formed, the end of the reaction being indicated by the disappearance of the blue colour of the solution. One gramme of the ore is treated in a flask with a mixture of nitric and sulphuric acids and evaporated until all the nitric acid is expelled. After cooling a little, water is added, and then a few grammes of aluminium foil free from copper. On this foil the copper in the solution is all precipitated by electrolytic action in a few minutes, and the aluminium is dissolved by the addition of an excess of sulphuric acid. Water is added, and as soon as the gangue and copper particles have settled the clear solution is decanted, and the residue washed several times in the same way. The copper is then dissolved in 5 cc. of nitric acid; if silver is present a drop or two of hydrochloric acid is added, the solution diluted to about 50 cc., and filtered. To the filtrate (or, if no silver is present, to the diluted nitric acid solution) 10 cc. of ammonia are added, and a standard solution of potassium cyanide is run in from a burette until the blue colour has nearly disappeared. The solution is filtered to get rid of the precipitate, and the titration is finished in the nearly clear filtrate, which should be always about 200 cc. in volume. The titration is complete when the blue colour is so faint that it is almost imperceptible after the flask has been vigorously shaken. The potassium cyanide solution is standardized by dissolving 0·5 gramme of pure copper in 5 cc. of nitric acid, diluting, adding 10 cc. of ammonia, and titrating exactly as described above.
When potassium iodide is added to a solution of cupric acetate, the reaction Cu(C2H3O2)2 + 2KI＝CuI + 2K(C2H3O2) + I takes place; that is, for each atom of copper one atom of iodine is liberated. If a solution of sodium thiosulphate (hyposulphite) is added to this solution, hydriodic acid, sodium iodide and tetrathionate are formed; and if a little starch solution has been added, the end of the reaction is indicated by the disappearance of the blue colour, due to the iodide of starch. The amount of iodine liberated is therefore a measure of the copper in the solution, and when the sodium thiosulphate has been carefully standardized the method is extremely accurate. The ore is treated as described in the cyanide method until the copper precipitated by the aluminium foil has been washed and dissolved in 5 cc. of nitric acid; then 0·25 gramme of potassium chlorate is added, and the solution boiled nearly dry to oxidize any arsenic present to arsenic acid. The solution is cooled, 50 cc. water added, then 5 cc. ammonia, and the solution is boiled for five minutes. Next 5 cc. of glacial acetic acid are added, the solution cooled, and 5 cc. of a solution of potassium iodide (300 grammes to the litre) and the standard solution of sodium thiosulphate run in from a burette until the brown colour has nearly disappeared. A few drops of starch solution are then added, and when the blue colour has nearly vanished a drop or two of methyl orange makes the end reaction very sharp. The thiosulphate solution is standardized by dissolving 0·3 to 0·5 gramme of pure copper in 3 cc. of nitric acid, adding 50 cc. of water and 5 cc. of ammonia, and titrating as above after the addition of 5 cc. of glacial acetic acid and 5 cc. of the potassium iodide solution.
Iron.—The methods used in the assay for iron are volumetric, and are all based on the property possessed by certain reagents of oxidizing iron from the ferrous to the ferric state. Two salts are in common use for this purpose, potassium permanganate and potassium bichromate. It is necessary in the first place, after the ore is in solution, to reduce all the iron to the ferrous condition; then the carefully standardized solution of the oxidizing reagent is added until all the iron is in the ferric state, the volume of the standard solution used being the measure of the iron contained in the ore. The end of the reaction when potassium permanganate is employed is known by the change in colour of the solution. As the solution of potassium permanganate, which is deep red in colour, is dropped into the colourless iron solution, it is quickly decolorized while the iron solution gradually assumes a yellowish tinge, the first drop of the permanganate solution in excess giving it a pink tint. With potassium bichromate solution, which is yellow, the iron solution becomes green from the chromium chloride or sulphate formed, and the end of the reaction is determined by removing a drop of the solution on the stirring-rod and adding it to a drop of a dilute solution of potassium ferricyanide on a white tile. So long as the solution contains a ferrous salt, the drop on the tile changes to blue; hence the absence of a blue coloration indicates the complete oxidation of all the ferrous salt and the end of the reaction. One gramme of ore is usually taken for assay and treated in a small flask or beaker with 10 cc. of hydrochloric acid. All the iron in the ore generally dissolves upon heating, and a white residue is left. Occasionally this residue contains a small amount of iron in a difficultly soluble form; in that case the solution is slightly diluted with water and filtered into a larger flask. The residue in the filter is ignited and fused with a little sodium carbonate and nitrate, or with sodium peroxide. The product is treated with water, filtered, and the residue dissolved in hydrochloric acid and added to the main solution. This solution, which should not exceed 50 cc. or 75 cc. in volume, contains the iron in the ferric state and is ready for reduction.
In the reduction by metallic zinc, about 3 grammes of granulated or foliated zinc are placed in the flask, which is closed with a small funnel; when the iron is reduced, add 10 cc. of sulphuric acid, and as soon as all the zinc is dissolved the solution is ready for titration. In the reduction by stannous chloride the solution of the ore in the flask is heated to boiling, and a strong solution of stannous chloride is added until the solution is completely decolorized; then 60 cc. of a solution of mercuric chloride (50 grammes to the litre) are run in and the contents of the flask poured into a dish containing 600 cc. of water and 60 cc. of a solution containing 200 grammes of manganous sulphate, 1 litre of phosphoric acid (1·3 sp. gr.), 400 cc. of sulphuric acid, and 1600 cc. of water. The solution is then ready for titration with the standard permanganate solution.
The permanganate or bichromate solution is standardized by dissolving 0·5 of a gramme of pure iron wire in a flask, in hydrochloric acid, oxidizing it with a little potassium chlorate, boiling off all traces of chlorine, deoxidizing by one of the methods described above, and titrating with the solution. As the wire always contains impurities, the absolute amount of iron in the wire must be determined and the correction made accordingly. Pure oxalic acid may also be used, which, in the presence of sulphuric acid, is oxidized by the standard solution according to the reaction:—
5(H2C2O42H2O) + 3H2SO4 + 2KMnO4＝10CO2 + 2MnSO4 + K2SO4 + 18H2O
The reaction in case of ferrous sulphate is:—
10FeSO4 + 2KMnO4 + 8H2SO4＝5Fe2(SO4)3 + K2SO4 + 2MnSO4 + 8H2O;
that is, the same amount of potassium permanganate is required to oxidize 5 molecules of oxalic acid that is necessary to oxidize 10 molecules of iron in the form of ferrous sulphate to ferric sulphate, or 63 parts by weight of oxalic acid equal 56 parts by weight of metallic iron. Ammonium ferrous sulphate may also be used; it contains one-seventh of its weight of iron. (A. A. B.)
ASSEGAI, or Assagai (from Berber-Arab as-zahayah, through Portuguese azagaia), a weapon for throwing or hurling, a light spear or javelin made of wood and pointed with iron, particularly the spear used by the Zulu and other Kaffir tribes of South Africa. In addition to the long-handled assegai there is a shorter weapon for use at close quarters.
ASSELIJN, HANS (1610–1660), Dutch painter, was born at Diepen, near Amsterdam. He received instruction from Esaias Vandevelde (1587–1630), and distinguished himself particularly in landscape and animal painting, though his historical works and battle pieces are also admired. He travelled much in France and Italy, and modelled his style greatly after Bamboccio (Peter Laer). He was one of the first Dutch painters who introduced a fresh and clear manner of painting landscapes in the style of Claude Lorraine, and his example was speedily followed by other artists. Asselijn’s pictures were in high estimation at Amsterdam, and several of them are in the museums of that city. Twenty-four, painted in Italy, were engraved.
