Ion-selective electrodes continue to be one of the more excIting developments in electro analytical chemistry in the last 10 years. This is evidenced in the large and continually growing literature in the field. It is important and necessary in such a rapidly growing area to be able to "take stock," i. e. , to present a well-rounded, up-to-date review of important developments. In this volume, reviews by many of the leading practitioners and pioneers in this field contribute to what we consider to be a generous coverage of both fundamental aspects of ion-selective electrodes and their applications to analytical chemistry. Although this volume is not intended to be exhaustive, we have attempted to produce a "stand alone" text dealing with all major current developments. Indeed, since some of the theoretical approaches are not yet universally agreed on, each of the first five chapters deals with theory and principles of the nature and behavior of ion-selective electrodes from the vantage point of the authors' own experience and understanding. In view of the rapid expansion of this field, plans for future volumes are now being formulated.
Henry Freiser Tucson, Arizona vii Contents Chapter 1 Theory and Principles of Membrane Electrodes R. P. Buck 1. Potential Generating Processes ...1 1. 1. Interfaces, Fixed Charges, Charged Sites, and Charge Carriers 1 1. 2. Ion Exchange as a Potential-Generating Process 5 1. 3. Diffusion and Migration ...8 1. 4. Electrochemical Potentials, Fluxes, and Mobility . . 10 1. 5.
Ion-selective electrodes continue to be one of the more excIting developments in electro analytical chemistry in the last 10 years. This is evidenced in the large and continually growing literature in the field. It is important and necessary in such a rapidly growing area to be able to "take stock," i. e. , to present a well-rounded, up-to-date review of important developments. In this volume, reviews by many of the leading practitioners and pioneers in this field contribute to what we consider to be a generous coverage of both fundamental aspects of ion-selective electrodes and their applications to analytical chemistry. Although this volume is not intended to be exhaustive, we have attempted to produce a "stand alone" text dealing with all major current developments. Indeed, since some of the theoretical approaches are not yet universally agreed on, each of the first five chapters deals with theory and principles of the nature and behavior of ion-selective electrodes from the vantage point of the authors' own experience and understanding. In view of the rapid expansion of this field, plans for future volumes are now being formulated.
Henry Freiser Tucson, Arizona vii Contents Chapter 1 Theory and Principles of Membrane Electrodes R. P. Buck 1. Potential Generating Processes ...1 1. 1. Interfaces, Fixed Charges, Charged Sites, and Charge Carriers 1 1. 2. Ion Exchange as a Potential-Generating Process 5 1. 3. Diffusion and Migration ...8 1. 4. Electrochemical Potentials, Fluxes, and Mobility . . 10 1. 5.
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Verlagsort
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Kluwer Academic Publishers Group
Zielgruppe
Für höhere Schule und Studium
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37 black & white illustrations, biography
ISBN-13
978-0-306-33907-3 (9780306339073)
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Schweitzer Klassifikation
1 Theory and Principles of Membrane Electrodes.- 1. Potential Generating Processes.- 1.1. Interfaces, Fixed Charges, Charged Sites, and Charge Carriers.- 1.2. Ion Exchange as a Potential-Generating Process.- 1.3. Diffusion and Migration.- 1.4. Electrochemical Potentials, Fluxes, and Mobility.- 1.5. Permeability, Permselectivity, and Co-Ion Exclusion.- 2. Potential-Generating Chemical Systems.- 2.1. Potential Profiles at Single Interfaces.- 2.2. Calculation of Net Interfacial Potentials.- 2.3. Connection between Salt Extraction, Solid Ion Exchangers, Crystals, and Semiconductor Electrodes.- 2.4. Potential Profiles in Bulk Phases and Total Membrane Potentials for Reversible Interface Systems.- 2.5. Potential Profiles and Differences at Blocked Interfaces.- 3. Electrode Materials, Membrane and Ion-Selective Electrode Classification.- 4. Electrode Organization.- 4.1. Electrodes of First, Second, and Third Kinds.- 4.2. Membrane Configurations Including All-Solid-State Versions.- 4.3. Blocked Electrodes, Coated Wires, and Immunoelectrodes.- 4.4. Corrosion Electrodes and Ion-Sensing Semiconductor Electrodes.- 5. Cell Organization.- 5.1. Membrane and Classical Cells.- 5.2. Junction and Junctionless Cells.- 5.3. Reference Electrodes.- 6. Potential-Activity Responses in the Steady State.- 6.1. Ideal Normal Form for Glass and Fixed-Site Ion-Exchanger Membrane Electrodes.- 6.2. Ideal Normal Form for Solid-State Membrane Electrodes (Including All-Solid-State Electrodes).- 6.3. Ideal Normal Form for Liquid Ion Exchanger Membranes (Mobile-Site Membranes).- 6.4. Ideal Normal Form for Neutral-Carrier Membrane Electrodes.- 6.5. Ideal Normal Form for Zeroth, First, Second, and Third Kinds of Electrodes.- 7. Nonideal Responses of Membrane Electrodes-Sources and Effects.- 7.1. Deviations from Ideality Associated with the Membrane.- 7.2. Deviations from Ideality Associated with Bathing Solutions.- 7.3. Deviations from Ideality Associated with Cell and Reference Electrodes.- 7.4. Deviations Expected in Electrode Calibration.- 7.5. Time Responses Affected by Electrode Properties.- 7.6. Time Responses Outside the Linear Regime.- 7.7. Potential-Time Responses after Activity Steps.- 7.8. Effects of Redox Reagents and Light.- 8. Selectivities and Selectivity Coefficients of Ion-Selective Membrane Electrodes.- Notation.- References.- 2 Precipitate-Based Ion-Selective Electrodes.- 1. Introduction.- 2. Theoretical Part.- 2.1. Interpretation of the Potential Response.- 2.2. Selectivity.- 2.3. The Standard Potential.- 2.4. The Potential-Activity Function.- 2.5. Response Time.- 2.6. Morphology of the Electrode Membrane.- 2.7. Nonaqueous Solvents.- 3. Electrode Materials.- 4. Practical Part.- 4.1. Measuring Techniques.- 4.2. Standardization of Ion-Selective Electrodes.- 4.3. Errors.- 5. Application of Ion-Selective Electrodes.- References.- 3 Ion-Selective Electrodes Based on Neutral Carriers.- 1. Introduction.- 2. Theoretical Description of the EMF Response.- 2.1. Universal Description of the EMF Response of Liquid-Membrane Electrodes.- 2.2. Response of Idealized Neutral-Carrier Membranes.- 2.3. Response Time of Neutral-Carrier Membrane Electrodes.- 3. Design Features of Ion-Selective Neutral Carriers and of the Corresponding Membrane Systems.- 4. Electrode Systems Based on Neutral Carriers.- 4.1. Electrode Structure.- 4.2. Electrodes for K+.- 4.3. Electrodes for NH4+.- 4.4. Electrodes for Na+.- 4.5. Electrodes for Li+.- 4.6. Electrodes for Ca2+.- 4.7. Electrodes for Sr2+.- 4.8. Electrodes for Ba2+.- 5. Future Prospects.- References.- 4 Poly(Vinyl Chloride) Matrix Membrane Ion-Selective Electrodes.- 1. Introduction.- 2. Design and Construction.- 3. Sensors and Mediators.- 4. Responses.- 5. Fundamental Aspects.- 6. Effect of pH on Electrode Behavior.- 7. Alternative Polymer Matrices to PVC.- 8. Conclusion.- References.- 5 Sources of Error in Ion-Selective Electrode Potentiometry.- 1. Introduction.- 2. Advantages.- 3. Sources of Error.- 3.1. pH/mV Meter.- 3.2. Ion-Selective Indicator Electrodes.- 3.3. Reference Electrodes.- 3.4. Electrode Drift.- 3.5. Standards.- 4. Conclusions.- References.- 6 Applications of Ion-Selective Electrodes.- 1. Introduction.- 2. Coordination Complexes and Reaction Kinetics.- 2.1. Complexation Equilibria.- 2.2. Solubility Product Phenomena.- 2.3. Applications in Reaction Kinetic Studies.- 3. Vegetation, Vegetables, Fruits, Juices, and Oils.- 3.1. Nitrate Levels.- 3.2. Chloride Levels.- 3.3. Miscellaneous Ion Levels.- 4. Beverages and Food.- 4.1. Milks.- 4.2. Cheeses.- 4.3. Miscellaneous.- 4.4. Salt Assay.- 4.5. Sulfur Dioxide in Wine.- 5. Rocks and Soils.- 5.1. Nitrate and Total Nitrogen.- 5.2. Cations.- 5.3. Fluoride and Chloride.- 6. Air and Stack Gases.- 6.1. Nitrogen Species in Air and Combustion Emission.- 6.2. Cigarette Smoke and Airborne Particulates.- 6.3. Sulfur Dioxide in Flue Gases.- 6.4. Fluoride in Stack Gases and Ambient Air.- 6.5. Snow and Rain.- 7. Water Supplies and Seawater.- 7.1. Fluoride in Potable Water, Effluents, and Seawater.- 7.2. Nitrate and Ammonia-Ammonium in Waters and Sewage.- 7.3. Miscellaneous Applications.- 8. Industrial Applications.- 8.1. Boilerfeeds and Steam Condensates.- 8.2. Paper Pulp and Leather Process Liquors.- 8.3. Plating and Pickling Baths.- 8.4. Coal, Petroleum, and Explosives.- 8.5. Nuclear Materials.- 8.6. Miscellaneous Applications.- 9. Mineralized Tissue and Dental Materials.- 9.1. Bone.- 9.2. Plaque.- 9.3. Saliva.- 9.4. Toothpastes.- 10. Biomedical Applications.- 10.1. Calcium.- 10.2. Fluoride.- 10.3. Chloride.- 10.4. Potassium and Sodium.- 10.5. Ammonia and Proteins.- 10.6. Carbon Dioxide-Carbonate.- 10.7. Bromide and Iodide.- 11. Applications of Microelectrodes.- 12. Organic and Pharmaceutical Compounds.- 12.1. Fluoride.- 12.2. Sulfur.- 12.3. Halogens Other Than Fluorine.- 12.4. Assay of Slow-Release Preparations for Alkali Metal Ions.- 13. Miscellaneous Applications.- 14. Continuous Monitoring with Electrodes.- 15. Applications in Potentiometric Titrations.- References.
