Contemporary Electroanalytical Chemistry

430 Pages·1990·12.979 MB·English

by  Ari Ivaska (auth.), Ari Ivaska, Andrzej Lewenstam, Rolf Sara (eds.)

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.