Fundamental considerations on the mechanisms of silver cementation onto zinc particles in the Merril–Crowe process

Studies on the Merrill–Crowe process as applied to silver recovery have shown that one half of the used zinc powder is wasted in water reduction at high cyanide concentrations, while the other half reduces silver ions from the cyanide solution. However, the cementation mechanisms as an electrochemical process taking place on the zinc surface do not explain the split of the electric current resulting from the anodic dissolution of zinc into two equal values. This study demonstrates that the mechanism for silver precipitation at high and low cyanide concentrations differs considerably. At low cyanide concentrations cementation is essentially an electrochemically-controlled process following a shrinking-core behavior. At high cyanide concentrations, the process seems not to be electrochemically controlled. The areas for zinc dissolution and silver deposition are not connected by an electrically-conducting medium and reduction of silver–cyano complex ions takes place by hydrogen adsorbed onto silver growing outward from the cementing zinc particles. The results are based on scanning electron microscopy of solids recovered from cementations in stirred reactors and in situ observations by optical microscopy of the cementation process on the edge of thin zinc disks in cyanide solutions.