When iodide is added to a solution of hexacyanoferrate(III), the following equilibrium exists:
Under strongly acidic solution, the above equilibrium lies far to the right hand side, but is reversed in almost neutral solution. This makes analysis of hexacyanoferrate(III) troublesome as the iodide and thiosulfate decomposes in strongly acidic medium. To drive the reaction to completion, an excess amount of zinc salt can be added to the reaction mixture containing potassium ions, which precipitates the hexacyanoferrate(II) ion quantitatively:
The precipitation occurs in slightly acidic medium, thus avoids the problem of decomposition of iodide and thiosulfate in strongly acidic medium, and the hexacyanoferrate(III) can be determined by iodometry as usual.