Principles of Electrochemistry Second Edition

Transcription

1 Principles of Electrochemistry Second Edition Jiri Koryta Institute of Physiology, Czechoslovak Academy of Sciences, Prague HKJin Dvorak Department of Physical Chemistry, Faculty of Science, Charles University, Prague Ladislav Kavan /. Heyrovsky Institute of Physical Chemistry and Electrochemistry, Czechoslovak Academy of Sciences, Prague JOHN WILEY & SONS Chichester New York Brisbane Toronto Singapore

2 Contents Preface to the First Edition Preface to the Second Edition xi xv Chapter 1 Equilibrium Properties of Electrolytes Electrolytes: Elementary Concepts Terminology Electroneutrality and mean quantities Non-ideal behaviour of electrolyte Solutions The Arrhenius theory of electrolytes Structure of Solutions Classification of solvents Liquid structure Ion solvation Ion association Interionic Interactions The Debye-Hückel limiting law More rigorous Debye-Hückel treatment of the activity coefficient The osmotic coefficient Advanced theory of activity coefficients of electrolytes Mixtures of strong electrolytes Methods of measuring activity coefficients Acids and Bases Definitions Solvents and self-ionization Solutions of acids and bases Generalization of the concept of acids and bases Correlation of the properties of electrolytes in various solvents The acidity scale Acid-base indicators Special Cases of Electrolytic Systems Sparingly soluble electrolytes 69 v

3 VI Ampholytes Polyelectrolytes 73 Chapter 2 Transport Processes in Electrolyte Systems Irreversible Processes Common Properties of the Fluxes of Thermodynamic Quantities Production of Entropy, the Driving Forces of Transport Phenomena Conduction of Electricity in Electrolytes Classification of conductors Conductivity of electrolytes Interionic forces and conductivity The Wien and Debye-Falkenhagen effects Conductometry Transport numbers Diffusion and Migration in Electrolyte Solutions The time dependence of diffusion Simultaneous diffusion and migration The diffusion potential and the liquid junction potential The diffusion coefficient in electrolyte Solutions Methods of measurement of diffusion coefficients The Mechanism of Ion Transport in Solutions, Solids, Melts, and Polymers Transport in Solution Transport in solids Transport in melts Ion transport in polymers Transport in a flowing liquid Basic concepts The theory of convective diffusion The mass transfer approach to convective diffusion 141 Chapter 3 Equilibria of Charge Transfer in Heterogeneous Electrochemical Systems Structure and Electrical Properties of Interfacial Regions Classification of electrical potentials at interfaces The Galvani potential difference The Volta potential difference The EMF of galvanic cells The electrode potential Reversible Electrodes Electrodes of the first kind Electrodes of the second kind 175

4 Vll Oxidation-reduction electrodes The additivity of electrode potentials, disproportionation Organic redox electrodes Electrode potentials in non-aqueous media Potentials at the interface of two immiscible electrolyte Solutions Potentiometry The principle of measurement of the EMF Measurement of ph Measurement of activity coefficients Measurement of dissociation constants 195 Chapter 4 The Electrical Double Layer General Properties Electrocapillarity Structure of the Electrical Double Layer Diffuse electrical layer Compact electrical layer Adsorption of electroneutral molecules Methods of the Electrical Double-layer Study The Electrical Double Layer at the Electrolyte-Non-metallic Phase Interface Semiconductor-electrolyteinterfaces Interfaces between two electrolytes Electrokinetic phenomena 242 Chapter 5 Processes in Heterogeneous Electrochemical Systems Basic Concepts and Definitions Elementary outline for simple electrode reactions Formal approach The phenomenological theory of the electrode reaction The Theory of Electron Transfer The elementary step in electron transfer The effect of the electrical double-layer structure on the rate of the electrode reaction Transport in Electrode Processes Material flux and the rate of electrode processes Analysis of polarization curves (voltammograms) Potential-sweep voltammetry The concentration overpotential Methods and Materials The ohmic electrical potential difference Transition and steady-state methods 293

5 Vlll Periodic methods Coulometry Electrode materials and surface treatment Non-electrochemical methods Chemical Reactions in Electrode Processes Classification Equilibrium of chemical reactions Chemical volume reactions Surface reactions Adsorption and Electrode Processes Electrocatalysis Inhibition of electrode processes Deposition and Oxidation of Metals Deposition of a metal on a foreign Substrate Electrocrystallization on an identical metal Substrate Anodic oxidation of metals Mixed potentials and corrosion phenomena Organic Electrochemistry Photoelectrochemistry Classification of photoelectrochemical phenomena Electrochemical photoemission Homogeneous photoredox reactions and photogalvanic effects Semiconductor photoelectrochemistry and photovoltaic effects Sensitization of semiconductor electrodes Photoelectrochemical solar energy conversion 406 Chapter 6 Membrane Electrochemistry and Bioelectrochemistry Basic Concepts and Definitions Classification of membranes Membrane potentials Ion-exchanger Membranes Classification of porous membranes The potential of ion-exchanger membranes Transport through a fine-pore membrane Ion-selective Electrodes Liquid-membrane ion-selective electrodes Ion-selective electrodes with fixed ion-exchanger sites Calibration of ion-selective electrodes Biosensors and other composite Systems Biological Membranes Composition of biological membranes The structure of biological membranes Experimental modeis of biological membranes Membrane transport Examples of Biological Membrane Processes 454

6 6.5.1 Processes in the cells of excitable tissues Membrane principles of bioenergetics 464 Appendix A Recaiculation Formulae for Concentrations and Acthity Coefficients 473 Appendix B List of Symbols 474 Index 477 ix