ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Methyl nitrate decomposition is accompanied by self-heating. Using very fine thermocouples, direct measurements of excess temperatures have been made to establish the intensity and extent of self-heating in nonisothermal reaction. The measurements are displayed as contourlines of equal degrees of temperature excess on the pressure-temperature ignition diagram.A twofold kinetic investigation has been made of the overall reaction. One part concentrates on achieving isothermal conditions and full characterization of intermediate products. It uses mass-spectrometric analyses both to establish stoichiometry throughout decomposition and to validate velocity constant measurements derived from continuous pressure-time records. The best value for E = 151 ± 3 kJ/mol is about 10 kJ/mol less than previously.The other part deliberately invades the nonisothermal region to test the qualitative and quantitative predictions of theory (1) that uncorrected reaction orders and activation energies will exceed their isothermal values, (2) that their relative excess (δn/n, δE/E) will be about the same, and (3) that they will be dependent in a simple and predictable way on the reduced excess central temperature.
Additional Material:
6 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550130906
