Antimony chloride, anhydrous

Replacement of either one or two of the chlorines of carbon tetrachloride by fluorine can be achieved readily with antimony trifluoride containing some antimony pentachloride. The reaction stops after two chlorines have been replaced. The antimony trifluoride can be regenerated continuously from the antimony chloride by addition of anhydrous hydrogen fluoride ... 

Derivation Reaction of chloroform with anhydrous hydrogen fluoride with antimony chloride catalyst. 

Antimony trichloride Potassium alum anhydrous Stannous chloride anhydrous lake mfg., pink Cochineal lake mfg., red Cochineal lakes... 

When metallic antimony is fumed with an excess of ammonium chloride, the latter acts like anhydrous hydrogen chloride at elevated temperatures. The result is the formation and sublimation of the volatile antimony chloride which can be detected by the redox reaction with alkaline mercury cyanide solution as described on page 105. 

Anhydrous bismuth and antimony chlorides (Bids and SbCD have no action on aluminium. 

Antimony Chloride (cont) anhydrous 60 9 Resistant tensile strength at yield and elongation at break unchanged Test specimen IB according to ISO 527-2 Lupolen Basell Specimen 50X25X1 mm... 

The result of direct anhydrous chlorination of naphthalene, using ferric or antimony chloride as catalyst, is a series of isomers, ranging from mono- to octa-chloro-(Fig. 1) 79 iosomers are theoretically possible, most of which have been isolated. The basic properties of the main commercial grades are shown in Table 3 the isomeric composition of these is shown in Table 7. 

In a generalized sense, acids are electron pair acceptors. They include both protic (Bronsted) acids and Lewis acids such as AlCb and BF3 that have an electron-deficient central metal atom. Consequently, there is a priori no difference between Bronsted (protic) and Lewis acids. In extending the concept of superacidity to Lewis acid halides, those stronger than anhydrous aluminum chloride (the most commonly used Friedel-Crafts acid) are considered super Lewis acids. These superacidic Lewis acids include such higher-valence fluorides as antimony, arsenic, tantalum, niobium, and bismuth pentafluorides. Superacidity encompasses both very strong Bronsted and Lewis acids and their conjugate acid systems. 

Towards metallic oxides the behaviour of thionyl chloride is similar to that of sulphur monochloride, which is perhaps hardly surprising in view of the course of its thermal decomposition. The reaction is fairly general, the oxide being converted into the corresponding anhydrous chloride. From the action of the chloride on zinc oxide (at 150° C.), cadmium oxide (at 200° C.), arsenious oxide (up to 200° C.), antimony trioxide (at room temperature), bismuth trioxide (at 150° to 200° C.), ferric oxide (at 150° C.), magnesium oxide (at 150° to 200° C.), cupric oxide (at 200° C.) and cuprous oxide (at 200° C.), it may be concluded that the main reaction, assuming a bivalent metal, M, is as follows ... 

Arsenic triiodide also dissolves, the saturated solution at 15° C. having density 3-661. Other soluble halides are potassium bromide, anhydrous ferric and aluminium chlorides 6 and tetramethyl ammonium iodide but the iodides of rubidium, cadmium, manganese and cobalt, also mercuric and stannic iodides, and cobalt and stannic bromides, are insoluble or only very slightly soluble in arsenic tribromide. The liquid also dissolves phosphoryl bromide and, very slightly, ammonium thiocyanate. In the mixed solutions of halides, the components may react chemically (cf. p. 106), but such is not always the case for example, with antimony tribromide a continuous series of solid solutions is formed.7... 

Solution of antimony pentafluoride in anhydrous HF was found to be an efficient medium for alkylation reactions of fluoroolefins. Compounds, known to give stable carbocations in superacidic media are excellent alkylating agents. For example, f-butyl chloride (57) reacts with TFE, giving the corresponding alkane 58 ... 

In the process (Fig. 1), anhydrous hydrogen fluoride and carbon tetrachloride (or chloroform) are bubbled through molten antimony pentachloride catalyst in a steam-jacketed atmospheric pressure reactor at 65 to 95°C. The gaseous mixture of fluorocarbon and unreacted chlorocarbon is distilled to separate and recycle the chlorocarbon to the reaction. Waste hydrogen chloride is recycled by use of water absorption and the last traces of hydrogen chloride and chlorine are removed in a caustic scrubbing tower. 

The metal chlorides should be carefully purified before use. The iron(III) chloride is obtained from the commercial anhydrous material by heating for about an hour under refluxing thionyl chloride ( 10 mL per gram of iron-(III) chloride). The solvent is then removed by distillation. The aluminum trichloride is sublimed in vacuo at ca. 120° onto a cold water finger the antimony(V) chloride is freshly distilled (e.g., at 68°/14 torr) under dry nitrogen. 

Inorganic Chemical Manufacture Anhydrous aluminum cliloride Antimony pentnclUoride Antimony trichloride Arsenic cliloride Bismutli trichloride Clilorinated isocyanurates Clilorine trifluoride Ferric chloride Hydrochloric acid... 

The complete replacement of the chlorine atoms in (trichloromethyl)benzene by fluorine to give (trifluoromethyl)bcnzene is possible under mild conditions. This transformation can be achieved with a variety of reagents with anhydrous hydrogen fluoride the reagent of choice due to cost and the lack of side reactions. "Substituted (trichloromethyl)benzenes are successfully transformed into the corresponding (trifluoronicthyl)benzenes 1-3 by hydrogen fluoride in the presence of a catalytic amount of antimony(V) chloride.A procedure is given for the formation of 1-(dichloromethyl)-2-(trifluoromethyl)benzene (4). ... 

Anhydrous antimony (III) chloride is prepared by distilling the commercial product at atmospheric pressure. It may be kept for some time in wax-sealed or well-stoppered containers. The transfer and weighing are facilitated by melting the anhydrous material (m.p. 73.4°). 

The preparation of trimethylantimony diiodide is identical to that of trimethylantimony dichloride up to the point of the addition of chlorine. Instead of a gas inlet tube, an addition funnel is mounted on the flask containing the ice-cold distillate of ethyl ether and trimethylstibine. For a reaction carried out on the basis of 0.25 mol of anhydrous antimony(III) chloride, a solution of 63,5 g. (0.25 mol) of iodine in 400 ml. of ethyl ether is prepared. This solution is added dropwise to the cold distillate. Stirring is maintained and the addition is continued until the color of iodine persists. The precipitate of trimethylantimony diiodide is filtered off on a fritted Buchner fuimel and washed with ethyl ether. The jdeld of the crude product is 47.7 to 65.3 g. (45.0 to 61.8% of theoretical based upon antimony (III) chloride). The diiodide may be recrystallized from ethanol. Anal. Calcd. for (CH3) 3Sbl2 Sb, 28.95 C, 8.55 H, 2.16. Found Sb, 29.31 C, 8.16 H, 2.25. The checkers report that the foregoing syntheses are also satisfactory using one-half the amounts prescribed. 

Tungsten Hexafluoride, WFg, is obtained by the action of anhydrous hydrogen fluoride upon tungsten hexaehloride in platinum vessels, or by the interaction of antimony peiitafluoride with the hexa-chloride. It is a solid at low temjreratures just above 0° C. it sublimes to a heavy gas which fumes in moist air it reacts with water with production of tungstic acid. It attacks both glass and mercury by alkalies it is decomposed, and with alkali fluorides it forms double salts. 

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