The Homogeneous Pyrolysis of Acetylene II: The High Temperature Radical Chain Mechanism
| Autor: | H. Chen, R. D. Kern, K. Xie, J. H. Kiefer, Lawrence B. Harding, S. S. Sidhu |
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| Rok vydání: | 1992 |
| Předmět: |
Reaction mechanism
General Chemical Engineering General Physics and Astronomy Energy Engineering and Power Technology General Chemistry Kinetic energy Dissociation (chemistry) chemistry.chemical_compound Fuel Technology Reaction rate constant Acetylene chemistry Ab initio quantum chemistry methods Thermochemistry Mass spectrum Physical chemistry |
| Zdroj: | Combustion Science and Technology. 82:101-130 |
| ISSN: | 1563-521X 0010-2202 |
| DOI: | 10.1080/00102209208951815 |
| Popis: | A comprehensive kinetic/thermochemical model for the high-temperature radical chain decomposition of acetylene and the polyacetylenes is presented. This mechanism is tested against new shock tube data: time-of-flight mass spectra in C4H2/H2, mixtures over 1600-2100K and laser schlieren experiments in C2H2; covering 2700-3500 K. Some earlier time-of-flight measurements on C2H2, are also modeled. The paper includes a very extensive consideration of species thermochemistry, and the model is in full accord with the current consensus, having Δƒ H0(C2H) = 135·5kcal/mol. Entropies are computed from recent determinations of molecular parameters for C,H and from new high-level ab initio calculations for C4H reported here.Thetime-of-flight measurementssupport Δƒ H0(C2H2)= 111 kcal/mol or 28·24kcal/mol for the [C,-(C1)] group. Rate constants for the key C-H fission reactions of the acetylenes are taken from RRKM calculations calibrated against the direct measurements of dissociation in C2;H2, and C4H2:. Alt... |
| Databáze: | OpenAIRE |
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