Hydrolysis and Condensation of Silicates: Effect on Structure

The hydrolysis and condensation reactions of monomeric alkoxysilanes and organylalkoxysilanes utilized in sol-gel processing are reviewed. Both reactions occur by acid or base-catalyzed bimolecular displacement reactions. The acid-catalyzed mechanisms are preceded by protonation of OH or OR substituents attached to Si, whereas under basic conditions hydroxyl or silanolate anions attack Si directly. Many of the observed structural trends are understood on the basis of the pH and [H2O] dependence of the hydrolysis, condensation, and dissolution reactions.