Antimony, electrolytic production

Arsenic is sometimes used in the manufacture of its compounds, but more often in alloys. Small quantities, o-i to o 2 per cent, are added to lead for the production of shot (p. 196). Arsenical lead anodes are used in the electrolytic production of zinc. Alloys with antimonial lead containing 1 to 2 per cent of arsenic and sometimes other elements are used for sheaths for electric cables, etc. Arsenical coppers and bronzes are used for high temperature work such as locomotive fireboxes, etc. 

Crude lead contains traces of a number of metals. The desilvering of lead is considered later under silver (Chapter 14). Other metallic impurities are removed by remelting under controlled conditions when arsenic and antimony form a scum of lead(II) arsenate and antimonate on the surface while copper forms an infusible alloy which also takes up any sulphur, and also appears on the surface. The removal of bismuth, a valuable by-product, from lead is accomplished by making the crude lead the anode in an electrolytic bath consisting of a solution of lead in fluorosilicic acid. Gelatin is added so that a smooth coherent deposit of lead is obtained on the pure lead cathode when the current is passed. The impurities here (i.e. all other metals) form a sludge in the electrolytic bath and are not deposited on the cathode. 

The final ceU product contains 250—300 g/L H2SO in the last stages of electrolyte purification, and antimony and bismuth precipitate, resulting in heavily contaminated cathodes that are recycled through the smelter. Arsenic and hydrogen evolved at the cathodes at these later stages react to form arsine, and hoods must be provided to collect the toxic gas. 

By-Product Recovery. The anode slime contains gold, silver, platinum, palladium, selenium, and teUurium. The sulfur, selenium, and teUurium in the slimes combine with copper and sUver to give precipitates (30). Some arsenic, antimony, and bismuth can also enter the slime, depending on the concentrations in the electrolyte. Other elements that may precipitate in the electrolytic ceUs are lead and tin, which form lead sulfate and Sn(0H)2S04. 

A.sahi Chemical EHD Processes. In the late 1960s, Asahi Chemical Industries in Japan developed an alternative electrolyte system for the electroreductive coupling of acrylonitrile. The catholyte in the Asahi divided cell process consisted of an emulsion of acrylonitrile and electrolysis products in a 10% aqueous solution of tetraethyl ammonium sulfate. The concentration of acrylonitrile in the aqueous phase for the original Monsanto process was 15—20 wt %, but the Asahi process uses only about 2 wt %. Asahi claims simpler separation and purification of the adiponitrile from the catholyte. A cation-exchange membrane is employed with dilute sulfuric acid in the anode compartment. The cathode is lead containing 6% antimony, and the anode is the same alloy but also contains 0.7% silver (45). The current efficiency is of 88—89%, with an adiponitrile selectivity of 91%. This process, started by Asahi in 1971, at Nobeoka City, Japan, is also operated by the RhcJ)ne Poulenc subsidiary, Rhodia, in Bra2il under Hcense from Asahi. 

The crystalline product produced by electrolytic oxidation of silver nitrate (and possibly as formulated) detonates feebly at 110°C. Mixtures with phosphorus and sulfur explode on impact, hydrogen sulfide ignites on contact and antimony trisulfide ignites when ground with the salt. 

Most metals entering the cuprate HTSC (with the exception of copper) during anodic polarization in aqueous solutions over a wide pH interval form either soluble products or loose oxide-hydroxide films with a poor adhesion. The passivation of such chemically active metals in electrolyte solutions has been incompletely studied. However, for bismuth, cadmium, antimony, and also for the corresponding chalco-... 

The unsaturated nucleoside (53) has been prepared in good yield by electrochemical elimination from either the 2 -bromo-arabino- or the 3-bromo-xylo-nucleoside indicated in Scheme 14 however, the electrolyte can control the product obtained, for whereas 2-bromo-2 -deoxy-3, 5-di-O-propanoyl-uracil gave the 2, 3-unsaturated nucleoside in presence of tetraethylammonium toluene-p-sulphonate in methanol, with sodium acetate a mixture of products was obtained 3-deoxy-3-iodo-adenosine yielded 3-deoxy-adenosine (cordycepin) besides the 2, 3-unsaturated nucleoside.1-Acetyl-glycenose derivatives have been condensed with purine and pyrimidine derivatives in presence of antimony... 

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