Measurement of desorption rates from octadecylsilyl bonded-phase HPLC particles and its characterization in terms of pore, surface, and film diffusion.

An instrument is developed to measure rates of desorption of solutes from particulate HPLC packing materials for processes that are quantitatively complete in a few tenths of a second. The instrument is a modified, pressure-driven, stopped-flow device. The major modifications include positioning a very short (0.6 mm) bed of the particles just upstream of the detector cell, eliminating the mixing chamber, and adding high-speed switching valves in order to allow sequential continuous flow of individual solutions. Instantaneous rate curves are measured for the desorption of 1,2-dimethyl-4-nitrobenzene (DMNB) from 12-microm-diameter porous particles of the bonded-phase packing Luna C-18 employing high linear velocities of the eluting solvent. The same experiment is performed for the nonsorbed compound phloroglucinol (PG) The PG rate curve is used in two ways (i.e., subtraction and deconvolution) in order to correct the observed rate curve of DMNB for experimental artifacts such as bed hold-up volume and instrument band broadening. The cumulative desorption rate curve of DMNB is obtained by integration. It is accurately described (R2 > 0.999) by a theoretical model that invokes both intraparticle diffusion (including both hindered pore diffusion and surface diffusion) and external film diffusion. The surface diffusion coefficient is (3.2 +/- 0.8) x 10(-6) cm(2)/s and the diffusion film thickness is 0.5 microm. The validity, of both the experimental technique and the theoretical model, is demonstrated by excellent agreement between a predicted and an observed chromatographic elution peak for DMNB on a 25-cm-long commercial column of Luna C-18.