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Kinetics and equilibria in the system Br + CH/sub 3/OOH in equilibrium HBr + CH/sub 3/OO. An upper limit for the heat of formation of the methylperoxy radical

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j150670a034· OSTI ID:5716367
;
Very low pressure reactor technique (VLPR) is used to study the reaction Br + CH/sub 3/OOH in equilibrium HBr + CH/sub 3/O/sub 2/ (1) at 298-333 K. The A factor for the reaction is estimated on the basis of the tight transition state model and is combined with the measured k/sub 1/ to give the Arrhenius equation: log (k/sub 1//(L/mol s)) = (9.2 +/- 0.3) - (3.2 +/- 0.4) / theta, where theta = 2.303RT kcal/mol. A lower limit of K/sub 1/ is measured at 333 K. Using an estimated ..delta..S/sub 1//sup 0/ = 3.6 +/- 1.1 eu, upper limits are placed on DH/sup 0/ (CH/sub 3/OO-H) < 89.6 kcal/mol and ..delta..H/sub f//sup 0/ (CH/sub 3/OO) < 6.6 kcal/mol. Other pathways for reaction 1 are shown to be unimportant and the secondary reaction Br + CH/sub 3/OO ..-->.. HBr + CH/sub 2/OO (the Criegee zwitterion) is shown to also be unimportant. From data on H/sub 2/O/sub 2/, t-BuO/sub 2/H and arguments about the probable upper limit for K/sub 1/, DH/sup 0/(CH/sub 3/O/sub 2/-H) = 88.5 +/- 0.5 kcal/mol is obtained as a best value. 25 references, 4 figures, 4 tables.
Research Organization:
Univ. of Southern California, Los Angeles
OSTI ID:
5716367
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 88:26; ISSN JPCHA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical &amp; Physicochemical Properties
400301* -- Organic Chemistry-- Chemical &amp; Physicochemical Properties-- (-1987)
400800 -- Combustion
Pyrolysis
&amp; High-Temperature Chemistry
500200 -- Environment
Atmospheric-- Chemicals Monitoring &amp; Transport-- (-1989)
54 ENVIRONMENTAL SCIENCES
ARRHENIUS EQUATION
BROMINE
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMBUSTION PRODUCTS
DATA
ELEMENTS
ENERGY LEVELS
ENTHALPY
ENTROPY
EQUATIONS
EXCITED STATES
EXPERIMENTAL DATA
FORMATION HEAT
HALOGENS
HYDROBROMIC ACID
HYDROGEN COMPOUNDS
INFORMATION
INFRARED SPECTRA
INORGANIC ACIDS
KINETICS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
PEROXY RADICALS
PHYSICAL PROPERTIES
RADICALS
REACTION HEAT
REACTION INTERMEDIATES
REACTION KINETICS
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
THERMODYNAMIC PROPERTIES
VIBRATIONAL STATES