A Dictionary of Arts: Chromium

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


CHROMIUM. The only one of this metal, which occurs in sufficient abundance for the purposes of art, is the octohedral chrome-ore, commonly called chromate of iron, though it is rather a compound of the oxydes of chromium and iron. The fracture of this mineral is uneven; its lustre imperfect metallic; its colour between iron-black and brownish-black, and its streak brown. Its specific gravity, in the purest state, rises to 4.5; but the usual chrome-ore found in the market varied from 3 to 4. According to Klaproth, this ore consists of oxyde of chromium, 43; protoxide of iron, 34.7; alumina, 20.3; and silica, 2; but Vauquelin's analysis of another specimen gave as above, respectively 55.5, 33, 6, and 2. It is infusible before the blowpipe; but it acts upon the magnetic needle, after having been exposed to the reducing smoky flame. It s entirely soluble in borax, at a height blowpipe heat, and imparts to it a beautiful green color.

Chrome-ore is found at the Bare Hills, near Baltimore, in Maryland; in the Shetland Isles, Unst and Fetlar; the department of Var, in France, in small quantity; and near Portsoy, in Banffshire; as also in Silesia and Bohemia.

The chief application of this ore is to the production of chromate of potash, from which salt the various other preparations of this metal used in the arts are obtained. The ore, freed, as well as possible, from its gangue, is reduced to a fine powder, by being ground in a mill under ponderous edge-wheels, and sifted. It is then mixed with one third or one half its weight of coarsely bruised nitre, and exposed to a powerful heat, for several hours, on a reverberatory hearth, where it is stirred about occasionally. In the large manufactories of this country, the ignition of the above mixture in pots is laid aside, as too operose and expensive. The calcined matter is raked out, and lixiviated with water. The bright yellow solution is then evaporated briskly, and the chromate of potash falls down in the form of a granular salt, which is lifted out from time to time from the bottom with a large ladle, perforated with small holes, and thrown into a draining-box. This saline powder may be formed into regular crystals of neutral chromate of potash, by solution in water and slow evaporation; or it may be converted into a more beautiful crystalline body, the bichromate of potash, by treating its concentrated solution with nitric, muriatic, sulphuric, or acetic acid, or indeed, any acid exercising a stronger affinity for the second atom of the potash than the chromic acid does.

Bichromate of potash, by evaporation of the above solution, and slow cooling, may be obtained in the form of square tables, with bevelled edges, or flat four-sided prisms. They are permanent in the air, have a metallic and bitter taste, and dissolve in about one tenth of their weight of water, at 60° F.; but in one half of their weight of boiling water. They consist of chromic acid 13, potash 6; or, in 100 parts, 68.4+31.6. This salt is much employed in calico-printing and in dyeing; which see.

Chromate of lead, the chrome-yellow of the painter, is a rich pigment of various shades, from deep orange to the palest canary yellow. It is made by adding a limpid solution of the neutral chromate (the above granular salt) to a solution, equally limpid, of acetate or nitrate of lead. A precipitate falls, which must be well washed, and carefully dried out of the reach of any sulphureted vapors. A lighter shade of yellow is obtained by mixing some solution of alum, or sulphuric acid, with the chromate, before pouring it into the solution of lead; and an orange tint is to be procured by the addition of subacetate of lead, in any desired proportion.

For the production of chromate of potash from chrome ore, various other processes have been recommended. The following formulæ, which have been verified in practice, will prove useful to the manufacturers of this important article: -
I. Two parts of chrome ore, containing about 50 per cent. of protoxide of chromium.
One part of saltpetre.
II. Four parts of chrome ore, containing 34 per cent. of protoxide of chromium.
Two parts of potashes.
One part of saltpetre.
III. Four parts of chrome ore. - 34 -
Two of potashes.
Four tenths of a part of peroxyde of manganese.
IV, Three parts of chrome ore.
Four parts of saltpetre.
Two parts of argal.

Some manufactures have contrived to effect the conversion of the oxyde into an acid, and of course to form the chromate of potash, by the agency of potash alone, in a calcining furnace, or in earthen pots fired in a pottery kiln.

After lixiviating the calcined mixtured with water, if the solution be a tolerably pure chromate of potash its value may be inferred, from its specific gravity, by the following table: -

At specific gravity 1.28 it contains about 50 per cent of the salt.
1.21 - - - 33
1.18 - - - 25
1.15 - - - 20
1.12 - - - 16
1.11 - - - 14
1.10 - - - 12

In making the red bichromate of potash from these solutions of the yellow salt, nitric acid was at first chiefly used; but in consequence of its relatively high price, sulphuric, muriatic, or acetic acid has been frequently substituted upon the great scale.

There is another application of chrome which merits some notice here; that of its green oxyde to dyeing and painting on porcelain. This oxyde may be prepared by decomposing, with heat, the chromate of mercury, a salt made by adding to nitrate of protoxide of mercury, chromate of potash, in equivalent proportions. This chromate has a fine cinnabar red, when pure; and, at a dull red heat, parts with a portion of its oxygen and its mercurial oxyde. From M. Dulong's experiments it would appear, that the purest chromate of mercury is not the best adapted for preparing the oxyde of chrome to be used in porcelain painting. He thinks it ought to contain a little oxyde of manganese and chromate of potash, to afford a green colour of a fine tint, especially for pieces that are to receive a powerful heat. Pure oxyde of chrome preserves its colour well enough in a muffle furnace; but, under a stronger fire, it takes a dead-leaf color.

The green oxyde of chrome has come so extensively into use as an enamel colour for porcelain, that a fuller account of the best modes of manufacturing it must prove acceptable to many of my readers.

That oxyde, in combination with water, called the hydrate, may be economically prepared by boiling chromate of potash, dissolved in water, with half its weight of flowers of sulphur, till the resulting green precipitate ceases to increase, which may be easily ascertained by filtering a little of the mixture. The addition of some potash accelerates the operation. This consists in combining the sulphur with the oxygen of the chromic acid, so as to form sulphuric acid, which unites with the potash of the chromate into sulphate of potash, while the chrome oxyde becomes a hydrate. An extra quantity of potash facilitates a deoxidizement of the chromic acid by the formation of hyposulphite and sulphuret of potash, both of which have a strong attraction for oxygen. For this purpose the clear lixivium of the chromate of potash is sufficiently pure, though it should hold some alumina and silica in solution, as it generally does. The hydrate may be freed from particles of sulphur by heating dilute sulphuric acid upon it, which dissolves it; after which t may be precipitated, in the state of a carbonate, by carbonate of potash, not added in excess.

By calcining a mixture of bichromate of potash and sulphur in a crucible, chromic acid is also decomposed, and a hydrated oxyde may be obtained; the sulphur being partly converted int osulphuret of potassium, and partly into sulphuric acid (at the expense of the chromic acid), which combines with the rest of the potash into a sulphate. By careful lixiviation, these two new compounds may be washed away, and the chrome green may be freed from the remaining sulphur, by a slight heat.

Liebig and Wöhler have lately contrived a process for producing a subchromate of lead of a beautiful vermilion hue. Into saltpetre, brought to fusion in a crucible at a gentle heat, pure chrome yellow is to be thrown by small portions at a time. A strong ebullition takes place at each addition, and the mass becomes black, and continues to while it is hot. The chrome yellow is to be added till little of the saltpetre remains undecomposed, care being taken not to overheat the crucible, lest the colour of the mixture should become brown. Having allowed it to settle for a few minutes, during which the dense basic salt falls to the bottom, the fluid part, consisting of chromate of potash and saltpetre, is to be poured off, and it can be employed again in preparing chrome yellow. The mass remaining in the crucible is to be washed with water, and the chrome red being separated from the other matters, is to be dried after proper edulcoration. It is essential for the beauty of the color, that the saline solution should not stand long over the red powder, because the colour is thus apt to become of a dull orange hue. The fine crystalline powder subsides so quickly to the bottom after every ablution, that the above precaution may be easily observed.

As Chromic Acid will probably ere long become an object of interest to the calico printer, I shall describe here the best method of preparing it. To 100 parts of yellow chromate of potash, add 136 of nitrate of barytes, each in solution. A precipitate of the yellow chromate of barytes falls, which being washed and dried would amount to 130 parts. But while still moist it is to be dissolved in water by the intervention of a little nitric acid, and then decomposed by the addition of the requisite quantity of sulphuric acid, whereby the barytes is separated, and the chromic acid remains associated with the nitric acid, from which it can be freed by evaporation to dryness. On re-dissolving the chromic acid residuum in water, filtering and evaporating to a proper degree, 50 parts of chromic acid may be obtained in crystals.

This acid may also be obtained from chromate of lime, formed by mixing chromate of potash and muriate of lime; washing the insoluble chromate of lime which precipitates, and decomposing it by the equivalent quantity of oxalic acid, or for ordinary purposes even sulphuric acid may be employed.

Chromic acid is obtained in quadrangular crystals, of a deep red color; it has a very acrid and styptic taste. It reddens powerfully litmus paper. It is deliquescent in the air. When heated to redness it emits oxygen, and passes into the deutoxide. When a little of it is fused along with vitreous borax, the compound assumes an emerald green color.

As chromic acid parts with its last dose of oxygen very easily, it is capable in certain styles of calico printing of becoming a valuable substitute for chlorine, where this more powerful substance would not from peculiar circumstances be admissible. For this ingenious application, the arts are indebted to that truly scientific manufacturer, M. Daniel Koechlin, of Mulhouse. He discovered that whenever chromate of potash has its acid set free by its being mixed with tartaric or oxalic acid, or a neutral vegetable substance, (starch or sugar for example,) and a mineral acid, a very lively action is produced, with disengagement of heat, and of several gases. The result of this decomposition is the active reagent, chromic acid, possessing valuable properties to the printer. Watery solutions of chromate of potash and tartaric acid being mixed, and effervescence is produced which has the power of destroying vegetable colours. But this power lasts no longer than the effervescence. The mineral acids react upon the chromate of potash only when vegetable colouring matter, gum, starch, or a vegetable acid are present, to determine the disengagement of gas. During this curious change carbonic acid is evolved; and when it takes place in a retort, there is condensed in the receiver a colorless liquid, slightly acid, exhaling somewhat of the smell of vinegar, and containing a little empyreumatic oil. This liquid heated with the nitrates of mercury or silver reduces these metals. On these principles M. Koechlin disharged indigo blue by passing the cloth through a solution of chromate of potash, and printing nitric acid thickened with gum upon certain spots. It is probable that the employment of chromic acid would supersede the necessity of having recourse in many cases to the more corrosive chlorine.

The following directions have been given for the preparation of a blue oxyde of chrome. The concentrated alkaline solution of chromate of potash is to be saturated with weak sulphuric acid, and then to every 8 lbs. is to be added 1 lb. of common salt, and half a pound of concentrated sulphuric acid; the liquid will now acquire a green color. To be certain that the yellow colour is totally destroyed, a small quantity of the liquor is to have potash added to it, and filtered; if the fluid is still yellow, a fresh portion of salt and of sulphuric acid is to be added; the fluid is then to be evaporated to dryness, redissolved, and filtered; the oxyde of chrome is finally to be precipitated by caustic potash. It will be of a greenish-blue color, and being washed, must be collected upon a filter.

Chromate of Potash, adulteration of, to detect. The chromate of potash has the power of combining with other slats up to a certain extent without any very sensible change in its form and appearance; and hence it has been sent into the market falsified by very considerable quantities of sulphate and muriate of potash, the presence of which has often escaped observation, to the great loss of the dyers who use it so extensively. The following test process has been devised by M. Zuber, of Mülhouse. Add a large excess of tartaric acid to the chromate in question, which will decompose it, and produce in a few minutes a deep amethyst color. The supernatant liquor will, if the chromate be pure, afford now to precipitate with the nitrated of barytes or silver; whence the absence of the sulphates and muriates may be inferred. We must, however, use dilute solutions of the chromate and acid, lest bitartrate of potash be precipitated, which will take place if less than 60 parts of water be employed. Nor must we test the liquid till the decomposition be complete, and till the colour verge rather toward the green than the yellow. Eight parts of tartaric acid should be added to one of chromate to obtain a sure and rapid result. If nitrate of potash (saltpetre) is the adulterating ingredient, it may be detected by throwing it on burning coals, when deflagration will ensue. The green colour is a certain mark of the transformation of the chromic acid partially into the chrome oxyde; which is effected equally by the sulphurous acid and sulphureted hydrogen. Here this metallic acid is disoxygenated by the tartaric, as has been long known. The tests which I should prefer are the nitrates of silver and baryta, having previously added so much nitric acid to the solution of the suspected chromate, as to prevent the precipitation of the chromate of silver of baryta. The smallest adulteration by sulphates or muriates will thus be detected.