Articles written in Journal of Chemical Sciences
Volume 121 Issue 5 September 2009 pp 579-588
We analyse the problem of impedance for a diffusion controlled charge transfer process across an irregular interface. These interfacial irregularities are characterized as two class of random fractals: (i) a statistically isotropic self-affine fractals and (ii) a statistically corrugated self-affine fractals. The information about the realistic fractal surface roughness has been introduced through the bandlimited power-law power spectrum over limited wave numbers. The details of power spectrum of such roughness can be characterized in term of four fractal morphological parameters, viz. fractal dimension ($D_H$), lower ($\ell$), and upper (𝐿) cut-off length scales of fractality, and the proportionality factor (𝜇) of power spectrum. Theoretical results are analysed for the impedance of such rough electrode as well as the effect of statistical symmetries of roughness. Impedance response for irregular interface is simplified through expansion over intermediate frequencies. This intermediate frequency expansion with sufficient number of terms offers a good approximation over all frequency regimes. The Nyquist plots of impedance show the strong dependency mainly on three surface morphological parameters i.e. $D_H$, $\ell$ and 𝜇. We can say that our theoretical results also provide an alternative explanation for the exponent in intermediate frequency power-law form.
Volume 129 Issue 8 August 2017 pp 1277-1292 REGULAR ARTICLE
Randles-Ershler admittance model is extensively used in the modeling of batteries, fuel cells, sensors etc. It is also used in understanding response of the fundamental systems with coupled processes like charge transfer, diffusion, electric double layer charging and uncompensated solution resistance. We generalize phenomenological theory for the Randles-Ershler admittance at the electrode with double layer capacitance and charge transfer heterogeneity, viz., non-uniform double layer capacitance and charge transfer resistance (c/d and R/CT ). Electrode heterogeneity is modeled through distribution functions of R/CT and c/d , viz., log-normal distribution function. High frequency region captures influence of electric double layer while intermediate frequency region captures influence from the charge transfer resistance of heterogeneous electrode. A heterogeneous electrode with mean charge transfer resistance RCT shows faster charge transfer kinetics over a electrode with uniform charge transfer resistance (R/CT ). It is also observed that a heterogeneous electrode having high mean with large variance in the RCT and cd can behave same as an electrode having low mean with small variance in the R/ CT and c/d. The origin of coupling of uncompensated solution resistance (between working and reference electrode) with the charge transfer kinetics is explained. Finally, our model provides a simple route to understand the effect of spatial heterogeneity
Volume 131 | Issue 7
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