Christopher J. Evenhuis

Joule heating effects and the experimental determination of temperature during CE

Joule heating is ubiquitous in electrokinetic separations. This review is in two major parts. The first part documents the effects of Joule heating on the physical properties of the electrolyte and efficiency of separations and the second part focuses on advances in the determination of electrolyte temperatures that have been described in the literature over the past 5 years. The focus is on methods that can be applied by practitioners without the need for elaborate experimental requirements. Although the emphasis is on CE, many of the conclusions also apply to microfluidic formats.

Separation of inorganic anions on a high capacity porous polymeric monolithic column and application to direct determination of anions in seawater.

A commercially available 4.6 mm id x 50 mm polymethacrylate-based monolithic strong anion exchange column (ProSwift SAX-1S) designed for the separation of proteins has been successfully used to separate small inorganic anions in the presence of a seawater sample matrix. Using a hydroxide eluent with suppressed conductivity detection the ion exchange capacity of this column declined over time; however, using KCl as the eluent, the column performance was stable with a capacity of 530 microequiv. for nitrate. The optimum conditions for the separation of iodate, bromate, nitrite, bromide and nitrate were assessed by constructing van Deemter plots using 1.00 and 0.100 M KCl. Efficiencies of up to 26 700 plates/m were recorded using 1.00 M KCl, at a flow rate of 0.20 mL/min but iodate was not baseline resolved from the void peak. By reducing the concentration of the eluent to 0.100 M, efficiencies of up to 39 900 plates/m could be obtained at 0.35 mL/min. By employing a linear gradient ranging from 0.05 to 1.00 M KCl the ions dissolved in distilled water or a salt water matrix could be baseline separated in less than 3 min at a flow rate of 2.50 mL/min.

Simplified universal method for determining electrolyte temperatures in a capillary electrophoresis instrument with forced-air cooling

Temperature increase due to resistive electrical heating is an inherent limitation of capillary electrophoresis (CE). Active cooling systems are used to decrease the temperature of the capillary, but their capacity is limited; and in addition, they leave “hot spots” at the detection interface and at the capillary ends. Until recently, the matter was complicated by the lack of a fast and generic method for temperature determination in efficiently and inefficiently cooled regions of the capillary. Our group recently introduced such a method, termed “Universal Method for determining Electrolyte Temperatures” (UMET). UMET is a probe‐less approach that requires only measuring current versus voltage for different voltages and processing the data using an iterative algorithm. Here, we apply UMET to develop a Simplified Universal Method of Temperature Determination (SUMET) for a CE instrument with a forced‐air cooling system using an Agilent 7100 CE instrument (Agilent Technologies, Saint Laurent, Quebec, Canada) as an example. We collected a wide set of empirical voltage–current data for a variety of buffers and capillary diameters. We further constructed empirical equations for temperature calculation in efficiently and inefficiently cooled parts of the capillary that require only the data from a single 1‐min voltage–current measurement. The equations are specific for the Agilent 7100 CE instrument (Agilent Technologies) but can be applied to all kinds of capillaries and buffers. Similar SUMET approaches can be developed for other CE instruments with forced‐air cooling using our approach.

Non-orthogonal-to-the-flow electric field improves resolution in the orthogonal direction: hidden reserves for combining synthesis and purification in continuous flow.

There is a pressing need for continuous purification of products of synthesis conducted in continuous-flow microreactors. An existing technique, micro free-flow electrophoresis (microFFE), could fulfill this niche if its resolving power for similar molecules was improved. MicroFFE continuously separates ions in the hydrodynamic flow by an electric field orthogonal to the flow. Here, we prove theoretically from first principles that the resolving power of microFFE can be greatly improved by the use of a nonorthogonal to the flow field. This result may be decisive in starting practical attempts to combine synthesis in continuous-flow microreactors with continuous-flow purification by microFFE.

Heat-associated field distortion in electro-migration techniques.

Electro-migration techniques, such as electrophoresis, are widely utilized in analytical sciences. If a single electrolyte is used, the field strength is typically assumed to be well-defined. Heat-associated field distortion (HAFD) has been suggested as a result of the nonuniform heat dissipation throughout the electrolyte; however, it has never been experimentally studied. Here, we experimentally demonstrated HAFD for the first time. We used capillary electrophoresis (CE) with a capillary having parts with different heat dissipation efficiencies. Our experiments showed a difference in field strength of approximately 1.5 times between the different parts of the capillary for a typical CE electrolyte. This result suggests that HAFD is a well pronounced phenomenon that can be a potential source of errors and instabilities in electro-migration experiments.

Determination of the surface heat-transfer coefficient in CE

A knowledge of the heat‐transfer coefficient, hs, for the external surface of the capillary or the overall heat coefficient, hOA, is of great value in predicting the mean increase in temperature of the electrolyte, ΔTMean, during electrokinetic separations. For CE, traditional indirect methods of determining hs were time‐consuming and tended to overestimate cooling efficiency; a novel method is introduced, which is based on curve‐fitting of plots of conductance versus voltage to calculate several important parameters including ΔTMean, hs, the conductance free of Joule heating effects (G0) and the voltage that causes autothermal runaway, Vlim. The new method is superior to previously published methods in that it can be performed more quickly and that it corrects for systematic errors in the measurement of electric current for voltages <5 kV. These errors tended to exaggerate the cooling efficiency of commercial instruments so that the calculated increases in electrolyte temperature were smaller than their actual values. Axially averaged values for hs were determined for three different commercial CE instruments ranging from 164 W m−2 K−1 for a passively cooled instrument in a drafty environment to 460 W m−2 K−1 for a liquid‐cooled instrument.