Unimolecular decomposition of t-C[sub 4]H[sub 9] radical
- Catholic Univ. of America, Washington, DC (United States)
The kinetics of the unimolecular decomposition of the t-C[sub 4]H[sub 9] radical has been studied. The reaction was isolated for quantitative study in a heated tubular flow reactor coupled to a photoionization mass spectrometer. Rate constants for the decomposition were determined in time-resolved experiments as a function of temperature (712-779 K) and bath gas density ((3-22) x 10[sup 16] molecules cm[sup [minus]3]) in He. The rate constants are in the falloff region under the conditions of the experiments. A transition-state model was created to obtain values of the microcanonical rate constants, k(E), needed to solve the master equation. The transition-state model provides the high-pressure limit rate constants for the decomposition reaction (k[sub 1][sup [minus]](t-C[sub 4]H[sub 9] [yields] i-C[sub 4]H[sub 8] + H) = 2.18 x 10[sup 9]T[sup 1.48] exp(-18120 K/T) s[sup [minus]1]) and the reverse reaction (k[sub [minus]1][sup [infinity]](H + i-C[sub 4]H[sub 8] [yields] t-C[sub 4]H[sub 9]) = 1.03 x 10[sup [minus]11] T[sup 0.25] exp(-737 K/T) cm[sup 3] molecule[sup [minus]1] s[sup [minus]1]). The results of earlier studies of reactions of decomposition of t-C[sub 4]H[sub 9] and the reverse reaction which reported the value of the enthalpy of formation of t-C[sub 4]H[sub 9] were reanalyzed, and the resultant value of [Delta]H[sub f][degrees][sub 298](t-C[sub 4]H[sub 9]) is in agreement with the most current measurements. 51 refs., 8 figs., 3 tabs.
- DOE Contract Number:
- FG05-89ER14015
- OSTI ID:
- 7019502
- Journal Information:
- Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 98:20; ISSN JPCHAX; ISSN 0022-3654
- Country of Publication:
- United States
- Language:
- English
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ALKYL RADICALS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
ELEMENTS
ENTHALPY
EXCIMER LASERS
EXPERIMENTAL DATA
FLUIDS
GAS LASERS
GASES
HELIUM
INFORMATION
INTEGRAL TRANSFORMATIONS
ISOBUTYL RADICALS
KETONES
KINETICS
LAPLACE TRANSFORMATION
LASERS
MASS SPECTROSCOPY
MATHEMATICAL MODELS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
PHYSICAL PROPERTIES
PYROLYSIS
RADICALS
RARE GASES
REACTION KINETICS
SPECTROSCOPY
THEORETICAL DATA
THERMOCHEMICAL PROCESSES
THERMODYNAMIC PROPERTIES
THERMODYNAMICS
TRANSFORMATIONS