By mineral pigments we understand those which consist of compounds of metals with elements such as sulphur, chlorine and iodine, or with compound radicals, such as cyanogen, or of metallic salts.

Looking at the classification of mineral pigments from the chemical standpoint, a grouping according to the constituents would appear preferable, and we should have groups of colours consisting of metallic oxides, sulphides, salts, etc. In such a division of pigments, according to their constituents, no regard would be taken of the colour of the pigment. The white zinc oxide would be placed in the same group with yellow lead oxide and red lead oxide; and red mercury sulphide and yellow cadmium sulphide would fall into the same group of the sulphur compounds.

The chemical composition of a pigment is of less importance to the colour manufacturer than its shade, and it therefore appears to us more reasonable to prefer to classify mineral pigments according to similarity of colour. We shall therefore place all those mineral pigments together which possess the same colour.

Common usage differs from the scientific in the description of colours. In the physical sense, yellow, red and blue are the so-called “simple colours,” between which lie orange, green and violet as “mixed colours”. Physics knows no white colour and no black colour, but describes white as a mixture of all the simple colours and black as the absence of colour. A grey or brown shade, produced by different mixtures of simple colours, is just as little known in the scale of colours as white or black.

The colour maker follows, as we have said above, the common manner of speaking; to him white and black are equally as much colours as red and green. Besides the pure principal colours (yellow, red and blue), and the mixed colours obtained from them (orange, green and violet), colour makers distinguish many shades of each colour—lemon yellow, sulphur yellow, cherry red, blood red, violet blue, etc. For the present purpose it is of great importance to accurately distinguish the several shades, for the value of many colours is in proportion to their beauty of shade. The colour maker is often required to produce a colour of some particular shade, which he accomplishes in many cases by a suitable alteration in the process by which the colour is made, in other cases by mixing different colours, in which event chemistry is of no help to him; he must depend on the sensitiveness of his eyes to colour.

White Mineral Pigments.—We are acquainted with a great number of white or, more properly, colourless mineral compounds; they possess the property of reflecting, undecomposed, all the rays of light which fall upon them, in consequence of which they produce that impression upon the eye which we call white. According as a white substance reflects every ray of light or absorbs a portion, we see it as a brilliant pure white or, in the latter case, as a white with a grey tinge. If a white body reflects the majority of the rays of light falling on it, but decomposes a small number, we perceive a white which has a yellow, blue or red tinge.

The most valuable white for the colour maker is evidently that which reflects, unaltered, all the rays of light; it is the most brilliant, and free from every tinge of colour. The physical condition of the substance is most important. Solid substances are either crystalline, that is, possess definite shapes formed according to a regular law, or they are amorphous, that is, are composed of irregularly formed particles. Snow and white lead may serve as representatives of these two classes. Snow is composed of small colourless crystals of ice, the flat surfaces of which reflect, undecomposed, the light falling on them. The smaller are the crystals, the more pure appears to us the whiteness of the snow, and the thinner is the layer of snow required to produce the sensation of whiteness. But if the snow crystals are larger, the white appears to have a bluish tinge, and only a thick layer of snow is opaque. White lead, being an amorphous substance in a condition of very fine division, reflects the light very regularly, so that a thin layer of white lead appears quite opaque.

Among the artificial pigments, crystalline or amorphous, exactly the same conditions hold good as between snow and white lead. Of amorphous pigments a very thin layer is in most cases sufficient to make the surface upon which they are spread invisible, or, as the technical expression runs, “to cover,” whilst crystalline substances possess a smaller covering power. A striking example of this is seen by a comparison of two white pigments, white lead and “patent white” (lead oxychloride). The former is amorphous, the latter crystalline. Both are completely colourless and reflect white light, but in consequence of its amorphous condition and finer particles, white lead possesses far greater covering power than “patent white”.

Among all other colours the same rule holds. Amorphous pigments have always a greater covering power than crystalline. The smaller the crystals of the latter the greater is their covering power, so that in preparing pigments of a crystalline character care must be taken to make the crystals as small as possible.

From the above definition of white pigments it follows that an immense number must exist, since every colourless substance in a state of fine division appears white. Generally only those bodies are used which are insoluble in water, or almost insoluble, and which possess great covering power. The following may be mentioned as white pigments, only a few of which are in use: white lead, white zinc, permanent white, lead oxychloride, lead sulphate and sulphite, zinc oxychloride, lead antimoniate, antimony white, tin white, tungsten white, and in addition certain earths, pipe clay, china clay, etc. Several of these pigments are far too expensive for ordinary use, and have no advantage over much cheaper pigments except for very special purposes, such, for example, as bismuth white for cosmetics.

In general use we find very few artificial white pigments; these are lead, zinc and barium compounds. Circumstances may arise which make it expedient for the colour maker to manufacture other white pigments, for example, a demand for them, or favourable opportunities for obtaining the requisite raw materials.

The white lead pigments, of which there is a large number, as we have indicated, all have the great disadvantage that they are not permanent, that is, are changed by atmospheric influences. It is well known that lead is a very delicate reagent for sulphuretted hydrogen, with the sulphur of which it forms a black compound. Now the air, especially in towns, contains sulphur in the form of sulphuretted hydrogen or ammonium sulphide; though the quantity is very small, the fate of every white or coloured lead pigment is decided by it; after a longer or shorter time it will be discoloured, will gradually darken, and finally be turned black. In spite of this great changeableness of lead pigments they are used by artists and painters, although the majority could be replaced by more permanent pigments entirely unaltered by the atmosphere.

White Lead.

This pigment, which in addition to other good properties has remarkable covering power, was amongst the earliest known artificial pigments. Already in the fourth century before Christ, Dioscorides described the preparation of white lead, which was obtained by exposing lead to the action of the vapours of vinegar, removing the white layer and treating it with water. The Roman writers describe a similar method; they use the name cerussa, under which white lead is known to-day in commerce.

Although white lead has been so long known, it was left to Bergmann, in 1774, to show that it contained carbonic acid; before that it was believed to be lead acetate. The development of analytical chemistry was followed by a knowledge of its constitution and the use of more rational methods of manufacture. Whilst in the middle ages the manufacture of white lead was almost exclusively in the hands of the Dutch and Venetians, in later years it gradually spread, and now many works are concerned in the manufacture of this pigment. That adulterations of white lead were not rare in former times appears from the writings of Basil Valentine, an alchemist of the fifteenth century.

Commercially white lead is known under most varied titles, of which the following are the principal: White lead, Venetian white, Dutch white, Krems white, Kremnitz white, flake white, etc.

According to its chemical composition, white lead is a compound of lead carbonate and lead hydroxide, that is, a basic lead carbonate. Commercial white lead, apart from intentional admixtures of other white substances, contains lead carbonate and lead hydroxide in varying proportions, as is shown by the following analyses by Mulder, who found that all the samples examined by him were composed according to one or other of the following formulæ:—

According to Hochstetter, the manufacture of white lead must be directed to obtaining the compound 2 PbCO₃.(OH)₂, which possesses the following percentage composition:—

The compound of this composition is distinguished by being completely amorphous, and so possesses the greatest covering power. Commercial white leads, as is seen from the formulæ of Mulder, may differ appreciably from this composition, when they will have a smaller covering power, since they will contain some quantity of neutral lead carbonate, PbCO₃ (containing 83·46 per cent. of PbO), which is crystalline.

White lead is prepared according to very different methods, the principle of which consists in subjecting a solution of tribasic lead acetate to the action of carbonic acid, by which the basic carbonate is produced and the neutral acetate formed, the latter being then reconverted into the basic acetate, which again serves to produce white lead and so on.