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 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 1% 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 and ), 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),