Cobalt , and oxidation

Nakayama M, Goto S, Uchimoto Y, WaMhara M, Kitayama Y (2004) Changes in electronic structure between cobalt and oxide ions of lithium cobalt phosphate as 4.8-V positive electrode material. Chem Mater 16 3399-3401... 

Besides stmctural variety, chemical diversity has also increased. Pure silicon fonns of zeolite ZSM-5 and ZSM-11, designated silicalite-l [19] and silicahte-2 [20], have been synthesised. A number of other pure silicon analogues of zeolites, called porosils, are known [21]. Various chemical elements other than silicon or aluminium have been incoriDorated into zeolite lattice stmctures [22, 23]. Most important among those from an applications point of view are the incoriDoration of titanium, cobalt, and iron for oxidation catalysts, boron for acid strength variation, and gallium for dehydrogenation/aromatization reactions. In some cases it remains questionable, however, whether incoriDoration into the zeolite lattice stmcture has really occurred. 

In the chemistry of nickel, we observe the continuing tendency for the higher oxidation states to decrease in stability along the first transition series unlike cobalt and iron, the -e3 state is rare and relatively unimportant for nickel and the +2 state is the only important one. 

This reaction is rapidly replacing the former ethylene-based acetaldehyde oxidation route to acetic acid. The Monsanto process employs rhodium and methyl iodide, but soluble cobalt and iridium catalysts also have been found to be effective in the presence of iodide promoters. 

Pentafluorobenzene. Pentafluoroben2ene has been prepared by several routes multistage saturation—rearomati2ation process based on fluorination of ben2ene with cobalt trifluoride reductive dechlorination of chloropentafluoroben2ene with 10% pabadium-on-carbon in 82% yield (226,227) and oxidation of penta uorophenylbydra2ine in aqueous copper sulfate at 80°C in 77% yield (228). Its ioni2ation potential is 9.37 V. One measure of toxicity is LD q = 710 mg/kg (oral, mouse) (127). 

The conversion of CO to CO2 can be conducted in two different ways. In the first, gases leaving the gas scmbber are heated to 260°C and passed over a cobalt—molybdenum catalyst. These catalysts typically contain 3—4% cobalt(II) oxide [1307-96-6] CoO 13—15% molybdenum oxide [1313-27-5] MoO and 76—80% alumina, JSifDy and are offered as 3-mm extmsions, SV about 1000 h . On these catalysts any COS and CS2 are converted to H2S. Operating temperatures are 260—450°C. The gases leaving this shift converter are then scmbbed with a solvent as in the desulfurization step. After the first removal of the acid gases, a second shift step reduces the CO content in the gas to 0.25—0.4%, on a dry gas basis. The catalyst for this step is usually Cu—Zn, which may be protected by a layer of ZnO. 

Ocean Basins. Known consohdated mineral deposits in the deep ocean basins are limited to high cobalt metalliferous oxide cmsts precipitated from seawater and hydrothermal deposits of sulfide minerals which are being formed in the vicinity of ocean plate boundaries. Technology for drilling at depth in the seabeds is not advanced, and most deposits identified have been sampled only within a few centimeters of the surface. 

Technical-Grade Terephthalic Acid. All technical-grade terephthahc acid is produced by catalytic, hquid-phase air oxidation of xylene. Several processes have been developed, but they all use acetic acid as a solvent and a multivalent heavy metal or metals as catalysts. Cobalt is always used. In the most popular process, cobalt and manganese are the multivalent heavy-metal catalysts and bromine is the renewable source for free radicals (51,52). 

Eigure 3 is a flow diagram which gives an example of the commercial practice of the Dynamit Nobel process (73). -Xylene, air, and catalyst are fed continuously to the oxidation reactor where they are joined with recycle methyl -toluate. Typically, the catalyst is a cobalt salt, but cobalt and manganese are also used in combination. Titanium or other expensive metallurgy is not required because bromine and acetic acid are not used. The oxidation reactor is maintained at 140—180°C and 500—800 kPa (5—8 atm). The heat of reaction is removed by vaporization of water and excess -xylene these are condensed, water is separated, and -xylene is returned continuously (72,74). Cooling coils can also be used (70). 

Eastman Chemical Co. uses only cobalt and bromine, and lower temperature oxidations are held at 175—230°C (83). Solution of 4-formylbenzoic acid is obtained by using hydroclones to replace the mother hquor from the first oxidation with fresh acetic acid. A residence time of up to 2 h is used in order to allow for sufficient digestion to take place and to reduce the 4-formylbenzoic acid content to 40—270 ppm (83). Recovery of dry terephthahc acid is as described above. 

Catalysts used for preparing amines from alcohols iaclude cobalt promoted with tirconium, lanthanum, cerium, or uranium (52) the metals and oxides of nickel, cobalt, and/or copper (53,54,56,60,61) metal oxides of antimony, tin, and manganese on alumina support (55) copper, nickel, and a metal belonging to the platinum group 8—10 (57) copper formate (58) nickel promoted with chromium and/or iron on alumina support (53,59) and cobalt, copper, and either iron, 2iac, or zirconium (62). 

Most commercial sorbic acid is produced by a modification of this route. Catalysts composed of metals (2inc, cadmium, nickel, copper, manganese, and cobalt), metal oxides, or carboxylate salts of bivalent transition metals (2inc isovalerate) produce a condensation adduct with ketene and crotonaldehyde (22—24), which has been identified as (5). 

Copper sulfate, in small amounts, activates the zinc dust by forming zinc—copper couples. Arsenic(III) and antimony(TTT) oxides are used to remove cobalt and nickel they activate the zinc and form intermetaUic compounds such as CoAs (49). Antimony is less toxic than arsenic and its hydride, stibine, is less stable than arsine and does not form as readily. Hydrogen, formed in the purification tanks, may give these hydrides and venting and surveillance is mandatory. The reverse antimony procedure gives a good separation of cadmium and cobalt. 

Metal-Catalyzed Oxidation. Trace quantities of transition metal ions catalyze the decomposition of hydroperoxides to radical species and greatiy accelerate the rate of oxidation. Most effective are those metal ions that undergo one-electron transfer reactions, eg, copper, iron, cobalt, and manganese ions (9). The metal catalyst is an active hydroperoxide decomposer in both its higher and its lower oxidation states. In the overall reaction, two molecules of hydroperoxide decompose to peroxy and alkoxy radicals (eq. 5). 

The reactive species that iaitiate free-radical oxidatioa are preseat ia trace amouats. Exteasive studies (11) of the autoxidatioa mechanism have clearly estabUshed that the most reactive materials are thiols and disulfides, heterocycHc nitrogen compounds, diolefins, furans, and certain aromatic-olefin compounds. Because free-radical formation is accelerated by metal ions of copper, cobalt, and even iron (12), the presence of metals further compHcates the control of oxidation. It is difficult to avoid some metals, particularly iron, ia fuel systems. 

Nonferrous alloys account for only about 2 wt % of the total chromium used ia the United States. Nonetheless, some of these appHcations are unique and constitute a vital role for chromium. Eor example, ia high temperature materials, chromium ia amounts of 15—30 wt % confers corrosion and oxidation resistance on the nickel-base and cobalt-base superaHoys used ia jet engines the familiar electrical resistance heating elements are made of Ni-Cr alloy and a variety of Ee-Ni and Ni-based alloys used ia a diverse array of appHcations, especially for nuclear reactors, depend on chromium for oxidation and corrosion resistance. Evaporated, amorphous, thin-film resistors based on Ni-Cr with A1 additions have the advantageous property of a near-2ero temperature coefficient of resistance (58). 

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