Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 13, Issue 26, Pages 12138-12145Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c1cp21018a
Keywords
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Funding
- U.S. Department of Energy by Lawrence Livermore National Laboratory [DE-AC52-07NA27344]
- Air Force Office of Scientific Research [FA9550-10-1-0521]
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Pair association in Ionic Liquids is an important quantity that affects many of their physical and chemical properties. However, the association constant is a complex function of the component ions as well as of the solvent environment, and no single theory can compute or predict it with quantitative accuracy. In this work we analyze infinite-dilution association data from a number of recent conductance measurements, and develop a linear model correlating the association constant with two relevant interaction energies, i.e., (1) the dielectrically screened Coulomb attraction and hydrogen bonding between ion-pairs, and (2) the ion solvation energy, which in turn takes into account solvent-specific interactions like hydrogen-bond acidity/basicity and hydrophobic/hydrophilic interactions. The results reveal the unique nature of water as a solvent in that it affects ionic association in ways qualitatively different from other common solvents.
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