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Hydration and Hydro...
Hydration and Hydrolysis of Thorium(IV) in Aqueous Solution and the Structures of Two Crystalline Thorium(IV) Hydrates
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- Torapava, Natallia (författare)
- Swedish University of Agricultural Sciences,Sveriges lantbruksuniversitet,Institutionen för kemi,Department of Chemistry
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- Persson, Ingmar (författare)
- Swedish University of Agricultural Sciences,Sveriges lantbruksuniversitet,Institutionen för kemi,Department of Chemistry
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- Eriksson, Lars (författare)
- Stockholms universitet,Avdelningen för oorganisk kemi och strukturkemi
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- Lundberg, Daniel (författare)
- Swedish University of Agricultural Sciences,Sveriges lantbruksuniversitet,Institutionen för kemi,Department of Chemistry
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(creator_code:org_t)
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- 2009-11-18
- 2009
- Engelska.
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 48:24, s. 11712-11723
- Relaterad länk:
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https://urn.kb.se/re...
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https://doi.org/10.1...
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https://res.slu.se/i...
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Abstract
Ämnesord
Stäng
- Solid octaaqua(kappa O-2-perchlorato)thorium(IV) perchlorate hydrate, [Th(H2O)(8)(ClO4)](ClO4)(3)center dot H2O, 1, and aqua-oxonium hexaaquatris(kappa O-trifluoromethanesulfonato)thorium(IV) trisaquahexakis(kappa O-trifluoromethanesulfonato)-thorinate(IV), H5O2[Th(H2O)(6)(OSO2CF3)(3)][Th(H2O)(3)(OSO2CF3)(6)], 2, were crystallized from concentrated perchloric and trifluoromethanesulfonic acid solutions, respectively. 1 adopts a severely distorted tricapped trigonal prismatic configuration with an additional oxygen from the perchlorate ion at a longer distance. 2 consists of individual hexaaquatris(kappa O-trifluoromethanesulfonato)thorium(IV) and trisaquahexakis(kappa O-trifluoromethanesulfonato)thorinate(IV) ions and an aquaoxonium ion bridging these two ions through hydrogen bonding. The hydrated thorium(IV) ion is nine-coordinated in aqueous solution as determined by extended X-ray absorption fine structure (EXAFS) and large angle X-ray scattering (LAXS). The LAXS studies also showed a second hydration sphere of about 18 water molecules, and traces of a 3rd hydration sphere. Structural studies in aqueous solution of the hydrolysis products of thorium(IV) have identified three different types of hydrolysis species: a mu O-2-hydroxo dimer, [Th-2(OH)(2)(H2O)(12)](6+), a mu O-2-hydroxo tetramer, [Th-4(OH)(8)(H2O)(16)](8+), and a mu O-3-oxo hexamer, [Th6O8(H2O)(n)](8+). Detailed structures of these three hydrolysis species are given A compilation of reported solid state structures of actinoid(IV) compounds with oxygen donor ligands show a strong correlation between the An-O bond distance and the coordination number. The earlier reported U-O bond distance in the hydrated uranium(IV) ion in aqueous solution, confirmed in this study, is related to nine-coordination. The hydrated tri- and tetravalent actinoid ions in aqueous solution all seem to be nine-coordinated The trivalent ions show a significant difference in bond distance to prismatic and capping water molecules in assumed tricapped trigonal prismatic configuration, while the tetravalent ions seem to form more regular structures, probably because of higher polarization.
Ämnesord
- NATURVETENSKAP -- Kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences (hsv//eng)
- LANTBRUKSVETENSKAPER -- Annan lantbruksvetenskap -- Miljö- och naturvårdsvetenskap (hsv//swe)
- AGRICULTURAL SCIENCES -- Other Agricultural Sciences -- Environmental Sciences related to Agriculture and Land-use (hsv//eng)
Nyckelord
- ray-absorption spectroscopy
- compton-scattering factors
- nitrate solutions
- free atoms
- aqua ion
- complexes
- spectra; exafs
- coordination
- perchlorate
- Chemistry
- Kemi
Publikations- och innehållstyp
- ref (ämneskategori)
- art (ämneskategori)
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