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Pure and Applied Chemistry

The Scientific Journal of IUPAC

Ed. by Burrows, Hugh / Stohner, Jürgen

12 Issues per year

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Volume 83, Issue 12


Gas-phase electrochemistry: Measuring absolute potentials and investigating ion and electron hydration

William A. Donald
  • Corresponding author
  • School of Chemistry, Bio21 Institute of Molecular Science and Biotechnology, and ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, University of Melbourne, Melbourne, Victoria, Australia
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Evan R. Williams
Published Online: 2011-10-07 | DOI: https://doi.org/10.1351/PAC-CON-11-08-15

In solution, half-cell potentials and ion solvation energies (or enthalpies) are measured relative to other values, thus establishing ladders of thermochemical values that are referenced to the potential of the standard hydrogen electrode (SHE) and the proton hydration energy (or enthalpy), respectively, which are both arbitrarily assigned a value of 0. In this focused review article, we describe three routes for obtaining absolute solution-phase half-cell potentials using ion nanocalorimetry, in which the energy resulting from electron capture (EC) by large hydrated ions in the gas phase are obtained from the number of water molecules lost from the reduced precursor cluster, which was developed by the Williams group at the University of California, Berkeley. Recent ion nanocalorimetry methods for investigating ion and electron hydration and for obtaining the absolute hydration enthalpy of the electron are discussed. From these methods, an absolute electrochemical scale and ion solvation scale can be established from experimental measurements without any models.

Keywords: absolute potentials; clusters; electrochemistry; electron capture dissociation; electron transfer; gaseous state; hydrated ions; hydration; ion nanocalorimetry; solvation; thermochemistry


About the article

Published Online: 2011-10-07

Published in Print: 2011-10-07

Citation Information: Pure and Applied Chemistry, Volume 83, Issue 12, Pages 2129–2151, ISSN (Online) 1365-3075, ISSN (Print) 0033-4545, DOI: https://doi.org/10.1351/PAC-CON-11-08-15.

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