title: Application of the tetraphenylphosphonium tetraphenylborate (TPTB) assumption to the thermodynamic properties of solvated ions in dimethylsulfoxide.
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 BPh(4)(-) and Ph(4)P(+) ions is sufficiently high to influence the DMSO molecules orientation with respect to the cation and to the anion. Apparently, the Ph(4)P(+) cation does not affect the structure of DMSO whereas the BPh(4)(-) 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.
authors.affiliation: Department of Physical Chemistry, Chemical Faculty, Gdańsk University of Technology, Narutowicza 11/12, 80-233 Gdańsk, Poland. dorota@chem.pg.gda.pl
authors.forename: Dorota
authors.initials: D
authors.lastname: Warmińska
authors.forename: Janusz
authors.initials: J
authors.lastname: Stangret