From the Oxides

Reaction temperatures of 1250 to 1300°C for the preparation of M2Se3 (M = La to Gd) from the oxides and H2Se were later recommended by Joulien-Pouzol, Guittard [15]. PreOn was used as the starting material for preparing Pr2Se3. The preparation was carried out in a double wall quartz reactor filled with Ar or H2 to prevent penetration of O2, Obolonchik, Mikhlina [17], also see [18]. 

The reaction of M2O3 with H2Se was used earlier by Klemm, Koczy [16] and also by Obolonchik, Mikhlina [19]. 

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The more noble metals (for example copper, mercury and silver) can form oxides, and exhibit variable oxidation state in such compounds (for example CU2O, CuO), but it is not easy to prepare such oxides by direct action of oxygen on the metal, and elevated temperatures are necessary. Moreover, in the case of silver and mercury, loss of oxygen from the oxide by heating is easy. The oxidesare, however, basic (for example Ag20 - Ag, CuO - Cu in acids). 

The presence of the unsaturated substituent along this polyester backbone gives this polymer crosslinking possibilities through a secondary reaction of the double bond. These polymers are used in paints, varnishes, and lacquers, where the ultimate cross-linked product results from the oxidation of the double bond as the coating cures. A cross-linked polyester could also result from reaction (5.J) without the unsaturated carboxylic acid, but the latter would produce a gel in which the entire reaction mass solidified and is not as well suited to coatings applications as the polymer that crosslinks upon drying. ... 

NO formation occurs by a complex reaction network of over 100 free-radical reactions, and is highly dependent on the form of nitrogen in the waste. Nitro-compounds form NO2 first, and then NO, approaching equiHbrium from the oxidized side. Amines form cyano intermediates on their way to NO, approaching equiHbrium from the reduced side. Using air as the oxidant, NO also forms from N2 and O2. This last is known as thermal NO. ... 

AHoys can be produced by the coreduction process, carried out at 1000°C with calcium, from the oxide mixture. For example, samarium oxide [12060-58-1] and cobalt oxide are coreduced to a SmCo [12017-68-4] powder, CaO then being removed. 

Lithium metal can also be produced by electrolysis in nonprotic solvents. Other methods based on reduction by metals, eg, aluminum or siHcon from the chloride or by magnesium from the oxide, have not had practical commercial appHcation. 

White Phosphorus Oxidation. Emission of green light from the oxidation of elemental white phosphoms in moist air is one of the oldest recorded examples of chemiluminescence. Although the chemiluminescence is normally observed from sotid phosphoms, the reaction actually occurs primarily just above the surface with gas-phase phosphoms vapor. The reaction mechanism is not known, but careful spectral analyses of the reaction with water and deuterium oxide vapors indicate that the primary emitting species in the visible spectmm are excited states of (PO)2 and HPO or DPO. Ultraviolet emission from excited PO is also detected (196). 

Chlorination. In some instances, the extraction of a pure metal is more easily achieved from the chloride than from the oxide. Oxide ores and concentrates react at high temperature with chlorine gas to produce volatile chlorides of the metal. This reaction can be used for common nonferrous metals, but it is particularly useful for refractory metals like titanium (see Titanium and titanium alloys) and 2irconium (see Zirconium and zirconium compounds), and for reactive metals like aluminum. 

Interest in synthetic naphthenic acid has grown as the supply of natural product has fluctuated. Oxidation of naphthene-based hydrocarbons has been studied extensively (35—37), but no commercially viable processes are known. Extensive purification schemes must be employed to maximize naphthene content in the feedstock and remove hydroxy acids and nonacidic by-products from the oxidation product. Free-radical addition of carboxylic acids to olefins (38,39) and addition of unsaturated fatty acids to cycloparaffins (40) have also been studied but have not been commercialized. 

Because very high conversions generally are not obtained or desired, the hydroperoxide is removed from the oxidation stream by extraction with aqueous alkah. 

Diacyl peroxides (20, R = R = alkyl or aryl) have been obtained from the oxidation of carboxyhc acid potassium salts by Kolbe electrolysis or by elemental fluorine (187). 

Oxidation of cumene to cumene hydroperoxide is usually achieved in three to four oxidizers in series, where the fractional conversion is about the same for each reactor. Fresh cumene and recycled cumene are fed to the first reactor. Air is bubbled in at the bottom of the reactor and leaves at the top of each reactor. The oxidizers are operated at low to moderate pressure. Due to the exothermic nature of the oxidation reaction, heat is generated and must be removed by external cooling. A portion of cumene reacts to form dimethylbenzyl alcohol and acetophenone. Methanol is formed in the acetophenone reaction and is further oxidized to formaldehyde and formic acid. A small amount of water is also formed by the various reactions. The selectivity of the oxidation reaction is a function of oxidation conditions temperature, conversion level, residence time, and oxygen partial pressure. Typical commercial yield of cumene hydroperoxide is about 95 mol % in the oxidizers. The reaction effluent is stripped off unreacted cumene which is then recycled as feedstock. Spent air from the oxidizers is treated to recover 99.99% of the cumene and other volatile organic compounds. 

Impurities in isophthahc acid from the oxidation process are analogous to those in terephthahc acid, eg, 3-formylbenzoic acid and y -toluic acid. 

Chemical degradation studies carried out on streptovaricias A and C, which are the primary components of the cmde complex, yielded substances shown ia Figure 1. Streptovaricia A (4), consumes two moles of sodium periodate to yield variciaal A [21913-68-8] (1), 0 2 200, which accounts for the ahphatic portion of the molecule, and prestreptovarone [58074-37-6] (2), C2C)H2C)N02, which accounts for the aromatic chromophore of the streptovaricias (Fig. 2). Streptovaricia G (9) is the only other streptovaricia that yields prestreptovaroae upoa treatmeat with sodium periodate. Treatmeat of streptovaricias A (4), B (5), C (6), E (8), and G (9) with sodium periodate and osmium tetroxide yields streptovarone [36108-44-8] (3), C24H23NO2, which is also produced by the reaction of prestreptovarone with sodium periodate and osmium tetroxide (4,65). A number of aliphatic products were isolated from the oxidation of streptovaricia C and its derivatives (66). 

Styrene. Commercial manufacture of this commodity monomer depends on ethylbenzene, which is converted by several means to a low purity styrene, subsequendy distilled to the pure form. A small percentage of styrene is made from the oxidative process, whereby ethylbenzene is oxidized to a hydroperoxide or alcohol and then dehydrated to styrene. A popular commercial route has been the alkylation of benzene to ethylbenzene, with ethylene, after which the cmde ethylbenzene is distilled to give high purity ethylbenzene. The ethylbenzene is direcdy dehydrogenated to styrene monomer in the vapor phase with steam and appropriate catalysts. Most styrene is manufactured by variations of this process. A variety of catalyst systems are used, based on ferric oxide with other components, including potassium salts, which improve the catalytic activity (10). 

Thallic oxide can be prepared by reaction of thallium with oxygen or hydrogen peroxide and an alkaline thallium(I) solution. However, it is more easily made from the oxidation of thaHous nitrate by chlorine ia aqueous potassium hydroxide solution. It is insoluble in water but dissolves in carboxyUc acids to give carboxylates. 

Pyridine carboxamide [98-92-0] (nicotinamide) (1) and 3-pyridine carboxylic acid [59-67-6] (nicotinic acid) (2) have a rich history and their early significance stems not from their importance as a vitamin but rather as products derived from the oxidation of nicotine. In 1867, Huber prepared nicotinic acid from the potassium dichromate oxidation of nicotine. Many years later, Engler prepared nicotinamide. Workers at the turn of the twentieth century isolated nicotinic acid from several natural sources. In 1894, Su2uki isolated nicotinic acid from rice bran, and in 1912 Funk isolated the same substance from yeast (1). 

Fig. 9. Genesis of acid tain (13). From the oxidation of C, S, and N during the combustion of fossil fuels, there is a buildup in the atmosphere (gas phase, aerosol particles, raindrops, snowflakes, and fog) of CO2 and the oxides of S and N, which leads to acid—base interaction. The importance of absorption of gases into the various phases of gas, aerosol, and atmospheric water depends on a number of factors. The genesis of acid rain is shown on the upper right as an acid—base titration. The data given are representative of the environment in the vicinity of Zurich, Switzedand.

Hydrocarbon Recovery. Toluene is typically recovered from the oxidizer vent gases through the use of refrigeration followed by activated carbon adsorption. 

Ethyl carbamate, C2HyN02, is developed naturally during the fermentation of alcohoHc beverages. It also appears in foods such as bread and yogurt. Since ethyl carbamate is not easily distilled, its formation most likely involves a distillable precursor. The mechanism of ethyl carbamate formation probably involves cyanate produced from the oxidation of cyanide or from urea-based compounds in the beer. Cyanate reacts with alcohol to form ethyl carbamate as follows ... 

The potential hquid-phase content at clinkering temperatures range from 18 to 25% and can be estimated from the oxide analysis of the raw mix. 

The potential compound composition of a cement or cement clinker can be calculated from the oxide analyses of any given raw materials mixture, or from the oxide analyses of the cement clinker or finished cement. The simplest and most widely used method is the Bogue calculation (23). The ASTM C150 (24) calculation is somewhat modified. 

Chromium oxide is mixed with aluminum powder, placed in a refractory-lined vessel, and ignited with barium peroxide and magnesium powder. The reaction is exothermic and self-sustaining. Chromium metal of 97—99% purity is obtained, the chief impurities being aluminum, iron, and silicon (Table 4). Commercial chromium metal may also be produced from the oxide by reduction with silicon in an electric-arc furnace. 

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