Nitrous oxide nitrogen yields from

Table VII. Observed and Calculated Nitrogen Yields from Nitrous Oxide-Cyclohexane Solutions...

A reactive intermediate may be responsible for the copper catalysis of the hydroxylamine reaction. The intermediate formed in the silver-catalyzed reaction, if it has any real existence, is not further oxidized but breaks down into nitrogen and water. Oxidation of hydroxylamine by cupric ion, on the other hand, yields predominately nitrous oxide. The intermediate formed by the removal of a single electron from the hydroxylamine in this reaction must be further oxidized to yield the final product. Such an intermediate may react readily with silver ions in solution. 

Obenauf et al. [271] have measured the quantum yield of fluorescence per molecule of target gas consumed in the reaction of barium vapour with nitrogen dioxide and nitrous oxide, obtaining values of 0.20—0.27 for the stronger fluorescence from the nitrous oxide reaction, and 0.015 0.003 for the nitrogen dioxide reaction. Using the values for total reaction cross-section reported by Jonah et al. [270], Obenauf et al. [271] estimate the cross-sections for the chemiluminescent reactions to be < 6—7 for the nitrous oxide reaction and about 2—3 for the nitrogen dioxide reaction. 

In attempts to find a suitable chemical dosimeter, both the nitrogen yield from the irradiation of nitrous oxide (7,8) and the hydrogen yield from the irradiation of ethylene (3, 12) have been used to measure the doses absorbed in gases. We have irradiated both of these gases and, using the dose from the calorimetry, we have measured the yields at very high dose rates. 

In this method, first established by Herz and later studied by Hale, hexamine is introduced into fuming nitric acid which has been freed from nitrous acid. The reaction is conducted at 20-30 °C and on completion the reaction mixture is drowned in cold water and the RDX precipitates. The process is, however, very inefficient with some of the methylene and nitrogen groups of the hexamine not used in the formation of RDX. The process of nitrolysis is complex with formaldehyde and some other fragments formed during the reaction undergoing oxidation in the presence of nitric acid. These side-reactions mean that up to eight times the theoretical amount of nitric acid is needed for optimum yields to be attained. 

The yield from this reaction is greatest if the medium is alkaline, for nitrous acid attacks hydrazoic acid oxidizing it with the liberation of nitrogen. If hydrazine sulfate37 is used in the mixture, the resulting hydrazoic acid is not available for the preparation of lead azide until it has been distilled out of the solution. (Lead ions added to the solution would cause the precipitation of lead sulfate.) The reaction mixture may be acidified with sulfuric acid, a little ammonium sulfate may be added in order that the... 

In the 1470-A. photolysis of cyclohexane-nitrous oxide solutions, nitrous oxide reacts with excited cyclohexane molecules to form nitrogen and oxygen atoms. The reaction of N20 with photoexcited 2,2,4-trimethylpentane molecules is much less efficient than with cyclohexane. In the radiolysis of these solutions, G(N2) is the same for different alkanes at low 5 mM) N20 concentrations. At higher concentrations, G(N2) from the radiolysis of cyclohexane is greater than G(N2) from the radiolysis of 2,2,4-trimethylpentane solutions. The N2 yields from 2,2,4-trimethylpentane are in excellent agreement with the theoretical yields of electrons expected to be scavenged by N20. The yield of N2 in the radiolysis of cyclohexane which is in excess of that formed from electrons is attributed to energy transfer from excited cyclohexane molecules to nitrous oxide. 

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