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Hydration of arsenic oxyacid species.
MedLine Citation:
PMID:  23135316     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
The bond distances in hydrated arsenic oxyacid species in aqueous solution have been studied by EXAFS spectroscopy and large angle X-ray scattering, LAXS. These results have been compared to structures in the solid state, as found in an extensive survey of available crystal structures. Protonated oxygen atoms can be distinguished with a longer As-O distance for both arsenic(v) and arsenic(iii) species in the crystalline state. However, the average As-O distance for the H(n)AsO(4)((3-n)-) species (0 ≤ n ≤ 3) remains the same. These average values are slightly shorter, ca. 0.02 Å, than in aqueous solution due to the hydration as determined by EXAFS and LAXS. The K absorption edges for arsenic(v) and arsenic(iii) species are separated by 4.0 eV, and the shape of the absorption edges differs as well. Small but significant differences in the absorption edge features are seen between the neutral acids and the charged oxyacid species. The most important arsenic species from an environmental point of view is arsenous acid, As(OH)(3). In addition to arsenous acid, we have used orthotelluric acid, Te(OH)(6), for comparison with arsenous acid and for detailed studies of the hydration of covalently bound hydroxo groups. Arsenous acid cannot be studied with the same accuracy as orthotelluric acid, due to a relatively low solubility of As(2)O(3)(s) in neutral to acidic aqueous solution. The results from the DDIR studies support the assignment of As(OH)(3) as a weak structure maker analogous to Te(OH)(6), both being neutral weak oxyacids.
Authors:
Johan Mähler; Ingmar Persson; Roger B Herbert
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-11-7
Journal Detail:
Title:  Dalton transactions (Cambridge, England : 2003)     Volume:  -     ISSN:  1477-9234     ISO Abbreviation:  Dalton Trans     Publication Date:  2012 Nov 
Date Detail:
Created Date:  2012-11-8     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  101176026     Medline TA:  Dalton Trans     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Affiliation:
Department of Chemistry, Swedish University of Agricultural Sciences, P.O. Box 7015, SE-750 07 Uppsala, Sweden. Ingmar.Persson@slu.se.
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