Abstract--Hydrated kaolinite (d(001) = 10/~) can be synthesized by mild healing of a kaolinite-organic suspension, allowing time for the clay to be intercalated by the organic solvent, and then dissolving a fluoride salt in the liquid. After mild heating of the suspension, the salt and organic solvent are removed by repeated water washings. The kaolinite retains interlayer water in the form of a l 0-& kaolinite hydrate. The influence of the intercalating agent, type of salt, concentration of salt, and the time of treatment on the synthesis of 10-& hydrate was examined for several kaolinites. The most effective salt is NH4F; much smaller yields were obtained using KF and RbF. Not all organic molecules gave high yields of the hydrate; dimethyl sulfoxide, formamide, and hydrazine worked well but N-methyl formamide did not. The reaction between clay and salt resulted in the replacement of some hydroxyls by fluoride. This replacement was rapid; after 1 min of fluoride treatment a substantial yield of hydrate was obtained. The intercalation step separated the layers and also disordered the kaolinite, facilitating the F for OH replacement at or near crystallite edges. This replacement weakens the interlayer bonding at the edges and thereby reduces the possibility of layer collapse and attendant dehydration.
Abstract--The rate of dissolution of phlogopite in an open system was measured at low temperature and pressure and at pH 3-5. The maximum dissolution rate was achieved by maintaining extremely low ionic concentrations in the solution using a cation-exchange resin (hydrogen form) as a trap for released cations. The resin also served as a source of hydrogen ions and acted as a buffer. The concentrations of ions adsorbed on the resin and remaining in solution were measured, along with surface area and cation-exchange capacity. The amount of phlogopite dissolved after 1010 hr was 67 times that dissolved using a COs-buffered, closed-system method. During the first hour of the experiment, dissolution was incongruent, but later became congruent from 1 to 1010 hr. From 1 to 200 hr the reaction had linear kinetics. The dissolution rate for the first 200 hr of the reaction was 2.0 x I0 14 mole KMg3A1Si~Olo(OH)JcmZ/sec. Since no evidence of parabolic kinetics was found, there is no reason to postulate the formation of a "protective layer."
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