Kinetics of the reactions between O( sup 3 P) and 1-butene from 335 to 1,110 K

Journal Article · Thu Nov 14 04:00:00 EST 1991 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100176a060· OSTI ID:7078487

Ko, Taeho; 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 O atoms by reaction with 1-butene have been measured by 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 their relative concentrations were monitored by resonance fluorescence. The data in the 335-1,110 K range are well fitted by the expression k(T) = 2.7 {times} 10{sup {minus}11} exp({minus}624 K/T) + 2.4 {times} 10{sup {minus}9} exp({minus}5,657 K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1} with 2{sigma} precision limits of {plus minus}13 to {plus minus}27%, depending upon temperature, and corresponding 2{sigma} accuracy limits of {plus minus}24 and {plus minus}34%. Good agreement exists among the rate coefficients measured here and those measured by other isolated elementary reaction technique; the authors derive a combined fit expression for the 190-1,110 K range of k(T) = 9.0 {times} 10{sup {minus}12} exp ({minus}230 K/T) + 22 {times} 10{sup {minus}10} exp({minus}2,612 K/T) cm{sup 3} molecule{sup {minus}1}s{sup {minus}1}, with a suggested 2{sigma} accuracy of {plus minus}30%. A transition-state theory calculation for the addition reaction, which had been shown to fit the data well till 490 K, is extended to 1,110 K and seen to reproduce the experimental data increasingly poorly. However, a good fit is obtained when the rate coefficients for H-atom abstraction from the alkyl group in 1-butene are added to those for addition. The conclusion that the interaction between O({sup 3}P) atoms and 1-butene involves both addition and abstraction is reflected in the desirability for the double-exponential fit expressions given. Standard three-parameter fits, given in the text for the convenience of data compilers, approximate the observations well.

• DOE Contract Number: FG02-84ER13224
• OSTI ID: 7078487
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 95:23; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

02 PETROLEUM
020400* -- Petroleum-- Processing
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
ALKENES
BUTENES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
ELEMENTS
EMISSION SPECTROSCOPY
ENERGY LEVELS
EXPERIMENTAL DATA
FLUORESCENCE SPECTROSCOPY
GROUND STATES
HYDROCARBONS
INFORMATION
KINETICS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDATION
OXYGEN
PHOTOCHEMICAL REACTIONS
REACTION KINETICS
SPECTROSCOPY
TEMPERATURE DEPENDENCE
TEMPERATURE RANGE
TEMPERATURE RANGE 0273-0400 K
TEMPERATURE RANGE 0400-1000 K
TEMPERATURE RANGE 1000-4000 K