Bismuth oxide fluorides

Perhaps the most reactive compound of the group is BiFs- It reacts extremely vigorously with H2O to form O3, OF2 and a voluminous brown precipitate which is probably a hydrated bismuth(V) oxide fluoride. At room temperature BiFs reacts vigorously with iodine or sulfur above 50° it converts paraffin oil to fluorocarbons at 150° it fluorinates UF4 to UF and at 180° it converts Brs to BrFs and BrFs, and CI2 to CIF. 

Complex fluorides (LiBiF6, and KBiF6) are known1 and they are weaker oxidizing agents than bismuth(V) fluoride itself. If parallels with potassium tetrafluorocobaltate(III) and co-balt(III) fluoride are valid (see Section 25.1.), then they will also be weaker fluorinating agents. 

The rate of oxidation of acetophenoximes with bismuth(V) fluoride in a mixture of hydrogen fluoride and perchloric acid follows first-order kinetics in both the oxime and Bi(V). The reaction is acid catalysed. A bridged outer-sphere mechanism, involving formation of an iminoxy radical, has been suggested.81... 

The white powder BiFg, like SbFg, is made from the oxide and HF with an excess of oxide, the oxide fluoride BiOF is formed. The trichloride, tribromide and tri-iodide of bismuth can all be made by direct combination. BiBrg is yellow and Bilg, black. The last is hydrolysed by hot water to bronze crystals of BiOL... 

BISMUTH (7440-69-9) Powder is a highly flammable solid. Reacts with strong acids and strong oxidizers chlorine, aluminum, fused ammonium nitrates bromine trifluoride chloric acid chlorine, halogens, iodine pentafluoride nitric acid perchloric acid and nitrosyl fluoride. Contact with fire releases bismuth oxide. 

A considerable number of cluster compounds of mercury, bismuth, the halogens and the chalcogens have now been prepared by the use of AsF 5 " and, to a lesser degree, SbFs and other oxidizing fluorides such as NbFs and TaFs. More recently, the use of catalysts to promote reactions in SO2 solutions has also been developed as an additional synthetic tool. ... 

Ammonium citrate dibasic Barium fluoride Barium nitrate Bismuth Calcium fluoride Calcium titanate Carbon Cobalt sulfate (ous) Gold Hydrogen peroxide y-Linolenic acid Niobium oxide Nitrogen Palmitoleic acid Polyester carbonate resin Selenium Sodium chlorite Strontium titanate electronics applies. 

The oxidations of formaldehyde and ethanolamine " with bismuth(V) fluoride complex in an HCIO4-HF mixture are both first order in each reactant and proceed via a mechanism in which electron transfer from the substrate to the oxidant involves a bridged outer sphere. 

Fused salt solutions may be found in which the solubility of these oxides is appreciable at high temperatures and from which crystals grow as the solution is cooled. Some of the fluxes which have been used for growth of the oxides of concern here are (a) potassium nitrate-sodium nitrate, (b) lead fluoride-bismuth oxide, (c) lead oxide-bismuth oxide, and (d) lithium hydroxide-boric acid-molybdenum oxide. Temperatures frequently are in the range of 1300°C. 

The reason for the ultramicrochemical test was to establish whether the bismuth phosphate would carry the plutonium at the concentrations that would exist at the Hanford extraction plant. This test was necessary because it did not seem logical that tripositive bismuth should be so efficient in carrying tetrapositive plutonium. In subsequent months there was much skepticism on this point and the ultramicrochemists were forced to make repeated tests to prove this point. Thompson soon showed that Pu(Vl) was not carried by bismuth phosphate, thus establishing that an oxidation-reduction cycle would be feasible. All the various parts of the bismuth-phosphate oxidation-reduction procedure, bulk reduction via cross-over to a rare earth fluoride oxidation-reduction step and final isolation by precipitation of plutonium (IV) peroxide were tested at the Hanford concentrations of... 

Beryllium chloride, 0221 Beryllium fluoride, 0223 Bis(l-chloroethylthallium chloride) oxide, 1586 Bismuth pentafluoride, 0227... 

Other ingredients that may be found in smokeless powders include camphor, carbazole, cresol, diethyleneglycoldinitrate (DEGDN), dimethylse-bacate, dinitrocresol, di-normal-propyl adipate, 2.4-dinitrodiphenylamine, PETN, TNT, RDX, acaroid resin, gum arabic, synthetic resins, aluminum, ammonium chlorate/oxalate/perchlorate, pentaerythritol dioleate, oxamide, lead carbonate/salicylate/stearate, magnesium oxide, sodium aluminum fluoride, sodium carbonate/bicarbonate, petrolatum, dioctylphthalate, stannic oxide, potassium cyrolate, triphenyl bismuth. 

The redistribution reaction in lead compounds is straightforward and there are no appreciable side reactions. It is normally carried out commercially in the liquid phase at substantially room temperature. However, a catalyst is required to effect the reaction with lead compounds. A number of catalysts have been patented, but the exact procedure as practiced commercially has never been revealed. Among the effective catalysts are activated alumina and other activated metal oxides, triethyllead chloride, triethyllead iodide, phosphorus trichloride, arsenic trichloride, bismuth trichloride, iron(III)chloride, zirconium(IV)-chloride, tin(IV)chloride, zinc chloride, zinc fluoride, mercury(II)chloride, boron trifluoride, aluminum chloride, aluminum bromide, dimethyl-aluminum chloride, and platinum(IV)chloride 43,70-72,79,80,97,117, 131,31s) A separate catalyst compound is not required for the exchange between R.jPb and R3PbX compounds however, this type of uncatalyzed exchange is rather slow. Again, the products are practically a random mixture. 

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