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Electrolyte Cathode Discharge (ELCAD) spectrometry, a novel sensitive multielement direct analytical method for metal traces in aqueous solutions, was introduced in 1993 as a new sensing principle. Since then several works have tried to develop an operational mechanism for this exotic atmospheric glow plasma technique, however these attempts cannot be combined into a valid model description. In this review we summarize the conceptual and technical problems we found in this upcoming research field of direct sensors. The T(G) gas temperature and the n(e) electron density values published up to now for ELCAD are very confusing. These data were evaluated by three conditions. The first is the gas composition of the ELCAD plasma, since T(G) was determined from the emitted intensity of the N(2) and OH bands. Secondly, since the ELCAD is an atmospheric glow discharge, thus, the obtained T(G) has to be close to the T(e) electron temperature. This can be used for the mutual validation of the received temperature data. Thirdly, as a consequence of the second condition, the values of T(G) and n(e) have to agree with the Engel-Brown approximation of the Saha-equation related to weakly ionized glow discharge plasmas. Application of non-adequate experimental methods and theoretical treatment leads to unreliable descriptions which cannot be used to optimize the detector performance.

A Critical Review of Published Data on the Gas Temperature and the Electron Density in the Electrolyte Cathode Atmospheric Glow Discharges