During the processing of gold, effluents that are discharged into the tailing dams contain free cyanide, metal cyanide complexes of zinc, copper, iron, etc and their oxidised products such as ammonia, cyanate and thiocyanate. A knowledge of how different cyanides behave in the solution is vital to metallurgists working in the area of cyanide waste treatment. Although the free cyanide ion is not stable in aqueous solutions and is expected to degrade in a natural environment by atmospheric oxidation, the metal cyanide complexes, especially of iron, are very stable. The CHEMIX program from the THERMODATA package, developed by the CSIRO Division of Mineral Products, was used to evaluate various copper-cyanide and iron-cyanide systems. The simulation of these systems show how the free cyanide and cyanide complexes behave at different conditions of solution composition and acidity (pH).