An EQCM Study of the Electrochemical Copper(II)/Copper(I)/Copper System in the Presence of PEG and Chloride Ions

The charge-transfer reaction between copper(II) and copper electrodes is studied in electrolytes that are similar to galvanic copper baths, 2.2 M M ions M), and polyethyleneglycol 1500 (PEG, M). Electrochemical quartz crystal microbalance (EQCM) measurements are conducted, mainly under conditions of cyclic voltammetry. The formation and dissolution of CuCl on the electrode surface at mM is demonstrated, a notable shift of the pseudo-equilibrium potential associated with CuCl deposition is analyzed, and the inhibition of the charge-transfer reaction by the surface layer is characterized. It is shown that the inhibiting layer forms by reaction between the adsorbate-covered copper electrode and PEG, i.e. , neither nor from the electrolyte are required. Numerical simulations of the processes as well as parallel experiments conducted with electrolytes not containing Cu(II) support the proposed mechanisms, in particular the role of the intermediate © 2003 The Electrochemical Society. All rights reserved.