The character of the animal matters employed varies so much that it is impossible to lay down hard and fast rules for the proportions of the several ingredients, or the duration of the roasting. Nor is the value of a raw material always in proportion to its richness in nitrogen, because the poorer material may waste less potash, consume less fuel, and require less labour. The addition of iron filings or turnings is useful only in prolonging the life of the cast-iron crucibles.
Combination of the Cyanide and Iron Solutions.—A great number of recipes are in vogue for combining the two solutions of ferrocyanide and an iron salt, both with reference to their proportions, and to the addition of foreign matters of various kinds. These variations in the formulæ give rise to distinct names for some kinds of Prussian blue, which will be referred to below. The ordinary common Prussian blue has a greenish tendency, and is chiefly made according to one or the other of the following directions:—
(1) Mix a solution of 100 lb. yellow prussiate with a solution of 100 lb. green copperas (ferrous sulphate) and 18 lb. alum, to which 9 lb. sulphuric acid has been added, and let the mixture stand for 2-3 hours, or until the solid portion has completely settled out. Decant the clear supernatant liquor, and well wash the precipitate with clean waters. Finally throw it on a filter and subject it to repeated disturbance, so as to ensure the admission of air to every particle, in order that the requisite oxidation may take place. The proportion of alum used is subject to very great variation according to individual fancy; it renders the subsequent grinding of the pigment a very much easier matter, but it causes the shade of blue to be paler than it otherwise would be.
(2) The simple solutions of green copperas and yellow prussiate in equal proportions are mixed together without any other ingredient being added, and the precipitate produced is washed, filtered, and aërated as in (1). It is, however, inferior by reason of the oxide of iron formed in the pigment spoiling the purity of the colour, and necessitating the treatment of the wet mass with hydrochloric acid, at some expense, for removal of the iron oxide.
Antwerp Blue.—This pale variety of Prussian blue has but little importance now. It is prepared by adding a solution of 4 lb. yellow prussiate in 5-6 gallons of water to one of 2 lb. sulphate of iron, and 1 lb. each of alum and sulphate of zinc in an equal quantity of water. The resulting pigment consists of a mixture of the ferrocyanides of iron, alumina, and zinc; it is washed, filtered, aërated, and dried as other forms of Prussian blue.
Bong’s Blue.—When cyanide of potassium is added to an acid solution of a copper salt, a red colour is produced, which has already been mentioned by different observers. The substance formed is very changeable, at least in the liquid where it is formed. It is decomposed by acids, alkalies, cyanide of potassium, and even decomposes spontaneously, the colour changing to yellow. It is precipitated by insoluble cyanides; hence when a dilute acid is added to the red solution, the dye is at once thrown down along with the cyanide of copper. If the precipitate thus obtained is treated with sulphuretted hydrogen, it is decomposed and the substance is set free. This substance can combine with iron, like cyanogen, so as to conceal the properties of the iron. This compound is very permanent, and has lately been studied by Bong, who gives the following directions for its preparation:—
Cyanide of potassium is added in excess to an acid solution of a copper salt until the red colour at first formed has disappeared, when a ferric salt is at once added. On the addition of the iron salt, of course, a copious precipitation of Prussian blue takes place, and the liquid again turns to a dark purple-red. To separate the colouring substance from the alkaline salts in the liquid, a dilute acid is added, which precipitates it and the cyanide of copper. This precipitate is combined with the Prussian blue, which also contains a considerable quantity of the colouring substance, and then treated with a boiling solution of carbonate of ammonia, in which it dissolves. As the cyanide of copper also goes into solution, it is separated by again precipitating it with an acid, and treating the precipitate with sulphuretted hydrogen. The colouring substance thus liberated now contains a certain amount of hydroferrocyanic acid, which is removed after neutralisation by acetate of lead. It is now filtered, and the purification is completed by precipitating with a silver salt and treating the precipitate with sulphuretted hydrogen.
This purple-coloured compound crystallises very indistinctly. To determine its composition, Bong precipitated it with acetate of copper. When dried at 212° F., the rose-coloured precipitate had the following composition: Carbon 24·31, nitrogen 28·04, hydrogen 1·88, iron 13·66, copper 17·67, oxygen 14·44. Total 100·00. These numbers correspond to the formula Cu, Fe Cy4 (HO)4.
This substance is likewise precipitated by salts of zinc, mercury, and silver. All these precipitates are pink or purple, very beautiful, and of remarkable brilliancy. They are soluble in alkalies. Iron salts yield no precipitate, nor do lead salts, except in the presence of ammonia, when a blue-violet precipitate is formed. When treated with sulphuretted hydrogen, these precipitates yield purple-red and acid liquids, which undergo change in the air, especially if warm, forming Prussian blue. When these liquids are neutralised with alkali, purple compounds are formed, which are permanent in the air, soluble in water, slightly so in alcohol, and insoluble in ether. Their colouring power is exceptionally great. These pigments will unite with ferrocyanides, and in its preparation such a compound is produced in considerable quantity; it is likewise of a purple colour, and gives a rose-coloured precipitate with acetate of lead. Both alone and in this compound it is very permanent; it resists the action of sulphurous acid, concentrated and boiling alkalies, and dilute acids, but is rapidly destroyed by chlorine and nitric acid. If this pigment could be prepared cheaply enough, it would probably be used with advantage in the arts, on account of its resistance to chemical reagents and light, the variety of its shades, and its brilliancy. It does not colour fibres directly, but can readily be fixed on them from slightly acid solutions, if they are previously mordanted with metallic oxides.
Brunswick Blue.—This pigment is made in pale, medium, and deep shades, and is an extremely useful colour, being very fine, requiring no grinding, thoroughly permanent in light and air, hardly acted upon by acids, but turned brown by alkalies, and liable on standing to separate into two portions—a white and a blue—the latter coming to the surface while the former sinks, and necessitating a thorough stirring of the paint before use.