This is based upon the fact that when potassic iodide in excess is added to a strong solution of a cupric salt in a faintly acid solution, cuprous iodide is formed and an equivalent of iodine liberated.[56] The iodine is measured by titrating with a solution of sodium hyposulphite,[57] using starch paste as indicator. The iodine is soluble in the excess of potassium iodide, forming a deep brown solution; the hyposulphite is added until this brown colour is almost removed. Starch paste is then added, and strikes with the remaining iodine a dirty blue colour. The addition of the "hypo" is continued until the blue colour is discharged. The end reaction is sharp; a drop is sufficient to complete it.
As regards the titration, the process leaves little to be desired; the quantity of "hypo" required is strictly proportional to the copper present, and ordinary variations in the conditions of working are without effect. The presence of salts of bismuth masks the end reaction because of the strong colour imparted to the solution by the iodide of bismuth. Under certain conditions there is a return of the blue colour in the assay solution after the finishing point has apparently been reached, which is a heavy tax on the patience and confidence of the operator. This is specially apt to occur when sodium acetate is present, although it may also be due to excessive dilution.
The standard "hypo" solution is made by dissolving 39.18 grams of the crystallised salt (Na2S2O3.5H2O) in water and diluting to one litre. One hundred c.c. will equal one gram of copper.
The starch solution is made by mixing 1 gram of starch into a thin paste with cold water, pouring it into 200 c.c. of boiling water, and continuing the boiling for a minute or so. The solution must be cold before use, and about 2 c.c. is used for each assay. It should not be added until the bulk of the iodine has been reduced.
To standardise the "hypo," weigh up 0.3 or 0.4 gram of pure copper, dissolve in 5 c.c. of dilute nitric acid, boil off nitrous fumes, and dilute with an equal bulk of cold water. Add "soda" solution until a permanent precipitate is obtained, and then 1 c.c. of acetic acid. This should yield a clear solution. Fill an ordinary burette with the "hypo." Add 3 grams of potassium iodide crystals to the copper solution, and, when these are dissolved, dilute to 100 c.c. with water. Run in the "hypo" solution rather quickly until the brown colour is nearly discharged—i.e., to within 3 or 4 c.c. of the finish. Add 2 c.c. of the starch solution, and continue the addition of the "hypo" a few drops at a time until the tint suddenly changes to a cream colour. The blue colour must not return on standing three or four minutes. Calculate the standard in the usual way.
In assaying ores, the copper is dissolved and separated with sulphuretted hydrogen as in the other processes, but the sulphide should be washed more completely to ensure the absence of iron salts.
The following experiments show the effect of variation in the conditions of the assay. Use a solution of copper sulphate containing 39.38 grams of copper sulphate crystals (CuSO4.5H2O) in the litre. 100 c.c. equal 1.00 gram of copper.
Effect of Varying Temperature.—The assay after the addition of the potassic iodide must be kept cold, else iodine may be volatilised.
Effect of Varying Potassium Iodide.—In various descriptions of the process the amount of iodide required is variously stated at from "a few crystals" to as much as 10 grams. The proportion required by theory for 1 gram of copper is a little over 5 grams: an excess, however, is required to keep the liberated iodine in solution. On economic grounds this excess should not be extravagant; if the student uses 10 parts of the iodide for each part of copper in the assay he will have sufficient. In the experiments there were used 20 c.c. of the copper sulphate, with varying amounts of potassic iodide, and the following results were got:—
| Potassic iodide added | 1.5 gram | 3 grams | 5 grams |
| "Hypo" required | 20.0 c.c. | 20.0 c.c. | 20.0 c.c. |