MODERN ASPECTS OF ELECTROCHEMISTRY. No. 14

Transcription

1 MODERN ASPECTS OF ELECTROCHEMISTRY No. 14

2 LIST OF CONTRIBUTORS JOHN O'M. BOCKRIS Department of Chemistry Texas A&M University College Station, Texas B.E.CONWAY Chemistry Department University of Ottawa Ottawa, Canada EUGENE FINDL Bio Research, Inc. Farmingdale, New York A. J. HOPFINGER Department of Macromolecular Science Case Institute of Technology Case Western Reserve University Cleveland, Ohio EUGENE J. KELLY Chemistry Division Oak Ridge National Laboratory Oak Ridge, Tennessee SHAHED U.M. KHAN Department of Chemistry Texas A&M University College Station, Texas K. KINOSHITA SRI International Menlo Park, California DIGBY D. MACDONALD Department of Metallurgical Engineering The Ohio State University Columbus, Ohio MICHAEL C. H. McKUBRE Materials Research Laboratory SRI International Menlo Park, California K. A. MAURITZ T. R. Evans Research Center Diamond Shamrock Corporation D.M.NOVAK Chemistry Department University of Ottawa Ottawa, Canada B. V. TILAK Hooker Research Center Grand Island, New York ERNEST B. YEAGER Department of Chemistry Case Western Reserve University Cleveland, Ohio RAOULZANA Centre de Recherches sur les Macromolecules, CNRS Strasbourg-Cedex, France A Continuation Order Plan is available for this series. A continuation order will bring delivery of each new volume immediately upon publication. Volumes are billed only upon actual shipment. For further information please contact the publisher.

3 MODERN ASPECTS OF ELECTROCHEMISTRY No. 14 Edited by J. O'M. BOCKRIS Department of Chemistry Texas A & M University College Station, Texas B. E.CONWAY Department of Chemistry University of Ottawa Ottawa, Canada and RALPH E. WHITE Department of Chemical Engineering Texas A & M University College Station, Texas PLENUM PRESS NEW YORK AND LONDON

4 Library of Congress cataloged the first volume of this title as follows: Modern aspects of electrochemistry. no. [I) Washington, Butterworth, v. illus. 23 cm. No. 1-2 issued as Modern aspects series of chemistry. Editors: no. 1- J. Bockris (with B. E. Conway, no. 3- Imprint varies: no. I, New York, Academic Press. - No.2, London, Butterworths. 1. Electrochemistry- Collected works. I. Bockris, John O'M., ed. II. Conway, B. E. ed. (Series: Modern aspects series of chemistry) QDS52.M rev ISBN ISBN (ebook) DOI / Plenum Press, New York Softcover reprint of the hardcover 1 st edition 1982 A Division of Plenum Publishing Corporation 233 Spring Street, New York, N.Y All rights reserved No part of this book may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher

5 Preface This volume contains eight chapters covering a wide range of topics: ultrasonic vibration potentials, impedance measurements, photoelectrochemical kinetics, chlorine production, electrochemical behavior of titanium, structural properties of membranes, bioelectroche mistry, and small-particle effects for electrocatalysis. Chapter 1, contributed by Zana and Yeager, discusses the little used but potentially important area of ultrasonic vibration potentials. The authors review the historical literature and the associated theoretical equations. They continue by discussing various aspects of the experimental technique and close with a review of the existing studies. They conclude by noting that vibration potentials may be useful for determining the effects of various agents on colloidal suspensions found in such important industries as paper production. Chapter 2 is a review of impedance techniques, written by Macdonald and McKubre. The authors include not only derivations of various impedance functions for electrochemical systems but also particularly useful discussions of instrumental methods. The authors close with an interesting claim: "the distribution of current and potential within a porous battery or fuel-cell electrode and within 'flow-through' electrodes is best analyzed in terms of the frequency dispersion of the impedance." Chapter 3, by Khan and Bockris, is a timely review of photoelectrochemical kinetics and related devices. Their work begins by reviewing critically important papers on photoelectrochemical kinetics. They continue by presenting detailed discussions concerning the conceptual ideas of the semiconductor-solution interface. The authors close by pointing out that photoelectrochemistry may v

6 vi Preface also be used to produce important chemical products such as chlorine and that, consequently, photo electrochemistry may become industrially useful in the future. In Chapter 4 Novak, Tilak, and Conway review the industrially important electrochemical production of chlorine. Their chapter covers both the fundamental and applied aspects of chlorine generation. They begin by discussing briefly the various materials that have been used through the years as anodes for chlorine production and continue by presenting detailed information about the currently used metal anodes. They also include, thoughtfully, a table of recently patented anode compositions together with their patent numbers. Mechanisms of chlorine production are discussed and kinetic parameters are presented. Finally, a review of the various industrial aspects of chlorine production is presented. Chapter 5, by Kelly, is a review of the electrochemical behavior of titanium. The author begins by reviewing the recent literature and points out that a majority of the existing work is plagued by "persistent attempts to interpret the behavior of irreversible electrochemical processes within the framework of reversible thermodynamics." He continues with a detailed explanation of his claim. Much more is included in his review, which will probably stimulate research in this area for quite some time. Mauritz and Hopfinger present in Chapter 6 various models for the structural properties of membranes and discuss briefly a transport model for ions through such membranes. This chapter will undoubtedly lead to a better understanding of extremely important ionomeric membranes, which are being used widely in industry. In Chapter 7 Findl presents a review of bioelectrochemistry. He includes in his review discussions of a number of practically important phenomena such as the generation of potentials in bone by the application of mechanical stress. His review may stimulate electrochemists to attempt to contribute to the growing field of bioelectrochemistry. Finally, Chapter 8, by Kinoshita, is a review of the important area of small particles and structural effects in electrocatalysis. He presents various models, with supporting data in some cases, and concludes by urging us to investigate more closely the interaction

7 Preface vii between a catalyst and its support and the effects of surface impurities. Texas A & M University University of Ottawa Texas A & M University J. O'M. Bockris B. E. Conway R. E. White

8 Contents Chapter 1 ULTRASONIC VIBRATION POTENTIALS Raoul Zan a and Ernest B. Yeager 1. Introduction II. Theory of Ionic Vibration Potentials (IVP) Derivation of the Expression for the IVP Physical Meaning of the Apparent Molar Masses W + and W _ and Their Relationship to the Partial Molar Volumes at Infinite Dilution of the Ions, V~ and V~ IVP of Mixtures of Electrolytes Case of Solutions in which Fast Physical or Chemical Processes Occur Solutions of Electrolytes in Organic Solvents III. Quantitative Measurements of Ultrasonic Vibration Potentials Generation of the Electrical Impulse Driving the Transducer The Transducer The Propagation System Double-Electrode Probe and Cell Assembly Detection Electronics Determination of Velocity Amplitudes False Effects.... IV. Review of IVP Studies Aqueous Solutions ix

9 x Contents 2. Solutions in Organic Solvents Factors which Determine the Partial Molar Volume of Ions IVPs and Solvation Numbers V. Miscellaneous Studies Colloidal Vibration Potentials Polyelectrolyte Vibration Potentials VI. Conclusion References & Chapter 2 IMPEDANCE MEASUREMENTS IN ELECTROCHEMICAL SYSTEMS Digby D. Macdonald and Michael C. H. McKubre I. Introduction II. Interfacial Impedance Definitions and General Concepts Electrochemical Systems III. Derivation of Impedance Functions for Electrochemical Systems Quasireversible Reaction Coupled Chemical-Electrochemical Reactions Surface-Controlled Processes Edge Effects and Porous Electrodes IV. Instrumental Methods Frequency Domain Measurements-Small-Amplitude Sinusoidal Perturbation Time Domain Measurements V. The Future References

10 Contents xi Chapter 3 PHOTO ELECTROCHEMICAL KINETICS AND RELATED DEVICES Shahed U. M. Khan and John O'M. Bockris I. Introduction II. Some Important Papers in Photoelectrochemical Kinetics Green: The Basic Dependence on Surface States Green, McBreen and Jendrassic: Determination of Surface States Bockris and Reddy: nip Junctions and eli Junctions Fujishima and Honda: Hydrogen Production? Ellis, Keizer, and Wrighton: Stabilizing by Adding S2- to the Solution Bockris and Uosaki: Photoelectrochemical Kinetics, Taking into Account the Effect of Surface States " Wilson: Recombination Kinetics Schoijet: Empiricistic Evaluation of Photovoltaics Hodes: Surface Etching Reichmann: No Schottky Barrier and Rate-Determining Charge Transfer in the Double Layer Bard: Tungstic Selenide Gditzel et at.: Colloidal Bielectrodes Guruswamy and Bockris: The Shift in Onset Potential Bard et at.: Fermi Level Pinning III. Theory The Structure of the Double Layer The Concept of a Schottky Barrier The Theory of the Onset Potential The Cutting Edge of Models in Semiconductor- Solution Interfaces

11 xii Contents 5. Questionable Aspects of the Theories of Semiconductor Photo electrochemistry The Rate-Determining Step The Nernst-Planck Equation The Photoelectrochemical Cell IV. Analysis of the Surface V. Practical Devices VI. Electricity Generation with Redox Couples VII. Carbon Dioxide Reduction VIII. Chlorine Production IX. Applications Redox Systems Hydrogen-Oxygen Production Hydrogen and Oxygen Production by Bioelectrochemical Methods' Ammonia Universal Photoelectrochemical Reactor X. Summary References Chapter 4 FUNDAMENTAL AND APPLIED ASPECTS OF ANODIC CHLORINE PRODUCTION D. M. Novak, B. V. Tilak, and B. E. Conway I. Introduction General Aspects of the Reaction Scope of the Review II. Anode Materials for Chlorine Evolution Electrode Preparation Other Anode Materials and Some Future Materials Trends Physical and Morphological Characteristics of (Ru02 + Ti02)-Based Electrodes

12 Contents xiii 4. Materials Requirements for Chlorine Anodes III. Fundamental Aspects of the Anodic Chlorine Evolution Reaction Thermodynamic Aspects of the Ch-Cr Reaction Coulombic Efficiency of the Ch Evolution Reaction IV. Kinetic Aspects of the Chlorine Evolution Reaction The State of Anode Surfaces Surface Oxidation of Pt Anodes in the Absence of Adsorbed CI State of Oxidation of Surfaces of Ru02 and Oxidized Ru and Ir Anodes State of Oxidation of Surfaces of Carbon Anodes Chloride Ion Adsorption and its Effects on Oxide Film Formation at Noble Metal Anodes Mechanisms of Anodic Chlorine Evolution Chlorine Reduction in Aqueous Solutions V. Industrial Aspects of Chlorine Evolution Wotld Production of Chlorine Commercial Electrolytic Methods for Chlorine Production References Chapter 5 ELECTROCHEMICAL BEHAVIOR OF TITANIUM Eugene J. Kelly I. Introduction II. Active State Dissolution and Passivation Experimental Background Mechanisms III. Effects of Ti(III) and Ti(IV) Ions Oxidation of Ti(III) Ions Reduction of Ti(IV) Ions Autopassivation of Electrolyte-Coupled Active- Passive Systems

13 xiv Contents IV. Noble Metal Alloys and the Hydrogen Evolution Reaction Noble Metal Alloys of Titanium Hydrogen Evolution Reaction References Chapter 6 STRUCTURAL PROPERTIES OF MEMBRANE IONOMERS K. A. Mauritz and A. J. Hopfinger I. Introduction II. General Aspects of Ionomeric Membranes Overall Structure and Swelling Donnan Exclusion III. Theoretical Models of Crosslinked Polyelectrolytes Gregor's Mechanical Model The Model of Katchalsky et al The Model of Harris and Rice IV. Ion Pairing in Ionomeric Membranes Dissociation Equilibrium of Counterions in Ionomers A Theory of Membrane Internal Water Activity V. Supermolecular Structure of Ionomeric Materials Introduction Polymer-Polymer Interfaces and Interphases Formation of Spherical Domains in Block Copolymers Application of Spherical Domain Block Copolymer Theory to Ionomeric Structure Experimental Investigations of the Structure of Ionomers Theories of Cluster Formation and Ionomer Structure 474 VI. Conclusion References

14 Contents xv Chapter 7 BIOELECTROCHEMISTRY - ELECTROPHYSIOLOGY-ELECTROBIOLOGY Eugene Findl I. Introduction II. Ions, Membranes, and Fields Fields and Ion Transport Transmembrane Potentials III. Bioelectrokinetics Cardiovascular System Bone and Cartilage IV. Medical and Biological Applications of Fields Bone, Limb, and Cartilage Regeneration Electroanalgesia Biomaterials and Surface Charge Miscellaneous Applications References Chapter 8 SMALL-PARTICLE EFFECTS AND STRUCTURAL CONSIDERATIONS FOR ELECTROCATAL YSIS K. Kinoshita I. Introduction II. Surface Structure of Small Particles III. Dependence of Metal Properties on Particle Size Melting Point Lattice Parameter Low-Temperature Specific Heat Magnetic Properties

15 xvi Contents 5. Electrical Properties Optical Properties Properties of Specific Metals IV. Electrocatalysis on Solid Metal Electrodes Pretreatment of Noble Metal Electrodes Potential Cycling of Metal Electrodes Single-Crystal Electrodes Effects of Applied Mechanical Stress V. Particle Size Effects in Electrocatalysis Oxygen Reactions on Platinum Hydrogen Reactions Oxidation of Hydrocarbons VI. Concluding Remarks References Index