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nydus/The Principles of Chemistry, Volume IPublic
Page 192 of 822
Table of Contents

CHAPTER IX COMPOUNDS OF CARBON WITH OXYGEN AND NITROGEN

are insoluble in water. They form double salts with potassium cyanide and similar metallic cyanides, an example of which we will consider in a further description of the yellow prussiate. Not only are some of the double salts remarkable for their constancy and comparative stability, but so also are the soluble salt HgC 2 N 2 , the insoluble silver cyanide AgCN, and even potassium cyanide in the absence of water. The last salt, when fused, acts as a reducing agent with its elements K and C, and oxidises when fused with lead oxide, forming potassium cyanate, KOCN, which establishes the connection between HCN and OHCN—that is, between the nitriles of formic and carbonic acids—and this connection is the same as that between the acids themselves, since formic acid, on oxidation, yields carbonic acid. Free cyanogen, (CN) 2 or CNCN, corresponds to hydrocyanic acid in the same manner as free chlorine, Cl 2 or ClCl, corresponds to hydrochloric acid. This composition, judging from what has been already stated, exactly expresses that of the nitrile of oxalic acid, and, as a matter of fact, oxalate of ammonia and the amide corresponding with it (oxamide, Note ), on being heated with phosphoric anhydride, which takes up the water, yield cyanogen , (CN) 2 . This substance is also produced by simply heating some of the metallic cyanides. Mercuric cyanide is particularly adapted for this purpose, because it is easily obtained in a pure state and is then very stable. If mercuric cyanide be heated, it decomposes, in like manner to mercury oxide, into metallic mercury and cyanogen: HgC 2 N 2 = Hg + C 2 N 2 . When cyanogen is formed, part of it always polymerises into a dark brown insoluble substance called paracyanogen , capable of forming cyanogen when heated to redness. Cyanogen is a colourless, poisonous gas, with a peculiar smell and easily condensed by cooling into a colourless liquid, insoluble in water and having a specific gravity of 0·86. It boils at about -21°, and therefore cyanogen may be easily condensed into a liquid by a strong freezing mixture. At -35° liquid cyanogen solidifies. The gas is soluble in water and in alcohol to a considerable extent—namely, 1 volume of water absorbs as much as 4½ volumes, and alcohol 23 volumes. Cyanogen resists the action of a tolerably high temperature without decomposing, but under the action of the electric spark the carbon is separated, leaving a volume of nitrogen equal to the volume of the gas taken. As it contains carbon it burns, and the colour of the flame is reddish-violet, which is due to the presence of nitrogen, all compounds of which impart more or less of this reddish-violet hue to the flame. During the combustion of cyanogen, carbonic anhydride and nitrogen are formed. The same products are obtained in the eudiometer with oxygen or by the action of cyanogen on many oxides at a red heat.

The relation of cyanogen to the metallic cyanides is seen not only in the fact that it is formed from mercuric cyanide, but also by its forming cyanide of sodium or potassium on being heated with either of those metals, the sodium or potassium taking fire in the cyanogen. On heating a mixture of hydrogen and cyanogen to 500° (Berthelot),59 or under the action of the silent discharge (Boilleau), hydrocyanic acid is formed, so that the reciprocity of the transitions does not leave any doubt in the matter that all the nitriles of the organic acids contain cyanogen, just as all the organic acids contain carboxyl and in it the elements of carbonic anhydride. Besides the amides,60 the nitriles (or cyanogen compounds, RCN), and nitro-compounds (containing the radicle of nitric acid, RNO2), there are a great number of other substances containing at the same time carbon and nitrogen, particulars of which must be sought for in special works on organic chemistry.

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