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Electroanalytical Methods: Guide to Experiments and Applications, 2Nd Electroanalytical Methods Fritz Scholz Editor Electroanalytical Methods Guide to Experiments and Applications Second, Revised and Extended Edition With contributions by A.M. Bond, R.G. Compton, D.A. Fiedler, G. Inzelt, H. Kahlert, Š. Komorsky-Lovric,´ H. Lohse, M. Lovric,´ F. Marken, A. Neudeck, U. Retter, F. Scholz, Z. Stojek 123 Editor Prof. Dr. Fritz Scholz University of Greifswald Inst. of Biochemistry Felix-Hausdorff-Str. 4 17487 Greifswald Germany [email protected] ISBN 978-3-642-02914-1 e-ISBN 978-3-642-02915-8 DOI 10.1007/978-3-642-02915-8 Springer Heidelberg Dordrecht London New York Library of Congress Control Number: 2009935962 © Springer-Verlag Berlin Heidelberg 2010 This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer. Violations are liable to prosecution under the German Copyright Law. The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Cover design: WMXDesign GmbH, Heidelberg Printed on acid-free paper Springer is part of Springer Science+Business Media (www.springer.com) Electroanalytical Methods Fritz Scholz dedicates this book to the memory of his late parents Anneliese and Herbert Scholz Preface to the Second Edition The authors are pleased to present here the second edition of the book “Electroanalytical Methods. Guide to Experiments and Applications.” All chapters have been carefully revised and updated, and a new chapter, devoted to the use of the electrochemical quartz crystal nanobalance, has been added. Greifswald, Germany, October 2009 Fritz Scholz ix Preface to the First Edition Electroanalytical techniques offer a unique access to information on chemical, biochemical, and physical systems. Both the instrumental basis and the theoretical fundamentals have been developed such that non-specialists can easily apply them. However, there is still a considerable lack in acceptance of these techniques by oth- ers except those who have experience and training in electrochemistry. The authors of this volume felt that it was time to write a volume that concentrates on the really important techniques together with the most essential information to make them applicable for potential users who do not possess specialist knowledge of electro- chemistry. All the authors have a long experience in teaching and know the most frequent experimental pitfalls as well as theoretical misunderstandings and mis- interpretations. This book has been written to become a bench book used in the laboratory. The “Electroanalytical Methods” addresses chemists and biochemists who are interested in using electroanalytical techniques to supplement spectroscopic and perhaps theoretical calculations. It also addresses biologists, environmental and material scientists, physicists, medical scientists, and, most importantly, students in all branches of science, who are confronted with the need to apply electroanalytical techniques. In the short first part of the book, entitled “Basic Electrochemistry,” the essentials of electrochemical thermodynamics and kinetics are given. The second part, entitled “Electroanalytical Techniques,” contains the most frequently utilized techniques, i.e., cyclic voltammetry, pulse and square-wave voltammetry, chrono- coulometry, etc. The third part is devoted to electrodes and electrolytes, which are the major constituents of an electrochemical cell. Throughout the book, special attention is given to guide the user to successful laboratory experiments and a sound data evaluation. This book focuses only on modern and widespread techniques. To give the interested reader a key to the historic background, a short list of seminal publications in electrochemistry and electroanalysis is provided in Chap. IV.1. There are many carefully written monographs on special electroanalytical tech- niques and textbooks on fundamental electrochemistry available. We refer to this fundamental literature (see Chap. IV.2) for a deeper insight into the subject. The World Wide Web is of steadily growing importance also for electrochemical infor- mation. Although it is constantly changing and renewing, some key addresses are provided to make access easier and the search more successful. Greifswald, Germany, 2001 Fritz Scholz xi Contents Part I Basic Electrochemistry I.1 The Electrical Double Layer and Its Structure .................. 3 Zbigniew Stojek I.1.1 Introduction . ....................................... 3 I.1.2 Double-Layer Models . ............................ 5 I.1.3 Thickness of the Electric Double Layer . ................. 8 I.1.4 Recent Developments . ............................ 8 References . .................................................. 8 I.2 Thermodynamics of Electrochemical Reactions ................. 11 Fritz Scholz I.2.1 Introduction . ....................................... 11 I.2.2 The Standard Potential . ............................ 12 I.2.3 TheFormalPotential................................... 19 I.2.4 Characteristic Potentials of Electroanalytical Techniques . 22 I.2.5 Thermodynamics of the Transfer of Ions Between Two Phases . .................................. 27 I.2.6 Thermodynamic Data Derived from Standard andFormalPotentials................................... 30 References . .................................................. 31 I.3 Kinetics of Electrochemical Reactions .......................... 33 György Inzelt I.3.1 Introduction . ....................................... 33 I.3.2 Relationship Between the Current Density and Potential Under Steady-State Conditions . ....................... 34 I.3.3 Current–Potential Transients ............................. 49 References . .................................................. 53 xiii xiv Contents Part II Electroanalytical Techniques II.1 Cyclic Voltammetry .......................................... 57 Frank Marken, Andreas Neudeck, and Alan M. Bond II.1.1 Introduction . ....................................... 57 II.1.2 BasicPrinciples ....................................... 63 II.1.3 Effects Due to Capacitance and Resistance ................. 71 II.1.4 ElectrodeGeometry,Size,andConvectionEffects........... 74 II.1.5 Determination of Redox State and Number ofTransferredElectrons ................................ 78 II.1.6 Heterogeneous Kinetics . ............................ 81 II.1.7 Homogeneous Kinetics . ............................ 87 II.1.8 Multi-phase Systems ................................... 98 References . ..................................................102 II.2 Pulse Voltammetry ...........................................107 Zbigniew Stojek II.2.1 Introduction . .......................................107 II.2.2 StaircaseVoltammetry..................................110 II.2.3 NormalPulseVoltammetry..............................111 II.2.4 ReversePulseVoltammetry..............................115 II.2.5 DifferentialPulseVoltammetry...........................117 References . ..................................................119 II.3 Square-Wave Voltammetry ...................................121 Milivoj Lovric´ II.3.1 Introduction . .......................................121 II.3.2 Simple Reactions on Stationary Planar Electrodes . ..........123 II.3.3 Simple Reactions on Stationary Spherical Electrodes and Microelectrodes . ..................................127 II.3.4 Reactions of Amalgam-Forming Metals on Thin Mercury Film Electrodes . .......................128 II.3.5 Electrode Reactions Complicated by Adsorption of the Reactant and Product . ...........................129 II.3.6 Applications of Square-Wave Voltammetry . ..........135 References . ..................................................143 II.4 Chronocoulometry ...........................................147 György Inzelt II.4.1 Introduction . .......................................147 II.4.2 Fundamental Theoretical Considerations . .................148 II.4.3 PracticalProblems.....................................151 II.4.4 Double-Step Chronocoulometry . .....................152 Contents xv II.4.5 Effect of Heterogeneous Kinetics on Chronocoulometric Responses . .........................................155 References . ..................................................157 II.5 Electrochemical Impedance Spectroscopy ......................159 Utz Retter and Heinz Lohse II.5.1 Introduction . .......................................159 II.5.2 Definitions, Basic Relations, the Kramers–Kronig Transforms . 159 II.5.3 Measuring Techniques . ............................161 II.5.4 Representation of the Impedance Data . .................164 II.5.5 EquivalentCircuits.....................................164 II.5.6 The Constant Phase Element . ............................164 II.5.7 Complex Non-Linear Regression Least-Squares (CNRLS) for the Analysis of Impedance Data .......................165 II.5.8 Commercial Computer Programs for Modelling of Impedance Data . ..................................166 II.5.9 Charge Transfer at the
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