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Title: Resolving Local Configurational Contributions to X-ray and Neutron Radial Distribution Functions Within Solutions of Concentrated Electrolytes – A Case Study of Concentrated NaOH

Abstract

Extreme conditions of complex materials often lead to a manifold of local environments that challenge characterization and require new advances at the intersection of modern experimental and theoretical techniques. In this contribution, highly caustic and viscous aqueous NaOD solutions were characterized with a combination of X-ray and neutron radial distribution function (RDF) analyses, molecular dynamics simulations and sub-ensemble analysis. The interpretation of the experimental RDFs extends beyond the traditional understanding of atom-pair interactions and to the individual contributions of specific molecular-scale configurations (below 3.5 Å). This integrated approach yields unique insight into the complex and significant breath of ion solvation and pairing structural motifs present, the experimental sensitivity of RDFs to changes in local geometries, and the challenge of experimentally differentiating the ensemble of all superimposed local environments — a feature of increasing importance within the extreme condition of high ionic strength. This study was facilitated by the development of a chemically resistant sample cell for in-situ neutron total scattering measurements of highly caustic materials at elevated temperature and pressure conditions. Advancing these integrated capabilities is critical for ongoing model validation efforts and for extending the predictive capabilities needed for the extremes of chemical composition, aiding a variety of industrialmore » processes that include advanced nuclear waste remediation and metal refining strategies.« less

Authors:
 [1];  [2];  [3];  [3];  [4]; ORCiD logo [3];  [2];  [4];  [1]
  1. WASHINGTON STATE UNIV
  2. OAK RIDGE NATIONAL LAB
  3. BATTELLE (PACIFIC NW LAB)
  4. Oak Ridge National Laboratory
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1530603
Report Number(s):
PNNL-SA-139609
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 21; Journal Issue: 13
Country of Publication:
United States
Language:
English

Citation Formats

Semrouni, David, Wang, Hsiu-Wen, Clark, Sue B., Pearce, Carolyn I., Page, Katherine, Schenter, Gregory K., Wesolowski, David J., Stack, Andrew G., and Clark, Aurora E. Resolving Local Configurational Contributions to X-ray and Neutron Radial Distribution Functions Within Solutions of Concentrated Electrolytes – A Case Study of Concentrated NaOH. United States: N. p., 2019. Web. doi:10.1039/c8cp06802j.
Semrouni, David, Wang, Hsiu-Wen, Clark, Sue B., Pearce, Carolyn I., Page, Katherine, Schenter, Gregory K., Wesolowski, David J., Stack, Andrew G., & Clark, Aurora E. Resolving Local Configurational Contributions to X-ray and Neutron Radial Distribution Functions Within Solutions of Concentrated Electrolytes – A Case Study of Concentrated NaOH. United States. doi:10.1039/c8cp06802j.
Semrouni, David, Wang, Hsiu-Wen, Clark, Sue B., Pearce, Carolyn I., Page, Katherine, Schenter, Gregory K., Wesolowski, David J., Stack, Andrew G., and Clark, Aurora E. Sun . "Resolving Local Configurational Contributions to X-ray and Neutron Radial Distribution Functions Within Solutions of Concentrated Electrolytes – A Case Study of Concentrated NaOH". United States. doi:10.1039/c8cp06802j.
@article{osti_1530603,
title = {Resolving Local Configurational Contributions to X-ray and Neutron Radial Distribution Functions Within Solutions of Concentrated Electrolytes – A Case Study of Concentrated NaOH},
author = {Semrouni, David and Wang, Hsiu-Wen and Clark, Sue B. and Pearce, Carolyn I. and Page, Katherine and Schenter, Gregory K. and Wesolowski, David J. and Stack, Andrew G. and Clark, Aurora E.},
abstractNote = {Extreme conditions of complex materials often lead to a manifold of local environments that challenge characterization and require new advances at the intersection of modern experimental and theoretical techniques. In this contribution, highly caustic and viscous aqueous NaOD solutions were characterized with a combination of X-ray and neutron radial distribution function (RDF) analyses, molecular dynamics simulations and sub-ensemble analysis. The interpretation of the experimental RDFs extends beyond the traditional understanding of atom-pair interactions and to the individual contributions of specific molecular-scale configurations (below 3.5 Å). This integrated approach yields unique insight into the complex and significant breath of ion solvation and pairing structural motifs present, the experimental sensitivity of RDFs to changes in local geometries, and the challenge of experimentally differentiating the ensemble of all superimposed local environments — a feature of increasing importance within the extreme condition of high ionic strength. This study was facilitated by the development of a chemically resistant sample cell for in-situ neutron total scattering measurements of highly caustic materials at elevated temperature and pressure conditions. Advancing these integrated capabilities is critical for ongoing model validation efforts and for extending the predictive capabilities needed for the extremes of chemical composition, aiding a variety of industrial processes that include advanced nuclear waste remediation and metal refining strategies.},
doi = {10.1039/c8cp06802j},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 13,
volume = 21,
place = {United States},
year = {2019},
month = {4}
}