TME, oxidation

As with TME oxidation, the vanadium (IV) complex, [(CsH oVClo], did not readily initiate cyclohexene oxidation. This complex, however, is an efficient catalyst for allylic alcohol epoxidation. The ability of the vanadium complex to initiate oxidation seems to be a function of its... 

Ti, B, Ni, Cr, Fe, Co, Mn) has been described, as was the synthesis of nonsiliceous materials such as oxides of W, Fe, Pb, Mo, and Sb [18]. Although these materials do not represent tme zeolites, they are highly interesting materials which are commonly covered in the zeolite literature with great potential for shape-selective catalysis of bulky molecules. 

The reactors were thick-waked stainless steel towers packed with a catalyst containing copper and bismuth oxides on a skiceous carrier. This was activated by formaldehyde and acetylene to give the copper acetyUde complex that functioned as the tme catalyst. Acetylene and an aqueous solution of formaldehyde were passed together through one or more reactors at about 90—100°C and an acetylene partial pressure of about 500—600 kPa (5—6 atm) with recycling as required. Yields of butynediol were over 90%, in addition to 4—5% propargyl alcohol. 

Partial Oxidation. It is often desirable to augment the supply of naturally occurring or by-product gaseous fuels or to produce gaseous fuels of well-defined composition and combustion characteristics (5). This is particularly tme in areas where the refinery fuel (natural gas) is in poor supply and/or where the manufacture of fuel gases, originally from coal and more recently from petroleum, has become well estabHshed. 

In a vacuum, uncoated molybdenum metal has an unlimited life at high temperatures. This is also tme under the vacuum-like conditions of outer space. Pure hydrogen, argon, and hehum atmospheres are completely inert to molybdenum at all temperatures, whereas water vapor, sulfur dioxide, and nitrous and nitric oxides have an oxidizing action at elevated temperatures. Molybdenum is relatively inert to carbon dioxide, ammonia, and nitrogen atmospheres up to about 1100°C a superficial nitride film may be formed at higher temperatures in the latter two gases. Hydrocarbons and carbon monoxide may carburize molybdenum at temperatures above 1100°C. 

Transition-metal-catalyzed oxidations may or may not proceed via peroxocomplexes. Twelve important industrial organic oxidation processes catalyzed by transition metals, many of which probably involve peroxo intermediates, have been tabulated (88). Even when peroxo intermediates can be isolated from such systems, it does not necessarily foUow that these are tme intermediates in the main reaction. 

The tendency of aliphatic ethers toward oxidation requires the use of antioxidants such as hindered phenoHcs (eg, BHT), secondary aromatic amines, and phosphites. This is especially tme in polyether polyols used in making polyurethanes (PUR) because they may become discolored and the increase in acid number affects PUR production. The antioxidants also reduce oxidation during PUR production where the temperature could reach 230°C. A number of new antioxidant products and combinations have become available (115,120,124—139) (see Antioxidants). 

The term alumina hydrates or hydrated aluminas is used in industry and commerce to designate aluminum hydroxides. These compounds are tme hydroxides and do not contain water of hydration. Several forms are known a general classification is shown in Figure 1. The most weU-defined crystalline forms ate the trihydroxides, Al(OH) gibbsite [14762-49-3], bayerite [20257-20-9], and nordstrandite [13840-05-6], In addition, two aluminum oxide—hydroxides, AIO(OH), boelimite [1318-23-6] and diaspote [14457-84-2], have been clearly defined. The existence of several other forms of aluminum hydroxides have been claimed. However, there is controversy as to whether they ate truly new phases or stmctures having distorted lattices containing adsorbed or intedameUar water and impurities. 

Antidegradants. Amine-type antioxidants (qv) or antiozonants (qv) such as the phenylenediamines (ppd) can significantly decrease scorch time. This is particulady tme in metal oxide curing of polychloroprene or in cases where the ppd had suffered premature degradation prior to cure. 

No tme melting point converts to bis-oxide at >120°C. N2C2H2 = 1, 2, 4-tria2ole. 

Crevice Corrosion. Crevice corrosion is intense locali2ed corrosion that occurs within a crevice or any area that is shielded from the bulk environment. Solutions within a crevice are similar to solutions within a pit in that they are highly concentrated and acidic. Because the mechanisms of corrosion in the two processes are virtually identical, conditions that promote pitting also promote crevice corrosion. Alloys that depend on oxide films for protection (eg, stainless steel and aluminum) are highly susceptible to crevice attack because the films are destroyed by high chloride ion concentrations and low pH. This is also tme of protective films induced by anodic inhibitors. 

Antimony pentafluoride is a strong Lewis acid and a good oxidizing and fluorinating agent. Its behavior as a Lewis acid leads to the formation of numerous simple and complex adducts. It reacts vigorously with water to form a clear solution from which antimony pentafluoride dihydrate [65277-49-8], SbF 2H2O, may be isolated. This is probably not a tme hydrate, but may well be better formulated as [H O] [SbF OH]. 

Cross-linked finishes are not permanent in the tme sense of the word however, under optimum conditions the finish can last for the usehil life of the material. Wet abrasion during laundering is probably the principal cause of gradual removal of the finish. In order to retain antistatic protection for extended use, an excess of finish is often appHed The extent of chemical interaction between the durable antistatic agents and the fiber substrates to which they are appHed is not perfectiy understood. Certain oxidizing agents such as hypochlorite bleaches tend to depolymerize and remove some durable antistatic finishes. Some of the durable finishes have also produced undesirable side effects on textile materials, ie, harsh hand, discoloration, and loss of tensile properties. 

Trialkyl- and triarylarsine sulfides have been prepared by several different methods. The reaction of sulfur with a tertiary arsine, with or without a solvent, gives the sulfides in almost quantitative yields. Another method involves the reaction of hydrogen sulfide with a tertiary arsine oxide, hydroxyhahde, or dihaloarsorane. X-ray diffraction studies of triphenylarsine sulfide [3937-40-4], C gH AsS, show the arsenic to be tetrahedral the arsenic—sulfur bond is a tme double bond (137). Triphenylarsine sulfide and trimethylarsine sulfide [38859-90-4], C H AsS, form a number of coordination compounds with salts of transition elements (138,139). Both trialkyl- and triarylarsine selenides have been reported. The trialkyl compounds have been prepared by refluxing trialkylarsines with selenium powder (140). The preparation of triphenylarsine selenide [65374-39-2], C gH AsSe, from dichlorotriphenylarsorane and hydrogen selenide has been reported (141), but other workers could not dupHcate this work (140). 

From Boric Oxide and Alcohol. To avoid removing water, boric oxide, B2O3, can be used in place of boric acid. The water of reaction (eq. 4) is consumed by the oxide (eq. 5). Because boric acid reacts with borates at high temperatures, it is necessary to filter the reaction mixture prior to distillation of the product. Only 50% of the boron can be converted to ester by this method. In cases where this loss can be tolerated, the boric oxide method is convenient. This is particularly tme for methyl borate and ethyl borate preparation because formation of the undesirable azeotrope is avoided. 

Tme supported catalysts are not favored for this reaction, but it can be effected by the use of finely divided rhenium metal or rhenium (VI) oxide as well as hydrated mthenium (IV) oxide. 

Palladium and platinum (5—10 wt % on activated carbon) can be used with a variety of solvents as can copper carbonate on siHca and 60 wt % nickel on kieselguhr. The same is tme of nonsupported catalysts copper chromite, rhenium (VII) sulfide, rhenium (VI) oxide, and any of the Raney catalysts, copper, iron, or nickel. 

Cr2 03 - 112 0, of indefinite composition occurs. This compound is commonly misnamed as chromic or chromium (ITT) hydroxide [1308-14-1], Cr(OH)2. A tme hydroxide, chromium (ITT) hydroxide trihydrate [41646-40-6], Cr(OH)2 3H20, does exist and is prepared by the slow addition of alkaU hydroxide to a cold aqueous solution of hexaaquachromium(III) ion (40). The fresh precipitate is amphoteric and dissolves in acid or in excess of hydroxide to form the metastable Cr(OH). This ion decomposes upon heating to give the hydrous chromium (ITT) oxide. However, if the precipitate is allowed to age, it resists dissolution in excess hydroxide. 

Acute and Chronic Toxicity. Although chromium displays nine oxidation states, the low oxidation state compounds, -II to I, all require Special conditions for existence and have very short lifetimes in a normal environment. This is also tme for most organ ochromium compounds, ie, compounds containing Cr—C bonds. Chromium compounds that exhibit stabiUty under the usual ambient conditions are limited to oxidation states II, III, IV, V, and VI. Only Cr(III) and Cr(VI) compounds are produced in large quantities and are accessible to most of the population. Therefore, the toxicology of chromium compounds has been historically limited to these two states, and virtually all of the available information is about compounds of Cr(III) and/or Cr(VI) (59,104). However, there is some indication that Cr(V) may play a role in chromium toxicity (59,105—107). Reference 104 provides an overview and summary of the environmental, biological, and medical effects of chromium and chromium compounds as of the late 1980s. 

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