The Continuous Automatic Cyanide Titrator

"A survey of possible methods for controlling cyanide concentration indicated that the simplest method would involve the use of a potentiometric technique. Such a method was suggested by a paper from the laboratory of Mines Safety Appliances, which described a method for determining hydrogen cyanide in air. In this application, the cyanide was absorbed in caustic and a silver electrode immersed in the caustic solution provided a measure of the cyanide concentration. However, our attempts to use the silver electrode in this simple manner to measure the cyanide concentration of solutions were not very successful. A study of the mechanism by which a silver electrode responds to cyanide concentration made it evident why this simple procedure is not satisfactory.Basically, the silver electrode provides an indication of the free silver ion concentration of a solution, and generally speaking, ignores the other ions' present. It can be used to measure an anion if this anion complexes silver. This technique has been used in complexing studies to determine the activities of such anions as acetate, citrate, oxalate and chloride. To do this, the electrode has to be placed in a solution which initially contains a known concentration of free silver ions. Addition of the complexing anion causes a drop in the free silver ion concentration and hence a change in the potential of the silver electrode. The change in potential can be expressed in terms of the concentration of the complexing anion, and used to indicate its concentration in the solution being analysed. The determination of chloride-ion by a silver-silver chloride electrode is an example of an application of this technique. The solubility of the silver chloride with which the electrode is coated provides the initial free silver-ion concentration. Depression of this free silver-ion concentration by the presence of the excess chloride ion of the sample solution results in a change in the potential of the electrode which is proportional to the chloride-ion concentration."