Crude silver

After extraction from its ores, crude silver is generally refined by the process of cupellation, mentioned earlier. Since ancient times the main use of silver has been for making articles of value such as ornaments, decorative objects, jewelry, and coins. In Mesopotamia, much silver was used between the twentieth and fifteenth centuries b.c.e. to make decorative and ornamental objects. It seems that in Egypt, during the same period of time, the metal was scarcer and perhaps even more costly than gold (Hess et al. 1998 Mischara and Myers 1974). 

The ore is crushed and ground in.ball mills to pass through a 30-mesh sieve. It is mixed with suitable fluxes (limestone and quartz) and smelted in small blast-furnaces having a capacity of 25 to 30 tons per twenty-four hours. The products obtained are (i) flue dust, which is returned to the furnaces, and crude arsenious oxide, which is resublimed and sold (ii) a silicate slag, which is thrown away unless it contains more than 10 ounces of silver per ton (iii) crude silver bullion, which is mechanically detached and cupelled to a fineness of 994 before it is sold to silver refiners and (iv) a speiss of cobalt, nickel, iron, and copper arsenides, containing considerable amounts of silver. The crude silver bullion contains about three-fourths of the silver present in the ore. 

Two different techniques for silver elec-trorefining are employed, the Mobius and Balbach-Thum cells. The main difference between them is that the electrodes are arranged vertically in the Mobius cell and horizontally in the Balbach-Thum cell (Fig. 22). In the Mobius cell cast, crude silver anodes are suspended in anode bags that collect anode slime. The spent anodes are replaced continuously by new anodes. The method uses stationary or rotating stainless steel cathodes. Deposited silver forms dendritic crystals on the cathode and these are removed manually or continuously by automatic scrapers. The Mobius electrolysis process is most suitable for crude silver containing >90% Ag. With high copper content, the electrolyte must be regenerated very often, and with... 

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. 

Iodine occurs to a minute extent (less than 0.001 %) in sea water, but is found in greater concentration, combined in organic form, in certain seaweeds, in oysters and in cod livers. Crude Chile saltpetre, or caliche contains small amounts of sodium iodate, NalOj. from which iodine can be obtained (see below). Some insoluble iodides, for example liiose of silver and mercury(II), occur in Mexico. Iodine is found in the human body in the compound thyroxin in the thyroid gland deficiency of iodine in diet causes enlargement of this gland (goitre). 

Allyl Iodide. Use 29 g. (34 ml.) of allyl alcohol and 340 g. (200 ml.) of 57 per cent, hydriodic acid 84 g. of crude iodide are obtained. Upon adding 29 g. (34 ml.) of allyl alcohol to the combined residue in the flask and the aqueous layer and distilling as before, a further 72 g. of crude allyl iodide may be isolated. B.p. 99-101° (mainly 100°). The compound is very sensitive to light the distillation should therefore be conducted in a darkened room and preferably in the presence of a little silver powder. 

In a 1-litre three-necked flask, fitted with a mechanical stirrer, reflux condenser and a thermometer, place 200 g. of iodoform and half of a sodium arsenite solution, prepared from 54-5 g. of A.R. arsenious oxide, 107 g. of A.R. sodium hydroxide and 520 ml. of water. Start the stirrer and heat the flask until the thermometer reads 60-65° maintain the mixture at this temperature during the whole reaction (1). Run in the remainder of the sodium arsenite solution during the course of 15 minutes, and keep the reaction mixture at 60-65° for 1 hour in order to complete the reaction. AUow to cool to about 40-45° (2) and filter with suction from the small amount of solid impurities. Separate the lower layer from the filtrate, dry it with anhydrous calcium chloride, and distil the crude methylene iodide (131 g. this crude product is satisfactory for most purposes) under diminished pressure. Practically all passes over as a light straw-coloured (sometimes brown) liquid at 80°/25 mm. it melts at 6°. Some of the colour may be removed by shaking with silver powder. The small dark residue in the flask solidifies on cooling. 

Add, with stirring, a solution of 6 8 g. of the fiis-diazo ketone in 100 ml. of warm dioxan to a suspension of 7 0 g. of freshly precipitated silver oxide in 250 ml. of water containing 11 g. of sodium thiosulphate at 75°. A brisk evolution of nitrogen occurs after 1 5 hours at 75°, filter the liquid from the black silver residue. Acidify the almost colourless filtrate with nitric acid and extract the gelatinous precipitate with ether. Evaporate the dried ethereal extract the residue of crude decane-1 10-dicarboxylic acid weighs 4 -5 g. and melts at 116-117°. RecrystaUisation from 20 per cent, aqueous acetic acid raises the m.p. to 127-128°. 

The process of isolation finally adopted by the former authors consists in precipitating as reineckates the water-soluble bases contained in a methyl alcoholic extract of the curare. The mixed reineckates are further purified, by solution in acetone and precipitation with water as often as may be necessary. The product so cleaned represents the bulk of the biological activity of the crude drug the mother liquors may contain curine (p. 374), which indicates a menisperm as one of the components of such curares. The mixed reineckates are then fractionated chromato-graphically over alumina and the components isolated as chlorides by the use of silver sulphate and barium chloride in succession. This process has been modified in detail by Schmid and Karrer, who have also found that with their curare, the more soluble reineckate fraction includes less potent quaternary alkaloids. 

Crude methyl 2-bromostearate (33 g, 0 087 mol) is dissolved in 200 mL of acetonitrile containing 0 5 mL of water, and silver(I) fluonde (50 g, 0 393 mol) is added rapidly in one portion The slurry is stirred vigorously for 20 h in an oil bath at 80 C At the end ot this time thin-layer chromatographic analysis (petroleum... 

Electrorefining has been used for the purification of many common as well as reactive metals. It has been seen that the emf or the potential required for such a process is usually small because the energy needed for the reduction of the ionic species at the cathode is almost equal to that released by the oxidation of the crude metal at the anode. Some metals, such as copper, nickel, lead, silver, gold, etc., are refined by using aqueous electrolytes whereas molten salt electrolytes are necessary for the refining of reactive metals such as aluminum,... 

Precious metals such as silver and gold, which are seldom oxidized even at high temperatures, are often refined by cupellation, a process for removing from them base metal impurities such as lead and tin, with which they are associated in many ores. Hot lead and tin are easily oxidized. In the cupellation process, a crude, impure precious metal is placed in a shallow cup or crucible made of bone ash, known as a cupel, and is then heated by a blast of hot air. At high temperatures, the base metal impurities are oxidized by oxygen in the hot air, and the oxides thus formed are absorbed by the porous bone ash. The Chaldeans are said to have been the first to have utilized (ca. 2500 b.c.e.) cupellation to remove lead and purify silver from lead-silver ores. 

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