Continuous desorption rate measurement from a shallow-bed of poly(styrene-divinylbenzene) particles with correction for experimental artifacts.

A 0.50 mm high bed, containing ca. 3 mg of the nominally non-porous poly(styrene-divinylbenzene) (PS-DVB) sorbent Hamilton PRP-infinity, is located in a valve. After the bed is pre-equilibrated with a (7/3) methanol/water solution of naphthalene (NA), the valve is switched and (7/3) methanol/water solvent flows continuously through the bed at a high linear velocity. This causes NA to desorb into a constantly refreshed solvent, creating a "shallow-bed" contactor with an "infinite bath" kinetic condition. The effluent from the bed passes through a UV-absorbance detector which generates the observed instantaneous desorption rate curve for NA. The same experiment is performed using the solute phloroglucinol (PG), which is not sorbed by PRP-infinity and serves as an "impulse response function marker" (IRF-Marker). The resulting peak-shaped IRF curve is used in two ways (i.e. subtraction and deconvolution) in order to correct the observed instantaneous rate curve of NA for the following experimental artifacts: hold-up volume of the bed and valve, transit-delay time between the bed and the detector and instrument bandbroadening of the NA zone. The cumulative desorption rate curve, which is a plot of moles NA desorbed versus time, is obtained by integration. It is found to be accurately described by the theoretical equation for homogeneous spherical diffusion. The diffusion coefficient of NA inside the PRP-infinity particles (5.0+/-0.6) x 10(-11) cm2/s, agrees with the literature value that was obtained from the sorption rate of NA into the same particles. This constitutes virtually conclusive evidence for diffusion control of intra-particle kinetics of NA in the PS-DVB matrix of PRP-infinity and related polymers. The influence of both sorbent and solute properties on the method is evaluated.