Effects of nitric oxide on the thermal decomposition of methyl nitrite: Overall kinetics and rate constants for the HNO + HNO and HNO + 2NO reactions

✍ Scribed by Y. He; M. C. Lin

• Publisher: John Wiley and Sons
• Year: 1992
• Tongue: English
• Weight: 771 KB
• Volume: 24
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550240808

✦ Synopsis

Abstract

The effects of NO on the decomposition of CH~3~ONO have been investigated in the temperature range 450–520 K at a constant pressure of 710 torr using He as buffer gas. The measured time‐dependent concentration profiles of CH~3~ONO, NO, N~2~O, and CH~2~O can be quantitatively accounted for with a general mechanism consisting of various reactions of CH~3~O, HNO, and (HNO)~2~. The results of kinetic modeling with sensitivity analyses indicate that the disappearance rate of CH~3~ONO is weakly affected by NO addition, whereas that of the HNO intermediate strongly altered by the added NO. In the presence of low NO concentrations, the modeling of N~2~O yields leads to the rate constant for the bimolecular reaction, HNO + HNO → N~2~O + H~2~O (25):

In the presence of high NO concentrations (P~NO~ > 50 torr), the modeling of CH~2~O yields gives the rate constant for the termolecular radical formation channel, HNO + 2NO → HN~2~O + NO~2~ (35):

Discussion on the mechanisms for reactions (25) and (35), and the alkyl homolog of (35), RNO + 2NO, is presented herein. © John Wiley & Sons, Inc.