A kaolinite-pyridine intercalation compound was prepared using hydrated kaolinite as an intermediate. Hydrated kaolinite having a basal spacing of 10 Å was treated with pyridine to form a well-ordered intercalation compound having a basal spacing of 12.0 Å. Infrared spectroscopy indicated the presence of hydrogen bonding between the hydroxyls of the kaolinite and the pyridine. 29Si nuclear magnetic resonance spectroscopy with cross polarization and magic-angle spinning revealed that intercalated pyridine affected the environment of silicon. The mono-substituted pyridine derivatives were also intercalated with hydrated kaolinite. On the basis of the basal spacings of the intercalation compounds and the stabilities of the derivatives between the layers, the pyridine appeared to be in an approximately perpendicular position, with the nitrogen facing the gibbsitic sheets.

What is truth? This famous question does not express merely the anguish—or the detachment—of the person who, at the moment of choosing, hesitates between deciding for one or the other of the contradictory theses being presented. At a second level, the question no longer concerns merely the content but the very conditions for the decision: in what name, by virtue of what criterion do we say that a given assertion is true while its contrary is false? We could limit ourselves to recognizing in this second phase a particular species of philosophical questioning, which proceeds reflexively from the constituted to the constituent, from the given of the experience to the conditions for the possibility of the experience in general. But in the question about truth, a prejudicial difficulty inevitably arises which is proper to this question and makes it incomparable to any other. How can I be assured of the truth of my assertions about truth without presupposing at the same time a theory for that truth which I am in tact in the process of seeking? In other words, any question about truth moves in a circle since, by demanding a true answer, just like every question it implies that the questioner already knows what is truth at the very moment when he is asking what it is.

Gabbroic saprolite at Mont Mégantic, Quebec, was studied in detail mineralogically to gain a better understanding of the origin of ferruginous smectite reported previously from these rocks. The parent rock is a ferrogabbro composed of plagioclase, augite, calc-alkalic amphiboles, biotite, olivine, magnetite, ilmenite, and apatite. Extensive weathering has decomposed most of the mafic minerals and magnetite to goethite, lepidocrocite, and iron-rich clay minerals, which occur in numerous microcracks distributed irregularly in the outer shells of boulders and in cracks and fissures in the bedrock. Some of the felsic minerals have altered to kaolinite. The secondary minerals and the more resistant primary minerals, such as plagioclase, ilmenite, and apatite, have subsequently moved to the lower part of the saprolite. The major ferruginous clay minerals present are smectite and vermiculite, which are compositionally similar, except that the smectite is slightly richer in SiO2 and MgO and poorer in Fe2O3 than the vermiculite.

To establish a structural formula for the ferruginous smectite, the oxidation state of Fe in a sample treated with dithionite-citrate-bicarbonate was examined by Mössbauer spectroscopy. All structural iron was found to be ferric. The calculated structural formula of a Na-saturated sample is:

$$N{a_{0.61}}\left( {M{g_{1.39}} + Fe_{0.85}^{3 + }A{l_{0.17}}M{n_{0.03}}} \right)\left( {S{i_{3.49}}A{l_{0.51}}} \right){O_{10}}{\left( {OH} \right)_2},$$

Pillared, regularly and randomly interstratified illite/smectite (I/S) was prepared by interacting aluminum chlorohydrate with I/S in aqueous dispersion. I/S samples from Kinnekulle, Sweden, ranging in composition from 30–60% smectite layers, were used as starting clays. The pillaring resulted in a separation of the smectite layers in the I/S of about 9 Å, as estimated by X-ray powder diffraction and by nitrogen adsorption studies. Only the smectite layers of the clay were modified by the pillaring procedure. The pillared products had surface areas of 200–260 m2/g and pore volumes of about 0.18 cm3/g. The uptake of Al by the clay and the micropore surface area of the pillared products were proportional to the fraction of smectite layers in the I/S. The thermal and hydrothermal stability of the pillared I/S was similar to that of pillared montmorillonite prepared using the same procedure.

The nature of organo-phosphate and carboxylate bonding in aqueous suspensions of noncrystalline alumina, boehmite, and gibbsite has been studied using the anionic nitroxide spin probes 3-carboxy-2,2,5,5-tetramethyl-1-pyrrolidinyloxyl and 4-hydroxy-2,2,6,6-tetramethyl-piperidinooxyl dihydrogen phosphate. Analysis of the electron spin resonance (ESR) spectra of these molecules revealed that adsorption of both molecules occurred rapidly on the high surface area alumina and boehmite, whereas only the organophosphate adsorbed on gibbsite. A loss in rotational motion of the molecules accompanied adsorption, with the greater degree of motional restriction observed for the carboxylate attributed to steric restrictions to rotation about the surface-bound C-COO− bond axis. The ease of displacement of adsorbed carboxylate from surface binding sites by weakly adsorbing anions (Cl−, ClO4−) compared to organophosphate suggests that the carboxylate adsorbed by ligand exchange of a single surface OH, whereas the organophosphate probably formed a bidentate bond. The carboxylate bound on noncrystalline alumina showed evidence of nonspecific electrostatic adsorption in addition to ligand exchange of surface OH. This weak bonding was indicated by a moderate loss in rotational motion and ease of exchangeability.

A corrensite from Taro Valley, Italy, was studied by infrared analysis at different temperatures in the natural state and after exchange with seven different cations. The vibrational bands in the OH-stretching region can be divided into three main absorption regions: 3690-3640, 3580-3560, and 3500-3000 cm−1. The influence of the cation hydration water was observed in the third region only, whereas the intensity, frequency, and shape of the residual bands were not related to the nature of the exchangeable cations. The bands of region I were unaffected by heating the sample to 500°C; however, those in regions II and III were destroyed. Deuteration was not observed for any of the three OH-stretching regions. The dichroic behavior of the OH-stretching bands in the three regions were relatively affected by the exchangeable cations. Generally, the bands in region I exhibited a more dichroic behavior than those in regions II and III.

From the IR data corrensite appears to consist of: (1) a trioctahedral silicate layer with an OH-stretching band at about 3685 cm−1, (2) a hydroxide layer with OH-stretching bands at about 3570 and 3420 cm−1, and (3) a distinct interlayer space that is not interstratified with the hydroxide layers.

The sorption of U and Ra on finely ground biotite, muscovite, and phlogopite was adequately described by the Freundlich adsorption equation, (x/m) = KCn, at low U and Ra concentrations despite Ra precipitation at the higher temperature. Radium and U sorption-efficiency curves derived from the Freundlich constants generally showed decreased distribution coefficients in response to increasing temperature and increasing Ra or U concentrations. Temperatures investigated were 5°C, 25°C, and 65°C. Solution compositions used were 0.1 M NaCl and 0.01 M NaHCO, for U, and 0.01 M NaCl for Ra. Uranium initial solution concentrations ranged from 1.00 × 10−4 M to 4.00 × 10−7 M; the Ra initial solution concentration range was 6.80 × 10−7 M to 8.60 × 10−9 M.

In 0.01 M NaHCO3 solutions, anionic uranyl carbonate complexes were prevalent, and because they are weakly sorbed relative to free uranyl ion and uranyl hydroxy complexes, the result was a relatively low U sorption efficiency on biotite and phlogopite and excellent sorption efficiency on muscovite. Uranyl carbonate complexes decreased in solubility with increasing temperature, so that U sorption efficiency on biotite increased with increasing temperature. Sorption of uranyl ion and uranyl hydroxy cations on biotite decreased with incresaing temperature.

A combination of X-ray diffraction, infrared, and chemical data has established that the ion exchange of vermiculite with singly charged benzidine cations in an aqueous solution at pH 1.6 results in a black, highly ordered benzidine-vermiculite intercalate. The intercalate has a basal spacing of 19.25 Å and a primitive unit cell with “a” and “b” edges parallel and equal to those of vermiculite. The number of benzidine molecules per cell is equal to its electric charge. In this structure the benzidine molecules are steeply inclined to the silicate surfaces and close-packed within domains. The domains contain alternating rows of benzidine cations; from row to row the planes are either approximately parallel or perpendicular to the (120) plane, but along any one row the planes of the aromatic rings are parallel to each other. Hydrogen bonding operates between amine nitrogens and surface oxygens.

Gibbs free energies for phases in the system Al2O3-SiO2-H2O have been calculated from reversed experiments in order to correct earlier values and to calculate a phase diagram consistent with more recent experiments. An internally consistent diagram could not be calculated that agreed with all published experiments, and choices of preferred data were made. The following Gibbs free energies, relative to the elements at STP (298.15 K, 1 bar), have been derived

The above values were calculated assuming literature values for corundum, quartz, and H2O (v).

Examination of available thermodynamic, experimental, and observational data on the aluminum hydroxides gibbsite, boehmite, bayerite, and nordstrandite suggests that these minerals are metastable with respect to diaspore + water at STP and at higher temperatures. Similarly, halloysite and dickite are metastable with respect to kaolinite at these conditions. The occurrence of these minerals in soils must therefore be ascribed to nonequilibrium processes, and the use of equilibrium phase diagrams to explain their occurrence is inappropriate.

Measurements of the differential heats of K-Ca exchange are used to show that 6 groups of sites (ranging from −13.8 to −5.1 kJ/eq and with as many as 4 in any one sample) exist in kaolins that range from 0 to 15% in their 2:1 phyllosillicate content. These heat values, coupled with entropies of exchange, suggest that 0.1−10% vermiculitic, micaceous, and smectitic layers are present, presumably interstratified with kaolinitic layers which are assumed to have no permanent charge. Changes in the activity coefficients of adsorbed K with K saturation confirm these conclusions qualitatively. Thus, fK values at x ↑ 0 correlate inversely (r2 = 0.655) with the content of vermiculite + partially expanding micas, and x values at maximum fK indicate the content of vermiculite + nonexpanding mica + partially expanding micas (r2 = 0.732).

The ability of a high surface-area gibbsite to adsorb Cu2+ was studied using a Cu2+ ion-selective electrode, electron spin resonance, infrared spectroscopy, and electron microscopy. The gibbsite chemi-sorbed small amounts of monomelic Cu2+ (<0.5 mmole/100 g) which was oriented with its z-axis perpendicular to the (001) plane of the mineral. The proposed chemisorption sites are at gibbsite crystal “steps” observed by electron microscopy. Although Cu2+ adsorption on gibbsite as a function of pH was largely reversible, exposure of the chemisorbed Cu2+ to NH3 did not result in desorption from the surface despite the displacement of several OH− or H2O ligands by NH3. The results indicate that at least one Cu-O-Al bond is formed in the process of chemisorption.

At pH > 5, the gibbsite appeared to promote the hydrolysis and polymerization of Cu2+, with further adsorption at the surfaces. Infrared spectroscopy revealed no effect of the adsorption on the (001) surface hydroxyl groups, although the anisotropic diffusion of protons in the gibbsite structure was verified from deuteration studies.

The dissolution behavior of five noncrystalline oxides, montmorillonite, kaolinite, chlorite, and sepiolite in a basic tiron solution was studied at pH 10.5 and 80°C. The results show that for montmorillonite the concentrations of Al and Fe ions dissolved in the treating solution were diminished because of cation-exchange reactions of the sample in the suspension. To explain these observations, a mass-balance equation for the specified cation in solution was formulated, which consisted of both a dissolution term and an ion-exchange term. The several parameters of this differential equation were fitted to allow the calculated results to represent the experimental findings. Using these values, an equation lacking an ion-exchange term was also solved numerically. Thus, a dissolution curve was described, which would have been obtained had no cation exchange taken place. From these equations, the error resulted from the cation-exchange capacity of samples in chemical dissolution methods can be evaluated. According to this estimation, and assuming the value for a 1-hr treatment, an error of about 15% was determined for the amount of noncrystalline components contained in the specimen in this investigation.

A kinetic study of the oxidation of hydroquinone by aqueous suspensions of hausmannite at pH 6 was conducted using an on-line analysis system. Electron transfer between hydroquinone and the oxide was monitored by ultraviolet and electron spin resonance spectroscopy to measure the loss of hydroquinone and the appearance of oxidation products. Although hydroquinone oxidized on the surface of the oxide and the oxide surface was altered after the reduction, hydroquinone and its oxidation products did not adsorb strongly on the surface. At a high concentration of hydroquinone, p-benzosemiquinone free radicals persisted in aqueous solution and were oxidized by dissolved O2. Calculations based on the thermodynamic stabilities of the oxide and the organic species involved show that the formation of p-benzosemiquinone radical by Mn reduction is feasible. The presence of the radicals indicates that the oxidation of hydroquinone by the oxide proceeded by a one-electron transfer process. At high organic/ oxide ratios, an increase in the amount of hausmannite dissolved with increasing hydroquinone concentration suggests that the reduction of the oxide by the organic was not limited to the surface layer of the oxide. At a high concentration of hydroquinone, polymers were detected in solution, suggesting that radical-mediated reactions played a role in the polymerization process. A reaction scheme is proposed to explain the effect of the Mn oxide to hydroquinone ratio on the consumption of O2 and the appearance of quinone, p-benzosemiquinone, and polymers in solution.

The catalytic power of Ca-nontronite (0.2–2 μm) for the polycondensation of phenols and glycine and the associated reactions that involve the ring cleavage of phenols and the decarboxylation and deamination of glycine was studied in systems free of microbial activity. At the end of a 90-hr reaction period, the amount of CO2 released from the Ca-nontronite-glycine-pyrogallol, Ca-nontronite-glycine-eatechol, and Ca-nontronite-glycine-hydroquinone systems were 5.1, 8.7, and 11.6 times higher, respectively, than those from the respective nontronite-free systems, showing the catalytic role of Ca-nontronite in the ring cleavage of phenols and the decarboxylation of glycine. The release of CO2 and NH3 from the Ca-nontronite-glycine system revealed that Ca-nontronite can catalyze decarboxylation and deamination of glycine. The ability of Ca-nontronite to catalyze the deamination of glycine was substantially enhanced by the presence of a phenol. The visible absorbances at both 472 and 664 nm of the supernatants, the total yields of N-containing humic polymers, and the fractions of glycine converted to nitrogenous polymers indicated that polycondensation of glycine and phenol was greatly catalyzed by Ca-nontronite. The total N-containing humic polymers formed in the systems decreased in the order: Ca-nontronite-glycine-pyrogallol > Ca-nontronite-glycine-cateehol > Ca-nontronite-glycine-hydroquinone > glycine-pyrogallol > glycine-hydroquinone > glycine-catechol. The infrared and electron spin resonance spectra of humic acid (HA) and fulvic acid (FA) formed in the supernatants of the reaction systems were quite similar to those of soil HA and FA. The catalytic power of Ca-nontronite in affecting the ring cleavage of phenols, deamination and decarboxylation of amino acids, and formation of humic substances derived from phenols with amino acids in soils and the related environments thus merits attention.

Emotion, as a “suprarational” property, transcends rationality in that it can be thought of as a group, contextual rather than as a solely individual trait, and thus is a higher order property, as the above quote suggests. This proposal arises from a metatheoretical analysis of models available to broach questions of emotion. I use metatheoretical in the sense of both the context of theory production and the theory of theory. From the first arose the idea that emotion, through the use of irrationality, has surfaced as a working equivalent to inexplicability or rational relativity, and can be modelled more adequately as suprarational, with a unique nature in its own right. The latter led me to propose that the concept of emotion as contextual, a higher order group level property, is possible and tentatively profitable.

Parallogic models the relationship between mind and context. It, as does the excerpt above, suggests that systems of logic are context specific and therefore parallel. This model points out that perceived departures in mental process, reasoning, may be more apparent than real. It also suggests a new way to conceive of mental illness by separating breakdowns in mental process from shifts in mental process.

High-Mg chlorites from Vermont and Quebec and high-Fe chlorites from Michigan and New Mexico were equilibrated at room temperature in the near-neutral pH range. Gibbsite, kaolinite, and hematite of known stability were added to the samples to control unmeasurable variables at calculable levels. Equilibrium solution compositions were obtained from undersaturation and from supersaturation. Other indicators of equilibrium were good agreement between successive analyses over a long period of time, between duplicate samples, between independent systems, and between independent measures of equilibrium. All four chlorites were stable relative to brucite and, with a few exceptions, relative to talc under the conditions of study. When in equilibrium with gibbsite, the pH − ½Mg2+ value of the chlorites ranged from 6.3 to 6.5, at a pH4SiO4 value of 4.0. These values are in good agreement with prior estimates of chlorite stability. The calculated standard free energy of formation of the chlorites is dependent upon solution Fe2+ calculated from the sample Eh and assumed equilibrium with hematite, with the assumption that the Fe2+-Fe3+ couple is at the same Eh as the sample.

Chemical activity diagrarns, prepared to illustrate the properties expected if mixed-layer mont-morillonite/illite is regarded as a solid solution, are compared to those derived from a treatment of these materials as a mixture of two phases. If the system is a solid solution, the coexisting aqueous solution should range from higher dissolved silica contents in the presence of kaolinite and a montmorillonite end member to lower dissolved silica in the presence of kaolinite and an illitic end member. Silica concentration in the aqueous solution might vary by a factor of as much as six. If the system is two phase, the silica content of a solution in equilibrium with kaolinite and both phases would be fixed at a given T and P, as would a solution equilibrated with both phases and K-feldspar. In the absence of a third phase, silica in equilibrium with both phases should be nearly constant, but increase with increasing ratio of K+/H+ in solution. Available data on coexisting aqueous solutions apparently are more nearly consistent with two phases than with a solid solution.