Halide liquids

All acetylenes with a terminal triple bond are instantaneously converted into the alkali acetylides by alkali amides in liquid ammonia. For many alkylations with primary alkyl halides liquid ammonia is the solvent of choice and the functionalization with oxirane can also be carried out in it with good results. Reactions of ROOM with sulfenyladng agents (R SSR1, R SON, R SSC R ) or elemental sulfur, selenium or tellurium are mostly very successful in ammonia, the same holds for the preparation of ROC1 from RC=CM and iodine. The results of couplings with carbonyl compounds are very variable. 

Figure 13.1 Schematic diagram showing various components of a CVD system (1 reactor 2 heating element 3 reaction tube 4 water-cooled end flanges 5 power controller 6 pressure indicator 7 temperature sensor 8,10,11. -precursor gas tanks, 9 metal halide (liquid) vaporizer 12 particulate trap 13 gas scrubber 14 flow meter 15 flow meter valves 16 gas tank regulators 17 substrate support 18 substrates).

The mercury electrode has been used by researches in melts up to about 250°C, especially for nitrate and chloroaluminate melts [82,83], Liquid lead (m.p. 327.5°C) is another liquid metal [84] used for molten halides. Liquid electrodes of bismuth (m.p. 271°C), indium (m.p. 157°C) and thallium (m.p. 303°C) have also been, used but to a limited extent [85],... 

PTC in liquid solid systems is often used for the synthesis and manufacturing of esters via the reaction of solid sodium or potassium salts of carboxylic acids with alkyl halides. Liquid-liquid systems are also applied for this purpose ... 

Sulphur monochloride, S2CI2, m.p. —80 C, b.p. I38"C. Yellow liquid hydrolysed by water to SO2, HCl and S. Lower halides S CIj (jt up to 5) are formed S2CI2 plus H2 at a hot surface with freezing of products. S2CI2 is used in the rubber industry as a solvent for S. 

When an element has more than one oxidation state the lower halides tend to be ionic whilst the higher ones are covalent—the anhydrous chlorides of lead are a good example, for whilst leadfll) chloride, PbCl2, is a white non-volatile solid, soluble in water without hydrolysis, leadflV) chloride, PbC, is a liquid at room temperature (p. 200) and is immediately hydrolysed. This change of bonding with oxidation state follows from the rules given on p.49... 

The V(IV) species are all d complexes, hence their colour. Besides the VO compounds, some halides VX4 are known, for example VCI4, a liquid with a tetrahedral, covalent molecule and properties similar to those of TiCl4, but coloured (red-brown). 

Metallic sodium. This metal is employed for the drying of ethers and of saturated and aromatic hydrocarbons. The bulk of the water should first be removed from the liquid or solution by a preliminary drying with anhydrous calcium chloride or magnesium sulphate. Sodium is most effective in the form of fine wire, which is forced directly into the liquid by means of a sodium press (see under Ether, Section II,47,i) a large surface is thus presented to the liquid. It cannot be used for any compound with which it reacts or which is affected by alkalis or is easily subject to reduction (due to the hydrogen evolved during the dehydration), viz., alcohols, acids, esters, organic halides, ketones, aldehydes, and some amines. 

In a 250 ml. separatory funnel place 25 g. of anhydrous feri.-butyl alcohol (b.p. 82-83°, m.p. 25°) (1) and 85 ml. of concentrated hydrochloric acid (2) and shake the mixture from time to time during 20 minutes. After each shaking, loosen the stopper to relieve any internal pressure. Allow the mixture to stand for a few minutes until the layers have separated sharply draw off and discard the lower acid layer. Wash the halide with 20 ml. of 5 per cent, sodium bicarbonate solution and then with 20 ml. of water. Dry the preparation with 5 g. of anhydrous calcium chloride or anhydrous calcium, sulphate. Decant the dried liquid through a funnel supporting a fluted Alter paper or a small plug of cotton wool into a 100 ml. distilling flask, add 2-3 chips of porous porcelain, and distil. Collect the fraction boiling at 49-51°. The yield of feri.-butyl chloride is 28 g. 

The liquid phosphorus oxychloride, b.p. 107°, is a by-product and is removed by fractional distillation under normal pressure. Unless the b.p. of the acid chloride differs very considerably (say, <] 100°) from that of the phosphorus oxychloride, the acyl halide is liable to contain traces of the latter. In such circumstances it is preferable to use thionyl chloride for the preparation of the acid chloride. 

Nitric acid, fuming Organic matter, nonmetals, most metals, ammonia, chlorosulfonic acid, chromium trioxide, cyanides, dichromates, hydrazines, hydrides, HCN, HI, hydrogen sulflde, sulfur dioxide, sulfur halides, sulfuric acid, flammable liquids and gases... 

Figure 12.1 The solubilities of liquid sodium in the liquid sodium halides...

Molten halides are liquid electrolytes in many instances, and their decomposition may be canned out in principle to produce the metal and halogen, usually in the gaseous state. The theoretical decomposition voltage, E°, is calculated from the Gibbs energy of formation tlrrough the equation... 

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