The Principles of Ion-Selective Electrodes and of Membrane Transport, Volume 2

Preface

1. Introduction and Preliminary Aspects

1.1. Organization and EMF Response of Membrane Electrode Cells

1.2. Membrane Materials and their Selectivity-Determining Principles

1.3. Single-Ion Activities

References

Part A - Theory of Membrane Potentials and Membrane Transport

2. Description of the Basic Membrane Model

References

3. The Phase-Boundary Potential (Donnan Potential)

References

4. The Diffusion Potential

4.1. General Formulation

4.2. Practical Solutions

References

5. Calculation of Liquid-Junction Potentials

References

6. Solutions for the Membrane Potential

References

7. Classical Concepts of Membrane Transport

7.1. The Nernst - Planck Flux Equation

7.2. The Goldman-Hodgkin-Katz Approximation

7.3. Simple Model for Symmetrical Membrane Cells

7.4. Schlögl's General Theory and its Applications

7.5. Electrical Properties and Ion-Transport Selectivity of Bulk Membranes

References

8. Free and Carrier-Mediated Ion Transport Across Bilayer Membranes

8.1. Description of the Ion Flux Across the Membrane Interior

8.2. Description of the Ion Flux Across the Interfaces

8.3. Consequences of a Closed-Circuit Flux of Carriers

8.4. Derivation of the General Result

8.5. Bilayer Model by Läuger and Stark

8.6. Bilayer Model by Ciani, Eisenmann, and Krasne

8.7. Comparison with the Bulk Membrane Model by Morf, Wuhrmann, and Simon

References

9. Summary of Fundamental Relationships

Part B - Ion- Selective Electrodes

10. Solid-State Membrane Electrodes

10.1. Characterization of Membrane Materials

10.2. Basic Theoretical Aspects of Solid-State Membrane Electrodes

10.3. Potential Response and Detection Limit of Silver Compound Membranes Unbuffed Solutions of the Primary Ions

10.4. Potential Response of Silver Halide Membranes to Different Cations

10.5. Selectivity of Silver Halide Membranes Towards Different Anions

10.6. Potential Reponse and Selectivity of Silver Halide Membranes Towards Different Ligands

References

11. Liquid-Membrane Electrodes Based on Liquid Ion-Exchangers

11.1. Membrane Materials and Observed Ion Selectivities

11.2. Implications of the General Membrane Theory

11.3. Theory of Sandblom, Eisenman, and Walker, and its Extensions

11.4. Interpretation of the Apparent Selectivity Behavior of Liquid Membranes

References

12. Liquid-Membrane Electrodes Based on Neutral Carriers

12.1. Characteristics of Neutral Carriers and Reported Selectivities for Membrane Electrodes

12.2. Mechanism of Cation Specificity (Permselectivity) of Neutral Carrier Membranes

12.3. Cation SelectiVity of Carrier Membrane Electrodes

12.4. Anion Effects in Carrier Membrane Electrodes

12.5. Molecular Aspects of Cation-Selective Carriers

References

13. Glass Electrodes

13.1. Introduction

13.2. Ion-Exchange Theories and n-Type Descriptions of Glass Membrane Potentials

13.3. Potential Responses of Na2 O-Al2 O3 SiO2 Glasses

13.4. Alternative Approaches to Heterogeneous-Site Glasses

13.5. Further Development of Glass Electrode Theory (Liquid-Membrane Concepts)

References

14. Dynamic Response Behavior of Ion-Selective Electrodes

14.1. Electrical Relaxation Processes

14.2. Kinetics of Interfacial Reactions

14.3. Diffusion Through a Stagnant Layer

14.4. Diffusion within the Ion-Sensing Membrane

References

15. Special Arrangements: Gas-Sensing Electrodes and Enzyme Electrodes

15.1. Gas-Sensing Electrodes

15.2. Enzyme Electrodes

References

Author Index

Subject Index

The Principles of Ion Selective Electrodes and of Membrane Transport is a collection of research works on the theory, principles, and fundamentals of ion-selective electrodes and of membrane transport. This book is organized into two parts encompassing 15 chapters that highlight the application of the membrane model.

Part A is a general discussion of membrane potentials and membrane transport. This part describes the formulations of the interfacial potential contribution due to phase boundaries. This part also explores the diffusion potential, the nonideality of diffusion layers or membrane phases, the liquid-junction potential arising in conventional potentiometric measuring cells. Other topics covered in this part include the practical solution for the membrane potential; the ion-transport and the electrical properties of bulk membranes; and the characteristics of lipid bilayer membranes. Part B considers the fundamentals of ion-selective electrodes. This part begins with discussions of the principles, response behavior, ion selectivity, and detection limits of solid-state membrane electrodes. This part also examines several important extensions and modifications of the Sandblom-Eisenman-Walker theory; the characteristics of neutral carrier membrane electrodes; and the theory of glass electrodes.