Application of the tetraphenylphosphonium tetraphenylborate (TPTB) assumption to the thermodynamic properties of solvated ions in dimethylsulfoxide

Literature Information

Publication Date 2012-01-30
DOI 10.1039/C2CP23051H
Impact Factor 3.676
Authors

Dorota Warmińska, Janusz Stangret


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Abstract

The extra-thermodynamic tetraphenylphosphonium tetraphenylborate assumption has been tested for dimethylsulfoxide using ATR FTIR spectroscopy. Solute-affected DMSO spectra show that, contrary to the TPTB assumption, the charge density on BPh4− and Ph4P+ ions is sufficiently high to influence the DMSO molecules orientation with respect to the cation and to the anion. Apparently, the Ph4P+ cation does not affect the structure of DMSO whereas the BPh4− anion clearly breaks it up. Our results indicate that the TPTB extra-thermodynamic assumption is not a sound basis for splitting thermodynamic values obtained for DMSO solutions into ionic contributions.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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