Abstract
A quantitative theory of kinetic-diffusive-convective adsorption in the flow cell for total internal reflection fluorescence spectroscopy is developed for arbitrary adsorption isotherms. The effect of the convective transport is estimated in an analytical form for the short-time and long-time approximations. The boundary condition for the rate of adsorption at the interface (y = 0) is derived for kinetics-diffusion-convection controlled adsorption (Vx ≠ 0) in the flow cell, taking into account both the normal and the axial fluxes in the flow cell. The adsorption process in the flow cell for short times (t - tm → 0) is controlled by adsorption kinetics or by diffusive transfer when the rates of adsorption and desorption are infinite, and for long times (t → ∞) is controlled by diffusive and convective transfer. The simple formulae are derived to calculate from the experimental data the adsorption isotherm and the diffusion coefficient.
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