Are positive ion radicals formed in pulse radiolysis of alkylbenzenesulfonates. [7 MeV linear accelerator]

Journal Article · Thu May 30 04:00:00 EDT 1991 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100164a032· OSTI ID:5973151

Behar, D ^[1]

---

1. Univ. of Notre Dame, IN (United States)

Oxidation of alkylbenzenesulfonates by OH radicals proceeds via two routes: 75-85% of the OH radicals react via addition to the benzene ring, while the rest abstract an H atom from the alkyl group. The relative distribution between the two paths of reaction depends on the nature of the alkyl group. No evidence for the formation of cation radicals from OH adducts was found. H radicals add to the benzene ring to form cyclohexadienyl type radicals, but when reacted with isopropylbenzenesulfonate about 15% of the H radicals abstract hydrogen from the alkyl to form the benzyl type radical. The reaction of SO{sub 4}{sup {sm bullet}{minus}} with alkylbenzenesulfonates produces 50-70% OH adducts and the rest are the benzyl type radicals. At high concentrations of solute and persulfate a short-lived precursor to the benzyl radicals has been observed. The precursors observed with p-toluenesulfonate, isopropylbenzenesulfonate, and m-toluenesulfonate decay in a first-order process with the rates 1.4 {times} 10{sup 6}, 9.4 {times} 10{sup 5}, and 2.5 {times} 10{sup 5} s{sup {minus}1}, respectively. The short-lived precursor is identified as an unstable OH adduct to the benzene ring.

• OSTI ID: 5973151
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 95:11; ISSN 0022-3654; 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
400201 -- Chemical & Physicochemical Properties
400500 -- Photochemistry
400600* -- Radiation Chemistry
ABSORPTION SPECTROSCOPY
ALKYLATED AROMATICS
AROMATICS
CATIONS
CHARGED PARTICLES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DECOMPOSITION
ELECTRON SPIN RESONANCE
ELECTRONS
ELEMENTARY PARTICLES
FERMIONS
HYDROXYL RADICALS
IONS
KINETICS
LEPTONS
MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXIDATION
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADIATION EFFECTS
RADICALS
RADIOLYSIS
REACTION KINETICS
RESONANCE
SOLVATED ELECTRONS
SPECTRA
SPECTROSCOPY
SULFONATES
TIME DEPENDENCE
ULTRAVIOLET SPECTRA