The conversion of smectite to illite by way of a mixed-layer illite/smectite (I/S) series was found to be the major depth-related reaction in clay-mineral assemblages from two cored sedimentary sequences in the Rocky Mountains. The I/S reaction occurred in both interbedded sandstone and shale of Upper Cretaceous and lower Tertiary age in the Green River basin, Wyoming, and in chalk and chalky shale of the Upper Cretaceous Niobrara Formation, Denver basin, Colorado. As the proportion of illite layers in I/S increased with depth in these rocks, the amount of I/S in the clay fraction decreased, and the amount of discrete illite increased. Scanning electron microscopy revealed that the morphologies of highly expansible, randomly interstratified I/S clay (samples from shallow cores) exhibited no distinctive intergrowth or overgrowth textures. In deeply buried rocks containing highly illitic, ordered I/S and abundant discrete illite, however, fibers or laths of illite were formed on earlier I/S substrates. Less commonly, I/S of low expandability shows morphological features of both smectite and illite whereby rigid laths of illite appear to have formed diagenetically from the wall surfaces of I/S honeycombs. This combined morphology suggests some dissolution and reprecipitation (or some reorganization) of materials from the I/S substrate as the substrate was transformed into a more illitic mixed-layer clay.

These data suggest that some I/S clay was destroyed by the selective cannibalization of smectite layers in I/S to provide the components needed to make a more illitic I/S. Moreover, discrete illite and other minerals apparently were formed during the reaction. Also, coarser mineral phases, such as potassium feldspar and detrital micas, may not have been required to supply the chemical components in the reaction. The observations provide an explanation for late diagenetic I/S reactions that occurred in restricted or relatively closed geochemical systems, as in early cemented rocks having extremely low permeability and little or no potassium feldspar.

With the current interest in the use of transition metal-exchanged phyllosilicates as catalysts for novel organic syntheses, investigations into the factors which affect the movement of reactant, product, and solvent molecules into and out of their interlamellar region are of considerable importance. Mixed organic-water intercalates of a Wyoming montmorillonite, exemplified by the Na-montmorillonitepyridine-water system which can form four different intercalates exhibiting basal spacing of 29.3, 23.3, 19.4, and 14.8 Å depending on the pyridine: water ratio, have been used as a model system. X-ray and neutron diffraction and quasielastic neutron scattering data relating to the interconversion of interlayer species indicate that access to and exit from the interlayer space is hindered at high partial pressures of water by a water-film diffusion barrier in the interparticulate voids which exist between the aggregated silicate layers. At lower water vapor pressures the rate-limiting step for interconversion from one intercalate to another is the rate of transport of reagents and products to and from the clay particles. Under conditions where these rates are fixed, the rate-limiting step is the rate of diffusion of the pyridine molecule in the lower-spacing intercalate. Processes which involve a change in basal spacing do not necessarily proceed via a single discrete step, but are also affected by the amount of water made available to the system. In organic reactions catalyzed in the interlamellar space of various cation-exchanged montmorillonites (e.g., the conversion of alk-1-enes to di-2,2’-alkyl ethers and the reaction of alcohols to form ethers), rate-determining steps similar to those found above are likely to be operative. In particular, for reactions carried out in the liquid phase, where mass transport is facile and where phase-transfer problems are avoided, such reactions are likely to be diffusion controlled.

High-pressure liquid chromatography columns were packed with quasi-spherical particles of bentonite (SP-bentonite) which were prepared from a predominantly Na-bentonite powder by spray drying. The strength of adsorption of ring-substituted dimethylanilines on bentonite was directly related to their basicity (pKa). The adsorption of the amino-substituted N, N-dimethylaniline was commonly much weaker than that predicted from its pKa, suggesting that the amino group was the dominant site of interaction between the substituted anilines and the clay.

A better separation between the dimethylaniline isomers was obtained on SP-bentonite than on a neutral silica under the same chromatographic conditions. A selectivity factor of 25 was achieved between the most strongly and the least strongly adsorbed ring substituted isomers (3, 5- and 2,6-dimethylaniline, respectively) on the SP-bentonite. The selectivity factor was 3.4 on the silica. This efficiency of separation demonstrated the potential advantage of the readily available bentonite in high-pressure liquid chromatography. The higher resolution achieved in column runs than in batch experiments may be utilized for the elucidation of mechanisms of interaction of organic molecules at clay surfaces by comparing the interaction of a number of closely related adsorbates.

The 57Fe Mössbauer spectra of a series of untreated and Ca-saturated nontronites showed a predominant Fe3+ resonance which was computer-fitted with two Fe3+ doublets defining iron in non-equivalent cis-FeO4(OH)2 octahedral sites. In most spectra a doublet indicating tetrahedral Fe3+ was fitted and in one untreated sample a doublet indicating interlayer Fe3+ was identified. In a further untreated sample the interlayer iron was present as Fe2+. Upon Ca-saturation the interlayer iron was displaced. It also appears that the interlayer iron was present in at least two different interlayer sites. From the computer-fitted data it was clear that the interlayer cations have a significant effect on the Mössbauer resonances of iron in the two non-equivalent cis-octahedral and the tetrahedral sites of nontronite.

X-ray powder diffraction studies were performed with propyl-, dodecyl-, and dodecyldiam-monium bentonites saturated with aqueous mixtures of eleven organic pollutants at concentrations of 0.01 to 100%. The alkylammonium salt treatment separated the montmorillonite unit layers, which increased the interlamellar volume and exposed the interlamellar surfaces for adsorption of the organic pollutants. Washing the salt-treated clays with distilled water removed excess, physically adsorbed alkylammonium ions that could interfere with adsorption of the organic pollutants. Adsorption isotherms conducted at organic pollutant concentrations of 100 and 1000 mg/liter indicated the three alkylammonium montmorillonites, especially propylammonium montmorillonite, were effective adsorbents from aqueous solution, but to a lesser extent than adsorbents currently used in the water and wastewater fields.

Reactions between hydroxy-Al ions and orthosilicic acid as influenced by citric acid were studied at an initial Si concentration of 1.6 × 10−3 M, Si/Al molar ratios of 0.5 and 1.0, OH/Al molar ratios of 1.0-3.0, and citric acid/Al molar ratios of 0-0.3. In the absence of citric acid and at OH/A1 ratios of 1.0-2.8, imogolite (>0.01 μm) was dominant in the precipitates. At citric acid/Al ratios of 0.01-0.1, imogolite and/or pseudoboehmite were dominant in the precipitates at OH/Al ratios of 1.0 and 2.0, and imogolite and/or ill-defined aluminosilicate complexes at OH/Al ratio of 2.8. Instead of allophane or “proto-imogolite” allophane being the predominant species in the precipitates, the formation of ill-defined aluminosilicate complexes at OH/Al ratio of 3.0 was steadily promoted by increasing the solution citric acid/Al ratios from 0 to 0.3. The freeze-dried soluble products (<0.01 μ) ranged from silica gel to “proto-imogolite,” depending upon the basicity of Al and the level of citric acid of the parent solution. The amount of “proto-imogolite” increased with increasing citric acid/Al ratios from 0 to 0.1 in solution. Complexing low molecular weight organic acids, such as citric acid, impeded the formation of the short-range ordered aluminosilicates, allophanes and imogolite.

The possible physical and chemical forces controlling the volume change behavior of kaolinite were ascertained from the sediment volume of kaolinite in various solvents under no external load condition and from conventional oedometer measurements of kaolinite in several pore fluids. The minimum sediment volume of 14.5 cm3/10 g clay occupied by kaolinite in water where repulsive (R) forces were dominant indicated that the R contribution was insignificant for kaolinite. The maximum sediment volume of 25.0 cm3/10 g clay in benzene where coulombic attraction forces were significant suggested that electrostatic attraction between silicate sheets and midplane cations and van der Waals forces were not appreciable for kaolinite. The positive edge-negative face bonding of kaolinite particles in benzene was unlikely because the protons required to impart a positive charge to the edges were not available in the nonpolar solvent. The 3688 cm−1 band in the infrared spectrum of a kaolinite-dimethylamine sample decreased by 10 cm−1 on H-bond formation of the solvent molecule with the exposed structural hydroxyls of the octahedral sheet. The adsorbed solvent molecules likely H-bonded with an adjacent clay particle. That such interparticle H-bonds controlled the sediment volume and interparticle attraction in kaolinite was indicated by the decrease in sediment volume with increase in dipole moment of the solvent molecule, i.e., 25.0 cm3/10 g clay in n-heptane (dipole moment, μ = 0), 23.5 cm3/10 g clay in toluene (μ = 0.36), 17.0 cm3/10 g clay in ethanol (μ = 1.67), and 14.5 cm3/10 g clay in water (μ = 1.84).

In the oedometer tests with various pore fluids, a high void ratio (i.e., volume of voids/volume of solids) of ≈ 1.3 was obtained for kaolinite in n-heptane, and hexane (μ ≅ 0) at an external pressure of 1 kg/cm2 probably because the weakly bonded kaolinite particles were randomly oriented. At the corresponding applied pressure a lower void ratio of 0.88 resulted in water (μ = 1.84) where the stronger hydrogen bond between flat layer surfaces of adjacent particles favored a parallel orientation of clay particles.

The variations in void ratio-external pressure relationship indicated that kaolinite underwent lower compressibility in a solvent with low dipole moment and vice versa. Thus, the interparticle H-bond did not play a significant role in controlling the shear resistance and volume change behavior. The volume change behavior was essentially controlled by frictional forces and clay fabric. In nonpolar solvents the random arrangement of kaolinite particles and the frictional forces mobilized a high shear resistance on the application of a consolidation pressure, resulting in a lower compressibility. In a solvent with high dipole moment the parallel array of clay particles mobilized less shear resistance and produced a greater compression.

Electric potentials as a function of distance were calculated for a model of the double layer on clays in which a surface zone a few water molecules thick has a low dielectric constant. This zone is followed by bulk water with a normal dielectric constant. The double layer potentials were found to be lower than those obtained from the Gouy model, in which water has a normal dielectric constant throughout the double layer.

The synthesis of 10-Å hydrated kaolinite was accomplished by: (1) direct reaction of HF with a dimethyl sulfoxide (DMSO)-kaolinite intercalate and water washing; (2) methanol washing of a DMSO-kaolinite intercalate followed by reaction with any alkali fluoride salt and water washing; and (3) room-temperature (RT) water-washing of a methanol-washed DMSO-kaolinite intercalate. In all syntheses the optimum yield required a kaolinite in which DMSO was bound strongly to the interlayer surface. In the first synthesis, water inclusion between clay layers appeared to be facilitated by the reduction of cohesive interlayer forces brought about by replacement of surface and edge OH− by F−. The fluorination reaction was accomplished either by direct reaction of HF or by HF produced through the hydrolysis of NH4F at 60°C. In the second synthesis, intercalated DMSO was replaced by methanol. F− solvated readily in methanol but not in DMSO. Consequently, F− produced through hydrolysis of the alkali fluoride salt entered the interlayer space and contributed to the fluorination reaction. Furthermore, the diffusion of methanol out of the interlayer space during the RT-washing step was slowed by F≈ solvation which aided the exchange of methanol for water. High yields of 10-Å kaolinite hydrate were obtained irrespective of choice of alkali fluoride salt. The third synthesis was dependent on matching the diffusion of methanol out of the interlayer space with diffusion of water into this space. At room temperature the diffusion rates were close enough to maintain the clay in the expanded state throughout the hydration process, and high yields of 10-Å kaolinite hydrate were obtained. At 60°C the diffusion rates were too dissimilar, and very low yields of hydrate were obtained.

The particle size distribution, total and exchangeable Mg, and mineralogical compositions were determined on eight well-drained, noncultivated subsoils from Pennsylvania. No correlation was found between the clay content and total Mg (r =.29), or between the clay content and exchangeable Mg (r =.35). Serpentine, talc, and hypersthene were found in the very fine sand and silt fractions of soils having relatively high exchangeable Mg. Mica and 14-Å clay minerals were the only Mg-bearing minerals noted in the same fractions of soils having relatively low exchangeable Mg. Of the Mg-bearing clay minerals found in the clay fractions (smectite, vermiculite, chlorite, illite, and interstratified chlorite/vermiculite), only smectite decreased as the exchangeable Mg in the soils decreased. Two distinctly different distribution patterns of Mg were found for soils having relatively high and low exchangeable Mg. The former soils showed a decreasing Mg content as the particle size decreased, and the latter soils showed the opposite. Exchangeable Mg correlated significantly with the amount of Mg in whole soil, sand, and silt, but not with the amount of Mg in the clay, an indication that sand and silt but not clay were the important sources of exchangeable Mg in these soils.

The size distribution of unit particles of two New Zealand allophanes (An and Rh), in dilute (0.8% w/v) aqueous suspensions, has been determined by small-angle neutron scattering (SANS). In addition, the specific surface area of the samples was measured by ethylene glycol retention, and their morphology examined by high-resolution transmission electron microscopy (HRTEM). The SANS data indicate that although both allophanes are somewhat polydisperse, the average diameter of their unit particles is significantly different, being 56 and 43 Å for allophane-An and allophane-Rh, respectively. Consistent with this observation, the specific surface area of allophane-Rh (897 mVg) is appreciably greater than that of allophane-An (638 m2/g). Under the electron microscope, both samples appear as aggregates of hollow spherules but HRTEM did not clearly distinguish between the two allophanes in that the largest population of spherules had diameters near 50 Å. Because of the assumptions and uncertainties involved in the SANS and surface area measurements, the data must be discussed in terms of their respective ratios. On this basis, the spherule diameter ratio is of the same order of magnitude as the inverse ratio of specific surface area. The latter value is also in reasonably good agreement with the corresponding ratios of phosphate adsorption capacity and BET nitrogen areas, derived from earlier studies.

The large amount of water in the interlamellar space of alkylammonium montmorillonites in aqueous solutions is not fixed by intercalated hexanol or octanol. The hydration of the NH3+-group and the filling of the empty spaces between the carbon chains are responsible for this phenomenon. Hydrogen bonds between the alcohols and the ammonium groups reduce the enthalpy of solution of hexanol and octanol in the interlamellar region at infinite dilution to +17.6 and +12.7 kJ/mole, respectively. Self-association of the alcohols further diminishes the enthalpy of solution at higher alcohol concentration. The interlamellar fixation of the RNH3 cations prevents a micellization as has been obtained in bulk solutions. At a given alcohol concentration smectic type aggregates, i.e., double layers of alcohol molecules, appear as shown by an increase of the basal spacing of the organo-clay complexes. The aggregate formation is favored by a longer chain length of both the cation and the alcohol.

Hydroxychromium montmorillonites were prepared from solutions containing chromium nitrate and varying amounts of NaOH. The reactant Cr ions were hydrolyzed and, in some experiments, were dimerized to a significant extent. The extent of polymerization in the product formed from a solution containing a maximum amount of [Cr2(H2O)8(OH)2]4+ was compared with that in products obtained from solutions containing monomer, [Cr(H2O)5OH]2+, and lesser amounts of the dimer. Despite the uncertainty about the nature and amounts of product interlamellar species, the catalytic effect of the montmorillonite interlayer on the hydrolysis and polymerization of Cr(III) appears to be independent of the nature of the reactant species. The validity of this conclusion depends to a large extent on the reliability of water determination in the clay mineral species, which is estimated to be no better than 5%. The assumption that H2O+ is 'combined’ and H2O— is 'free’ water is shown to be partially true, thereby causing some uncertainty in the interpretations of interlayer compositions.