Abstract
Reactions in gas phase mixtures of H2O2 vapour, NO2 and CO at 292±2 K have been studied by measurement of the variation of yield of the CO2 product. It has been shown that the mechanism is the chain reaction sequence H2O2+ NO2→ OH + HNO3(1), OH + CO → CO2+ H (2), H + NO → OH + NO (3), OH + NO2(+M)→ HNO3(+M)(4) provided that excess NO2 is present.An estimate of k4/k2 is obtained which is rationalised in terms of reaction (4) being between second and third order for M = CO at pressures of 8 and 13.3 kN m–2.Addition of n-butane to the mixture induces the reaction OH + n-C4H10→ H2O + n-C4H9. (8).From the resultant decrease in the kinetic chain length a ratio of k8/k2= 14.8 ± 0.9 is deduced, in good agreement with ratios of available absolute values of k8 and k2.It is considered that the H2O2+ NO2+ CO + substrate reaction system provides a useful non-photolytic source of OH + substrate rate constant data relative to k2, of wider application than photolytic sources so far developed.
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Schedule a callMore From: Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases
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