✦ LIBER ✦

The gas-phase pyrolysis of alkyl nitrites. VII. Primary and secondary nitrites in the presence of nitric oxide

✍ Scribed by L. Batt; T. S. A. Islam; H. Scott

Publisher: John Wiley and Sons
Year: 1978
Tongue: English
Weight: 351 KB
Volume: 10
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550101202

No coin nor oath required. For personal study only.

✦ Synopsis

Although our pyrolytic studies of five alkyl nitrites (RONO) have shown that it is possible to determine precise, acceptable values for k 1:

(0 RONO -RO + NO we have been uncertain about the mechanism for the first order production of nitroxyl from primary and secondary nitrites. Nitroxyl could arise either from the direct elimination process (5) or from the disproportionation of the alkoxyl radical concerned and nitric oxide:

If the route is reaction (6), Eexp should be identical to E l , since the ratio kc/kZ is temperature independent. We preferred the elimination process because Eexp < El and Aexp was in agreement with transition-state calculations for such elimination processes. This study was concerned with the pyrolyses of ethyl and i-propyl nitrites in the presence of nitric oxide. The results show that nitroxyl is produced via the disproportionation of the alkoxyl radical and nitric oxide, as originally suggested by Levy. This is supported by the wealth of particularly photochemical data in the literature. Our and other previous spuriously low Arrhenius parameters are attributed to heterogeneous effects.

RO + NO -RONO RO + NO -RO-H + HNO

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