Chemical Behavior of Intermediates Produced in Sulfuric Acid Glass by Gamma Irradiation. I. Reactivities of Mobile Electrons with Inorganic Ions

• Published in: Bulletin of the Chemical Society of Japan Vol. 47; no. 3; pp. 529 - 533
• Main Author: Sasaki, Teikichi
• Format: Journal Article
• Language: English
• Published: Tokyo The Chemical Society of Japan 01.03.1974; Chemical Society of Japan
• ISSN: 0009-2673; 1348-0634
• DOI: 10.1246/bcsj.47.529

The yield of the trapped hydrogen atom, Ht, produced in the 6 M sulfuric acid matrix at 77 K was decreased by the presence of an electron scavenger. Based on the competition reaction kinetics, the reactivities of mobile electrons, em−, with metallic and oxygen-containing ions were determined from the decrease in the Ht yield. It was found that em− is scavenged most efficiently with the TeO42− ion. The relative reaction rates of em− with oxyanions were generally larger than those of the corresponding eaq− reactions. On the other hand, a good accordance in the reaction rates for both forms of electrons was observed in the cases of the reactions with metallic ions. An interpretation was given to the discrepancy in the observed reaction rates that em− in the epithermal energy region goes over the Coulomb barrier, which is too high for eaq− to pass through, and thus reacts more efficiently with anionic species than does eaq−. Some unstable intermediates produced at 77 K polymerized with the solute during the thermal annealing. The ESR and optical spectra of the polymerized cadmium and molybdenum are shown, together with those of the primarily-produced species.