Electrolysis separation

In the case of molten salts, the functional electrolytes are generally oxides or halides. As examples of the use of oxides, mention may be made of the electrowinning processes for aluminum, tantalum, molybdenum, tungsten, and some of the rare earth metals. The appropriate oxides, dissolved in halide melts, act as the sources of the respective metals intended to be deposited cathodically. Halides are used as functional electrolytes for almost all other metals. In principle, all halides can be used, but in practice only fluorides and chlorides are used. Bromides and iodides are thermally unstable and are relatively expensive. Fluorides are ideally suited because of their stability and low volatility, their drawbacks pertain to the difficulty in obtaining them in forms free from oxygenated ions, and to their poor solubility in water. It is a truism that aqueous solubility makes the post-electrolysis separation of the electrodeposit from the electrolyte easy because the electrolyte can be leached away. The drawback associated with fluorides due to their poor solubility can, to a large extent, be overcome by using double fluorides instead of simple fluorides. Chlorides are widely used in electrodeposition because they are readily available in a pure form and... 

The separation of substances by membranes is essential in industry and human life. Of the various separation membranes, the ion exchange membrane is one of the most advanced and is widely used in various industrial fields electrodialysis, diffusion dialysis, separator and solid polymer electrolyte in electrolysis, separator and solid polymer electrolyte of various batteries, sensing materials, medical use, a part of analytical chemistry, etc. 

This electrolysis of molten NaCl is used commercially to obtain sodium metal from sodium chloride. A Downs cell is a commercial electrochemical cell used to obtain sodium metal by the electrolysis of molten sodium chloride (Figure 20.20). The cell is constructed to keep the products of the electrolysis separate, because they would otherwise react. Calcium chloride is added to the sodium chloride to lower the melting point from 801°C for NaCl to about 580°C for the mixture. (Remember that the melting point, or freezing point, of a substance is lowered by the addition of a solute.) You obtain the ceU reaction by adding the half-reactions. 

Although isotopes have similar chemical properties, their slight difference in mass causes slight differences in physical properties. Use of this is made in isotopic separation pro cesses using techniques such as fractional distillation, exchange reactions, diffusion, electrolysis and electromagnetic methods. 

Sodium hydroxide is manufactured by electrolysis of concentrated aqueous sodium chloride the other product of the electrolysis, chlorine, is equally important and hence separation of anode and cathode products is necessary. This is achieved either by a diaphragm (for example in the Hooker electrolytic cell) or by using a mercury cathode which takes up the sodium formed at the cathode as an amalgam (the Kellner-Solvay ceW). The amalgam, after removal from the electrolyte cell, is treated with water to give sodium hydroxide and mercury. The mercury cell is more costly to operate but gives a purer product. 

On a large scale, hydrogen peroxide is produced by the electrolysis of ammonium hydrogensulphate, using a platinum anode and a lead cathode separated by a diaphragm. The essential process occurring is ... 

Electrolysis, under similar conditions, of a mixture of two carboxylic acids RCOOH and R COOH leads, in addition to normal coupling products R—R and R —R, to cross coupling R—R. If a mixture of a saturated carboxylic acid and a half ester of an ato-dicarboxylic acid is electrolysed, there are three main products, viz., a hydrocarbon (I), a mono-ester (II), and a di-ester (HI) and these are readily separable by distillation. Some unsaturated ester (IV) is often present in small quantity. 

Air separation plants produce about 99% of the gas, while electrolysis plants produce about 1%. 

Separation of tantalum from niobium requires several complicated steps. Several methods are used to commercially produce the element, including electrolysis of molten potassium fluorotantalate, reduction of potassium fluorotantalate with sodium, or reacting tantalum carbide with tantalum oxide. Twenty five isotopes of tantalum are known to exist. Natural tantalum contains two isotopes. 

United States, LaSalle, IH. 1918 continuous Hquid-phase oxidation (since ca 1961) K MnO separation from Hquid phase is without prior dilution continuous electrolysis of filtered electrolyte in bipolar ceUs Monel anodes, mild steel cathodes, vacuum crystallization 14,000 ... 

Other Metals. AH the sodium metal produced comes from electrolysis of sodium chloride melts in Downs ceUs. The ceU consists of a cylindrical steel cathode separated from the graphite anode by a perforated steel diaphragm. Lithium is also produced by electrolysis of the chloride in a process similar to that used for sodium. The other alkaH and alkaHne-earth metals can be electrowon from molten chlorides, but thermochemical reduction is preferred commercially. The rare earths can also be electrowon but only the mixture known as mischmetal is prepared in tonnage quantity by electrochemical means. In addition, beryIHum and boron are produced by electrolysis on a commercial scale in the order of a few hundred t/yr. Processes have been developed for electrowinning titanium, tantalum, and niobium from molten salts. These metals, however, are obtained as a powdery deposit which is not easily separated from the electrolyte so that further purification is required. 

The matte can be treated in different ways, depending on the copper content and on the desired product. In some cases, the copper content of the Bessemer matte is low enough to allow the material to be cast directly into sulfide anodes for electrolytic refining. Usually it is necessary first to separate the nickel and copper sulfides. The copper—nickel matte is cooled slowly for ca 4 d to faciUtate grain growth of mineral crystals of copper sulfide, nickel—sulfide, and a nickel—copper alloy. This matte is pulverized, the nickel and copper sulfides isolated by flotation, and the alloy extracted magnetically and refined electrolyticaHy. The nickel sulfide is cast into anodes for electrolysis or, more commonly, is roasted to nickel oxide and further reduced to metal for refining by electrolysis or by the carbonyl method. Alternatively, the nickel sulfide may be roasted to provide a nickel oxide sinter that is suitable for direct use by the steel industry. 

Tetrapotassium peroxodiphosphate is produced by electrolysis of a solution containing dipotassium phosphate and potassium fluoride (52). Alkalinity favors the formation of the P20 g anion, whereas the PO anion is produced in larger yields in acidic solution. It is therefore possible to obtain an 80% yield of K4P20g by choosing the proper conditions. The tetrapotassium peroxodiphosphate can be crysta11i2ed from solution by evaporation of water to form a slurry. The crystals can be separated from the slurry and dried. The material is noncorrosive and cannot be catalyticaHy decomposed by iron ions. 

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