Theoretical interpretation of Warburg's impedance in unsupported electrolytic cells

Literature Information

Publication Date 2017-11-23
DOI 10.1039/C7CP07101A
Impact Factor 3.676
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Abstract

We discuss the origin of Warburg's impedance in unsupported electrolytic cells containing only one group of positive and one group of negative ions. Our analysis is based on the Poisson–Nernst–Planck model, where the generation-recombination phenomenon is neglected. We show that to observe Warburg-like impedance the diffusion coefficient of the positive ions has to differ from that of the negative ones, and furthermore the electrodes have to be not blocking. We assume that the non-blocking properties of the electrodes can be described by means of an Ohmic model, where the charge exchange between the cell and the external circuit is described by means of an electrode conductivity. For simplicity we consider a symmetric cell. However, our analysis can be easily generalized to more complicated situations, where the cell is not symmetric and the charge exchange is described by the Chang–Jaffe model, or by a linearized version of the Butler–Volmer equation. Our analysis allows justification of the expression for Warburg's impedance proposed previously by several groups, based on wrong assumptions.

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DOI: 10.1039/B706704F

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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