A spectrophotometric study of the formation and deprotonation of thioarsenite species in aqueous solution at 22 °C

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The ionization constants of thioarsenous acid have been determined at 22 °C by measuring the ultraviolet and visible spectra of thioarsenite species in dilute, aqueous sulfide solutions having S/As = 4.18, As = 1.1 × 10-4 mol/dm3 and pH ≈ 6-10.4. No oxidized species such as arsenate, thioarsenate or polysulfides were detected in the experimental solutions. The equilibrium constants for the thioarsenous acid ionization reactions were obtained from a principal component analysis treatment of the spectra and are as follows:HAsS=H+HAsS3-forwhichpK=3.77(±0.15) H2-AsS32-=H+HAsS3-forwhichpK=6.53(±0.08) HAsS32-=H+AsS33-forwhichpK=9.29(±0.08) The pKa's for the oxythioarsenous ionization reactions have also been estimated by analogy with those for the end member arsenous and thioarsenous acids. The data emphasize the important role of the simple arsenic(III) thioanions in defining the transport and redox chemistry of arsenic in sulfide-containing natural waters.

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