Copper Nitrate, Cu(NO₃)₂.6H₂O.—This salt may occasionally be obtained in colour works as a by-product. When nitric acid is poured over copper, there follows a copious evolution of nitric oxide, which produces brown fumes of nitrogen peroxide in air. Nitric oxide may be used to convert ferrous into ferric salts, a transformation required in making Prussian blue. In working in this way, nitric acid is poured over copper contained in a vessel provided with a delivery tube for the gas. The blue solution is at once used. Pure copper nitrate forms fine blue crystals, which very readily deliquesce in the air. The solution is therefore generally used as it is prepared.
Copper Acetate, Cu(C₂H₃O₂)₂.H₂O.—Copper is readily attacked by acetic acid. A number of salts are formed, of which some are used as pigments. For our purpose it will be sufficient to describe the manufacture of verdigris; few colour makers prepare any other copper acetate. A solution of this salt is most simply prepared in the following manner: Slaked lime is stirred with strong vinegar, and the solution left in contact with the excess of lime so long as it has a weak acid reaction. The solution, which contains acetate of lime, is poured into a solution of copper sulphate so long as a precipitate of sulphate of lime is formed. When this has been separated from the liquid, the latter is ready for further treatment. It contains only a very small quantity of dissolved sulphate of lime, which is not harmful in the preparation of colours.
In addition to the copper compounds mentioned here, several others were formerly used as pigments, or in the preparation of pigments which are no longer employed, because copper compounds of good colour can be obtained in a cheaper manner.
The same precautions should be taken in the use of copper colours which were mentioned for lead pigments; copper compounds are equally sensitive towards sulphuretted hydrogen, by which they are gradually discoloured.
Mercury Compounds.—Mercury forms compounds which, vermilion in particular, are used as pigments, and others which are used in the preparation of pigments. In many cases metallic mercury is the starting point in the preparation of the mercury compounds. The compounds commonly known as calomel and corrosive sublimate are also used.
Mercurous Nitrate, HgNO₃.—Nitric acid acts upon mercury in a manner differing according to its strength, and according to whether the mercury or the nitric acid is used in excess. In order to prepare mercurous nitrate, acid free from chlorine must be diluted at least with four times its volume of water, and the mercury must be in excess. On warming, the mercury is gradually dissolved, and, on cooling, the solution deposits colourless crystalline needles of the salt. A further crop of crystals is obtained after evaporating the solution.
When the action of nitric acid is over, the solution must be at once separated from the excess of mercury to prevent the formation of basic salts. If the salt has been properly made, it is completely soluble in water, but if a lemon yellow precipitate is formed on dissolving, the nitrate contains a basic salt, which can only be dissolved by warming and adding more nitric acid.
Mercuric Nitrate, Hg(NO₃)₂, is most simply obtained by warming mercury with very strong nitric acid. The heating must be continued until a test portion of the solution no longer gives a precipitate with hydrochloric acid. When this solution is evaporated, nitric acid is given off, and a salt crystallising in white needles is obtained, which dissolves in water with the separation of a yellow basic salt. It is therefore better to use the hot solution, which contains a little free acid, without evaporating.
Instead of mercurous and mercuric nitrates, the corresponding sulphates may be used, but the chlorides are more frequently employed since they can be readily obtained from the makers.
Mercurous Chloride (Calomel), HgCl, is obtained pure by adding common salt solution to a solution of mercurous nitrate and washing the precipitate, which is insoluble in water.