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Solute-Solute Interactions in Aqueous Solutions

Authors: John J. Kozak; William S. Knight; Walter Kauzmann;

Solute-Solute Interactions in Aqueous Solutions

Abstract

Solute-solute interactions in aqueous solutions of nonelectrolytes are interpreted using both lattice and distribution function theories of the dissolved state. Experimental activity data of high precision can be obtained from the literature for aqueous solutions of many nonelectrolytes. If the logarithm of the solvent activity coefficient (γ1) is expressed as a power series in the mole fraction of the solute (x2), lnγ1 = Bx22 + Cx23 + ···, then the coefficients B and C can be determined analytically from the experimental measurements. Values of B were obtained for 52 aqueous mixtures; values of C were obtained for 39 of these mixtures. The solutes considered include aliphatic alcohols, amines, amides, ketones, fatty acids, amino acids, and sugars. In some cases, experimental data were available from which the temperature dependence of the quantities B and C could also be determined. The effect of solute size on the coefficients B and C was investigated using the lattice theories of Flory, Huggins, and Guggenheim and McGlashan. More detailed conclusions concerning solute-solute interactions can be drawn by using experimental activity data in conjunction with the McMillan-Mayer theory of solutions. The minimum attractive contributions to the second virial coefficient of the osmotic pressure were estimated for most of the systems studied in this paper. Pairwise attractions seem to increase with (1) increasing aliphatic chain length (from the temperature dependence of the coefficient B it is also found that pairwise association due to aliphatic chains increases with increasing temperature); (2) an increase in the number of solute functional groups capable of participating in hydrogen-bond formation; (3) increasing dipole moment of the solute molecule for a series of amino acids and peptides. The minimum attractive contributions to the third virial coefficient were determined and interpreted for 12 of the systems. Finally, the relative importance of pairwise versus triplet interactions in aqueous solution was investigated.

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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
410
Top 1%
Top 1%
Top 10%
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