Toward the understanding of hydration phenomena in aqueous electrolytes from the interplay of theory, molecular simulation, and experiment

Journal Article · Fri May 22 00:00:00 EDT 2015 · Fluid Phase Equilibria

DOI:https://doi.org/10.1016/j.fluid.2015.05.014· OSTI ID:1225420

Chialvo, Ariel A. ^[1]; Vlcek, Lukas ^[1]

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1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

We confront the microstructural analysis of aqueous electrolytes and present a detailed account of the fundamentals underlying the neutron scattering with isotopic substitution (NDIS) approach for the experimental determination of ion coordination numbers in systems involving both halides anions and oxyanions. We place particular emphasis on the frequently overlooked ion-pairing phenomenon, identify its microstructural signature in the neutron-weighted distribution functions, and suggest novel techniques to deal with either the estimation of the ion-pairing magnitude or the correction of its effects on the experimentally measured coordination numbers. We illustrate the underlying ideas by applying these new developments to the interpretation of four NDIS test-cases via molecular simulation, as convenient dry runs for the actual scattering experiments, for representative aqueous electrolyte solutions at ambient conditions involving metal halides and nitrates.

• Research Organization: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
• Sponsoring Organization: USDOE Office of Science (SC)
• Grant/Contract Number: AC05-00OR22725
• OSTI ID: 1225420
• Alternate ID(s): OSTI ID: 1396425
• Journal Information: Fluid Phase Equilibria, Vol. 407, Issue C; ISSN 0378-3812
• Publisher: Elsevier
• Country of Publication: United States
• Language: English

Related Subjects

75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
molecular simulation
aqueous electrolytes
ion pair association
neutron diffraction with isotopic substitution
heavy water
null-environments