Peroxide fluorides

Thermal decomposition of peroxide fluoride species provides a convenient route to titanium oxide fluorides [246]. Decomposition of(NH4)3Ti(02)F5 and K3Ti(02)F5 at 640 and 450°C yields TiOF2 and K3TiOF5, respectively, which were identified by elemental analysis and vibrational spectroscopy. 

The crystal structure of the yellow hemihydrate, K2Ti(02)F4 H20, contains the dimeric [Ti2(02)2F8]2 anion which has previously been found in the structure of K2Ti(02)F4 [259], The peroxide fluorides K2Ti(02)F4-xH20 (x = 0, V2, 1) have been characterized by infrared and Raman spectroscopy. 

Thermal decomposition of the previously known peroxide fluorides, K2V0(02)2F and K2V203(02)2F2, at 275°C and 325°C yields the oxide fluorides, K2V03F and K2V205F2, respectively, which were identified by infrared spectroscopy and elemental analysis [246]. Both K2V03F and K2V205F2 were shown by powder X-ray diffraction to crystallize in the hexagonal system [260]. 

Magnesium Air, beryllium fluoride, ethylene oxide, halogens, halocarbons, HI, metal cyanides, metal oxides, metal oxosalts, methanol, oxidants, peroxides, sulfur, tellurium... 

In 1973 the Semiconductor Equipment and Materials Institute (SEMI) held its first standards meeting. SEMI standards are voluntary consensus specifications developed by the producers, users, and general interest groups in the semiconductor (qv) industry. Examples of electronic chemicals are glacial acetic acid [64-19-7] acetone [67-64-17, ammonium fluoride [12125-01 -8] and ammonium hydroxide [1336-21 -6] (see Ammonium compounds), dichloromethane [75-09-2] (see Cm.OROCARBONSANDcm.OROHYDROCARBONs), hydrofluoric acid [7664-39-3] (see Eluorine compounds, inorganic), 30% hydrogen peroxide (qv) [7722-84-1] methanol (qv) [67-56-1] nitric acid (qv) [7697-37-2] 2-propanoI [67-63-0] (see Propyl alcohols), sulfuric acid [7664-93-9] tetrachloroethane [127-18-4] toluene (qv) [108-88-3] and xylenes (qv) (see also Electronic materials). 

Fluorine forms very reactive halogen fluorides. Reaction of CI2 and F2 at elevated temperatures can produce GIF, CIF, or CIF 3 be obtained from the reaction of Br2 and F2. These halogen fluorides react with all nonmetals, except for the noble gases, N2, and O2 (5). Fluorine also forms a class of compounds known as hypofluorites, eg, CF OF (6). Fluorine peroxide [7783-44-0], O2F2, has also been reported (6). 

Trifluoromethylpyridine can be prepared ia 54% yield from picolinic acid and sulfur tetrafluoride—hydrogen fluoride (434). 2-Trifluoromethylpyridine is a weak base no hydrochloride salt is formed. However, 2-trifluoromethylpyridine 1-oxide [22253-71-0] (bp 132—133°C/2.7 kPa (20 mm Hg)) is prepared ia 81% yield usiag 30% hydrogen peroxide—acetic acid (438). 

Tetrafluoroethylene undergoes addition reactions typical of an olefin. It bums in air to form carbon tetrafluoride, carbonyl fluoride, and carbon dioxide (24). Under controlled conditions, oxygenation produces an epoxide (25) or an explosive polymeric peroxide (24). Trifluorovinyl ethers,... 

Other Reactions. Dry hydrated lime adsorbs halogen gases, eg, CI2 and F2, to form hypochlorites and fluorides. It reacts with hydrogen peroxide to form calcium peroxide, a rather unstable compound. At sintering temperatures, quicklime combines with iron to form dicalcium ferrite. 

Acid-cataly2ed hydroxylation of naphthalene with 90% hydrogen peroxide gives either 1-naphthol or 2-naphthiol at a 98% yield, depending on the acidity of the system and the solvent used. In anhydrous hydrogen fluoride or 70% HF—30% pyridine solution at — 10 to + 20°C, 1-naphthol is the product formed in > 98% selectivity. In contrast, 2-naphthol is obtained in hydroxylation in super acid (HF—BF, HF—SbF, HF—TaF, FSO H—SbF ) solution at — 60 to — 78°C in > 98% selectivity (57). Of the three commercial methods of manufacture, the pressure hydrolysis of 1-naphthaleneamine with aqueous sulfuric acid at 180°C has been abandoned, at least in the United States. The caustic fusion of sodium 1-naphthalenesulfonate with 50 wt % aqueous sodium hydroxide at ca 290°C followed by the neutralization gives 1-naphthalenol in a ca 90% yield. 

Fluoroformyl peroxide [692-74-0] (20, R = R = F), has been prepared by the reaction of carbon monoxide, fluorine, and oxygen or by the photolytic reaction of oxalyl fluoride with oxygen (187). 

The plutonium extracted by the Purex process usually has been in the form of a concentrated nitrate solution or symp, which must be converted to anhydrous PuF [13842-83-6] or PuF, which are charge materials for metal production. The nitrate solution is sufficientiy pure for the processing to be conducted in gloveboxes without P- or y-shielding (130). The Pu is first precipitated as plutonium(IV) peroxide [12412-68-9], plutonium(Ill) oxalate [56609-10-0], plutonium(IV) oxalate [13278-81-4], or plutonium(Ill) fluoride. These precipitates are converted to anhydrous PuF or PuF. The precipitation process used depends on numerous factors, eg, derived purity of product, safety considerations, ease of recovering wastes, and required process equipment. The peroxide precipitation yields the purest product and generally is the preferred route (131). The peroxide precipitate is converted to PuF by HF—O2 gas or to PuF by HF—H2 gas (31,132). 

Eor curing copolymers of tetrafluoroethylene and perfluorovinyl ether, addition of ca 4% TAG has been proposed (118). TEE—propylene copolymers have been cured by TAG and organic peroxide (119). Copolymers of TEE-propylene-vinyUdene fluoride are cured with TAG by heating at 200°C. 

Trifluoromethanesulfonic acid, also known as triflic acid [1493-13-6] is widely used ia organic syntheses and has been thoroughly reviewed (93,94). It was first prepared ia 1954 via the oxidation of bis(trifluoromethylthio)mercury with hydrogen peroxide [7722-84-1] (95). Several other routes of preparation have been disclosed (96—98). The acid exhibits excellent thermal and hydrolytic stabiUty, it is not readily oxidized or reduced, nor is it prone to fluoride anion generation. 

Cobalt salts are used as activators for catalysts, fuel cells (qv), and batteries. Thermal decomposition of cobalt oxalate is used in the production of cobalt powder. Cobalt compounds have been used as selective absorbers for oxygen, in electrostatographic toners, as fluoridating agents, and in molecular sieves. Cobalt ethyUiexanoate and cobalt naphthenate are used as accelerators with methyl ethyl ketone peroxide for the room temperature cure of polyester resins. 

Other Polymerization Methods. Although none has achieved commercial success, there are a number of experimental alternatives to clay-catalyzed or thermal oligomeriza tion of dimer acids. These iaclude the use of peroxides (69), hydrogen fluoride (70), a sulfonic acid ion-exchange resia (71), and corona discharge (72) (see Initiators). 

TABLE 2-52 [Fe,(S04)3] Ferric Sulfate TABLE 2-53 [FeCNOala] Ferric Nitrate TABLE 2-58 Hydrogen Fluoride (HF) TABLE 2-59 Hydrogen Peroxide (H O ) ... 

H-Bond Acceptor (HBA) Acyl chlorides Acyl fluorides Hetero nitrogen aromatics Hetero oj gen aromatics Tertiary amides Tertiary amines Other nitriles Other nitros Isocyanates Peroxides Aldehydes Anhydrides Cyclo ketones Ahphatic ketones Esters Ethers Aromatic esters Aromatic nitriles Aromatic ethers Sulfones Sulfolanes... 

The polymers were first described by Newkirk. Polymerisation may be brought about by subjecting acetylene-free vinyl fluoride to pressures to up to 1000 atm at 80°C in the presence of water and a trace of benzoyl peroxide. 

Hydrogen cyanide Calcium cyanide Potassium cyanide Sodium cyanide Hydrogen fluoride as F Hydrogen peroxide Hydrogen selenide as Se Hydrogen sulphide Hydroquinone... 

Mercury, chlorine, calcium hypochlorite, iodine, bromine or hydrogen fluoride Acids, metal powders, flammable liquids, chlorates, nitrites, sulphur, finely-divided organics or combustibles Nitric acid, hydrogen peroxide... 

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