Abstract
A detailed thermodynamic study of water (W)-ethylene glycol (EG) mixtures has been carried out as function of temperature (5, 25 and 45°C) and over the entire composition range. The data comprise heats of mixing, densities, heat capacities and compression coefficients. Using excess free energy data from earlier work, molar excess functions were calculated for free energies GE, enthalpies HE and entropies TSE, volumes VE, isobaric and isochoric heat capacities C EP , C EV , adiabatic and isothermal compression KE, K ET and thermal expansion EE, as well as the temperature derivatives of K, C and E functions. The corresponding partial molar quantities were also calculated except for G, H and S and are reported for both EG and W. Also calculated were cohesive energy density, internal pressure and Kirkwood-Buff integrals. The data reported here for EG-W mixtures are compared with similar data for other mixtures as available in order to gain insight into: 1) the relative discriminating ability of various thermodynamic coefficients towards weak cooperative intermolecular interactions in liquids; 2) the quantitative similarities and differences between liquid water and ethylene glycol; 3) the intermolecular phenomena which dominate the properties of EG-W mixtures of varying composition; 4) the usefulness of a qualtitative description of liquid water proposed by Lumry et al. which involves hydrogen-bonding interactions, hydrogen-bonding connectivity and small cooperative fluctuation units.
Similar content being viewed by others
References
D. Eisenber and W. Kauzmann,The Structure and Properties of Water (Oxford University Press, Oxford, 1969).
K. Trincher,Water Research 15, 433 (1981); (b) F. H. Stillinger,Science 209, 451 (1980); (c) H. S. Frank, inWater, a Comprehensive Treatise Vol. 1, F. Franks, ed. (Plenum Press, New York, 1972), Chap. 14; (d) C. A. Angell,La Recherche, 584 (1982); (e) S. A. Rice and M. G. Sceats,J. Phys. chem. 85 1108 (1981).
C. A. Angell,Ann. Rev. Phys. Chem. 34, 593 (1983); (b) C. A. Angell, inWater, a Comprehensive Treatise, F. Franks, ed., Vol. 7, p. 215.
C. Tanford,The Hydrophobic Effect (Wiley, New York, 1980), p. 11.
M. H. Abraham,J. Am. Chem. Soc. 104, 2085 (1982).
R. J. Speedy and C. A. Angell,J. Chem. Phys. 65, 851 (1976).
R. L. Blumberg, H. E. Stanley, A. Geiger, and P. Mausbach,J. Chem. Phys. 80, 5230 (1984).
C. A. Angell,J. Phys. Chem. 75, 3698 (1971).
R. Speedy,J. Phys. Chem. 88, 3364 (1984).
R. Lumry, E. Battistel, and C. Jolicoeur,Faraday Symp. Chem. Soc. 17, 93 (1982).
J. Y. Huot and C. Jolicoeur, inThe Chemical Physics of Ionic Solvation, Part A., J. Ulstrup, ed. (Elsevier, Amsterdam, 1985), Chap. 11.
H. S. Frank and W. Y. Wen,Disc. Faraday Soc. 24, 133 (1957).
R. E. Gibson and O. H. Loeffler,J. Am. Chem. Soc. 63, 898 (1941).
M. R. J. Dack,Chem. Soc. Rev. 4, 211 (1975).
A. Ray,J. Am. Chem. Soc. 91, 6511 (1969); (b) L. G. Ionescu and D. S. Fung,Bull. Chem. Soc. Jap. 54, 2503 (1981).
J. C. Lee and S. N. Timasheff,J. Biol. Chem. 256, 7193 (1981); (b) M. B. Smith, D. G. Oakenfull, and J. P. Back,Aust. Biochem. Soc. Proc. 11, 4 (1978).
T. Arakawa and S. N. Timasheff,Biochemistry 21, 6536 (1982); (b) H. B. Bull and K. Breese,Biophysics 17, 2121 (1978); (c) T. T. Herskovits and J. P. Harrington,Biochemistry 25, 4800 (1972).
K. Gekko and T. Morikawa,J. Biochem. 90, 51 (1981); (b) Y. Fujita, Y. Iwasa, and Y. Noda,Bull. Chem. Soc. Jap. 55, 1896 (1982); (c) A. C. I. Anusiem and A. A. Oshodi,Arch. Biochem. Biophys. 189, 392 (1978).
R. V. McDaniel, T. J. McIntosh, and S. A. Simon,Biochem. Biophys. Acta 731 97 (1983).
D. W. Larsen, S. R. Rananavare, F. E. Stary, M. Elnokaly, and S. E. Friberg,J. Phys. Chem. 88, 4015 (1984); (b) A. Blume,Biophys. Chem. 10, 371 (1979).
M. Oguni and C. A. Angell,J. Chem. Phys. 73, 1948 (1980).
P. A. Giguere,J. Chem. Educ. 60, 399 (1983); (b) A. G. Mitchell and W. F. K. Wynne-Jones,Disc. Faraday Soc. 15, 161 (1953).
M. Allen, D. F. Evans, and R. Lumry,J. Solution Chem. 14, 549 (1985).
M. Oguni and C. A. Angell,J. Chem. Phys. 78, 7334 (1983).
C. DeVisser, W. J. M. Heuvelsland, L. A. Dunn, and G. Somsen,J. Chem. Soc., Faraday Trans. I 74, 1159 (1978).
D. F. Evans, S.-H. Chen, G. W. Schriver, and E. M. Arnett,J. Am. Chem. Soc. 103, 481 (1981); (b) D. Mirejovsky and E. M. Arnett,J. Am. Chem. Soc. 105, 1112 (1983).
D. F. Evans, A. Yamauchi, R. Roman, and E. Z. Casassa,J. Colloid Interface Sci. 88, 89 (1982).
D. K. Magnuson, J. W. Bodley, and D. F. Evans,J. Solution Chem. 13, 583 (1984); (b) T. J. O'Leary and I. W. Levin,J. Phys. Chem. 88, 4074 (1984).
E. Wilhelm and R. Battino,J. Chem. Phys. 56, 563 (1972); (b) R. Lumry, inBioenergetics and Thermodynamics: Model Systems, A. Braibanti, ed. (Reidel, New York, 1980), p. 405.
M. S. Ramadan, D. F. Evans, and R. Lumry,J. Phys. Chem. 87, 4538 (1983).
P. Picker, E. Tremblay, and C. Jolicoeur,J. Solution Chem. 3, 377 (1974).
P. Picker, P. A. Leduc, P. Philip, and J. E. Desnoyers,J. Chem. Thermodyn. 3, 631 (1971).
R. Garnse, y R. J. Boe, R. Mahoney, and T. A. Litovitz,J. Chem. Phys. 50, 5222 (1969).
I. Davidson, G. Perron, and J. E. Desnoyers,Can. J. Chem. 59, 2212 (1981).
V. A. DelGrosso and C. W. Mader,J. Acoust. Soc. 52, 1442 (1972).
P. Picker, C. Jolicoeur, and J. E. Desnoyers,J. Chem. Thermodyn. 1, 469 (1969).
J. C. R. Reis,J. Chem. Soc., Faraday Trans. II 78, 1595 (1982).
G. Douheret and A. Viallard,J. Chim. Phys. 80, 809 (1983).
C. Gonzalez and H. C. VanNess,J. Chem. Eng. Data 28, 410 (1983).
M. A. Villamanan, C. Gonzalez, and H. C. VanNess,J. Chem. Eng. Data 29, 427 (1984).
Y. Matsumoto, H. Touhara, K. Nakanishi, and N. Watanabe,J. Chem. Thermodyn. 9, 801 (1977).
H. G. Konnecke, H. Steinert, and E. Leibnitz,Z. Phys. Chem (Leipzig)208, 147 (1958); (b) K. Rehm and H.-J. Bittrich,Z. Phys. Chem. (Leipzig)251, 109 (1972).
J. M. Corkill, J. F. Goodman, and J. R. Tate,Trans. Faraday Soc. 65, 1742 (1969); (b) N. Nichols, R. Skold, C. Spink, and I. Wadsö,J. Chem. Thermodyn. 8, 993 (1976).
M. Morenas and G. Douheret,Thermochim. Acta 25, 217 (1978); (b) A. Ray and G. Nemethy,J. Chem. Eng. Data 18 309 (1978); (c) G. Gotze and G. M. Schneider,J. Chem. Thermodyn. 12, 661 (1980).
N. M. Murthy and S. V. Subrahmanyan,Indian J. Pure Appl. Phys. 15, 485 (1977).
F. Franks and D. J. G. Ives,Quart. Rev. (London)20, 1 (1966).
M. L. McGlashan and A. G. Williamson,J. Chem. Eng. Data 21, 196 (1976).
R. Battino,Chem. Rev. 71, 5 (1971).
G. C. Benson and O. Kiyohara,J. Solution Chem. 9, 791 (1980).
C. DeVisser, G. Perron, and J. E. Desnoyers,Can. J. Chem. 55, 856 (1977).
K. Nakanishi, N. Kato, and M. Maruyama,J. Phys. Chem. 71, 814 (1967).
G. C. Benson, P. J. D'Arcy, and O. Kiyohara,J. Solution Chem. 9, 931 (1980).
O. Kiyohara and G. C. Benson,J. Solution Chem. 10, 281 (1981).
S. N. Bhattacharyya and D. Patterson,J. Solution Chem. 9, 247 (1980); (b) D. Patterson and M. Barbe,J. Phys. Chem. 80, 2435 (1976).
C. Jolicoeur and G. Lacroix,Can. J. Chem. 54, 624 (1976).
T. Nakajima, T. Komatsu, and T. Nakagawa,Bull. Chem. Soc. Jap. 48, 783 (1975).
T. Nakajima, T. Komatsu, and T. Nakagawa,Bull. Chem. Soc. Jap. 48, 788 (1975).
J. Lara and J. E. Desnoyers,J. Solution Chem. 10, 465 (1981).
G. Roux, D. Roberts, G. Perron, and J. E. Desnoyers,J. Solution Chem. 9, 629 (1980).
M. Sakurai and T. Nakagawa,Bull. Chem. Soc. Jap. 55, 1641 (1982).
M. Sakurai and T. Nakagawa,J. Chem. Thermodyn. 16, 171 (1984).
W. L. Masterton and H. K. Seiler,J. Phys. Chem. 72, 4257 (1968).
Y. DeGrandpré, Ph.D. Thesis, University of Sherbrooke, 1984.
J. E. Desnoyers, G. Caron, R. DeLisi, D. Roberts, A. Roux, and G. Perron,J. Phys. Chem. 87, 1397 (1983); (b) S. W. Benson,J. Am. Chem. Soc. 100, 5640 (1978); (c) C. Jolicoeur, L.-L. Lemelin, and R. Lapalme,J. Phys. Chem. 83, 2806 (1979).
G. DiPaola and B. Belleau,Can. J. Chem. 55, 3825 (1977).
S. Harada, T. Nakajima, T. Komatsu, and T. Nakagawa,J. Solution Chem. 7, 463 (1978).
C. Dethlefsen and A. Hvidt,J. Chem. Thermodyn. 17, 193 (1985).
C. Jolicoeur, inMethods of Biochemical Analysis, G. Glick, ed., Vol. 27 (Wiley, New York, 1981), p. 171.
G. Roux, G. Perron, and J. E. Desnoyers,J. Solution Chem. 7, 639 (1978).
M. V. Kaulgud and S. M. Rao,J. Chem. Soc., Faraday Trans. 1,75, 2237 (1979).
A. LoSurdo, C. Shin, and F. Millero,J. Chem. Eng. Data 23, 197 (1978).
S. D. Christian and E. E. Tucker,J. Solution Chem. 11, 749 (1982).
I. R. Tasker and R. H. Wood,J. Solution Chem. 12 315 (1983).
O. Kiyohara, G. Perron, and J. E. Desnoyers,Can. J. Chem. 53, 3263 (1975).
H. Chebib, C. Jambon, J.-C. Merlin, G. Perron, and J. E. Desnoyers,J. Chim. Phys. Phys.-Chim. Biol. 81, 99 (1984).
Handbook of Chemistry and Physics, 55th ed. (CRC Press, Cleveland, 1976).
D. D. MacDonald, J. B. Hyne, and F. L. Swinton,J. Am. Chem. Soc. 92, 6355 (1970).
D. D. MacDonald and J. B. Hyne,Can. J. Chem. 49, 611 (1971).
M. R. J. Dack,Aust. J. Chem. 28, 1643 (1975).
M. Roseman and W. P. Jencks,J. Am. Chem. Soc. 97, 631 (1975); (b) A. Holtzer and M. F. Emerson,J. Phys. Chem. 73, 26 (1969).
E. Matteoli and L. Lepori,J. Chem. Phys. 80, 2856 (1984).
M. C. A. Donkersloot,J. Solution Chem. 8, 293 (1979).
A. Ben-Naim,Hydrophobic Interactions (Plenum Press, New York, 1980).
A. Ben-Naim,J. Chem. Phys. 67, 4884 (1977).
K. J. Patil,J. Solution Chem. 10, 315 (1981).
D. G. Least, J.-J. Murray, M. L. Post, and D. W. Davidson,J. Phys. Chem. 86, 4175 (1982).
J. G. Priest, E. M. Woolley, J. B. Ott, and J. R. Goates,J. Chem. Thermodyn. 15, 357 (1983).
J. B. Ott, J. R. Goates, and J. D. Lamb,J. Chem. Thermodyn. 4, 123 (1972).
G. Atkinson, M. M. Emara, H. Endo, and B. L. Atkinson,J. Phys. Chem. 84, 259 (1980) (b) S. Nishikawa, M. Tanaka, and M. Mashima,J. Phys. Chem. 85, 686 (1981) (c) W. D. L. Dale, P. A. Flavelle, and P. Kruus,Can. J. Chem. 54, 355 (1976).
N. Takenaka and K. Arakawa,Bull. Chem. Soc. Jap. 47, 566 (1974).
C. J. Burton,J. Acous. Soc. Am. 20, 186 (1947).
S. Nishikawa,J. Chem. Soc., Faraday Trans. I 79, 2651 (1983).
G. Atkinson, S. Rajagopalan, and B. L. Atkinson,J. Phys. Chem. 85, 733 (1981).
P. Buckley and P. A. Giguere,Can. J. Chem. 45, 397 (1967); (b) T.-K. Ha, H. Frei, R. Meyer, and H. H. Gunthard,Theorit. Chim. Acta 34, 277 (1974); (c) D. R. Truax and H. Wieser,Chem. Soc. Rev. 5, 411 (1976); (d) K. G. R. Pachler and P. L. Wessels,J. Mol. Structure 6, 471 (1970).
H. Endo,Bull. Chem. Soc. Jap. 46, 1106 and 1586 (1973).
F. S. Jerome, J. T. Tseng, and C. T. Fan,J. Chem. Eng. Data 13, 496 (1968); (b) O. Landauer, G. Costeanu, and C. Mateescu,Rev. Roumaine de Chim. 19, 1429 (1974) (c) M. Ageno and C. Frontali,Proc. Natl. Acad. Sci. U. S. A. 57, 856 (1967).
M. F. Eaton, A. G. Mitchell, and W. F. K. Wynne-Jones,Trans. Faraday Soc. 48, 796 (1952).
J. L. Hales and J. H. Ellender,J. Chem. Thermodyn. 8, 1177 (1976).
International Critical Tables, E. W. Washburn, Vols. 3 and 4 (McGraw-Hill, New York, 1929).
C. Jolicoeur, J. Boileau, S. Bazinet, and P. Picker,Can. J. Chem. 53, 716 (1975) F. Timmermans,Physico. Chemical Constants of Pure Organic Compounds (Elsevier, Amsterdam, 1950), p. 197.
H. Høiland,J. Solution Chem. 9, 857 (1980).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Huot, JY., Battistel, E., Lumry, R. et al. A comprehensive thermodynamic investigation of water-ethylene glycol mixtures at 5, 25, and 45°C. J Solution Chem 17, 601–636 (1988). https://doi.org/10.1007/BF00645974
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF00645974