Study of Temperature and Mobile-Phase Effects in Reversed-Phase High-Performance Liquid Chromatography by the Use of the Solvatochromic Comparison Method

Peter W. Carr, Ruth M. Doherty, Mortimer J. Kamlet, Robert W. Taft, Wayne Melander, Csaba Horvath

Research output: Contribution to journalArticlepeer-review

184 Scopus citations

Abstract

Retention of a series of aromatic solutes in reversed-phase HPLC has been studied as a function of temperature and mobile-phase composition in acetonitrile-water mixtures. The chief factors that control retention are the solute size (molar volume) and hydrogen bond basicity. Less important factors are the polarizability-dipolarity and hydrogen bond acidity of the solute. Through the use of the solvatochromic comparison method and linear solvation energy relationships, the key system parameters are seen to decrease In magnitude as the mobile phase becomes richer In organic modifier. That Is, the endoergic cavity formation energy and the exoergic hydrogen bond formation processes both become less significant as the temperature increases. Relationships between the logarithmic capacity factor and mobile-phase composition are predicted to be more linear for small nonpolar solutes and hydrogen bond bases than for large nonpolar solutes.

Original languageEnglish (US)
Pages (from-to)2674-2680
Number of pages7
JournalAnalytical chemistry
Volume58
Issue number13
DOIs
StatePublished - Nov 1986

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