Vapor halides

Decomposition of halide vapors. Readily vaporized halides, especially the chlorides of elements such as Al, Si, Ti, Zr, Sn and so forth, may also be converted to oxides in the gas phase. This may be done in either of the following ways ... 

Mote stable catalysts ate obtained by using fluorinated graphite or fluorinated alumina as backbones, and Lewis acid halides, such as SbF, TaF, and NbF, which have a relatively low vapor pressure. These Lewis acids ate attached to the fluorinated soHd supports through fluorine bridging. They show high reactivity in Friedel-Crafts type reactions including the isomerization of straight-chain alkanes such as / -hexane. 

Halides. Indium trichloride [10025-83-8] InCl, can be made by heating indium in excess chlorine or by chlorinating lower chlorides. It is a white crystalline soHd, deUquescent, soluble in water, and has a high vapor pressure. InCl forms chloroindates, double salts with chlorides of alkaLi metals, and organic bases. 

Lithium Iodide. Lithium iodide [10377-51 -2/, Lil, is the most difficult lithium halide to prepare and has few appHcations. Aqueous solutions of the salt can be prepared by carehil neutralization of hydroiodic acid with lithium carbonate or lithium hydroxide. Concentration of the aqueous solution leads successively to the trihydrate [7790-22-9] dihydrate [17023-25-5] and monohydrate [17023-24 ] which melt congmendy at 75, 79, and 130°C, respectively. The anhydrous salt can be obtained by carehil removal of water under vacuum, but because of the strong tendency to oxidize and eliminate iodine which occurs on heating the salt ia air, it is often prepared from reactions of lithium metal or lithium hydride with iodine ia organic solvents. The salt is extremely soluble ia water (62.6 wt % at 25°C) (59) and the solutions have extremely low vapor pressures (60). Lithium iodide is used as an electrolyte ia selected lithium battery appHcations, where it is formed in situ from reaction of lithium metal with iodine. It can also be a component of low melting molten salts and as a catalyst ia aldol condensations. 

Nitrogen and sodium do not react at any temperature under ordinary circumstances, but are reported to form the nitride or azide under the influence of an electric discharge (14,35). Sodium siHcide, NaSi, has been synthesized from the elements (36,37). When heated together, sodium and phosphoms form sodium phosphide, but in the presence of air with ignition sodium phosphate is formed. Sulfur, selenium, and tellurium form the sulfide, selenide, and teUuride, respectively. In vapor phase, sodium forms haHdes with all halogens (14). At room temperature, chlorine and bromine react rapidly with thin films of sodium (38), whereas fluorine and sodium ignite. Molten sodium ignites in chlorine and bums to sodium chloride (see Sodium COMPOUNDS, SODIUM HALIDES). 

Phosphorus exists as white and red phosphorus. The former allotrope may be preserved in the dark at low temperatures but otherwise reverts to the more stable red form. The white form is a waxy, translucent, crystalline, highly-toxic solid subliming at room temperature and inflaming in air at 35°C, so it is handled under water. The red form is a reddish violet crystalline solid which vaporizes if heated at atmospheric pressure and condenses to give white phosphorus. The red form ignites in air at 260°C. Both are insoluble in water, and white phosphorus can be stored beneath it. Phosphorus forms a host of compounds such as phosphine, tri- and penta-halides, tri-, tetra- and penta-oxides, oxyacids including hypophosphorous, orthophosphorous and orthophosphoric acids. 

Organic Chlorides/Halides — Several organic compounds also are hydrolyzed (or react with water) to produce corrosive materials. Notable inclusions among these compounds are acetic anhydride ([CH3COJ2O), and acetyl chloride (CH3COCI), both of which produce acetic acid upon reaction with water. Both acetic anhydride and acetyl chloride are corrosive in addition, mixtures of the vapors of acetic anhydride and acetic acid are flammable in air, and acetyl chloride itself is flammable. 

Codeposition of silver vapor with perfluoroalkyl iodides at -196 °C provides an alternative route to nonsolvated primary perfluoroalkylsilvers [272] Phosphine complexes of trifluaromethylsilver are formed from the reaction of trimethyl-phosphme, silver acetate, and bis(trifluoromethyl)cadmium glyme [755] The per-fluoroalkylsilver compounds react with halogens [270], carbon dioxide [274], allyl halides [270, 274], mineral acids and water [275], and nitrosyl chloride [276] to give the expected products Oxidation with dioxygen gives ketones [270] or acyl halides [270] Sulfur reacts via insertion of sulfur into the carbon-silver bond [270] (equation 188)... 

Perfluoroalkyl or -aryl halides undergo oxidative addition with metal vapors to form nonsolvated fluonnated organometallic halides and this topic has been die subject of a review [289] Pentafluorophenyl halides react with Rieke nickel, cobalt, and iron to give bispentafluorophenylmetal compounds, which can be isolated in good yields as liquid complexes [290] Rieke nickel can also be used to promote the reaction of pentafluorophenyl halides with acid halides [297] (equation 193)... 

The only parts of Fig. 5 which can meaningfully be described as solubility in a compressed gas are WX and XV. However, a very different situation arises if the saturated vapor pressure curve cuts the critical curve (M—N of Fig. 3). Figure 4 shows that this does not happen for the three sodium halides. The complete course of the critical curve is not known, but enough is known in the case of the sodium chloride system51 75 for it to be clear that it rises well above the maximum of the saturated vapor pressure curve. However, it is cut by the vapor pressure curves of less soluble salts such as sodium carbonate and sodium sulphate.40 87 The (p, T) projection of a system of the type water + sodium chloride is... 

Properties of some halides useful in CVD are listed in Table 3.3. As can be seen, some of these halides are gaseous or liquid at room temperature and, as such, are easily transported in the reaction chamber. The solid halides, however, must be heated to produce sufficient vapor. This sometimes presents a problem which can be bypassed by generating the halide in situ (see Ch. 5). Most halides are available commercially. 

The hydrogen reduction of the metal halides, described in Sec. 1.2, is generally the favored reaction for metal deposition but is not suitable for the platinum-group metals since the volatilization and decomposition temperatures of their halides are too close to provide efficient vapor transport. 1 1 For that reason, the decomposition of the carbonyl halide is preferred. The exception is palladium which is much more readily deposited by hydrogen reduction than by the carbonyl-halide decomposition. 

Solids. Reactants which are solid at room temperature present more of a problem since they must be heated to their vaporization temperature, which in some cases may be relatively high. This is particularly true with metal halides as shown in Ch. 3, Table 3.3. It is often preferable to generate the reactant in situ. An example is the deposi-... 

CVD Reactions. The rhodium halides, like those of the other platinum group metal s, are volatile with a decomposition pointtoo close to the vaporization point to make them usable for CVD transport. The metal is commonly produced by the decomposition of metallo-organic precur-... 

Ottosson, M., Harsta, A., and Carlsson, J., Thermodynamic Analysis of Chemical Vapor Deposition of YBa2Cu307 from Different Halide Precursors, Prac. 11th. Int. Conf. on CVD, (K. Spear and G. Cullen, eds ), pp. 180-187, Electrochem. Soc., Pennington, NJ 08534 (1990)... 

Although belonging to a slightly different class of reactions, the reaction of trifluoromethyl radicals with sulfur vapor has been shown to provide a route to trifluoromethyl polysulfide compounds (20). Instead of using sulfur halides, which undoubtedly would also give positive results, elemental sulfur (Ss) was vaporized and dissociated into atomic and polyatomic sulfur species. 

Growth of single crystals. Crystals of the aluminum selenide halides (needles, maximum length 15 mm) were grown by vapor transport in sealed ampoules between two temperatures (380 and 320°C for Al-SeCl, and 350 and 300°C for AlSeBr and AlSel) over a period of two months. A large excess of the halogenide was used (266). 

Dihydro-l,2-azaborolyl sandwich complexes, available by metal-vapor synthesis ( 6.5.3.3), can be prepared in a greater variety by reaction of metal halides with azaborolyl anions, e.g. " ° ... 

At 570 K Zn metal is involatile, but at this T it sublimes into a vapor of Zn dichloride. The sublimate analyzes as ca. ZnCI. With similar experiments involving the vapors of ZnBrj and Znl2, Zn metal also sublimes, but analysis of the sublimates shows only ca. 20% of ZnBr from Zn + ZnBrj and 10% of Znl from Zn + Znl2. The monohalides may form at 570 K, but they disproportionate on cooling, in agreement with the known formation of halides ZnX at high T. 

The vapor above mixtures of Cd and CdCl2 contains Cd(I) as CdCl. Solutions of Cd in anhyd Cd(II) salts arc deep red-black and diamagnetic, which implies an absence of Cd ions. At 600°C the solubility of Cd in the molten halides drops from 18 and 14 mol% for CdCl2 and CdBr2, respectively, to 1.5 mol% for Cdl2. The equilibrium ... 

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