Unimolecular reaction mechanisms involving C sub 3 H sub 4 , C sub 4 H sub 4 , and C sub 6 H sub 6 hydrocarbon species
- Sandia National Labs., Livermore, CA (United States)
- Paris-6 Univ., 75 (France). Dynamique des Interactions Moleculaires
The unimolecular rearrangement processes of unsaturated aliphatic hydrocarbons representative of intermediates in rich hydrocarbon flames have been investigated using the quantum chemical BAC-MP4 method. In particular, we have investigated the unimolecular reaction mechanisms involving (1) allene-cyclopropene-propyne rearrangement, (2) vinylacetylene pyrolysis leading to acetylene and diacetylene, and (3) various C{sub 6}H{sub 6} compounds, including 1,5-hexadiyne, 1,2,4,5-hexatetraene, and 1,2-hexadin-5-yne leading to 3,4-dimethylenecyclobutene, fulvene, benzene, 2-ethynyl-1,3-butadiene, and other C{sub 6}H{sub 6} species. Rate constants for various reaction steps give food agreement with available experimental measurements. The reaction mechanisms are also consistent with various deuterium isotope labeling experiments. The results indicate that many different types of reaction mechanisms occur, including concerted pathways involving carbene and vinylidene intermediates and insertion reactions of vinylidenes into C-H bonds and C-C multiple bonds. New decomposition pathways are presented for vinylacetylene pyrolysis, for conversion of 1,2-hexadien-5-yne to fulvene, and for conversion of fulvene to benzene.
- Research Organization:
- Sandia National Labs., Livermore, CA (United States)
- Sponsoring Organization:
- USDOE; USDOE, Washington, DC (United States)
- DOE Contract Number:
- AC04-76DR00789
- OSTI ID:
- 5649544
- Report Number(s):
- SAND-91-8718; CONF-920707-5; ON: DE92005326
- Resource Relation:
- Conference: 24. international symposium on combustion, Sydney (Australia), 5-10 Jul 1992
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
THERMOCHEMICAL PROCESSES
CHEMICAL REACTION KINETICS
ACETYLENE
ALLENE
HARTREE-FOCK METHOD
PERTURBATION THEORY
REACTION INTERMEDIATES
ALKYNES
DIENES
HYDROCARBONS
KINETICS
ORGANIC COMPOUNDS
POLYENES
REACTION KINETICS
400800* - Combustion
Pyrolysis
& High-Temperature Chemistry