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The variation with time of exchangeable surface charge of amorphous ferric hydroxide in aqueous suspension was monitored by a titration technique. After 120 days, the surface charge of suspensions with initial pH from 8.5 to 10.5 was about one-fourth of the initial value, and goethite had formed from the ferric hydroxide. After the same time interval, the exchangeable surface charge of suspensions with initial pH from 5.5 to 8.0 was about two thirds the original value and the ferric hydroxide was still largely amorphous. The initial rate of crystallization and surface charge reduction increased with initial pH for suspensions with pH from 8.5 to 10.5, whereas the rate of surface charge reduction appeared to be independent of pH for suspensions with initial pH between 5.5 and 8.0. Based on these results it is suggested that at pH from 8.5 to 10.5 ferric hydroxide ages to goethite via a solution stage involving the Fe(OH)4- ion, whereas at pH values below 8.5 ferric hydroxide aging proceeds via mechanisms which do not involve the particle surface or bulk solution.
A deposit of kaolin clay, the site of the General Zaragosa Mine, located about 50 km northwest of San Luis Potosi, S. L. P., Mexico, has produced more than 250,000 tons of refractory clay by room and pillar mining methods during the last 32 years. The clay was formed by hydrothermal argillation of part of a fault block of rhyolite flow-breccia and probably welded tuff, presumably lower Tertiary in age. A silica-rich gossan now exposed at the surface caps the clay deposit.
Samples collected sequentially from the fresh rock to the most highly altered kaolin and studied by optical, X-ray, DTA, and chemical methods, show progressively:
Bleaching of the breccia matrix accompanied by mobilization of much of the iron, which was concentrated locally as spots of reddish oxide in the least altered areas.
Mobilization, and removal of considerable alkali and alkaline earth metals, in excess of that required to form montmorillonite; mobilization of silica, which was redeposited as fine anhedral quartz crystals disseminated within the montmorillonite and associated kaolinite-halloysite, or developed tripolitic, argillized rock peripheral to the clay ore body.
Further desilication of the silica and clay yielding relatively pure, but poorly ordered, kaolinite-halloysite as the most intense end product of argillation. Much silica removed during intense argillation was reprecipitated as tripolitic clay, as minor cristobalite in microscopic globules and massive aggregates characteristic of colloform opal, and in vastly larger amounts as opal and chalcedony replacing the rock overlying the clay (forming a silica gossan).
Minor amounts of alunite are present at two places in the deposit, which are interpreted tentatively as being the most probable loci of rising solutions.
Protein complexes of smectites in soils are difficult to detect if the usual smectite tests show no peculiarities. Andalusian black earths are typical examples. Investigation of the alkylam-monium derivatives, however, allows detection of adhered macromolecules which might be protein-like although this cannot be proved exactly.
Investigation of artificial clay-protein complexes reveals different types of clay protein interactions. Calcium smectites adsorb proteins mainly on the external surfaces, the macromolecules being anchored in the interlayer spaces. Sodium smectites give partial crystalline products in which the silicate layers are distributed in the protein matrix.
Exchange of alkylammonium ions can be used as a tool for detection of the protein. If this is adsorbed on external surfaces (calcium smectites) the increased layer separation during the cation exchange enables the macromolecules to slip between the layers and the basal spacing of the alkylammonium derivatives are changed in characteristic ways. The partial crystalline sodium clay-protein complexes are reorganized by alkylammonium ions to regular structures. The proteins are not displaced completely from the silicate surfaces so that the basal spacing of the alkylammonium derivatives are enhanced in comparison with pure montmorillonite.
The exchange of various alkylammonium cations from aqueous solution by sodium laponite has been studied. The affinity of the clay for these organic cations was linearly related to the molecular weight, molecular size or chain length of the alkylammonium ions. The affinity for the clay increases regularly with increasing chain length of the primary amines. A comparison of primary, secondary, and tertiary amines, containing the same alkylgroups shows that the affinity increases in the order R1NH3+ < R2NH2+ < R3NH+. These affinity sequences were attributed to important van der Waals contributions and changes in ion hydration states. The thermodynamic excess function, ΔGmE, was calculated and indicated that with respect to the pure homoionic forms the heterogeneous Na+-alkylammonium surface phases were more stable than they would be if the mixing were ideal.
Fibrous sepiolite crystals derive much of their commercial value from their molecular size channels and grooves. The crystals fold upon drying and these channels and grooves are lost. A model for the folding and unfolding of the crystals is presented. Extensive i.r., X-ray and thermogravimetric evidence shows that folding occurs when approximately half of the water of hydration, which is coordinated to the edge magnesium atoms inside of the channels, is removed. This occurs near 175°C under vacuum and near 300°C in air. When the crystals fold, all remaining water molecules enter a new environment, that of the hexagonal holes of the neighboring silica surface. A true anhydride is produced at about 500°C under vacuum when the final water is lost, but this final dehydration produces no important structural change. Rehydration of the anhydride to the normal hydrated sepiolite does not occur at room temperatures in 100% r.h. However, above, 60°C rehydration does occur.
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 mechanism of boron uptake by clays, especially illitic clays, and the factors which control such uptake have long been debated issues. In an attempt to answer some of the questions of the controversy, three illites were treated in solutions containing boron. In the study, boron concentration, salinity, temperature, and time were varied independently over rather wide ranges.
For the illites studied, irreversible uptake of boron was increased by increasing boron concentration, salt concentration, temperature, and time of treatment. The amount of boron which was fixed also varied with the type of illite treated. The amount of fixation was controlled primarily by the specific surface area of the clay and also by the crystallinity, K content, and/or amount of mixed-layer material (“frayed-edge” development?), and apparently was independent of the original boron content of the clay.
A two-step mechanism is proposed for boron fixation by illite, consisting of rapid chemical adsorption of the tetrahedral B(OH)4− anion at the “frayed-edge” of the illite flake followed by much slower diffusion of boron into the tetrahedral part of the structure.
Several new salt intercalation complexes of halloysite have been prepared and characterized using X-ray powder diffraction techniques taking into account both the position and the shape of the d001 peaks. The amount of intercalated ion in some fully complexed halloysites has been directly determined using conventional analytical techniques. The results show that less than half of the theoretical amount of salt is intercalated into the clay; the amount of salt depending on its nature and, where hydrolyzable ions are present, on the pH. Infrared spectra taken of some complexes give an indication of the nature of the interaction within interlayer space and elsewhere. The interactions are weak and are either dipolar attractions or hydrogen bonds. The ions which show the greatest tendency to intercalate with halloysite are water structure-breaking cations or hydrogen-bonding anions.
Solubility diagrams defined by log [Al3+] and log [H4SiO4] are given for hydrous alumina or aluminum silicate minerals which appear in bauxite, kaolin and pyrophyllite-diapore deposits. They are constructed based on thermodynamic data of relevant reactions both at the room temperature and at elevated temperatures.
An aqueous solution reacts to a mineral, in this case K-feldspar, and, by dissolving it, becomes saturated with respect to a certain mineral. This mineral begins to be precipitated and the solution changes its composition as a result of the precipitation as well as further dissolution of the original mineral. Then, it attains saturation with respect to another mineral, which is precipitated thereafter. Thus, different minerals are precipitated in turn.
The sequences of precipitation of minerals can be shown on the diagrams under different conditions. A sequence, aluminum hydroxide → kaolinite or pyrophyllite → silica mineral plus kaolinite or pyrophyllite is expected in a weakly acid solution. In contrast, a sequence, silica mineral → silica mineral plus kaolinite or pyrophyllite is expected in a strongly acid solution. The possibility of application of the sequence of precipitation thus expected to alteration zoning is also discussed.
The basal spacings of long chain n-alkanol complexes of nontronite saturated with Li+, K+ Mg2+, Ca2+, Sr2+ and Ba2+ were measured for temperatures increasing from −70°C up to 130°C. With rising temperatures the complexes rearrange from a low temperature form into a high temperature form.
In the low temperature form the alkyl chains of the alkanol molecules form bilayers with their chain axes perpendicular to the silicate layers. The chains may not be in all cases in the planar all trans conformation but in special ‘kink’-conformations.
The transition into the high temperature form is explained by cooperative transition from a form with a low number of ‘jogs’ to one with a high number of ‘jogs’ and ‘kinks’.
Jesus' response to the Syrophoenician woman in Mark 7.27 is sometimes seen as sexist, racist, or abusive. The force of his response depends in part on the diminutive form κυναριον, which is often dismissed as a faded diminutive that lacks true force. But a statistical, semantic, and contextual analysis of the word indicates that it does, in fact, have diminutive force in Mark 7:27. Because of this, the pejorative force found in direct insults employing the word ‘dog’ is lacking in Jesus' response. In addition to failing to recognise the diminutive force of κυναριον, interpreters sometimes assume a social context in which Jews routinely referred to Gentiles as dogs. Finally, the analogy that Jesus makes is often read allegorically, assuming that ‘children’ and ‘dogs’ have direct counterparts in ‘Jews’ and ‘Gentiles’. These assumptions are found to be dubious. The point of Jesus' analogy is about the proper order of events: children eat before the puppies; Jews receive the benefits of his ministry before Gentiles. The Syrophoenician woman outwits Jesus by arguing that the puppies may eat simultaneously with the children. The interpretive upshot is that Jesus' saying is unlikely to be misogynistic or abusive, but simply asserts Jewish priority, a priority that admits of exceptions and change.
Three samples of bluish chromium-bearing dickite and chromium-bearing kaolinite were examined by X-ray powder diffraction, chemical analysis, electron microprobe, optical, and infrared techniques to determine whether chromium is part of the mineral structure or present in an impurity phase. Two of the samples studied contain a single dominant chromium-bearing phase (either dickite or kaolinite); the third contains equal proportions of both minerals. The optical absorption and infrared spectra are consistent with the presence of octahedrally coordinated chromium. The range of Cr3+-Al3+ substitution is rather limited: up to 0.06 atoms per unit cell. The electron microprobe study revealed the presence of very rare, minute grains of chromite, as well as a uniform distribution of chromium in dickite and kaolinite, indicating that chromium occupies octahedral sites in the structure of these minerals.
I discuss a certain kind of emotionally charged negative reaction to defences of non-monogamous love, which I call collective-identity reactions. Expanding on work by Audrey Yap and Jonathan Ichikawa, who consider defensive reactions grounded in individual identity, I argue that collective-identity reactions are characteristically associated with claims about who we are, and motivated by a sense that the relevant we is in some way under threat. Looking into which we might be threatened by defences of non-monogamy, and why, reveals that this apparently personal subject matter is in fact entangled with global political issues like capitalism and American cultural imperialism. I conclude with some thoughts about ameliorative strategies for situations structurally similar to this one.