On-Line Gas-Free Electrodialytic Eluent Generator for Capillary Ion Chromatography

Abstract

Both low- and high-pressure, gas-free, capillary-scale electrodialytic generators for eluents in ion chromatography are described. While the low-pressure devices rely on planar or tubular membranes, the high-pressure devices rely on ion-exchange beads used both as one-way ionic gates and as ball-on-seat valves to provide sealing. The high-pressure device is easily implemented in the form of a commercial cross fitting and can withstand at least 1400 psi. By design these devices do not produce gas in the eluent channel; hence, it is not necessary to remove gas afterward. With appropriate electrolytes and electrode polarities, such devices can produce either acid or base or salt. In regard to ionic transport, the behavior of these devices fully corresponds to that of a semiconductor diode. To our knowledge, this is the first time such complete equivalence of ion transport through ion-exchange media and with the more familiar example of electron transport through a semiconductor diode under both forward- and reverse-biased conditions have been demonstrated. Reverse bias can be applied to minimize/prevent Donnan-forbidden leakage or ion exchange. Even with 4 M KOH in the electrode compartments and 4 μL/min water flowing through the eluent channel, with a reverse bias of −12 V, the leakage KOH concentration is <30 μM, whereas the KOH concentration with zero voltage applied, hereinafter termed open circuit penetration (OCP), is 1600 μM. It is suggested that this OCP occurs not as much through Donnan-forbidden leakage but via ion exchange. Chromatograms and reproducibility data are presented for both isocratic and gradient chromatography, using ion-exchange, latex-modified, open tubular and packed monolithic columns.