Diode laser probes of tert-butyl radical reaction kinetics: Reaction of C(CH sub 3 ) sub 3 with HBr, DBr, and HI
Journal Article
·
· Journal of Physical Chemistry; (USA)
- Northwestern Univ., Evanston, IL (USA)
The rate constants for reaction of tert-butyl radical with HBr, DBr, and HI have been measured by use of a tunable infrared diode laser probe. The measured rate constants at room temperature are 1.0 {times} 10{sup {minus}11}, 8 {times} 10{sup {minus}12}, and 2.5 {times} 10{sup {minus}11} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}, respectively. The reaction with HI exhibits a negative activation energy of 1.5 kcal mol{sup {minus}1}. The reaction rates of HBr and DBr with tert-butyl radical at elevated temperatures are also slower than the corresponding rates at room temperature. The rate constant for reaction of tert-butyl radicals with HBr is in excellent agreement with the faster of the two conflicting previously reported measurements for the tert-butyl-HBr system. From this study the heat of formation of the tert-butyl radical has been calculated to be 11.5 {plus minus} 0.8 kcal mol{sup {minus}1}.
- OSTI ID:
- 6439744
- Journal Information:
- Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 94:9; ISSN JPCHA; ISSN 0022-3654
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKYL RADICALS
BROMINE COMPOUNDS
BUTYL RADICALS
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
HALOGEN COMPOUNDS
INFORMATION
KINETICS
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
RADICALS
REACTION KINETICS
400201* -- Chemical & Physicochemical Properties
ALKYL RADICALS
BROMINE COMPOUNDS
BUTYL RADICALS
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
HALOGEN COMPOUNDS
INFORMATION
KINETICS
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
RADICALS
REACTION KINETICS