The Separation of the Copper and Arsenic Groups from the Zinc Group.
Solubilities vary from salt to salt, and we have already found that, in the zinc group, zinc sulphide is less soluble than the sulphide of a second member of the group, ferrous sulphide, and that the difference is revealed in a somewhat different behavior of their salts toward hydrogen sulphide, when the action is studied in some detail. Similar differences must be expected to exist among the sulphides of the groups that hydrogen sulphide precipitates even in the presence of an excess of hydrochloric acid. As these differences are the sources of some of the most common and most serious errors which analysts are liable to commit, the detailed study of the action of hydrogen sulphide must be continued a little further.
The Effect of a Large Excess of Acid.
In fact, if a large excess[417] of hydrochloric acid is added to 50 c.c. [p212] of the 0.1 molar solution of cadmium sulphate, hydrogen sulphide fails to precipitate any of the sulphide (exp.).
But, if a few cubic centimeters of a 0.1 molar solution of cupric sulphate (25.0 grams of CuSO4, 5 H2O, per liter) are added to the solution from which hydrogen sulphide fails to precipitate cadmium sulphide, cupric sulphide is at once precipitated. And, if 15 c.c. of concentrated hydrochloric acid are added to 50 c.c. of the 0.1 molar cupric sulphate solution, there results a mixture corresponding to the cadmium sulphate solution from which hydrogen sulphide fails to precipitate CdS; we find that hydrogen sulphide will precipitate the sulphide of copper very readily, even under these adverse conditions (exp.). Cupric sulphide must be even less soluble in water than cadmium sulphide,[418] and there is no difficulty in showing that such is the case. If ammonium sulphide, or hydrogen sulphide, is gradually introduced into a mixture of 25 c.c. each of the 0.1 molar sulphate solutions, cupric sulphide is precipitated first, and, if the precipitate is collected in fractions, [p213] pure yellow cadmium sulphide is precipitated last.[419] Or, if 25 c.c. of 0.1 molar cupric sulphate is added to the mixture in which a precipitate of cadmium sulphide displaced the more soluble zinc sulphide (p. [210]), the yellow sulphide will, in turn, give way to the less soluble black sulphide of copper (exp.).
We find thus that the precipitation of cadmium sulphide, by hydrogen sulphide in acid solution, can be prevented by the presence of an excess of hydrochloric acid, which does not prevent the precipitation of the less soluble cupric sulphide.[420] The fact, then, that, in an analysis of some unknown mixture, hydrogen sulphide produces a precipitate in acid solution, must not be considered as evidence that the conditions are such as to insure the precipitation of all the sulphides of the groups, which we intend to precipitate. To avoid error, conditions must be such as to insure the complete precipitation of the more soluble as well as the less soluble sulphides. The sulphides of cadmium and lead, in particular, and, to a lesser degree, the sulphides of antimony and tin, are most liable to remain unprecipitated and thus escape detection in systematic analysis. This is a matter of special importance, also, in detecting traces of the ions of these metals, especially of lead, which is a slow cumulative poison, even when absorbed in minute amounts, and which analysts must therefore be able to detect, even in traces, with absolute certainty. It is clear, from a consideration of the product of the ion concentrations, as affecting the precipitation or nonprecipitation of such a sulphide, that a much smaller excess of acid will prevent the precipitation of the last traces of lead sulphide, and, therefore, of all of it, if only traces are present, than will interfere with the precipitation of the sulphide in bulk.
The Desirable Concentration of Acid (of Hydrogen-ion) and an Indicator for Correct Acidification.
If an analyst aims to find even smaller quantities of a particular metal ion, e.g. traces of lead, the ordinary method of analysis [p215] may be modified, the source of error in the precipitation of traces of lead sulphide being kept in mind.[424]
Besides the complications mentioned, and provided against in the way discussed, there is still one more complication in the use of hydrogen sulphide: this is in the matter of the precipitation of arsenic sulphide from solutions containing arsenic in the pentavalent condition. Since the interpretation of this complication and the explanation of the methods for avoiding the errors, which may arise therefrom, are necessarily intimately connected with the chemical behavior of arsenic acid, this subject will be considered in the discussion of the arsenic group (Chapter XIII).