Cation Hydration in Supercritical NaOH and HCl Aqueous Solutions
| Autor: | Keith Gilmore, Christian Schmidt, Christoph J. Sahle, Christian Sternemann, Johannes Stefanski, Max Wilke, Johannes Niskanen, Yury Forov, Sandro Jahn |
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| Rok vydání: | 2017 |
| Předmět: |
Aqueous solution
Hydrogen bond Chemistry Inorganic chemistry Ab initio Cation hydration aqueous solutions of NaOH and HCl non resonant X ray Raman scattering core level spectra oxygen K edge Thermodynamics 02 engineering and technology Electrolyte 021001 nanoscience & nanotechnology 01 natural sciences Spectral line Supercritical fluid Surfaces Coatings and Films symbols.namesake Molecular dynamics 0103 physical sciences Materials Chemistry symbols Institut für Geowissenschaften Physics::Chemical Physics Physical and Theoretical Chemistry 010306 general physics 0210 nano-technology Raman scattering |
| Zdroj: | Journal of Physical Chemistry B Scopus-Elsevier |
| ISSN: | 1520-5207 1520-6106 |
| DOI: | 10.1021/acs.jpcb.7b09688 |
| Popis: | We present a study of the local atomic environment of the oxygen atoms in the aqueous solutions of NaOH and HCl under simultaneous high-temperature and high-pressure conditions. Experimental nonresonant X-ray Raman scattering core-level spectra at the oxygen K-edge show systematic changes as a function of temperature and pressure. These systematic changes are distinct for the two different solutes and are described well by calculations within the Bethe- Salpeter formalism for snapshots from ab initio molecular dynamics simulations. The agreement between experimental and simulation results allows us to use the computations for a detailed fingerprinting analysis in an effort to elucidate the local atomic structure and hydrogen-bonding topology in these relevant solutions. We observe that both electrolytes, especially NaOH, enhance hydrogen bonding and tetrahedrality in the water structure at supercritical conditions, in particular in the vicinity of the hydration shells. This effect is accompanied with the association of the HCl and NaOH molecules at elevated temperatures. |
| Databáze: | OpenAIRE |
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