Cesium essentiality

Na -loess clay, where batch experiments were analyzed by X-ray diffraction and infrared and far-infrared measurements. The adsorption isotherm (Fig. 8.36) shows that loess clay is selective for cesium cations. The raw material contained a large amount of quartz, and the clay material was a mixture of kaolinite and an interstrati-fied iUite-smectite mineral as a result, equilibrium Cs" adsorption data are not consistent with a single site Langmuir model. Cesium adsorption on this particular soil clay occurs by cation exchange on sites with various cesium affinities. At low concentration, far-infrared spechoscopy shows the presence of very selective adsorption sites that correspond to internal collapsed layers. At high concentration, Cs MAS-NMR shows that cesium essentially is adsorbed to external sites that are not very selective. 

Cesium was first produced ia the metallic state by electrolysis of a molten mixture of cesium and barium cyanides (2). Subsequentiy the more common thermochemical—reduction techniques were developed (3,4). There were essentially no iadustrial uses for cesium until 1926, when it was used for a few years as a getter and as an effective agent ia reduciag the electron work function on coated tungsten filaments ia radio tubes. Development of photoelectric cells a few years later resulted ia a small but steady consumption of cesium and other appHcations for cesium ia photosensing elements followed. 

Eutectics melting at about —30, —47, and —40° C are formed in the binary systems, cesium—sodium at about 9% sodium, cesium—potassium at about 25% potassium, and cesium—mbidium at about 14% mbidium (34). A ternary eutectic with a melting point of about —72°C has the composition 73% cesium, 24% potassium, and 3% sodium. Cesium and lithium are essentially completely immiscible in all proportions. 

Huggins, who has particularly emphasized the fact that different atomic radii are required for different crystals, has recently [Phys. Rev., 28, 1086 (1926)] suggested a set of atomic radii based upon his ideas of the location of electrons in crystals. These radii are essentially for use with crystals in which the atoms are bonded by the sharing of electron pairs, such as diamond, sphalerite, etc. but he also attempts to include the undoubtedly ionic fluorite and cesium chloride structures in this category. 

The polymerization catalysts that are preferred because of their selectivity are the alkali metal (especially cesium) carbonates, tetraalkylammonium and bis(triphenylphosphoranylidene)ammonium (PPN) chlorides and bicarbonates (Table 4.2). Undesired side reactions are minimized by using relatively low (< 5% by weight) catalyst levels. Under these conditions, the fraction of cyclic oligomer was usually 5% or less and was easily removed from the desired polymer by Kugelrohr distillation. Conversions of 5 were essentially quantitative as judged by product weights and lack of detectable amounts of unreacted monomer by GPC. 

If we examine Table 2 in a stepwise fashion, proceeding from cesium to potassium, there is no information that stands out as being anomalous. The atoms with smaller atomic numbers have smaller atomic radii, and as the radii gradually decrease, the respective AG (M , g) increase. As the atomic radii decrease, the increase in AG iM" ", g) is offset to some extent by increasingly negative AGJ thus AG (M" (aq)) (and E°) remain essentially constant. It appears that the only exception to this trend might be AG (Na+(aq)), but the unusually small... 

Alkali metals (K, Rb, Cs) behave similarly and sometimes one is accumulated preferentially when another is deficient. A similar case is made for Sr and Ca (Whicker and Schultz 1982a). The most important alkali metal isotope is Cs because of its long physical half-life (30 years) and its abnndance as a fission prodnct in fallout from nuclear weapons and in the inventory of a nuclear reactor or a fuel-reprocessing plant. Cesium behaves much like potassium. It is rapidly absorbed into the bloodstream and distribnted throughout the active tissues of the body, especially muscle. The P and y radiation from the decay of Cs and its daughter, Ba, result in essentially whole-body irradiation that harms bone marrow (Hobbs and McClellan 1986). 

The alkali halogenide gas molecules MX present a still more extreme case, the bonds being essentially ionic with only a small amount of covalent character. For cesium chloride, involving the most electropositive of the metals and one of the most electronegative of the nonmetals, the electron affinity of the nonmetal (86 kcal/mole) is about as great as the ionization potential of the metal (89 kcal/mole), so that at large intemuclear distances the ionic structure Cs+Cl is about as... 

In all of the molecules discussed above the bond is intermediate between theeovalent extreme M X and the ionic extreme M+X , varying from an essentially covalent bond with only a small amount of ionic character (hydrogen iodide), through a bond with about equal amounts of covalent and ionic character (hydrogen fluoride), to an essentially ionic bond with only a small amount of covalent character (cesium chloride). 

As a rule, the distortion of the water lattice that is found in water without a solute (1) can easily take place in cooperation with the accompanying cation except in the cases of potassium, rubidium, and cesium. These ions are large enough to fill the cavities of the water lattice and to attenuate the lattice vibrations, thus preventing a local collapse of the structure and an increase in the number of interstitial water molecules. The normal water structure is essentially retained, and the lattice, stabilized by cations of the proper size, rejects the complex nonfitting ion (2). 

Figure 2. Chemistry occurring in three sections of a simple flowsheet in solvent extraction using CSSX as an example. In the extraction step, essentially all of the Cs+ and a minor fraction of the K+ ions in the waste are extracted (i.e., M+ = Cs+ or K+). The K+ ions are removed in scrubbing as shown, while the calixcrown-Cs+ complex effectively remains in the solvent so that a pure cesium nitrate product is obtained on stripping.

Solution X-ray diffraction measurements for saturated aqueous solutions of the KCl-MgCl2-6H20 and CsCl-MgCl2-6H20 double salts at 25°C reveal that magnesium(II) ions in the solutions are fully hydrated as [Mg(H20)6]2+ with a Mg-0 bond length of 208-209 pm. This is essentially the same bond length as in the double salt crystals, and the K+ and Cs+ ions have both water molecules and chloride ions in their first coordination sphere. The coordination numbers for water molecules and chloride ions around a K+ ion are 4.7 and 2.4, respectively, and those around a Cs+ ion are 4.7 and 2.0, respectively. The K+-OH2 and K+-C1 interatomic distances are found to be 227 and 320 pm, respectively, and the Cs+-OH2 and Cs + -Cl distances are 315 and 339 pm, respectively (58). The interatomic distances determined are essentially the same as those that have been reported in the literature for aqueous solutions of potassium and cesium salts. 

The existence of these different practices was not sufficient to create a discipline or subdiscipline of physical chemistry, but it showed the way. One definition of physical chemistry is that it is the application of the techniques and theories of physics to the study of chemical reactions, and the study of the interrelations of chemical and physical properties. That would mean that Faraday was a physical chemist when engaged in electrolytic researches. Other chemists devised other essentially physical instruments and applied them to chemical subjects. Robert Bunsen (1811—99) is best known today for the gas burner that bears his name, the Bunsen burner, a standard laboratory instrument. He also devised improved electrical batteries that enabled him to isolate new metals and to add to the list of elements. Bunsen and the physicist Gustav Kirchhoff (1824—87) invented a spectroscope to examine the colors of flames (see Chapter 13). They used it in chemical analysis, to detect minute quantities of elements. With it they discovered the metal cesium by the characteristic two blue lines in its spectrum and rubidium by its two red lines. We have seen how Van t Hoff and Le Bel used optical activity, the rotation of the plane of polarized light (detected by using a polarimeter) to identify optical or stereoisomers. Clearly there was a connection between physical and chemical properties. 

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