P1: TIX/XYZ P2: ABC JWST129-fm JWST129-Pollet December 1, 2011 19:12 Printer: Yet to come Power Ultrasound in Electrochemistry P1: TIX/XYZ P2: ABC JWST129-fm JWST129-Pollet December 1, 2011 19:12 Printer: Yet to come Power Ultrasound in Electrochemistry From Versatile Laboratory Tool to Engineering Solution Edited by BRUNO G POLLET The University of Birmingham Edgbaston, United Kingdom A John Wiley & Sons, Ltd., Publication P1: TIX/XYZ P2: ABC JWST129-fm JWST129-Pollet December 1, 2011 19:12 Printer: Yet to come This edition first published 2012 © 2012 John Wiley & Sons, Ltd Registered office John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, United Kingdom For details of our global editorial offices, for customer services and for information about how to apply for permission to reuse the copyright material in this book please see our website at www.wiley.com The right of the author to be identified as the author of this work has been asserted in accordance with the Copyright, Designs and Patents Act 1988 All rights reserved No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, except as permitted by the UK Copyright, Designs and Patents Act 1988, without the prior permission of the publisher Wiley also publishes its books in a variety of electronic formats Some content that appears in print may not be available in electronic books Designations used by companies to distinguish their products are often claimed as trademarks All brand names and product names used in this book are trade names, service marks, trademarks or registered trademarks of their respective owners The publisher is not associated with any product or vendor mentioned in this book This publication is designed to provide accurate and authoritative information in regard to the subject matter covered It is sold on the understanding that the publisher is not engaged in rendering professional services If professional advice or other expert assistance is required, the services of a competent professional should be sought The publisher and the author make no representations or warranties with respect to the accuracy or completeness of the contents of this work and specifically disclaim all warranties, including without limitation any implied warranties of fitness for a particular purpose This work is sold with the understanding that the publisher is not engaged in rendering professional services The advice and strategies contained herein may not be suitable for every situation In view of ongoing research, equipment modifications, changes in governmental regulations, and the constant flow of information relating to the use of experimental reagents, equipment, and devices, the reader is urged to review and evaluate the information provided in the package insert or instructions for each chemical, piece of equipment, reagent, or device for, among other things, any changes in the instructions or indication of usage and for added warnings and precautions The fact that an organization or Website is referred to in this work as a citation and/or a potential source of further information does not mean that the author or the publisher endorses the information the organization or Website may provide or recommendations it may make Further, readers should be aware that Internet Websites listed in this work may have changed or disappeared between when this work was written and when it is read No warranty may be created or extended by any promotional statements for this work Neither the publisher nor the author shall be liable for any damages arising herefrom Library of Congress Cataloging-in-Publication Data Power ultrasound in electrochemistry : from versatile laboratory tool to engineering solution sonoelectrochemistry / edited by Bruno G Pollet p cm Includes bibliographical references and index ISBN 978-0-470-97424-7 (cloth) Sonochemistry Sonic waves–Industrial applications Electrochemistry I Pollet, Bruno G QD801.P69 2012 541 370284–dc23 2011043940 A catalogue record for this book is available from the British Library HB ISBN: 9780470974247 Set in 10/12pt Times by Aptara Inc., New Delhi, India P1: TIX/XYZ P2: ABC JWST129-fm JWST129-Pollet December 1, 2011 19:12 Printer: Yet to come I dedicate this book to: A wonderful Man and a brilliant Scientist – Professor John Phil Lorimer and Mes parents et ma petite soeur que j’aime e´ norm´ement P1: TIX/XYZ P2: ABC JWST129-fm JWST129-Pollet December 1, 2011 19:12 Printer: Yet to come Contents Foreword About the Editor List of Contributors Acknowledgements Introduction to Electrochemistry Bruno G Pollet and Oliver J Curnick I.1 I.2 I.3 I.4 Introduction Principles of Electrochemistry Electron-Transfer Kinetics Determination of Overpotentials I.4.1 Decomposition Voltages I.4.2 Discharge Potentials I.5 Electroanalytical Techniques I.5.1 Voltammetry I.5.2 Amperometry References An Introduction to Sonoelectrochemistry Timothy J Mason and Ver´onica S´aez Bernal 1.1 Introduction to Ultrasound and Sonochemistry 1.2 Applications of Power Ultrasound through Direct Vibrations 1.2.1 Welding 1.3 Applications of Power Ultrasound through Cavitation 1.3.1 Homogeneous Reactions 1.3.2 Heterogeneous Reactions Involving a Solid/Liquid Interface 1.3.3 Heterogeneous Liquid/Liquid Reactions 1.4 Electrochemistry 1.5 Sonoelectrochemistry – The Application of Ultrasound in Electrochemistry 1.5.1 Ultrasonic Factors that Influence Sonoelectrochemistry 1.6 Examples of the Effect of Ultrasound on Electrochemical Processes under Mass Transport Conditions 1.7 Experimental Methods for Sonoelectrochemistry xiii xv xvii xix 1 10 10 10 11 11 17 20 21 21 23 23 25 26 26 27 27 28 29 32 34 P1: TIX/XYZ P2: ABC JWST129-fm JWST129-Pollet viii December 1, 2011 19:12 Printer: Yet to come Contents 1.7.1 Cell Construction 1.7.2 Stability of the Electrodes Under Sonication 1.7.3 Some Applications of Sonoelectrochemistry References The Use of Electrochemistry as a Tool to Investigate Cavitation Bubble Dynamics Peter R Birkin 2.1 Introduction 2.2 An Overview of Bubble Behaviour 2.3 Mass Transfer Effects of Cavitation 2.4 Isolating Single Mechanisms for Mass Transfer Enhancement 2.5 Electrochemistry Next to a Tethered Permanent Gas Bubble 2.6 Mass Transfer from Forced Permanent Gas Bubble Oscillation 2.7 Mass Transfer Effects from Single Inertial Cavitation Bubbles 2.8 Investigating Non-inertial Cavitation Under an Ultrasonic Horn 2.9 Measuring Individual Erosion Events from Inertial Cavitation 2.10 Conclusions Acknowledgements References Sonoelectroanalysis: An Overview Jonathan P Metters, Jaanus Kruusma and Craig E Banks 3.1 Introduction 3.2 Analysis of Pesticides 3.3 Quantifying Nitrite 3.4 Biogeochemistry 3.5 Quantifying Metal in ‘Life or Death’ Situations 3.6 Analysis of Trace Metals in Clinical Samples 3.7 Biphasic Sonoelectroanalysis 3.8 Applying Ultrasound into the Field: The Sonotrode 3.9 Conclusions References Sonoelectrochemistry in Environmental Applications Pedro L Bonete Ferr´andez, Mar´ıa Deseada Esclapez, Ver´onica S´aez Bernal and Jos´e Gonz´alez-Garc´ıa 4.1 4.2 4.3 4.4 4.5 Introduction Sonoelectrochemical Degradation of Persistent Organic Pollutants 4.2.1 Sonoelectrochemical Applications 4.2.2 Hybrid Sonoelectrochemical Techniques Applications Recovery of Metals and Treatment of Toxic Inorganic Compounds Disinfection of Water by Hypochlorite Generation Soil Remediation 34 36 38 40 45 45 46 48 48 51 55 62 65 67 73 73 73 79 79 87 87 88 89 90 92 93 93 94 101 101 102 102 115 121 129 130 P1: TIX/XYZ P2: ABC JWST129-fm JWST129-Pollet December 1, 2011 19:12 Printer: Yet to come Contents 4.6 Conclusions List of Symbols and Abbreviations References Organic Sonoelectrosynthesis David J Walton 5.1 5.2 5.3 5.4 Introduction Scale-Up Considerations Early History of Organic Sonoelectrochemistry Electroorganic Syntheses 5.4.1 Electroreductions 5.4.2 Organochalcogenides 5.4.3 Synthetic Electrooxidations 5.4.4 Sonoelectrochemically Produced Electrode Coatings: Desirable and Undesirable 5.5 Other Systems 5.5.1 Hydrodynamics 5.5.2 Low-temperature Effects 5.6 Conclusions Acknowledgements References Sonoelectrodeposition: The Use of Ultrasound in Metallic Coatings Deposition Jean-Yves Hihn, Francis Touyeras, Marie-Laure Doche, C´edric Costa and Bruno G Pollet 6.1 6.2 6.3 6.4 6.5 Introduction to Metal Plating 6.1.1 Why the Need to Cover Surfaces with Metals? 6.1.2 Process and Technology of Plating The Use of Ultrasound in Surface Treatment 6.2.1 Ultrasound in the Cleaning Step for Surface Treatment Processes Ultrasound and Plating: Why Study Plating under Sonication? Electrodeposition Assisted by Ultrasound 6.4.1 The Electrodeposition Process 6.4.2 Ultrasonic Effects on Electrodeposited Coating Properties 6.4.3 Microscopic Effects of Ultrasound on Electrodeposited Metal Coatings 6.4.4 The Influence of Acoustic Energy Distribution on Coatings 6.4.5 Influence of Ultrasound on Copper Electrodeposition in Unconventional Solvents 6.4.6 Incorporation of Particles Assisted by Ultrasound Electroless Coating Assisted by Ultrasound 6.5.1 The Electroless Process 6.5.2 Ultrasound Effects upon Electroless Coating Properties ix 134 134 135 141 141 142 143 144 144 149 151 157 161 161 162 163 163 163 169 169 169 170 170 170 172 173 173 175 179 182 187 195 198 198 198 P1: TIX/XYZ P2: ABC JWST129-fm JWST129-Pollet x December 1, 2011 19:12 Printer: Yet to come Contents 6.5.3 Copper Coating on Non-conductive Substrates under Insonation References Influence of Ultrasound on Corrosion Kinetics and its Application to Corrosion Tests Marie-Laure Doche and Jean-Yves Hihn 7.1 Introduction to Metal Corrosion 7.1.1 What Exactly is Corrosion? 7.1.2 Why Do Metals Corrode? 7.1.3 The Price to Pay: the Economical Impact of Corrosion 7.1.4 Corrosion Control Technology: the Need for Reliable Corrosion Tests 7.1.5 Why Study Corrosion Under Sonication? 7.1.6 Corrosion and Corrosion-Cavitation Mechanisms 7.1.7 Corrosion Rate 7.1.8 Electrochemical Study of Corrosion Reactions 7.1.9 Forms of Corrosion 7.1.10 Cavitation-Corrosion 7.2 Influence of Ultrasound on the Corrosion Mechanisms of Metals 7.2.1 Influence of Ultrasound on General Corrosion 7.2.2 Influence of Ultrasound on Passivity of Metals 7.3 Ultrasound as a Tool to Develop Accelerated Corrosion Testing 7.3.1 Atmospheric Corrosion of Zinc Plated Steel 7.3.2 Accelerated Corrosion Test for Stainless Steel Used in Exhaust Systems 7.3.3 Accelerated Corrosion Test for Evaluating Oilfield Corrosion Inhibitors 7.3.4 Accelerated Corrosion Test for Surgical Implant Materials in Body Fluids References Sonoelectropolymerisation Fabrice Lallemand, Jean-Yves Hihn, Mahito Atobe and Abdeslam Et Taouil 8.1 8.2 8.3 8.4 8.5 8.6 Introduction to Electropolymerisation Innovative Processes for Electrode Activation Solubilisation of Monomers with Ultrasound Chemical Polymerisation Electropolymerisation under Ultrasonic Irradiation Effects of Ultrasound on Film Properties 8.6.1 Mass-Transfer Effect 8.6.2 Morphology Effect 8.6.3 Doping Effect 8.6.4 Effect on Local Control of Surfaces References 201 209 215 215 215 215 216 217 219 220 221 222 223 223 231 232 240 242 242 243 243 244 244 249 249 251 256 257 259 262 262 264 272 276 278 P1: TIX/XYZ P2: ABC JWST129-fm JWST129-Pollet December 1, 2011 19:12 Printer: Yet to come Contents Sonoelectrochemical Production of Nanomaterials Jonathan P Metters and Craig E Banks 9.1 9.2 9.3 10 xi 283 Introduction Experimental Configurations Pure Metals 9.3.1 Cobalt, Iron and Nickel 9.3.2 Silver 9.3.3 Copper 9.3.4 Magnesium 9.3.5 Aluminium 9.3.6 Lead and Cadmium 9.3.7 Core Shell Nanoparticles 9.3.8 Gold 9.3.9 Tungsten 9.4 Alloy Nanoparticles 9.5 Polymer Nanoparticles 9.6 Conclusions References 283 286 287 287 287 288 288 289 290 290 292 295 295 296 296 296 Sonochemistry and Sonoelectrochemistry in Hydrogen and Fuel Cell Technologies Bruno G Pollet 301 10.1 Introduction 10.2 Sonoelectrochemical Production of Hydrogen 10.3 Sonochemical Production of Noble Metals and Fuel Cell Electrocatalysts 10.3.1 Sonochemical Mono-Metallic Syntheses 10.3.2 Sonochemical Bi-Metallic Syntheses 10.3.3 Sonochemical Perovskite Oxides Syntheses 10.4 Sonoelectrochemical Production of Noble Metals and Fuel Cell Electrocatalysts 10.4.1 Effect of Surfactants and Polymers 10.4.2 Effect of Aqueous Solutions 10.5 Sonochemical and Sonoelectrochemical Preparation of Fuel Cell Electrodes 10.6 Industrial Applications of the Use of Ultrasound for the Fabrication of Fuel Cell Materials 10.7 Conclusions Acknowledgement List of Abbreviations References Appendix: Sonochemical Effects on Electrode Kinetics Index 301 303 305 306 309 311 311 315 317 318 319 320 321 321 322 327 335 P1: TIX/XYZ P2: ABC JWST129-bpreface JWST129-Pollet December 1, 2011 13:30 Printer: Yet to come Foreword When I think back to my first excursions into the world of ultrasound and its effects on chemical reactions it takes me back to 1975 when I obtained my first permanent academic post as an organic chemist at an institution that was then called Lanchester Polytechnic but later became Coventry University The department I joined was Chemistry and Metallurgy, reflecting the applied nature of science courses at that time One day I was walking through a metallurgy laboratory and saw an ultrasonic bath being used to clean metal samples The process intrigued me for I could see that the ultrasonic bath was producing a large amount of energy as evidenced by the disturbance of the water with which it was filled It occurred to me that this was perhaps a form of energy which might be employed to influence chemical reactivity using as an example a simple solvolysis reaction However, the initial results were puzzling but I was sharing an office with a physical chemist, the late Phil Lorimer, but neither of us had heard of using ultrasound as a source of energy to promote chemical reactivity Together we pursued this new subject and met many problems in convincing the UK science fraternity that we were ‘on to something big’ We produced our first paper in 1980 as a Chemical Communication, in which we reported a small (twofold) enhancement in the hydrolysis rate of 2-chloro-2-methylpropane By 1986 the idea of using ultrasound to influence reactions had greatly expanded worldwide and we were involved in organising the first ever international conference on sonochemistry at Warwick University So where does electrochemistry fit into the development of sonochemistry? Phil Lorimer was originally an electrochemist and so had an interest in all things that might influence electrochemical processes Together with another colleague, David Walton, we began to apply ultrasound to electrochemistry in the late 1980s and discovered that it could, for example, modify the electrochemical oxidation mechanism of cyclohexanecarboxylate In 1990 we published a review using the term ‘Sonoelectrochemistry’ for the first time in a peer-reviewed journal This review forced us to look at the literature surrounding the uses of ultrasound in electrochemistry and brought to light a number of research publications that had not previously been drawn together Other sources have been unearthed since then, including the pioneering work of Young and Kersten in 1936 on the effects of ultrasonic radiation on electrodeposits This was perhaps the first observation of improvements in hardness and brightness induced by ultrasound Walker reinvestigated and advanced the work in the 1970s and in 1993 wrote a comprehensive review of his and other work entitled ‘Ultrasonic Agitation in Metal Finishing’ It is surprising to me that the very early work on sonoelectrochemistry has not been cited extensively This is the case with the 1953 paper of Yeager and Hovorka entitled ‘Ultrasonic Waves and Electrochemistry’ It provided a survey of the electrochemical applications of ultrasonic waves that were discussed in terms P1: TIX/XYZ P2: ABC JWST129-bapp JWST129-Pollet December 1, 2011 13:1 Printer: Yet to come Appendix: Sonochemical Effects on Electrode Kinetics (b) (a) CYLINDER ELECTRODE ‘Face-on’ geometry ELECTRODE PROBE mm ψ y 11.2 mm 15.8 mm 329 α Flow of Solution “ANGULAR” GEOMETRY on Sonication mm 16.4 mm ψ y =0 α = π/4 ULTRASONIC PROBE d’ = mm Sonicated Areas PROBE Y “FACE-ON” GEOMETRY ‘Angular’ geometry (c) X CYLINDER ELECTRODE 200 “Face-on” geometry “Angular” geometry Limiting Current / mA ULTRASONIC PROBE ψk ψo 150 α ψ y α = π/4 100 50 0 Ultrasonic Intensity1/2/W1/2 cm−1 Figure A.1 (a) Two geometries employed during the study – the face-on’ and ‘angular’ geometries The figure shows the two sonicated areas for both geometries (b) Co-ordinate system used to describe the ‘face-on’ geometry and ‘angular’ geometry in terms of ultrasonic intensity (c) Limiting currents plotted against the square root of ultrasonic intensity (20 kHz) for the reduction of silver (4 g dm–3 ) on a sonicated cylinder electrode at 298 (±1) K for the face-on’ and ‘angular’ geometries indicates the ultrasonic intensity at x = or/and y = 0, f.o the ‘face-on’ geometry and ang the ‘angular’ geometry (i) Influence of the incident flow – The first possible explanation is to consider the two geometries and resolve the flows into the component parts [see Figure A.1(a,b)] For example, it is assumed that the total ultrasonic intensity, , is given by Equation A.3: = x + y (A.3) P1: TIX/XYZ JWST129-bapp P2: ABC JWST129-Pollet 330 December 1, 2011 13:1 Printer: Yet to come Power Ultrasound in Electrochemistry It has been also demonstrated that the ultrasonic intensity within a fluid depends on distance d travelled thought that fluid with an absorption coefficient α, according to: = exp ( − 2αd ) (A.4) Using 8.6 × 10–8 cm–1 for the absorption coefficient of water at 298 K and at 20 kHz, Equation A.4 leads to = (incident ultrasonic intensity) in the range and 10 mm electrode–probe distances Thus, if the acoustic absorption is neglected, Equation A.4 may be reduced to: = 0,x + 0,y (A.5) For the ‘face-on’ geometry (see Figure A.1), the ultrasonic intensity components are in the x and y directions, that is, 0,x,f.o (= 0) and 0,y,f.o (= ) respectively For the ‘angular’ geometry [see Figure A.1(b)], the ultrasonic intensity components are in the x and y directions, that is, 0,x,ang = sin (45◦ ) = 0.707 and 0,y,s.o = cos (45◦ ) = 0.707 respectively The ratio of the ultrasonic intensity on the y-axis for the two geometries gives o,y,f.o o,y,ang = 0.707 = 1.41 (A.6) Assuming that the limiting current (I lim ) is proportional to the square root of the ultrasonic intensity ( 1/2 ) [see Figure A.1(c)], Equation A.6 may be reduced to: √ Ilim,f.o = 1.41 = 1.18 (A.7) Ilim,ang Whilst the value of 1.18 can account in part for some of the observed 1.5 value for I lim,f.o /I lim,ang , it cannot account for it all and again suggests that the ultrasonic probe positioning is crucial for the determination of limiting currents For both cases, ‘face-on’ and ‘angular’ geometries, the current density is variable over the total electrode area and therefore simple mathematical treatments and equations have obvious limitations It is interesting to note that the electrode area in both cases may be regarded as two areas: (i) a high current density area and (ii) a low current density area Ideally, it would be useful to treat the resulting system using Equation A.6 containing two terms at high current density and low current density However, low current density area is difficult to evaluate because of the complexity of the cylinder electrode and the ‘angular’ geometries (ii) Influence of hydrodynamics on the diffusion layer thickness – This difference in limiting current between the two geometries may be attributed to a greater thinning of the diffusion layer in the case of the ‘face-on’ geometry where electroactive species reaches all points of the electrode uniformly In the ‘angular’ geometry, the diffusion layer is nonuniform and roughly resembles that of a channel electrode Further, it is interesting to note that the sonicated areas for the two geometries are different [see Figure A.1(a)] It was deduced that the sonicated area for the ‘face-on’ geometry is 2.13 cm2 (CE base area) and for the ‘angular’ geometry is 2.65 cm2 (ellipsoid area) In order to compare diffusion layer thicknesses for both ‘face-on’ and ‘angular’ geometries, a hydrodynamic study can be made as follows P1: TIX/XYZ JWST129-bapp P2: ABC JWST129-Pollet December 1, 2011 13:1 Printer: Yet to come Appendix: Sonochemical Effects on Electrode Kinetics 331 For the ‘face-on’ geometry, the limiting current is given by Ilim,f.o = nFAf.o DC∗ δf.o (A.8) and for the ‘angular’ geometry, the limiting current is given by Ilim,ang = nFAang DC∗ δang (A.9) provided that the non-sonicated areas of the electrode for both the ‘face-on’ and ‘angular’ geometries are not considered The ratio of the limiting currents for the two geometries gives Af.o δang Ilim,f.o = Iang Aang δf.o (A.10) [Assuming that the diffusion coefficients (D) are similar for both geometries.] Inserting experimental values of limiting current density and surface area for both geometries in Equation A.10, a ratio of diffusion layer thicknesses at 30 W cm–2 power output may be deduced: Ilim,f.o Aang δang 150.4 × 2.65 = = = 1.84 δf.o Ilim,ang Af.o 101.5 × 2.13 (A.11) Thus, the overall ‘average’ diffusion layer thickness is 1.8 times thinner for a ‘face-on’ geometry than a ‘angular’ geometry under identical conditions (iii) Influence of localised temperature variations on diffusion coefficients – The observed difference in limiting current between the two geometries may also be attributed to a change in diffusion coefficients due to localised temperature variations Assuming that the diffusion coefficient for the ‘face-on’ (D0,f.o ) and the ‘angular’ (D0,ang ) geometries are different and assuming that the diffusion layer for the ‘face-on’ geometry is ‘hotter’ than that for the ‘angular’ geometry [for example, 400 K for the ‘face-on’ geometry (value deduced in Lorimer et al [9]) compared to 298 K for the ‘angular’ geometry], it is possible to deduce the ratio of the diffusion coefficients of silver for the two geometries at maximum power (30 W cm–2 ), that is Ilim,f.o 6.17 × 10−5 D0,f.o = = = 3.76 D0,ang Ilim,ang 1.64 × 10−5 (A.12) Since, in our conditions, the ratio of the limiting currents for the two geometries for 30 W cm–2 power output is Ilim,f.o = 1.5 Ilim,ang (A.13) this suggestion may be dismissed [The diffusion coefficient of silver at 400 K was deduced by assuming linearity of the plot of ln(D) versus 1/T The equation of the line was in the form of ln(D) = –1553/T – 5.8 Values of D were obtained from the rotating disc experiments at 298, 310.5 and 323 K] However, it is possible to deduce an ‘apparent’ temperature by deducing an ‘apparent’ diffusion coefficient for the ‘face-on’ geometry Assuming that the ratio of the limiting P1: TIX/XYZ JWST129-bapp P2: ABC JWST129-Pollet 332 December 1, 2011 13:1 Printer: Yet to come Power Ultrasound in Electrochemistry currents for both geometries is true (Equation A.13), a value of the ‘apparent’ diffusion coefficient may be deduced employing Equation A.12: Df.o = Ilim,f.o Dang = 1.5 × 1.62 × 10−5 = 2.43 × 10−5 cm2 s−1 Ilim,ang (A.14) value of D = 1.62 × 10–5 cm2 s–1 at 298 K Thus, by assuming linearity between ln(D) versus 1/T, the ‘apparent’ temperature was deduced to be approximately 350 K This result suggests that if the 1.5-increase in limiting current for the ‘face-on’ geometry compared to the ‘angular’ geometry was solely due to an increase in diffusion coefficient for the ‘face-on’ geometry, this would lead to a bulk temperature of approximately 350 K, a value which was never achieved under sonication at 298 K However, it is interesting to note that this result compares favourably with the temperature of the diffusion layer for the ‘face-on’ geometry is 400 K (value deduced in Lorimer et al [9, 10]) Apart from the remarkable effects of ultrasound on mass-transport processes, it has been shown that sonication alters the electrode potential Several workers such as Morigushi [11] and Pollet et al [12] showed that the overpotential of hydrogen evolution on gold and platinum electrodes decreases in a sonicated environment This finding was later observed by the Compton group on other metals a few years ago [13] Pollet et al speculated that this decrease in overpotential was due to both a reduction in concentration gradients and in nucleation overpotential at the electrode surface and in the removal of adhered hydrogen bubbles and adsorbed materials Even now, some controversy still surrounds the effect of ultrasound upon electrode kinetic parameters such as the formal (E0 ) and half-wave (E1/2 ) potentials and apparent heterogeneous rate constant (k0 ), which are related to equilibrium potentials However, a detailed study by Pollet et al in 1998 [14] showed that ultrasound affects heterogeneous electron-transfer kinetic parameters of a typical quasi-reversible system providing that the electrode receives a strict cleaning procedure (for surface reproducibility) prior to any sonoelectrochemical experiments It was shown that the half-wave potential (E1/2 ) shifts cathodically and the apparent heterogeneous rate constant (k0 ) increases with increasing ultrasonic intensity Also, it was shown that these parameters appear to be little affected by the frequency of simultaneous ultrasonic irradiation in the range 20–800 kHz, and is not influenced by choice of ultrasonic bath or probe as sonic source, provided measurements are made at constant ultrasonic intensity All these aspects at low and high ultrasonic frequencies have been reviewed in 2003 by Compton et al [6] and recently by Pollet and Hihn [15] The authors concluded that the electrochemical processes in the presence of high-frequency ultrasound are governed by processes (microjetting and micromixing) considerably different from those that are important at lower frequencies (acoustic streaming) References (1) Gonz´alez-Garc´ıa, J., Esclapez, M.D., Bonete, P., Hern´andez, Y.V., Garret´on, L.G and S´aez, V 2010 Current topics on sonoelectrochemistry, Ultrasonics 50: 318–322 (2) Compton, R.G., Eklund, J.C., Page, S.D., Sanders, G.H.W and Booth, J 1994 Voltammetry in the presence of ultrasound Sonovoltammetry and surface effects Journal of Physical Chemistry, 98: 12410–12414 P1: TIX/XYZ JWST129-bapp P2: ABC JWST129-Pollet December 1, 2011 13:1 Printer: Yet to come Appendix: Sonochemical Effects on Electrode Kinetics 333 (3) Compton, R.G., Eklund, J.C and Page, S.D 1995 Sonovoltammetry – heterogeneous electron transfer processes with coupled ultrasonically induced chemical reaction – The sono-EC reaction Journal of Physical Chemistry, 99: 4211–4214 (4) Compton, R.G., Eklund, J.C and Marken, F 1997 Sonoelectrochemical processes: A review Electroanalysis, 9: 509–522 (5) Compton, R.G., Eklund, J.C., Marken, F., Rebitt, T.O., Akkermans R.P and Waller, D.N 1997 Dual activation: coupling ultrasound to electrochemistry – An overview Electrochimica Acta, 42: 2919–2927 (6) Compton, R.G., Hardcastle, J.L and del Campo, J 2003 Sonoelectrochemistry, Physical Aspects, in: Bard-Stratmann (Ed.), Encyclopedia of Electrochemistry, in: Pat Unwin (Ed.), Instrumentation and Electrochemical Chemistry, vol 3: pp 312–327 (7) Pollet, B.G., Hihn, J.Y., Doche, M.L., Lorimer, J.P., Mandroyan A and Mason, T.J 2007 Transport limited current close to an ultrasonic horn: equivalent flow velocity determination Journal of Electrochemical Society, 154: E131–R138 (8) Pollet, B.G., Lorimer, J.P., Phull, S.S., Mason, T.J and Hihn, J.Y 2003 A novel angular geometry for the sonochemical silver recovery process at cylinder electrodes Ultrasonic Sonochemistry, 10: 217–222 (9) Lorimer, J.P., Pollet, B., Phull, S.S., Mason, T.J and Walton, D.J 1998 Disc and cylindrical electrode with ultrasound Electrochimica Acta, 43: 449–455 (10) Lorimer, J.P., Pollet, B., Phull, S.S., Mason, T.J., Walton, D.J and Geissler, U 1996 The effect of ultrasonic frequency and intensity upon limiting currents at rotating disc and stationary electrodes Electrochimica Acta, 41: 2737–2741 (11) Moriguchi, N 1934, The influence of supersonic waves on chemical phenomena III – the influence on the concentration polarisation Journal of Chemical Society Japan, 55: 349 (12) Pollet, B.G., Hihn, J.Y., Lorimer, J.P., Phull, S.S., Mason, T.J and Walton, D.J 2002 The effect of ultrasound upon the oxidation of thiosulphate on stainless steel and platinum electrodes Ultrasonic Sonochemistry, 9: 267–274 (13) Hyde, M.E., Compton, R.G 2002 How ultrasound influences the electrodeposition of metals Journal of Electroanalytical Chemistry, 531: 19–24 (14) Pollet, B.G 1998 The effect of ultrasound upon electrochemical processes, PhD Thesis Coventry University (15) Pollet, B.G and Hihn, J.-Y 2012 Sonoelectrochemistry: from Theory to Applications, in: Chen, D., Sharma, S.K and Mudhoo, A (Eds), Handbook on Applications of Ultrasound: Sonochemistry for Sustainability, CRC Press, USA P1: TIX/XYZ JWST129-bind P2: ABC JWST129-Pollet December 2, 2011 13:50 Printer: Yet to come Index Acid Black decolorization, 103 acoustic focal area, 277 acoustic streaming, 29, 48, 81–2 acoustoelectrochemical cell, 53 activation overpotential, 10 activity, adsorptive stripping, 80 alkaline fuel cells (AFCs), 302 alloy nanoparticles, 295–6 aluminium nanoparticles, 289–90 sonoelectrochemical etching, 239–40 5-aminosalicylic acid sonoelectroanalysis, 85 amperometry, 17–20 chronocoulometry, 17 electrolysis, 17–19 anodic stripping voltammetry (ASV), 81 Apfel and Holland model, 46–8 aromatic derivatives, sonoelectrochemical degradation, 108–14 arsenic sonoelectroanalysis, 84 ascorbic acid sonoelectroanalysis, 84 Bayer–Villiger reaction, 160 benzaldehyde reduction, 146–8 benzoic acid reduction, 147 Besanc¸on cell, 189 biogeochemistry, 88–9 biphasic analysis, 92–3 bismuth-modified electrodes, 91 Blake pressure, 46 Blake threshold, 47 border effect, 230 boron-doped diamond (BDD) electrode, 103, 109–11 Brilliant Red X-3B decolorization, 103 bubble motion, 48 bubble skin effects, 50 Butlet–Volmer equation, 6, cadmium nanoparticles, 290 sonoelectroanalysis, 84, 85 catalyst-coated membrane (CCM), 319 cathodic current, cathodic efficiency, 176 cavitation, 25, 227 bubble implosion sequence, 31 microjets, 30, 37 turbulent flow, 29–30 cavitation bubble dynamics, 45, 73 bubble behaviour, 46–8 electrochemistry next to tethered permanent gas bubble, 51–5 erosion events from inertial cavitation, 67–73 mass transfer effects, 48 mass transfer from forced permanent gas bubble oscillation, 55–62 mass transfer from single inertial cavitation bubbles, 62–5 Power Ultrasound in Electrochemistry: From Versatile Laboratory Tool to Engineering Solution, First Edition Edited by Bruno G Pollet © 2012 John Wiley & Sons, Ltd Published 2012 by John Wiley & Sons, Ltd P1: TIX/XYZ JWST129-bind P2: ABC JWST129-Pollet 336 December 2, 2011 13:50 Printer: Yet to come Index cavitation bubble dynamics (Continued ) non-inertial cavitation under ultrasonic horn, 65–7 single mechanisms for mass transfer enhancement, 48–51 cavitation corrosion effect, 219 cavitation erosion effect, 219 cell construction, 34–6 cell potential, centrifugal electrolytic cell, 253–4 charge transfer resistance, chemical processing applications of macrosonics, 23 chlorinated pollutants, sonoelectrochemical degradation, 104–8 p-chlorophenyl acetate oxidation, 155–6 1,1-bis-(4-chlorophenyl)-2,2,2trichloroethane, 143 chronocoulometry, 17 cleaning applications of macrosonics, 23 cleaning using ultrasound, 26 clinical samples, trace metals, 90–1 coating of electrodes, 157–61 cobalt nanoparticles, 287 sonoelectrodeposition microscopic properties, 181, 182 colony-forming units (CFUs), 129 concentration overpotential, 9–10 convection, 14 copper deposition, 62 electroless deposition, 200 non-conductive substrates, 201–9 nanoparticles, 288 sonoelectroanalysis, 84, 85 sonoelectrodeposition macroscopic properties, 177 microscopic properties, 180 unconventional solvents, 187–95 wastewater removal, 122–3 wastewater removal EDTA complexes, 124–5 core shell particles, 290–2 corrosion classification, 224–6 ASTM classification, 227 control technology, 217 corrosion acceleration factors, 217 corrosion testing, 217 laboratory tests, 218 definition, 215 economical impact, 216 electrochemical study, 222–3 experimental study of corrosion-cavitation mechanisms and parameters, 229–31 setup, 228–9 forms, 223 influence of ultrasound on metal corrosion, 231–2 general corrosion, 232–40 passivity of metals, 240–2 mechanisms electrochemical principles, 220–1 nature of, 215–16 protection, 269–72 rate of corrosion, 221–2 sonication studies cavitation corrosion, 219 cavitation erosion test, 219 synergistic effect of corrosion and cavitation, 219–20 ultrasound accelerated corrosion testing, 242 atmospheric corrosion of zinc plated steel, 242–3 oilfield corrosion inhibitor evaluation, 243–7 stainless steel, 243 surgical implant materials in body fluids, 244 corrosion fatigue test, 218 counter electrode (C.E.), crevice corrosion, 224 cyanide wastewater treatment, 127–9 P1: TIX/XYZ JWST129-bind P2: ABC JWST129-Pollet December 2, 2011 13:50 Printer: Yet to come Index cyclic voltammetry (CV), 11–14 irreversible reactions, 13–14 quasi-reversible reactions, 12–13 reversible reactions, 12 cyclohexane carboxylate oxidation, 151–3 cyclopentadienyl titanium pentaselenide, 150 dealloying, 226 decomposition voltages, 10 deep eutectic solvents (DESs), 188 determination of overpotentials, 10–11 decomposition voltages, 10 discharge potentials, 10–11 diagnostic ultrasound, 21 di-azo dyes, 103 dibutydiglyme (DBDG), 288 dichloroacetic acid (DCAA), 106 2,4-dichlorophenol, 104 2,4-dichlorophenoxyacetic acid (2,4-D), 104, 116–19 didodecyldimethyl ammonium bromide (DDAB), 143 diffusion, 14 2,4-dihydroxybezoic acid (2,4-DHBA), 111 1,3-dinitrobenzene, 108 2,4-dinitrotoluene, 108 dip dry test (DDT), 243 direct methanol fuel cells (DMFCs), 302 direct transmission of energy, 22 discharge potentials, 10–11 doping, 272–6 Eisenberg equation, 15–17 electric double layer, 1, electro- and electroless deposition, 38, 39 copper coating on non-conductive substrates influence of acoustic power, 203–7 influence on coating properties, 207–9 sonoreactor, 202–3 surface preparation, 201 337 electroless process, 198 ultrasound effects, 198–200 electroanalysis, 38 electroanalytical techniques, 11 amperometry chronocoulometry, 17 electrolysis, 17–19 voltammetry, 11 cyclic voltammetry (CV), 11–14 hydrodynamic voltammetry, 14–17 electrochemical corrosion tests, 218 electrochemical impedance spectroscopy (EIS), 223 electrochemical noise (EN), 223 electrochemical spectrum, 11 electrochemical technology (ECT), 101 electrochemistry, 1, 27–8 electron-transfer kinetics, 2–10 principles, 1–2 electrode activation, 251–5 electrode potentials, electrodeposition process, 173 characterisation techniques, 175 important parameters, 173–5 electrolysis, 17–19 constant potential, 20 important parameters, 18–19 electron-transfer coefficient, electron-transfer kinetics, 2–10 electroorganic synthesis, 144 electrooxidations, 151–7 electroreductions, 144–49 organochalcogenides, 149–51 electropolymerisation, 249–51 ultrasound irradiation, 259–62 electrosynthesis, 40 emulsions, 27 environmental applications of sonoelectrochemistry, 101, 134 degradation of persistent organic pollutants (POPs), 102 aromatic and phenolic derivatives, 108–14 chlorinated pollutants, 104–8 nitro compounds, 108 P1: TIX/XYZ JWST129-bind P2: ABC JWST129-Pollet 338 December 2, 2011 13:50 Printer: Yet to come Index environmental applications of sonoelectrochemistry (Continued ) textile dyes, 102–3 wastewater with high organic content, 114–15 metal recovery and toxic inorganic compound treatment, 121–9 soil remediation, 130–4 water disinfection by hypochlorite generation, 129 environmental protection, 39, 88–9 equilibrium potential, erosion events from inertial cavitation, 67–73 Escherichia coli, 129, 267–9 ethylenediaminetetraacetic acid (EDTA), 124 copper complexes, 124–5, 180 3,4-ethylenedioxythiophene (EDOT), 252, 255, 256–7 exchange current, exchange current density, Eyring equation, Faradaic current, Faradaic resistance, Faraday constant, 18 Faraday wave, 46, 57 image, 58 Faraday’s law, 5, 221 Fenton reaction, 115–16 field applications of sonotrode, 93 film properties, effects of ultrasound, 262 doping, 272–6 mass-transfer effect, 262–4 morphology effect, 264–5 biological applications, 265–9 corrosion protection, 269–72 surface local control effects, 276–8 forced permanent gas bubble oscillation, 55–62 frosted bubble, 59 fuel cells electrodes, 318–19 industrial fabrication, 319–20 noble metal sonoelectrochemical production, 311–14 effect of aqueous solutions, 317–18 effect of surfactants and alcohols, 315–17 fuels cells, 301–3 Galton, 21 galvanic corrosion, 224 gas diffusion electrode (GDE), 319 gas diffusion layer (GDL), 319 general corrosion, 224 influence of ultrasound aluminium etching, 239–40 effect on electrochemical behaviour of steel, 235–6 effect on electrochemical behaviour of various alloys, 232–5 resistance of metals in water, 232 zinc, 236–9 gold nanoparticles, 258, 292–5, 309 sonochemical production, 312, 313 Helmholtz planes inner (IHP), 1, outer (OHP), 1, high intensity focused transducers (HIFUs), 182, 261 Hofer–Moest reaction, 151 human osteosarcoma cell line Saos-2 267, 268 hybrid sonoelectrochemical techniques ozonation, 120–1 sonoelectro-Fenton (SEF), 115–19 hydrodynamic voltammetry, 14–17 hydrodynamics, 161–2 hydrogen sonoelectrochemical production, 303–5 hydrogen cells, 301–3 hydrogen evolution reaction (HER), 304 hypochlorite generation for water disinfection, 129 immersion corrosion tests, 218 indirect transmission of energy, 22 P1: TIX/XYZ JWST129-bind P2: ABC JWST129-Pollet December 2, 2011 13:50 Printer: Yet to come Index inertial cavitation, 46 inner Helmholtz plane (IHP), 1, interfacial region, intergranular corrosion, 225 iridium sonoelectrodeposition macroscopic properties, 179 iron corrosion (rusting), 220–1 nanoparticles, 287 irreversible reactions, 13–14 Klebsiella pneumonia, 129 Kolb´e reaction, 141, 151 Koutecky–Levich equation, 17 Langevin, 21 Langmuir trough, 54–5 lead nanoparticles, 290 sonoelectroanalysis, 84, 85 microscopic properties, 181 Levich equation, 15 limiting current density, 33 linear polarization resistance (LPR), 222–3 Lissamine Green B decolorization, 103 low-temperature effects, 162–3 machining applications of macrosonics, 23 macrosonics, 22 industrial applications, 23 magnesium nanoparticles, 288–9 manganese sonoelectroanalysis, 85 mass transfer coefficient, 262 Maxilion Blue decolorization, 103 mean depth of penetration (MDP), 231 mean depth of penetration rate (MDPR), 231 mechanically assisted corrosion tests, 218 medical imaging, 22 mercury sonoelectrodeposition microscopic properties, 181 339 metal forming applications of macrosonics, 23 metal plating benefits of ultrasound, 172–3 need for, 169–70 process and technology, 170 sonooelectrodeposition, 173 characterisation techniques, 175 contact angles, 205 electroless deposition, 198–209 important parameters, 173–5 influence of acoustic energy distribution on coatings, 182–7 influence of ultrasound on copper electrodeposition, 187–95 macroscopic ultrasonic effects on electrodeposited coating properties, 175–9 microscopic ultrasonic effects on electrodeposited coating properties, 179–82 particle incorporation, 195–7 plating rates, 203–4, 206 sonoreactor, 183 metal quantification, 89–90 metal recovery with sonoelectrochemistry, 121–9 metal welding applications of macrosonics, 23 methyl halide reduction, 148–9 Methyl Orange decolorization, 103, 120–1 Methylene Blue decolorization, 103 microbial fuel cells (MFCs), 302 microjets, 30, 37, 48, 51 micromosaic electrode, 50 microstreaming, 48, 49 migration, 14 Minnaert equation, 46 molten carbonate fuel cells (MCFCs), 302 mono-azo dyes, 103 multibubble sonoluminescence (MBSL), 70, 71–2 nanomaterials, 39, 40, 283–6, 296 alloy nanoparticles, 295–6 experimental configurations, 286–7 P1: TIX/XYZ JWST129-bind P2: ABC JWST129-Pollet 340 December 2, 2011 13:50 Printer: Yet to come Index nanomaterials (Continued ) polymer nanoparticles, 296 pure metals aluminium, 289–90 cobalt, iron and nickel, 287 copper, 288 core shell nanoparticles, 290–2 gold, 292–5 lead and cadmium, 290 magnesium, 288–9 silver, 287–8 tungsten, 295 nanopowder production, 37 Nernst equation, 3, 6–7 diffusion layer model, 33, 82 nickel electroless deposition, 199 nanoparticles, 287 sonoelectrodeposition macroscopic properties, 178 microscopic properties, 180–1 nitrate sonoelectroanalysis, 85 nitrite sonoelectroanalysis, 84, 87–8 nitro compounds, sonoelectrochemical degradation, 108 N-nitroso compounds, 87 noble metals, 305 fuel cell electrocatalysis, 311–14 effect of aqueous solutions, 317–18 effect of surfactants and alcohols, 315–17 sonochemical bi-metallic synthesis, 309 effect of surfactants and alcohols, 309–11 sonochemical mono-metallic synthesis, 306 effect of alcohols, 307–8 effect of atmospheric gases, 308 effect of sonification time, 308–9 effect of surfactants, 306–7 effect of ultrasonic frequency, 309 sonochemical perovskite oxides synthesis, 311 non-inertial cavitation, 46 ohmic overpotential, 10 ohmic resistance, Ohm’s law, oilfield corrosion inhibitor evaluation, 243–7 open circuit potential (OCP), 190 organic synthesis see electroorganic synthesis; sonoelectrosynthesis organochalcogenides, 149–51 organoselenium derivatives, 149 organotellurium derivatives, 149 Ostwald ripening, 317 outer Helmholtz plane (OHP), 1, overpotential, 7, 8–9 activation, 10 concentration, 9–10 determination, 10–11 decomposition voltages, 10 discharge potentials, 10–11 ohmic, 10 overpotential deposition (OPD), 190 oxidation reactions, 151–7 ozonation, 120–1 palladium nanoparticles, 306 sonochemical production, 312, 313 particle image velocimetry (PIV), 182 particle incorporation into metal coatings, 195–7 passivity of metals, 240–2 perchloroethylene (PCE), 104 persistent organic pollutants (POPs) soil remediation, 130–4 wastewater treatment, 102 degradation by sonoelectrochemistry aromatic and phenolic derivatives, 108–14 chlorinated pollutants, 104–8 nitro compounds, 108 textile dyes, 102–3 wastewater with high organic content, 114–15 pesticide analysis, 87 phenol, 108 sonoelectrochemical degradation, 110 P1: TIX/XYZ JWST129-bind P2: ABC JWST129-Pollet December 2, 2011 13:50 Printer: Yet to come Index phenolic derivatives, sonoelectrochemical degradation, 108–14 phenyacetate oxidation, 154–5 phenyl-2,3-dihydro-1,4-diazepinium reduction, 158–9 phenylhydroxylamine, 108 phosphoric acid fuel cells (PAFCs), 302 piezoelectric effect, 21 pitting corrosion, 225 plastic welding applications of macrosonics, 23 platinum nanoparticles, 258, 306, 307–9 sonochemical production, 312, 313 Pollet equation, 328 polyaniline (PANI), 250, 253 poly(N-chloroethanediyl) (PVC), 288 polychlorinated biphenyls (PCBs), 130 polycyclic aromatic hydrocarbons (PAHs), 130 poly(3,4-ethylenedioxythiophene) (PEDOT), 252–3, 257, 275–6 poly(N-vinylpyrrolidone) (PVP), 288 polymer nanoparticles, 296 polymerisation, 257–9 polypyrrole (PPy), 250–1, 253 films, 255, 266 doping–undoping properties, 260, 272–6 gold nanoparticle coating, 258 polytetrafuoroethylene (PTFE) particle incorporation into metal coatings, 195–7 polythiophene (PT), 250, 253 potential of zero charge (PZC), 86 potentiodynamic polarization, 222 potentiostatic electrode potential measurements, power ultrasound, 21 applications using cavitation, 25–7 heterogeneous liquid/liquid reactions, 27 heterogeneous reactions at solid/liquid interface, 26–7 homogeneous reactions, 26 341 applications using direct transmission, 23 welding, 23–4 effect under mass transport conditions, 32–4 Procion Blue decolorization, 103 proton exchange membrane fuel cells (PEMFCs), 302 9H-pyrido(3,4-b)indole-3-3-carboxylic acid methyl ester (BCCM), 260 pyrone reaction, 160–1 quartz crystal microbalance (QCM), 291 quasi-reversible reactions, 12–13 Reactive Black decolorization, 103 Reactive Blue 19 decolorization, 103 Reactive Brilliant X-3B decolorization, 103 redox processes, reduction reactions, 144–49 reference electrode (R.E.), reversible potential, reversible reactions, 12 Reynolds number, 18–19, 174–5 Rhodamine B decolorization, 103 rhodium sonochemical production, 312 room temperature ionic liquids (RTILs), 187–8, 290 copper reduction, 191–5 rotating disc electrode (RDE), 15–17, 105 silver recovery, 125–7 ruthenium sonochemical production, 313 salt spray corrosion test, 218 Sandolan Yellow decolorization, 102–3 satellite electrodes, 50 saturated calomel electrode (SCE), scanning electrochemical microscopy (SECM), 51, 52 Schmidt number, 19, 174–5 selective leaching, 226 Sherwood number, 174–5 shimmer on bubble surface, 59 P1: TIX/XYZ JWST129-bind P2: ABC JWST129-Pollet 342 December 2, 2011 13:50 Printer: Yet to come Index shock wave emission, 30–1 silver nanoparticles, 287–8 recovery from photographic fixative solutions, 124–7, 179, 181 sonochemical production, 312, 313 sonoelectrodeposition macroscopic properties, 179 microscopic properties, 181–2 wastewater removal, 125–7 single electron transfer (SET), 254–5 single inertial cavitation bubbles, 62–5 soil remediation, 130–4 solid oxide fuel cells (SOFCs), 302 sonochemical technology (SCT), 101 hybrid techniques, 115–21 sonochemistry, 21–3 sonocryelectrochemistry, 162–3 sonoelectroanalysis, 39, 79, 93–4 analytes, 84–5 biogeochemistry, 88–9 biphasic, 92–3 field applications, 93 metal quantification, 89–90 pesticide analysis, 87 trace metals in clinical samples, 90–1 sonoelectrochemical effects on electrode kinetics, 327–33 sonoelectrochemical technology (SECT), 101 sonoelectrochemistry, 27, 28–9, 320–1 applications, 38 electro- and electroless deposition, 38 electroanalysis, 38 electrosynthesis, 40 environmental protection, 39 nanomaterials, 40 environmental applications, 101, 134 degradation of persistent organic pollutants (POPs), 102–21 metal recovery and toxic inorganic compound treatment, 121–9 soil remediation, 130–4 water disinfection by hypochlorite generation, 129 experimental methods, 34–40 cell construction, 34–6 electrode stability, 36–8 fuel cell electrodes, 318–19 industrial applications, 319–20 hydrogen production, 303–5 noble metals, 305 bi-metallic synthesis, 309–11 mono-metallic synthesis, 306–9 perovskite oxides synthesis, 311 noble metals and fuel cell electrocatalysis, 311–14 effect of aqueous solutions, 317–18 effect of surfactants and alcohols, 315–17 ultrasonic factors, 29 acoustic streaming, 29 chemical effects, 31–2 microjets, 30, 37 shock wave emission, 30–1 turbulent flow, 29–30 ultrasound and sonochemistry, 21–3 sonoelectrodeposition electrodeposition process, 173 characterisation techniques, 175 important parameters, 173–5 electroless deposition copper coating on non-conductive substrates, 201–9 process, 198 ultrasound effects, 198–200 influence of acoustic energy distribution on coatings, 182–7 influence of ultrasound on copper electrodeposition, 187–9 aqueous solutions, 189–91 RTILs, 191–5 macroscopic ultrasonic effects on electrodeposited coating properties, 175–9 metal plating benefits of ultrasound, 172–3 need for, 169–70 process and technology, 170 sonoreactor, 183 P1: TIX/XYZ JWST129-bind P2: ABC JWST129-Pollet December 2, 2011 13:50 Printer: Yet to come Index microscopic ultrasonic effects on electrodeposited coating properties, 179–82 particle incorporation, 195–7 ultrasound surface treatment cleaning prior to further treatments, 170–2 sonoelectro-Fenton (SEF) reactions, 116–19 sonoelectroorganic synthesis, 39 sonoelectropolymerisation electrode activation, 251–5 electropolymerisation, 249–51 monomer solubilsation with ultrasound, 256–7 sonoelectrosynthesis, 141–2, 163 early history, 143–4 electrode coatings, 157–61 other systems hydrodynamics, 161–2 low-temperature effects, 162–3 scale-up considerations, 142 sonotrode, 90, 93, 94 sonovoltammograms, 104 stable cavitation, 46 standard hydrogen electrode (SHE), steel general corrosion, 235–6 passivity, 240–1 stainless steel, 243 Stern–Geary equation, 222 stress corrosion cracking (SCC) tests, 218, 226 stripping voltammetry, 79–81 surface treatment methods, 171 surgical implant material accelerated corrosion testing, 244 Tafel equations, 8–9 tandem acoustic emulsification processing, 257 tethered permanent gas bubble, 51–5 tetrahydrofuran (THF), 288 tetraphenylcyclopentadienone (tetracyclone), 160–1 343 textile dyes, sonoelectrochemical degradation, 102–3 toxic inorganic compound treatment with sonoelectrochemistry, 121–9 trace metals in clinical samples, 90–1 transient cavitation, 46 trichloroacetic acid (TCAA), 104–6 Trupocor Red decolorization, 103 tungsten nanoparticles, 295 turbulent flow, 29–30 ultrasonic horn non-inertial cavitation, 65–7 ultrasound, 21–3 effect on soil pores, 133 ultrasound accelerated corrosion testing, 242 atmospheric corrosion of zinc plated steel, 242–3 oilfield corrosion inhibitor evaluation, 243–7 stainless steel, 243 surgical implant materials in body fluids, 244 ultrasound surface treatment cleaning prior to further treatments, 170–2 under potential deposition (UPD), 190 uniform corrosion, 224 vanadium sonoelectroanalysis, 84 N-vinylcarbazole polymerization, 157–8 voltammetry, 11 cyclic voltammetry (CV), 11–14 wastewater treatment high organic content, 114–15 metal recovery and toxic inorganic compound treatment, 121–9 water disinfection by hypochlorite generation, 129 P1: TIX/XYZ JWST129-bind P2: ABC JWST129-Pollet 344 December 2, 2011 13:50 Printer: Yet to come Index welding using ultrasound, 23–4 machining, 24 metal forming, 24 working electrode (W.E.), World Health Organization (WHO), 89 xanthate electrooxidation, 143 zinc general corrosion, 236–9 sonoelectroanalysis, 84 sonoelectrodeposition microscopic properties, 181 wastewater removal, 123–4 zinc plated steel, atmospheric corrosion, 242–3 ... 19:12 Printer: Yet to come Power Ultrasound in Electrochemistry From Versatile Laboratory Tool to Engineering Solution Edited by BRUNO G POLLET The University of Birmingham Edgbaston, United Kingdom... any damages arising herefrom Library of Congress Cataloging -in- Publication Data Power ultrasound in electrochemistry : from versatile laboratory tool to engineering solution sonoelectrochemistry... where the double layer act as a capacitor C and the ionic medium as a Power Ultrasound in Electrochemistry: From Versatile Laboratory Tool to Engineering Solution, First Edition Edited by Bruno