Absolute rate expressions for the abstraction of hydrogen by primary, secondary, and tertiary alkyl radicals from thiophenol

Journal Article · Wed Jan 04 04:00:00 EST 1989 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00183a040· OSTI ID:7071707

Franz, J A; Bushaw, B A; Alnajjar, M S ^[1]

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1. Pacific Northwest Lab., Richland, WA (USA)

Absolute rate expressions for the abstraction of hydrogen from thiophenol in nonane by tert-butyl, isopropyl, n-butyl, and n-octyl radicals were determined by kinetic absorption spectroscopy (KAS). Alkyl radicals were produced by photolysis of dialkyl disulfides or by photolysis of mixtures of di-tert-butyl peroxide and trialkylphosphine in the presence of thiophenol. Arrhenium expressions for alkyl radicals from the phosphine method from 225 to 355 K were as follows: n-butyl, log (k/M{sup {minus}1} s{sup {minus}1}) = (9.40 {plus minus} 0.13) - (1.74 {plus minus} 0.21)/{theta}, {theta} = 2.303RT kcal/mol; isopropyl, log (k/M{sup {minus}1} s{sup {minus}1}) = (9.26 {plus minus} 0.19) - (1.70 {plus minus} 0.21)/{theta}; tert-butyl, log (k/M{sup {minus}1} s{sup {minus}1}) = (9.26 {plus minus} 0.26) - (1.50 {plus minus} 0.20)/{theta}. Rate constants at 298 K vary from 0.8 {times} 10{sup 8} to 1.5 {times} 10{sup 8} M{sup {minus}1} s{sup {minus}1} for the hydrogen-transfer reactions. 32 refs., 2 figs., 2 tabs.

• DOE Contract Number: AC06-76RL01830
• OSTI ID: 7071707
• Journal Information: Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 111:1; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKYL RADICALS
BUTYL RADICALS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
ELEMENTS
EXPERIMENTAL DATA
HYDROGEN
INFORMATION
ISOPROPYL RADICALS
KINETICS
NONMETALS
NUMERICAL DATA
OCTYL RADICALS
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
RADICALS
REACTION KINETICS
REMOVAL
THIOPHENOLS