Retention of ionisable compounds on high-performance liquid chromatography XVIII: pH variation in mobile phases containing formic acid,piperazine, tris,boric acid or carbonate as buffering systems and acetonitrile as organic modifier

In the present work dissociation constants of commonly used buffering species, formic acid, piperazine, tris(hydroxymethyl)–aminomethane, boric acid and carbonate, have been determined for several acetonitrile–water mixtures. From these pK_a values a previous model has been successfully evaluated to estimate pH values in acetonitrile–aqueous buffer mobile phases from the aqueous pH and concentration of the above mentioned buffers up to 60% of acetonitrile, and aqueous buffer concentrations between 0.005 (0.001 mol L⁻¹ for formic acid–formate) and 0.1 mol L⁻¹. The relationships derived for the presently studied buffers, together with those established for previously considered buffering systems, allow a general prediction of the pH variation of the most commonly used HPLC buffers when the composition of the acetonitrile–water mobile phase changes during the chromatographic process, such as in gradient elution. Thus, they are an interesting tool that can be easily implemented in general retention models to predict retention of acid–base analytes and optimize chromatographic separations.