ELECTROCHEMISTRY. The present article deals with processes that involve the electrolysis of aqueous solutions, whilst those in which electricity is used in the manufacture of chemical products at furnace temperatures are treated under Electrochemistry, although, strictly speaking, in some cases (e.g. calcium carbide and phosphorus manufacture) they are not truly metallurgical in character. For the theory and elemental laws of electro-deposition see Electrolysis; and for the construction and use of electric generators see Dynamo and Battery: Electric. The importance of the subject may be gauged by the fact that all the aluminium, magnesium, sodium, potassium, calcium carbide, carborundum and artificial graphite, now placed on the market, is made by electrical processes, and that the use of such processes for the refining of copper and silver, and in the manufacture of phosphorus, potassium chlorate and bleach, already pressing very heavily on the older non-electrical systems, is every year extending. The convenience also with which the energy of waterfalls can be converted into electric energy has led to the introduction of chemical industries into countries and districts where, owing to the absence of coal, they were previously unknown. Norway and Switzerland have become important producers of chemicals, and pastoral districts such as those in which Niagara or Foyers are situated manufacturing centres. In this way the development of the electrochemical industry is in a marked degree altering the distribution of trade throughout the world.
Electrolytic Refining of Metals.—The principle usually followed in the electrolytic refining of metals is to cast the impure metal into plates, which are exposed as anodes in a suitable solvent, commonly a salt of the metal under treatment. On passing a current of electricity, of which the volume and pressure are adjusted to the conditions of the electrolyte and electrodes, the anode slowly dissolves, leaving the insoluble impurities in the form of a sponge, if the proportion be considerable, but otherwise as a mud or slime which becomes detached from the anode surface and must be prevented from coming into contact with the cathode. The metal to be refined passing into solution is concurrently deposited at the cathode. Soluble impurities which are more electro-negative than the metal under treatment must, if present, be removed by a preliminary process, and the voltage and other conditions must be so selected that none of the more electro-positive metals are co-deposited with the metal to be refined. From these and other considerations it is obvious that (1) the electrolyte must be such as will freely dissolve the metal to be refined; (2) the electrolyte must be able to dissolve the major portion of the anode, otherwise the mass of insoluble matter on the outer layer will prevent access of electrolyte to the core, which will thus escape refining; (3) the electrolyte should, if possible, be incapable of dissolving metals more electro-negative than that to be refined; (4) the proportion of soluble electro-positive impurities must not be excessive, or these substances will accumulate too rapidly in the solution and necessitate its frequent purification; (5) the current density must be so adjusted to the strength of the solution and to other conditions that no relatively electro-positive metal is deposited, and that the cathode deposit is physically suitable for subsequent treatment; (6) the current density should be as high as is consistent with the production of a pure and sound deposit, without undue expense of voltage, so that the operation may be rapid and the “turnover” large; (7) the electrolyte should be as good a conductor of electricity as possible, and should not, ordinarily, be altered chemically by exposure to air; and (8) the use of porous partitions should be avoided, as they increase the resistance and usually require frequent renewal. For details of the practical methods see Gold; Silver; Copper and headings for other metals.
Electrolytic Manufacture of Chemical Products.—When an aqueous solution of the salt of an alkali metal is electrolysed, the metal reacts with the water, as is well known, forming caustic alkali, which dissolves in the solution, and hydrogen, which comes off as a gas. So early as 1851 a patent was taken out by Cooke for the production of caustic alkali without the use of a separate current, by immersing iron and copper plates on opposite sides of a porous (biscuit-ware) partition in a suitable cell, containing a solution of the salt to be electrolysed, at 21°-65° C. (70°-150° F.). The solution of the iron anode was intended to afford the necessary energy. In the same year another patent was granted to C. Watt for a similar process, involving the employment of an externally generated current. When an alkaline chloride, say sodium chloride, is electrolysed with one electrode immersed in a porous cell, while caustic soda is formed at the cathode, chlorine is deposited at the anode. If the latter be insoluble, the gas diffuses into the solution and, when this becomes saturated, escapes into the air. If, however, no porous division be used to prevent the intermingling by diffusion of the anode and cathode solutions, a complicated set of subsidiary reactions takes place. The chlorine reacts with the caustic soda, forming sodium hypochlorite, and this in turn, with an excess of chlorine and at higher temperatures, becomes for the most part converted into chlorate, whilst any simultaneous electrolysis of a hydroxide or water and a chloride (so that hydroxyl and chlorine are simultaneously liberated at the anode) also produces oxygen-chlorine compounds direct. At the same time, the diffusion of these compounds into contact with the cathode leads to a partial reduction to chloride, by the removal of combined oxygen by the instrumentality of the hydrogen there evolved. In proportion as the original chloride is thus reproduced, the efficiency of the process is of course diminished. It is obvious that, with suitable methods and apparatus, the electrolysis of alkaline chlorides may be made to yield chlorine, hypochlorites (bleaching liquors), chlorates or caustic alkali, but that great care must be exercised if any of these products is to be obtained pure and with economy. Many patents have been taken out in this branch of electrochemistry, but it is to be remarked that that granted to C. Watt traversed the whole of the ground. In his process a current was passed through a tank divided into two or three cells by porous partitions, hoods and tubes were arranged to carry off chlorine and hydrogen respectively, and the whole was heated to 120° F. by a steam jacket when caustic alkali was being made. Hypochlorites were made, at ordinary temperatures, and chlorates at higher temperatures, in a cell without a partition in which the cathode was placed horizontally immediately above the anode, to favour the mixing of the ascending chlorine with the descending caustic solution.
The relation between the composition of the electrolyte and the various conditions of current-density, temperature and the like has been studied by F. Oettel (Zeitschrift f. Elektrochem., 1894, vol. i. pp. 354 and 474) in connexion with the production of hypochlorites and chlorates in tanks without diaphragms, by C. Häussermann and W. Naschold (Chemiker Zeitung, 1894, vol. xviii. p. 857) for their production in cells with porous diaphragms, and by F. Haber and S. Grinberg (Zeitschrift f. anorgan. Chem., 1898, vol. xvi. pp. 198, 329, 438) in connexion with the electrolysis of hydrochloric acid. Oettel, using a 20% solution of potassium chloride, obtained the best yield of hypochlorite with a high current-density, but as soon as 114% of bleaching chlorine (as hypochlorite) was present, the formation of chlorate commenced. The yield was at best very low as compared with that theoretically possible. The best yield of chlorate was obtained when from 1 to 4% of caustic potash was present. With high current-density, heating the solution tended to increase the proportion of chlorate to hypochlorite, but as the proportion of water decomposed is then higher, the amount of chlorine produced must be less and the total chlorine efficiency lower. He also traced a connexion between alkalinity, temperature and current-density, and showed that these conditions should be mutually adjusted. With a current-density of 130 to 140 amperes per sq. ft., at 3 volts, passing between platinum electrodes, he attained to a current-efficiency of 52%, and each (British) electrical horse-power hour was equivalent to a production of 1378.5 grains of potassium chlorate. In other words, each pound of chlorate would require an expenditure of nearly 5.1 e.h.p. hours. One of the earliest of the more modern processes was that of E. Hermite, which consisted in the production of bleach-liquors by the electrolysis (according to the 1st edition of the 1884 patent) of magnesium or calcium chloride between platinum anodes carried in wooden frames, and zinc cathodes. The solution, containing hypochlorites and chlorates, was then applied to the bleaching of linen, paper-pulp or the like, the solution being used over and over again. Many modifications have been patented by Hermite, that of 1895 specifying the use of platinum gauze anodes, held in ebonite or other frames. Rotating zinc cathodes were used, with scrapers to prevent the accumulation of a layer of insoluble magnesium compounds, which would otherwise increase the electrical resistance beyond reasonable limits. The same inventor has patented the application of electrolysed chlorides to the purification of starch by the oxidation of less stable organic bodies, to the bleaching of oils, and to the purification of coal gas, spirit and other substances. His system for the disinfection of sewage and similar matter by the electrolysis of chlorides, or of sea-water, has been tried, but for the most part abandoned on the score of expense. Reference may be made to papers written in the early days of the process by C. F. Cross and E. J. Bevan (Journ. Soc. Chem. Industry, 1887, vol. vi. p. 170, and 1888, vol. vii. p. 292), and to later papers by P. Schoop (Zeitschrift f. Elektrochem., 1895, vol. ii. pp. 68, 88, 107, 209, 289).
E. Kellner, who in 1886 patented the use of cathode (caustic soda) and anode (chlorine) liquors in the manufacture of cellulose from wood-fibre, and has since evolved many similar processes, has produced an apparatus that has been largely used. It consists of a stoneware tank with a thin sheet of platinum-iridium alloy at either end forming the primary electrodes, and between them a number of glass plates reaching nearly to the bottom, each having a platinum gauze sheet on either side; the two sheets belonging to each plate are in metallic connexion, but insulated from all the others, and form intermediary or bi-polar electrodes. A 10-12% solution of sodium chloride is caused to flow upwards through the apparatus and to overflow into troughs, by which it is conveyed (if necessary through a cooling apparatus) back to the circulating pump. Such a plant has been reported as giving 0.229 gallon of a liquor containing 1% of available chlorine per kilowatt hour, or 0.171 gallon per e.h.p. hour. Kellner has also patented a “bleaching-block,” as he terms it, consisting of a frame carrying parallel plates similar in principle to those last described. The block is immersed in the solution to be bleached, and may be lifted in or out as required. O. Knöfler and Gebauer have also a system of bi-polar electrodes, mounted in a frame in appearance resembling a filter-press.
Other Electrochemical Processes.—It is obvious that electrolytic iodine and bromine, and oxygen compounds of these elements, may be produced by methods similar to those applied to chlorides (see Alkali Manufacture and Chlorates), and Kellner and others have patented processes with this end in view. Hydrogen and oxygen may also be produced electrolytically as gases, and their respective reducing and oxidizing powers at the moment of deposition on the electrode are frequently used in the laboratory, and to some extent industrially, chiefly in the field of organic chemistry. Similarly, the formation of organic halogen products may be effected by electrolytic chlorine, as, for example, in the production of chloral by the gradual introduction of alcohol into an anode cell in which the electrolyte is a strong solution of potassium chloride. Again, anode reactions, such as are observed in the electrolysis of the fatty acids, may be utilized, as, for example, when the radical CH3CO2—deposited at the anode in the electrolysis of acetic acid—is dissociated, two of the groups react to give one molecule of ethane, C2H6, and two of carbon dioxide. This, which has long been recognized as a class-reaction, is obviously capable of endless variation. Many electrolytic methods have been proposed for the purification of sugar; in some of them soluble anodes are used for a few minutes in weak alkaline solutions, so that the caustic alkali from the cathode reaction may precipitate chemically the hydroxide of the anode metal dissolved in the liquid, the precipitate carrying with it mechanically some of the impurities present, and thus clarifying the solution. In others the current is applied for a longer time to the original sugar-solution with insoluble (e.g. carbon) anodes. F. Peters has found that with these methods the best results are obtained when ozone is employed in addition to electrolytic oxygen. Use has been made of electrolysis in tanning operations, the current being passed through the tan-liquors containing the hides. The current, by endosmosis, favours the passage of the solution into the hide-substance, and at the same time appears to assist the chemical combinations there occurring; hence a great reduction in the time required for the completion of the process. Many patents have been taken out in this direction, one of the best known being that of Groth, experimented upon by S. Rideal and A. P. Trotter (Journ. Soc. Chem. Indust., 1891, vol. x. p. 425), who employed copper anodes, 4 sq. ft. in area, with current-densities of 0.375 to 1 (ranging in some cases to 7.5) ampere per sq. ft., the best results being obtained with the smaller current-densities. Electrochemical processes are often indirectly used, as for example in the Villon process (Elec. Rev., New York, 1899, vol. xxxv. p. 375) applied in Russia to the manufacture of alcohol, by a series of chemical reactions starting from the production of acetylene by the action of water upon calcium carbide. The production of ozone in small quantities during electrolysis, and by the so-called silent discharge, has long been known, and the Siemens induction tube has been developed for use industrially. The Siemens and Halske ozonizer, in form somewhat resembling the old laboratory instrument, is largely used in Germany; working with an alternating current transformed up to 6500 volts, it has been found to give 280 grains or more of ozone per e.h.p. hour. E. Andreoli (whose first British ozone patent was No. 17,426 of 1891) uses flat aluminium plates and points, and working with an alternating current of 3000 volts is said to have obtained 1440 grains per e.h.p. hour. Yarnold’s process, using corrugated glass plates coated on one side with gold or other metal leaf, is stated to have yielded as much as 2700 grains per e.h.p. hour. The ozone so prepared has numerous uses, as, for example, in bleaching oils, waxes, fabrics, &c., sterilizing drinking-water, maturing wines, cleansing foul beer-casks, oxidizing oil, and in the manufacture of vanillin.
For further information the following books, among others, may be consulted:—Haber, Grundriss der technischen Elektrochemie (München, 1898); Borchers and M‘Millan, Electric Smelting and Refining (London, 1904); E. D. Peters, Principles of Copper Smelting (New York, 1907); F. Peters, Angewandte Elektrochemie, vols. ii. and iii. (Leipzig, 1900); Gore, The Art of Electrolytic Separation of Metals (London, 1890); Blount, Practical Electro-Chemistry (London, 1906); G. Langbein, Vollständiges Handbuch der galvanischen Metall-Niederschläge (Leipzig, 1903), Eng. trans. by W. T. Brannt (1909); A. Watt, Electro-Plating and Electro-Refining of Metals (London, 1902); W. H. Wahl, Practical Guide to the Gold and Silver Electroplater, &c. (Philadelphia, 1883); Wilson, Stereotyping and Electrotyping (London); Lunge, Sulphuric Acid and Alkali, vol. iii. (London, 1909). Also papers in various technical periodicals. The industrial aspect is treated in a Gartside Report, Some Electro-Chemical Centres (Manchester, 1908), by J. N. Pring. (W. G. M.)