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Nonelectrolyte Solvation in Aqueous Dimethyl Sulfoxide—A Calorimetric and Infrared Spectroscopic Study

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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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Authors and Affiliations

  1. Department of Chemistry, University College Dublin, Belfield, Dublin 4, Ireland

    G. Reza Bebahani, David Dunnion, Patrick Falvey, Kenneth Hickey, Mary Meade, Yvonne McCarthy & W. Earle Waghorne

  2. Department of Chemistry, de Montfort University, Leicester, UK, LE1 9BH

    Martyn C. R. Symons

Authors
  1. G. Reza Bebahani
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  2. David Dunnion
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  3. Patrick Falvey
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  4. Kenneth Hickey
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  5. Mary Meade
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  6. Yvonne McCarthy
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  7. Martyn C. R. Symons
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  8. W. Earle Waghorne
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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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