Reactions of sulfhydryl and sulfide radicals with oxygen, hydrogen sulfide, hydrosulfide, and sulfide: formation of SO2-, HSSH-, HSS.2- and HSS.

摘要: An electron spin resonance investigation of the reactions HS{sup {sm bullet}} and S{sup bullet}{minus}} produced from H{sub 2}S, {minus}}, 2{minus}} in glassy matrices at low temperatures is presented. Co-60 irradiation 8 M NaClO{sub 4}, 12 LiCl, alkali-metal hydroxide glasses 77 K results formation O{sup bullet}{minus}}, Cl{sub 2}{sup e{sup {minus}}. Upon annealing to about 150 or reacts with solutes form radicals. In presence molecular oxygen each react sulfur dioxide anion radical, SO{sub bullet}{minus}}. {sup 17}O isotopic studies verify source dissolved matrices. absence oxygen, competing processes are clearly observed; i.e., attack 2}S {minus}} dimer radicals HSSH{sup HSS{sup bullet}2{minus}}. At pH authors find that attacks HSS{supmore » bullet}}. Mechanisms for these species proposed, hyperfine couplings g values reported. Ab initio orbital calculations performed aid their understanding electronic structure various radical formed energetics reactions.« less