M. J. Pilling's Low-Temperature Combustion and Autoignition PDF

By M. J. Pilling

ISBN-10: 0444824855

ISBN-13: 9780444824851

Combustion has performed a critical function within the improvement of our civilization which it keeps at the present time as its principal resource of strength. the purpose of this booklet is to supply an realizing of either basic and utilized points of low-temperature combustion chemistry and autoignition. the subject is rooted in classical observational technological know-how and has grown, via an expanding realizing of the linkage of the phenomenology to coupled chemical reactions, to rather profound advances within the chemical kinetics of either advanced and ordinary reactions. the driver has been either the intrinsic curiosity of an outdated and interesting phenomenon and the centrality of its functions to our fiscal prosperity. the quantity offers a coherent view of the topic whereas, even as, every one bankruptcy is self-contained.

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Extra info for Low-Temperature Combustion and Autoignition

Example text

In the initial stages of reaction, the mechanism in KCl-coated vessels, where H 0 2 and H 2 0 2 are efficiently destroyed at the vessel surface, is very simple. 5). Rco = *if[HCHO][0 2 ] + 2 M W ^ ) [ H C H O ] 2 [ 0 2 ] . 5) Reaction (23) is extremely fast ( f c ~ 5 x 10~12 cm3 molecule -1 s _ 1 ), so that HCO is removed solely in (23) and cannot lead to radical branching or secondary initiation. Furthermore [H 2 0 2 ] is negligible, particularly as initial rates are used. 6) and from excellent plots of Rco /[HCHO] [0 2 ] against [HCHO], k1{ was obtained directly from the intercept.

Unfortunately, at the moment the available thermochemical data, namely, entropies and enthalpies of formation of radicals, are far from reliable. The reaction H + CH4—> CH 3 + H 2 gives a good indication of the problem. Apparently, both rate constants are known accurately [9], and the thermochemical data for the simple species involved are considered very reliable. Nevertheless, the value of Kc calculated from the individual rate constants differs by a factor of 3 to 4 from that calculated thermochemically.

Alkenes, alkylbenzenes). , CH,=CHCH g CH=CH,). range of oxidation conditions. 9 is recommended for use between 600 and 1200 K. They are based on the experimental data available, the principle of bond additivity and that E = AH for the reaction. The decreasing values of A from I to III are consistent with the extra loss of entropy of activation (ca 1 8 J K _ 1 m o l _ 1 per lost rotation) in the emerging electron-delocalized radicals. The data base is probably reliable to a factor of 2 between 600 and 1200 K unless there is a very marked non-Arrhenius behaviour in kx.

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Low-Temperature Combustion and Autoignition by M. J. Pilling

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