Magnesium electrolytic reduction

Electrolytic Reduction. The largest manufacturers of magnesium use processes based on the electrolytic reduction of magnesium chloride... 

In 1808, Sir Humphry Davy reported the production of Mg in the form of an amalgam by electrolytic reduction of its oxide using a Hg cathode. In 1828, the Fr scientist A. Bussy fused Mg chloride with metallic K and became the first to produce free metallic Mg. Michael Faraday, in 1833, was the first to produce free metallic Mg by electrolysis, using Mg chloride. For many years, however, the metal remained a laboratory curiosity. In 1886, manuf of Mg was undertaken on a production scale in Ger, using electrolysis of fused Mg chloride. Until 1915, Ger remained the sole producer of Mg. However, when a scarcity of Mg arose in the USA as a result of the Brit blockade of Ger in 1915, and the price of Mg soared from 1.65 to 5.00 per lb, three producers initiated operations and thus started a Mg industry in the USA. Subsequently, additional companies attempted production of Mg, but by 1920 only two producers remained — The Dow Chemical Co (one of the original three producers) and. the American Magnesium Corn. In 1927. the latter ceased production, and Dow continued to be the sole domestic producer until 1941. The source of Mg chloride was brine pumped from deep wells. In 1941, Dow put a plant into operation at Freeport, Texas, obtaining Mg chloride from sea-... 

Metallic magnesium is produced by either chemical or electrolytic reduction of its compounds. In chemical reduction, first magnesium oxide is obtained from the decomposition of dolomite. Then ferrosilicon, an alloy of iron and silicon, is used to reduce the MgO at about 1200°C. At this temperature, the magnesium produced is immediately vaporized and carried away. The electrolytic method uses seawater as its principal raw material magnesium hydroxide is precipitated by adding slaked lime (Ca(OH)2, see Section 14.10), the precipitate is filtered off and treated with hydrochloric acid to produce magnesium chloride, and the dried molten salt is electrolyzed. 

Thermal magnesium, i.e., magnesium produced by the Pidgeon process earlier and by the magnefherm process at present, constitutes only 30% of the total magnesium production. The rest is produced electrolytically in which the leading examples are (i) the Dow electrolytic reduction process, and (ii) Norsk hydro process. 

Cyclohexanones are readily reduced to the hydrocarbon in a sulphuric acid electrolyte. Reduction of ketosteroids in dioxan - aqueous sulphuric acid at a lead cathode in a divided cell is a convenient process for converting the carbonyl group to methylene [84,85] and affords as good yields as the alternative non-electrocheniical processes. Menthone is reduced to the hydrocarbon under mild conditions at a mercury cathode when the electrolyte is either magnesium chloride or zinc perchlorate in ethanol [86]. 

Although many commercial processes have heen developed since the first electrolytic isolation of Mg metal hy Davy and Faraday, and Bussy, hy chemical reduction, the principles of the manufacturing processes have not changed. At present, the metal is most commonly manufactured by electrolytic reduction of molten magnesium chloride, in which chlorine is produced as a by-product. In chemical reduction processes, the metal is obtained by reduction of magnesium oxide, hydroxide, or chloride at elevated temperatures. 

Reduction of add solutions of vanadium pentoxide to the tetravalent state also takes place with bismuth amalgam 5 magnesium gives the trivalent salts of vanadium, while by using zinc, zinc coated with cadmium, electrolytically deposited cadmium, or sodium amalgam in the absence of air, divalent vanadium salts are obtained in solution.7 Vanadous salts and hypovanadous salts are, however, much more conveniently prepared by electrolytic reduction of acid solutions of vanadium pentoxide in an atmosphere of carbon dioxide.8... 

There are no chemical reducing agents strong enough to reduce compounds of the most active metals, so these metals are produced by electrolytic reduction (Section 18.12). Lithium, sodium, and magnesium, for example, are obtained by the electrolysis of their molten chlorides. Aluminum is manufactured by the electrolysis of purified AI2O3 in molten cryolite (NaaAlFg). 

The only practical method for the preparation of pinacol hydrate is the reduction of acetone and the procedure described above is a modification of that of Holleman.1 The more common reducing agents that have been used are magnesium amalgam,2 aluminum amalgam,3 sodium,4 and sodium amalgam.5 Electrolytic reduction has also been used.6 1 Rec. trav. chim. 25, 206 (1906). 

Electrolytic reduction of benzylic (18) and allylic halides (equation 17) in the presence of anhydrides affords the corresponding ketones in good yields. The electrolysis was conducted in an undivided cell using aluminum or magnesium anode and under constant-current conditions. Similarly, benzylic halides were reported to react with acid chlorides under controlled potential conditions, in acetonitrile or DMF as solvent as shown in equation 1841. 

Preparation of secondary (or tertiary) carbinols from pyridines and an aldehyde (or a ketone) in the presence of magnesium or aluminum and mercuric chloride is known in pyridine chemistry as the Emmert reaction. 7 70 For example, dimethyl-2-pyridylcarbinol is obtained in this way from pyridine and acetone. When a mixture of pyridine and acetone is subjected to an electrolytic reduction in dilute sulfuric acid at lead electrodes, a mixture of two main products results, namely, 2-(2-hydroxy-2-propyl)-3-piperideine and 4-(2-hydroxy-2-propyl)piperidine. Analogous compounds are obtained with the use of methyl ethyl ketone as the reactant. The mixed electrolytic reduction of 2-methylpyridine and acetone affords 2-(2-hydroxy-2-propyl)-6-methyl-3-piper ideine (74) and 2-methyl-4-(2-hydroxy-2-propyl)-piperidine.71... 

As a first approximation one can view metallation and electrolytic reduction as a single class of reactions differing only in the ease with which electrons are transferred to the substrate. Ordinarily mercury metal does not react with alkyl halides because of its high ionization potential of 240 kcal mol as compared with 124,176 and 216 kcal mol for lithium, magnesium and zinc, respectively. However, if one places a potential across mercury then it will readily react with alkyl halides in an electrolytic reaction. 

A somewhat similar cell design has been used in the equipment for electrolytic reductions in liquid ammonia for both static and circulating media in this case the center electrode is a sacrificial magnesium anode [54]. 

Vacuum reduction of oxides of the alkali and alkaline earth metals, has proved a very useful technique, of which the Pidgeon ferrosilicon process for reduction of magnesium (Bl) has been an outstanding example. Although this process is not currently competitive with electrolytic reduction, the cost differential is not so great that improved vacuum equipment and vacuum techniques could not swing the balance in favor of this process. 

Electrolytic reduction is suitable for very electropositive metals, such as sodium, magnesium, and aluminum. The process is usually carried out on the anhydrous molten oxide or halide of the metal ... 

In 1885 C. A. von Welsbach isolated two elements as oxides, praseodymium (the word meaning green twin ) and neodymium (meaning new twin ), from a mixture of lanthanide oxides called didymia. The oxides can be transformed to fluorides by reaction with HF at 700°C (1,292°F), or with NH4HF2 at 300°C (572°F). The hydrated fluorides are then dehydrated in vacuo in a current of HF gas. The metals praseodymium and neodymium are obtained via metallothermic reduction with calcium at approximately 1,450°C (2,642°F), or via electrolytic reduction of the melts. The metals can also be obtained from anhydrous chlorides, obtained via reaction of the oxides with ammonium chloride at 350°C (662 °F), which are then reduced with lithium-magnesium at approximately 100°C (212°F). 

Preparation. Uranium metal may be prepared by several methods the reduction of uranium oxides with carbon In an arc-melting furnace reduction of uranium oxides with magnesium, aluminum, calcium or calcium hydride the reduction of uranium halides with alkali or alkaline-earth metals electrolytic reduction of uranium halides and the themal decomposition of uranium Iodide. 

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