Silent discharge, hydrogen

Autoxidation of Olefins Accompanying a Novel Hydrogen Transfer in a Silent Discharge... 

The first step of the reaction may be the formation of cyclohexyl radicals and cyclohexenyl radicals from cyclohexene by silent discharge. These free radicals might be formed by a cyclohexenyl radical and a hydrogen atom s being generated by electron impact, and the hydrogen atom may add to cyclohexene to give a cyclohexyl radical. 

The formation of the n-propyl radical from propylene suggests that this hydrogen transfer should proceed through some energetic process caused by silent discharge because a normal hydrogen atom addition to propylene proceeds almost exclusively to the terminal carbon (15). Thus, two molecular processes similar to those in the reactions of cyclohexene may be plausible to interpret the hydrogen transfer. 

Eliasson et al. [1, 73-77] reported a silent discharge C02 hydrogenation in the presence or absence of a catalyst to produce methanol. A radical reaction mechanism [75] has been presented to explain the observed phenomena, and can be expressed as ... 

Methyl Alcohol.—According to Maquenne,2 the vapor of methyl alcohol is decomposed by the silent discharge chiefly into methane and carbon monoxide some hydrogen, ethylene, and acetylene and very little carbonic acid, are also produced. The quantity of hydrogen increases with increasing pressure (from 3-100 mm. mercury pressure), that of the other products decreases ... 

Ethylenediamine.—The volume of this compound is rapidly increased by the action of the silent electric discharge. Hydrogen is primarily developed, with some ammonia, nitrogen, and methane or ethane. Absorption of nitrogen and ammonia soon occurs, and hydrogen is split off. In the second stage the formation of condensation products (polyamines) presumably predominates, while in the first period the decomposition of the material started with prevails. 

All compounds taking up nitrogen by simple addition— without giving off hydrogen—i.e., hydrocarbons, alcohols, aldehydes, acids, and bases, when subjected to the influence of the silent discharge, yield substances which behave like amides or amines. Since the formation of these substances cannot, of course, be based upon a substitution of NH2, NH, or N in place of hydrogen, we must ascribe cyclic constitutions to the products obtained. 

Hydrogen peroxide-0 has been prepared by a silent discharge (Jarnagin and Wang, 1958), and nitric oxide by a spark discharge (Clusius and Schleich, 1958). 

At that time, the possibility of producing chemically even traces of ammonia from its elements was disputed. Only the method of electrical production by silent discharge was proven.. . . Of course, the stability of the compound at ordinary temperatures seemed probable, in view of the amount of heat necessary for its formation. But after the numerous fmitless experiments of the previous generation, it seemed beyond doubt that nitrogen and hydrogen would not unite spontaneously at this temperature. Experiments at high temperatures, on the other hand, had up to that time proved nothing but its rate of decomposition, and... 

With Nitrogen.—Donkin has shown that when a mixture of hydrogen and nitrogen is subjected to the silent electric discharge, a partial union of the two gases takes place, with the formation of ammonia —... 

The silent electric discharge in the presence of hydrogen causes transformation of thionyl chloride into sulphur monoclxloridc and sulphur dioxide, with hydrogen chloride 10... 

Carbon Monosulphide, CS.—This sulphur analogue of carbon monoxide is described as resulting8 on passing carbon disulphide vapour over spongy platinum, pumice stone or red-hot charcoal. It is also formed by the action of the silent electric discharge 7 on carbon disulphide or on a mixture of the latter with either hydrogen or carbon monoxide, thus ... 

By subjecting potassium arsenate in a slowly moving stream of hydrogen to a silent electric discharge, reduction to arsenic occurs.9 Suitable conditions for this result are to apply 80 volts to the primary circuit and 15,000 volts to the reaction vessel, using a transformer instead of an induction coil the hydrogen should pass at the rate of 2 litres per hour. 

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