Comparison of the kinetics of O([sup 3]P) reactions with the four butenes over wide temperature ranges

Journal Article · Thu Apr 07 04:00:00 EDT 1994 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100065a031· OSTI ID:7165856

Adusei, G Y; Fontijn, A ^[1]

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

Rate coefficients for reactions of ground-state oxygen atoms with isobutene, trans-2-butene, and cis-2-butene have been measured using the high-temperature photochemistry (HTP) technique. The oxygen atoms were generated by flash photolysis of either O[sub 2] or CO[sub 2] and the relative atom concentrations were monitored by resonance fluorescence. We find, in cm[sup 3] molecule[sup [minus]1] s[sup [minus]1] units, for isobutene, k(284-1015 K) = 2.0 x 10[sup [minus]15](T/K)[sup 1.28] exp(543 K/T); trans-2-butene, k(292-1022 K) = 3.9 x 10[sup [minus]17](T/K)[sup 1.87] exp(743 K/T); and cis-2-butene, k(292-1086 K) = 2.4 x 10[sup [minus]17](T/K)[sup 1.94] exp(716 K/T). The 2[sigma] precision limits are around [+-]10%, and the corresponding 2[sigma] accuracy limits are estimated to be about [+-]25%. Conventional transition-state-theory calculations for the electrophilic O-addition to the double bond yield at high temperatures rate coefficients smaller than observed. A method is developed for estimating rate coefficients for H abstraction. When the results are added to those of the addition, good agreement with experiments is attained. The differences between the k(T) expressions for the present three reactions and the corresponding 1-butene reaction are discussed. Based on these observations, a method is presented for estimating rate coefficients for O-atom reactions with higher olefins over wide temperature ranges. 38 refs., 8 figs., 4 tabs.

• OSTI ID: 7165856
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 98:14; 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
99 GENERAL AND MISCELLANEOUS
990200 -- Mathematics & Computers
ALKENES
ARGON
BUTENES
CARBON COMPOUNDS
CARBON DIOXIDE
CARBON OXIDES
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
COMPILED DATA
DATA
DECOMPOSITION
ELEMENTS
FLUIDS
FLUORESCENCE
GASES
HELIUM
HYDROCARBONS
INFORMATION
KINETICS
LUMINESCENCE
MATHEMATICAL MODELS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDES
OXYGEN
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOLYSIS
RARE GASES
REACTION KINETICS
RESONANCE FLUORESCENCE