Reaction intermediates produced in 2-methyltetrahydrothiophene and its solutions in 2-methyltetrahydrofuran by. gamma. radiolysis and photolysis at 77 K

Journal Article · Thu Sep 09 04:00:00 EDT 1976 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100560a005· OSTI ID:7330576

Dismukes, G C; Willard, J E

The optical and ESR spectra of the trapped intermediates produced by ..gamma.. irradiation of the cyclic thioether 2-methyltetrahydrothiophene (MTHT) in the glassy state at 77 K have been investigated for the purpose of comparing the radiation chemistry of MTHT with that of the much studied oxygen analogue 2-methyltetrahydrofuran (MTHF). The MTHT, in contrast to MTHF, does not physically trap electrons. The electrons react with the MTHT producing a product or products, with a broad absorption at 460 nm, assigned to paramagnetic anions such as CH/sub 3/CH/sub 2/CH/sub 2/CH/sub 2/CHS- or CH/sub 3/CH/sub 2/CH/sub 2/C(CH/sub 3/)S-. A band centered at 625 nm, which is reduced by positive charge scavengers, is attributed to the cation radical of MTHT. Both the ESR and optical spectra show selective bleaching effects with near-ultraviolet and visible light. The products of ..gamma.. radiolysis of solutions of 10 percent of MTHT in MTHF glass reveal both the electron scavenging ability of MTHT and positive charge stabilization by MTHF. Photolysis of MTHT glass at 254 nm produces thiyl radicals. Photoionization of tetramethyl-p-phenylenediamine (TMPD) in MTHT glass is accompanied by formation of MTHT radicals.

• Research Organization: Univ. of Wisconsin, Madison
• OSTI ID: 7330576
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 80:19; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400600* -- Radiation Chemistry
ABSORPTION SPECTRA
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
DECOMPOSITION
ELECTROMAGNETIC RADIATION
ELECTRON SPIN RESONANCE
FURANS
GAMMA RADIATION
GLASS
HETEROCYCLIC COMPOUNDS
INTERMEDIATE STRUCTURE
IONIZING RADIATIONS
KINETICS
LOW TEMPERATURE
MAGNETIC RESONANCE
MTHF
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
REACTION KINETICS
RESONANCE
SOLVENT PROPERTIES
SPECTRA
TRAPPING