Table Of ContentIon-Selective
Electrode
Methodology
Volume I
Editor
Arthur K. Covington
Reader in Physical Chemistry
University of Newcastle
Newcastle upon Tyne
England
Boca Raton London New York
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Ion-selective electrode methodology.
Includes index.
1. Electrodes, Ion selective. I. Covington, Arthur
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ISBN 0-8493-5247-9 (v.1)
ISBN 0-8493-5248-7 (v.2)
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PREFACE
The idea for a volume of ion-selective electrodes, hailed as an important advance in
analytical chemistry, in CRC's UNISCIENCE Series arose out of the great interest
shown in my article for CRC's Critical Reviews in Analytical Chemistry published in
1974 (Crit. Rev. Anal. Chem., 1973, 3 (4), 355-406). In inviting experts to join me in
the project, I was very much concerned to have those who were actively engaged in
working with ion-selective electrodes and who could write on practical matters from
firsthand experience. Their enthusiasm is apparent from the result which grew to two
volumes.
The intention was to produce a book which perforce would never be far from the
laboratory, although CRC's use of Handbook in another connection precludes our use
of that word in the title.
I have, intentionally, wielded a strong editorial hand bringing, I hope, terminology
and symbols to a common basis. I thank the contributors for their forebearance and
their ready compliance with my suggestions. We trust you, the reader, will find these
two volumes valuable in this second decade of ion-selective electrode potentiometry.
A.K.C.
Newcastle upon Tyne, England
January 1979
THE EDITOR
Arthur Kenneth Covington, B.Sc., Ph.D. , D.Sc. (Reading) C.Chem. FRIC, is
Reader in Physical Chemistry in the University of Newcastle upon Tyne, U.K. and is
well known for his work on glass, ion-selective and reference electrode systems, as well
as for his studies of electrolyte solutions by thermodynamic and spectroscopic meth-
ods. Dr. Covington represents The Chemical Society (London) on the British Stand-
ards Institution Committees on the pH Scale, pH meters and Glass Electrodes, is Prin-
cipal U.K. Expert on, and Leader of, the International Standards Organization
Working Group on "pH and Potentiometry", and Titular Member of IUPAC Com-
mission V5 on Electroanalytical Chemistry. He co-edited Physical Chemistry of Or-
ganic Solvent Systems, Plenum, London, 1973 and Hydrogen-Bonded Solvent Sys-
tems, Taylor and Francis, London, 1968.
CONTRIBUTORS
D. M. Band, Ph.D. E. Pungor, Ph.D., C. Sc.
Senior Lecturer Professor, Head,
Sherington School of Physiology Institute for General and Analytical
St. Thomas Hospital Medical School Chemistry
London, England Technical University
Budapest, Hungary
Richard P. Buck, Ph.D.
Professor of Chemistry
Malcom Riley, Ph.D.
University of North Carolina
Chief Chemist
Chapel Hill, North Carolina
Electronic Instruments, Ltd.
Chertsey, Surrey, England
Peter Burton
Formerly Electronics Engineer
Electronic Instruments, Ltd. R. J. Simpson
Chertsey, Surrey, England Senior Research Officer
SIRA Institute
Arthur K. Covington, D. Sc. Chislehurst, Kent, England
Reader in Physical Chemistry
University of Newcastle J. D. R. Thomas, D. Sc.
Newcastle upon Tyne, England University Reader in Chemistry
University of Wales Instutute of
Robert W. Cattrall, Ph.D. Science and Technology
Senior Lecturer in Inorganic and Cardiff, Wales
Analytical Chemistry
La Trobe University KlaraToth, Ph.D., C. Sc.
Bundoora, Victoria, Australia Associate Professor
Institute for General and Analytical
Phillip Davison, Ph.D. Chemistry
Assistant Analytical Superintendent Technical University
BP Chemicals, Ltd. Budapest, Hungary
Salt End, Hull, England
T. Treasure, M.S., F.R.C.S.
G. J. Moody, Ph.D. Senior Registrar in
Senior Lecturer in Chemistry Cardiac Thoracic Surgery
University of Wales Institute of Brompton Hospital
Science and Technology London, England
Cardiff, Wales
Pankaj Vadgama, M.B., B.S., B.Sc.,
Geza Nagy, Ph.D., C. Sc. M.R.C. Path.
Senior Research Fellow Medical Research Council Training
Institute for General and Analytical Fellow
Chemistry Department of Clinical Biochemistry
Technical University Royal Victoria Infirmary
Budapest, Hungary Newcastle upon Tyne, England
TABLE OF CONTENTS
Volume I
Chapter 1
Introduction: Basic Electrode Types, Classification, and Selectivity Considerations . . 1
A. K. Covington
Chapter 2
Instrumentation for Ion-Selective Electrodes 21
P. R. Burton
Chapter 3
Practical Techniques for Ion-Selective Electrodes 43
R. J. Simpson
Chapter 4
pX Standards 67
A. K. Covington
Chapter 5
Glass Electrodes 77
A. K. Covington
Chapter 6
Liquid Ion Exchange Types 85
A. K. Covington and P. Davison
Chapter 7
Poly vinyl Chloride Matrix Membrane Ion-Selective Electrodes Ill
G. J. Moody and J. D. R. Thomas
Chapter 8
Heterogeneous Membrane, Carbon Support, and Coated Wire Ion-Selective Elec-
trodes 131
Robert W. Cattrall
Chapter 9
Crystalline and Pressed Powder Solid Membrane Electrodes 175
Richard P. Buck
Index 251
Volume II
Chapter 1
Gas-Sensing Probes 1
M. Riley
Chapter 2
Enzyme Electrodes 23
P. Vadgama
Chapter 3
Ion-Selective Electrodes in Medicine and Medical Research 41
D. M. Band and T. Treasure
Chapter 4
Analytical Methods Involving Ion-Selective Electrodes (Including Flow Methods). . .65
E. Pungor, G. Nagy, and K. Toth
Index 123
Chapter 1
INTRODUCTION: BASIC ELECTRODE TYPES, CLASSIFICATION,
AND SELECTIVITY CONSIDERATIONS
A. K. Covington
TABLE OF CONTENTS
I. Introduction and Scope 1
II. Historical Development 3
III. Classification of Materials 8
A. Glass 9
B. Insoluble Inorganic Salts 9
C. Organic Ion Exchangers and Chelating Agents 10
IV. Electrode Forms and Construction 12
V. Theoretical Considerations 13
A. Derivation of the Nernst Relations 13
B. Selectivity and Interferences 15
References 19
I. INTRODUCTION AND SCOPE
The term "ion-selective electrodes" is applied to a range of membrane electrodes
which respond selectively towards one (or several) ion species in the presence of others.
The formerly used but less preferred term "ion-specific" is not favored1 because these
electrodes are rarely specific in their response to one ionic species over others, although
this is a desirable property sought by the designer of new electrodes. The description
"membrane" is used here in its broadest sense to denote a thin section of electrically
conducting material separating two solutions across which a potential develops. Often,
the term "membrane" has associated with it the notion of permeability to a species
present in the flanking solutions. However, although this is undoubtedly true with
certain porous biological and synthetic membranes, the actual mechanism of electrical
conduction in general varies with the type of membrane material; indeed, it may
change within it.
The hydrogen ion-responsive glass electrode, well known for its use in pH measure-
ments, falls within the definition given above. A number of reviews" and two books4 5
have dealt with its properties, use, suggested mechanism of functioning, and related
studies of glass itself, so it is not the author's intention to devote space to a discussion
of these. Glass electrodes responsive to alkali metal cations are a more recent devel-
opment, and are discussed in Chapter 5, Volume I. All types of glass electrode are,
however, considered as ion-selective electrodes.
Unlike some developments in science, no startling new principle heralded the arrival
