Kinetics of polyelectrolyte adsorption

The kinetics of polyelectrolyte adsorption has been investigated theoretically. In analogy with Kramers' rate theory for chemical reactions we present a model which is based on the assumption that a polyelectrolyte encounters a barrier in its motion towards an adsorbing surface. The height of the barrier, which is of electrostatic origin, is calculated with a self-consistent-field (SCF) model. The salt concentration strongly affects the height of the barrier. At moderate salt concentrations (similar to 0.2 mol l(-1)) equilibrium in the adsorption is attained; at low salt concentration (similar to 0.01 mol l(-1)) equilibrium is not reached on the time scale of experiments. The attachment process shows resemblances to the classical DLVO theory.