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Abstract：The retention behaviours of n-aliphatic alcohols with mobile phase of n-aliphatic acids-water in reversed-phase liquid chromatography (RPLC) were studied with stoichiometric displacement model for retention (SDM-R) and Snyder′s empirical equation. The results obtained showed that SDM-R was superior to Snyder′s empirical equation when they were employed to characterize the retention behaviours of homologue and the solvent strength of homologous displacers. The slope, 1/q, of the plot of logK0w versus S has no clear physical meaning and can not be measured accurately, while the slope, j (a constant relating to the affinity of 1 mole solvent to bonded stationary phase ), of the plot of logI (a constant relating to the affinity of 1 mole of solute to bonded stationary phase) versus Z (the number of solvent molecules released from the contact surface region of 1 mole of solvated solute absorbed onto solvated bonded stationary phase) is not only determined accurately but also has a clear physical meaning and follows the rule of carbon number. Therefore, if it is possible, j can be used to characterize the solvent strength employed in RPLC. The conclusion is that with a given displacer, the retention of homologue in RPLC increases with their Z and logI increasing. If a solute is given, with the increment in carbon chain of homologous displacers, the values of Z and logI of the solute decrease and thus lead to the decrease of the solute retention, and the elution strength of a solvent becomes strong as the j value of a homologous displacer becomes small.
Keywords：Reversed-phase liquid chromatography, stoichiometric displacement model for retention, retention mechanism, homologues, mobile phases, n-fatty acids
基金项目：本文系国家自然科学基金资助课题(296750,39880003)。
作者单位：张养军（西北大学现代分离科学研究所，陕西省现代分离科学重点实验室，西安 710069）
张维平（西北大学现代分离科学研究所，陕西省现代分离科学重点实验室，西安 710069）
高娟（西北大学现代分离科学研究所，陕西省现代分离科学重点实验室，西安 710069）
耿信笃（西北大学现代分离科学研究所，陕西省现代分离科学重点实验室，西安 710069）
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原载于《分析化学》2001 Vol.29 No.1 P.1-5
http://www.periodicals.com.cn/qikan/periodical/fxhx/fxhx2001/0101/0101ml.htm