Hydration of tetraphenylphosphonium and tetraphenylborate ions by dielectric relaxation spectroscopy

The Journal of Physical Chemistry. B
Wolfgang WachterGlenn Hefter

Abstract

A systematic study of the dielectric relaxation spectra of aqueous solutions of NaBPh4 and Ph4PCl has been made at solute concentrations of 0.02 < or = c/M < or = 0.82 and 0.20, respectively, and over a wide range of frequencies (0.2 < or = nu/GHz < or = 89) at 25 degrees C. The spectra were best described by a superposition of four Debye processes, consisting of a very small ion-pair contribution with an average relaxation time of about 300 ps, a "slow"-water relaxation at 17 ps, and two bulk-water relaxations at 8 ps and 0.25 ps, respectively. The slow-water process has been assigned to the presence of a sheath of water molecules surrounding BPh4- and Ph4P+, whose structure has been enhanced by its proximity to the bulky hydrophobic phenyl rings. A structure-making effect on the remaining solvent water can also be observed at low concentrations. More importantly, BPh4- and Ph4P+ show almost identical hydration characteristics, which provides indirect support for the use of the tetraphenylphosphonium tetraphenylborate reference electrolyte assumption in deriving single-ion thermodynamic properties.

References

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Citations

Oct 9, 2009·Physical Chemistry Chemical Physics : PCCP·Richard Buchner, Glenn Hefter
Jan 1, 2011·Annual Review of Chemical and Biomolecular Engineering·Sumanth N JamadagniShekhar Garde
Jun 24, 2008·The Journal of Chemical Physics·Weixin Xu, Yuguang Mu
Feb 18, 2016·The Journal of Physical Chemistry Letters·Odile CarrierDaniel Bonn
Jul 22, 2014·Angewandte Chemie·Rüdiger ScheuSylvie Roke
Aug 4, 2015·The Journal of Chemical Physics·Elisa I MartínEnrique Sánchez Marcos
Dec 25, 2010·Physical Chemistry Chemical Physics : PCCP·Chandrashekhar V KulkarniSilvia Ahualli
Jul 22, 2016·Journal of Chemical Theory and Computation·Michael SchauperlKlaus R Liedl
Oct 7, 2016·Physical Chemistry Chemical Physics : PCCP·H F M C Martiniano, N Galamba
Nov 10, 2018·The Journal of Chemical Physics·Mateusz Leśniewski, Maciej Śmiechowski
Oct 13, 2007·Physical Review Letters·Y L A Rezus, H J Bakker
May 11, 2007·The Journal of Physical Chemistry. B·Simon SchrödleRichard Buchner
Nov 10, 2006·Chemical Reviews·Yizhak Marcus, Glenn Hefter
Jul 3, 2007·The Journal of Physical Chemistry. B·Wolfgang WachterGlenn Hefter
Aug 18, 2009·Accounts of Chemical Research·Artem A BakulinMaxim S Pshenichnikov
Oct 13, 2010·The Journal of Physical Chemistry. B·Johannes HungerGlenn Hefter
Mar 31, 2012·The Journal of Physical Chemistry. B·Johannes HungerHuib J Bakker
May 24, 2011·The Journal of Physical Chemistry. B·Katherine L MunroeNathan I Hammer
Mar 27, 2012·The Journal of Physical Chemistry. B·Lorenzo RossatoPier Luigi Silvestrelli
Nov 22, 2011·The Journal of Physical Chemistry. B·Hafiz M A RahmanRichard Buchner
Apr 1, 2015·The Journal of Physical Chemistry. B·Andreas EiberweiserRichard Buchner
Feb 5, 2019·The Journal of Physical Chemistry. B·Nicolás Moreno-GómezRichard Buchner
Jul 12, 2011·Journal of the American Chemical Society·Van-Thai PhamMajed Chergui
Jan 26, 2013·The Journal of Physical Chemistry. B·Hafiz M A RahmanRichard Buchner
Jan 31, 2013·The Journal of Physical Chemistry. B·N Galamba
Oct 1, 2019·The Journal of Physical Chemistry. B·Shrikant P MusaleDilip H Dagade

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