Patent GB-1120364-A (GB)
Title: Detection method and apparatus for chromatography
IPC: G01N30/84
Filed: 1966-10-03
Abstract: 1, 120, 364. Analyzing fluids electro-chemically. V. PRETORIUS and H. H. HAHN. Oct. 3, 1966 [Oct. 6, 1965; Aug. 2, 1966], No. 44025/66. Heading G1N. The eluate from a chromatographic separation process passes through an electrolytic detection cell in which two electrodes are maintained at such a potential difference as to cause an electrolytic oxidation/reducion of the constituents being monitored and the applied voltage and the electric current flowing through the cell are measured. The separation process may be carried out in a chromatographic column or by paper chromatography or starch or gel chromatography (electrophoresis). The eluting agent may be a liquid or a gas. If it is a gas, a film of water may be caused to run at a constant rate over the electrodes or the gas may be bubbled through a liquid in the cell or the gas may flow co-currently with a constant stream of liquid through the detector cell. The liquid may include a solubilising agent for the constituents of the gas. As shown in Fig. 2, a liquid eluent, which is first freed of oxygen by bubbling nitrogen through it, passes through an electro-chemical purifier 14, Figs. 3 and 4 (not shown) and a chromatographic column 1 to the detector cell 3. A compensating cell 9 may be located in a dummy column 1a or at the inlet to column 1. The two cells are connected as shown in Fig. 5 to a recorder 31. Various cell constructions are described. In Fig. 6 (not shown), a conductive tube wall (40) is used as one electrode, the other electrode being a central wire (42). In Fig. 7 (not shown), two parallel wire electrodes extend across the cell. In Fig. 8 (not shown), the electrodes comprise two series connected conductive capillaries through which the eluate passes, the capillaries being of smaller cross-section than the column and separated by a short non-conductive capillary. In Figs. 9 and 10 (not shown), a plate comprising two electrodes (57, 58) joined by epoxy resin (59) and having a central aperture (60) is intercalated in the tube wall (45). In Fig. 11 (not shown), the electrodes are formed by layers of conductive particles (66, 69) intercalated in the main column packing (65). In Fig. 12 (not shown), two mesh electrodes are used. In Fig. 15 (not shown), the column has a capillary outlet dipping into an overflow vessel, one electrode being formed by a conductive portion of the capillary, the other electrode being a calomel electrode. In Figs. 16 and 17 (not shown), thin wire and graphite lines constitute electrodes in cells for use in thin film and paper chromatography. In order to induce a turbulent flow of eluate through the cell, the cell may be subjected to ultrasonic vibrations. Several pairs of electrodes at different potentials may be used. Examples of electrode materials and eluting agents given are : Cu (cathode) and Pt (anode) with 6% ethanol containing KCl as an eluting agent; and platinum amalgam (cathode) and graphite (anode) with KCl solution (pH = 5) eluting agent for detecting Cd<SP>++</SP>, Pb<SP>++</SP> and Cu<SP>++</SP>. Other suitable electrode materials are: Au, Ni, pyrolized graphite and glassy carbon. Standard calomel or silver/silver chloride reference electrodes may be used. Other eluting agents are: benzene, toluene, pyridine, water, ethanol, methanol, carbon tetrachloride, chloroform, pentane, hexane, heptane, octane and dioxan. Electrolytes such as potassium chloride, lithium nitrite, tetraethyl or methyl chloride, bromide or iodide may be incorporated in the eluent before it enters the column or may be added to the eluate between the end of the column and the detector cell. If necessary, the eluting agent may contain water. As described with reference to Fig. 18 (not shown), a sine wave or squarewave A.C. is applied to the electrodes and the cell current and voltage are simultaneously displayed on an oscilloscope.