Development and characterization of chlorine-selective pulsed discharge emission detector for gas chromatography

A novel chlorine-selective pulsed discharge emission detector (Cl-PDED) for gas chromatography has been developed based on a reaction of krypton with chlorine and a unique design of the detector. A krypton ion produced in the krypton-doped helium pulsed discharge reacts with chlorinated compounds within the pulsed discharge to produce an excited species of KrCl* which emits at 221-222 nm. The reaction has the following advantages in respect to the detection of chlorinated compounds: (1) the reaction is an ion-molecule reaction that is 100-1000 times faster than a reaction of neutrals, which greatly enhances the sensitivity; (2) the KrCl* emission wavelength is far separated from interfering C emissions at 193. and 247.3 nm; (3) the KrCl* emission is transparent to air and can be recorded without a helium purge of the monochromator. The detector itself has been designed to have the following features: (1) the detector has a microvolume of the pulsed discharge region, ca. 0.35 microl, which increases the discharge power density to enhance the sensitivity; (2) this microvolume detector allows the use of a low flow-rate of approximately 5 ml/min, which enhances the sensitivity by the lower dilution of the column effluent; (3) the pulsed discharge is sufficiently narrow to replace the monochromator entrance slit, which gives much greater light gathering power; (4) the discharge electrodes are protected with a helium purge to prevent carbon deposition on the electrodes. This new Cl-PDED is the most sensitive chlorine-selective detector with a minimum detectability of approximately 50 fg Cl/s. The selectivity to carbon is 1000. There are no significant carbon emission lines in the KrCl* emission wavelength region, but the carbon continuum interference (stray light) limits the selectivity. The selectivity could be increased if a double monochromator were used to diminish the stray light. The detector linear range is over three orders of magnitude from 40 fg Cl to approximately 130 pg Cl, and the dynamic range is approximately 4 orders of magnitude. The relative standard deviation of the elemental response to chlorinated compounds is about 5%.