Ethyl nitrate pyrolysis

Houser and Lee [J. Phys. Chem., 71 (3422), 1967] have studied the pyrolysis of ethyl nitrate using a stirred flow reactor. They iiave proposed the following mechanism for the reaction. 

Pyrolysis of ethyl nitrate. Data from a CSTR... 

P2.03.12. PYROLYSIS OF ETHYL NITRATE. DATA FROM A CSTR... 

A chain reaction was proposed for the pyrolysis of ethyl nitrate Houser Lee ( J Phys Chem 1 3422, 1967) ... 

Pyrolysis Kinetics of Ethyl Nitrate , JPhysChem 71 (11) (1967V 3422-26 21) DX. 

The first step in the pyrolysis of the alkyl nitrates has been supposed to be O N bond fission to give NO2 and an alkoxy radical. The activation energy is 39-5 kcal for methyl nitrate and 39-9 or 34-6 kcaP <> for ethyl nitrate. If the latter value for ethyl nitrate is taken, and assumed to be i)(EtO -NO2) a value for the heat of formation of the ethoxy radical in good agreement with that given by Rebbert and Laidler is obtained, so apparently we may put D(MeO -NO2) =40 kcal, and i)(EtO -NO2) =34 kcal. In the opinion of the present author, however, the mechanism of the reaction is not sufficiently well established to allow this to be done. The discrepancy between the result of Adams and Bawn and that of Phillips 390 is large and may well be because of the different pressure ranges in which these authors worked. A further examination of the effect of pressure on rate constant is necessary before it can be taken as established that the reaction is of the first order. 

R. A. Fifer and H. E. Holmes, High temperature pyrolysis of methyl and ethyl nitrate, in "Proceedings of the Seventeenth Symposium (International) of the Combustion Institute", Combustion Institute, Pittsburgh (1979). 

N 13 59% oxygen-rich monomer no props are reported except 1R spectrum was prepd by reaction of ethyl methyl ketone with formaldehyde, hydrogenation of the product with Gi chromite catalyst, acetylation to the triacetate, pyrolysis, deacerylation, and nitration of 3,3"bis(hydroxymethyl) -butene-1. The subject compd was synthesized as a binder constituent, which might be polymer-... 

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