Electrolyser

When the molten ionic hydrides are electrolysed, all yield hydrogen at the anode, the metal at the cathode. 

Ozone is formed in certain chemical reactions, including the action of fluorine on water (p. 323) and the thermal decomposition ofiodic(VII) (periodic) acid. It is also formed when dilute (about 1 M) sulphuric acid is electrolysed at high current density at low temperatures the oxygen evolved at the anode can contain as much as 30% ozone. 

Electrolysis, under similar conditions, of a mixture of two carboxylic acids RCOOH and R COOH leads, in addition to normal coupling products R—R and R —R, to cross coupling R—R. If a mixture of a saturated carboxylic acid and a half ester of an ato-dicarboxylic acid is electrolysed, there are three main products, viz., a hydrocarbon (I), a mono-ester (II), and a di-ester (HI) and these are readily separable by distillation. Some unsaturated ester (IV) is often present in small quantity. 

Myristic acid from hexanoic acid and methyl hydrogen sebacate). Dissolve 23 -2 g. of redistilled hexanoic acid (re caproic acid), b.p. 204-6-205-5°/760 mm., and 21-6 g. of methyl hydrogen sebacate in 200 ml. of absolute methanol to which 0 13 g. of sodium has been added. Electrolyse at 2 0 amps., whilst maintaining the temperature between 30° and 40°, until the pH is about 8 0 (ca. 6 hours). Neutralise the contents of the electrolysis cell with a little acetic acid and distil off the methyl alcohol on a water bath. Dissolve the residue in 200 ml. of ether, wash with three 50 ml. portions of saturated sodium bicarbonate solution, once with water, dry with anhydrous magnesium sulphate, and distil with the aid of a fractionating column (see under Methyl hydrogen adipate). Collect the re-decane at 60°/10 mm. (3 0 g.), the methyl myristate at 158-160°/ 10 mm. (12 5g.) and dimethyl hexadecane-1 16-dicarboxylate at 215-230°/ 7 mm. (1 -5 g.)... 

To a 250-ml not-partitioned electrochemical cell, 135 ml of CH3CN, 15 ml ofHiO, 6.20 g of NaBr and 2.82 g of olefin ( ) is added. The mixture, kept at 2(f C, is electrolysed by using the same electrodes as of Example 1, but with a constant current density of 1.7 A being used,until through the cell 4,000 Coulombs have been passed. The reaction mixture is then processed as described in Example 4.2.56 g is obtained of ketone (III), with a yield of 83.2%, as computed relatively to the olefin (I) used as the starting material. 

Mixtures of trichloroacetate and dichloroacetate are analyzed by selecting an initial potential at which only the more easily reduced trichloroacetate is reduced. When its electrolysis is complete, the potential is switched to a more negative potential at which dichloroacetate is reduced. The total charge for the first electrolysis is used to determine the amount of trichloroacetate, and the difference in total charge between the first and second electrolyses gives the amount of dichloroacetate. 

Fig. 3. Aluminum electrolysing cell with piebaked anode.

Dipl.-Chem. U. Heinzelmann Guldager Electrolyse GmbH Postfach 141... 

Many metals are extracted from their compounds, as found in ores, by electrolytic processes. By far the most important is the Hall-Heroult process, invented in 1886, for producing aluminium from alumina, itself refined from bauxite ore. Alumina is dissolved in molten cryolite, Na3Alp6, and electrolysed, using carbon anodes and the aluminium itself as cathode. While various details are being steadily improved, the basic process is still the same today. 

Other industrial applications of electrolysis include extraction/purification of metals from ores, electroplating, and the manufacture of certain chemicals such as sodium hydroxide. In the latter, sodium chloride solution when electrolysed is converted to sodium hydroxide to produce chlorine at the anode and hydrogen at the cathode. Both of these gaseous by-products are collected for industrial use chlorine is used in the production of bleach and PVC hydrogen is used as a fuel, to saturate fats, and to make ammonia. 

It is clear that, if synthetic routes could be devised which would mechanistically hinder disproportionation, such compounds might be preparable. Although univalent compounds of the Group 2 metals have not yet been isolated, there is some evidence for the formation of Mg species during electrolysis with Mg electrodes. Thus H2 is evolved at the anode when an aqueous solution of NaCl is electrolysed and the amount of Mg lost from the anode corresponds to an oxidation state of 1.3. Similarly, when aqueous Na2S04 is electrolysed, the amount of H2 evolved corresponds to the oxidation by water of Mg ions having an average oxidation state of 1.4 ... 

Other oxides of phosphorus are less well characterized though the suboxide PO and the peroxide P2O6 seem to be definite compounds. PO was obtained as a brown cathodic deposit when a saturated solution of Et3NHCl in anhydrous POCI3 was electrolysed between Pt electrodes at 0°. Alternatively it can be made by the slow reaction of POBrs with Mg in Et20 under reflux ... 

The final route to fluorine compounds is electrofluorination (anodic fluorination) usually in anhydrous or aqueous HF. The preparation of NF tFl3 j (x = 1, 2, 3) has already been described (p. 818). Likewise a reliable route to OF2 is the electrolysis of 80% FIF in the presence of dissolved MF (p. 638). Perchloryl fluoride has been made by electrolysing NaC104 in FIF but a simpler route (p. 879) is the direct reaction of a perchlorate with fluorosulfuric acid ... 

The isolation of zinc, over 90% of which is from sulfide ores, depends on conventional physical concentration of the ore by sedimentation or flotation techniques. This is followed by roasting to produce the oxides the SO2 which is generated is used to produce sulfuric acid. The ZnO is then either treated electrolytically or smelted with coke. In the former case the zinc is leached from the crude ZnO with dil H2SO4, at which point cadmium is precipitated by the addition of zinc dust. The ZnS04 solution is then electrolysed and the metal deposited — in a state of 99.95% purity — on to aluminium cathodes. 

In working Example 18.8, we have in effect assumed that the electrolyses were 100% efficient in converting electrical energy into chemical energy. In practice, this is almost never the case. Some electrical energy is wasted in side reactions at the electrodes and in the form of heat This means that the actual yield of products is less than the theoretical yield. 

Discussion, Copper may be deposited from either sulphuric or nitric acid solution, but, usually, a mixture of the two acids is employed. If such a solution is electrolysed with an e.m.f. of 2-3 volts the following reactions occur ... 

Separate the copper and antimony by dissolving the deposit in a mixture of 5 mL concentrated nitric acid, 5 mL 40 per cent hydrofluoric acid (CARE), and 10 mL water boil off the nitrogen oxides, dilute to 150 mL, and add dropwise a solution of potassium dichromate until the liquid is distinctly yellow. Deposit the copper by electrolysing the solution at room temperature and limiting the cathode vs S.C.E. potential to —0.36 volt. Evaluate the weight of antimony by difference. 

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