A Dictionary of Arts, Manufactures, and Mines; containing A Clear Exposition of Their Principles and Practice
by Andrew Ure, M. D.;
F. R. S. M. G. S. Lond.: M. Acad. M. S. Philad.; S. PH. DOC. N. GERM. Ranow.; Mulh. Etc. Etc.
Illustrated with nearly fifteen hundred engravings on wood
Eleventh American, From The Last London Edition.
To which is appended, a Supplement of Recent Improvements to The Present Time.
New York: D Appleton & company, 200 Broadway. Philadelphia: George S. Appleton, 148 Chestnut St.
MDCCCXLVII
1847
PRUSSIAN BLUE, and PRUSSIATE OF POTASH, are two important articles of chemical manufacture, which must be considered together. The first is called by English chemists, Ferrocyanodide of iron, the Cyanure ferroso-ferrique of Berzelius, Eisenblausaures eisenoxyd, or eisencyanür + eisencyanid, Germ.; the second is called Ferrocyanodide of potassium, the Cyanure ferroso-potassique of Berzelius; Eisencyanur-kalium, cyaneisen + cyankalium or Blausaures eisenoxydul-kali, Germ.
Prussian blue (Berliner-blau, Germ.), is a chemical compound of iron and cyanogen. When organic matters, abounding in nitrogen, as dried blood, horns, hair, skins, or hoofs of animals, are triturated along with potash in a strongly ignited iron pot, a dark gray mass is obtained, that affords to water the liquor originally called lixivium sanguinis, or blood-ley, which, by evaporation, yields lemon-colored crystals in large rectangular tables, bevelled at the edges. This salt is called in commerce, prussiate of potash, and has for its ultimate constituents, potassium, iron, oxygen, and hydrogen (the latter two in such proportions as to form water), and the peculiar compound Cyanogen the blaustoff of the Germans.
These crystals consist, in 100 parts, of potassium 37.02, iron 12.82, cyanogen 37.40, water 12.76; or, cyanide of potassium 61.96, cyanide of iron 25.28, and water 12.76. They may be represented also by the following composition: 44.58 of potassa, 38.82 of hydrocyanic or prussic acid, and 16.60 of oxide of iron, in 100 parts; but the first appears to be their true chemical constitution. Dry ferrocyanodide of potassium is a compound of one atom of cyanide of iron, 54=(28+26), and 2 atoms of cyanide of potassium, 132,=(26x2+40x2); the sum being 186; hydrogen being 1.0 in the scale of equivalents. The crystals of prussiate of potash are nearly transparent, soft, of a sweetish saline and somewhat bitterish taste, soluble in 4 parts of water at 52° F., and in 1 part boiling water, but insoluble in alcohol. They are permanent in the air at ordinary temperatures, but in a moderately warm stove-room they part with 12 3/4 per cent. of water, without losing their form or coherence, and becomes thereby a white friable anhydrous ferrocyanodide of potassium, consisting of 42.44 potassium, 42.87 cyanogen, and 14.69 iron, in 100 parts.
This salt is an excellent reagent for distinguishing metals from each other, as the following TABLE of the precipitates which it throws down from their saline solutions will show:-
Metallic solutions. - colour of precipitate.
Antimony - white.
Bismuth - white.
Cadmium - white, a little yellowish.
Cerium (protoxide) - white, soluble in acids.
Cobalt - green, soon turning to reddish-gray.
Copper (protoxide) - white, changing to red.
- Do. (peroxyde) - brown-red.
Iron (protoxide) - white, rapidly turning blue.
- Do. (peroxyde) - dark blue.
Lead - white, with a yellowish cast.
Manganese (protoxide) - white, turning quickly peach or blood-red.
Manganese (deutoxide) - greenish-gray.
Mercury (protoxide) - white.
- Do. (peroxyde) - white, turning blue.
Molybdenum - dark brown.
Nickel (oxyde) - white, turning greenish.
Palladium (protoxide) - green (gelatinous.)
Silver - white, turning brown in the light.
Tantalum - yellow, dark burned color.
Tin (protoxide) - white, (gelatinous.)
- Do. (peroxyde) - yellow, do.
Uranium - red-brown.
Zinc - white.
No precipitations ensue with solutions of the alkaline or earthy salts, except that of yttria, which is white; nor with those of gold, platinum, rhodium, iridium, osmium, (in concentrated solutions) tellurium, chromium, tungsterium. All the precipitates by the ferrocyanodide of iron, are double compounds of cyanide of iron with cyanide of the metal thrown down, which is produced by the reciprocal decomposition of the cyanide of potassium and the peculiar metallic oxide present in the solution. The precipitate from the sulphate of copper has a fine brown color, and has been used as a pigment; but it is somewhat transparent, and therefore does not cover well. The precipitate from the peroxyde salts of iron is a very intense Prussian blue, called on the continent, Paris blue. It may be regarded as a compound of prussiate of protoxide and prussiate of peroxyde of iron; or as a double cyanide of the protoxide and peroxyde of iron, as the denomination cyanure ferroso-ferrique denotes. In numbers, its composition may be therefore stated thus: prussic or hydrocyanic acid, 48.48; protoxide of iron, 20.73; peroxyde of iron, 30.79; or cyanogen, 46.71; iron, 37.36; water, 15.93; which represent its constitution when it is formed by precipitation with the prussiate of potash or a salt of iron that contains no protoxide. If the iron be but partially peroxidized in the salt, it will afford a precipitate, at first pale blue, which turns dark blue in the air, consisting of a mixture of prussiate of protoxide and prussiate of peroxyde. In fact, the white cyanide of iron (the prussiate of the pure protoxide), when exposed to the air in a moist condition, becomes, as above stated, dark blue; yet the new combination formed in this case through absorption of oxygen, is essentially different from that resulting from the precipitation by the peroxyde of iron, since it contains an excess of the peroxyde in addition to the usual two cyanides of iron. It has been therefore called called Prussian blue, and, from its dissolving in pure water, soluble Prussian blue.
Both kinds of Prussian blue agree in being void of taste and smell, in attracting humidity from the air when they are artificially dried, and being decomposed at a heat above 348° F. The neutral or insoluble Prussian blue is not affected by alcohol; the basic, when dissolved in water, is not precipitated by that liquid. Neither is acted upon by dilute acids; but they form with concentrated sulphuric acid a white pasty mass, from which they are again reproduced by the action of cold water. They are decomposed by strong sulphuric acid at a boiling heat, and by strong nitric acid at common temperatures; but they are hardly affected by the muriatic. They become green with chlorine, but resume their blue colour when treated with disoxidizing reagents. When Prussian blue is digested in warm water along with potash, soda, or lime, peroxyde of iron is separated, and a ferroprussiate of potash, soda, or lime remains in solution. If the Prussian blue has been previously purified by boiling in dilute muriatic acid, and washing with water, it will afford by this treatment a solution of ferrocyanodide of potassium, from which by evaporation this salt may be obtained in its purest crystalline state. When the powdered Prussian blue is diffused in boiling water, and digested with red oxide of mercury, it parts with all its oxide of iron, and forms a solution of bi-cyanodide, improperly called prussiate of mercury; consisting of 79.33 mercury, and 20.67 cyanogen; or, upon the hydrogen equivalent scale, of 200 mercury, and 52=(26x2) cyanogen. When this salt is gently ignited, it affords gaseous cyanogen. Hydrocyanic or prussic acid, which consists of 1 atom of cyanogen = 26, +1 of hydrogen = 1, is prepared by distilling the mercurial bi-cyanide in a glass retort with the saturating quantity of dilute muriatic acid. Prussic acid may also be obtained by precipitating the mercury by sulphureted hydrogen gas from the solution of its cyanide; as also by distilling the ferrocyanide of potassium along with dilute sulphuric acid. Prussic acid is a very volatile light fluid, eminently poisonous, and is spontaneously decomposed by keeping, especially when somewhat concentrated.
Having expounded the chemical constitution of Prussian blue and prussiate of potash, I shall now treat of their manufacture upon the commercial scale.
1- Of blood-ley, the phlogisticated alkali of Scheele. Among the animal substances used for the preparation of this lixivium, blood deserves the preference, where it can be had --- enough[?]. It must be evaporated to perfect dryness, reduced to powder, and sifted. Hoofs, parings of horns, hides, old woollen rags, and other animal offals, are, however, generally had recourse to, as condensing most azotized matter in the smallest bulk. Dried funguses have been also prescribed. These animal matters may either be first carbonized in cast iron cylinders, as for the manufacture of sal ammoniac (which see), and the residual charcoal may be then taken for making the ferroprussiate; or the dry animal matters may be directly employed. The latter process is apt to be exceedingly offensive to the workmen and neighborhood, from the nauseous vapors that are exhaled in it. Eight pounds of horn (hoofs), or ten pounds of dry blood, afford upon an average one pound of charcoal. This must be mixed well with good pearlash, (freed previously from most of the sulphate of potassa, with which it is always contaminated), either in the dry way, r by soaking the bruised charcoal with a strong solution of the alkali; the proportion being one part of carbonate of potassa from 1½ to 2 parts of charcoal, or to about eight parts of hard animal matter. Gautier has proposed to calcine three parts of dry blood with one of nitre; with what advantage to the manufacturer, I cannot discover.
The pot for calcining the mixture of animal and alkaline matter is egg-shaped as represented at a, fig. 928, and is considerably narrowed at the neck e, to facilitate the closing of the mouth with a lid i. It is made of cast iron, about two inches thick in the belly and bottom; this strength being requisite because the chemical action of the materials wears the metal fast away. It should be built into the furnace in a direction sloping downwards, (more than is shown in the figure), and have a strong knob b, projecting from its bottom to support it upon the back wall, while its should is embraced at the arms c, c, by the brickwork in front. The interior of the furnace is so formed as to leave but a space of a few inches round the pot, in order to make the flame play closely over its whole surface. The fire-door f, and the draughthole z, of the ash-pit, are placed in the posterior part of the furnace, in order that the workmen may not be incommoded by the heat. The smoke vent o, issues through the arched top h of the furnace, towards the front, and is thence led backwards by a flue to the main chimney of the factory. d is and iron or stone shelf, inserted before the mouth of the pot, to prevent loss in shovelling out the semi-liquid paste. The pot may be half filled with the materials.
The calcining process is different, according as the animal substances are fresh or carbonized. In the first case, the pot must remain open, to allow of diligent stirring of its contents, with a slightly bent flat iron bar or scoop, and of introducing more of the mixture as the intumescence subsides, during a period of five or six hours, till the nauseous vapors cease to rise, till the flame becomes smaller and brighter, and till a smell of ammonia be perceived. At this time, the heat should be increased, the mouth of the pot should be shut, and opened only once every half hour, for the purpose of working the mass with the iron paddle. When on opening the mouth of the pot, and stirring the pasty mixture, no more flame rises, the process is finished.
If the animal ingredients are employed in a carbonized state, the pot must be shut as soon as its contents are brought to ignition by a briskly urged fire, and opened for a few seconds only every quarter of an hour, during the action of stirring. At first, a body of flame bursts forth every time that the lid is removed; but by degrees this ceases, and the mixture soon agglomerates, and then softens into a paste. Though the fire be steadily kept up, the flame becomes less and less each time that the pot is opened; and when it ceases, the process is at an end. The operation, with a mass of 50 pounds of charcoal and 50 pounds of purified pearlash, lasts about 12 hours, the first time that the furnace is kindled; but when the pot has been previously brought to a state of ignition, it takes only 7 or 8 hours. In a well-appointed factory, the fire should be invariably maintained at the proper pitch, and the pots should be worked with relays of operatives.
The molten mass is now to be scooped out with an appropriate iron shovel, having a long shank, and caused to cool in small portions, as quickly as possible; but not by throwing it into water, as has sometimes been prescribed; for in this way a good deal of the cyanogen is converted into ammonia. If it be heaped up and kept hot in contact with air, some of the ferrocyanide is also decomposed, with diminution of the product. The crude mass is to be then put into a pan with cold water, dissolved by the application of a moderate heat, and filtered through cloths. The charcoal which remains upon the filter possesses the properties of decoloring sirups, vinegars, &c., and of destroying smells in a pre-eminent degree. It may also serve, when mixed with fresh animal coal, for another calcining operation.
As the iron requisite for the formation of the ferrocyanide is in general derived from the sides of the pot, this is apt to wear out into holes, especially at its under side, where the heat is greatest. In this event, it may be taken out of the furnace, patched up with iron-rust cement, and re-inserted with the sound side undermost. The erosion of the pot may be obviated in some measure by mixing iron borings or cinder (hammerschlag) with the other materials, to the amount of one or two hundredths of the potash.
The above lixivium is not a solution of pure ferroprussiate; it contains not a little cyanide of potassium, which in the course of the process had not absorbed the proper dose of iron to form a ferrocyanide; it contains also more or less carbonate of potash, with phosphate, sulphate, hydrogenated sulphuret, muriate, and sulpho-cyanide of the same base, as well as phosphate of lime; substances derived partly from the impure potash, and partly from the incinerated animal matters. Formerly that very complex impure solution was employed directly for the precipitation of Prussian blue; but now, in all well regulated works, it is converted by evaporation and cooling into crystallized ferroprussiate of potash. The mother-water is again evaporated and crystallized, whereby a somewhat inferior ferroprussiate is obtained. Before evaporating the ley, however, it is advisable to add as much solution of green sulphate of iron to it, as will re-dissolve the white precipitate of cyanide of iron which first falls, and thereby convert the cyanide of potassium, which is present in the liquor, into ferrocyanide of potassium. The commercial prussiate of potash may be rendered chemically pure by making its crystals effloresce in a stove, fusing them with a gentle heat in a glass retort, dissolving the mass in water, neutralizing any carbonate and cyanide of potash that may be present with acetic acid, then precipitating the ferroprussiate of potash by the addition of a sufficient quantity of alcohol, and finally crystallizing the precipitated salt over in water. The sulphate of potassa may be decomposed by acetate of baryta, and the resulting acetate of potassa removed by alcohol.
2. The precipitation of Prussian blue. - Green sulphate of iron is always employed by the manufacturer, on account of its cheapness, for mixing with solution of the ferroprussiate, in forming Prussian blue, though the red sulphate, nitrate, or muriate of iron would afford a much richer blue pigment. Whatever salt of iron be preferred, should be carefully freed from any cupreous impregnation, as this would give the pure blue a dirty brownish cast. The green sulphate of iron is the most advantageous precipitant, on account of its affording protoxide, to convert into ferrocyanide any cyanide of potassium that may happen to be present in the uncrystallized lixivium. The carbonate of potash in that lixivium might be saturated with sulphuric acid before adding the solution of sulphate of iron; but it is more commonly done by adding a certain portion of alum; in which case, alumina falls along with the Prussian blue; and though it renders it somewhat paler, yet it proportionally increases its weight; whilst the acid of the alum saturates the carbonate of potash, and prevents its throwing down iron-oxyde, to degrade by its brown-red tint the tone of the blue. For every pound of pearlash used in the calcination, from two to three pounds of alum are employed in the precipitation. When a rich blue is wished for, the free alkali in the Prussian ley may be partly saturated with sulphuric acid, before adding the mingled solutions of copperas and alum. One part of the sulphate of iron is generally allowed for 15 or 20 parts of dried blood, and 2 or 3 of horn-shavings of hoofs. But the proportion will depend very much upon the manipulations, which, if skilfully conducted, will produce more of the cyanides of iron, and require more copperas to neutralize them. The mixed solutions of alum and copperas should be progressively added to the ley as long as they produce any precipitate. This is not a t first a fine blue, but a greenish gray, in consequence of the admixture of some white cyanide of iron; it becomes gradually blue by the absorption of oxygen from the air, which is favored by agitation of the liquor. Whenever the colour seems to be as beautiful as it is likely to become, the liquor is to be run off by a spigot or cock from the bottom of the precipitation vats, into flat cisterns, to settle. The clear supernatant fluid, which is chiefly a solution of sulphate of potash, is then drawn off by a syphon; more water is run on with agitation to wash it, which after settling is again drawn off; and whenever the washings become tasteless, the sediment is thrown upon filter sieves, and exposed to dry, first in the air of a stove, but finally upon slabs of chalk or Paris plaster. But for several purposes, Prussian blue may be best employed in the fresh pasty state, as it then spreads more evenly over paper and other surfaces.
A good article is known by the following tests: it feels light in the hand, adheres to the tongue, has a dark lively blue color, and gives a smooth deep trace; it should not effervesce with acids, as when adulterated with chalk; nor become pasty with boiling water, as when adulterated with starch. The Paris blue, prepared without alum, with a peroxyde salt of iron, displays, when rubbed, a copper-red lustre, like indigo. Prussian blue, degraded in its colour by an admixture of free oxide of iron, may be improved by digestion in dilute sulphuric or muriatic acid, washing, and drying. Its relative richness in the real ferroprussiate of iron may be estimated by the quantity of potash or soda which a given quantity of it requires to destroy its blue color.
Sulphureted hydrogen passed through Prussian blue diffused in water, whitens it; while prussic acid is eliminated, sulphur is thrown down, and the sesquicyanide of iron is converted into the single cyanide. Iron and tin operate in the same way. When Prussian blue is made with two atoms of ferrocyanide of potassium, instead of one, it becomes soluble in water.
For the mode of applying this pigment in dyeing, see Calico-printing.
Sesquiferrocyanate of potash is prepared by passing chlorine gas through a solution of ferrocyanide of potassium, till it becomes red, and ceases to precipitate the peroxyde salts of iron. The liquor yields, by evaporation, prismatic crystals, of a ruby-red transparency. They are soluble in 38 parts of water, and consist of 40-42 parts of sesquicyanide of iron, and 59-58 of cyanide of potassium. The solution of this salt precipitates the following metals, as stated in the table: -
Bismuth - pale yellow.
Cadmium - yellow.
Cobalt - dark brown-red.
Copper (protoxide) - red-brown.
- Do. (peroxyde) - yellow-green.
Iron, protoxide salts of - blue.
Manganese - brown.
Mercury (protoxide) - red-brown.
Mercury (peroxyde) - yellow.
Molybdenum - red-brown.
Nickel - yellow-green.
Silver - red-brown.
Tin (protoxide) - white.
Uranium - red-brown.
Zinc - orange-yellow.
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