LOW-PRESSURE CHEMILUMINESCENT REACTION OF MOLECULAR FLUORINE WITH DIMETHYL-SULFOXIDE AND THE EFFECTS OF ADDED OXYGEN

The spectra from the chemiluminescent reaction of dimethyl sulfoxide ( DMSO) with molecular fluorine have been studied at pressures below 1 T orr. The spectra were examined for changes occurring upon variation of the reactant partial pressures, substitution of deuterated DMSO and t he coaddition of molecular oxygen. In the wavelength region 4500-8800 Angstrom the spectra are dominated by emission from HCF (A) or DCF (A) at high F-2 concentrations or by emission from CH2S (a) or CD2S (a) a t low F-2 concentrations. Emission from vibrationally excited HF is ob served in the hydrogen system but DF is not observed in the deuterium system. Fluorescence and phosphorescence from SO2 are observed between 2700 and 4500 Angstrom. A weak set of emission bands near 2600 Angstr om is tentatively assigned to SO(A). The addition of O-2 leads to the production of intense emission from OH(A) or OD(A) in the reactions of DMSO-h(6) or DMSO-d(6) respectively. The addition of O-2 to the DMSO- d(6)F(2) system leads to the production of intense chemiluminescence f rom CD2O, while CH2O was totally absent in the analogous reaction of t he hydrogen-containing compound. Mechanisms for the formation of the e mitters are proposed based on this and previous work.