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Estimation of electrochemical quartz crystal microbalance frequencies from cyclic voltammetric data:—underpotential deposition of metals as an illustration

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Abstract

The estimation of electrochemical quartz crystal microbalance (EQCM) frequencies from a given cyclic voltammetric data is analysed using underpotential deposition (UPD) of metals as an illustrative process. The crucial role played by the surface roughness of electrodes and electrosorption valency of the depositing species is pointed out. The computed EQCM frequency shifts for the UPD of Cd and Tl on polycrystalline Ag electrodes are in satisfactory agreement with the experimental data.

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Scheme 1
Fig. 1
Fig. 2

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Notes

  1. Figures 1c and 3c from ref. [19] depict the surface coverages as a function of potential albeit only the deposition process. Surface coverage, θ, is defined as θ i =Δq idep /qmax where qmax=ze/(2r)2, z denotes the valency of the species, e is the electronic charge, Δqdep is the charge density corresponding to the appropriate potentials evaluated using Eqns. 1 and 2 and r is the ionic radii of the depositing species [23] (r=0.95 Å for Cd2+ and 1.5 Å for Tl+. The plots of surface coverage, θ vs E plot so deduced are in excellent agreement with those of Ref. [19], thus validating the Scheme 1 for computing charge densities.

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  30. The experimental data of Figs. 1 and 2 were reproduced with permission from Elsevier Science Publishers

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Acknowledgement

The financial support by the Council of Scientific and Industrial Research, Government of India is gratefully acknowleged.

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  1. Department of Chemistry, Indian Institute of Technology Madras, Chennai, 600 036, Tamil Nadu, India

    T. C. Girija & M. V. Sangaranarayanan

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  1. T. C. Girija
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  2. M. V. Sangaranarayanan
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Correspondence to M. V. Sangaranarayanan.

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Girija, T.C., Sangaranarayanan, M.V. Estimation of electrochemical quartz crystal microbalance frequencies from cyclic voltammetric data:—underpotential deposition of metals as an illustration. J Solid State Electrochem 9, 621–626 (2005). https://doi.org/10.1007/s10008-004-0617-7

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