Polymethylmethacrylate Open Tubular Ion Exchange Columns: Nondestructive Measurement of Very Small Ion Exchange Capacities

摘要

We describe an approach to prepare an open tubular ion exchange (OTIE) column by coating a monolayer of anion exchange nanoparticle to a 16-20 μm bore polymethylmethacrylate (PMMA) capillary. The latex nanoparticle was electrostatically attached to carboxylate groups on the inner wall of capillary, pretreated with strong base for hydrolyzing the ester. Several approaches to nondestructively measure ion exchange capacities (IEC) of the columns were examined: (a) adsorption--desorption of an intensely fluorescent ion, e.g. fluorescein, and off-line fluorometry, (b) loading a weakly retained ion (e.g., IO_3~-), frontal displacement by a strongly bound ion (e.g., Cl~-), and online optical or conductometric boundary detection, and (c) similar to the above except displacement being accompanied by reaction (e.g., acid-base titration). To our knowledge, this is the first time on-column titration has been used to measure capacities. By using different pH displacer solutions, we demonstrate for the first time the possibility of pK_a-differentiated ion exchange capacity measurements. The cation exchange capacity of bare PMMA capillaries was on the order of 1 pequiv/mm~2 with little dependence on time and temperature of hydrolysis conditions. After AS18 latex coating, the strong base anion exchange capacity was on the order of 10 pequiv/mm~2, very close to what would be estimated on the basis of monolayer coverage of the surface by individual latex particles. The latex used contained a significant, additional amount of weak base character, about the same as the strong base ion exchange capacity.