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Rates of reactions of O(/sup 3/P) with xylenes

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100206a041· OSTI ID:6462377
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Absolute rate coefficients for the reactions of O(/sup 3/P) with o-xylene (k/sub 1/), m-xylene (k/sub 2/), p-xylene (k/sub 3/), o-xylene-d/sub 10/ (k/sub 4/), and m-xylene-d/sub 10/ (k/sub 5/) were measured over the temperature range 298 to 970 K by using the technique of flash photolysis-resonance fluorescence. Between 298 and 600 K, the rate coefficients obeyed the following Arrhenius relationships (in cm/sup 3/ molecule/sup -1/ s/sup -1/): k/sub 1/ = (3.90 +- 0.82) x 10/sup -11/ exp(-(1.54 +- 0.08) x 10/sup 3//T), k/sub 2/ = (3.78 +- 0.84) x 10/sup -11/ exp(-(1.35 +- 0.09) x 10/sup 3//T), k/sub 3/ = (3.91 +- 0.77) x 10/sup -11/ exp(-(1.54 +- 0.09) x 10/sup 3//T), k/sub 4/ = (3.42 +- 0.61) x 10/sup -11/ exp(-(1.55 +- 0.07) x 10/sup 3//T), and k/sub 5/ = (2.78 +- 0.59) x 10/sup -11/ exp(-(1.29 +- 0.08) x 10/sup 3//T). Above 600 K, the Arrhenius plots were found to curve upward. The isotopic substitution of deuterium for hydrogen decreased the rate coefficient at T > 600 K, while not affecting the values at T < 600 K. Kinetic and mechanistic information derived from these measurements is discussed.

Research Organization:
Georgia Inst. of Tech., Atlanta
OSTI ID:
6462377
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 86:9; ISSN JPCHA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical &amp; Physicochemical Properties-- (-1987)
400302 -- Organic Chemistry-- Isotope Effects-- (-1987)
400500 -- Photochemistry
AROMATICS
ATOMS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
DEUTERIUM
DEUTERIUM COMPOUNDS
ELEMENTS
ENERGY LEVELS
EXPERIMENTAL DATA
GROUND STATES
HIGH TEMPERATURE
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
MEDIUM TEMPERATURE
NONMETALS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
OXYGEN
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
REACTION KINETICS
STABLE ISOTOPES
TEMPERATURE DEPENDENCE
XYLENES