Other Metal Chlorides

Metal chlorides with only a small-scale production are boron trichloride, antimony chlorides, tantalum pentachloride, tungsten chlorides, vanadium chlorides. Their properties, manufacture and uses are discribed in [346]. 

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Sa.lts Salting out metal chlorides from aqueous solutions by the common ion effect upon addition of HCl is utilized in many practical apphcations. Typical data for ferrous chloride [13478-10-9] FeCl2, potassium chloride [7447-40-7] KCl, and NaCl are shown in Table 9. The properties of the FeCl2-HCL-H2 0 system are important to the steel-pickling industry (see Metal SURFACE TREATMENTS Steel). Other metal chlorides that are salted out by the addition of hydrogen chloride to aqueous solutions include those of magnesium, strontium, and barium. 

Substitution at the Carbon—Chlorine Bond. Vinyl chloride is generally considered inert to nucleophilic replacement compared to other alkyl halides. However, the chlorine atom can be exchanged under nucleophilic conditions in the presence of palladium [7440-05-3] Pd, and certain other metal chlorides and salts. Vinyl alcoholates, esters, and ethers can be readily produced from these reactions. 

Reaction of Ethyl Alcohol and Hydrochloric Acid. For many years this reaction was the only estabhshed technical process for ethyl chloride, but it was abandoned because of the high cost of ethyl alcohol [64-17-5] when petrochemicals became available. Zinc and other metallic chlorides have been used as catalysts and ethyl chloride is recovered by distillation (30,31). 

Other metal chlorides and salts can also be used lea ding to formation of numerous other metal dichloroisocyanurates (34). Other routes to SDCC iuclude reaction of a moistened powdered mixture of TCCA, CA, and NaHCO (35), reaction of cmde CA with NaOCl (36), and reaction of NaH2 with HOCl (37) or CI2O (38). 

Kitatani et al. found that tungsten(VI) chloride would catalyse the formation of a range of oxazoles from benzoyl(phenyl)diazomethane and nitriles (Scheme 17).<74TL1531, 77BCJ1647> The reaction with acetonitrile was studied with a range of other metal chlorides, but all proved less satisfactory than WCle. They attributed the catalytic nature of tungsten(Vl) chloride to both its Lewis acidity and the affinity of tungsten for carbenes. 

At this time we do not have a firm nnderstanding of how CrCl2 and VCI3 catalyze the double bond isomerization and why other metal chlorides are less effective. We propose that CrCh" or VCh" anion plays a role in hydride transfer, facilitating donble bond isomerization. CnCh is less effective and both lactic acid and pyruvaldehyde are formed. FeCh" and MnCh" anions are ineffective in the transformation and only pyruvaldehyde is formed. The fact that only a small amount of 1,3-dihydroxyacetone is formed is consistent with the NMR observation that the compounds exist as hemiacetal dimers in ionic hquids and not as monomers. Otherwise 1,3-dihydroxyacetone would be expected as a major product (16). 

Gallium(III) chloride also combines with other metal chlorides such as CaCls or CrCls to form mixed chlorides that have halogen bridge structures i.e., Cl4Ta(-Cl)2. Many such compounds are volatile. 

Ogawa HI, Shibahara T, Iwata H, et al. 1994. Genotoxic activities in vivo of cobaltous chloride and other metal chlorides as assayed in the Drosophila wing spot test. Mutat Res 320 133-140. 

Catalysts. It was shown by Friedel and Crafts that while aluminum chloride is a very active alkylation catalyst, other metal chlorides (ferric chloride, zinc chloride, etc.) are also effective. They also showed that other aluminum halides (aluminum... 

With respect to iron catalysts, iron(III) chloride is one of the most common catalysts known for electrophilic aromatic substitutions and has been widely used in the past. In genera], it is an inexpensive and eco-friendly reagent featuring a higher catalytic activity than other metal chlorides [5, 6]. 

Now that you have learned to make ferrous chloride, you can apply this new skill to making other metal chlorides. Let s try one more using a different metal anode, and then we will move onto something more advanced. 

Complexes of N6P6(NMe2)12 with other metal chlorides and nitrates have essentially similar structures as indicated by infrared and electronic spectroscopic data (98). Compounds N4P4Me8 and N5P5Me10(L ) react with molybdenum and tungsten hexacarbonyls... 

The boiling-point of the saturated solution in contact with excess of the salt is 113-71° C. at 760 mm. pressure,8 and the heat of solution is -4-5 Cal.9 At 25° C. 100 grams of ethyl alcohol dissolve 0-078 gram.10 The salt unites with free halogens, yielding various polyhalides,11 and also forms double chlorides with other metallic chlorides.12 It exhibits radioactivity.13... 

Ferrous chloride readily unites with other metallic chlorides to form double salts, a considerable variety of which is known. Those of formula M2FeCl4 recall the chlor-ruthenites, M2RuC14, already discussed.6 The best-known double salts are as follow —... 

Experiments similar to those described in Fig. 1, and titrations of Aryl2CH + MCl,T+]/MCl mixtures with NR4+C1 solutions have been performed to characterize the relative chloride affinities of other Lewis acids MCI, [40], It turned out, however, that the well-defined behavior of BCI3 could not be observed with other systems. The positions of all other metal chlorides in Scheme 7, therefore, have only qualitative character. Relatively small concentrations of SbCl5 and GaCl3 were sufficient to completely ionize (p-CICeHUhCHCl, the weakest chloride donor of this series. The values of these ionization constants could not be deter-... 

As described previously, flame s3mthesis reactions include the oxidation of silicon chloride to produce silica the oxidation of titanium chloride to produce titania and the oxidation of other metal chlorides (see Table 7.2 also). 

Other metal chlorides are sometimes added as trace gasses in this combustion process to alter the crystal phase and particle morpholep of the product... 

The first group of catalysts is just MoCls and WC16. These metal chlorides polymerize various monosubstituted acetylenes. Table 4 demonstrates that WC16 and MoCl5 are specifically effective for phenylacetylene polymerization among various transition metal chlorides. It is noted that NbCl5 and TaCl5 selectively cyclotrimerize phenylacetylene, and that other metal chlorides hardly induce any reactions. 

The process of ethane oxidative chlorination imposes heavy demands on the catalysts. The conventional salt supported catalysts are composed of Cu, K, Ca, Mn, Co, Fe, Mg, and other metal chlorides containing various additives these salts are precipitated on alumina, zeolites, silica gel, and other supports. Catalytic systems that represent solid solutions of iron cations in the lattice of the a-A Oa and a-Ct203 phases doped with cations, such as K, Ba, Ce, and Ag are also known [7]. 

Reaction R4 indicates the possible decomposition of the active (oxy)chloride into the oxide and chlorine by reaction with the activated oxygen. For CuCl this reaction does not occur in the temperature r on, where it is catalytically active (550-650 K). However, for other metal chlorides bulk oxidation occurs at relatively low t nperatures, evoi in the presence of soot, as was discussed previously. At these low temperatures transfo of activated oxygen to the carbon (soot) sur ce is not fiist enough to compensate for reaction R4. 

Many catalytic formulations have been proposed to enhance the-performance of cupric chloride, the only active phase developed to the industrial stage. Hence other metallic chlorides are combined with it (potassium, rare earths, etc.) to increase the selectivity of the reaction, reduce the volatility of the copper compounds, prolong catalyst life, etc. Various supports are also used, generally based on alumina, but also kieselguhr, sflico-aluminates and diatomaceous earths. 

Concerning BiCl3, this weak Lewis acid proved an unexpected catalyst in the Mukaiyama-cross aldol and -Michael reactions from enoxysilanes (ref. 28), because other metallic chlorides (TiCl4, A1C13, SnCl4...) and stronger Lewis acids, are required in stoichiometric proportion for these reactions (ref. 29). On the other hand, more recently, i has been shown that ... 

As electronic effects of additives have been claimed for the selective hydrogenation of a,p unsaturated aldehydes [9-14], the influence of metal salts was examined in the hydrogenation of acrolein with Co/silica-alumina catalysts. As shown in Table 2, a small amount of Fe (II or III) chloride added into the hydrogenation mixture exerted a favourable effect on the selectivity to allyl alcohol. TTie other metal chlorides examined were less effective on the catalyst performance. Therefore, not chloride anion but Fe cation seems to have positive effects on the hydrogenation of carbonyl group as illustrated by Richard et al.[12j. 

However, the reaction employing ArB(OH)2 can be induced by a wide range of catalysts thus, besides SbClj, other metal chlorides, such as TiCl4, AsClj, and, to a lesser extent, BiClj, AlClj, SnCl, MoClj, and CeClj, are active. 

A similar approach has been adopted in a number of other reaction systems. A common example is the use of supported melts of copper chloride (with possibly other metal chlorides incorporated to reduce volatility or provide a... 

Chlorine is produced not only by the electrolysis of sodium chloride solutions but also from HCl, KCl, and other metal chlorides, by both chemical and electrochemical methods. The amount of chlorine from alternative processes is about 5.9% of the total world production. In the United States, it was about 4.0% of the total in 2002 [1]. Most of this chlorine was from the electrolysis of KCl in mercury or membrane cells (Table 15.1) and from HCl. Only small amounts are produced by the electrolysis of other metal chlorides. 

Electrowinning of Other Metals. Magnesium, like aluminum, is a low-density metal and is also manufactured by electrolysis. The electrolysis of molten magnesium chloride (in the presence of other metal chlorides to lower the melting point) yields mj ne-sium at the cathode. The scale of ms nesium production is not as large as that of aluminum, amounting to several hundred thousand metric tons per year. Ms -nesium is used in aircraft alloys, flares, and chemical syntheses. 

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