Abstract
Enthalpies of solution were measured for tetraphenylphosphonium bromide (Ph 4PBr), sodium tetraphenylborate (NaBPh 4) and sodium bromide (NaBr) in mixtures of N, N-dimethylformamide (DMF) and water over the whole composition range at 298.15 K. Single ion enthalpies of transfer were calculated with a number of assumptions. A convention by Krishnan and Friedman [ J. phys. Chem. 71, 2487 (1971)] was preferred over the BPh − 4 = Ph 4P + assumption for Δ tr H 0 (W → DMF). For transfer to the mixed solvents the assumption that Na + and Br − are not specifically solvated provides a physically realistic description also for tetraalkyl- and tetraphenylcations. The deviating behaviour of the BPh − 4 ion might be due to steric effects in addition to its higher polarizability. Entropic effects agree with these conclusions.
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