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MASS CHANGES DURING ADSORPTION OF METAL BIPYRIDYL COMPLEXES BY CLAY FILMS MONITORED WITH AN ELECTROCHEMICAL QUARTZ CRYSTAL MICROBALANCE

Department of Chemistry, University of New Brunswick, PO Box #45222, Fredericton New Brunswick E2B 6E2, Canada

^* E-mail address of corresponding author: gvd{at}unb.ca

The adsorption of [M(bpy)₃]²⁺ ions (M = Ru or Os) by clay films immersed in pure water and in electrolyte solutions was investigated by electrochemical quartz crystal microbalance (EQCM), UV-visible spectroscopy and powder X-ray diffraction. In water, the adsorption of the cations resulted in a decrease in the mass of the films. This decrease in mass is attributed to the expulsion of some 50 water molecules from the clay interlayer spaces for each cation adsorbed. Water is lost to make room for the large metal complex cations in the interlayer spaces, and because of decreases in the volume of the interlayer spaces during adsorption of the cations. In 0.05 M NaCl or 0.05 M Na₂SO₄, UV-visible measurements show a rapid initial adsorption of the cations by ion exchange, followed by a slower additional adsorption of the cations above the clay’s CEC, presumably as ion pairs with the electrolyte counter ions. The EQCM show initial reductions in the mass of the films that were two to three times larger in pure water. These initial mass decreases were followed by smaller mass ‘re-increases’ at longer times that were not observed in water. The larger initial mass losses are attributed to the loss of more water from the clay interlayer spaces. In 0.5 M Na₂SO₄ or 1.0 M NaCl, adsorption of the cations never exceeded the clay’s CEC. The initial decreases in mass upon addition of the cations all but disappeared, leaving only the smaller positive mass changes at longer times.

Key Words: Clay-modified Electrodes • Clay Films • EQCM • Ion Exchange • Microgravimetry • UV-visible Spectroscopy