Electrolysis calcium

The existence of the hydride ion is shown by electrolysis of the fused salt when hydrogen is evolved at the anode. If calcium hydride is dissolved in another fused salt as solvent, the amount of hydrogen evolved at the anode on electrolysis is 1 g for each Faraday of current (mole of electrons) passed, as required by the laws of electrolysis. 

The method of obtaining aluminum metal by the electrolysis of alumina dissolved in cryolite was discovered in 1886 by Hall in the U.S. and at about the same time by Heroult in France. Cryolite, a natural ore found in Greenland, is no longer widely used in commercial production, but has been replaced by an artificial mixture of sodium, aluminum, and calcium fluorides. 

The metal has a silvery color, is rather hard, and is prepared by electrolysis of the fused chloride to which calcium fluoride is added to lower the melting point. 

Metallic cerium is prepared by metahothermic reduction techniques, such as reducing cerous fluoride with calcium, or using electrolysis of molten cerous chloride or others processes. The metahothermic technique produces high-purity cerium. 

Several methods are available for producing thorium metal it can be obtained by reducing thorium oxide with calcium, by electrolysis of anhydrous thorium chloride in a fused mixture of sodium and potassium chlorides, by calcium reduction of thorium tetrachloride mixed with... 

Uranium can be prepared by reducing uranium halides with alkali or alkaline earth metals or by reducing uranium oxides by calcium, aluminum, or carbon at high temperatures. The metal can also be produced by electrolysis of KUF5 or UF4, dissolved in a molten mixture of CaCl2 and NaCl. High-purity uranium can be prepared by the thermal decomposition of uranium halides on a hot filament. 

Mercury layers plated onto the surface of analytical electrodes serve as Hquid metal coatings. These function as analytical sensors (qv) because sodium and other metals can be electroplated into the amalgam, then deplated and measured (see Electro analytical techniques). This is one of the few ways that sodium, potassium, calcium, and other active metals can be electroplated from aqueous solution. In one modification of this technique, a Hquid sample can be purified of trace metals by extended electrolysis in the presence of a mercury coating (35). 

The cell bath in early Downs cells (8,14) consisted of approximately 58 wt % calcium chloride and 42 wt % sodium chloride. This composition is a compromise between melting point and sodium content. Additional calcium chloride would further lower the melting point at the expense of depletion of sodium in the electrolysis 2one, with the resulting compHcations. With the above composition, the cells operate at 580—600°C, well below the temperature of highest sodium solubiUty in the salt bath. Calcium chloride causes problems because of the following equiUbrium reaction (56) ... 

Salt that is substantially free of sulfate and other impurities is the cell feed. This grade may be purchased from commercial salt suppHers or made on site by purification of cmde sea or rock salt. Dried calcium chloride or cell bath from dismanded cells is added to the bath periodically as needed to replenish calcium coproduced with the sodium. The heat required to maintain the bath ia the molten condition is suppHed by the electrolysis current. Other electrolyte compositions have been proposed ia which part or all of the calcium chloride is replaced by other salts (61—64). Such baths offer improved current efficiencies and production of cmde sodium containing relatively Htde calcium. 

Strontium [7440-24-6] Sr, is in Group 2 (IIA) of the Periodic Table, between calcium and barium. These three elements are called alkaline-earth metals because the chemical properties of the oxides fall between the hydroxides of alkaU metals, ie, sodium and potassium, and the oxides of earth metals, ie, magnesium, aluminum, and iron. Strontium was identified in the 1790s (1). The metal was first produced in 1808 in the form of a mercury amalgam. A few grams of the metal was produced in 1860—1861 by electrolysis of strontium chloride [10476-85-4]. 

Titanium Silicides. The titanium—silicon system includes Ti Si, Ti Si, TiSi, and TiSi (154). Physical properties are summarized in Table 18. Direct synthesis by heating the elements in vacuo or in a protective atmosphere is possible. In the latter case, it is convenient to use titanium hydride instead of titanium metal. Other preparative methods include high temperature electrolysis of molten salt baths containing titanium dioxide and alkalifluorosiUcate (155) reaction of TiCl, SiCl, and H2 at ca 1150°C, using appropriate reactant quantities for both TiSi and TiSi2 (156) and, for Ti Si, reaction between titanium dioxide and calcium siUcide at ca 1200°C, followed by dissolution of excess lime and calcium siUcate in acetic acid. 

Because of its high reactivity, production of barium by such processes as electrolysis of barium compound solution or high temperature carbon reduction is impossible. Electrolysis of an aqueous barium solution yields Ba(OH)2, whereas carbon reduction of an ore such as BaO produces barium carbide [50813-65-5] BaC2, which is analogous to calcium carbide (see Carbides). Attempts to produce barium by electrolysis of molten barium salts, usually BaCl25 met with only limited success (14), perhaps because of the solubiUty of Ba in BaCl2 (1 )-... 

The word calcium is derived from calx, the Latin word for lime. The Romans used large quantities of calcium oxide or lime as mortar in constmction (see Lime and limestone). Because calcium compounds are very stable, elemental calcium was not produced until 1808 when a mercury amalgam resulted from electrolysis of calcium chloride in the presence of a mercury cathode. However, attempts to isolate the pure metal by distilling the mercury were only marginally successful. 

Calcium metal was produced in 1855 by electrolysis of a mixture of calcium, strontium, and ammonium chlorides, but the product was highly contaminated with chlorides (1). By 1904 fairly large quantities of calcium were obtained by the electrolysis of molten calcium chloride held at a temperature above the melting point of the salt but below the melting point of calcium metal. An iron cathode just touched the surface of the bath and was raised slowly as the relatively chloride-free calcium solidified on the end. This process became the basis for commercial production of calcium metal until World War II. 

Electrolysis. Although in Western countries the aluminothermic process has now completely replaced the electrolytic method, electrolysis is beheved to be the method used for calcium production in the People s RepubHc of China and the Commonwealth of Independent States (CIS). This process likely involves the production of a calcium—copper alloy, which is then redistilled to give calcium metal. 

Brine Preparation. Rock salt and solar salt (see Chemicals frombrine) can be used for preparing sodium chloride solution for electrolysis. These salts contain Ca, Mg, and other impurities that must be removed prior to electrolysis. Otherwise these impurities are deposited on electrodes and increase the energy requirements. The raw brine can be treated by addition of sodium carbonate and hydroxide to reduce calcium and magnesium levels to below 10 ppm. If further reduction in hardness is required, an ion-exchange resin can be used. A typical brine specification for the Huron chlorate ceU design is given in Table 6. 

There have been a number of cell designs tested for this reaction. Undivided cells using sodium bromide electrolyte have been tried (see, for example. Ref. 29). These have had electrode shapes for in-ceU propylene absorption into the electrolyte. The chief advantages of the electrochemical route to propylene oxide are elimination of the need for chlorine and lime, as well as avoidance of calcium chloride disposal (see Calcium compounds, calcium CHLORIDE Lime and limestone). An indirect electrochemical approach meeting these same objectives employs the chlorine produced at the anode of a membrane cell for preparing the propylene chlorohydrin external to the electrolysis system. The caustic made at the cathode is used to convert the chlorohydrin to propylene oxide, reforming a NaCl solution which is recycled. Attractive economics are claimed for this combined chlor-alkali electrolysis and propylene oxide manufacture (135). 

Sodium metal is produced commercially on the kilotonne scale by the electrolysis of a fused eutectic mixture of 40% NaCl, 60% CaCh at 580°C in a Downs cell (introduced by du Pont, Niagara Falls, 1921). Metallic Na and Ca are liberated at the cylindrical steel cathode and rise through a cooled collecting pipe which allows the calcium to solidify and fall back into the melt. Chlorine liberated at the central graphite anode is collected in a nickel dome and subsequently purified. Potassium cannot be produced in this way because it is too soluble in the molten chloride to float on top of the cell for collection and because it vaporizes readily... 

Magnesium is reduced from a mixture of magnesium, calcium, and sodium chlorides. Electrolysis from aqueous solution is also possible zinc, copper, and manganese dissolved as sulfates in water can be reduced electrolytically from aqueous solution. 

Molten bath deposition The interchange reaction also takes place when the coating metal halide is dissolved in a fused salt. Alternatively, deposition may be by electrolysis. Another technique uses the coating metal dissolved in molten calcium ... 

The hydrogen and oxygen produced create a safety hazard. Beyond that, they can cause Pb, Pb02, and PbS04 to flake off the plates. In a modem maintenance-free battery, the lead plates are alloyed with small amounts of calcium, which inhibits the electrolysis reaction. 

WEB Calcium metal can be obtained by the direct electrolysis of molten CaCl2, at a voltage of 32 V. 

Oxides of very reactive metals such as calcium or aluminum are reduced by electrolysis. In the case of aluminum, bauxite ore, AI2O3, is used. 

The true alkaline earth metals—calcium, strontium, and barium—are obtained either by electrolysis or by reduction with aluminum in a version of the thermite process (see Fig. 6.8) ... 

C19-0116. Calcium metal is obtained by the direct electrolysis of molten CaCl2. If a metallurgical electrolysis apparatus operates at 27.6 A and 1.2 V, what mass of calcium metal will it produce in 24 hours of operation ... 

In general, the electrolysis of a molten salt at inert electrodes produces the metal at the cathode, e.g., calcium from calcium chloride (melting point 774 °C). The anion is often a halide ion which, on discharge, yields the halogen, e.g., chlorine from calcium chloride. 

A number of electrolytic processes are used for the industrial production of metals. Some metals such as zinc, copper, manganese, gallium, chromium, etc. are electrowon from aqueous baths. Another common electrolytic process used is molten salt electrolysis. The most important application of molten salt electrolysis till now has been in the electrowinning of metals. Today aluminum, magnesium, lithium, sodium, calcium, boron, cerium, tantalum, and mischmetal are produced in tonnage quantities by molten salt electrolysis. As a representative example, the electrowinning process for aluminum is taken up. 

The electrolyte is made by in situ chlorination of vanadium to vanadium dichloride in a molten salt bath. Higher valent chlorides are difficult to retain in the bath and thus are not preferred. The molten bath, which is formed by sodium chloride or an equimolar mixture of potassium chloride-sodium chloride or of potassium chloride-lithium chloride or of sodium chloride-calcium chloride, is contained in a graphite crucible. The crucible also serves as an anode. Electrolysis is conducted at a temperature about 50 °C above the melting point of the salt bath, using an iron or a molybdenum cathode and a cathode current density of 25 to 75 A dnT2. The overall electrochemical deposition reaction involves the formation and the discharge of the divalent ionic species, V2+ ... 

Sodium chloride is found in salt beds, salt brines, and sea water throughout the world, and it is also mined is some locations. Consequently, sodium chloride is the source of numerous other sodium compounds. A large portion of the sodium chloride utilized is consumed in the production of sodium hydroxide (Eq. (11.23)). The production of sodium metal involves the electrolysis of the molten chloride, usually in the form of a eutectic mixture with calcium chloride. Sodium carbonate is an important material that is used in many ways such as making glass. It was formerly produced from NaCl by means of the Solvay process, in which the overall reaction is... 

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