Reactions of HS sup sm bullet and S sup sm bullet minus with molecular oxygen, H sub 2 S, HS sup minus , and S sup 2 minus : Formation of SO sub 2 sup sm bullet minus , HSSH sup sm bullet minus , HSS sup sm bullet 2 minus , and HSS sup sm bullet. [Gamma radiation]

Journal Article · Thu May 02 00:00:00 EDT 1991 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100162a044· OSTI ID:6011426

Zhu, J; Petit, K; Colson, A O; DeBolt, S; Sevilla, M D ^[1]

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1. Oakland Univ., Rochester, MI (United States)

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

• DOE Contract Number: FG02-86ER60455
• OSTI ID: 6011426
• Journal Information: Journal of Physical Chemistry; (United States), Vol. 95:9; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
SULFHYDRYL RADICALS
CHEMICAL REACTIONS
THIYL RADICALS
ANIONS
ANNEALING
COBALT 60
ELECTRON SPIN RESONANCE
ELECTRONIC STRUCTURE
EXPERIMENTAL DATA
G VALUE
GAMMA RADIATION
HYDROGEN SULFIDES
HYPERFINE STRUCTURE
ISOTOPE EFFECTS
MATRIX ISOLATION
MOLECULAR ORBITAL METHOD
OXYGEN
OXYGEN 17
PH VALUE
SULFIDES
SULFUR OXIDES
THEORETICAL DATA
BETA DECAY RADIOISOTOPES
BETA-MINUS DECAY RADIOISOTOPES
CHALCOGENIDES
CHARGED PARTICLES
COBALT ISOTOPES
DATA
ELECTROMAGNETIC RADIATION
ELEMENTS
EVEN-ODD NUCLEI
HEAT TREATMENTS
HYDROGEN COMPOUNDS
INFORMATION
INTERMEDIATE MASS NUCLEI
INTERNAL CONVERSION RADIOISOTOPES
IONIZING RADIATIONS
IONS
ISOMERIC TRANSITION ISOTOPES
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
MINUTES LIVING RADIOISOTOPES
NONMETALS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
OXIDES
OXYGEN COMPOUNDS
OXYGEN ISOTOPES
RADIATIONS
RADICALS
RADIOISOTOPES
RESONANCE
STABLE ISOTOPES
SULFUR COMPOUNDS
YEARS LIVING RADIOISOT
400600* - Radiation Chemistry
400201 - Chemical & Physicochemical Properties
400202 - Isotope Effects
Isotope Exchange
& Isotope Separation