Abstract
The rate of change of the standard chemical potential with solvent composition,\(\partial \bar G_0 /\partial Z\), has been calculated from precise vapor-pressure measurements for urea at three temperatures and for thiourea at 298.15°K in water-tetrahydrofuran (THF) mixtures. From these results the standard free energy of transfer ΔG ot of the solutes from water to various water-THF mixtures has been obtained together with the standard molar entropy ΔS ot and the standard molar enthalpy ΔH ot of transfer at 298.15°K in the case of urea. The quantity ΔG ot for urea is negative in the water-rich region and positive for mole fractions THF>0.2. There is a nearly complete compensation between ΔH ot andTΔS ot at 298.15°K up to mole fraction THF=0.5. These phenomena can be partly related to the structure in H2O-THF mixtures.
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References
D. B. Wetlaufer, S. K. Malik, L. Stoller, and R. I. Coffin, Jr.,J. Am. Chem. Soc. 86, 509 (1964).
S. A. Shuchukarev and T. A. Tolmacheva,Zh. Strukt. Khim. 9, 21 (1968).
A. Ben-Naim and S. Baer,Trans. Faraday Soc. 60, 1736 (1964).
V. A. Mikhailov, E. F. Grigor'eva, and I. I. Semina,Zh. Strukt. Khim. 9, 958 (1968).
V. A. Mikhailov and E. F. Grigor'eva,Zh. Strukt. Khim. 9, 788 (1968).
E. J. Cohn, T. L. McMeekin, J. T. Edsall, and J. H. Weare,J. Am. Chem. Soc. 56, 2270 (1934).
D. Bax, M. Alfenaar, and C. L. De Ligny,Rec. Trav. Chim. 90, 1002 (1971).
G. Akerlof,J. Am. Chem. Soc. 52, 2353 (1930).
D. Feakins and P. J. Voice,J. Chem. Soc. Faraday Trans. 1 68, 1390 (1972), and references therein.
K. K. Kundu, A. K. Rakshit, and M. N. Das,Electrochim. Acta 17, 1921 (1972).
Y. Pointud, J. Juillard, J. P. Morel, and L. Avédikian,Electrochim. Acta 19, 229 (1974).
R. N. Roy and B. Sen,J. Chem. Eng. Data 13, 79 (1968).
R. N. Roy and A. L. M. Bothwell,J. Chem. Eng. Data 16, 747 (1971).
R. G. Bates, inHydrogen-Bonded Solvent Systems, A. K. Covington and P. Jones, eds. (Taylor and Francis, Ltd., 1968), and references therein.
J. P. Morel and J. Morin,J. Chim. Phys. 67, 2018 (1970).
C. Treiner,J. Chim. Phys. 70, 1183 (1973).
E. Grünwald and A. L. Bacarella,J. Am. Chem. Soc. 80, 3840 (1958).
H. C. Van Ness,Classical Thermodynamics of Non-Electrolyte Solutions (Pergamon Press, 1964).
C. Treiner, J. F. Bocquet, and M. Chemla,J. Chim. Phys. 70, 68 (1973).
J. L. Hawes and R. L. Kay,J. Phys. Chem. 69, 2420 (1965).
G. Scatchard, W. J. Hamer, and S. E. Wood,J. Am. Chem. Soc. 60, 3061 (1938).
Ei. Koizumist Shinichi Ouchi,Nippon Zasshi 91, 501 (1970).
V. A. Shnitko and V. B. Kogan,Zh. Prikl. Khim. 41, 1305 (1968).
F. Franks, M. A. Quickenden, D. S. Reid, and B. Watson,Trans. Faraday Soc. 66, 582 (1970).
R. Signer, H. Arm, and H. Daeniker,Helv. Chim. Acta 52, 2347 (1969).
S. Cabani, G. Conti, and L. Lepori,Trans. Faraday Soc. 67, 1943 (1971).
D. N. Glew and H. Watts,Can. J. Chem. 51, 1933 (1973).
D. N. Glew, H. D. Mak, and N. S. Rath, inHydrogen-Bonded Solvent Systems, A. K. Covington and P. Jones, eds. (Taylor and Francis, Ltd., 1968), p. 195.
F. Franks, inHydrogen-Bonded Solvent Systems, A. K. Covington and P. Jones, eds. (Taylor and Francis, Ltd., 1968), p. 31.
M. D. Zeidler, inWater, A Comprehensive Treatise, Vol. 2, F. Franks, ed. (Plenum Press, 1973), Chap. 10.
C. L. De Ligny, D. Bax, M. Alfenaar, and M. G. L. Elferink,Rec. Trav. Chim. 88, 1183 (1969).
E. Angelsecu and F. Cornea,An. Univ. C.I.Parhon, Bucuresti, Ser. Stiint. Nat. 15, 87 (1957).
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Treiner, C., Tzias, P. Thermodynamic transfer functions for urea and thiourea from water to water-tetrahydrofuran mixtures from precise vapor-pressure measurements. J Solution Chem 4, 471–483 (1975). https://doi.org/10.1007/BF00650686
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DOI: https://doi.org/10.1007/BF00650686