BIBLIOS

Document type
Journal articles

Document subtype
Full paper

Title
Modeling Preferential Solvation in Ternary Solvent Systems

Participants in the publication
Ne?lson Nunes (Author)
Cristina Ventura (Author)
Filomena Martins (Author)
Dep. Química e Bioquímica
CQB
Ruben Elvas-Leitão (Author)
CQE

Summary
The theoretical solvent exchange model of Bosch and Rose ?s for binary solvents was extended to ternary solvent mixtures. The model was applied to ENT values for the mixture methanol/1-propanol/acetonitrile, in terms of 48 new values in a total of 79, measured at 25°C over the whole range of solvent compositions. It was also applied to the mixture methanol/ethanol/acetone at the same temperature using 93 ENT 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 non consideration 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.


Institution
FACULDADE DE CIÊNCIAS DA UNIVERSIDADE DE LISBOA

Where published
The Journal of Physical Chemistry B

Publication Identifiers

Publisher
American Chemical Society (ACS)



Document Identifiers
DOI - https://doi.org/10.1021/jp804157b
URL - http://dx.doi.org/10.1021/jp804157b

Rankings
SCIMAGO Q1 (2009) - 2.266 - Physical and Theoretical Chemistry
Web Of Science Q2 (2010) - 3.471 - Physical Chemistry