Electrical discharge theory

Note The acronyms used here are OSPED (optical spectroscopy in a pulsed electrical discharge), FAMS (flowing afterglow mass spectrometry), SIFT (selected ion flow tube), TRAPI (time-resolved atmospheric pressure ionization mass spectrometry), PHPMS (pulsed high-pressure ionization mass spectrometry), ICRMS (ion cyclotron resonance mass spectrometry), and ADO (averaged dipole orientation collision rate theory). 

There are many other important branches of optics in which it is found that the particle theory is much more successful than the wave theory, for example, the theory of the radiation from hot bodies and the theory of the light emitted by gases when excited by an electric discharge, but it is not proposed to discuss these questions here. We shall, however, consider one more important effect which seems to require very definitely the particle theory for its explanation. 

Depending upon the forms in which electrical energy is employed in organic chemistry, we can distinguish three processes, electrolytic, electrothermic, and electric-discharge reactions. A threefold division into theory, methodics and experimental results, hence, naturally follows for the disposition of each of the three resulting chapters. 

Unfortunately, the simple fact is that in radiation chemistry, which has now been elaborately studied by a larger and larger group of very competent scientists for the last 20 years or so, the details are not thoroughly understood. There is even a question whether any of them are well understood although there is no question that there is very much study of these individual effects and that new ones are being found. It is the very complexity of the number of phenomena in radiation chemistry which makes it difficult to develop a theory which is adequate for purposes of comparison with the chemistry of the electric discharge. 

When it is considered that oxidation reactions may be conducted in the presence of various solid and gaseous catalysts, under the influence of electrical discharges, under alpha radiation, etc., it will lie realized that no one theory can be expected to account for the diverse results. Indeed it is reasonable to suppose that the mechanism may be quite different in the different cases. However, in all the methods so far proposed, if any oxygenated compounds at all are formed, aldehydes are present. This would indicate that the aldehyde stage is intermediate in all of the processes. 

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