Page:EB1911 - Volume 06.djvu/313

 W. Hittorf thinks that two allotropic forms of chromium exist (Zeit. für phys. Chem., 1898, 25, p. 729; 1899, 30, p. 481; 1900, 34, p. 385), namely active and inactive chromium; while W. Ostwald (ibid., 1900, 35, pp. 33, 204) has observed that on dissolving chromium in dilute acids, the rate of solution as measured by the evolution of gas is not continuous but periodic. It is largely made as ferro-chrome, an alloy containing about 60-70% of chromium, by reducing chromite in the electric furnace or by aluminium.

Chromium and its salts may be detected by the fact that they give a deep green bead when heated with borax, or that on fusion with sodium carbonate and nitre, a yellow mass of an alkaline chromate is obtained, which, on solution in water and acidification with acetic acid, gives a bright yellow precipitate on the addition of soluble lead salts. Sodium and potassium hydroxide solutions precipitate green chromium hydroxide from solutions of chromic salts; the precipitate is soluble in excess of the cold alkali, but is completely thrown down on boiling the solution. Chromic acid and its salts, the chromates and bichromates, can be detected by the violet coloration which they give on addition of hydrogen peroxide to their dilute acid solution, or by the fact that on distillation with concentrated sulphuric acid and an alkaline chloride, the red vapours of chromium oxychloride are produced. The yellow colour of normal chromates changes to red on the addition of an acid, but goes back again to yellow on making the solution alkaline. Normal chromates on the addition of silver nitrate give a red precipitate of silver chromate, easily soluble in ammonia, and with barium chloride a yellow precipitate of barium chromate, insoluble in acetic acid. Reducing agents, such as sulphurous acid and sulphuretted hydrogen, convert the chromates into chromic salts. Chromium in the form of its salts may be estimated quantitatively by precipitation from boiling solutions with a slight excess of ammonia, and boiling until the free ammonia is nearly all expelled. The precipitate obtained is filtered, well washed with hot water, dried and then ignited until the weight is constant. In the form of a chromate, it may be determined by precipitation, in acetic acid solution, with lead acetate; the lead chromate precipitate collected on a tared filter paper, well washed, dried at 100° C. and weighed; or the chromate may be reduced by means of sulphur dioxide to the condition of a chromic salt, the excess of sulphur dioxide expelled by boiling, and the estimation carried out as above.

The atomic weight of chromium has been determined by S. G. Rawson, by the conversion of pure ammonium bichromate into the trioxide (Journal of Chem. Soc., 1899, 55, p. 213), the mean value obtained being 52.06; and also by C. Meinecke, who estimated the amount of silver, chromium and oxygen in silver chromate, the amount of oxygen in potassium bichromate, and the amount of oxygen and chromium in ammonium bichromate (Ann., 1891, 261, p. 339), the mean value obtained being 51.99.

Chromium forms three series of compounds, namely the chromous salts corresponding to CrO, chromous oxide, chromic salts, corresponding to Cr2O3, chromium sesquioxide, and the chromates corresponding to CrO3, chromium trioxide or chromic anhydride. Chromium sesquioxide is a basic oxide, although like alumina it acts as an acid-forming oxide towards strong bases, forming salts called chromites. Various other oxides of chromium, intermediate in composition between the sesquioxide and trioxide, have been described, namely chromium dioxide, Cr2O3·CrO3, and the oxide CrO3·2Cr2O3.

Chromous oxide, CrO, is unknown in the free state, but in the hydrated condition as CrO·H2O or Cr(OH)2 it may be prepared by precipitating chromous chloride by a solution of potassium hydroxide in air-free water. The precipitate so obtained is a brown amorphous solid which readily oxidizes on exposure, and is decomposed by heat with liberation of hydrogen and formation of the sesquioxide. The sesquioxide, Cr2O3, occurs native, and can be artificially obtained in several different ways, e.g., by igniting the corresponding hydroxide, or chromium trioxide, or ammonium bichromate, or by passing the vapours of chromium oxychloride through a red-hot tube, or by ignition of mercurous chromate. In the amorphous state it is a dull green, almost infusible powder, but as obtained from chromium oxychloride it is deposited in the form of dark green hexagonal crystals of specific gravity 5.2. After ignition it becomes almost insoluble in acids, and on fusion with silicates it colours them green; consequently it is used as a pigment for colouring glass and china. By the fusion of potassium bichromate with boric acid, and extraction of the melt with water, a residue is left which possesses a fine green colour, and is used as a pigment under the name of Guignet’s green. In composition it approximates to Cr2O3·H2O, but it always contains more or less boron trioxide. Several forms of hydrated chromium sesquioxide are known; thus on precipitation of a chromic salt, free from alkali, by ammonia, a light blue precipitate is formed, which after drying over sulphuric acid, has the composition Cr2O3·7H2O, and this after being heated to 200° C. in a current of hydrogen leaves a residue of composition CrO·OH or Cr2O3·H2O which occurs naturally as chrome ochre. Other hydrated oxides such as Cr2O3·2H2O have also been described. Chromium trioxide, CrO3, is obtained by adding concentrated sulphuric acid to a cold saturated solution of potassium bichromate, when it separates in long red needles; the mother liquor is drained off and the crystals are washed with concentrated nitric acid, the excess of which is removed by means of a current of dry air. It is readily soluble in water, melts at 193° C., and is decomposed at a higher temperature into chromium sesquioxide and oxygen; it is a very powerful oxidizing agent, acting violently on alcohol, converting it into acetaldehyde, and in glacial acetic acid solution converting naphthalene and anthracene into the corresponding quinones. Heated with concentrated hydrochloric acid it liberates chlorine, and with sulphuric acid it liberates oxygen. Gaseous ammonia passed over the oxide reduces it to the sesquioxide with formation of nitrogen and water. Dissolved in hydrochloric acid at –20°, it yields with solutions of the alkaline chlorides compounds of the type MCl·CrOCl3, pointing to pentavalent chromium. For salts of this acid-forming oxide and for perchromic acid see.

The chromites may be looked upon as salts of chromium sesquioxide with other basic oxides, the most important being (q.v.).

Chromous chloride, CrCl2, is prepared by reducing chromic chloride in hydrogen; it forms white silky needles, which dissolve in water giving a deep blue solution, which rapidly absorbs oxygen, forming basic chromic salts, and acts as a very strong reducing agent. The bromide and iodide are formed in a similar manner by heating the metal in gaseous hydrobromic or hydriodic acids.

Chromous sulphate, CrSO4·7H2O, isomorphous with ferrous sulphate, results on dissolving the metal in dilute sulphuric acid or, better, by dissolving chromous acetate in dilute sulphuric acid, when it separates in blue crystals on cooling the solution. On pouring a solution of chromous chloride into a saturated solution of sodium acetate, a red crystalline precipitate of chromous acetate is produced; this is much more permanent in air than the other chromous salts and consequently can be used for their preparation. Chromic salts are of a blue or violet colour, and apparently the chloride and bromide exist in a green and violet form.

Chromic chloride, CrCl3, is obtained in the anhydrous form by igniting a mixture of the sesquioxide and carbon in a current of dry chlorine; it forms violet laminae almost insoluble in water, but dissolves rapidly in presence of a trace of chromous chloride; this action has been regarded as a catalytic action, it being assumed that the insoluble chromic chloride is first reduced by the chromous chloride to the chromous condition and the original chromous chloride converted into soluble chromic chloride, the newly formed chromous chloride then reacting with the insoluble chromic chloride. Solutions of chromic chloride in presence of excess of acid are green in colour. According to A. Werner, four hydrated chromium chlorides exist, namely the green and violet salts, CrCl3·6H2O, a hydrate, CrCl3·10H2O and one CrCl3·4H2O. The violet form gives a purple solution, and all its chlorine is precipitated by silver nitrate, the aqueous solution containing four ions, probably Cr(OH2)6 and three chlorine ions. The green salt appears to dissociate in aqueous solution into two ions, namely CrCl2(OH2)4 and one chlorine ion, since practically only one-third of the chlorine is precipitated by silver nitrate solution at 0° C. Two of the six water molecules are easily removed in a desiccator, and the salt formed, CrCl3·4H2O, resembles the original salt in properties, only one-third of the chlorine being precipitated by silver nitrate. In accordance with his theory of the constitution of salts Werner formulates the hexahydrate as CrCl2·(OH2)4·Cl·2H2O.

Chromic bromide, CrBr3, is prepared in the anhydrous form by the same method as the chloride, and resembles it in its properties. The iodide is unknown.

The fluoride, CrF3, results on passing hydrofluoric acid over the heated chloride, and sublimes in needles. The hydrated fluoride, CrF3·9H2O, obtained by adding ammonium fluoride to cold chromic sulphate solution, is sparingly soluble in water, and is decomposed by heat.

Oxyhalogen derivatives of chromium are known, the oxychloride, CrO2Cl2, resulting on heating potassium bichromate and common salt with concentrated sulphuric acid. It distils over as a dark red liquid of boiling point 117° C., and is to be regarded as the acid chloride corresponding to chromic acid, CrO2(OH)2. It dissolves iodine and absorbs chlorine, and is decomposed by water with formation of chromic and hydrochloric acids; it takes fire in contact with sulphur, ammonia, alcohol, &c., and explodes in contact with phosphorus; it also acts as a powerful oxidizing agent. Heated in a closed tube at 180° C. it loses chlorine and leaves a black residue of trichromyl chloride, Cr3O6Cl2, which deliquesces on exposure to air.