A Dictionary of Arts, Manufactures and Mines / containing a clear exposition of their principles and practice

by Andrew Ure

Another process has lately been practised to a considerable extent in France, though it does not afford a white lead equal in body and opacity to the products of the preceding operations. M. Thenard first established the principle, and MM. Brechoz and Leseur contrived the arrangements of this new method, which was subsequently executed on a great scale by MM. Roard and Brechoz.

A subacetate of lead is formed by digesting a cold solution of uncrystallized acetate, over litharge, with frequent agitation. It is said that 65 pounds of purified pyrolignous acid, of specific gravity 1·056, require, for making a neutral acetate, 58 pounds of litharge; and hence, to form the subacetate, three times that quantity of base, or 174 pounds, must be used. The compound is diluted with water, as soon as it is formed, and being decanted off quite limpid, is exposed to a current of carbonic acid gas, which, uniting with the two extra proportions of oxide of lead in the subacetate, precipitates them in the form of a white carbonate, while the liquid becomes a faintly acidulous acetate. The carbonic acid may be extricated from chalk, or other compounds, or generated by combustion of charcoal, as at Clichy; but in the latter case, it must be transmitted through a solution of acetate of lead before being admitted into the subacetate, to deprive it of any particles of sulphuretted hydrogen. When the precipitation of the carbonate of lead is completed, and well settled down, the supernatant acetate is decanted off, and made to act on another dose of litharge. The deposit being first rinsed with a little water, this washing is added to the acetate; after which the white lead is thoroughly elutriated. This repetition of the process may be indefinitely made; but there is always a small loss of acetate, which must be repaired, either directly or by adding some vinegar.

In order to obtain the finest white lead by the process with earthen pots containing vinegar buried in fermenting tan, and covered by a grating of lead, the metal should be so thin as to be entirely convertible into carbonate; for whenever any of it remains, it is apt to give a gray tint to the product: if the temperature of the fermenting mass is less than 90° Fahr., some particles of the metal will resist the action of the vinegar, and degrade the colour; and if it exceeds 122°, the white verges into yellow, in consequence of some carbonaceous compound being developed from the principles of the acetic acid. The dung and tan have been generally supposed to act in this process by supplying carbonic acid, the result of their fermentation; but it is now said that this explanation is inexact, because the best white lead can be obtained by the entire exclusion of air from the pots in which the carbonation of the metal is carried on. We are thence led to conclude that the lead is oxidized at the expense of the oxygen of the vinegar, and carbonated by the agency of its oxygen and carbon; the hydrogen of the acid being left to associate itself with the remaining oxygen and carbon, so as to constitute an ethereous compound: thus, supposing the three atoms of oxygen to form, with one of lead and one of carbon, an atom of carbonate, then the remaining three atoms of carbon and three of hydrogen would compose olefiant gas.

It is customary on the continent to mould the white lead into conical loaves, before sending them into the market. This is done by stuffing well-drained white lead into unglazed earthen pots, of the requisite size and shape, and drying it to a solid mass, by exposing these pots in stove-rooms. The moulds being now inverted on tables, discharge their contents, which then receive a final desiccation; and are afterwards put up in pale-blue paper, to set off the white colour by contrast. Nothing in all the white-lead process is so injurious as this pot operation; a useless step, fortunately unknown in Great Britain. Neither greasing the skin, nor wearing thick gloves, can protect the operators from the diseases induced by the poisonous action of the white lead; and hence they must be soon sent off to some other department of the work.

It has been supposed that the differences observed between the ceruse of Clichy and the common kinds, depend on the greater compactness of the particles of the latter, produced by their slower aggregation; as also, according to M. Robiquet, on the former containing considerably less carbonic acid. See infrà.

Mr. Ham proposed, in a patent dated June, 1826, to produce white lead with the aid of the following apparatus, a, a, ([fig. 1201.]) are the side-walls of a stove-room, constructed of bricks; b, is the floor of bricks laid in Roman cement; c, c, are the side-plates, between which and the walls, a quantity of refuse tanner’s bark, or other suitable vegetable matter, is to be introduced. The same material is to be put also into the lower part at d (upon a false bottom of grating?) The tan should rise to a considerable height, and have a series of strips of sheet lead e, e, e, placed upon it, which are kept apart by blocks or some other convenient means, with a space open at one end of the plates, for the passage of the vapours; but above the upper plates, boards are placed, and covered with tan, to confine them there. In the lower part of the chamber, coils of steam-pipe f, f, are laid in different directions to distribute heat; g, is a funnel-pipe, to conduct vinegar into the lower part of the vessel; and h, is a cock to draw it off, when the operation is suspended. The acid vapours raised by the heat, pass up through the spent bark, and on coming into contact with the sheets of lead, corrode them. The quantity of acid liquor should not be in excess; a point to be ascertained by means of the small tube i, at top, which is intended for testing it by the tongue. k, is a tube for inserting a thermometer, to watch the temperature, which should not exceed 170° Fahr. I am not aware of what success has attended this patented arrangement. The heat prescribed is far too great.

A magnificent factory has been recently erected at West Bromwich, near Birmingham, to work a patent lately granted to Messrs. Gossage and Benson, for making white lead by mixing a small quantity of acetate of lead in solution with slightly damped litharge, contained in a long stone trough, and passing over the surface of the trough currents of hot carbonic acid, while its contents are powerfully stirred up by a travelling-wheel mechanism. The product is afterwards ground and elutriated, as usual. The carbonic acid gas is produced from the combustion of coke. I am told that 40 tons of excellent white lead are made weekly by these chemico-mechanical operations.

Messrs. Button and Dyer obtained a patent about a year and a half ago, for making white lead by transmitting a current of purified carbonic acid gas, from the combustion of coke, through a mixture of litharge and nitrate of lead, diffused and dissolved in water, which is kept in constant agitation and ebullition by steam introduced through a perforated coil of pipes at the bottom of the tub. The carbonate of lead is formed here upon the principle of Thenard’s old process with the subacetate; for the nitrate of lead forms with the litharge a subnitrate, which is forthwith transformed into carbonate and neutral nitrate, by the agency of the carbonic acid gas. I have discovered that all sorts of white lead produced by precipitation from a liquid, are in a semi-crystalline condition; appear, therefore, semi-transparent, when viewed in the microscope; and do not cover so well as white lead made by the process of vinegar and tan, in which the lead has remained always solid during its transition from the blue to the white state; and hence consists of opaque particles.