The kinetics of disproportionation–combination reactions between the s-butoxy-radical and nitric oxide, and of the pyrolysis of the O–O bond in di-s-butyl peroxide in the gas phase
- 1 January 1968
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc. A
- p. 2103-2106
- https://doi.org/10.1039/j19680002103
Abstract
A study of the reactions of the s-butoxy-radical, produced by pyrolysis of di-s-butyl peroxide, with nitric oxide in the gas phase at 100–140°: BusO·+ NO HNO + EtCOMe (2); BusO·+ NO BusONO (3) shows that the disproportionation–combination ratio, k2/k3, is 0·25–0·27 and temperature-independent, with k2=A2 1·3 × 1010 mole–1 cm.3 sec.–1. Determination of the rate of depletion of the peroxide by product analysis shows that fission of the O–O bond is first-order, with k1= 1·8 × 1015 exp(–36,400/)RT sec.–1, from which it can be shown that the rate constant k–1(assumed temperature-independent) for recombination of the s-butoxy-radical is 8·5 × 1011 mole–1 cm.3 sec.–1. From E1 and the calculated value of ΔHt° for the peroxide, the heat of formation of the s-butoxy-radical is found to be –17·5 kcal. mole–1.Keywords
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