Alkylammonium ion exchange on mixed-layer minerals gives detailed information about the variation of cation density in succeeding interlayer spaces. Three mixed layer samples from Japan (supplied by Dr. H. Kodama) were investigated. Their nearly 1:1 interstratification is based on regularly alternating high- and low-charged interlayer spaces, which are caused by a regular sequence of polar layers. The cation density in the high-charged interlayer spaces is >0.8 eq/(Si, Al)4O10. The low-charged interlayer spaces have an average cation density of 0.4 eq/(Si, Al)4O10 and heterogeneous charge distribution. The kind of heterogeneity of the Goto Mine sample differs from that of the Yonago Mine and the Honami Mine samples.

The Goto Mine specimen has a rather regular sequence of the low- and high-charged interlayers in proportions close to 0.50:0.50. The other two samples contain interlayer spaces with pronounced unsymmetrical charge distribution. The Yonago Mine sample probably has in random distribution with the polar layers about 10% mica-like layers segregated to packets of three and more layers; the ratio of high-charged interlayers to the low-charged ones is increased to about 0.55:0.45. The Honami Mine sample probably contains isolated mica-like layers or pairs of them. The proportion of the high-charged interlayers is estimated to be about 0.53:0.47 and is lower than determined by Kodama from the glycerolated sample.

The samples investigated may be considered as end-members of a series of interstratified specimens which begins with smectites with mixed-layer like charge distribution.

Dimensional changes in kaolinite pellets as a function of temperature show two sharp shrinkage “steps,” at about 450–550°C and 900–980°C, which are roughly comparable in magnitude. Isothermal heat-soaking tests confirm that the rates for both are kinetically controlled. Water vapor inhibits shrinkage at low temperature but promotes shrinkage at high temperature. Both the former reaction, related to dehydroxylation, and the latter reaction, related to “mullitization,” take place at temperatures well below those observed in DTA, TG, and other measurements, indicating that bond-breaking is a necessary prelude to transitions at higher temperatures.

Bonding energy changes, as measured by X-ray fluorescence shifts, were used in interpreting the phenomena involved. The relative absence of bonding energy changes in the aluminum until the range 950–1100°C, and the presence of such changes in the silicon, suggest that high-temperature energy release is probably related to segregation or crystallization of silica, rather than of an aluminum-containing phase. Caution must be used in interpreting bonding energy changes, and in distinguishing kinetic and thermodynamic contributions to dynamic phenomena.

The reaction between the herbicide “Roundup,” (PAH)3G, which is the commercial name of the iso-propylammonium salt of glyphosate (H3G, N-phosphonomethyl glycine), and montmorillonite was studied. The adsorption of the anionic component of Roundup glyphosate anion, G−3, from an ethanol solution is achieved by repeated immersion of the clay film in the alcohol solution followed by drying for 6–12 hr after each immersion. During the adsorption process the surface acidity of the interlayer space must be sufficiently high to protonate the anion. A zwitterion glyphosate is thereby formed in the interlayer space. Association forms are obtained in the interlayer space in which the COOH and the PO3H groups are linked to the exchangeable cations through water bridges. Adsorption of the glyphosate anion from aqueous solution of Roundup occurs when this anion forms a neutrally or positively charged complex with the exchangeable cation. This may occur with Al- and Fe-montmorillonite, when the molar ratio glyphosate:metal is such that a complex with a 1:1 ratio can be formed in the interlayer space. To clarify the reaction mechanism, adsorption of glycine by montmorillonite from ethanol solution was also studied. The associations obtained between glyphosate and exchangeable cations are less variable than those obtained between glycine and exchangeable cations in the interlayer space of montmorillonite. The following species of adsorbed glycine were identified: glycinium cation, zwitterion glycine, glycine complexed with metal cations either as a monodentate or as a bidentate ligand. In the latter case a chelate is formed.

The adsorption mechanism of iso-propylammonium (PAH+), the cationic component of Roundup, by various homoionic montmorillonites and the structures of the associations obtained in the interlayer space were investigated, using infrared, X-ray, and carbon analysis methods. Adsorption from aqueous and ethanol solutions of Roundup was studied. The infrared spectra were compared with those obtained by the treatment of montmorillonites with ethanol and CCl4 solutions of the free iso-propylamine (PA). The adsorption of PA from ethanol gives rise to protonation of the amine. PA sorbed from CCl4 solution forms an ammonium-amine association. Adsorption of PAH+ from alcohol solution of Roundup occurs by the mechanism of cation exchange. With transition metal exchangeable cations, PAH+ is sorbed in excess, forming hydrogen bonds between NH3+ groups and hydroxyls resulting from dissociation of water molecules. The process of adsorption of PAH+ from aqueous solutions of Roundup depends on the concentration of the solution. If montmorillonite is reacted with 0.5% solution of Roundup, PAH+ is adsorbed by exchanging metal cations and the adsorption capacity of the clay does not exceed the c.e.c. If the montmorillonite is reacted with 5.0% solution of Roundup, the PAH+ exchanges protons originating from the hydrolysis of the interlayer water. Protons which are transferred from the interlayer space to the water solution are accepted by the anion component of Roundup. The amounts of PAH+ adsorbed from concentrated Roundup solutions are much higher than the cation exchange capacity of montmorillonite. Hydrogen bonds are formed between the ammonium and water or hydroxyl groups on the interlayer space. With the trivalent exchange ions Al and Fe, which tend to polymerize in the interlayer space, excess sorption gives rise to hydrogen bonding of NH3+ to oxygen of the polymer.

The use of neutron diffraction to determine some of the structural properties of montmorillonite-water systems at low water concentrations is described. The samples were prepared by compression or suction to give clay samples with between one and three molecular layers of water between the plates.

About 10% of the platelets in the clay are randomly oriented. The remainder are partially oriented in the plane of the sample, with an angular spread of 40° about the mean orientation. It is suggested that these oriented domains are formed from the larger platelets present in the system. The Bragg diffraction pattern is better explained by a disordered lattice model rather than by a mixture model with small particles having a well-defined lattice spacing. We have fitted both the intensities of (00l) reflections and the shape of the (001) reflection quantitatively to a model which allows for a Gaussian spread of platelet spacing about a mean value. The half width of the spread is about 10% of the lattice spacing.

No significant structural differences are found between Li, Na, K, and Cs montmorillonites. The method of preparation has no effect on the structural properties of the large platelet particles but does affect the randomly oriented fraction. The lattice spacing of the latter appears to be better defined for samples prepared by compression.

Experiments on the variation of lattice spacing with humidity indicate that the structural model we have used is adequate except at humidities where the system is changing over from one to two, or two to three water layers.

The trimethylsilyl derivative from halloysite was prepared by the reaction of halloysite powder with a trimethylsilylating reagent. The product was organophilic and the results of its infrared spectrum, X-ray powder diffraction pattern, and elemental analysis indicated that the trimethylsilylation occurred on silanol groups in the tetrahedral layer of halloysite after the acid decomposition of the octahedral layer. The thermal stability of the product was evaluated by means of differential thermal analysis. It was not possible to obtain the organic derivative from kaolinite by the same procedure. It is suggested that the differences in the reactivity between halloysite and kaolinite is due to the difference in susceptibility of the clay minerals to acid attack.

K-saturated kaolinite was titrated in 13 different solvents with tetrabutylammonium hydroxide using a combination electrode for potentiometric determination. The titer of base required to reach the final potentiometric endpoint was dependent on the solvent and increased according to the following solvent order in both the presence and absence of excess neutral salt: methanol ⩽ water < ethanol ⩽ 1-propanol < 1-butanol < 2-propanol < DMF < t-butanol < DMSO < pyridine ⩽ acetonitrile ⩽ methylethyl ketone < acetone. With the protic solvents, titratable acidity increased according to decreasing dielectric constant of the solvent and increasing size and/or branching of the aliphatic constituent. The largest titratable acidities were obtained in the dipolar aprotic solvents with negligible basic character (e.g., acetonitrile, acetone, methylethyl ketone). These results are discussed in terms of solvent properties, solvation characteristics of ions in the solvents, and acid-base behavior of crystalline edge sites.

Infrared and Mössbauer spectroscopy show that the extent of the reduction of nontronite is dependent on the chemical composition of the nontronite and on the nature of the reducing agent. Hydrazine reversibly reduces about 10% of the iron in all of the nontronites studied irrespective of composition and it is suggested that the resulting ferrous iron occurs only in distorted octahedral sites. Similar conclusions are reached for the dithionite reduction of the nontronites containing little tetrahedral iron, but for those with more than one in eight silicons replaced by iron, changes brought about by dithionite treatment are irreversible due to dissolution of appreciable quantities of iron. Results from both spectroscopic techniques suggest that iron in tetrahedral sites is preferentially dissolved and that up to 80% of the structural iron can be reduced.

Evidence is presented for the formation in these extensively reduced nontronites of a small amount of a mica-like phase resembling celadonite or glauconite, and, as dithionite is used for the pretreatment of soils, the implication of this observation is briefly discussed.

The use of deuterated hydrazine as a reducing agent has enabled the nontronite absorption band near 850 cm-1 to be assigned to a Si-O (apical) stretching vibration, which is inactive in the infrared for perfect hexagonal symmetry, but which is activated by distortions in the tetrahedral layer.

The adsorption-catalyzed degradation of parathion on clay surfaces is a hydrolysis process, proceeding either directly or through a rearrangement step. The rate and mechanism of degradation are dependent on the nature of the clay, its hydration status, and saturating cation. A mechanism for parathion degradation at adsorption sites on clay surfaces, in the absence of a liquid phase, is proposed.