Determination Of Lead

The nitric solution of lead acts similarly to that of manganese. When the amount of peroxide separated is so large that it does not adhere firmly, and becomes mechanically precipitated on the negative electrode, it becomes impossible to complete the estimation without loss from the solution of the peroxide, and the results cannot be accepted.

If the double oxalate is submitted to electrolysis, the whole of the lead is separated out in its metallic state, but it is so rapidly oxidized by the air that it is very seldom that it can be dried without decomposition even when the operation is conducted in a current of illuminating gas. The electrolytic estimation of this element cannot be recommended.

Determination Of Copper

The copper may be very easily and rapidly separated from the double ammonium oxalate salt, provided a sufficient excess of ammonium oxalate is present. Weak currents cannot be employed for the determination of this element when it is present in large quantities, for under such circumstances the metal does not adhere with sufficient firmness to the electrode. We employed a current which corresponded to an evolution of 330 c.c. of gas per hour, and we were able to precipitate 0.15 gramme metallic copper in about twenty-five minutes.

Determination Of Cadmium

When the cadmium ammonium oxalate is submitted to the action of the electric current, the metal is thrown down in the form of a gray coating, which does not adhere very firmly to the electrode, but, however, sufficiently so as not to become separated on careful washing.

Determination Of Tin

Tin may be easily estimated by electrolysis; it can be separated from its hydrochloric acid solution, or from its double salt with ammonium oxalate, as a beautiful silver gray coating on the platinum. When the ammonium oxalate is substituted by the potassium salt, the operation becomes more difficult, as a basic salt is formed at the opposite pole, and is not easily reduced. If the tin is separated from an acid solution, the current must not be interrupted while the washing takes place, a precaution which it is not necessary to follow when the ammonium oxalate is used. When the tin is dissolved from the platinum dish, it acts like the zinc; that is to say, a black coating is left on the electrode.

Determination Of Antimony

Antimony may be precipitated in its metallic state from a hydrochloric acid solution, but it does not adhere very firmly to the electrode. If potassium oxalate is added to a solution of the trichloride, the antimony may be readily reduced, but the metal adheres still less firmly to the electrode than it did in the first instance. An adherent coating may be obtained by adding an alkaline tartrate, but in that case the separation takes place too slowly. The precipitation of antimony may be very readily effected from solutions of its sulpho salts.

To a liquid, which may contain free hydrochloric acid, hydrogen sulphide is added, then neutralized with ammonium hydrate, and saturated with ammonium sulphide in excess. The reduction may be accelerated by the addition of some ammonium sulphate. The antimony separates out as a fine, light gray precipitate on the electrode, and which adheres very firmly, provided the precipitation has not been carried on too rapidly, i. e., if the current employed for the reduction was not too strong.

When the reduction has been completed, the supernatant liquid is poured off, and the residue washed in the ordinary manner.

Determination Of Arsenic

Arsenic cannot be completely separated from either its aqueous hydrochloric acid, or from a solution to which ammonium oxalate has been added in excess. From its aqueous as well as from its oxalate solution, a portion of the metal may be separated, but if the current is passed through its hydrochloric acid solution for a sufficient length of time, all the arsenic will be volatilized as arsenious hydride (AsH).