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.
STANDARDIZATION
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.