Physical Chemistry Of Copper Cementation

Copper cementation was studied from both thermodynamic and kinetic aspects. The temperature effect of copper cementation, which has been recognized as an anomalous result, and the rate enhancement phenomenon observed after the initial linear step are, in particular, focused in this work. The main results obtained are as follows; 1) Free energy changes of copper cementation reactions, calculated by the use of the "Correspondence Principle" of Criss and Cobble are rather insensitive to temperature. 2) A Flow-cell assembly consisting of a special cupric ion electrode, a calomel electrode and a potentiometer is particularly useful for the continuous measurements of copper cementation rate. 3) Two first-order reaction rate constants for the CU2+- Fe system were successfully determined by the use of the flow-cell assembly. 4) Activation energies determined for the initial rate and the 9 maximum rate of CU2+ - Fe system are both 4.6 kcal/mole. This fact suggests that the mechanisms of the initial reaction and the final reaction are essentially the same and both reactions are rate controlled by the diffusion in a boundary layer. The difference in the rate constants of them may fie explained by the effect of the nature of surface deposits. 5) Qualitative explanation of the rate enhancement phenomenon from the initial rate was successfully made by applying Bockris "Penetration Model."