Experimental parameters affecting hypercoulometric response in gas-phase coulometry.

The response of an electron-capture detector designed for coulometric response was examined as a function of solute, pulse interval, carrier-gas type, solute amount, carrier-gas flow rate, and chromatographic-peak profile. For CCl3F, it was shown that the average numbers of electrons absorbed per molecule ranged from 1.0 to 4.1, varying primarily with pulse interval but also displaying a complex dependence on sample amount. Comparison of these results with theoretical expectations leads to the conclusion that a 1:1 "coulometric response" may not be observed under certain operating conditions. Because the specific conditions required depend on many variables, including, to some extent, sample amount, true coulometric operation of an electron-capture detector is difficult to establish and maintain. Effects which may contribute to the production of hypercoulometric response are critically discussed.