Electrolysis specials

Measurement of the conductivity can be carried out to high precision with specially designed cells. In practice, tiiese cells are calibrated by first measuring the conductance of an accurately known standard, and then introducing the sample under study. Conductances are usually measured at about 1 kHz AC rather than with DC voltages in order to avoid complications arismg from electrolysis at anode and cathode [8]. 

Fluorine cannot be prepared directly by chemical methods. It is prepared in the laboratory and on an industrial scale by electrolysis. Two methods are employed (a) using fused potassium hydrogen-fluoride, KHFj, ill a cell heated electrically to 520-570 K or (b) using fused electrolyte, of composition KF HF = 1 2, in a cell at 340-370 K which can be electrically or steam heated. Moissan, who first isolated fluorine in 1886, used a method very similar to (b) and it is this process which is commonly used in the laboratory and on an industrial scale today. There have been many cell designs but the cell is usually made from steel, or a copper-nickel alloy ( Monel metal). Steel or copper cathodes and specially made amorphous carbon anodes (to minimise attack by fluorine) are used. Hydrogen is formed at the cathode and fluorine at the anode, and the hydrogen fluoride content of the fused electrolyte is maintained by passing in... 

Fluorocarbons are made commercially also by the electrolysis of hydrocarbons in anhydrous hydrogen fluoride (Simons process) (14). Nickel anodes and nickel or steel cathodes are used. Special porous anodes improve the yields. This method is limited to starting materials that are appreciably soluble in hydrogen fluoride, and is most useflil for manufacturing perfluoroalkyl carboxyflc and sulfonic acids, and tertiary amines. For volatile materials with tittle solubility in hydrofluoric acid, a complementary method that uses porous carbon anodes and HF 2KF electrolyte (Phillips process) is useflil (14). 

Hydrogen produced by the electrolysis of water is used in special circumstances only where electric power is plentiful, inexpensive, and light hydrocarbons are not available. 

Chlorine gas is usually used, but electrolysis of alkaline salt solutions in which chlorine is generated in situ is also possible and may become more important in the future. The final pH of solutions to be sold or stored is always adjusted above 11 to maximize stabiUty. The salt is usually not removed. However, when the starting solution contains more than 20.5% sodium hydroxide some salt precipitates as it is formed. This precipitate is removed by filtration to make 12—15% NaOCl solutions with about one-half of the normal amount of salt. Small amounts of such solutions are sold for special purposes. Solutions with practically no salt can be made by reaction of high purity hypochlorous acid with metal hydroxides. 

Many related processes use charged membranes and/or EMF. Electrodialytic water dissociation (water splitting), diffusion dialysis, Donnan dialysis, and electrolysis are related processes. Electrowsis (chlorine-caustic) is a process of enormous importance much of which is processed through very special membranes. 

Industrially, it is manufactured either by fractional distillation of air, or by electrolysis of sodium hydroxide and it is distributed as a non-liquefied gas in pressurized black cylinders at ca 2200 psig at 21°C. Since it is non-corrosive no special materials of construction are required. 

The quantitative execution of chemical reactions is the basis of the traditional or classical methods of chemical analysis gravimetry, titrimetry and volumetry. In gravimetric analysis the substance being determined is converted into an insoluble precipitate which is collected and weighed, or in the special case of electrogravimetry electrolysis is carried out and the material deposited on one of the electrodes is weighed. 

The electrodes are made of platinum gauze as the open construction assists the circulation of the solution. It is possible to use one of the electrodes as stirrer for the solution, but special arrangements must then be made for connection of the electrolysis current to this electrode, and an independent glass-paddle stirrer or a magnetic stirrer offer a simple altemative.Typical electrodes are the Fischer type depicted in Fig. 12.4 a glass tube is slid into... 

Electrolysis Highly conductive (both nickel Requires specialized equipment/... 

At this point, special mention37 should be made of the behaviour of highly conjugated ethylenic sulphones in weakly acidic media. For example, in the case when R1 =Ph (Z isomer), a fairly stable anion radical was obtained in dry DMF. However, either in aprotic (consecutive two one-electron transfer) or in protic media (ECE process, occurrence of the protonation step on anion radical), C—S bond cleavage is observed. The formation of the corresponding olefins by C—S bond cleavage may occur in high yield, and is nearly quantitative when R1 = H and R2 = Ph for an electrolysis conducted in... 

The formation of new nuclei and of a fine-crystalline deposit will also be promoted when a high concentration of the metal ions undergoing discharge is maintained in the solution layer next to the electrode. Therefore, concentration polarization will have effects opposite those of activation polarization. Rather highly concentrated electrolyte solutions, vigorous stirring, and other means are employed to reduce concentration polarization. Sometimes, special electrolysis modes are employed for the same purposes currents that are intermittent, reversed (i.e., with periodic inverted, anodic pulses), or asymmetric (an ac component superimposed on the dc). 

Electrochemical reactors (cells, tanks) are used for the practical realization of electrolysis or the electrochemical generation of electrical energy. In developing such reactors one must take into account the purpose of the reactor as well as the special features of the reactions employed in it. Most common is the classical reactor type with plane-parallel electrodes in which positive and negative electrodes alternate and all electrodes having the same polarity are connected in parallel. Reactors in which the electrodes are concentric cylinders and convection of the liquid electrolyte can be realized by rotation of one of the electrodes are less common. In batteries, occasionally the electrodes are in the form of two long ribbons with a separator in between which are wound up as a double spiral. 

In the general introduction of this book, we promised to pay special attention to the electrolysis in non-aqueous media in view of its growing importance as a result of the fact that in comparison with aqueous media it extends the electro-analytical possibilities considerably for the following reasons ... 

Columbium (also known as niobium) and tantalum metals are produced from purified salts, which are prepared from ore concentrates and slags resulting from foreign tin production. The concentrates and slags are leached with hydrofluoric acid to dissolve the metal salts. Solvent extraction or ion exchange is used to purify the columbium and tantalum. The salts of these metals are then reduced by means of one of several techniques, including aluminothermic reduction, sodium reduction, carbon reduction, and electrolysis.19-21 Owing to the reactivity of these metals, special techniques are used to purify and work the metal produced. 

The special requirements of the indigo dyeing of cotton warp yarns for denim are capable of being met by indirect electrolysis systems [241]. Examples of four suitable redox systems are shown in Table 12.37. Uniform build-up of depth was observed with each successive step, the results being at least equal to those from the conventional dithionite-based process. Apparendy these processes are amenable to scaling up to bulk production levels [241]. 

Next, some special methods for preparing organotinhalides are presented. 1,2-Dichlorotetraalkyldistannanes ClR2SnSnR2Cl (R = Me, Et, Bu) have been prepared by the electrolysis of acetonitrile solutions of the appropriate dialkyltin dichloride using... 

Electrochemical cofactor reduction can be achieved by direct reduction of the cofactor at the electrode surface, or indirectly by using a mediator molecule to shuttle electrons between the electrode and the cofactor. For details on the direct approach the reader is referred elsewhere [31, 32], since here no transition-metal complexes are involved. One point to be considered in the direct approach is the issue of selectivity. Whereas direct cofactor oxidation can be successfully achieved, special care must be taken to produce enzyme active reduced cofactors by direct electrolysis. 

SNPE in France has developed a new technology specially adapted to electrolysis with consumable electrodes. SNPE has been operating for a few years a multi-purpose lOt/year pilot unit located in ISOCHEM s plant in Pithiviers (France), Fig. 14. 

Viton hoses were instead selected for the feed brine to the electrolysis cells. These are chemically resistant to chlorine-containing brine. There are several specifications of Viton hose available. For working with brine in an electrolysis environment, special attention had to be given to rupture resistance of the hoses with respect to operator safety. 

Schuster had an informed interest in chemical problems. He taught a course in chemical physics that was attended by chemistry honors students. Topics included spectrum analysis, saccharimetry, and electrolysis. In 1894, he organized a fortnightly "physical colloquium" for second- and third-year physics students joined by some chemistry honors students. He closely followed the chemical research of his colleagues, Roscoe and Harold Baily Dixon. In interpreting results in his special field of spectroscopy and in electrochemistry, Schuster visualized an "ionic" mechanism of electrical conduction in liquids and gases.60... 

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