Scientific American Supplement, No. 455, September 20, 1884 | Page 5

The boiling must be well kept up, otherwise the precipitate assumes a yellow-green color, from the formation of copper arsenite; in that case acetic acid must be added, and the boiling continued a few minutes longer. The precipitate then becomes crystalline, and acquires the fine green color peculiar to the aceto-arsenite." I do not know from personal knowledge, but I have always understood that the copper salt employed in its manufacture in France is the acetate. This would account, in my opinion, for the larger crystalline flakes in which it is obtained in France than can be produced by the English method of manufacturing it. Cupric acetate is never employed, I believe, in England--the much cheaper copper salt, the sulphate, being always employed.
In "Miller's Chemistry" it is stated it "may be obtained by boiling solutions of arsenious anhydride and cupric acetate, and adding to the mixture an equal bulk of cold water." Why it should be recommended to add cold water, I am at a loss to understand.
In Drs. Roscoe and Schorlemmer's large work on "Chemistry," and in the English edition of "Wagner's Handbook of Chemical Technology," edited by Mr. Crookes, the process as described by Dr. Ehrmann in the "Ann. Pharm.," xii., 92, is given. It is thus stated in Wagner's work: "This pigment is prepared by first separately dissolving equal parts by weight of arsenious acid and neutral acetate of copper in boiling water, and next mixing these solutions while boiling. There is immediately formed a flocculent olive-green colored precipitate of arsenite of copper, while the supernatant liquid contains free acetic acid. After a while the precipitate becomes gradually crystalline, at the same time forming a beautiful green pigment, which is separated from the liquid by filtration, and after washing and carefully drying is ready for use. The mode of preparing this pigment on a large scale was originally devised by M. Braconnot, as follows: 15 kilos. of sulphate of copper are dissolved in the smallest quantity of boiling water, and mixed with a boiling and concentrated solution of arsenite of soda or potassa, so prepared as to contain 20 kilos. of arsenious acid. There is immediately formed a dirty greenish-colored precipitate which is converted into Schweinfurt green by the addition of some 15 liters of concentrated wood-vinegar. This having been done, the precipitate is immediately filtered off and washed."
As I have already stated, the copper salt used in the manufacture of this pigment in England is the sulphate, and it is carried out pretty much according to Braconnot's method as described by Dr Ehrmann; but any one would infer, from reading his description of the manufacturing process, that the compound, aceto-arsenite of copper, was formed almost immediately after the addition of the acetic acid, a higher or lower atmospheric temperature having no effect in hastening or retarding the formation. Furthermore, it is not stated whether the compound forms more readily in an acid or neutral solution, or whether it can or cannot be formed in a neutral one; now both these points are important to notice in describing its manufacture. As regards the former I shall notice it presently, and, as far as my knowledge extends, the pigment will not form when the solution is neutral.
The operation is conducted in the following manner in the factory: The requisite quantity of sulphate of copper is placed in a large wooden vat, and hot water added to dissolve it; the requisite quantity of arsenic (arsenious anhydride) and carbonate of soda, the latter not in quantity quite sufficient to neutralize the whole of the sulphuric acid set free from the sulphate of copper on the precipitation of the copper as arsenite, are placed in another wooden vessel; water is then added, and the formation of the arsenite of soda and its solution are aided by the introduction of steam into the liquid. When complete solution has been effected the arsenic solution is run off into the vat containing the solution of the sulphate of copper, arsenite of copper being at once precipitated. The necessary quantity of acetic acid is afterward added. In warm weather the formation of the aceto-arsenite soon commences after the addition of the vinegar; but, even in that case, it takes a week or more to have the whole of a big batch of arsenite converted into the aceto-arsenite; and perfect conversion is necessary, as the presence of a very minute quantity of unchanged arsenite lowers very much the price of the emerald pigment, and a by no means large quantity renders the pigment unsalable, owing to its dirty yellowish-green color. In cold weather a much longer time is required for its complete conversion; even at the end of a fortnight or three weeks there frequently remains sufficient unconverted arsenite to affect seriously the selling price of