Production of O2(1? + g ) in the H + O2 system

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Abstract
Chemiluminescence is observed in the reaction between atomic hydrogen and molecular oxygen. Bands at λ= 1265, 1430 and 1510 nm are ascribed to transitions involving HO2, while that at λ= 762 nm is due to the O2(1Σ+ g→3Σ– g) transition. Evidence is adduced to show that O2(1Σ+ g) is not produced by energy-pooling from O2(1Δg), and that O2(1Δg) is itself only a minor contributor to the band at λ= 1265 nm. The bands at λ= 762 and λ= 1430 nm both show a first order dependence on [H] and on [O2]. We examine several reactions which are possible sources of O2(1Σ+ g) and conclude on the basis of the kinetic evidence, that the most probable reaction sequence is H + O2+ M → HO2+ M (4), H + HO2→ H2+ O2(1Σ+ g). (6c′) Measurement of absolute concentrations of H and O2(1Σ+ g) allows estimation of the efficiency of reaction (6c′) relative to the overall loss of HO2 in reaction (6) H + HO2→ products. (6) The value obtained for the efficiency is 2.8 ± 1.3 × 10–4, so that 10–3 of the molecular oxygen formed in the reaction is in the 1Σ+ g state. Alternative excitation mechanisms are also assessed.

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