Kinetics of disproportionation–combination reactions between the n-propoxyl radical and nitric oxide, and of the pyrolysis of the O–O bond in di-n-propyl peroxide in the gas phase
- 1 January 1970
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc. A
- p. 331-334
- https://doi.org/10.1039/j19700000331
Abstract
A study of the reactions of the n-propoxyl radical, from the gas-phase pyrolysis of di-n-propyl peroxide at 100–150°, with nitric oxide shows that the disproportionation–combination ratio Δ=ki/kii is 0·40–0·45, and is temperature- PrnO·+ NO → HNO + EtCHO (i), PrnO·+ NO → PrnONO (ii) independent with k1= Ai= 5–6 × 1010 mole–1 cm.3 sec.–1. The pyrolysis of the O–O bond in the peroxide is of the first order with k1= 9·1 × 1014 exp (–35,000/RT) sec.–1, from which it is shown that k1 for the reverse of this pyrolysis, i.e., recombination of n-propoxyl radicals, is 4·7 × 1011 mole–1 cm.3 sec.–1. From E1 and the calculated value of ΔHf° for the peroxide, ΔHf° for the n-propoxyl radical is found to be –10·3 kcal. mole–1.Keywords
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