Ferrihydrite was transformed to goethite and/or hematite at various temperatures, [OH], and [Al]. Increasing temperature and [Al] favored hematite, increasing [OH] favored goethite. A given [Al] induces hematite more effectively at lower [OH]. Al substitution in goethites increased linearly with log[Al], but was independent of temperature. At a given [Al], substitution increased with decreasing [OH]. In a plot of Al/Fe in the goethite against [Al]/[Fe(OH)4−] in solution a straight line was obtained for all preparations independent of [OH].

Phosphate in the form of organic compounds can be bound in soils containing the aluminosilicate allophane. A significant part of this phosphorus is believed to be present as nucleic acids. The interaction of yeast RNA with allophane was studied to further the understanding of the allophane/organic macro molecule interaction as well as the binding of organic phosphorus by allophanic soils. The extent of RNA adsorption on the allophane was dependent upon the pH, the charge and concentration of simple cations, the concentration of RNA, and the time of interaction. From a mixture containing 145 mg/liter RNA and 2.9 g/liter allophane in 10−2 M NaCl, the amount of RNA adsorbed increased from 6% at pH 10 to 98% at pH 3. The adsorption also increased as the concentration of added NaCl was increased from 10−4 M to 10−1 M, but only when the pH was greater than 5, i.e., above the isoelectric point of the clay. Mg2+ and Ca2+ were equally much more effective at promoting adsorption than Na+ at the same concentrations. There was no difference in the effectiveness of SO4−2, Cl−, or NO3− at pH 5 or higher. The adsorption isotherm at pH 7 can be described by the Langmuir equation; the apparent adsorption maximum was 38 mg/g. Van der Waals and simple electrostatic forces appear to dominate the interaction leading to the adsorption of RNA by allophane.

The electron spin resonance (ESR) technique has been used to study the motion and segregation of an organic spin probe cation (4-amino-2,2,6,6-tetramethylpiperidine N-oxide) on K+-hectorite as a function of average surface concentration. The organic cation tends to concentrate in certain interlayers of aqueous hectorite suspensions even when it occupies a small fraction of the cation-exchange sites. This demixing effect is not evident in methanol-solvated hectorite. The average mobility of the probe increases at higher adsorption levels as a result of the shift of the equilibrium in favor of the solution state. Calculated time-averaged orientations of the probe on the clay surfaces are quite different for methanol- and water-solvated systems, emphasizing the importance of the solvent in modifying the surface-cation interaction.

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 water adsorption capacity of zeolites is a function of pressure and temperature. Desorption of zeolites may be of three types, wherein the crystal lattice undergoes (1) no or little change, (2) a reversible change, or (3) an irreversible change. In the first two cases, the divariance of the zeolite-water vapor equilibrium results in networks of isobars, isotherms, and isosteres which can be transformed into a “characteristic” curve following the Polanyi-Dubinin theory. Because the volume of the micropores of a zeolite structure is constant, the isotherms and “characteristic” curve can be transformed linearly. During desorption, if the volume of the micropores varies due to a change of structure, the curves show linearity breaks.

On the basis of X-ray diffraction, differential thermal, and thermal gravimetric analyses, the equilibrium curves and structural changes of heulandite and stilbite were determined, using specially designed equipment. In the reversible adsorption range, heulandite shows no linearity breaks in the transforms and no structural variation. Stilbite, however, shows a linearity break in the transforms corresponding to a structural change.

When aqueous dispersions of Na+-smectite or n-butylammonium-vermiculite react with sulfate salts of Fe(II), Co(II), or Ni(II) bipyridyl or 1, 10-phenanthroline complexes in excess of the cation-exchange capacities, intersalated phases with spacings of about 29.5 Å are obtained. Thermal decomposition of the intersalated complex cations affords expanded phases with a d(001) spacing near 18 Å for the smectites and near 28 Å for the vermiculites. These phases are stable to temperatures of at least 550°C. Nitrogen surface areas of the fired products are as high as 400 m2/g.

Biotite in deeply weathered granitic rocks in southwestern Australia has altered to exfoliated grains composed of biotite, mixed-layer clay minerals, kaolinite, vermiculite, gibbsite, goethite, and hematite. Discrete vermiculite and vermiculite-dominant mixed-layer clay minerals are not major weathering products. Oxidation of octahedral iron in biotite is associated with ejection of octahedral cations, loss of interlayer K, and a contraction of the b-dimension of the biotite sheet. Si, Mg, Ca, Mn, K, and Na are lost from biotite during weathering, and Ti, Al, Ni, and Cr are retained. Fe and water have been added to the grains during weathering. Much Fe occurs as aggregates of microcystalline, aluminum-rich goethite particles on flake surfaces and within etchpits, with smaller amounts occurring as hexagonal arrangements of lath-shaped crystals of goethite on flake surfaces.

Aluminum-substituted hematites (Fe2−xAlxO3) were synthesized from Fe-Al coprecipitates at pH 5.5, 7.0, and in 10−1, 10−2, and 10−2 M KOH at 70°C. As little as 1 mole % Al suppressed goethite completely at pH 7 whereas in KOH higher Al concentrations were necessary. Al substitution as determined chemically and by XRD line shift was related to Al addition up to a maximum of 16–17 mole %. The relationship between the crystallographic a0 parameter and Al substitution deviated from the Vegard rule. At low substitution crystallinity of the hematites was improved whereas higher substitution impeded crystal growth in the crystallographic z-direction as indicated by differential XRD line broadening. At still higher Al addition crystal growth was strongly retarded. The initial Al-Fe coprecipitate behaved differently from a mechanical mixture of the respective “hydroxides” and was, therefore, considered an aluminous ferrihydrite.

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 nature of the complexes in aqueous solutions of Cu(II) and Ni(II) with diethylenetriamine (dien) and tetraethylenepentamine tetren) is pH-dependent. At M(II):dien = 2 and M(II):tetren = 1, the main complexes are [M(dien H)2(H2O)2]4+ and [M(tetren H)(H2O)2]3+. In excess ligand (pH = 10.30), the majority species are [M(dien)2]2+ and [M(tetren)(H2O)]2+, and considerable amounts of monoprotonated amines are adsorbed. The surface of hectorite prefers the tetragonally distorted complexes in all cases studied. The complexes readily lose their axially coordinated water molecules to form planar complexes on the interlamellar surface. The planar Ni(II)-complexes are diamagnetic, showing that the surface is a very weak axial ligand. The divalent complexes [M(dien)2]2+ and [M(tetren)(H2O]2+ can also be partially transformed to the corresponding planar forms on the surface, especially in the case of [Cu(dien)2]2+. The driving forces are thought to be the acid nature of the clay-adsorbed water and the gain in crystal field stabilization energy of the transition metal ions.

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.

Single grain X-ray and electron diffraction patterns of weathered biotite flakes exhibit groupings of 001 and hk reflections of biotite, vermiculite, mixed-layer clay minerals, and kaolinite indicating that the secondary minerals are in parallel crystallographic orientation to the parent biotite. Asterism of biotite reflections is enhanced by weathering. Gibbsite crystals developed in parallel basal orientation to biotite flakes. Most goethite in weathered biotite occurs as aggregates of randomly oriented crystals in cleavages and on grain surfaces. Some goethite is present on micaceous fragments as 0.05-μm size, lathlike crystals in a hexagonal arrangement with their (100) face resting on the (001) biotite face. Selected area electron diffraction patterns of aggregates of lathlike goethite crystals contain 0kℓ, 1kℓ, and 2kℓ reflections due to undulation of the aggregates and the extreme thinness of the crystals. These patterns indicate that the close packed anion layers in goethite coincide with the brucite-like layer of the micaceous minerals.

The adsorption of acetamide and partly hydrolyzed Polyacrylamides onto montmorillonite has been investigated with emphasis on the valency of the exchangeable cation of the clay and the ionic strength of the medium. A difference in the adsorption of acetamide from 3 mg/g to 0.6 mg/g was observed when a Na+-clay was changed to a Al3+-clay. For Polyacrylamide, an opposite effect was observed, and the fixation increased from 3 mg/g (Na+-clay) to 18 mg/g (Al3+-clay). This difference in behavior may be accounted for by the decrease in adsorption sites due to partial flocculation in the presence of polyvalent cations (tactoid formation). Adsorption in a saline medium is two- to fivefold greater for diverse polymers and substantially less for acetamide (from 3.0 mg/g to 0.77 mg/g). An increase in the degree of hydrolysis of the polymer results in a significant increase in adsorption. In contrast, a change of molecular weight has practically no influence upon the adsorption ratio. The results obtained in saline medium may be explained by a size decrease of the macromolecules, allowing a closer approach to the surface of the mineral substrate, and by a chain lengthening as the degree of hydrolysis increases, induced by the electrostatic repulsions between the COO− groups.

Infrared spectroscopic, X-ray powder diffraction, diffuse reflectance, and electron-spin resonance examination of homoionic bentonite from Sardinia treated with diazomethane indicates that poly-methylene was formed in the interlayer position. Polymerization can be attributed to the acidic properties of the residual water in the interlamellar space, depending on the nature of the exchanged ion. The presence of an interlayer polymer causes the clay to assume strong hydrophobic properties.

Imogolite occurs as tiny bumps less than 0.05 µm in diameter and about 0.3 µm long on amorphous thin layers on the surface of weathered plagioclase. The bumps grow outward from the surface to form projections, which then develop into a fibrous imogolite. The fibers branch out and grow into widespread networks or thin films which finally cover the entire surface of the plagioclase grain. The fibers are about 0.05 µm in diameter as seen by transmission electron microscopy.

Acidified suspensions of Al-saturated kaolinite, montmorillonite, mica, illite, and biotite in 10−3 M NaNO3 were potentiometrically titrated with 0.1 N NaOH and 0.1 N HNO3 in succession in a CO2-free nitrogen atmosphere. The resulting curves were compared with those for Al(NO3)3 solutions of similar Al concentration in the supernatant solution and corrected for Al in the entrained solution in the clay.

Base titrations of Al ions adsorbed on all the minerals, except montmorillonite, showed two pH inflections separated by a buffering range. With montmorillonite, there were three pH inflections similar to those for Al in solution. The first inflections in the titration of suspensions occurred at lower pHs and were less pronounced than for Al in solution. These represent the titration of H3O+ sorbed during the pretreatment. The buffering by adsorbed Al ions is also less than that by Al in solution.

The OH− used up by adsorbed Al ions between the first and last inflections was equal to, or slightly greater than, the CEC of the minerals, except for mica where it was more than twice the CEC, because new interlayer surfaces were formed during the acid pretreatment. Acid titration curves of Al ions in the adsorbed and solution states showed hysteresis when related to the base titration curves. The use of two titration speeds (3 and 0.3 pH units/hr) only slightly affected the titration curves of the minerals suggesting that the observed effects were not caused by lack of equilibrium with added base or acid.

The presence of Al-bearing goethites has been unequivocally established in Venezuelan laterite sediments by means of infrared spectroscopy (IR), chemical dissolution, and X-ray powder diffraction (XRD) methods. The composition of these samples ranges from [Fe0.89Al0.11]O(OH) to [Fe0.76Al0.24]O(OH). The data of dissolution experiments using a modified dithionite (CDB) treatment suggest a parallel behavior between Fe and Al; the gradual dissolution of Al is associated with the destruction of the Al-containing goethite. The interpretation of the CDB dissolution results for SiO2/Fe2O3 is different; silica was only slightly extracted from phases other than goethite. Substitution of Fe3+ by Al3+ in these goethites was represented on the XRD patterns by a lowering of the (110) and (111) reflections corresponding to a reduction in size of the unit cell of goethite. IR spectroscopy showed the formation of such solid solutions by a shift of the 405 cm−1 absorption band, assigned to v (Fe-O) in synthetic goethite, to >460 cm−1 in the spectrum of Al-bearing natural goethite. Moreover, this spectrum shows a shift of the 3140 cm−1 absorption, due to v (OH), to higher frequencies, indicating a H-bond weakening in [FexAl(1−x)]O(OH) compared to FeO(OH).

Exchange reactions of Na-montmorillonite with zirconyl chloride solutions give products with basal spacings near 18 Å which are stable to 500°C and have surface areas of the order of 300–400 m2/g. The Na ions are exchanged with tetrameric hydroxy cations [Zr4(OH)14•nH2O]2+. The high surface area is attributed to the porosity formed by stable zirconium oxide “pillars” formed by dehydroxylation of the complex cation. The nitrogen adsorption isotherms are of Langmuir type and are consistent with adsorption in interlayer micropores. Reduced-charge montmorillonites, formed by application of the Hofmann-Klemen procedure, give either similar or slightly smaller surface areas.

Results of adsorption studies of several pesticides on soils and clays show that the application of the reduced concentration concept to adsorption can either reduce the temperature effect on the isotherms, eliminate it altogether (e.g., parathion adsorption on Netanya soil), increase the temperature dependence (e.g., (β-BHC adsorption on Ca-bentonite) or even reverse the temperature dependence of the isotherms (e.g., parathion adsorption on Ca-attapulgite).

Literature and experimental data for the adsorption of parathion by Ca-attapulgite and by attapulgite with organic exchangeable cations of different sizes demonstrate that for many surface interactions the terms organophilic or hydrophilic are misleading. Organic compounds which are insoluble in water and soluble in apolar solvents will not necessarily adsorb preferentially on “organophilic“ surfaces. The specific interactions between adsorbate and adsorbent and steric considerations (in addition to the relative solubility of the organic molecule in water and apolar solvents and the organophilic or hydrophilic nature of the surface) will determine the partition between the adsorbed and the solution phase. An outstanding example is the order of adsorption of parathion on attapulgite: HDMA-attapulgite > Ca-attapulgite > TMA-attapulgite. This order is neither directly nor inversely related to the “organophilic” nature of the surfaces.

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.