[Note 6: The electrodes must be washed nearly or quite free from the nitric acid solution before the circuit is broken to prevent re-solution of the copper.
If several solutions are connected in the same circuit it is obvious that some device must be used to close the circuit as soon as the beaker is removed.]
[Note 7: The electrodes upon which the copper has been deposited may be cleaned by immersion in warm nitric acid. To remove the lead dioxide, add a few crystals of oxalic acid to the nitric acid.]
Most brasses contain small percentages of iron (usually not over 0.1 per cent) which, unless removed, is precipitated as phosphate and weighed with the zinc.
Procedure.—To the solution from the precipitation of copper and lead by electrolysis, add dilute ammonia (sp. gr. 0.96) until the precipitate of zinc hydroxide which first forms re-dissolves, leaving only a slight red precipitate of ferric hydroxide. Filter off the iron precipitate, using a washed filter, and wash five times with hot water. Test a portion of the last washing with a dilute solution of ammonium sulphide to assure complete removal of the zinc.
The precipitate may then be ignited and weighed as ferric oxide, as described on page 110.
Calculate the percentage of iron (Fe) in the brass.
Procedure.—Acidify the filtrate from the iron determination with dilute nitric acid. Concentrate it to 150 cc. Add to the cold solution dilute ammonia (sp. gr. 0.96) cautiously until it barely smells of ammonia; then add !one drop! of a dilute solution of litmus (Note 1), and drop in, with the aid of a dropper, dilute nitric acid until the blue of the litmus just changes to red. It is important that this point should not be overstepped. Heat the solution nearly to boiling and pour into it slowly a filtered solution of di-ammonium hydrogen phosphate containing a weight of the phosphate about equal to twelve times that of the zinc to be precipitated. (For this calculation the approximate percentage of zinc is that found by subtracting the sum of the percentages of the copper, lead and iron from 100 per cent.) Keep the solution just below boiling for fifteen minutes, stirring frequently (Note 2). If at the end of this time the amorphous precipitate has become crystalline, allow the solution to cool for about four hours, although a longer time does no harm (Note 3), and filter upon an asbestos filter in a porcelain Gooch crucible. The filter is prepared as described on page 103, and should be dried to constant weight at 105 deg.C.
[Footnote 1: The ammonium phosphate which is commonly obtainable contains some mono-ammonium salt, and this is not satisfactory as a precipitant. It is advisable, therefore, to weigh out the amount of the salt required, dissolve it in a small volume of water, add a drop of phenolphthalein solution, and finally add dilute ammonium hydroxide solution cautiously until the solution just becomes pink, but do not add an excess.]