Complexes of silver(III) with oxoanions |
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Authors: | James D Rush Louis J Kirschenbaum |
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Institution: | Department of Chemistry, University of Rhode Island, Kingston, RI 02881, U.S.A. |
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Abstract: | Silver(III) has a half-life at pH 11 of several hundred seconds in aqueous solutions in the presence of 0.1–1.0 M concentrations of certain basic oxoanions (Oxo) (phosphate, carbonate, borate, pyrophosphate, and arsenate). This compares with a lifetime of a few seconds at pH 11 in the absence of these oxoanions. UV-visible spectra and kinetic data for these solutions are interpreted as evidence for the following equilibria in the pH range 9–13.Ag(OH)4?1 + H2O ? Ag(OH)3H2O + OH? (1)Ag(OH)4?1 + Oxo ? Ag(OH)3Oxo + OH? (2)Ag(OH)3Oxo + H2O ? Ag(OH)2(Oxo)H2O + OH? (3) Values of K3 lie in the range 10?3 < K3 <104 M for the systems studied. K2 is estimated to be ~102 for phosphate and slightly smaller for the other systems. Ag(OH)4? undergoes an unusual reaction with pyrophosphate at pH ~ 8 to form a novel silver(II) complex, Ag(P2O7)2]6?, for which EPR and electronic absorption spectral parameters are reported. |
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Keywords: | Address correspondence to this author at the University of Rhode Island |
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