnitzc 2636 2155 415 3.29 2.34 6.91 -50.16 17.34 31.26
(i) no. of points (ii) % av dev (iii) % max dev
2333 3.23 36.85
400 8.53 35.82
2741 3.78 36.85
overall
11'
modified Rackett overall
11'
IIIb
overall
2636 3.12 31.26
2155 2.28 -22.55
475 6.18 -53.14
-53.14
400 12.28 38.66
2741 4.98 38.66
2333 3.37 37.81
400 9.10 36.31
2741 3.99 37.81
429 8.89 38.90
2614 3.45 38.90
2636
2.12
(b) LiC
(i) no. of points (ii) % av dev (iii) % max dev
2333 3.85 37.82 (c) H a r m e d 2182 2.5 1 28.38 (d) Chiu et d . C
(i) no. of points (ii) % av dev (iii) % may dev
2232 3.29 48.99
'Region I1 0.4 < T, < 0.95.
407 6.47 -38.93 Region I11 0.95
2647 3.75 48.99
< Tr < 1.00.
Mixing rule for pseudocritical temperature.
J. Chem. Eng. Data 1980, 25, 271-273
Table V. Deviations for 2600 Common Points combination of density correlation and mixing rule for T,,
ij % av dev
i modified Rackett equation with Chueh-Prausnitz mixing rule ii generalized Guggenheim equation with (a) Chiu et al. mixing rule (b) Li mixing rule
Literature Cited 3.55 3.32
density model
(i) % av dev (ii) % max dev
modified Rackett
I-Ialm and Stiel
(a) Chueh-Prausnitz (824)a 3.50 -23.30
2.67 -26.63
1.55 -20.75
6.27 -70.50
(b) Harmens (830)a (i) % av dev (ii) % rnax dev
2.61
- 17.88 (c) Chiu et al. (826)=
(i) % av dev (ii) % max dev
3.19 -28.39
a Mixing rule for pseudocritical temperature. The numbers in parentheses indicate the number of points.
V X
ZRA
i-j binary interaction mixture value reduced value
2.67
Table VI. Summary of the Deviations for Polar Systems generalized Guggenheim Harmens
m r
27 1
saturated liquid volume, cm3/g-mol mole fraction constant in modified Rackett equation
Subscripts ciritical value iJ components
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C
Received for review May 7, 1979. Accepted January 28, 1980.
Vapor-Liquid Equilibrium Data for the Systems H,0-H2S04-HCI, H20-H,S04-HBr, and H,O-HBr at 780 mmHg Pressure
Jean-Louis
E. Chevalier
and Yves H. Gaston-Bonhomme
Laboratoire de G6nie Chimique, Universit6 d'Aix-Marseille111, 13397 Marseille Cedex 4, France
With the help of a dynamlc still made of tantalum, the liquid-vapor equlllbrla In the ternary systems H20-H2S04-HCI and H20-H2S04-HBr have been determlned for the range of concentratlons used In extractlve dlstlllatlon wlth sulfurlc acld as solvent. Liquid-vapor equlllbrlum In the blnary system H20-HBr has been determlned for concentratlons lower than that of the azeotrope. Hila's correlation Is used to calculate the equlllbrlum composltlons. Equlllbrlum temperatures are correlated wlth an emplrlcal relation. All the measurements found in the literature ( 1 , 2) relating to isobaric liquid-vapor equilibrium of the system H,O-H,SO-HCI cover a very small range of low hydrogen acid mole fractions only. For the system H20-H2S04-HBr no result has been published at this date. 0021-9568/80/1725-0271$01.00/0
The importance of the knowledge of phase equilibria, particularly for the design of extractive distillation columns destined to completely recover the hydracid by removing the azeotrope H20-HCI or H20-HBr in the presence of sulfuric acid as solvent, has involved us in determining liquid-vapor equilibria in the two ternary systems H,0-H2S04-HBr and H,O-H,SO,-HCI. The equilibrium of the binary H,O-HBr has been also determined for concentrations lower than that of the azeotrope.
Experimental Method Liquid-vapor equilibria are realized with the help of a dynamic Aubry-Gilot' pattern still (3). It consists of a tantalum coil mounted in a vessel through which circulates a thermoregulated fluid. The investigatedsolution passes continuously through the tantalum coil at a rate which permits sufficient contact time to establish thermal and phase equilibrium. At the outlet, the liquid
0 1980 American
Chemical Society
