The development of organic porous polymer monoliths represents an alternative approach to stationary phase design. The use of these materials has helped to rekindle interest in capillary electrochromatography. Although a large number of investigations have explored different monolith recipes, polymerization conditions, and application challenges, few investigations have addressed the fundamentals of this separation mode with this type of material. This study addresses the thermodynamics of the reversed phase retention mechanism on 100% butyl acrylate and 1:3 butyl:lauryl acrylate (volume/volume ratio) porous polymer monoliths used in a capillary electrochromatography mode. Linear van't Hoff plots yield enthalpies of retention of −3.9 to −14.3 kJ/mol on two different, but related columns for five selected hydrophobic analytes across a thirty degree temperature range. Minimum plate heights were only moderately impacted over this temperature range.
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