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Gas-phase Reaction of Hydroxyl Radicals with Alkyl Nitrite Vapors in H2O2+NO2+CO Mixtures

DOI: 10.1039/f19827800611

Source and publish data:

Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 611 - 618 (1982)

Update date:2022-08-11

Topics:

Authors:

Audley, Gary J.Audley, Gary J.

Baulch, Donald L.Baulch, Donald L.

Campbell, Ian M.Campbell, Ian M.

Waters, Des J.Waters, Des J.

Watling, GillianWatling, Gillian

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Article abstract of DOI:10.1039/f19827800611

The yields of CO2 from the chain reaction in H2O2+NO2+CO+alkyl nitrite mixtures, in wich OH is the chain carrier and alkyl nitrites induce a chain termination step, have been used to deduce rate constants (ks) for OH attack on alkyl nitrites (RONO) in the vapour phase at ambient temperatures.Values of ks/E9 dm3 mol-1 s-1 as a function of R were determined as follows: 0.71 +/-0.12 (CH3), 1.15+/-0.23 (C2H5), 1.56+/-0.32 (n-C3H7), 3.41+/-1.48 (n-C4H9), 3.89+/-0.58 (sec-C4H9), 3.47+/-0.52 (i-C4H9), 0.91+/-0.15 (t-C4H9), all based on ks=(1.63+/-0.16)E9 dm3 mol-1 s-1 for OH +n-butane.The small increase in ks from R=CH3 to t-4H9 is considered to support a recent postulate that both H-abstraction and NO-abstraction pathways are operative, at least for R=CH3.Under typical, sunlit urban atmosphere conditions it is deduced that OH attack on alkyl nitrites is a minor removal process compared to their photodissociative destruction.

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