The thermal decompositions of carbamates. IV. The ethyl Nmethylcarbamate system

✍ Scribed by N. J. Daly; F. Ziolkowski

• Publisher: John Wiley and Sons
• Year: 1980
• Tongue: English
• Weight: 600 KB
• Volume: 12
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550120405

✦ Synopsis

Abstract

Ethyl __N__methylcarbamate decomposes thermally over the temperature range of 600–650 K by competing first‐order reactions, one forming methylamine, carbon dioxide, and ethylene, the other forming methyl isocyanate and ethanol. The first‐order rate constants are described in S^1^ units by the equations
equation image
where R = 1.986 cal/deg mol. The appareance of __sym__dimethylurea among the products raised the possibility of gas‐phase transesterifications. These were ruled out by the study of the reactions of sym‐dimethylurea at 604 K which showed its behavior to be well explained by the rapid decomposition in the gas phase
equation image
which is reversed in the condensation stage in the analysis.