Pii: S0021-9673(02)01769-7

Modification of ionic strength of an aqueous or non-aqueous carrier solution can have profound effects on the particle retention behavior in thermal field-flow fractionation (ThFFF). These effects can be considered as either advantageous or not depending on the performance criteria under consideration. Aside from the general increase in retention time of particulate material (latexes and silica particles), our experiments indicate improvement in resolution with increases in electrolyte concentration. Absence of an electrolyte in the carrier solution causes deviations from the theoretically expected linear behavior between the retention parameter l (a measure of the extent of interaction between the applied field and the particle) and the reciprocal temperature drop across the channel walls. A negative interaction parameter d of about 20.170 was w determined for 0.105and 0.220-mm polystyrene (PS) latex particles suspended in either a 0.25 or a 1.0 mM TBAPcontaining acetonitrile carrier and for 0.220 mm PS in 0.50 and 1.0 mM NaCl-containing aqueous medium. This work also demonstrates that optimum electrolyte concentrations can be chosen to achieve reasonable experimental run-times, good resolution separations, and shifts in the steric inversion points at lower field strengths, and that too high electrolyte concentrations can have deleterious effects such as band broadening and sample loss through adsorption to the channel accumulation surface. The advantages of using ionic strength rather than field strength to effect desired changes are lowered power consumption and possible application of ThFFF to high temperature-labile samples.  2002 Elsevier Science B.V. All rights reserved.