Molecular Emission Spectrometric Detection of Low Level Sulfur Using Hollow Cathode Glow Discharge

A highly sensitive detecting method has been developed for determining part per billion of sulfur in $H_2S$/Ar plasma. The method is based on the excitation of Ar/$H_2S\;or\;Ar/H_2S/O_2$ mixture in hollow cathode glow discharge sustained by radiofrequency (RF) or 60 Hz AC power and the spectroscopic measurement of the intensity of emission lines from electronically excited $S_2^*\;or\;SO_2^*$ species, respectively. The RF or AC power needed for the excitation did not exceed 30 W at a gas pressure maintained at several mbar. The emission intensity from the $SO_2^*$ species showed excellent linear response to the sulfur concentration ranging from 5 ppbv, which correspond to S/N = 5, to 500 ppbv. But the intensity from the $S_2^*$ species showed a linear response to the $H_2S$ only at low flow rate under 20 sccm (mL/min) of the sample gas. Separate experiments using $SO_2$ gas as the source of sulfur demonstrated that the presence of $O_2$ in the argon plasma is essential for obtaining prominent $SO_2^*$ emission lines.