The Cuprous-Cupric Complex in Hydrochloric Acid Solution

In the process described by Diehl and Brouns (1) for the direct determination of copper in bronze by electrodeposition from hydrochloric acid solution using hydroxylammonium chloride as anodic depolarizer and controlling the cathode potential automatically (3), the sample of bronze is dissolved in hydrochloric acid by the dropwise addition of nitric acid or of hydrogen peroxide. Subsequently the solution is diluted and electrolyzed, the cathode reaction being· first the reduction of cupric ion to the chlorocuprous ion, CuCl3==, and then the deposition of copper. The time of electrolysis can be materially shortened if the first reduction is effected chemically, by the addition of hydrocxylammonium chloride or of stannous chloride. If the reducing agent be added to the solution before it is diluted, that is, to a fairly concentrated hydrochloric acid solution, the solution turns dark brown or black, the color being due to some material in solution which disappears on dilution. It became of interest to learn more of this dark colored solution, particularly since it was observed that a small amount of antimony did or did not deposit with the copper depending on whether the reduction was made before or after the dilution.