Spectroscopy and mechanism of chemiluminescent reactions between group V hydrides and ozone

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Abstract
Chemiluminescence spectra are reported for the reactions of arsine, phosphine and stibine with ozone at reduced pressure. Phosphine gives rise to a visible continuum only, arsine to AsO bands and a visible continuum, and stibine apparently to SbO bands only. The species responsible for the visible continua are unknown but we suggest that they may be PO2 and AsO2. At low pressures in a flow system both the visible (vis.) and discrete ultraviolet (u.v.) chemiluminescent emissions from the AsH3+ O3+ O2 system increased to a maximum well downstream of the injection port. This induction period, the subsequent decay, peak and total intensities were found to be dependent on [O3], [O2] and pressure. A numerical kinetic model was constructed which reproduces several of the observed phenomena including a decreasing u.v./vis. ratio, decreasing u.v. and vis. intensities and increasing induction periods as [O2] is increased. The model features a slow initiation reaction of arsine with ozone and a subsequent branched chain reaction involving the odd hydrogen radicals OH and HO2.

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