Calcium chemistry

A very suitable probe for calcium chemistry is europium (II). This cation has a good NMR nucleus, a good Mossbauer nucleus, useful spectra and fluorescence, and can be studied by EPR or by using its eflFect on proton (or other nuclear) resonances. We have shown. Table X, that europium(II) has a chemistry closely similar to that of calcium(II) 42). We are now studying the interaction between europium (II) and enzymes and proteins. We believe that europium (II) parallels calcium (II) to some degree in the triggering of muscle. 

On the other hand, hfe took the extra calcium as a threat, ejecting it, hut in the process, new calcium chemistry happened outside each cell that was key to the whole Cambrian explosion. 

We will also see that calcium compounds still figure in mortar formulations. Figures 13.10 and 13.11 summarize many of the commercial aspects of calcium chemistry. Figure 13.10 shows the uses of limestone, CaC03. Some of these have been mentioned elsewhere, but the Solvay process, smokestack scrubbers, and Portland cement need further explanation. 

Normally, a slight excess of sulfuric acid is used to bring the reaction to completion. There are, of course, many side reactions involving siHca and other impurity minerals in the rock. Fluorine—silica reactions are especially important as these affect the nature of the calcium sulfate by-product and of fluorine recovery methods. Thermodynamic and kinetic details of the chemistry have been described (34). 

Although a few simple hydrides were known before the twentieth century, the field of hydride chemistry did not become active until around the time of World War II. Commerce in hydrides began in 1937 when Metal Hydrides Inc. used calcium hydride [7789-78-8J, CaH2, to produce transition-metal powders. After World War II, lithium aluminum hydride [16853-85-3] LiAlH, and sodium borohydride [16940-66-2] NaBH, gained rapid acceptance in organic synthesis. Commercial appHcations of hydrides have continued to grow, such that hydrides have become important industrial chemicals manufactured and used on a large scale. 

In general, the chemistry of inorganic lead compounds is similar to that of the alkaline-earth elements. Thus the carbonate, nitrate, and sulfate of lead are isomorphous with the corresponding compounds of calcium, barium, and strontium. In addition, many inorganic lead compounds possess two or more crystalline forms having different properties. For example, the oxides and the sulfide of bivalent lead are frequendy colored as a result of their state of crystallisation. Pure, tetragonal a-PbO is red pure, orthorhombic P PbO is yeUow and crystals of lead sulfide, PbS, have a black, metallic luster. 

Calcium Oxalate. The monohydrate [5794-28-5], CaC2 04-H2 0, mol wt 128.10,is of importance principally as an intermediate in oxahc acid manufacture and in analytical chemistry it is the form in which calcium is frequentiy quantitatively isolated. Its solubihty in water is very low, lower than that of the other aLkahne-earth oxalates. The approximate solubihties of this and several related salts are indicated in Table 6. 

Emulsifiers are incorporated in oil and synthetic mud formulations to maintain a stable emulsion of the internal brine phase. These materials include calcium and magnesium soaps of fatty acids and polyamines and amides and their mixtures (123,127). The specific chemistry of these additives depends on the nature of the continuous phase of the mud, ie, whether diesel oil, mineral oil, or a synthetic Hquid. Lime is added along with the fatty acid to form the... 

Causticization, the reaction of hydrated lime [1305-62-0], Ca(OH)2, with sodium carbonate to regenerate sodium hydroxide and precipitate calcium carbonate, is an important part of the Bayer process chemistry. 

First Carbonation. The process stream OH is raised to 3.0 with carbon dioxide. Juice is recycled either internally or in a separate vessel to provide seed for calcium carbonate growth. Retention time is 15—20 min at 80—85°C. OH of the juice purification process streams is more descriptive than pH for two reasons first, all of the important solution chemistry depends on reactions of the hydroxyl ion rather than of the hydrogen ion and second, the nature of the C0 2 U20-Ca " equiUbria results in a OH which is independent of the temperature of the solution. AH of the temperature effects on the dissociation constant of water are reflected by the pH. 

Juice Purification Chemistry. Lime in juice purification serves as a source of calcium, a source of alkalinity, and a source of calcium carbonate which serves as the clarification—filtration medium. 

Chlorine. Nearly all chlorine compounds are readily soluble in water. As a result, the major reservoir for this element in Figure 1 is the ocean (5). Chloride, as noted earHer, is naturally present at low levels in rain and snow, especially over and near the oceans. Widespread increases in chloride concentration in mnoff in much of the United States can be attributed to the extensive use of sodium chloride and calcium chloride for deicing of streets and highways. Ref. 19 points out the importance of the increased use of deicing salt as a cause of increased chloride concentrations in streams of the northeastern United States and the role of this factor in the chloride trends in Lake Ontario. Increases in chloride concentration also can occur as a result of disposal of sewage, oil field brines, and various kinds of industrial waste. Thus, chloride concentration trends also can be considered as an index of the alternation of streamwater chemistry by human development in the industrialized sections of the world. Although chlorine is an essential element for animal nutrition, it is of less importance for other life forms. 

Ion Selective Electrodes Technique. Ion selective (ISE) methods, based on a direct potentiometric technique (7) (see Electroanalytical techniques), are routinely used in clinical chemistry to measure pH, sodium, potassium, carbon dioxide, calcium, lithium, and chloride levels in biological fluids. 

Tertiary bismuthines appear to have a number of uses in synthetic organic chemistry (32), eg, they promote the formation of 1,1,2-trisubstituted cyclopropanes by the iateraction of electron-deficient olefins and dialkyl dibromomalonates (100). They have also been employed for the preparation of thin films (qv) of superconducting bismuth strontium calcium copper oxide (101), as cocatalysts for the polymerization of alkynes (102), as inhibitors of the flammabihty of epoxy resins (103), and for a number of other industrial purposes. 

Organometallic Chemistry. Only a few organocalcium compounds have been reported. Alkyl calcium haUdes have been prepared by reaction of the hahdes and calcium ia tetrahydrofuran (17). 

Lime-Sulfuric. Recovery of citric acid by calcium salt precipitation is shown in Figure 3. Although the chemistry is straightforward, the engineering principles, separation techniques, and unit operations employed result in a complex commercial process. The fermentation broth, which has been separated from the insoluble biomass, is treated with a calcium hydroxide (lime) slurry to precipitate calcium citrate. After sufficient reaction time, the calcium citrate slurry is filtered and the filter cake washed free of soluble impurities. The clean calcium citrate cake is reslurried and acidified with sulfuric acid, converting the calcium citrate to soluble citric acid and insoluble calcium sulfate. Both the calcium citrate and calcium sulfate reactions are generally performed in agitated reaction vessels made of 316 stainless steel and filtered on commercially available filtration equipment. 

Fluidized beds are ideal for the combustion of high sulfur coals since the sulfur dioxide produced by combustion reacts with the introduced calcined limestone to produce calcium sulfate. The chemistry involved can be simplified and reduced to two steps, calcination and sulfation. 

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