Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 14, Issue 9, Pages 3176-3180Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c2cp23051h
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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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