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Engineering topics

Golden, D. M.

Publications and source records attributed to Golden, D. M..

23 records · Page 2

Experimental and theoretical examples of the value and limitations of transition state theory

Value and limitations of transition-state theory (TST) are reviewed. TST analyses of the temperature dependence of the 'direct' reactions CH3 + CH3CHO yields CH4 + CH3CO(1) and O + CH4 yields OH + CH3(2) are presented in detail, and other examples of TST usefulness are recalled. Limitations are discussed for bimolecular processes in terms of 'complex' vs. 'direct' mechanisms. The reaction OH + CO yields CO2 + H is discussed in this context. Limitations for unimolecular processes seem to arise only for simple bond fission processes, and recent advances are noted.

Golden, D. M.↗

Pyrolysis and oxidation of aromatic compounds

A study of the questions associated with the use of alternate fuels demands knowledge of the chemical mechanism of pyrolysis and oxidation of aromatic compounds. Both pyrolysis and oxidation are important, because fuel-rich conditions may mean that pyrolysis is competitive with oxidation. Soot formation is certainly a pyrolysis problem. The complexity of system characteristics makes a detailed study of thermodynamical and kinetic conditions difficult. The matter can be simplified somewhat by generalizing the chemistry by classes of molecules. The criteria for such a generalization of the chemistry are discussed along with an evaluation of the rate constants and their temperature and pressure dependences. Attention is given to the pyrolysis of hydrocarbons, the oxidation of hydrocarbons, the oxidation reactions of alkanes, aspects of codification and extrapolation, group additivity, structural consideration, kinetics, and the pyrolysis of aromatic compounds.

Golden, D. M.↗

Estimation of rate constants of elementary processes - A review of the state of the art.

'Thermochemical kinetics,' the codification and extrapolation of empirical observations, as applied to certain elementary reactions of importance to combustion studies, is described. This approach allows the critical scrutiny of experimental data in areas where sufficient previous data exist, while, at the same time, illuminating those key areas where more experimentation is crucial. It is shown that combination of transition-state theory with an understanding of the molecular basis of entropy puts fairly rigid constraints on the values of the Arrhenius A-factor for most reactions. This, in turn, means that the activation energy is often the key datum that is missing, and that such data can be obtained with some degree of confidence, even from measurements of rate constants at only one temperature. In complex mechanisms, it is often possible to distinguish among alternate pathways and pinpoint key processes.

Golden, D. M.↗

The kinetics of reaction of the by-products of ablative materials at high temperatures and the rate of heat transfer between hot surfaces and reactive gases

Research has been conducted by means of laboratory experiments to enhance understanding of the fundamental mechanisms of heterogeneous and homogeneous chemical reactions taking place during ablative processes that accompany the reentry or manned space vehicles into planetary atmospheres. Fundamental mechanisms of those chemical reactions believed to be important in the thermal degradation of ablative plastic heat shield materials, and the gases evolved, are described.

Spokes, G. N.↗