An Introductory Course of Quantitative Chemical Analysis · Chapter 22Determination of Silver by the Thiocyanate Process
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The addition of a solution of potassium or ammonium thiocyanate to one of silver in nitric acid causes a deposition of silver thiocyanate as a white, curdy precipitate. If ferric nitrate is also present, the slightest excess of the thiocyanate over that required to combine with the silver is indicated by the deep red which is characteristic of the thiocyanate test for iron.
The reactions involved are:
AgNO_{3} + KSCN —> AgSCN + KNO_{3}, 3KSCN + Fe(NO_{3}){3} —> Fe(SCN){3} + 3KNO_{3}.
The ferric thiocyanate differs from the great majority of salts in that it is but very little dissociated in aqueous solutions, and the characteristic color appears to be occasioned by the formation of the un-ionized ferric salt.
The normal solution of potassium thiocyanate should contain an amount of the salt per liter of solution which would yield sufficient (CNS)^{-} to combine with one gram of hydrogen to form HCNS, i.e., a gram-molecular weight of the salt or 97.17 grams. If the ammonium thiocyanate is used, the amount is 76.08 grams. To prepare the solution for this determination, which should be approximately 0.05 N, dissolve about 5 grams of potassium thiocyanate, or 4 grams of ammonium thiocyanate, in a small amount of water; dilute this solution to 1000 cc. in a liter bottle and mix as usual.
Prepare 20 cc. of a saturated solution of ferric alum and add 5 cc. of dilute nitric acid (sp. gr. 1.20). About 5 cc. of this solution should be used as an indicator.
PROCEDURE.—Crush a small quantity of silver nitrate crystals in a mortar (Note 1). Transfer them to a watch-glass and dry them for an hour at 110°C., protecting them from dust or other organic matter (Note 2). Weigh out two portions of about 0.5 gram each and dissolve them in 50 cc. of water. Add 10 cc. of dilute nitric acid which has been recently boiled to expel the lower oxides of nitrogen, if any, and then add 5 cc. of the indicator solution. Run in the thiocyanate solution from a burette, with constant stirring, allowing the precipitate to settle occasionally to obtain an exact recognition of the end-point, until a faint red tinge can be detected in the solution.
From the data obtained, calculate the relation of the thiocyanate solution to the normal.
[Note 1: The thiocyanate cannot be accurately weighed; its solutions must, therefore, be standardized against silver nitrate (or pure silver), either in the form of a standard solution or in small, weighed portions.]
[Note 2: The crystals of silver nitrate sometimes inclose water which is expelled on drying. If the nitrate has come into contact with organic bodies it suffers a reduction and blackens during the heating.
It is plain that a standard solution of silver nitrate (made by weighing out the crystals) is convenient or necessary if many titrations of this nature are to be made. In the absence of such a solution the liability of passing the end-point is lessened by setting aside a small fraction of the silver solution, to be added near the close of the titration.]
PROCEDURE.— Weigh out two portions of the coin of about 0.5 gram each. Dissolve them in 15 cc. of dilute nitric acid (sp. gr. 1.2) and boil until all the nitrous compounds are expelled (Note 1). Cool the solution, dilute to 50 cc., and add 5 cc. of the indicator solution, and titrate with the thiocyanate to the appearance of the faint red coloration (Note 2).
From the corrected volume of the thiocyanate solution required, calculate the percentage of silver in the coin.
[Note 1: The reaction with silver may be carried out in nitric acid solutions and in the presence of copper, if the latter does not exceed 70 per cent. Above that percentage it is necessary to add silver in known quantity to the solution. The liquid must be cold at the time of titration and entirely free from nitrous compounds, as these sometimes cause a reddening of the indicator solution. All utensils, distilled water, the nitric acid and the beakers must be free from chlorides, as the presence of these will cause precipitation of silver chloride, thereby introducing an error.]
[Note 2: The solution containing the silver precipitate, as well as those from the standardization, should be placed in the receptacle for "silver residues" as a matter of economy.]