ORGANIC CHEMISTRY: an Oxygen Compound

JANUARY 25, 1845. the case, the residue we are speaking of has become completely L E C T U R E S converted into cyanuric acid. ON Sulphocyanide of ammonium contains no oxygen, nor does the residue remaining upon its distillation, whilst cyanuric acid is ORGANIC CHEMISTRY: an oxygen compound. It is evident, therefore, that this acid must owe its formation to double decomposition. It is not easy DELIVERED DURING THE WINTER SESSION, 1844, IN THE to designate positively the ultimate link in the chain of this de- the substance from which its forma- University of Giessen. composition-i. e., precise tion proceeds immediately, since the residue in question is ob- BY JUSTUS LIEBIG, M.D., PH. D., F.R.S., M.R.I.A. viously a mixture of several compounds, which hardly admit of£ isolation without alteration. Professor of Chemistry in the University of Giessen. by solvents, undergoing If the residue remaining upon the distillation of sulphocyanide of ammonium is treated with boiling potass lye, the solution CYANOGEN AND ITS COMPOUNDS, CONTINUED-PRODUCTS RESULT- speedily filtered from off the portion remaining undissolved, and ING FROM THE DEC’OMPOSITION OF SULPHOCYANIDE OF AM- the filtrate made to cool quickly, a white heavy powder pre- MONIUM—MELAM—MELAMINE—AMELINE—AMELIDE. cipitates, which, upon being washed with cold water, exhibits only slight traces of alkali. This pulverulent substance seems GENTLEMEN,—Having in my last lecture concluded my obser- to be the principal product of the decomposition of the sulpho- vations on mellon, I will now proceed to the examination of cer- cyanide of ammonium; but if the residue in question is kept tain substances from the of one of the resulting decomposition boiling for some time with the potass lye, it becomes completely of ammonium. The com- sulphocyanides-viz., sulphocyanide dissolved, and the solution, upon no of of ammonium to that of cooling, yields longer any position sulphocyanide corresponds precipitate, and contains now only the products of the decom- of or with this that the cyanate ammonia, urea, difference, oxygen position of that precipitate. The name of melam has been of the cyanate is replaced by sulphur in the sulphocyanide. It assigned to this substance. was to be expected, therefore, that sulphocyanide of ammonia would, upon distillation, yield products bearing a certain relation to the products obtained from sulphocyanogen by the action of heat, on the one hand, and to those resulting from the decomposition of urea, on the other. We have in sulphocyanide of ammonium, hydrosulphocyanic acid in combination with ammonia, and therefore we have the elements of bisulphuret of carbon, ammonia, mellon, and sulphuretted hydrogen, in the following proportions :- It is only after long protracted boiling that the residue remaining upon the distillation of sulphocyanide of ammonium (which residue we will designate by the term crude and impure melam) dissolves completely in dilute solution of caustic potass with evo- lution of ammonia. If this solution is concentrated at a high temperature, and, from time to time, allowed to cool, it deposits lustrous, hard, rhomboidal octahedrons, possessing all the proper- This arrangement of the elements composing sulphocyanide of[- ties of a salifiable base, but without alkaline reaction. The name . of melamine has been to this substance. It is free from ammonium will at once readily explain the decomposition of this assigned substance by the action of heat, and account for the resulting oxygen, and its composition is expressed by the following products. Upon submitting sulphocyanide of ammonium to the formula :- action of heat, bisulphuret of carbon, ammonia, and sulphuretted Ca Ns H,3 hydrogen, are evolved, or sulphuretted hydrogen is evolved in This formula indicates the proportion of this substance combining combination with the ammonia-i. e., as hydrosulphuret of am- with one equivalent of acid, to form a neutral salt. monia-and there remains in the residue a yellow substance, MELAMINE. exhibiting the same deportment as mellon, inasmuch as upon You that melamine contains the elements of one atom being heated to redness, it yields nitrogen gas and cyanogen gas; perceive of mellon and two atoms of ammonia- or if only a moderate degree of heat is made to act upon the sulphocyanide of ammonium, there remains in the residue com- 1 atom of mellon = Ca N4 pounds containing the elements of mellon and of ammonia; and 2 atoms of ammonia = N2 Ha thus we see that this residue is, at all events, convertible into the product which urea yields under the same circumstances- Melamine = Cg N6 Ha acid. To understand this need viz., cyanuric readily, you only All the salts of melamine are Melamine combines is crystallizable. recollect that mellon converted into cyanuric acid by the with the and with the of the action of acids and alkalies. The action of heat directly hydracids so-called hydrates upon sulphocyanide acids. Solution of melamine in water of ammonium as I now a residue oxygen precipitates hydrated yields, just stated, containing from solutions of salt of upon either mellon or combinations of mellon with the elements of magnesia magnesia, boiling ; from salts of ammonia it evolves ammonia at a ammonia; the residue must therefore be convertible, in either high temperature; with perchloride of platinum, melamine forms a crystalline com- case, into acid, or into acid and ammonia. cyanuric cyanuric pound, and also with nitrate of silver it forms a basic double salt. The residuary powder which remains upon submitting sul- If the alkaline solution from which the melamine has been de- of ammonium to a moderate of heat, is of a phocyanide degree posited is supersaturated with acetic acid, a shining-white, some- dirty-grey colour; its composition varies exceedingly, according what gelatinous, precipitate is obtained. This is another base, to to the lower or of heat for the decom- higher degree applied which the name of ameline has been assigned. position of the sulphocyanide of ammonium; it dissolves almost completely when gently heated in concentrated sulphuric acid, AMELINE. only a very inconsiderable portion remaining undissolved; The In order to obtain this base perfectly pure, the precipitate procured simple addition of water to this solution does not disturb it; but upon supersaturating the alkaline solution of the crude and impure if the solution be diluted with water and then kept boiling for melam, after the crystallization of melamine, is washed, and, whilst a few hours, and afterwards allowed to cool, a copious amount still moist, projected into dilute and hot nitric acid until the acid is of crystals of cyanuric acid is obtained, and in the solution there saturated; the solution thus obtained is filtered, and evaporated at a remains sulphate of ammonia. It is easy to ascertain the exact gentle heat. When the solution has thus become somewhat con- moment when this transformation of the residue into cyanuric acid centrated, nitrate of ameline crystallizes in fine, white, transparent is completed. The test employed for this purpose is carbonate prisms, which are then re-dissolved in very dilute nitric acid, and of ammonia. Upon adding this substance to the solution of the the solution treated with carbonate of ammonia, when the pure residue in sulphuric acid, after its dilution with water, a white ameline precipitates. This precipitate of pure ameline has a precipitate is obtained, which is insoluble in water. After’ the silkylustre, and exhibits under the microscope the form of fine solution has been kept boiling for some time, the addition of this transparent needles. Ameline is a very weak base, which, like re-agent causes it simply to become turbid, and subsequently pre- melamine, combines with- acids, but without destroying their acid puces not the slightest alteration in its appearance. When this is reaction; with perchloride of it forms a neutral double No. 1117. platinum 82 compound, and with nitrate of silver a basic double compound. phate of melamine. But upon dissolving melamine at a high The formula- I temperature, in moderately concentrated hydrochloric acid, this substance and the solution - - - disappears completely, hydrochloric expresses its composition. contains ameline and ammonia instead. This decomposition is This substance therefore contains the elements of one atom of readily explained: two atoms of water join the elements of one mellon, one atom of ammonia, and two atoms of water- I atom of melamine, whilst, on the other hand, the elements of one atom of ammonia separate If melam is dissolved in concentrated nitric acid, or melamine and ameline in concentrated sulphuric acid, and the solutions obtained are mixed, in the first place, with double their volume of and afterwards with four times their volume of It is doubtless owing to this decomposition that the crude water, alcohol, and when treated with concentrated another white substance separates, which contains all the carbon impure melam, hydrochloric acid, in the same manner as as the of the melam, or of the melamine and ameline, and exhibits in its melamine, yields principal of the one atom of a resemblance to but differs product ensuing decomposition, simply ameline; physical properties great ameline, melam and four atoms of water two atoms of from this last substance in its and chemical yield ameline, whilst essentially composition one atom of ammonia properties. Upon being heated in moderately concentrated nitric separates acid,

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