Abstract
The retention of ionizable solutes in reversed-phase liquid chromatography (RPLC) was predicted using retention equations for the monoprotic and diprotic species. In RPLC, with acetonitrile (ACN)/water mobile phases, the influence of pH and ACN cluster fraction can be quantitatively described by two general equations. The cluster solute solvation energies in an ACN/water mixture over a 0.50−0.80 water fraction were calculated. The energetics of the ACN cluster exchange process in the mobile phase was investigated in relation to the difference in pKa (ΔpKa) between a solute used as reference and the other solutes. A linear correlation was found between the Gibbs free energy change of the solvent exchange process and ΔpKa confirming that the solute solvation by ACN clusters was enhanced for the lesser polar solutes.
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