Sorption of aniline and its derivatives by montmorillonite substituted by cations of widely different acidity depends upon the polarizing power of the interlayer cations. Infra-red spectra indicate that the anilines are mostly bound to the interlayer cations through water molecules, except in Cs montmorillonite, where bonding to the oxygen surfaces of the alumino-silicate sheets seems to predominate. Anilines are weak bases, which compete with the oxygen surfaces for protons of acidic interlayer water. Consequently, the tendency of anilines to act as proton donors in the clay interlayers increases with the polarizing power of the exchangeable cation. The concept of ‘basic’ water is introduced to account for some of the features of the spectra of Cs montmorillonite treated with the organic ligands.

Mössbauer spectroscopy of dioctahedral phyllosilicates showed that on dehydroxylation iron which originally occupied M(2) and M(l) sites became, respectively, 5- and 6-coordinated. The 6-coordinated sites are very distorted. No migration of cations occurs in the course of heating the specimens for 1–3 hr at 600°–700°C.

By using a combination of several physicochemical methods, different successive stages of the dehydroxylation process could be distinguished: (1) migration of protons; (2) localized dehydroxylation of individual associations without significant change in the overall configuration of the octahedral sheets; and (3) loss of most of the hydroxyl groups with concomitant changes in the cell dimensions. Penetration of Li into the octahedral sheets does not affect the course of the reaction, but reduces the dehydroxylation temperature and the stability of the products.

Dehydroxylation was preceded by or associated with the oxidation of any divalent iron present. Fe3+ derived from Fe2+ was indistinguishable by Mössbauer spectroscopy from iron initially present in the trivalent form. High concentrations of Fe lower the dehydroxylation temperature and reduce the stability of the dehydroxylate to the extent that partial disintegration may precede complete dehydroxylation.

The reaction products obtained when montmorillonites react with potassium halide at elevated temperatures, which were described in a previous publication, are further characterized. On the basis of their X-ray powder diffraction patterns, i.r. spectra, CEC and chemical composition they could be regarded as montmorillonite-illite interstratifications. Changes in morphology of various montmorillonites heated with and without K halide are related to the size, charge and position of interlayer cations. Scanning electron-micrographs of samples heated with KBr resemble those of well-crystallized illite. It is speculated that reactions of clay minerals with halides or other proton acceptors may account for some diagenetic processes in nature, e.g. the conversion of montmorillonite to illite on deep burial.

Fe3+ ions in palygorskite occupy sites at the edges and in the interior of the alumino-silicate chains. The Mössbauer parameters of the doublets associated with Fe3+ ions in edge sites indicate that the sites have a regular 6 coordination. Fe3+ ions in the interior of the chains occupy M(1) sites in three of the samples examined and M(2) sites in the fourth. Fe3+ ions in edge positions of palygorskite become 5-coordinated when water is lost on heating. They maintain this coordination on dehydroxylation, probably by cross-linking of the chains. The temperatures at which changes occur in the X-ray powder diffraction patterns and the Mössbauer and infrared (IR) spectra differ from sample to sample. The intermediate stages observed also vary, either due to different reaction paths or to different stabilities of the intermediate phases. The deduced distribution of cations in the octahedral sheets is in good qualitative agreement with the observed IR hydroxyl absorptions.

Two different types of interstratified illite-smectite are found in a section of Paleozoic sediments in the Negev, Israel. One of these is detectable only by a decrease in peak width and a concomitant increase in symmetry of the 10 Å peak on glycolation. This material is regarded as illite, randomly interstratified with about 20 per cent expanding layers.

Mössbauer spectra of 15 smectites were investigated. In these samples, ferric iron occupies both M(1) and M(2) octahedral sites, the distribution being partly determined by the relative covalency of the bonds formed.

The quadrupole splittings are linearly related to b−3. They show that Fe3+ octahedra are much more distorted in montmorillonite and beidellite than in nontronite and volkonskoite and that M(1) sites are more prone to change than M(2). Ferrous iron occurs in relatively undistorted octahedra in some otherwise distorted octahedral sheets and vice versa.

Hydrazine and dithionite, both of which are strong reducing agents, react differently with various dioctahedral smectites. Both the nature of the reducing agent and the structure of the clay affect the course of the reaction. Hydrazine reduces octahedral Fe3+ efficiently if the mineral has a low tetrahedral charge. The reducing action of dithionite does not depend upon the charge.

The results obtained by different physical methods of investigation suggest that reduction of iron is associated with protonation of an adjacent OH group. The Fe2+ formed is readily re-oxidised but the structural changes occurring on reduction are reversible only when Al-OH-Fe, but not when Fe-OH-Fe associations are involved. Reaction mechanisms are proposed and changes in the distribution of iron in the octahedral sites are discussed.

Structural Fe2+ in montmorillonite is readily oxidized by contact with water, salt solutions or on mild heating. This is shown clearly by the Mössbauer spectra and is associated with a sharpening of the infrared absorption near 880 cm−1. It was inferred that this band comprises the Fe2+—OH—Al and Fe3+—OH—Al deformations. The rate at which oxidation occurs depends on the exchangeable cations. High acidity of the interlayers is conducive to oxidation, as is contact with Cu2+-containing solutions or concentrated H2O2 solutions.

The results show clearly that any chemical treatment of montmorillonite causes changes in the oxidation state of structural iron.

Reaction with Na2S solutions at high pH led to almost complete, reversible reduction of iron in montmorillonite, whereas the structural iron of nontronite persisted in the ferric form. Concentrated Na2S solutions caused severe corrosion of nontronite and extracted appreciable amounts of iron, which was precipitated as sulphides. In contrast the morphology of montmorillonite was preserved and only very minor amounts of iron were extracted. These differences were attributed to the high concentration of Fe-OH-Fe groups in nontronite, which are unstable on reduction. The difference between Na2S and other reducing agents is discussed.

The sorption of commercial K-Cu chlorophyllin by a sample of montmorillonite saturated with different exchange ions was studied. The organic anions are sorbed on external surfaces while K displaces most of the exchangeable cations. The samples sorb the constituents of chlorophyllin selectively and in different amounts, depending on the exchangeable cations of the clay. These also affect the amount of material peptized and the relative orientation and aggregation of the particles.

Possible assignments are suggested for some of the absorption bands in the 1150–400 cm−1 region of the i.r. spectra of serpentines. Polarized light was used to identify the out-of-plane vibrations in antigorites and platy lizardites and the vibrations parallel to the fibre axis in chrysotiles and fibrous lizardites. An attempt is made to correlate some known structural characteristics and the chemical composition of the serpentines with some features of the i.r. spectra.

A clinical decision support system, EvalMpox, was developed to apply person under investigation (PUI) criteria for patients presenting with rash and to recommend testing for PUIs. Of 668 patients evaluated, an EvalMpox recommendation for testing had a positive predictive value of 35% and a negative predictive value of 99% for a positive mpox test.

Clays may catalyze chemical reactions by acting as Brönsted acids, Lewis acids, and/or Lewis bases. The changes occurring when limonene (p-menthadiene) is heated in the presence of montmorillonite illustrate how Brönsted and Lewis acidity may operate competitively, the nature of the interlayer cations determining which reaction dominates. The rate at which the starting material disappears increases with the acidity of the clay, which depends upon the interlayer cations (Na < Mg < Al < H). The concentration of disproportionation and isomerization products reaches a maximum after reaction times which decrease with increasing surface acidity of the clay, p-cymene is produced by oxidation in concentrations inversely related to the surface acidity of the clay. The course of the chemical reaction can thus be steered in the preferred direction by an appropriate choice of interlayer cations.

Smectite close to the pure Fe end member of the nontronite-beidellite series was found in the fine clay separated from a 354-cm deep sediment core in the southwestern Pacific Basin. The mineral has a b-axis of 9.09 Å and an unusually low dehydroxylation temperature of 454°C and is composed of sheaves of fibers less than 50 Å wide. Its charge density is 5.09 × 10~4 esu/cm2. The charge originates mainly from the presence of 18% of the total Fe in tetrahedral positions, as determined by Mössbauer analysis. Slight deviations of the infrared spectra from those reported for nontronites are probably due to the presence of more octahedral Mg. The presence of authigenic quartz in the same sample permits some speculation on the concentration of dissolved silicon during nontronite genesis. A δ18O value of 26 ± 0.3‰ indicates a temperature of formation of about 22°C. The Sr isotope ratio suggests that the nontronite formed at least 12 million years ago.

Conversion of tertiary butylacetate to isobutylene and acetic acid and cracking of n-octane were used as model reactions to monitor the catalytic activity of a condensate and aqueous extract derived from a sample of montmorillonite. The condensate was obtained by condensing the vapor phase evolved on heating the clay and the extract was derived from the clay by prolonged water extraction. Both condensate and extract were colloidal systems, which were separated into solid and liquid fractions by distillation. Reactions carried out in a dynamic system established that the solid components acted as true acid catalysts, whereas the liquid fractions were inactive under the experimental conditions adopted. The catalytic activity per weight of the condensate exceeded that of either the parent clay or the extract.

The present results confirm that colloidal size catalysts of high activity can be generated from clays. Such materials, mobilized and transported alone or with formation fluids, may act as catalysts in places removed in space and time from their source. This finding refutes objections previously raised to the operation of bulk clays as catalysts for reactions with particulate organics and supports the concept that acid catalysts derived from clays may participate in organic geochemical reactions in an aqueous medium.