AbstractThe extraction of silver(I) from argentocyanide aqueous cyanide solutions using LIX® 79 has been studied. Different variables that could affect the extraction system were evaluated: equilibration time, aqueous pH, metal and extractant concentrations, and organic phase diluent. The extraction of the Ag(CN)2− complex with respect to other metal‐cyano complexes has also been studied on both synthetic and real leach solutions. Experimental data relating to silver have been analysed numerically to determine the stoichiometry of the extracted species and its equilibrium constant. It was found that silver(I) was extracted into the organic phase by the formation of the species RHAg(CN)2 (LIX 79 = R). Copyright © 2004 Society of Chemical Industry