Abstract: The hydrolysis and decomposition of M-hectorite (M being Na, Li, Mg, or Ca) in dilute solutions of M-chlorides were studied by recording the changes in electrical conductivity (EC) of the clay suspensions with time, and by chemical analyses of the interclay solutions and resulting solid phases. The rate of hydrolysis of the hectorites in suspension, as evaluated by the change of EC with time, was found to decrease with increase in salt concentration (to zero for Na-hectorite in NaCl concentration of 47 meq/liter), and to decrease with increase in the valency of the adsorbed cation (the rate of hydrolysis of Ca-hectorite was one sixth of that of Na-hectorite). The rate of Na-hectorite hydrolysis was determined by the concentration of protons at the clay surface as calculated from the diffuse double layer theory.
Conversely, in suspensions of Al-hectorite saturated with Na, the hydrolysis rates were not dependent on the electrolyte concentrations. This result can be explained by assuming that the hydroxy-Al polymers at the clay surface determine the proton concentration at the clay surface. Hectorites saturated with structural cations (such as Mg and Li) are chemically more stable than those saturated with Na and Ca. The presence of Li and Mg at the clay surface slowed down the diffusion release of these octahedral ions to the clay surface, compared with Na and Ca hectorite, respectively.