Retention mechanisms in subcritical water reversed-phase chromatography

Differences in the properties of subcritical water and conventional water/acetonitrile and water/methanol mobile phases for reversed phase separations are explored. Using van’t Hoff plots enthalpies and entropies of transfer are compared among the mobile phases while linear solvation energy relation...

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Bibliographic Details
Published in:Journal of Chromatography A 2009-06, Vol.1216 (26), p.5106-5111
Main Authors: Allmon, Steven D., Dorsey, John G.
Format: Article
Language:English
Subjects:
Analytical chemistry
Chemistry
Chromatographic methods and physical methods associated with chromatography
Exact sciences and technology
Linear solvation energy relationships
Other chromatographic methods
Retention
Subcritical water chromatography
Superheated water chromatography
Thermodynamics
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Summary:Differences in the properties of subcritical water and conventional water/acetonitrile and water/methanol mobile phases for reversed phase separations are explored. Using van’t Hoff plots enthalpies and entropies of transfer are compared among the mobile phases while linear solvation energy relationships are used to quantify contributions to retention based on a solute's polarizability, dipolarity, hydrogen bond donating ability, hydrogen bond accepting ability, and molecular size. Results suggest the presence of acetonitrile or methanol in the mobile phase may decrease dispersive interactions of the solute with the stationary phase compared to subcritical water, thereby lowering enthalpic contributions to retention. Enthalpic contributions are found to drive the retention of a methylene group in all systems studied.
ISSN:0021-9673
DOI:10.1016/j.chroma.2009.04.068