Abstract
We report enthalpies of solution of formamide, N,N-dimethylformamide,N,N-dimethylacetamide, acetic acid, methyl acetate, and acetonitrile in water +dimethylsulfoxide mixed solvents. These, along with literature data for additional solutes,are analyzed in terms of the extended coordination model of solvation. We alsoanalyze infrared data for several of these solutes. These analyses show thatN,N-dimethylformamide and N,N-dimethylacetamide are preferentially hydrated,while the other solutes appear to be preferentially solvated by dimethylsulfoxide.In all cases, the extent of preferential solvation is relatively small. It is also foundthat the degrees of preferential solvation recovered from analyses of the enthalpydata correspond closely to those recovered from the infrared data, although thelatter refer only to the polar chromophores on the solute molecules. It is foundthat the extent to which the solutes disrupt the solvent-solvent interactions variessystematically with the area of the nonpolar surfaces of the solute molecules.
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REFERENCES
J. G. Kirkwood and F. P. Buff, J. Chem. Phys. 19, 774 (1951).
K. E. Newman, J. Chem. Soc. Faraday Trans. I, 84, 1387 (1988).
Y. Marcus, Aust. J. Chem. 36, 1719 (1983).
Y. Marcus, J. Chem. Soc., Faraday Trans I 85, 3019 (1989).
A. K. Covington and K. E. Newman, Pure Appl. Chem. 51, 2041 (1979).
B. G. Cox and W. E. Waghorne, Chem. Soc. Rev. 9, 381 (1980).
W. E. Acree, Fluid Phase Equilibria 92, 19 (1994).
W. E. Acree and S. S. Tucker, Fluid Phase Equilibria 102, 17 (1994).
W. E. Acree and A. I. Zvaigze, Thermochem. Acta 178, 151 (1991).
W. E. Acree and S. S. Tucker, Fluid Phase Equilibria 101, 199 (1994).
S. Goldman and R. G. Bates, J. Amer. Chem. Soc. 94, 1476 (1972).
National Bureau of Standards (U.S.) circ. 500 (U.S. Government Printing Office, Washington D.C., 1961), pp. 1–139.
J. T. W. Lai, F. W. Lau, D. Robb, P. Westh, G. Nielson, C. Trandum, A. Hvidt, and Y. Koga, J. Solution Chem. 24, 89 (1995).
D. Feakins, E. de Valera, and W. E. Waghorne J. Chem. Soc. Faraday Trans. I 79, 1061 (1983).
D. Feakins, E. de Valera, and W. E. Waghorne, J. Chem. Soc. Faraday Trans. I 81, 2703 (1985).
B. G. Cox and W. E. Waghorne, J. Chem. Soc. Faraday Trans. I 80, 1267 (1984).
D. Feakins, C. C. O'Duinn, and W. E. Waghorne, J. Solution Chem. 16, 907 (1987).
A. Costigan, D. Feakins, I. McStravick, C. O'Duinn, J. Ryan, and W. E. Waghorne, J. Chem. Soc. Faraday Trans. I 87, 2443 (1991).
G. Carthy, D. Feakins, C. O'Duinn, and W. E. Waghorne, J. Chem. Soc. Faraday Trans. I 87, 2447 (1991).
D. Feakins, P. Hogan, C. O'Duinn, and W. E. Waghorne, J. Chem. Soc. Faraday Trans. I 88, 4423 (1992).
G. Eaton and M. C. R. Symons, J. Chem. Soc. Faraday Trans I 84, 3429 (1988); (b) G. Eaton, M. C. R. Symons, and P. P. Rastogi, J. Chem. Soc. Faraday Trans I 85, 3257 (1989).
G. Eaton, M. C. R. Symons, P. P. Rastogi, C. O'Duinn, and W. E. Waghorne, J. Chem. Soc. Faraday Trans. I 88, 1137 (1992).
M. Meade, M. C. R. Symons, and W. E. Waghorne, J. Chem. Soc. Faraday Trans. I 92, 4395 (1996).
M. Meade, K. Hickey, Y. McCarthy, W. E. Waghorne, M. C. R. Symons, and P. P. Rastogi, J. Chem. Soc. Faraday Trans I 93, 563 (1997).
B. G. Cox, J. Chem. Soc. Perkin Trans. II p. 607 (1973).
C. Cronnolly, K. C. Pillai, and W. E. Waghorne, J. Electroanal. Chem. 207, 177 (1986).
C. O'Duinn, D. Feakins, and W. E. Waghorne, J. Solution Chem. 16, 907 (1987).
T. G. Clune, B. G. Cox, A. J. I. Ward and W. E. Waghorne, J. Chem. Soc., Faraday Trans. I 76, 1131 (1980).
B. G. Cox, Ann. Rep. A Phys. Inorg. Chem. p. 265 (1973).
D. Feakins, J. Mullally, and W. E. Waghorne, J. Solution Chem 22, 311 (1993).
K. B. Patel, G. Eaton, and M. C. R. Symons, J. Chem. Soc. Faraday Trans. I 85, 2775 (1985).
M. C. R. Symons and G. Eaton, J. Chem. Soc. Faraday Trans. I 81, 1963 (1985).
J. Burgess, Metal Ions in Solution (Ellis Horwood, Chichester, 1978), p. 32.
W. E. Waghorne, Chem. Soc. Rev. 22, 285 (1993).
F. Rallo, F. Rodante, and P. Silvestroni, Thermochem. Acta 1, 311 (1970).
J. T. W. Lai, F. W. Lau, D. Robb, P. Westh, G. Nielson, C. Trandum, A. Hvidt, and Y. Koga, J. Solution Chem. 24, 89 (1995).
R. Jellema, J. Bulthuis, G. van der Zwan, and G. Somsen, J. Chem. Soc. Faraday Trans. 92, 2563 (1996).
G. Carthy, D. Feakins, and W. E. Waghorne J. Chem. Soc. Faraday Trans. I 83, 2585 (1987).
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Bebahani, G.R., Dunnion, D., Falvey, P. et al. Nonelectrolyte Solvation in Aqueous Dimethyl Sulfoxide—A Calorimetric and Infrared Spectroscopic Study. Journal of Solution Chemistry 29, 521–539 (2000). https://doi.org/10.1023/A:1005142112945
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DOI: https://doi.org/10.1023/A:1005142112945