Volume 65, 1969

Spectroscopic and kinetic studies of the SO radical and the photolysis of thionyl chloride

Abstract

The primary processes occurring in the photolysis of SOCl2 have been examined using kinetic absorption spectroscopy in the ultra-violet and vacuum ultra-violet. Photodissociation involves the fission of one sulphur-chlorine bond, leaving an energized SOCl radical which may then undergo unimolecular decomposition to yield an SO radical and a further chlorine atom, or is stabilized by collision. The kinetics of the SO radical so formed are examined and a mechanism for removal is proposed. Two new electronic states of the SO radical are identified via new absorption systems in the vacuum ultra-violet designated SO(D3IIâ†�X3) and SO(E3IIâ†�X3). The D and E states are successive members of a Rydberg series and yield an approximate value for the first ionization potential of SO as 10.0 ± 0.1 eV. Molecular constants for the two states are given as [graphic omitted] The extinction coefficient of the (7,0) band for the transition SO(B3â†�X3) is determined as 8.0 ± 1.5 × 106 cm2 mol–1.

Article information

Article type
Paper

Trans. Faraday Soc., 1969,65, 2930-2940

Spectroscopic and kinetic studies of the SO radical and the photolysis of thionyl chloride

R. J. Donovan, D. Husain and P. T. Jackson, Trans. Faraday Soc., 1969, 65, 2930 DOI: 10.1039/TF9696502930

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