Publication Type Journal Article
Title Modeling Preferential Solvation in Ternary Solvent Systems
Authors N. G. C. Nunes Cristina Ventura F. Martins R. Elvas-Leitão
Groups MET
Journal JOURNAL OF PHYSICAL CHEMISTRY B
Year 2009
Month March
Volume 113
Number 10
Pages 3071-3079
Abstract The theoretical solvent exchange model of Bosch and Roses for binary solvents was extended to ternary solvent mixtures. The model was applied to ENT Values for the mixture methanol/1-propanot/acetonitrile, in terms of 48 new values in a total of 79, measured at 25 degrees C over the whole range of solvent compositions. It was also applied to the mixture methanol/ethanol/acetone at the same temperature using 93E(T)(N) values obtained from literature. Very good fits between experimental and calculated values, substantiated by external validation methods, were achieved for both sets of data. The use of the developed extended model allowed the interpretation of measured solvatochromic shifts in terms of solute-solvent and solvent-solvent interactions in the local environment of the solute s dye for the two ternary systems and the underlying binary mixtures. It also provided the identification of various complex solvent entities and the quantification of their relative concentrations in the probe s cybotactic region, thus leading to new and significant physicochemical insights at a molecular level, regardless of the nonconsideration of the formation of solvent complexes in the bulk. Results clearly showed a different solvent composition in the vicinity of the solute. The further extension of the model to four and five components is also presented.
DOI http://dx.doi.org/10.1021/jp804157b
ISBN
Publisher
Book Title
ISSN 1520-6106
EISSN
Conference Name
Bibtex ID ISI:000263974900014
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