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

Chialvo, Ariel A.; Vlcek, Lukas

doi:10.1016/j.fluid.2015.05.014

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

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Abstract

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.

Authors:

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

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

Publication Date:: Fri May 22 00:00:00 EDT 2015

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Science (SC)

OSTI Identifier:: 1225420

Alternate Identifier(s):: OSTI ID: 1396425

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Fluid Phase Equilibria

Additional Journal Information:: Journal Volume: 407; Journal Issue: C; Journal ID: ISSN 0378-3812

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

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

Citation Formats


                    Chialvo, Ariel A., and Vlcek, Lukas. Toward the understanding of hydration phenomena in aqueous electrolytes from the interplay of theory, molecular simulation, and experiment.  United States: N. p., 2015. 
Web.  doi:10.1016/j.fluid.2015.05.014.

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                    Chialvo, Ariel A., & Vlcek, Lukas. Toward the understanding of hydration phenomena in aqueous electrolytes from the interplay of theory, molecular simulation, and experiment.  United States.  https://doi.org/10.1016/j.fluid.2015.05.014

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                    Chialvo, Ariel A., and Vlcek, Lukas. Fri .  
"Toward the understanding of hydration phenomena in aqueous electrolytes from the interplay of theory, molecular simulation, and experiment".  United States.  https://doi.org/10.1016/j.fluid.2015.05.014.  https://www.osti.gov/servlets/purl/1225420.

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@article{osti_1225420,

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

  author       = {Chialvo, Ariel A. and Vlcek, Lukas},

  abstractNote = {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.},

  doi          = {10.1016/j.fluid.2015.05.014},

  journal      = {Fluid Phase Equilibria},

  number       = C,

  volume       = 407,

  place        = {United States},

  year         = {Fri May 22 00:00:00 EDT 2015},

  month        = {Fri May 22 00:00:00 EDT 2015}

}

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