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Chemistry - Electrochemistry | Electrochemical Impedance Spectroscopy and its Applications

Electrochemical Impedance Spectroscopy and its Applications

Lasia, Andrzej

2014, XIII, 367 p. 224 illus., 48 illus. in color.

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  • Only comprehensive recent book on EIS to present applications and theory to students
  • Includes numerous exercises and examples
  • Presents a systematic overview of EIS

This book presents a complete overview of the powerful but often misused technique of Electrochemical Impedance Spectroscopy (EIS). The book presents a systematic and complete overview of EIS. The book carefully describes EIS and its application in studies of electrocatalytic reactions and other electrochemical processes of practical interest. This book is directed towards graduate students and researchers in Electrochemistry. Concepts are illustrated through detailed graphics and numerous examples. The book also includes practice problems. Additional materials and solutions are available online.

Content Level » Graduate

Keywords » AC Impedance - EIS - Electrochemical - Impedance - Lasia - Spectroscopy - circuits - fuel cells

Related subjects » Analytical Chemistry - Electrochemistry

Table of contents 

1 Introduction 1.1 Why impedance? 1.2 Short history of impedance 1.3 Publications on impedance 2 Definition of the impedance and impedance of electrical circuits 2.1 Introduction 2.2 Electrical circuits containing resistances 2.2.1 Ohm’s law 2.2.2 Kirchhoff’s laws 2.3 Capacitance 2.4 Inductance 2.5 Laplace transform 2.6 Complex numbers 2.7 Fourier transform 2.7.1 Leakage 2.7.2 Aliasing 2.8 Impedance of electrical circuits 2.8.1 Application of the Laplace transform to the determination of impedances 2.8.2 Definition of the operational impedance 2.8.3 Application of the Fourier transform to the determination of impedances 2.8.4 Definition of the impedance 2.9 Circuit description code 2.10 Impedance plots 2.10.1 Interpretation of the Bode magnitude plots 2.10.2 Circuits with two semicircles 2.10.3 Circuits containing inductances 2.11 Summary 2.12 Exercises 3 Determination of impedances 3.1 Ac bridges 3.2 Lissajous curves 3.3 Phase sensitive detection (PSD), lock-in amplifiers 3.4 Frequency response analyzers (FRA) 3.5 Ac voltammetry 3.6 Laplace transform 3.7 Methods based on Fourier transform 3.7.1 Pulse or step excitation 3.7.2 Noise perturbation 3.7.3 The sum of sine waves excitation signal 3.7.4 Dynamic electrochemical impedance spectroscopy (DEIS) 3.8 Perturbation signal 3.9 Conclusions 3.10 Exercises 4 Impedance of the faradaic reactions in the presence of mass transfer 4.1 Impedance of an ideally polarizable electrode 4.2 Impedance in the presence of redox process in semi-infinite linear diffusion. Determination of parameters 4.2.1 General case 4.2.2 Dc reversible case 4.3 Analysis of impedance in the case of semi-infinite diffusion 4.3.1 Randles analysis 4.3.2 De Levie-Husovsky analysis 4.3.3 Analysis of cot φ 4.3.4 CNLS analysis 4.4 Finite length linear diffusion 4.4.1 Transmissive boundary 4.4.2 Reflective boundary 4.5 Generalized Warburg element 4.6 Spherical diffusion 4.6.1 Semi-infinite external spherical diffusion 4.6.2 Finite length internal spherical diffusion 4.7 Cylindrical diffusion 4.8 Diffusion to disk electrode 4.9 Rotating disk electrode 4.10 Homogeneous reaction, Gerischer impedance 4.11 Conclusions 4.12 Exercises 5 Impedance of the faradaic reactions in the presence of adsorption 5.1 Faradaic reaction involving one adsorbed species, no desorption 5.2 Faradaic reaction involving one adsorbed species with subsequent desorption 5.2.1 Determination of the impedance 5.2.2 Impedance plots 5.2.3 Distinguishability of the kinetic parameters of the Volmer-Heyrovsky reaction 5.3 Faradaic reaction involving two adsorbed species 5.4 Exercises 6 General method of obtaining impedance of complex reactions 7 Electrocatalytic reactions involving hydrogen 7.1 Hydrogen underpotential deposition reaction 7.2 Hydrogen evolution reaction 7.3 Influence of the hydrogen mass transfer on the HER 7.4 Hydrogen absorption into metals 7.4.1 Hydrogen adsorption-absorption reaction in the presence of hydrogen evolution 7.4.2 Direct hydrogen absorption and hydrogen evolution 7.4.3 Hydrogen absorption in the absence of hydrogen evolution 7.4.4 Hydrogen absorption in spherical particles 7.5 Conclusions 8 Dispersion of impedances at solid electrodes 8.1 Constant phase elements 8.2 Fractal model 8.3 Origin of the CPE dispersion 8.3.1 Dispersion of time constants 8.3.2 Dispersion due to surface adsorption/diffusion processes 8.4 Determination of the time constant distribution function 8.4.1 Regularization methods 8.4.2 Least-squares deconvolution methods 8.4.3 Differential impedance analysis 8.4.4 Summary 8.5 Conclusion 9 Impedance of porous electrodes 9.1 Impedance of the ideally polarizable porous electrodes 9.1.1 Cylindrical pore with the ohmic drop in the solution only (idc=0, re=0, rs0,) 9.1.2 Other pore geometry with the ohmic drop in the solution only 9.1.4 Porous electrode with the ohmic drop in the solution and in the electrode material 9.2 Porous electrodes in the presence of redox species in solution 9.2.1 Ohmic drop in the solution only in the absence of dc current ( , , ) 264 9.2.2 Ohmic drop in the solution and electrode material in the absence of dc current 9.2.3 Porous electrodes in the presence of dc current, potential gradient in pores and no concentration gradient, ideally conductive electrodes 9.2.4 Porous electrodes in the presence of dc current, concentration gradient in pores and no potential gradient, ideally conductive electrode 9.2.5 General case: potential and concentration gradient 9.3 Distribution of pores 9.4 Continuous porous model 9.5 Conclusions 9.6 Exercises 10 Semiconductors and Mott-Schottky plots 10.1 Semiconductors in solution 10.2 Determination of the flatband potential 11 Coatings and paints 11.1 Electrical equivalent models 11.2 Water absorption in organic coating 11.3 Analysis of impedances of organic coatings 11.4 Conclusions 12 Self-assembled monolayers, biological membranes, and biosensors 12.1 Self-assembled monolayers 12.2 Lipid bilayers 12.3 Biosensors 12.4 Conclusions 13 Conditions for obtaining good impedances 13.1 Kramers-Kronig relations 13.1.1 Polynomial approximation 13.1.2 Checking Kramers-Kronig compliance by approximations 13.2 Linearity 13.3 Stability 13.3.1 Drift 13.3.2 Dealing with non-stationary impedances 13.3.3 Stability of electrochemical systems 13.3.4 Nyquist criterion of stability 13.3.5 Negative dynamic resistances and their origin 13.4 Z-HIT transform 13.5 Summary 13.6 Exercises 14 Modeling of experimental data 14.1 Acquisition of “good” data 14.2 Types of modeling 14.4 Classification of errors 14.5 Methods of finding the best parameters 14.6 Weighting procedures 14.6.1 Statistical weighting 14.6.2 Unit weighting 14.6.3 Modulus weighting 14.6.4 Proportional weighting 14.6.5 Weighting from the measurement model 14.7 Statistical tests 14.7.1 Chi-square 14.7.2 Test F 14.7.3 t- test for the importance of the parameters of regression 14.8 Conclusion 14.9 Exercises 15 Nonlinear impedances (higher harmonics) 15.1 Simple electron transfer reaction without mass transfer effects 15.2 Other reaction mechanism 15.3 Conclusions 16 Instrumental limitations 16.1 Measurements of high impedances 16.2 Measurements at high frequencies 16.3 Measurements of low impedances 16.4 Reference electrode 16.5 Conclusions 17 Conclusions 18 Index 19 Appendix. Laplace transforms 20 References

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