Spectral properties and redox potentials of silver atoms complexed by chloride ions in aqueous solution

Pulse radiolysis is used to determine the absorption spectra of the transient species formed during the decay of the hydrated electron in an aqueous solution containing AgCl43-. The mechanisms of AgCl43- reduction by solvated electrons and hydroxyalkyl radicals of 2-propanol are discussed. The redox potential of the couples AgCl43-/(AgCl44-)-Cl-0 and AgCl43-/Ag-0 + 4Cl(-) is evaluated. It is shown that the redox potential of the solvated silver atom couple is lowered by the presence of Cl- ligands. The value of the E-o(AgCl43-/(AgCl44-)-Cl-0) is estimated to be around -2.3 V-NHE.