Kinetics of the reaction between O([sup 3]P) atoms and 1,3-butadiene between 280 and 1015 K

Journal Article · Thu Feb 18 04:00:00 EST 1993 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100109a025· OSTI ID:6257632

Adusei, G Y; Fontijn, A ^[1]

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1. Rensselaer Polytechnic Inst., Troy, NY (United States)

Rate coefficients for consumption of ground-state oxygen atoms by reaction with 1,3-butadiene have been measured using the high-temperature photochemistry (HTP) technique. The oxygen atom were generated by either laser photolysis of SO[sub 2] or flash photolysis of O[sub 2] or CO[sub 2], and the relative atom concentrations were monitored by resonance fluorescence. The data are well fitted by the expression k(283--1016 K) = 9.7 [times] 10[sup [minus]16] (T/K)[sup 1.46] exp(432 K/T) cm[sup 3] molecule[sup [minus]1] s[sup [minus]1] with 2[sigma] precision limits varying from [+-]7% to [+-]11%, depending upon temperature, and corresponding 2[sigma] accuracy limits of [+-]21% to [+-]23%. Good agreement is found with earlier isolated elementary reaction rate measurements for the 297--488 K range. The combined data are best represented by the expression k(283--1016 K) = 1.0 [times] 10[sup [minus]15] (T/K)[sup 1.45] exp(432 K/T) cm[sup 3] molecule[sup [minus]1] s[sup [minus]1] with the same precision and accuracy limits as above. Comparison of this result to simple transition state theory calculations and structural arguments indicate that O-atom addition to the double bonds dominates over the whole temperature range investigated. This is confirmed by comparing rate coefficients for abstraction of vinylic H to the present results. 19 refs., 2 figs., 1 tab.

• OSTI ID: 6257632
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 97:7; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
400500* -- Photochemistry
BUTADIENE
CARBON COMPOUNDS
CARBON DIOXIDE
CARBON OXIDES
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
DATA
DECOMPOSITION
DIENES
ELEMENTS
EXPERIMENTAL DATA
FLUORESCENCE
HYDROCARBONS
INFORMATION
KINETICS
LUMINESCENCE
MATHEMATICAL MODELS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDATION
OXIDES
OXYGEN
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOLYSIS
POLYENES
REACTION KINETICS
SULFUR COMPOUNDS
SULFUR DIOXIDE
SULFUR OXIDES