Measuring cyanide in the leach liquors associated with high copper and/or sulfide ores is a non-trivial exercise. It is well known that copper complexes with cyanide and reduces the amount of cyanide available for gold leaching. What is not so well known is that the rhodanine end point overestimates the amount of cyanide available for leaching in the presence of copper._x000D_
Sulfide ions also interfere with a rhodanine end point titration, although this is less of a problem as the black silver sulfide precipitate formed clearly indicates to the operator that something is wrong._x000D_
Thiosulfate, which forms readily from the alkaline oxidation of sulfides, causes an overestimation of the cyanide available for leaching due to the formation of Ag(S2O3)-._x000D_
The net result of these observations is that rhodanine is rarely of value as an end point indicator in complex solutions. It generally overestimates the amount of cyanide available, providing plant metallurgists with a false sense of security._x000D_
Potentiometric titrations are generally much more capable of accurately measuring cyanide in complex solutions. The interfering effect of copper can be resolved and it is even possible to estimate the copper concentration using the inflexions associated with the titration of CN- + Cu(CN)43- versus Cu(CN)32-._x000D_
Using the potentiometric method sulfide ions can be determined before the cyanide measurement is made due to the formation of AgS2, although the electrode will foul with repeated measurements. Thiosulfate can also be distinguished from cyanide with a potentiometric titration._x000D_
Rhodanine and potentiometric titrations are both affected by the pH of the liquor. At pH 9.2 half the cyanide will be present as CN- and half as HCN(aq) with only the CN- being titratable. This does not hold in the presence of a buffer active around pH 9. In the presence of sufficient buffer, both the CN- and HCN(aq) are titrated. Ca(OH)+ may buffer the pH when large amounts of lime have been added.