Quantum-yield studies of group V hydride chemiluminescent reactions

Abstract

Quantum yields (photons per hydride molecule introduced) are reported in the wavelength region 275–825 nm for the chemiluminescent reactions of the Group V hydrides phosphine, arsine and stibine with ozone in oxygen, ozone in nitrogen and oxygen atoms in oxygen under excess oxidant conditions. Typical values are shown below [graphic omitted] Under some conditions the quantum yield for the PH₃+ O/O₂ system approaches unity. In the chemiluminescent reaction between SbH₃ and O/O₂ a film is deposited on the flow tube walls which has been observed to enhance the intensity of the ultraviolet SbO band systems. It is attributed to energy transfer from O₂(A³Σ) formed by recombination of oxygen atoms on the film. A separate ultraviolet emission system is shown to be markedly enhanced by the absence of oxygen in the chemiluminescent reaction between phosphine and ozone. This continuum is spectroscopically and kinetically distinct from the visible continua observed from the reaction of PH₃ with O₃ and O atoms.