The sensitivity is likely to be fairly high, probably approaching that of the FID. The response of the detector is proportional to the pressure of the gas in the sensor from about 0.02 mm to 1.5 mm of mercury. In this region of pressure it was claimed that the response of the detector was linear . Hinkle et al. who also examined the performance of the detector, suggested the sensor must be operated under conditions of molecular flow i.e. where the mean freepathofthe molecules is about the same as the electrode separation. Very pure helium was necessary to ensure a low noise and base signal. The detector had a "fast" response but its main disadvantage was the need to operate at very low pressures so that it required a vacuum pump; furthermore, forstability, thesensorpressureneeded to be very precisely controlled.
The Discharge Detector
About the same time that Ryce and Bryce were developing the thermionic ionization detector, Harley and Pretorious and (independently) Pitkethly and his co-workers were developing the discharge detector. By applying the appropriate potential, a discharge can be maintained between two electrodes situated in a gas providing the pressure is maintained between 0.1–10 mm of mercury. After the discharge has been initiated, the electrode potential can be reduced and the discharge will still continue. Under stable discharge, the electrode potential remains constant and independent of the gas pressure and the electrode current.The electrode potential, however, depends strongly on the composition of the gas. It follows, that the system could function as a GC detector. Pitkethly modified a small domestic neon lamp for this purpose and a diagram of his sensor is shown in figure 48.The lamp was operated at about 3 mm of mercury pressure with a current of 1.5. Under these conditions the potential across the electrodes was 220 V. Pitkethly reported that a concentration of 10-6 g/l gave an electrode voltage change of 0.3 V.
The noise level was reported to be about 10 mV thus at a signal–to–noise level of 2 the minimum detectable concentration would be about 3 x 10-11g/ml. This sensitivity is comparable to that of the FID and the argon ionization detector. The detector was claimed to be moderately linear with a linear dynamic range of three orders of magnitude but values for the response index were not reported. It was not apparent whether the associated electronics contained non linear signal modifying circuitry or not. Unfortunately, there were several disadvantages to this detector. One disadvantage was the erosion of the electrodes due to "spluttering" In addition, the electrodes were contaminated by sample decomposition and it was essential that it was used with a well–controlled vacuum system.
