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Redox potential of isolated silver atom in water

It was also observed, in 1973, that the fast reduction of Cu ions by solvated electrons in liquid ammonia did not yield the metal and that, instead, molecular hydrogen was evolved [11]. These results were explained by assigning to the quasi-atomic state of the nascent metal, specific thermodynamical properties distinct from those of the bulk metal, which is stable under the same conditions. This concept implied that, as soon as formed, atoms and small clusters of a metal, even a noble metal, may exhibit much stronger reducing properties than the bulk metal, and may be spontaneously corroded by the solvent with simultaneous hydrogen evolution. It also implied that for a given metal the thermodynamics depended on the particle nuclearity (number of atoms reduced per particle), and it therefore provided a rationalized interpretation of other previous data [7,9,10]. Furthermore, experiments on the photoionization of silver atoms in solution demonstrated that their ionization potential was much lower than that of the bulk metal [12]. Moreover, it was shown that the redox potential of isolated silver atoms in water must... [Pg.579]

Experiments on the photoionization of silver atoms in solution have shown that their ionization potential is much lower than that of the bulk metal. It was also shown that the redox potential of isolated silver atoms in water ( °(Ag+/Ag )) must be lower than that of the silver electrode ( °(Ag+/Agmet)) by the sublimation energy of the metal - 2.6 V. Later, reactions of Ag or Ag2" with different oxidizing molecules were systematically studied by pulse radiolysis the high rate constants found were indicative of the electron-donating character of atomic silver,... [Pg.1213]


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