US EPA

1337527 

Journal Article 

Hydration of arsenic oxyacid species 

Mähler, J; Persson, I; Herbert, RB 

2013 

Yes 

Dalton Transactions
ISSN: 1477-9226
EISSN: 1477-9234 

42 

5 

1364-1377 

English 

23135316 

10.1039/c2dt31906c 

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 HnAsO4(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 As2O3(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.