Diaphragm, chloride electrolysis

Alkaline Chloride Electrolysis by the Diaphragm Process System Hooker, Uhde GmbH, Dortmund, Germany, 1985. 

Production. Today, potassium hydroxide is manufactured almost exclusively by potassium chloride electrolysis. The diaphragm, mercury, and membrane processes are all suitable for the production of potassium hydroxide, but the mercury process is preferred because it yields a chemically pure 50 % potassium hydroxide solution. 

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. 

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. 

Other commercial cells designed for the electrolysis of fused sodium chloride iaclude the Danneel-Lon2a cell and the Seward cell, both used before World War I. The former had no diaphragm and the sodium was confined to the cathode 2one by salt curtains (ceramic walls) the latter utili2ed the contact-electrode principle, where the cathode was immersed only a few millimeters ia the electrolyte. The Ciba cell was used over a longer period of time. 

Manufacture. Most chlorate is manufactured by the electrolysis of sodium chloride solution in electrochemical cells without diaphragms. Potassium chloride can be electroly2ed for the direct production of potassium chlorate (35,36), but because sodium chlorate is so much more soluble (see Fig. 2), the production of the sodium salt is generally preferred. Potassium chlorate may be obtained from the sodium chlorate by a metathesis reaction with potassium chloride (37). 

Recycle and cathodic reduction. The most elegant solution for the Diaphragm Electrolysis Plant (DEP) appears to be recycling of the hypochlorite solution and reduction of the chlorate and bromate on the cathode of the electrolysis cell - the hypochlorite solution is added to the feed brine of the cells and the chlorate and bromate are converted to chloride and bromide at the cathode. 

There are two electrolytic methods that are of major importance. One involves the electrolysis of fused sodium chloride using the Downs cell. This method currently is most prevalent. The Downs cell consists of a steel cell with brick lining containing the fused bath. The multiple electrode arrangement consists of four cylindrical graphite anodes that project upward from the hase of the cell. Each anode is surrounded hy a diaphragm of iron gauge and a steel cathode. 

Sodium hydroxide is manufactured together with chlorine by electrolysis of sodium chloride solution. Various types of electrolytic cells are used commercially. They include the mercury cell, the diaphragm cell, and the membrane cell. 

Since the products of the electrolysis of aqueous NaCl will react if they come in contact with each other, an essential feature of any chloralkali cell is separation of the anode reaction (where chloride ion is oxidized to chlorine) from the cathode reaction (in which OH- and H2 are the end products). The principal types of chloralkali cells currently in use are the diaphragm (or membrane) cell and the mercury cell. 

Preparation of Potassium Hydroxide by the Electrolysis of a Potassium Chloride Solution. Assemble an electrolyzer (see Fig. 130, p. 231). Place small cylinder 2 (8 cm in height and 4 cm in diameter) made from uncalcined clay into 0.5-litre thick-walled beaker 1. Pour a saturated potassium chloride solution into both vessels so that the level of the liquid in them will be the same. Add a few drops of phenolphthalein to the electrolyte. Use carbon rod 4 as the anode and thick iron wire 3 as the cathode. Secure both electrodes with corks in the electrolyzer lid. A d-c source at 10 V is needed for the experiment. After assembling the electrolyzer, switch on the current. What happens in the anode and cathode compartments Write the equations of the reactions. What substances can form in the absence of a diaphragm ... 

Chlorine is produced almost entirely by the electrolysis of aqueous solutions of alkali metal chlorides (Fig. 1), or from fused chlorides. Brine electrolysis produces chlorine at the anode and hydrogen along with the alkali hydroxide at the cathode. At present, three types dominate the industry the diaphragm cell, the membrane cell, and the mercury cell, and there are many variations of each type. 

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