The Thermal Decomposition of Nitrate Esters. I. Ethyl Nitrate¹

Thermal decomposition of nitrate esters

“…K. This high positive entropy of activation is typical of homolytic first-order dissociation and is comparable to Levy's value for ethanol nitrate decomposition of 62.8 J/mol . K. 4 The volume of activation determined for n-pentanol nitrate in a tetralin solution (10wt%) at 160 o C was +173 mL. This value is outside the usual range (3 to 10 mL) for homolytic reactions at normal temperatures but is appropriate for reaction at 160 o C.…”

“…This hypothesis is based on the observation that NO2 added to the gas-phase thermolysis of ethanol nitrate retarded the decomposition. [2][3][4] We have shown by two methods that the cleavage is reversible. The first involves the effect of solvent viscosity on the rate of thermolysis of pentanol and neopentanol nitrate.…”

“…The thermal decomposition of ethanolnitrate was examined by a number of researchers, and it was proposed that the first, and rate-determining, step was the reversible loss of NO2: [2][3][4][5] RCH2O-NO2 <--> RCH2O . + NO2…”

The mechanism of super-rate burning of catalyzed double base propellants

“…The burning surface temperature was estimated in a different way by Wilfong, Penner, and Daniels.1 5 They observed that copper particles, smaller than 4p, mixed with the propellant sample were melted into spheres on the quenched burning surface after a rapid pressure decay. Similar results were observed when finely powdered alkaline earth carbonates were incorporated in the propellant.…”

“…Instrumentation for measuring burning rates and temperature profiles in 1 -100 atm range CIlI C- 4 Ynsensitivity of burning rate of double base propellant on N 2 purge gas rate C12 C- 5 Apparatus for measuring burning rates and temperature profiles at subatmospheric pressures C13…”