The remarks made in the preceding article concerning the distinctive properties of arsenic and antimony need not be repeated here. The search for antimony is likewise executed by aid of Marsh's apparatus. We will confine ourselves to a description of a modification to this apparatus proposed by MM. Flandin and Danger, and employed in the separation of antimony and arsenic, when a mixture of these metals is under examination. Another process, by means of which we arrive at the same result with greater certainty and by the use of a less expensive apparatus, will then be mentioned. We will, however, first indicate the preferable method of destruction of the organic substances.
Were the decomposition performed by means of sulphuric acid, sulphate of antimony, a slightly soluble salt and one not well adapted to the subsequent treatment with nascent hydrogen, would be formed. In order to obtain the metal in a soluble state, the formation of a double tartrate of antimony and soda is desirable. This may be accomplished in the following manner:
1. A cold mixture of nitrate of soda, sulphuric acid, and the suspected materials is prepared in the proportion of 25 grammes of the nitrate to 39 grammes of the acid, and 100 grammes of the substance under examination. This mixture is heated and evaporated to dryness, and the decomposition of the organic matter completed in the usual manner. The carbonaceous residue obtained is pulverized, and then boiled with a solution of tartaric acid. By this treatment the antimonate of soda present is converted into a double tartrate of antimony and soda, which is easily soluble in water. The solution is filtered and then introduced into Marsh's apparatus.
2. Another method consists in heating the substances under examination with one half of their weight of hydrochloric acid for six hours on a sand-bath, avoiding boiling. The temperature is then increased until the liquid is in a state of ebullition, and 15 to 20 grammes of chlorate of potassa, for every 100 grammes of the suspected matter taken, added in successive portions, so that a quarter of an hour is required for the operation. The liquid is next filtered, and the resinous matter remaining on the filter well washed with distilled water; the washings being added to the principal solution. A strip of polished tin is then immersed in the liquid: in presence of a large amount of antimony the tin becomes covered with a black incrustation: if but a minute quantity of the metal is contained, only a few blackish spots are perceptible. After the tin has remained immersed for 24 hours, it is withdrawn and placed in a flask together with an amount of hydrochloric acid sufficient for its solution in the cold. If, after several hours, blackish particles are still observed floating in the liquid, they can be dissolved in a few drops of aqua regia. The solution may then be directly introduced into Marsh's apparatus.
APPARATUS PROPOSED BY FLANDIN AND DANGER.
Fig. 7.
This apparatus consists of a wide necked jar A (Fig. 7) for the generation of the gas, the mouth of which is closed with a cork having two openings. The safety tube S, which is funnel-shaped at its upper extremity and has its lower end drawn out to a point, passes through one of these apertures; the other opening contains the small delivery tube B, open at both ends, and terminating in a point at its upper extremity: it is also provided with lateral openings, in order to prevent the solution being carried up to the flame. The second part of the apparatus is the condenser C, 0.03 metre in diameter, and 0.25 metre in length. This terminates at its lower extremity with a cone, and connects at the side with the tube T, slanting slightly downwards. In the interior of the condenser, the cooler E is contained, the lower end of which is nearly in contact with the sides of the opening O. The combustion tube D, 0.01 metre in diameter, is connected by means of a cork with the tube T; it is bent at right angles, and encloses the tube B, in such a manner as to allow the evolved gas to burn in its interior. The dish F is placed beneath the opening O. If the gas which burns in the combustion tube contains arsenetted hydrogen, water and arsenious acid are produced. A portion of this acid is retained in the tube D, the remainder is carried over, with the aqueous vapor, into C, where it condenses, and finally falls into the dish F. Both portions are subsequently examined by means of reactions necessary to establish the presence of the acid. If the ignited gas contains antimonetted hydrogen, water and an intermediate oxide of antimony are formed. The latter compound is entirely retained in the tube D separated from the greater part of the arsenious acid, if this body be present, and can be brought into solution by means of a mixture of hydrochloric and tartaric acids. A fluid is then obtained which can be introduced into Marsh's apparatus, or otherwise examined for antimony.
NAQUET'S APPARATUS.
