Abstract
The chemisorption of hydrogen ions by silicas chemically modified with aliphatic amines was discussed. The sorption kinetics followed the model of sorption from a semi-infinite solution, with sorption being of a two-stage nature. The first stage, involving the overwhelming majority of sorption centres, was very fast. In contrast, the second stage was rather slow and diffusion-controlled.
A proper description of the protolytic equilibria on the aminosilica surface required account to be taken not only of the protonization of the grafted amino groups but also of their homoconjugation. The latter reaction resulted from interactions between neighbouring groups and led to the non-random (islandlike) coverage of the surface by amino groups. Both the nature of the background electrolyte in the solution and its concentration had no effect on the model structure.
The thermodynamic equilibrium constants for the heterogeneous protonization reaction were determined from the dependencies of the mixed equilibrium constants on the concentration of the background electrolyte in solution. Chemisorption of H+ ions, accompanied by penetration of the counterions into the subsurface layer, was of an endothermic nature and associated with increasing entropy.