Metals oxidative fluorination

Hydrazine Alkali metals, ammonia, chlorine, chromates and dichromates, copper salts, fluorine, hydrogen peroxide, metallic oxides, nickel, nitric acid, liquid oxygen, zinc diethyl... 

High Purity Aluminum Trifluoride. High purity anhydrous aluminum triduoride that is free from oxide impurities can be prepared by reaction of gaseous anhydrous HF and AlCl at 100°C, gradually raising the temperature to 400°C. It can also be prepared by the action of elemental fluorine on metal/metal oxide and subsequent sublimation (12) or the decomposition of ammonium duoroaluminate at 700°C. 

CoF is used for the replacement of hydrogen with fluorine in halocarbons (5) for fluorination of xylylalkanes, used in vapor-phase soldering fluxes (6) formation of dibutyl decalins (7) fluorination of alkynes (8) synthesis of unsaturated or partially fluorinated compounds (9—11) and conversion of aromatic compounds to perfluorocycHc compounds (see Fluorine compounds, organic). CoF rarely causes polymerization of hydrocarbons. CoF is also used for the conversion of metal oxides to higher valency metal fluorides, eg, in the assay of uranium ore (12). It is also used in the manufacture of nitrogen fluoride, NF, from ammonia (13). 

The mixed halides TeClFs and TeBrFs are made by oxidative fluorination of TeCU or TeBr4 in a stream of Fi diluted with N2 at 25°. Under similar conditions Tel4 gave only TeFg and IF5. TeClFs can also be made by the action of GIF on TcF4, TeCU or Te02 below room temperature it is a colourless liquid, mp —28°, bp 13.5°, which does not react with Hg, dry metals or glass at room temperature. 

The interaction between metal oxides and ammonium hydrofluoride at 100-250°C yields complex fluorometalates of ammonium and water. The water formed evaporates from the mixture, but can also lead to hydrolysis of the fluorination product in the process. In the very common form the fluorination of metal oxides by ammonium hydrofluoride can be described as follows ... 

Nickel and copper containing compounds have been prepared in a similar manner. The phases obtained by the simultaneous fluorination of niobium oxide and other bivalent metal oxides were MHNbOF5, M21,Nb03F3 and M4UNb209, where M11 = Co Ni, Cu [129, 131],... 

Hydrofluoric acid, at relatively high concentrations and at elevated temperatures, dissolves columbite-tantalite concentrates at a reasonable rate. The dissolution process is based on the fluorination of tantalum, niobium and other metal oxides and their conversion into soluble complex fluoride acids yielding complex fluoride ions. 

The fluorination of metal oxides by fluorine, represented by the reaction... 

Chlorine dioxide Copper Fluorine Hydrazine Hydrocarbons (benzene, butane, propane, gasoline, turpentine, etc) Hydrocyanic acid Hydrofluoric acid, anhydrous (hydrogen fluoride) Hydrogen peroxide Ammonia, methane, phosphine or hydrogen sulphide Acetylene, hydrogen peroxide Isolate from everything Hydrogen peroxide, nitric acid, or any other oxidant Fluorine, chlorine, bromine, chromic acid, peroxide Nitric acid, alkalis Ammonia, aqueous or anhydrous Copper, chromium, iron, most metals or their salts, any flammable liquid, combustible materials, aniline, nitromethane... 

See Fluorine Non-metal oxides Hydrogen, Nitrous oxide... 

Halogens, or Interhalogens See Bromine pentalluoride Acids, etc. Chlorine trilluoride Metals, etc. Fluorine Non-metal oxides... 

In the fifth paper of this chapter on cathodes, an investigation of thin-film oxide-hydroxide electrodes containing Cr, Ni, and Co compounds was authored by N. Vlasenko et al. The thin-films were produced by electrochemical deposition from transition metal aqueous fluorine-containing electrolytes onto steel substrates. These thin-films were tested in Li coin cells. Electrochemical activity appears to scale with the amount of fluoride used in the deposition the larger concentration of fluoride in the bath, the greater the capacity. One Ni oxide-hydroxide film electrode showed greater than 175 mAh/g reversible capacity on the 50th cycle with excellent coulombic efficiency. 

We managed to obtain dense and solid thin films of 3d-metal oxides using the techniques of electrochemical deposition from aqueous fluorine-containing electrolytes. The films have been studied as a possible cathode material for secondary cells. The best samples show good cycle retention and acceptable specific capacity in the range of 180 mAh/g. They also feature a plateau of electrochemical potential at approximately 3,5 V, which is acceptable for present industrially produced electrochemical devices. 

The actual composition present in the Br2/BrF3 mixture is not known, and any fluorination reaction may be a composite reaction of BrF, BrF3 and BrF5. It is not necessary to assume that BrFa is the reactive constituent, although this is probable. Consider the fluorination of a species X—a metal, oxide, oxysalt, halide, etc.—to the fluoride XF by a mixture of bromine fluorides BrFgj. The general reaction is... 

Chlorine trifluoride dioxide resembles chlorine fluorides and oxy-fluorides in its corrosive and oxjidizing properties. It must be handled in systems consisting of corrosion-resistant metals, Teflon, or sapphire. It appears to be marginally stabli in a well-passivated system at ambient temperature, It is a strong oxidative fluorinator as evidenced by its... 

The reaction is explosive with fluorine and occurs under all conditions. With chlorine and bromine reaction occurs rapidly when exposed to light, undergoing a photochemical chain reaction. With iodine, the reaction is very slow, even at elevated temperatures. Hydrogen is a strong reducing agent. At high temperatures, the gas reduces many metal oxides to lower oxides or metals ... 

The general structure of this class of materials can, therefore, be summarized as a fine dispersion of metal oxide in a polymer matrix very similar to plasma polytetrafluoroethylene and in principle any metal should be able to be incorporated. Clearly, if the films are protected from the atmosphere, for metals which form involatile fluorides having a relatively weak metal-fluorine bond strength, it should be possible to produce films having metal atoms dispersed in the matrix. It is expected that these films will have many interesting chemical, optical, electrical and magnetic properties., ... 

Arsenic(III) fluoride, like antimony(III) fluoride (see Section 12.1.), is used to substitute fluorine for chlorine, bromine and iodine not only at carbon but also at other atoms, such as phosphorus, boron or metals. Chlorophosphanes undergo oxidative fluorination with arsenic(III) fluoride [or antimony(III) fluoride] to trifluoro-A5-phosphanes 1. 

Tungsten(VI) fluoride (WF6) and molybdenum(VI) fluoride (MoF6) are available commercially, and can be made by reaction of the metals with fluorine.4 In the case of uranium(VI) fluoride (UF6), a preparation that is claimed5 to be feasible in the laboratory uses uranium metal and chlorine trifluoride uranium(VI) fluoride is prepared6 commercially by the fluorination of uranium(IV) fluoride, itself prepared from an oxide and hydrogen fluoride. 

Many [M(dik)4] complexes are volatile, especially those that contain fluorinated diketonate ligands. Mass spectra and gas chromatographic behavior of several of these complexes have been studied (see Table 10). Isenhour and coworkers240 241 have employed fluorinated diketonates in mass spectrometric procedures for determination of Zr and Zr/Hf ratios in geological samples. The most intense peak in mass spectra of [M(dik)4] complexes is [M(dik)3]+. Sievers et al.242 have used gas chromatography of metal trifluoroacetylacetonates to separate Zr from Al, Cr and Rh. However, attempts to separate [Zr(tfacac)4] and [Hf(tfacac)4] by gas chromatography were unsuccessful. Zirconium and hafnium can be separated by solvent extraction procedures that employ fluorinated diketones.105 [M(dik)4] (M = Zr or Hf dik = acac, dpm, tfacac or hfacac) have been used as volatile source materials for chemical vapor deposition of thin films of the metal oxides.243,244... 

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