The adsorption of butanol, hexanol, and octanol on alkylammonium clays of different chain length is studied. The adsorption at infinite dilution compares to the distribution of alcohol between alkane and water in bulk solution. The interlamellar phase of the montmorillonite acts as a solvent even more reactive than carbon tetrachloride. Hydrogen bonds probably occur between the OH group of the alcohol and the NH3+ group. The exchange of water by alcohol on the interlamellar alkylammonium ion is the major factor in the transfer process.

The binding of tris-bipyridyl metal complexes of the type M(bp)32+ (M = Fe2+, Cu2+, Ru2+) to hectorite surfaces is shown to occur by two mechanisms. (1) replacement of Na+ ions in the native mineral by cation exchange up to its cation exchange capacity and (2) intersalation of excess salt beyond the exchange capacity. In the cation exchange mechanism, the binding of metal complex is strongly favored over Na+. The intersalation reactions are dependent on the nature of the counter-anion: SO42-, Br- > CIO4−, Cl−. The homoionic M(bp)32+-hectorites, which exhibit rational 18 Å X-ray reflections, have been characterized with regard to their BET surface areas, water adsorption isotherms, types of water present, selected reactions in the intercalated state, and orientation of the complex ions in the interlayer regions. Mixed Fe(bp)32+, Na+-hectorites have also been examined and the results suggest segregation of the two ions between interlayers or within interlayers. Solid state intersalated phases have been isolated with 18 Å and 29.5 Å spacings. In general, surface areas of the intersalated phases are low, but the 18 Å phase derived from [Fe(bp)3]SO4 adsorption shows a high surface area, which even exceeds the surface area of homoionic Fe(bp)32+-hectorite.

Several dioctahedral clay minerals are related through reaction series. These series can be produced hydro-thermally from beidellite gel and montmorillonite by making simple changes in interlayer and solution chemistry. The series are:

• gel-K-beidellite-random illite/smectite-K-rectorite-illite

• K-montmorillonite-K-rectorite-illite

• Na-montmorillonite or beidellite-Na-rectorite-paragonite

• Li-montmorillonite-Li-tosudite-Li-rectorite-cookeite(?)

• Mg-montmorillonite-Mg-rectorite-tosudite-sudoite(?)

• Ca-montmorillonite-Ca-rectorite-margarite(?)

• Al-Ca-montmorillonite-kaolinite/smectite-kaolinite (150°C)

• Al-Ca-montmorillonite-pyrophyllite/smectite-pyrophyllite (320°C).

Assuming stability for the mixed-layer phases, paragenesis is a function of P, T, and X conditions. If the phases are considered to be metastable, paragenesis is a function of the speed and path of reaction.

A correlation was made of crystallochemical data from 15 smectites with the half time of dissolution (t05) in 6 N hydrochloric acid at 96°C. From this the relation

ln t05 = 3.95 - 1.96 FeVI - 2.30 MgVI

was developed. It shows a remarkable dependence of the apparent dissolution rate of the octahedral layer of the smectites on the substitution of Fe3+ and Mg2+ for Al+3 in the octahedral position.

From swelling and surface area measurements, it was found that the swelling of a montmorillonite depends linearly on the fraction of its layers that fully expand in water and that this fraction, in turn, depends linearly on the b dimension of the unit cell. Therefore, swelling is a linear function of the b dimension. However, the specific surface area of a montmorillonite is a linear function of its b dimension only if no partially expanded layers exist. It was also found that the distance between fully expanded layers at a given applied pressure is the same for all montmorillonites.

Morphological changes occurring in naturally weathered micas in seven residual soils from Ontario were studied. Splitting, exfoliation of the (100) planes, surface coats, filling of spaces with soil material as well as cracking and crumbling of (001) surfaces were the main morphological changes found to be taking place during natural weathering of mica particles. The significance of the observed feature in relation to the general theory of mica weathering is discussed.

Organic matter present in clayey sediments may act as a cement between the clay particles as well as a blocking agent for the swelling of clay minerals like montmorillonite.

Removal of the organic matter is important when a clay sample is to be characterized by X-ray powder diffraction, or when it is to be separated into the composing minerals on the basis of differences in density.

Eight different methods for the removal of organic matter from a North Sea clay sample have been studied. Of all methods tried bromine oxidation was found to be the most effective.

The effect of pH, time and temperature on the interaction of zinc with acid and base saturated dickites has been investigated. Increase in pH resulted in an increase in adsorption of zinc in the higher concentration range. The adsorption increased rapidly and then slowly with increase in the time of interaction. The variation of rate constants and the half times of reaction suggested an exchange process controlled by film and possibly particle diffusion and thereafter fixation processes. The inferences found support from the nature of adsorption isotherms. Temperature affected adsorption with exothermic interactions. The activation energy of adsorption of zinc on Na-dickite was 14.0 kcal mole−1.