The pyrolysis of 2-nitrosoisobutane and the bond dissociation energies of nitroso compounds

✍ Scribed by K. Y. Choo; G. D. Mendenhall; D. M. Golden; S. W. Benson

• Publisher: John Wiley and Sons
• Year: 1974
• Tongue: English
• Weight: 593 KB
• Volume: 6
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550060605

✦ Synopsis

Abstract

Study of the reaction by very‐low‐pressure pyrolysis (VLPP) in the temperature range of 550–850°K yields for the high‐pressure Arrhenius parameters

where θ = 2.303__RT__ in kcal/mole. These in turn yield for the high‐pressure second‐order recombination of __t__Bu + NO, k~−1~ = (3.5 ± 1.7) × 10^9^ 1./mole·sec at 600°K. For the competing reaction l./mole·sec and E~4~ ≥ 4.2 kcal/mole. The bond dissociation energy DH^o^ (tBu‐NO) was determined to be (39.5 ± 1.5) kcal/mole, both from the equilibrium constant and from the activation energy of reaction (1), obtained from RRKM calculations. A ‘free‐volume’ model for the transition state for dissociation is consistent with the data. A limited study of the system at 8–200 torr showed an extremely rapid inhibition by products and a very complex set of products.