J. Chem. Eng. Data 1904,29,427-429
Glossary A , 6, C
d nIJ P x,Y W
Y
constants of the Antolne equation constants of the Redllch-Klster equation density refractive index pressure mole fraction in liquid and vapor, respectively weight fraction activity coefficient
Registry No. TAME, 994-05-8; methanol, 67-56-1.
Literature Clted (1) Chase,J. D.; Qalvez, B. 8. Hy&ocarbon Process. 1081, 60, 89-93. (2) Penln, D. D.; Armarego, W. F. L.; Penin, D. R. “Puriflcetbn of Laboratory Chemicals”; Pergamon Press: Oxford, 1966 p 200. (3) Reld, C. R.; Prausnltz, J. M.; Sherwood, T. K. “The Properties of Qases and Llquids”, 3rd ed.;The Kingsport Press: New York, 1977, pp 632, 635. (4) Dvo%k, K.; Boublik. T. collect. Czech. Chem. Commun. 1983, 28, 1249~55. ( 5 ) Boubllk, T.; Frled. V.; H&, E. “The Vapour Pressures of Pure Substances”, Elsevier: Amsterdam, 1973; pp 4, 36.
427
(6) H&, E.; A h , K.; et al. “Rovnovh kapallna-pIra za normHlrdbh a nlzk9ch tlaku” (“Vapor-Liquid Equllibrlum at Normal and Low Pressures”); Academla: Prague, 1982. (7) Evans, T. W.; Edlund, K. R. Ind. €ng. Chem. 1983, 28, 1186-8. (8) Alm, K.; Clprian, M. J . Chem. Eng. Data 1980, 25, 100-3. (9) Gibbard, H. F.; Creek, J. L. J . Chem. €ng. Data 1974, 19, 308-10. (10) Ambrose, D.; Sprake. C. H. S. J . Chem. 7Ym-n. 1070, 2 , 83 1-45. (11) WoJciechowski, M. J . Res. h f / . Bur. Sfand. ( U S . ) 1938, 17, 721-45. (12) Scatchard, 0.;Wood, S. E.; Mochei, J. M. J . Am. Chem. SOC. 1946. 68, 1957-82. (13) Hales, J. L.; Ellender, J. H. J. Chem. 7Ymmm@yn. 1978, 8 , 1177-84. (14) Boubllk. T.; Aim, K. Collect. Czech. Chem. Commun. 1972, 37, 3513-21. (15) “Selected Values of Properties of Hydrocarbons and Related Compounds”, API Research ProJoct 44; Thermodynamics Research Center, Texas ABM University: Colt8g-a Station, TX, 1972. (16) Rkldlck, J. A.; Bungw, W. B. “Techniques of Chemlstry (Organic Solvents)”; Webberger, A., Ed.; Wlley: New York, 1970; Vol. 11, p 145. (17) Klrk, R. E.; Othmer, D. F. “Encyclopedia of Chemical Technology”, 2nd ed.; Interscience: New York, 1985; Vol. 8, p 471. 1967; Voi. 13, p 370. (18) Weast, R. C.; Melvin, J. A. “Handbook of Chemlstry and Physics”; CRC Press: Boca Raton, FL, 1982; pp C-374, C-376. (19) Tlmmermans, J. “Physlcochemlcal Constants of Pure Organic Compounds”, Elsevier: Amsterdam, 1950; Vol. I. 1965; Vol. 11. Received for revlew October 25, 1983. Accepted April 25, 1984.
Excess Thermodynamic Properties for Water/Ethylene Glycol Mlguel A. VlllamaRQn,tCarlos Gonzalez, and Hendrlck C. Van Ness’ Chemical and Envlronmental Engineering Department, Rensseker Polytechnic Institute, Troy, New York 12 180
Isothermal P-x data at 60 OC and heatofmlxlng data at 50 OC are reporled for the blnary system water/ethylene glycol. These data, together wlth P-x data at 50 OC and H e data at 25 OC from the llterature, are reduced to provide correlatlons for He, GE, and S‘ as functions of both comwsltlon and temperature.
The heat-of-mixing measurements reported here for water/ethylene glycol at 50 O C combine with the comprehensive data set at 25 O C of Touhara and Nakanishl (1) to establish the temperature dependence of HE. The vapor/llquid equllibdum measurements reported for 60 O C augment a comparable set of P-x data at 50 O C published earlier (2),and together they form the basis for correlation of GE. The ethylene glycol was 99’ mol % reagent from MCB Manufacturing Chemists,Inc. The water was doubly deionized. For P-x measurements In the static VLE apparatus of Qibbs and Van Ness (3)both reagents were thoroughly degassed. The Isothermal dilution calorimeter used for the HE measurements was essentially thet of Winterhalter and Van Ness (4). We have found that for aqueous systems the usual procedure of loading the cakrbneter at room temperature with undegassed reagents is unsatisfactory, because subsequent heating to 50 O C and mixing lead to the evolution of dissolved gases. Loading the calorimeter with reagents at temperatures greater than 50 OC and then sealing it solves the problem. Results and Correlatlon Table I presents the experimental values of total vapor pressure at 60 O C as a function of composition; Table I1 gives values of H E at 50 O C . Permanent address: Dpto. de Termologla, Facultad de Clenclas, Unlversldad de Valladolid. Valladolld, Spain.
0021-9568/84/1729-0427$01.50/0
Table I. P-x Data for Water (l)/Ethylene Glycol (2) at 60
OC” x1
22
PJkPa
0.0 0.0188 0.0487 0.1008 0.1497 0.1989 0.2479 0.2973 0.3477 0.3975 0.4478 0.4982 0.4987 0.5487 0.5989 0.6489 0.6988 0.7489 0.8003 0.8504 0.9001 0.9495 0.9797 1.oooO
1.oooO 0.9812 0.9513 0.8992 0.8503 0.8011 0.7521 0.7027 0.6523 0.6025 0.5522 0.5018 0.5013 0.4513 0.4011 0.3511 0.3012 0.2511 0.1997 0.1496 0.0999 0.0505 0.0203 0.0
0.214 0.543 1.058 1.997 2.892 3.813 4.760 5.790 6.678 7.724 8.718 9.721 9.717 10.713 11.751 12.746 13.757 14.836 15.880 16.879 17.906 18.923 19.428 19.931
‘Bll = -930,Bzz = -1697, Blz
-1050, ViL = 18, VzL = 58.
Correlation of all data is through the four-parameter Margules equation, written for H~ as HE/(x1x2RT)= A21’Xl
+ A 121x2 - (C21’xi + C121xp)xiX2 (1)
and for GE as GE/(X1X2RT)= Azixi -I-A i G z
- ( C Z I X I+ C12X2)X1X2 (2)
0 1984 American Chemical Society
428 Journal of Chemical and Engineering Data, Vol. 29, No. 4, 1984
Table 11. HE-x Data for Water (l)/Ethylene Glycol (2) at
so o c
XI
22
HEl(Jlmo1)
0.0234 0.0523 0.1094 0.1699 0.2343 0.2880 0.3382 0.3973 0.4483 0.5468 0.5965 0.6470 0.6908 0.7297 0.7575 0.7582 0.8199 0.8808 0.9344 0.9786
0.9766 0.9477 0.8906 0.8301 0.7657 0.7120 0.6618 0.6027 0.5517 0.4532 0.4035 0.3530 0.3092 0.2703 0.2425 0.2418 0.1801 0.1192 0.0656 0.0214
-42.3 -95.3 -188.5 -282.1 -370.7 -436.8 -495.0 -555.1 -605.4 -676.5 -697.3 -705.1 -699.8 -684.7 -665.6 -660.4 -593.1 -469.7 -300.6 -113.5
Table 111. Constants in Eq 3 and 4 for Calculation of Correlating Parameters for Water (l)/Ethylene Glycol (2) Mia Mii, Miiz A210 = -2059.209 A211 = 31.24356 A212 = 4.33806 Aim = 258.827 A121 = -9.50026 A122 = -1.47594 Czlo = -4535.562 C211 82.06843 C2l2 = 11.80013 C1m = -1994.695 Clzl = 36.25889 C122 = 5.23041 XI
0
5 0.5
GE
where all parameters are functions of temperature. As a resuR of the Gibbs/Heimholtz equation
J
-750L
(constant x )
Flguro 1. Excess properties for water (l)/ethyleneglycd (2) at 50 O C
In J/mol. the parameters Murin eq 1 are related to the parameters M, of eq 2 by MIr = -T(dMq/dT) I f we assume that HE Is linear in T, then the parameters MI and M,,' are glven by (5) M9 = Mqo/T+ Mti
-4
2
in T
(3) (4)
The HEdata at 50 OC reported here were fmed by eq 1 with a rms deviatlon of 2.5 J/mol. Similarly, the HEdata at 25 OC of Touhara and Nakanishi ( 7 ) were fltted with a rms deviation of 2.3 J/mol. These results provide two sets of parameter values My" In eq 1 from which sets of values for Mu, and MU2 are found by eq 4. Substitution in eq 3, which provides paramater values for eq 2, leaves only the Mvlvalues to be found from VLE data. We have available the P-x data at 60 OC reported here and the P-x data at 50 OC of Gonzalez and Van Ness (2). These two sets of data were reduced simultaneously by Barker's method (6) to find the values of the M, in eq 3 (and hence the M,, values In eq 2) which minimize the sum of squares of the deviations between observed and calculated pressures. The resulting rms value of the pressure deviations is 0.024 kPa. The constants in eq 3 and 4 determined by reduction of ail data are listed in Table 111.
Equations 1-6 should provide reliable values of the excess properties HE,GE,and SEfor the water/glycol binary system over a temperature range of at least 25-75 OC, and reasonable values from 0 to 100 OC. At 50 OC (T = 323.15 K), eq 1, 2, and 5 become H E / ( x 1 x 8 T )= -2.O3424X1 - 0.67499X2
+ (2.23534Xl + O.g4225X2)X1X2
GE/(xlx2RT) = -0.19456~1- 0.17116~2 (0.14957~1 0 . 1 3 5 6 9 ~ 2 ) ~ 1 ~ 2
+
SE/(xlx2R) = -1.83966X 1 O.5O383X2
-
+
+ (2.08577X1 + 0 . 8 0 6 5 6 ~ 2 ) ~ 1 ~ 2
Flgure 1 shows these results in graphical form. Although the system is strongly exothermlc at thls temperature, it shows relatively small deviations from Raoult's law. Recently, Nath and Bender (7) have published P-x data for waterlethylene glycol at 65.1, 77.7, and 90.3 O C . We have calculated values of P from our correlation at the temperatures and x 1 values of these data and find that calculated and expeerknentai values are In qulte satisfactoryagreement, with rms dlfferences of from 0.40 to 0.53 kPa. These BUBL P calculations are described by Van Ness and Abbott (5). I n addition to liquid-phase activity coefficients, they require vapor-phase fugacity coefficients, calculated here from the two-term viriai equation with second vklai coefficients from the correlation of Hayden and O'ConneU ( 8 ) . For pure-component vapor pressures, we used the values reported by Nath and Bender for water, but since they did not report values for ethylene glycol, we calculated values from the equation given by Hales et al.
(9). Glossary A1i, parameters in eq 1 A 21 A 12,A 21 parameters in eq 2 Blll second virlal coefficients, cm3/mol B 229 B 12
J. Chem. Eng. Data 1984, 29, 429-431
parameters in eq 1
429
Literature Clted (1) Touhara, H.; Nakanlshi, K. “Internatlonal Data Series B”; Engineerlng Sciences Data Unh Ltd: London, 1979; Vol. 1, Table 67. (2) Gonzalez, C.; Van Ness, H. C. J . Chem. Eng. Data 1983, 28, 410. (3) Gibbs, R. E.; Van Ness, H. C. Ind. Eng. Chem. Fundam. 1972. 1 7 , 410. (4) Winterhalter, D. R.; Van Ness, H. C. J . Chem. Eng. Data 1966, 7 7 , 189. (5) Van Ness, H. C.; Abbott, M. M. “Classical Thermodynamics of Nonelectrolyte Solutions: Wlth Applications to Phase Equlllbrla”; McGrawHill: New York, 1982; pp 296-9, 348-55. (8) Barker, J. A. A u t . J . Chem. 1953, 6 , 207. (7) Nath. A.; Bender, E. J . &em. Eng. Data 1983, 28, 370. (8) Hayden, J. 0.;O’Connell, J. P. Ind. Eng. Chem. Process Des. D e v . 1975, 14, 209. (9) Hales, J. L.; Cogman, R. C.; Frith, W. J. J . Chem. TYwrmodyn. 1961, 73. 591.
parameters in eq 2 excess Gibbs energy excess enthalpy generic parameter, eq 1 generic parameter, eq 2 constants, eq 3 and 4 total pressure unlversal gas constant excess entropy absolute temperature, K iiouid molar volume of Dure sDecies. cm3/moi mole fractions r
7
Received for review November 9, 1983. Accepted April 23, 1984. M.A.V. is grateful to the U.S.-Spanlsh Jolnt Committee for Scientific and Technological Cooperation for the award of a postdoctoral research grant.
Regglrrtry No. Ethylene glycol, 107-21-1.
Excess Thermodynamic Properties for Water/Acetone Miguei A. ViiiamaABnt and Hendrick C. Van Ness* Chemical and Environmental Engineering Department, Rensseker Polytechnic Institute, Troy, New York 12 180 Table I. HE-x Data for Water (l)/Acetone (2) at 50 “C x1 XI HE,J/mol
Heatofmlxlng data at 50 OC are reported for the blnary system waterlacetone. These data, together wlth H e data at 25 OC from the Ilterature and a previously publlshed correlation for 0‘ at 50 OC, are combined to provlde correlstlons for HE,GE, and SE that are functlons of both composltlon and temperature.
0.0045 0.0176 0.0606 0.1170 0.1957 0.2611 0.3347 0.4090 0.4842 0.5530 0.6152 0.6687 0.7213 0.7664 0.7963 0.8213 0.8547 0.8929 0.9252 0.9486 0.9687 0.9828 0.9914 0.9973
The HEdata reported here for water/acetone at 50 OC along with the data set at 25 OC of Coomber and Wormald ( 7 ) are fitted simuttaneously to determine temperaturedependent pa-’ rameters in the Marequatbn. These results combine with the correlation of Loehe et al. (2) for G E at 50 OC to yield Margules equations with temperaturedependent parameters for both G E and SE. Heatof-mixing data were taken with an isothermal dilution calorimeter as descrlbed by Winterhalter and Van Ness (3). The acetone was OminSolv reagent from MCB Manufacturing Chemlsts, Inc., with an assay of 99.5 mol %; the water was doubly deionized. Boiling the reagents accompllshed partial degassing, and they were loaded into the calorimeter while hot. Thls prevented the evolution of dissolved gases during mixing. Results and Correlatlon
+
- (C21’Xl
+ C12’Xp)X1X2 + D’(X1X2)2
19.3 70.4 210.9 328.8 404.2 400.8 344.8 248.6 127.7 4.1 -109.7 -205.2 -289.7 -350.7 -382.6 -387.5 -399.7 -384.5 -334.3 -265.1 -185.6 -110.8 -58.5 -18.5
0.1071 0.0748 0.0514 0.0313 0.0172 0.0086 0.0027
where ail parameters are functions of temperature. Since SE = (HE- G E ) / T ,we also have
Correlation of all data is by the five-parameter Margules equation, written for H E as H ~ / ( +,RT) x = A 2 1 ’ ~ 1 A 12‘X2
0.9955 0.9824 0.9394 0.8830 0.8043 0.7389 0.6653 0.5910 0.5158 0.4470 0.3848 0.3313 0.2787 0.2336 0.2037 0.1787 0.1453
SE/(X1X2R)
MZI’- A z i ) X 1 M i z ’ - A 1 2 N 2 - C12)X21XlX* + @’- ”1X2)2
[(CPl’ - C21)Xl + 6 1 2 1 (1)
(3)
The assumption that HE is linear in T and the imposition of the Gibbs/Helmholtz equation lead to the relations (4)
and for G E as G ~ / ( x ~ x =~ ~ T )
MJ’ = MlJo/T + Mq2
+ A i s 2 - ( C 2 1 ~ 1+ C i z X 2 ) X i X z + D ( X I X Z ) ~ (2)
M// = MVO/T+
- M#2 In T
(5)
where My’and Mf represent the parameters in eq 1-3, and Mfo, Mql,and Mq2are constants.
+Permanent address: Dpto. de Termologla, Facuttad de Ciencias, Unhrersidad de Valladolid, ValladolM. Spain. 0 0 2 1-9568/84/ 1729-0429$01.50/0
Mq1
(4)
0
1984 American Chemical Society
