Kinetics of spur reactions of electrons in ethylene glycol--water glassy ice. A pulse radiolytic study

Ethylene glycol--water glasses were pulse irradiated at 1730K. It was found that Cd2+ ions react with both trapped electrons (e-/sub t/, k = (2.5 +- 1) x 105 M-1 sec-1) and with their precursors (k greater than 109 M-1 sec-1). Cd2+ ions which react with e-/sub t/ produce Cd+ ions in the bulk of the glasses. This is demonstrated by the subsequent second-order decay of Cd+. Cd2+ ions which react with the precursors of e-/sub t/ produce Cd+ ions in the spurs. Such Cd+ ions decay away later by a process which is in agreement with the model of Schuler and coworkers. The fraction of Cd+ ions which is produced in the spurs increases with [Cd2+] in accordance with the competition scheme e-/sub m/ → e-/sub t/, Cd2+ + e-/sub m/ → Cd+ where e-/sub m/ represents a precursor of e-/sub t/. From the effect of [Cd2+] on the initial e-/sub t/ and Cd+ absorptions, it was found that k(e-/sub m/ → e-/sub t/)/k(Cd2+ + e-/sub m/) = (0.24 +- 0.02) M. Results are also reported for the recombination of Cd+ and the molar absorptivities of Cd+ and similar cations in aqueous solution