Nanosecond Pulse Radiolysis of Ammoniacal Solutions of Silver Salts

In pulse radiolysis of silver salts in liquid ammonia at 23/sup 0/C, the reaction of e/sub am//sup -/ with Ag + produces Ag, and subsequently the reaction of Ag with Ag/sup +/ produces Ag/sub 2//sup +/ which probably disproportionates to Ag/sub 2/. The maxima in absorption spectra at 435, 390, and 300 nm are ascribed to Ag, Ag/sub 2//sup +/, and Ag/sub 2/, respectively. The measured specific rate of the reaction of e/sub am//sup -/ with Ag/sup +/ is 1.5 x 10/sup 12/ M/sup -1/ sec/sup -1/ at 23/sup 0/C. The calculated specific rate with the Smoluchowski--Debye equation for a diffusion-controlled reaction of e/sub am//sup -/ with Ag/sup +/ is 1.4 x 10/sup 12/ M/sup -1/ sec/sup -1/ at 25/sup 0/C. The specific rate for the reaction of Ag with Ag/sup +/ is 1.3 x 10/sup 10/ M/sup -1/ sec/sup -1/ at 23/sup 0/C. At the same temperature, the ratio of the specific rate for the disproportionation of Ag/sub 2//sup +/ and extinction coefficient of Ag/sub 2//sup +/ at the 390 nm is 10/sup 6/ cm sec/sup -1/. A comparison of the spectra of various silver species dissolved in water with the spectra for same species dissolved in liquid ammoniamore » shows that spectra in liquid ammonia are shifted toward longer wavelengths.« less