Pulse radiolysis of aqueous hydrogen solutions. I. Rate constants for reaction of e_aq^- with itself and other transients. II. The interconvertibility of e_aq^- and H

The technique of pulse radiolysis has been applied to aqueous solutions with (up to 100 atm.) and without dissolved H₂ in the pH range 7-14. This work demonstrated the reaction H + OH_aq^- → e_aq^-, by direct observation of the absorption of the e_aq^- formed as a product. The rate constants for this and several other reactions in this system have been determined. The values obtained are: k(H + OH_aq^-) = (1.8 ± 0.6) × 10⁷; 2k(e_aq^- + e_aq^-) = (1.1 ± 0.15) × 10¹⁰ at pH 13.3; k(e_aq^- + O_aq^-) = (2.2 ± 0.6) × 10¹⁰ at pH 13; k(O_aq^- + H₂) = (8 ± 4) × 10⁷; k(e_aq^- + H) = (2.5 ± 0.6) × 10¹⁰; k(e_aq^- + OH) = (3.0 ± 0.7) × 10¹⁰ M^-1 sec.^-1.