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430 Pages·1990·12.979 MB·English
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Contemporary Electroanalytical Chemistry Contemporary Electroanalytical Chemistry Edited by Ari I vaska, Andrzej Lewenstam, Rolf Sara and Abo Akademi University Turku-Abo, Finland Springer Science+Business Media, LLC L1brary of Congress Cataloging-in-Pub11cat1on Data ElectroFinnAnalysis International Conference an Electroanalytical Chemlstry (1988 Turku. Finlandl Contemporary electroanalytical chemistry I edited by Ari Ivaska. Andrzej Lewenstam. and Rolf Sara. p. cm. Proceedings of the ElectroFlnnAnalysis International Conference an Electraanalytical Chemlstry. held June 6-9. 1988. i~ Turku-Abo. Finland. Includes bibliographlcal references and 1ndex. 1. Electrochemlcal analysis--Congresses. I. Ivaska. Ari. 11. Lewenstam. Andrzej. III. Sara. Rolf. IV. T1tle. QD115.E527 1988 543' .0871--dc20 90-27542 CIP ElectroFinnAnalysis An International Conference on Electroanalytical Chemistry ISBN 978-1-4899-3706-3 ISBN 978-1-4899-3704-9 (eBook) DOI 10.1007/978-1-4899-3704-9 Proceedings of the ElectroFinnAnalysis International Conference on Electroanalytical Chemistry, held June 6-9, 1988, in Turku-Ăbo, Finland Ci'! 1990 Springer Science+Business Media New York Originally published by Plenum Press, New York in 1990. Softcover reprint of the hardcover 1s t edition 1990 AII rights reserved No part of this bOOK may be reproduced, stored in a retrieval system. or transmitted in.any farm or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher PREFACE This volume is ba.sed on the presentations gi ven at the ElectroFinnAnalysis conference held on J une 6-9, 1988 in Turku-Äbo, Finland. This event was the second in a series of electroanalytical conferences. The first was held in Ireland 1986 and the next will be held in Spain 1990. The aim of these conferences is tobring tagether scientists who use electroanalytical methods in their research. This is also reflected in the disposition of this volume where instrumentation and applications from the different fields have their own chapters. The editors are grateful to Mr. Johan Nyman, Mr. Kent Westerbolm and Mr. Markku Lehto for their technical assistance during the editorial work of this volume. Ari Ivaska Andrzej Lewenstam Ralf Sara V CONTENTS lntroduction Ari Ivaska ELECTROCHEMICAL INSTRUMENTATION AND METHODS New Instrumental Approaches to Fast Electro-Chemistry at Ultramicroelectrodes .......... . 5 Larry R. Faulkner, Michael R. Walshand Chuanjing Xu Photoelectroanalytical Chemistry - Methods and Instrumentation . . . 15 J ouko J. Kaukare Experiences of an On-Line Fourier Transform Faradaic Admittance Measurement (FT-FAM) SystemBasedon Digital Signal Processors ............................... . 21 Sten 0. Engblom, Mikael Wasberg, Johan Bobacka and Ari Iva.ska Processor-Controlled Fast Potentiostat . '... 31 J. Kaukare and J. Lukka.ri Smoothing of AC Polaragraphie Data by FFT Filtering . ' .... 37 J oha.n Bobacka. a.nd Ari Jvaska Reverse Pulse Voltammetry at Microelectrodes. New Possibilities in Analytical Chemistry ............ . .. ... 47 Zbigniew Stojek Multiple Sensor Arrays: Advantages and lmplications 51 Dermot Diamond Simultaneaus ESR-Electrochemical Investigations at Solid Electrodcs .. 59 Lothar Dunsch INDUSTRIAL APPLICATIONS Iudustrial Applications and Perspectives of Electro-Analytical Methods ......................... . . .... '........ 71 E. Pungor, Zs. !\iegreisz a.nd L. Polos Examples of Electrometric Methods Applied to Process and Product Control in the Explosives lndustry .. ' .. ' ''. '' ...... ' ... ' .... 85 Jan Asplund Applied Polarography and Voltammetry in Day-to-Day Enviromnental Analysis, Possibilities and Limitations 109 Pierre M. Bersier a.nd J a.cques Bersier vii The Use of Eleetro-Analytieal Teehniques in Bioteehnology .............................. 139 Bauke te Nijenhuis Potentiometrie Determination of Copper in Various Plating Baths ...................... 145 Adam Hulanicki, Tomasz Sokalski and Andrzej Lewenstam Controlled-Growth Mereury Drop Electrode and Perspeetives in Proeess Monitoring Applieation .................... . . .... 149 Zygmunt Kowalski and Jan Migdalski ELECTROCHEMICAL SENSORS Solid State Potentiometrie Sensors .................. 159 Jifi Janata Biosensing Based on Gas Sensitive Semieonduetor Devices .... 173 l. Lundström and F. Winquist Chemically Modified Eleetrodes for the Electroeatalytic Oxidation of N ADH ............ . . ................. 183 L. Gorton, B. Persson, M. Polasek and G. Johansson Solid Polymer Electrolytes for Gas Sensing Electrodes 191 Lionel S. Goldring Carbon Fiber Microelectrodes .................. . . ... 199 Karin Potje-Kamloth, Petr Janata and Mira Josowicz Voltammetrie Determination of Organic Compounds Using Clay Modified Carbon Paste Electrodes ........................... . . .. 205 Lucas Hernandez, Pedro Hemandez and Encarna Lorenzo The RoJe of Surface Processes in Signal Formation with Solid-State Ion-Selective Electrodes - Chloride Interference on Copper Ion-Selective Electrode . . . . . . . . . . . . . . . . . ............................. 213 A. Lewenstam, A. Hulanicki and E. Ghali FTIR-ATR and Ion Chromatographie Investigations of the Ion Transport through Ion-Selective PVC-Membranes ..... . . ... 223 R. Kellner, E. Zippel, E. Pungor, K. Tothand E. Lindner On the Electrochemical Approach to Solid-State Ion Selective Membrane Preparation ........................... . . ................. 231 M. Neshkova Sensor Technique for Monitoring Changes in pH, Ca2+, po,, Pco, and Electrical Conductivity in Milk During Fermentation. . ...................... 237 Pekka 0. Lehtonen, Hanna Laitinen, Tuomo Thpasela and Matti Antila ELECTROCHEMICAL FLOW ANALYSIS Exploitation of Electrochemical Techniques by Flow Iujection Analysis . . . . . . . . . . . . . . . . ........ . ............ 245 Elo Harald Hansen Potentiometrie Detection in High-Performance Ion-Chromatography ............... 255 Marek Trojanowicz Stahle Modified Electrodes for Use in Amperometric Detectors in Flow Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........ . . .......... 267 J ames A. Cox and Thomas J. Gray Flow Stream Detectors Based on the Electrocatalytic Oxidation of Polyhydroxy Compounds at Silver Oxide Electrodes ............. 275 Terrence P. Tougas, Edwin G.E. Jahngen and Michael Swartz viii Application of Modified Electrodes for Analysis in Flowing Solutions ......... 283 Gordon G. Wallace, Mary Meaney and Maleolm R. Smyth Studies of the Modulated Flow Technique for Flow Potentiometrie Stripping Analysis ........................... . . ............. 289 Gerhard Schulze, Raymond Sänger and Edzard Han Electroluminescence Detector for Flow Analysis ....... 293 K. Haapakka, J. Kankare and K. Lipiäinen Determination of Polyamines (Spermine, Spermidine, Putrescine) in Biological Sampies ........................ . . . 299 R. Rips and C. Guette CLINICAL APPLICATIONS Opportunities and Limitations in the Use of ISEs in Clinical Chemistry: Assays Without Calibration? .................. . . .. 305 Gudrun G. Rumpf, Lucas F.J. Dürselen, Hans W. Bühler and Wilhelm Sirnon Proposed IFCC Recommendations for Electrolyte Measurements with ISEs in Clinical Chemistry ........ . . .. 311 Anton H .J. Maas and Ron Sprokholt Influcncc of Somc Drugs on ISE Measurements of Serum Electrolytes 317 Ryszard Lewandowski, Tomasz Sokalski and Adam Hulanicki Buffer System for the Simultaneaus Standardization of pH and Electrolytes by ISE Determination in Whole Blood 323 Angelo Manzoni and Mario Belluati An Analytical Approach to the Determination of Some Mixtures of Selected Pteridines by Adsorptive Stripping Voltammetry 329 P. Thii6n Blanco, J .M. Fernandez Alvarcz and A. Costa Garcia Electrochemical Behaviour of Metronidazole ..... 339 P. Siva Sankar and S.J. Reddy PHARMACEUTICAL APPLICATIONS The Determination of Selected Antibiotics, Antibaderials and Anticonvulsants by Voltammetrie and Liquid Chromatographie Techniques 349 W.F. Smyth Applications and Potentiality of Electroanalytical Methods for Inorganic Trace Analysis in the Pharmaceutical lndustry Juerg B. Reust Direct Electrochemical lmmunoassays lnvolving Adsorbed or Immobilised Species ..... 367 Maleolm R. Smyth, Eileen Buckley, Juana Rodriguez Flores, Richard John and Gordon G. Wallace Electrochemical Behaviour at Solid Electrodes and Metabolie Fate of Drugs ................ . 373 J-M. Kauffmann, J-C. Vire, 0. Chastel and G.J. Patriarche Adsorptive Stripping Square-Wave Voltammetry of Pharmaceutical Quinonic Derivatives . . . . ........ . 379 J-C. Vire, G.J. Patriarche, H. Zhang, B. Gallo and R. Alonso The Determination of Timolol in Biological Fluids by Adsorptive Stripping Voltammetry . . . ................ . 387 R.J. Barrio Diez-Caballero and J .F. Arranz Valentin ix Pulse Voltammetrie Determination of Sulphur Containing Organie Compounds ... . ..................... . 395 Zenon J. Karpinski GENERAL Adsorptive Stripping Voltammetry in Traee Analysis ........ 403 Robert Kalvoda Adsorption Effects Used in Electroanalysis .................. 407 Hendrik Emons and Gerhard Werner Mieroanalytieal Applieation of a Kissinger Type Thin Layer Cell Polarized by LSV, NPV and DPV Excitation ........ 413 G. Farsang and T. Dankbazi Differential Pulse Polaragraphie Determination of Teo~- and V03 in Presenee of some Oxyhalide Anions ..... . . ........ ·········· 419 M.M. Kamal, Z.A. Ahmed and Y.M. Temerk Differential Pulse Polaragraphie Determination of some Substituted Benzylidene Acethydrazones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. ...................... 423 M.M. Kamal, Y.M. Temerk, Z.A. Ahmed and G. Abd-El-Wahab Simultaneaus Determination of Copper, Cadmium, Lead and Zine in Indian Snuff Sampies by Differential Pulse Anodie Stripping Voltammetry (DPASV) ...... 431 M.S. Nayak and S.S. Dhaktode Electroehemieal Behaviour of EPN ...... 437 T.N. Reddy and S. J ayarama Reddy Eleetroanalysis of the Acrylic Monomer/Polymer System ....... 443 Lothar Dunsch Contributors ........ . .453 Index ............................... . . 455 X INTRODUCTION Ari lvaska Labaratory of Analytica/ Chemistry Abo Akademi University SF-20500 Turku-Abo, Finland Elcctroanalysis is perhaps the branch of electrochemistry with the greatest number of practical applications of all the different areas of electrochemistry. One of the main advantages of electroanalytical methods is that they allow both qu antitative and qualitative determinations. Thc electrical signal of an electrochemical system can easily be used in electronic instrumentation and computer processing. Improvements in instrumentation are of central importance in developing new instrumental analytical met hods. Instruments are like vehicles which scientists use to take them over difficult terrain into new areas. Electroanalytical chemistry is rather instrument oriented and good instrumen tation is of great importance in obtaining high quality data. The strong impact of research on instrumentation can clearly be seen in the instrumentation section of these Proceedings. Automation and instrumentation always go together. The development of flow methods with electrochemical detection is a good example of how combination of the two approaches can give good results. Progress and current activity in the field of chemically modified electrodes is rapid and remarkable. By coating an inert electrode with redox polymers and polymers with suitable mediators the electrochemical signal can be transferred through insulating layers. The use of conductive polymers to modify electrodes is also increasing. Specific compounds can also be incorporated into a polymeric matrix to increase the selectivity and specificity of a given method. Examples of this are the use of enzymes and antigen-antibody systems for specific determination of single compounds. Combining biochemical systems with electroanalytical techniques is certainly a field where a Iot of progress will be made in the future. Another way of increasing specificity is to use a chromatographic method toseparate electrochemically similar compounds and then measure them by a less specific method which is selective for this family of compounds. In this case the specificity is obtained by chromatographic separation. Electrode reactions are heterogeneaus reactions taking plac2 at the surface of the electrode. Sensitivity in detection of some compounds has been increased by several or ders of magnitude by taking advantage of the adsorption phenomena at the electrode surface. In adsorptive stripping methods accumulation of compounds can be improved by proper selection of the electrode potential. The importance of electroanalytical methods in industrial applications is clearly evident from the papers in that section of the Proceedings. There are cases where a whole chemical plant prodncing explosive materials is mainly controlled by electroanalytical methods. Clinical and pharmaceutical applications of electroanalytical methods arealso numerous and they have been accorded an established status in these laboratories. One method is never enongh when analysing samples with complicated matrices and a combination of electroanalytical techniques with other techniques like spectroscopy and chromatography offers new possibilities in analytical work. These combined methods form another line of development in electroanalysis and progress on these lines will certainly be seen in the future.

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