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The linear dependence of the logarithm of the capacity factor (log  k ‵) on the composition of the aqueous binary mobile phase is examined systematically in reversed-phase liquid chromatography. In discussing the physical significance of the intercept (log  k  w ) and the slope ( S ), it is found that log  k  w  is linearly related to  S  by regression analysis. Simultaneously, the nonlinear quantitative relationships between either log k w  or  S  and the structure parameters of the solutes are derived from the chromatographic thermodynamic theory, which involves two-parameter models consisting of the total solubility parameter (δ T ) and the  n -octanol—water partition coefficient ( P ). Results indicate that the indices of log  k  w  and  S  are solute-related constants that reflect the influences of hydrophobicity and hydrophilicity, respectively, and play opposite roles in solute retention. Additionally, the methods estimating log  P  with molecular structure parameters are proposed and justified by the practical calculation of  P , which provides the possibility of predicting the  P  values of compounds. On the basis of the linear summation of free energy change, we establish a fundamental retention equation that includes the influences of the properties of solute and mobile phase on the retention process, and we use the general retention equation to successfully predict the retention values of the tested solutes. We have also done multi-regression analysis of a great deal of data and have proved the quantitative equations discussed above. Finally, the selectivity of the chromatographic system is discussed in detail, and a basic relationship between the relative retention and the influencing factors is given.

Relationship Between Retention Behavior of Substituted Benzene Derivatives and Properties of the Mobile Phase in RPLC