FACTORS AFFECTING THE COMPOSITION OF THE BONDED STATIONARY PHASE IN LIQUID CHROMATOGRAPHY.
AuthorZWIER, THOMAS ALAN.
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PublisherThe University of Arizona.
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AbstractThe stationary phase on chemically modified supports for liquid chromatography is described as a mixture of the surface-bonded species, the active unmodified surface, and associated mobile phase components. Each of these three factors in stationary phase formation is examined and improved qualitative and quantitative descriptions of the stationary phase are provided. The role of the active unmodified surface was examined by synthesizing a carbon support and chemically modifying it with octyl groups. The modified carbon had a greater affinity for lipophilic probes than an octyl silica. The lipophilicity of the octyl carbon was attenuated relative to the unmodified carbon. The physical state of the bonded species in C(,18) and C(,8) packings was studied using carbon-13 NMR. Peak widths of 2-7 ppm indicated a liquid-like nature but with restricted movement. Only the 7 to 10 carbons in a C(,18) chain farthest from the surface were sufficiently motile to produce a signal. The C(,8) packing showed more rigid chains with only the top 3 or 4 carbons responding. The liquid-like nature of a C(,18) chain increased with the lipophilic character of the solvent, indicating that solvation of the bonded species was directly related to the mobile phase composition. Changes in temperature had little effect on the physical state of the bonded species, but chromatographic enthalpy measurements showed that changes in stationary phase composition could be induced by warming the column and held by subsequent cooling. Quantitative measurements of stationary phase compositions revealed linear distribution isotherms for the organic modifiers methanol, acetonitrile, and tetrahydrofuran. Chromatographic selectivities for homologous n-alkanols correlated linearly with organic modifier concentrations in the stationary phases. The stationary phase volumes, which increased with increasing modifier concentrations, are interpreted as constituting filling of the pores in the support with a gradient of modifier enrichment toward the surface.