pH programming in capillary electrophoresis by means of temperature programming

When using a background electrolyte with a buffer having strong temperature dependence of pK, different operating temperatures result in different operating pH values, using the same background electrolyte (BGE). It has been shown that this can be used to fine-tune selectivities of sample mixtures of weak analytes. Capillary electrophoresis (CE) equipment is designed to operate under isothermal conditions, but by proper programming, a very reproducible temperature and thus BGE pH program during the analysis can be realized. This was experimentally verified and illustrated by computer simulations. Equipment characteristics have been determined, and possibilities and restrictions to make use of this feature are presented.