Universität zu Köln

Sahle, Christoph J., Niskanen, Johannes, Schmidt, Christian, Stefanski, Johannes, Gilmore, Keith ORCID: 0000-0002-9231-3551, Forov, Yury, Jahn, Sandro ORCID: 0000-0002-2137-8833, Wilke, Max ORCID: 0000-0002-1890-3940 and Sternemann, Christian ORCID: 0000-0001-9415-1106 (2017). Cation Hydration in Supercritical NaOH and HCl Aqueous Solutions. J. Phys. Chem. B, 121 (50). S. 11383 - 11390. WASHINGTON: AMER CHEMICAL SOC. ISSN 1520-6106

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Abstract

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.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Sahle, Christoph J. UNSPECIFIED UNSPECIFIED UNSPECIFIED Niskanen, Johannes UNSPECIFIED UNSPECIFIED UNSPECIFIED Schmidt, Christian UNSPECIFIED UNSPECIFIED UNSPECIFIED Stefanski, Johannes UNSPECIFIED UNSPECIFIED UNSPECIFIED Gilmore, Keith UNSPECIFIED orcid.org/0000-0002-9231-3551 UNSPECIFIED Forov, Yury UNSPECIFIED UNSPECIFIED UNSPECIFIED Jahn, Sandro UNSPECIFIED orcid.org/0000-0002-2137-8833 UNSPECIFIED Wilke, Max UNSPECIFIED orcid.org/0000-0002-1890-3940 UNSPECIFIED Sternemann, Christian UNSPECIFIED orcid.org/0000-0001-9415-1106 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-207709
DOI:	10.1021/acs.jpcb.7b09688
Journal or Publication Title:	J. Phys. Chem. B
Volume:	121
Number:	50
Page Range:	S. 11383 - 11390
Date:	2017
Publisher:	AMER CHEMICAL SOC
Place of Publication:	WASHINGTON
ISSN:	1520-6106
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language X-RAY-ABSORPTION; MICROSCOPIC STRUCTURE; IN-SITU; WATER; DYNAMICS; IONS; SPECTROMETER; SPECTROSCOPY; TEMPERATURE; TRANSPORT Multiple languages Chemistry, Physical Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/20770