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Anauxite crystals are reported to contain a higher SiO2:Al2O3 ratio than the 2:1 ratio found in kaolinite. A structure proposed for anauxite places the excess silica in double silica sheets, but an exact structure for anauxite has never specifically been determined. Many workers believe that anauxite is kaolinite associated with some extremely fine-grained excess silica which is not a part of the structure. Eight specimens studied in this work included portions of type materials from Bilin, Czechoslovakia, and the lone formation in California.
Amorphous silica and alumina are readily soluble in boiling (N/2)NaOH. Kaolinite is only slowly soluble in this reagent, but becomes readily soluble after dehydroxylation. Weight loss, differential solution rate, kinetic and X-ray diffraction studies were used to establish that the kaolinite clay fraction in the anauxite specimens had the composition of:
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Some of the anauxite grains are single crystals, while others are aggregates. The latter appear to be bound together by an amorphous silica phase. Hot caustic leaching extracts the amorphous silica and breaks up the aggregates producing “fines.” Improved characterizations of minor impurities were obtained when the residues from hot caustic treatments were studied with X-ray diffraction techniques.
For almost a century, the Supreme Court has not invalidated a law using the nondelegation doctrine. Recognizing that Congress seldom has expertise to address the ever-increasing complexities of society, the Court has long held that Congress can legislate broadly and seek help from federal agencies to fill up the details. Accordingly, courts defer to Congress’s delegation choices, as long as it lays down an intelligible principle to guide the agencies entrusted with implementing legislation. Under that approach, the Court has upheld broad delegations of authority to federal agencies. This approach has been the bedrock of meaningful agency action, especially in health policy in which agencies must leverage their expertise to respond to highly technical issues, emergencies, advances in technology, and the need to address health disparities. While this deferential approach has guided the courts and Congress for decades, delegation is increasingly under attack. Braidwood Management, Inc. v. Becerra, which challenges the Affordable Care Act’s preventive services requirement, exemplifies nondelegation-based attacks on agency authority. With several members of the Supreme Court signaling interest in revisiting the current deferential delegation standard, Braidwood likely provides an opportunity for the Supreme Court to do so. Reinvigorating the nondelegation doctrine — coupled with the major questions doctrine and rolling back of Chevron deference — will hurt U.S. health policy. It will not only constrain how agencies work, but also aggrandize the courts and limit how Congress may achieve legislative goals.
Infrared spectroscopy affords a useful method for the determination of the orientation of molecules sorbed on layer silicates. The orientation of the molecules can be inferred from the observed dichroism of specific absorption bands. Examples of the analysis are illustrated in three complexes with pyridine. One flat and one vertical orientation are observed for the ionic form dependent on layer charge. A different vertical orientation is observed for the neutral molecule. The interpretation of the infrared absorption analysis is confirmed by X-ray diffraction.
A vermiculite-piperidine complex was investigated by a single crystal three dimensional X-ray diffraction procedure. The complex was prepared by ion exchange of a Na-vermiculite at pH 8. A total of 453 reflections was observed and used in the least squares refinement of the structure. The complex is monoclinic, C2/m, a = 5.346(2) Å, b = 9.256(3) Å, c = 17.57(1) Å, ß = 96.29(9)°. The final R value was 0.17 using anisotropic temperature factors for the silicate atoms and isotropic temperature factors for the carbon atoms. The occupancy factors of the C atoms were considered as variable parameters. The diffraction data were of poor quality because of stacking faults. The results show that the molecules are randomly distributed over the crystallographic sites in the interlayer space and the peaks appearing in the electron density maps can be interpreted as being due to 2 piperidine molecules and two H2O molecules. The orientation of the organic molecules is ambiguous. The electron density peaks fit a model in which the molecules are vertical and their planes form a small dihedral angle, and also fit a model in which the plane of the molecules is parallel to (001). It is quite possible that both types of orientations are present.
Qin imperial unification in 221 bce is often conceived of as the ‘unification of China’. Although from the long-term perspective of Chinese history this view is surely valid, it obscures some of the major trends of the Warring States period (453–221 bce). Back then, the Zhou (‘Chinese’) world was moving in the direction of the internal consolidation of large territorial states amid increasing political and cultural separation from their neighbours. This process unmistakably recalls similar developments in early modern Europe, where, as is well known, these resulted in the formation of nation-states. In China, by contrast, the development trajectory was markedly different. The potential transformation of the competing Warring States into fully fledged separate entities never materialized. The unified empire was eventually accepted as the sole legitimate solution to political turmoil, whereas individual states were denied the right to exist. Why, despite strong parallels, did the Chinese development trajectory ultimately diverge so conspicuously from what happened in modern Europe?
In search of an answer, this article focuses on the extraordinary role played by politically active intellectuals of the Warring States period. By prioritizing the common good of ‘All-under-Heaven’ over that of an individual polity, by denigrating local identities, and by rejecting the legitimacy of regional states, these intellectuals paved the way for the political unification of the Zhou world long before it occurred. This article addresses the idealistic and egoistic reasons for this choice and explores the cosmopolitan undertones of the universalist outlook of the Warring States-period intellectuals.
The effect of varying concentrations of Al3+ and H+ upon the simultaneous diffusion of 85Sr and 86Rb was measured in salt-free aliquots of clay having different Al:H ratios. The Sr and Rb saturation of the CEC was held constant while the exchangeable Al and H were varied from Al52:H1 to Al12:H34. Aliquots of each clay-treatment were dually tagged with 85Sr and 86Rb. Self-diffusion of Sr and Rb was measured at 4, 24, 48, and 75°C. Radioassay of 85Sr and 86Rb was made with an automatic gamma-detection system equipped with a 400 channel analyzer and card punch unit. The selfdiffusion equation was programmed for the 7040 computer to permit the simultaneous calculation of 85Sr and 86Rb self-diffusion coefficients. Rb diffusion was not significantly altered as the Al3+ concentration was increased from 12 to 52 per cent. The diffusion of Sr was significantly increased as Al3+ increased from 12 to 52 per cent. The faster diffusing Rb ion had a greater energy of activation than Sr (4·8 to 3·6 kcal/mole), however the Arrhenius frequency factor for Rb (a measure of the probability of ion exchange) was much greater for Rb than Sr (28·8 and 0·4 × 10−4, respectively). Altering the Rb and Sr saturation and the complementary ions resulted in changes in the diffusivity, the energy of activation, and the frequency factor for these ions, but not always in the same direction or to the same degree.
Tosudite from the Takatama mine is found as an alteration mineral of the wall rocks (tuff and tuffaceous sediments of Tertiary age) of gold-silver-quartz veins. A specimen free from impurities was obtained by the sedimentation method. Chemical composition: SiO2 42·14%; Al2O3 37·38%; Fe2O3 0·30%; MgO 0·08%; CaO 1·65%; Na2O 0·15%; K2O 1·40%; H2O+ 11·22%; H2O− 6·16%; total 100·48%. A negligible amount of MgO indicates that both octahedral sheets of the chlorite structure are dioctahedral. Structural formula is given as (K0.58 Na0.09 Ca0.57)(Mg0.04 Fe3+0.07 Al12.05) (Al2.28 Si13.72) O40.00(OH)20.008.88H2O.
A reflection at 30 Å with its higher order reflections and another reflection at 1·493 Å are observed. After heating at 300°C, a 27 Å phase has appeared, in which a single plane of water molecules was confirmed as the interlayer water of montmorillonite. The structures in air-dried state and in dehydrated steps were proved by comparing the calculated and observed F-values, and by Fourier synthesis. The DTA and TG curves and the i.r. absorption spectrum are reported in this paper.
Single crystal X-ray diffraction patterns reveal that the structure of selected anauxite crystals is the same as the structure of macroscopic kaolinite crystals. Anauxite and kaolinite crystals are intergrowths on a domain scale of units in pseudotwin orientations. Individual domains in anauxite have the triclinic geometry of kaolinite, and give X-ray reflections that compare closely in intensity with those calculated from the atomic parameters of kaolinite. Large crushed crystals of anauxite give powder patterns identical with that of kaolinite. Because it has been shown recently that the chemical composition of anauxite is also identical with that of kaolinite, it is recommended that the term “anauxite” no longer be used.
To examine the effects of clay swelling and dispersion on electrolyte concentration-permeability relationships of low clay content soils, flow experiments were conducted on a silt of fixed particle size distribution containing 0, 5, 7·5, 10 and 15 per cent clay (sodium illite, 2 μm fraction). Flocculated specimens were sedimented using both slow and rapid procedures. After compression each specimen was permeated successively with electrolyte solutions which caused (1) swelling of the clay fraction (0·10 N), and (2) dispersion (0·05 N). Absolute permeabilities varied with clay content, sedimentation procedure, compression rate, and electrolyte concentration; however, the form of this variation plotted against through-put volume was similar for all specimens containing electrolyte solutions causing only swelling of the clay. Increasing the hydraulic gradient above a critical value apparently increased the swelling slightly as evidenced by further reductions in permeability. The permeability of mixtures permeated with electrolyte solution causing dispersion of the clay was more complex and depended on clay content, the hydraulic gradients used to introduce the dispersing electrolyte solution and the pre-dispersion gradients to which the specimens had been subjected. Permeability decreases were attributed to the last stages of swelling prior to dispersion and to pore plugging. Increases in permeability were the result of erosion of dispersed particles. Specimens previously subjected to the highest gradients while swelling dispersed more rapidly and had a greater tendency to erode. The effects of predispersion gradients diminished with increasing clay contents. It is concluded that both compositional and mechanical factors play an important role in determining electrolyte concentration-permeability relationships for soils containing active clay minerals.
Sericite was K-depleted with molten LiNO3. The sample was changed into an interstratified structure in the presence of a small amount of LiNO3 after prolonged treatment, and in the presence of a considerable amount of LiNO3 a similar structure was formed after about 3 hr of reaction. In the case of the presence of the proper amount of NaCl, a mixed-layer structure was easily obtained by treatment for a long period of time with a considerable amount of molten LiNO3.
The interstratified mineral had a basal spacing of 22 Å–23·3 Å which was expanded to 25 Å–27·6 Å by treatment with ethylene glycol.
Nitrogen surface areas and pore-size distribution curves of various chrysotiles have been measured using a continuous flow method. A model founded on a hexagonal close packing of fibers has been adjusted to fit the frequency distribution curve of the fiber outside diameters obtained from electron micrographs. From this model, theoretical distribution functions of the surface area versus the pore diameter were computed and compared to the experimental data. For one fiber only (i.e. Coalinga chrysotile), the good agreement between the computed and experimental data allows one to conclude that the external pores (between the fibers) and the internal pores (within the fibers) are free from any amorphous material. For the other studied chrysotiles, the degree of filling of the pore system by amorphous materials was always higher than 50%. Under these conditions, hydration water cannot be removed unless the samples are pretreated in the 300°–400°C temperature range. On the contrary, water is driven off from the “clean” Coalinga fibers at temperatures lower than 100°C. Surface area measurements derived from water-adsorption isotherms correspond to those obtained with nitrogen after the hydration water has been removed.
Equivalent conductivities of adsorbed cations were determined in clays saturated with Na+, Cs+, Ca++ and with mixtures of these cations. Measurements were also made on Ca++ clays which had been forced by previous drying into bundles of platelets or tac-toids. The average mobility of adsorbed Ca++ and Cs+ is much lower than that of adsorbed Na+.
It was concluded that the average mobility of adsorbed Ca++ is low because most of this Ca++ is on the internal surfaces of tactoids. Ca++ adsorbed between these internal surfaces appears to have a mobility much lower than Ca++ on the external surfaces which has a mobility of the same order of magnitude as Na+. Polarization of adsorbed Cs+ accounts at least partially for its low mobility in these clays.
Demixing of adsorbed cations (segregation with Na+ dominant between some platelets and Ca++ between others) is suggested as an initial step leading to breakup of a Na+-Ca++ clay mass into tactoids. The tactoid model, with Ca++ and Na+ preferentially on the internal and external surfaces respectively, furnishes an explanation of the instability of clay and soil aggregates with 15% exchangeable sodium.
Adsorption studies have been performed on Georgia kaolins having a broad range of crystallinity and particle size distributions (from 0·1μ to 44μ) using N2 (78°K.), H2O (273°K.), and BuNH2 (298°K.). Using both vapor and liquid phase adsorption techniques, surface affinities of the adsorbates were determined.
Modified Frenkel-Halsey-Hill plots were used to compute the preferential adsorptivity of H2O vapor over N2 (hydrophilicity index, H.I.) as a function of crystallinity index, C.I., and particle size. For amine adsorptivity, non-aqueous adsorption isotherms were obtained.
Within any geographic deposit, crystallinity exhibits an inconsistent pattern with respect to particle size. A single generality is the tendency for crystallinity to increase toward the fine particle size range, D → 0·2μ. Adsorptivities of N2, H2O, and BuNH2 show no dependence upon crystallinity within a given particle size range. However, F.H.H. compensated slopes, describing the preferential adsorptivity over N2, show a definite decrease as crystallinity increases. A striking anomaly occurs in the vicinity of 0·2 > C.I. > 0·7 where H.I. increases briefly then returns to the original trend. The rate of decrease of H.I. vs. C.I. is consistently steeper with increasing particle size. Adsorption of water vapor most likely occurs as a 1:1 configuration on each silica-alumina edge group, 1:1 on each basal silica, and 1:2 (hindered configuration) on each basal alumina group.
The data suggest that amines adsorb preferentially and quantitatively on the edges, i.e. the Lewis and Bronsted acid sites, and follow a Langmuir pattern.
The implication by Murthy and Ferrell (1972) that interstitial water studies are in a confused state is criticized on the basis that the authors have not drawn on a considerable body of data, especially Soviet studies since the 1950’s, and results of the Deep Sea Drilling Project. Pressure filtration systems for extracting interstitial waters are currently the methods of choice for marine studies and have achieved substantial reliability and reproducibility. Although gaps and problems remain, many aspects of interstitial composition of marine sediments have been clarified; these include the substantial constancy of composition of interstitial waters in deep sea pelagic deposits, depletion of interstitial cations owing to authigenic mineral formation in more rapidly accumulated (especially terrigenous) sediments, and special phenomena in sediments overlying salt deposits.
The basic salts of this system were prepared and their structures and physico-chemical properties were studies by electron microscopy, chemical analysis, X-ray powder diffraction, thermal analysis, i.r. absorption spectra, BET absorption, and acidity-basicity measurements. The salts were found to be new compounds analogous to hydrotalcite. They can be expressed by the formula; where M2+ and M3+ denote di- and trivalent cations, A− and A2− denote mono- and divalent anions, respectively, and y = z1 + 2z2; z1 ≫ z2.
The structures consist of positively charged Cd(OH)2-like basic layers and intermediate layers formed from anions and water molecules with the solid solution of divalent cation (M2+) and trivalent cation (M3+) being formed in the range of 0.6 < x/(x + y) < 0.9. The anions of Cl−, NO3− and ClO4− are easily substituted by CO32−. A large part of the NO3− makes a monodentate-type bond and the ClO4− a bridge-type bond.