Electrolytic Mercury Cells

The ozone concentration in the atmosphere is only a few pphm. In certain chemical plants as in electrolytic mercury cell houses in the chloralkali industry, the ozone concentration is higher. Although the atmospheric ozone level is low, it reacts with rubber double bonds rapidly and causes cracking of rubber products. Especially when rubber is under stress (stretching and bending as in the case of flexible cell covers), the crack development is faster. Neoprene products resist thousands of parts per hundred million of ozone for hours without surface cracking. This nature of neoprene is quite suitable for cell house application in chlor-alkali industries. Natural rubber will crack within minutes when subjected to ozone concentration of only 50 pphm. 

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. 

Conversion of aqueous NaCl to Cl and NaOH is achieved in three types of electrolytic cells the diaphragm cell, the membrane cell, and the mercury cell. The distinguishing feature of these cells is the manner by which the electrolysis products are prevented from mixing with each other, thus ensuring generation of products having proper purity. 

Chloiine is pioduced at the anode in each of the three types of electrolytic cells. The cathodic reaction in diaphragm and membrane cells is the electrolysis of water to generate as indicated, whereas the cathodic reaction in mercury cells is the discharge of sodium ion, Na, to form dilute sodium amalgam. 

The catholyte from diaphragm cells typically analyzes as 9—12% NaOH and 14—16% NaCl. This ceUHquor is concentrated to 50% NaOH in a series of steps primarily involving three or four evaporators. Membrane cells, on the other hand, produce 30—35% NaOH which is evaporated in a single stage to produce 50% NaOH. Seventy percent caustic containing very Httie salt is made directiy in mercury cell production by reaction of the sodium amalgam from the electrolytic cells with water in denuders. 

Another important primary battery is the mercury cell. It usually comes in very small sizes and is used in hearing aids, watches, cameras, and some calculators. The anode of this cell is a zinc-mercury amalgam the reacting species is zinc. The cathode is a plate made up of mercury(II) oxide, HgO. The electrolyte is a paste containing HgO and sodium or potassium hydroxide. The electrode reactions are... 

What is (a) the electrolyte and (b) the oxidizing agent in the mercury cell shown here (c) Write the overall cell reaction for a mercury cell. 

The glass tubes contain mercury and are firmly fixed in the ebonite cover of the cell so that the distance between the electrodes may not change during the experiment. Contact with the platinum electrodes is made by dipping the copper wires of the circuit in the mercury contained in the tubes. The coating of the electrodes with platinum black is carried out in order to inhibit polarization. When examining certain electrolytes, platinized electrodes cannot be used since platinum black may catalyze the decomposition or the oxidation of the electrolyte. The cell is maintained at constant temperature thermostatically, as conductivity increases rather significantly with temperature. 

De Nora An electrolytic process for making chlorine and sodium hydroxide solution from brine. The cell has a mercury cathode and graphite anodes. It was developed in the 1950s by the Italian company Oronzio De Nora, Impianti Elettrochimici, Milan, based on work by I. G. Farbenindustrie in Germany during World War II. In 1958 the Monsanto Chemical Company introduced it into the United States in its plant at Anniston, AL. See also Mercury cell. 

Griesheim (1) An early process for producing chlorine by electrolysis, developed by Chemische Fabrik Griesheim-Elektron, in Germany, and commercialized in 1890. The electrolyte was saturated potassium chloride solution, heated to 80 to 90°C. The byproduct potassium hydroxide was recovered. The process was superseded in the United States by several similar electrolytic processes before being ousted by the mercury cell, invented by H. Y. Castner and K. Kellner in 1892. See Castner-Kellner. 

Two common types of button batteries both use a zinc container, which acts as the anode, and an inert stainless steel cathode, as shown in Figure 11.11 on the next page. In the mercury button battery, the alkaline electrolyte paste contains mercury(II) oxide, HgO. In the silver button battery, the electrolyte paste contains silver oxide, Ag20. The batteries have similar voltages about 1.3 V for the mercury cell, and about 1.6 V for the silver cell. 

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. 

Mercury cells, like dry cells, have a zinc anode and a use a mercuric oxide (HgO) cathode. The electrolyte is potassium hydroxide, KOH. These small, flat, metallic cells are widely used in watches, calculators, cameras, hearing aids, and other applications where small size is a premium. The reactions in the mercury cell are ... 

Castner turned his interest to gold extraction, which required high-quality sodium hydroxide. Castner developed a three-chambered electrolytic cell. The two end chambers contained brine and graphite electrodes. The middle chamber held water. The cells were separated excepted for a small opening on the bottom, which contained a pool of mercury that served as the cell s cathode. When current flowed through the cell and the cell was rocked, sodium reduced from the brine came into contact with water in the middle cell to produce a sodium hydroxide solution. As Castner built his mercury cell, Kellner was working on a similar design. Rather than compete with each other, Castner and Kellner joined forces to establish the Castner-Kellner Alkali Company to produce sodium hydroxide, which competed with soda ash and potash as an industrial base, and chlorine, which was used primarily to make bleach. 

This system, commonly known as the mercury cell , is based on an amalgamated zinc anode, a concentrated aqueous potassium hydroxide electrolyte - saturated with zincate ion by zinc oxide - and a mercuric oxide/graphite cathode ... 

Figure 19.16. Basic designs of electrolytic cells, (a) Basic type of two-compartment cell used when mixing of anolyte and catholyte is to be minimized the partition may be a porous diaphragm or an ion exchange membrane that allows only selected ions to pass, (b) Mercury cell for brine electrolysis. The released Na dissolves in the Hg and is withdrawn to another zone where it forms salt-free NaOH with water, (c) Monopolar electrical connections each cell is connected separately to the power supply so they are in parallel at low voltage, (d) Bipolar electrical connections 50 or more cells may be series and may require supply at several hundred volts, (e) Bipolar-connected cells for the Monsanto adiponitrile process. Spacings between electrodes and membrane are 0.8-3.2 mm. (f) New type of cell for the Monsanto adiponitrile process, without partitions the stack consists of 50-200 steel plates with 0.0-0.2 ram coating of Cd. Electrolyte velocity of l-2 m/sec sweeps out generated Oz.

Primary alkaline cells use sodium hydroxide or potassium hydroxide as tlie electrolyte. They can be made using a variety of chemistries and physical constructions. The alkaline cells of the 1990s are mostly of the limited electrolyte, dry cell type. Most primary alkaline cells are made sing zinc as the anode material a variety of cathode materials can be used. Primary alkaline cells are commonly divided into tW o classes, based on type of construction the larger, cylindrically shaped batteries, and the miniature, button-type cells. Cylindrical alkaline batteries are mainly produced using zinc-manganese dioxide chemistry, although some cylindrical zinc-mercury oxide cells are made. 

Cathode in the electrolytic production of chlorine and caustic soda lamps arc rectifiers mercury cells switches thermometers barometers laboratory apparatus dental amalgams raw material for various mercury compounds fungicides antiseptics preservatives pharmaceuticals electrodes reagents... 

Early demand for clilorine centered on textile bleaching, and clilorine generated through the electrolytic decomposition of salt (NaQ) sufficed. Sodium hydroxide was produced by the lime —soda reaction, using sodium carbonate readily available from the Solvay process. Increased demand for clilorine for PVC manufacture led to the production of clilorine and sodium hydroxide as coproducts. Solution mining of salt and the availability of asbestos resulted in the dominance of the diaphragm process in North America, whereas solid salt and mercury availability led to the dominance of the mercury process in Europe. Japan imported its salt in solid form and, until the development of the membrane process, also favored the mercury cell for production. 

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