Diffraction techniques, x-ray

Analyses of electron density distributions have enabled the positions of major elements of high atomic weights such as iron and other transition elements to be located relative to lighter elements such as magnesium and aluminium in mineral crystal structures. The widespread availability of automated X-ray dif-fractometry and least squares refinement programs have increased the availability of site occupancy data for transition metal ions in most contemporary crystal structure refinements. 

Site populations of less abundant cations estimated from X-ray diffraction measurements have limited accuracies particularly when iron is present, since diffraction phenomena involve the cooperative scattering effects of many atoms in the unit cell. It is very difficult, and sometimes impossible in X-ray structure refinements, to distinguish between cations of different valences, such as Fe2+ and Fe3+, Mn2+ and Mn3+ or Ti3+ and Ti4+, and between neighbouring elements in the periodic table with similar scattering factors, such as iron 

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Figure 4.7c illustrates how x-ray diffraction techniques can be applied to the problem of evaluating 6. If the intensity of scattered x-rays is monitored as a function of the angle of diffraction, a result like that shown in Fig. 4.7c is obtained. The sharp peak is associated with the crystalline diffraction, and the broad peak, with the amorphous contribution. If the area A under each of the peaks is measured, then... 

Free Silica. Free siUca down to 1% can be deterrnined with x-ray diffraction techniques (xrd). 

Instrumental Methods for Bulk Samples. With bulk fiber samples, or samples of materials containing significant amounts of asbestos fibers, a number of other instmmental analytical methods can be used for the identification of asbestos fibers. In principle, any instmmental method that enables the elemental characterization of minerals can be used to identify a particular type of asbestos fiber. Among such methods, x-ray fluorescence (xrf) and x-ray photo-electron spectroscopy (xps) offer convenient identification methods, usually from the ratio of the various metal cations to the siUcon content. The x-ray diffraction technique (xrd) also offers a powerfiil means of identifying the various types of asbestos fibers, as well as the nature of other minerals associated with the fibers (9). 

Surface Area. Overall catalyst surface area can be determined by the BET method mentioned eadier, but mote specific techniques are requited to determine a catalyst s active surface area. X-ray diffraction techniques can give data from which the average particle si2e and hence the active surface area may be calculated. Or, it may be necessary to find an appropriate gas or Hquid that will adsorb only on the active surface and to measure the extent of adsorption under controUed conditions. In some cases, it maybe possible to measure the products of reaction between a reactive adsorbent and the active site. Radioactively tagged materials are frequentiy usehil in this appHcation. Once a correlation has been estabHshed between either total or active surface area and catalyst performance (particulady activity), it may be possible to use the less costiy method for quaHty assurance purposes. 

Bleaching Powder. This material, known siace 1798, is made by chlorination of slightly moist hydrated lime, calcium hydroxide [1305-62-0] Ca(OH)2- It has the empirical formula Ca(OCl)2 CaCl2 Ca(OH)2 2H20. Its compositioa, loag a subject of coatroversy, was estabHshed by phase studies, microscopy, and x-ray diffraction techniques (241). The initial chlorination products are monobasic calcium chloride [14031-38-4] and dibasic calcium hypochlorite [12394-14-8] ... 

EXAFS is a nondestructive, element-specific spectroscopic technique with application to all elements from lithium to uranium. It is employed as a direct probe of the atomic environment of an X-ray absorbing element and provides chemical bonding information. Although EXAFS is primarily used to determine the local structure of bulk solids (e.g., crystalline and amorphous materials), solid surfaces, and interfaces, its use is not limited to the solid state. As a structural tool, EXAFS complements the familiar X-ray diffraction technique, which is applicable only to crystalline solids. EXAFS provides an atomic-scale perspective about the X-ray absorbing element in terms of the numbers, types, and interatomic distances of neighboring atoms. 

Polyester fibers contain crystalline as well as noncrystalline regions. The degree of crystallinity and molecular orientation are important in determining the tensile strength of the fiber (between 18-22 denier) and its shrinkage. The degree of crystallinity and molecular orientation can be determined by X-ray diffraction techniques. ... 

Films on stainless steel, analysis by x-ray emission spectrography, 230 Film thickness, determination, 146-159 by attenuation of monochromatic x-rays from substrate, 149-152 by attenuation of unresolved beam from substrate, 147-149 by x-ray diffraction techniques, 147 intercomparison of three methods used in, 158... 

The characteristic feature of solid—solid reactions which controls, to some extent, the methods which can be applied to the investigation of their kinetics, is that the continuation of product formation requires the transportation of one or both reactants to a zone of interaction, perhaps through a coherent barrier layer of the product phase or as a monomolec-ular layer across surfaces. Since diffusion at phase boundaries may occur at temperatures appreciably below those required for bulk diffusion, the initial step in product formation may be rapidly completed on the attainment of reaction temperature. In such systems, there is no initial delay during nucleation and the initial processes, perhaps involving monomolec-ular films, are not readily identified. The subsequent growth of the product phase, the main reaction, is thereafter controlled by the diffusion of one or more species through the barrier layer. Microscopic observation is of little value where the phases present cannot be unambiguously identified and X-ray diffraction techniques are more fruitful. More recently, the considerable potential of electron microprobe analyses has been developed and exploited. 

On the structure of concentrated ionic solutions by X-ray diffraction techniques. R. Caminiti, G. Licheri, G. Piccaluga, G. Pinna and M. Magini, Rev. Inorg. Chem., 1979,1,334-385 (83). 

The geometric parameters of the three-membered ring sulfones and sulfoxides have been determined via X-ray diffraction techniques and gas-phase microwave spectroscopy. The accumulated data for some selected thiirane and thiirene oxides and dioxides (16-19) as well as for the corresponding thiirane (20) and the acyclic dimethyl sulfone (for the sake of comparison) are given in Table 3, together with the calculated values. 

Although these nmr results offer convincing support for the fl-form of 4GT taking the structure proposed by Hall and Pass as their model 7, in the case of the a-form none of the proposed structures were in good agreement with the nmr measurements. This discrepancy highlights the sensitivity of the nmr technique to the exact conformation of the methylene chain, in contrast to the X-ray diffraction technique which is more sensitive to the terephthalolyl residue. 

The technique as we have described it works only for polar molecules, because only they can interact with microwave radiation. However, variations of these spectroscopic methods can be used to investigate nonpolar molecules, too. A major limitation of the technique is that only the spectra of simple molecules can be interpreted. For complex molecules, we use solid samples and x-ray diffraction techniques. 

Besides synthesis, current basic research on conducting polymers is concentrated on structural analysis. Structural parameters — e.g. regularity and homogeneity of chain structures, but also chain length — play an important role in our understanding of the properties of such materials. Research on electropolymerized polymers has concentrated on polypyrrole and polythiophene in particular and, more recently, on polyaniline as well, while of the chemically produced materials polyacetylene stih attracts greatest interest. Spectroscopic methods have proved particularly suitable for characterizing structural properties These comprise surface techniques such as XPS, AES or ATR, on the one hand, and the usual methods of structural analysis, such as NMR, ESR and X-ray diffraction techniques, on the other hand. 

The Sr-Cu system has been critically assessed. The most recent phase diagram, determined by combining differential thermal analysis and x-ray diffraction techniques, contains two intermediate compounds, both of which form in peritectic reactions, SrCu (588°C) and SrCu, (845°C) SrCu has also been prepared for independent structural analysis-. ... 

Since the vibrational spectra of sulfur allotropes are characteristic for their molecular and crystalline structure, vibrational spectroscopy has become a valuable tool in structural studies besides X-ray diffraction techniques. In particular, Raman spectroscopy on sulfur samples at high pressures is much easier to perform than IR spectroscopical studies due to technical demands (e.g., throughput of the IR beam, spectral range in the far-infrared). On the other hand, application of laser radiation for exciting the Raman spectrum may cause photo-induced structural changes. High-pressure phase transitions and structures of elemental sulfur at high pressures were already discussed in [1]. 

A first study refers to liquid water [77]. The signals AS q,x) and A5[r, x] were measured using time-resolved X-ray diffraction techniques with 100 ps resolution. Laser pulses at 266 nm and 400 nm were employed. Only short times X were considered where thermal expansion was assumed to be negligible, and... 

Many ionic compounds contain what used to be referred to as water of crystallization . For example, magnesium chloride can exist as a fully hydrated salt which was formerly written MgCla.bHjO, but is more appropriately written Mg(OH2)eCl2, since the water molecules occupy coordination sites around the magnesium ions. This is typical. In most compounds that contain water of crystallization, the water molecules are bound to the cation in an aquo complex in the manner originally proposed by Alfred Werner (1866-1919) in 1893 (Kauffman, 1981). Such an arrangement has been confirmed in numerous cases by X-ray diffraction techniques. 

X-ray diffraction technique M = microwave spectroscopy. Values in parentheses are the calculated geometries (see Table 1). Point group C2V... 

Herbette and co-workers [425-428,445] studied the structures of drugs bound to liposomes using a low-angle X-ray diffraction technique. Although the structural... 

Lenhert and Hodgkin (15) revealed with X-ray diffraction techniques that 5 -deoxyadenosylcobalamin (Bi2-coenzyme) contained a cobalt-carbon o-bond (Fig. 3). The discovery of this stable Co—C-tr-bond interested coordination chemists, and the search for methods of synthesizing coen-zyme-Bi2 together with analogous alkyl-cobalt corrinoids from Vitamin B12 was started. In short order the partial chemical synthesis of 5 -de-oxyadenosylcobalamin was worked out in Smith s laboratory (22), and the chemical synthesis of methylcobalamin provided a second B 12-coenzyme which was found to be active in methyl-transfer enzymes (23). A general reaction for the synthesis of alkylcorrinoids is shown in Fig. 4. 

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