Cobalt -Ion

Various ways of overcoming the PTA oxidation problem have been incorporated into commercial processes. The predominant solution is the use of high concentrations of manganese and cobalt ions (2,248—254), optionally with various cocatalysts (204,255,256), in the presence of an organic or inorganic bromide promoter in acetic acid solvent. Operational temperatures are rather high (ca 200°C). A lesser but significant alternative involves isolation of intermediate PTA, conversion to methyl/)-toluate, and recycle to the reactor. The ester is oxidized to monomethyl terephthalate, which is subsequentiy converted to DMT and purified by distillation (248,257—264). 

A thkd method utilizes cooxidation of an organic promoter with manganese or cobalt-ion catalysis. A process using methyl ethyl ketone (248,252,265—270) was commercialized by Mobil but discontinued in 1973 (263,264). Other promoters include acetaldehyde (248,271—273), paraldehyde (248,274), various hydrocarbons such as butane (270,275), and others. Other types of reported activators include peracetic acid (276) and ozone (277), and very high concentrations of cobalt catalyst (2,248,278). 

Cobalt as a Colorant in Ceramics, Glasses, and Paints. Cobalt(II) ion displays a variety of colors in soHd form or solution ranging from pinks and reds to blues or greens. It has been used for hundreds of years to impart color to glasses and ceramics (qv) or as a pigment in paints and inks (see CoLORANTS FOR CERAMICS). The pink or red colors are generally associated with cobalt(II) ion in an octahedral environment and the chromophore is typically Co—O. The tetrahedral cobalt ion, Co—chromophore, is sometimes green, but usually blue in color. 

The influence of flow rates of eluent and sample solution, amount of ligand, types and least amount of eluent for elution of Cobalt ion from column were investigated. 

The effects of vaiious cationic interferences on percent recovery of Cobalt were studied. The method was successfully applied for the determinations of Cobalt ion from synthetic and water samples. 

Reagents. Standard nickel and cobalt ion solutions. Prepare solutions of nickel and cobalt ion (ca 10 mgmL"1) from pure ammonium nickel sulphate and pure ammonium cobalt sulphate respectively. 

Discussion. An excellent method for the colorimetric determination of minute amounts of cobalt is based upon the soluble red complex salt formed when cobalt ions react with an aqueous solution of nitroso-R-salt (sodium 1-nitroso-2-hydroxynaphthalene-3,6-disulphonate). Three moles of the reagent combine with 1 mole of cobalt. 

It is worthwhile to point out that lithium extraction from inverse spinels V[LiM]04, such as V[LiNi]04 and V[LiCo]04 takes place at high voltage, typically between 4 and 5V [153]. Lithium is extracted from the octahedral 16d sites of these spinels with a concomitant oxidation of the divalent nickel or cobalt ions. From a structural point of view, this can be readily understood because lithium must be dislodged from the 16d octahedral sites, which are of low-energy, into neighboring energetically unfavorable 8b tetrahedra, which share all four faces with 16d sites that are occupied by nickel or cobalt and by lithium. Lithium extraction reactions... 

This method involves measurement of the oxidation rate of an aqueous sodium sulfite solution catalyzed by cupric or cobaltous ions. The oxygen absorbed reacts with the sulfite according to the equation ... 

Caprolactam is a thermally unstable compound which on distillation may form methyl-, ethyl-, propyl-, and n-amylamines. Also, at high temperatures, CL reacts widi oxygen to form hydroperoxides which in the presence of iron or cobalt ions are converted into adipimide. /V-alkoxy compounds are also formed by the reaction of CL with aldehydes during storage. 

The enzymes in the so-called "isomerase reactions contain 5 -deoxy-adenosylcorrinoids. Labeling experiments have been used to identify the C, H, and O atoms vv hich have moved in the course of the rearrangement and to show that during the reaction the hydrogen atoms of the substrate exchange with the hydrogen atoms of the C-5 atom coordinated to the cobalt ion, but not with the solvent. There is also some spectroscopic evidence that the Co—C bond is broken during the reaction. 

Sometimes, the physicochemical properties of ionic species solubilized in the aqueous core of reversed micelles are different from those in bulk water. Changes in the electronic absorption spectra of ionic species (1 , Co ", Cu " ) entrapped in AOT-reversed micelles have been observed, attributed to changes in the amount of water available for solvation [2,92,134], In particular, it has been observed that at low water concentrations cobalt ions are solubihzed in the micellar core as a tetrahedral complex, whereas with increasing water concentration there is a gradual conversion to an octahedral complex [135],... 

The NHase responsible for aldoxime metabolism from the i -pyridine-3-aldoxime-degrading bacterium, Rhodococcus sp. strain YH3-3, was purified and characterized. Addition of cobalt ion was necessary for the formation of enzyme. The native enzyme had a Mr of 130000 and consisted of two subunits (a-subunit, 27 100 (3-subunit, 34500). The enzyme contained approximately 2 mol cobalt per mol enzyme. The enzyme had a wide substrate specificity it acted on aliphatic saturated and unsaturated as well as aromatic nitriles. The N-terminus of the (3-subunit showed good sequence similarities with those of other NHases. Thus, this NHase is part of the metabolic pathway for aldoximes in microorganisms. 

Based on previous studies [15, 22-25], the band at 1941 cm-i is assigned to Co2+(NO), and the pair of bands at 1894 and 1815 cm-i, to Co2+(NO)2- The shoulders at 1874 and 1799 cm may be due to a second dinitrosyl species. While little is known about the location and coordination of the Co 2+ in ZSM-5, it is likely that cobalt ions are associated with both [Si-0-Al]- and [Al-0-Si-0-AI]2- structures in the zeolite. In the former case, the cobalt cations are assumed to be present as Co2+(OH-) cations and in the latter case as Co2+ cations. The presence of cobalt cations in different environments could account for the appearance of two sets of dinitrosyl bands. The band at 2132 cm-> is present not only on Co-ZSM-5 but also on H-ZSM-5 and Na-ZSM-5, and has been observed by several authors on Cu-ZSM-5 [26-28]. 

Cobaltites with spinel stractnre have compositions MC02O4, where M is a metal forming divalent cations, snch as zinc, cadminm, magnesinm, nickel, manganese, and divalent cobalt. In contrast to the perovskites, the cobaltites have a rather high catalytic activity already at room temperatnre. Experiments show that the activity increases with increasing spinel structure content (i.e., increasing number of Co ions) of the catalyst snrface. The trivalent cobalt ions promote the withdrawal of... 

The given structure shows two molecules of TTA to have reacted with a cobalt ion to form the cobalt-TTA complex, in which the cobalt atom forms a valence bond solid lines) with one, and a coordinate bond (broken lines) with the other, oxygen atom of each TTA molecule. Thus, in the cobalt-TTA complex there is a six-membered ring formed by each TTA molecule with the cobalt atom. Metal chelate complexes of this type have good stability, they are nonpolar and soluble in the organic phase. The usefulness of the chelating extractants in solvent extraction is therefore obvious. 

The liquid-phase autoxidation of cyclohexane is carried out in the presence of dissolved cobalt salts. A lot of heterogeneous catalysts were developed for this process but most catalysts lacked stability. The incorporation of cobalt ions in the framework of aluminophosphate and aluminosilicate structures opens perspectives for heterogenization of this process. CoAPO (cobalt aluminophosphate) molecular sieves were found to be active heterogeneous catalysts of this oxidation.133 Site isolation was critical to get active catalysts.134... 

Ans. (a) Barium phosphate and (b) cobalt(III) sulfate. We recognize that cobalt has a 3+ charge because two cobalt ions are needed to balance three sulfate ions, each of which has a 2- charge. 

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