The Reactions of Active Nitrogen with Simple Alcohols

Abstract

The reactions of active nitrogen with CH3OH, C2H5OH, n-C3H7OH and iso-C3H7OH have been studied as a function of temperature. The rate constants for these reactions fit the following expressions:[Formula: see text](Activation energies are in kJ/mol. Rate constants are in 1 mol−1 s−1.)Experiments with CH3OH, CH3OD, and CD3OD indicate a small primary isotope effect for OH and a secondary isotope effect for CH. This, with other data, implies that abstraction of a H atom from the alcohol is not an important initial step.Consumption of N atoms ranged from 4.7 to 7.1 times the alcohol consumed. With the exception of the reaction of active nitrogen with iso-C3H7OH, the only detectable stable reaction product was HCN. Intervention of O atoms as intermediates appears to be important in all the reactions. In the reaction of active nitrogen with iso-C3H7OH, acetone, and acetonitrile were also found as products in amounts of about 26% and 14% respectively of the HCN yield. These products appear to arise through O atom intervention.Mechanisms for the reactions and the nature of the activated state in the initial step are discussed.