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The effects of NaOAc removal of carbonates, H2O2 removal of organic materials, and sodium citrate-bicarbonate-dithionite (SCBD) removal of iron oxides upon the X-ray powder diffraction (XRD) characteristics of clay minerals present within weathered volcanic ash deposits were examined. All pretreatments of samples derived from the Ae and Bhf horizons containing volcanic ash resulted in dramatic increases in XRD peak intensities, while the treatment of IIC-horizon samples resulted in subdued XRD peak intensities. Also, the chemical treatments produced an apparent increase in the amount of expandable clay minerals within the Ae horizon, due probably to the hydrolysis and removal of interlayer Al3+ when H2O2 and SCBD were used. Hence, poorly ordered and pedogenically modified vermiculite or vermiculite/montmorillonite interstratifications became “weathered” by H+ attack and Al3+ removal in a manner similar to the natural processes which take place in the acid and eluvial A horizon. In addition, possible XRD peak modification due to the dilution of crystalline clay concentrations by amorphous clay-size material appeared to be subordinate to the laboratory-induced chemical alteration of the weathered clay minerals.
The major mechanism by which fulvic acid removed Cu2+ from Cu2+-montmorillonite was complexation, most likely chelation. This was confirmed by the use of a specific cupric ion electrode which showed that whereas the total Cu2 + concentration in the supernatant solutions increased with rise in pH, about 7 per cent of the total Cu2+ solubilized by fulvic acid occurred in the ‘free’ or ‘uncomplexed’ form at pH 2.5, only 0.6 per cent was similarly distributed at pH 4.5 and 0.0009 per cent at pH 6.5. External surface area measurements by a dynamic BET method showed the following surface areas: 2.5 m2g-1 for the fulvic acid, 8.0 m2 g-1 for the Cu2+-montmorillonite but 16.1 m2 g-1 for the FA-Cu2+-montmor-illonite complex. Electron micrographs of the FA-clay complex confirmed that fulvic acid was adsorbed in interlamellar spaces and on external surfaces of the Cu2+-montmorillonite.
The history of education and transmission of knowledge in Islamicate societies has long recognized the importance of scholarly circles centered around scholars in medieval Muslim societies. As an illustration of the persistence of similar patterns of knowledge transmission in later periods, this paper focuses on the scholarly circle gathered around Bahāʾ al-Dīn Muḥammad al-ʿĀmilī (d. 1030/1621), the prominent Shiite scholar of the Safavid era, exploring the intellectual exchanges and personal interactions between this circle's members through the lens of the manuscripts they copied, read, collated, and studied. Drawing on information gleaned from manuscripts, I argue that Bahāʾ al-Dīn's highly mobile lifestyle, which was an offshoot of his socio-political engagements, rendered the scholarly circle around him into a mobile college, detached from localized madrasas and other educational institutions. This mobile scholarly circle helped propagate Shiite intellectual heritage in places far from the centers.
With the use of a BaCl2 solution containing radioactive Ba2+ ions, kinetics of cation exchange have been done on a Kenya vermiculite, natural on one hand and previously oxidized either by 50°C water or oxygenated water on the other hand. Correlatively, the quantity of ferric iron in the layer has been determined by E.P.R. These two methods have shown that during an oxidation the proportion of iron which stays in the octahedral layer depends upon the nature of the oxidizing agent. During a weak oxidation, the iron stays entirely in an octahedral layer and the exchange capacity of the vermiculite decreases; on the other hand, during an oxidation by oxygenated water, part of the iron is extracted from the octahedral layer and the exchange capacity of the vermiculite is not changed, as established by the studies of Farmer (Farmer et al., 1971). Kinetic data for Llano vermiculite also are reported and compared with those for the Kenya vermiculite.
Micaceous clays (“illites”) of a number of sediments, subjected to quantitative mineralogical analysis, ranged in different samples from 58 to 65% of a dioctahedral mica of muscovite type, from 3 to 8% vermiculite, from 0 to 10% montmorillonite, from 2 to 12% quartz, from 0 to 4% feldspars, from 1 to 2% rutile and anatase, from 0.3 to 1.2% free iron oxides, and from 16 to 30% chlorite. The soil clays contained less mica (13 to 35%) but more vermiculite (13 to 16%), montmorillonite (6 to 14%) and chlorite (30 to 33%), besides kaolinite (3 to 8%) and amorphous material (6 to 15%). The presence of the various minerals was verified by X-ray diffraction. When the interlayer K of these micaceous clays was replaced by hydrated Na ions through treatment with 0.2 n sodium tetraphenylboron in 1 n NaCl, the analytically determined vermiculite and montmorillonite contents increased. The freshly produced vermiculites had an interlayer charge of 177 to 198 me/100 g. During this replacement of interlayer K in a 1 N salt solution, the pH of the equilibrium matrix solution was observed to increase instead of decreasing as would be expected if oxonium (OH3+) ions were associated with K in the interlayer space, thus precluding the possibility of interlayer ONz+. The calculated stoichiometric equivalent of the pH rise established a significant uptake of protons by the lattice as K was released.
Thermal analyses of vermiculites show 0.5 to 0.7% higher OH water content than the parent micas. Oxidation of ferrous iron in the silicate structure, suggested as a possible mechanism for lowering of layer charge during weathering of mica to vermiculite, accounted for about 66% of this in samples high in iron (16.0% FeO) and only 30% of this in samples fairly low in iron. The rate of extraction of K from muscovite with no ferrous iron was found to be pH dependent, increasing at lower pH values. The data indicate proton incorporation with structural oxygens of the silicate sheet to form OH as a charge reduction mechanism in weathering of mica, independent of and additional to that involving the oxidation of ferrous iron.
The absorption of dioxane, morpholine and piperidine from dilute aqueous solutions by Li-, Ca-, and Cu-montmorillonite is measured by means of a differential refractometer. This instrument measures small differences in the refractive indices of two liquids and provides a useful method for determining the amount of organic material removed from solution by the clay. Corrections are required for the effect of desorbed cations on the differential refraction measurements. Neutral molecules are absorbed in amounts related to the exchange capacity of the clay probably by cation-dipole interactions. The results are consistent with the formation of complexes Li+-fi and R-Ca2+-R for the three organic materials used; Cu2+ ions behave like Ca2+ ions for dioxane, but form $\mathop >\limits_R^R C{u^{2 + }} - R$ complexes with morpholine and piperidine. Under acid conditions, morpholine and piperidine form organic cations RH+ which take part in cation exchange reactions and which are dominant at pH below about 5. Neutral molecule absorption also occurs by virtue of the presence of RH+ ions on the clay which form RH+-R complexes (hemisalt formation). When this last mechanism of absorption occurs, the total absorption is approximately twice that when a cation-dipole reaction or cation exchange alone operates. One-dimensional Fourier 00l syntheses of complexes in equilibrium with aqueous organic solutions indicate that water molecules are associated with the clay-organic complexes to the extent of about 5H2O/unit cell.
During the Great War, J.P. Morgan bankers Thomas W. Lamont, Henry P. Davison, and Dwight W. Morrow expanded their visions of organizing across distances and supported the development of spaces where like-minded individuals could make coordinated decisions regarding the stability of industrial capitalism. These financial elites focused not only on profits but also on deeper ideas. Their experience organizing across distances, first domestically and then across the Atlantic, demonstrates the importance of these financiers to visions of global economic governance centered on information exchange and communication, intimate long-distance relationships, and deliberation among perceived equals, which are essential elements of merchant banking. Their visions further reflected a hierarchical and racial understanding of a liberal global order. Highly flexible in their strategies, these bankers possessed long-term views of national and global development that engaged overlapping connections among networks, institutions, and the public that privileged the creation of transatlantic spaces for deliberation and socialization among Western economic elites.
A series of organic ammonium ions were exchanged onto clay minerals montmorillonite and hectorite. Thermal effects on these surface modified organic-inorganic complexes were investigated by means of differential thermal analysis and heating-oscillating X-ray diffraction methods. It was found that the organo-clay complexes were dehydrogenated at temperatures from 180 to 350°C, depending on the organic cation used. Following the dehydrogenation, hydrolysis took place leaving a layer of “carbon” on the clay surface. The “carbon” was then oxidized at a temperature of about 550°C. Investigation of possible correlations between the activation energy of dehydrogenation and basicity, boiling point, ionization potential, molecular structure, and carbon-carbon bond distances of the organic cations showed that the geometric factors outweighed the acid, chemical and electronic factors in determining the effect of montmorillonite and hectorite toward the dehydrogenation of organic ions exchanged on the surfaces of these clay minerals.
The complexation of benzene and several methyl substituted benzenes with exchangeable silver(I) on the interlamellar surfaces of Ag(I)-montmorillonite has been studied using spectroscopic methods. There are no physically adsorbed molecules interacting with the internal silicate surfaces and the only chemisorbed species present are those which are coordinated through π electrons to the exchangeable Ag(I) ions. In each case the coordinated species are similar to the previously studied Cu(II)-montmorillonite Type I complexes where aromaticity is retained. Complete replacement of coordinated and other interlamellar water molecules was accomplished with relative ease. Stoichiometric determinations indicate a 2:1 benzene: Ag(I) complex. Similarities between the Cu(II) and Ag(I) complexes are discussed in relation to electronic configurations.