The Reaction of Active Nitrogen With Methanol

Abstract

The reaction of active nitrogen with methanol has been investigated a t several temperatures in the range 30 to 48OoC using a fast-flow system. The only condensable products found in appreciable amou~lts were water and hydrogen cyanide. The overall activation energy is 3.0 and 3.2 kcal/mole and the steric factors 1.3X10-3 and 2.1X10-3 for streamline and turbulent flow respectively. I t is postulated that the mechanism consists of the initial formation of a collision complex, [NCH30H], which breaks down to two fragments, S C H 3 and OH, from which the two condensable products are formed, NCH3 -+ H C N + 2H or Hz &qttack of the r~letharlol n~olecules b y hydrogen atoms resulting from the main reaction occurs t o a lesser extent and is responsible for the production of small quantities of methane, carbon monoxide, and additional water. INTRODUCTIOS

The Reactions of Active Nitrogen with Simple Alcohols

“…The reaction products CH,OH witll active nitrogen gave an activation could be sampled directly with a Toepler pump for analysis by gas chromatography, or they could be energy l 3 kJ/mO1, in excel1ent agreement with collected in traps cooled in liquid nitrogen, dissolved in a the results of the earlier work (1). The alcohol suitable solvent, and then analyzed.…”

Comment on “Thermochemical and Kinetics of the CH3OH + (4S)N Reactional System”

“…I was drawn to this paper because we had studied the system many years ago and I was interested to see how the authors’ calculations agreed with our experimental results. It quickly became apparent that the authors were unaware of our work and an earlier report of the kinetics of this reaction . This “comment” is intended to provide a link between theory and experiment for the system and to identify a reaction channel that was not considered in the computational work but which we concluded was the dominant channel on the basis of our deuterium kinetic isotope effect measurements.…”

The Reactions of Triplet NH with Olefins

“…The flash photolysis and spectrographic equipment were described previously, in connection with polyatomic nitrenes.3 The steady photolyses were carried out in a Rayonet photochemical reactor (Southern New England Ultraviolet Co., Middletown, Conn.) with 16 RPR-2573A lamps and a reactor temperature of approximately 40°. The sample vessel was a clear, fused silica tube, 43 X 2 cm.…”