دانلود کتاب General Analytical Chemistry. Electrochemical Analysis Methods

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Cover
Half Title
Other books from the same author
Title Page
Copyright Page
Dedication
Preface
Acknowledgment
Table of Contents
Part I: Generalities
1. Thermodynamics and Equilibrium
1. Chemical Potential
2. Activity
3. Energy of a Cell Reaction
4. The Molar Reaction Gibbs Function ΔrG – Equilibrium of the System
5. Nernst’s law - Electrode Potentials
6. Chemical Equilibrium and Chemical Potentials
2. Recallings and Definitions Concerning the Electrochemical Cells
1. Terminology
2. Recallings Concerning the Electrochemical Cell
3. Characteristics of the Electrochemical Reactions
3. Present Views on the Interface Metal/Solution
1. Simplified Model of the Electrochemical Double-Layer
2. Other Models of the Double-Layer
3. Difference of Potential at the Level of the Double Layer
4. Consequences
4. More on the Potential of an Electrode
1. Absolute Potential of one Electrode: Its Measurement?
2. An Explanation
3. Measurement of the Changes of Absolute Potentials
4. Potential and Energy of the Electrons
5. Kinetics of the Electrode Reaction
1. Meaning of the Intensity
2. Notion of Energy of Activation of a Reaction
3. Rate of the Electrochemical Reactions
6. A Qualitative Study of the Current-Potential Curves
1. Definition of the Current-Potential Curves
2. Current-Potential Curves: Interpretation
3. Slow or Polarizable Systems and Rapid or Non-polarizable Systems
4. Current-potential Curves of Systems Perfectly Non-polarizable or Polarizable
7. Nernst’s Equation–Electrode Potentials–Electrochemical Potentials
1. Nernst’s Law
2. Electrode Potentials
3. Electrochemical Potential
4. Looking Back
8. Equation of Butler–Volmer
1. Some Factors Affecting Electrodic Reaction Rates and Current
2. Stationary Regime
3. Electrochemical Reaction Rates and Concentrations of the Forms Red and Ox Close to the Electrode
4. Expressions of the Butler–Volmer’s Relations
5. A Few Comments Upon the Values of Some Kinetic Constants
6. Some Comments Relative to the Butler–Volmer’s Equation
7. The Exchange Current io, a Quantitative Criterium of Reversibility of the Electrochemical System
8. Tafel’s Straight Lines
9. Extensions of the Equation of Butler–Volmer—“Inadequacy” of the Equation of Butler–Volmer-Effect of Mass-transfer
9. Transport Phenomena in Solution: Diffusion
1. The Phenomenon of Diffusion: First Fick’s Law
2. A Presentation of the Phenomenon of Diffusion
3. Fick’s Laws
4. Transport of the Electroactive Species Towards the Working Electrode During Electrolysis
5. Steady State
10. Limiting-Intensity-Real Current-Potential Curves-Consequences of the Stationary State of Activation-Diffusion
1. The Limiting-Intensity
2. Real Current-Potential Curves
3. Equations of the Real Curves Intensity-Potential; Stationary Regime
4. Equations of the Real Curves Intensity-Potential—Regime Non-Stationary
11. Reversible and Irreversible Systems
1. General Considerations
2. Place of the Concept of Reversibility in the Theoretical Study of the Electrochemical Methods of Analysis
3. On the Concept of Reversibility in Chemistry
12. Electrochemical Indicators
1. General Aspects
2. Some Examples
13. Forecasting Electrochemical Reactions at the Electrodes
1. Forecasting of Electrochemical Processes when the Charge-Transfer and the Transport of the Electro-Active Species are Infinitely Fast
2. Forecasting of Electrochemical Reactions when the Charge-Transfer Kinetics is Limitative
3. Forecastings When the Kinetics of Charge-Transfer and of the Transport are Both Slow
14. Forecasting Electrochemical Reactions in an Electrochemical Cell: Conditions of Electrolysis
1. The Electrochemical Reactions and the Displacement of the Species are Infinitely Fast
2. Using the Current-Potential Curves
3. Minimum of the Potential Difference to Apply for the Functioning of an Electrolysis cell
15. Transports by Migration
1. The Two Types of Conductors: the Metallic Conductors and the Ionic Ones
2. Conductivity of Solutions of Strong Electrolytes
3. Molar Conductivity of Ions at Infinite Dilution
4. Ionic Mobility
5. Equivalence Ionic Mobility: Molar Concentration
6. Transport Numbers
16. Current-Potential Curves During a Chemical Reaction
1. Qualitative Study
2. Quantitative Study
17. Techniques Based on Concept of Impedance: Impedance Spectroscopy
1. Impedance Spectroscopy
2. A Few Words About the Polarography
3. Followed Strategy
4. Equivalent Electrical Circuits
5. Equivalent Circuit of a Cell
6. Applying ac Impedance Methods to Study the Electrode Processes
7. The Example of an Impedance Constituted by a Resistor and a Capacitor in Series
8. Electrical Behavior of the Equivalent Circuit
9. Instrumentation
10. Applying ac Impedance Methods to Obtain Information on Electrode Processes
11. Interests of These Methods
Part II: Electrochemical Methods of Analysis
18. Conventional Polarography
1. General Aspects of the Method: Voltammetric Techniques
2. The Dropping Mercury Electrode (DME)
3. Notions Concerning the Equipment in Polarography
4. Theoretical Aspects
5. Influence of Different Factors on the Polarographic Current
6. Some Practical Aspects of the Polarography
7. Analytical Possibilities of the Method
8. The Polarography in the Domain of the Physical Chemistry
9. Some Examples of Applications
19. Pulse Voltammetry
1. Residual Current and Capacitance Charging Current in Conventional Polarography
2. Pulse Polarographies
3. Apparatus
4. Analytical Characteristics of the Methods
5. Analytical Aspects of the Pulse Polarographies
20. Chronoamperometry
1. Principle
2. Relation of Cottrell
3. Applications
21. Cyclic Voltammetry
1. Generalities
2. Voltammetric Methods with a Linear Sweeping of Potential
3. Principle of Cyclic Voltammetry
4. Qualitative Description of the Phenomena
5. Theoretical Aspects
6. Applications of Cyclic Voltammetry
7. Difficulties in Cyclic Voltammetric Measurements
22. Voltammetric Methods by Redissolution: Stripping Analysis
1. Anodic Stripping Voltammetry
2. Voltammetry by Cathodic Redissolution
3. Adsorptive Stripping Voltammetry
23. Voltammetry at Ultramicroelectrodes
1. Kinds of Ultramicroelectrodes
2. Experimental Conditions of Use of the UMES and Theoretical Results
3. Conclusions
24. Amperometry
1. Principle
2. Generalities
3. Amperometry with an Indicator Electrode and a Reference Electrode
4. Amperometry with two Indicator Electrodes or Biamperometry
5. Apparatus
6. Analytical Possibilities of the Amperometry
7. Some Examples of Applications
25. Conductometry
1. Theoretical Recallings
2. Measurement of the Resistance and of the Conductivity of Solutions
3. Conductometric Titrations
4. Conductometry, a Linear Method of Titration
5. Characteristics of Conductometric Titrations
6. Conductometry in Physical Chemistry: Determination of Equilibrium Constants in Solution
7. Some Applications of Conductometry
8. Removal of the Migration Current
26. Generalities on Potentiometry
1. General Principle of the Method
2. Instrumentation
3. Equilibrium Potential and Potential Taken by the Indicator Electrode
27. Definitions and PH Determination
1. Definitions of pH and Consequences
2. Difficulty Inherent to the Formal Definition of pH
3. Operational Definition of pH
4. Determination of pH
5. Sensitive Electrodes to the Ions H+
6. The pH-meter
28. Potentiometry with Chemical Sensors: Ion Selective Electrodes (I.S.E)
1. The Selective Electrodes: Some General Properties
2. Some Selective Electrodes
29. Potentiometric Titrations
1. Principles
2. Titrations at Null Intensity with an Indicator Electrode and one of Reference
3. Potentiometric Titrations at Imposed Intensity
4. Practical Aspects
5. Some Characteristics of Potentiometric Titrations
6. Domains of Applications
7. Examples of Applications
30. Chronopotentiometry
1. Different Types of Chronopotentiometry
2. Conditions of Use of the Technique
3. Theoretical Aspects; Sand’s Equation
4. Analytical Applications of the Chronopotentiometry
31. Electrogravimetry—Separation by Electrolysis
1. Generalities
2. Electrolysis at a Constant Current
3. Electrolysis at Controlled Potential
32. Coulometry
1. Faraday’s Laws
2. Conditions Required in Order to Achieve a Coulometric Determination
3. Direct Coulometry at Imposed Potential
4. Direct Coulometry at Constant Intensity
5. Coulometric Titrations
6. Superimposition of the Direct Coulometry at Constant Intensity and Coulometric Titration
7. Detection of the Equivalent Point of the Chemical Reaction
8. Back-Titration
9. Domains of Applications of the Indirect Coulometry at Constant Intensity
10. Characteristics of the Method
11. Applications
33. Chemical Sensors (Following)
1. Some Elements of Bioanalytical Chemistry
2. Definition of the Chemical Sensors and Their Constitution
3. Classification of Chemical Sensors
4. Potentiometric Sensors
5. Faradaic (or Amperometric Sensors)
6. Conductometric Sensors
7. Photoelectrochemistry-Electrochemiluminescence
8. Characteristics that Must Possess the Sensors
34. Electrochemical Biosensors
1. Generalities Concerning the Biosensors
2. Amperometric Biosensors
3. Potentiometric Biosensors
4. Conductometric Biosensors
5. Actual and Future Tendencies
6. Some Examples of Applications
35. Electrochemical Detectors in Liquid Chromatography
1. The Different Detectors in Liquid Chromatography (LC) and The Electrochemical Detectors
2. General Schema of one Apparatus LCEC
3. Forced Convection, Hydrodynamic Phenomenon
4. Essential Conditions for a good Functioning of an Apparatus of LCED and Properties of an Ideal Electrochemical Detector
5. Amperometric Detectors
6. Coulometric Detectors
7. Devices Permitting to Improve the Selectivity—Detectors in Series and in Parallel
8. Potentiometric Detectors
9. Conductometric Detectors
10. Performance of Electrochemical Detectors
11. Electrochemical Detection and Liquid Chromatographies with Capillary Microcolumns (Ultraperformant Chromatography)
12. Domains of Applications and Derivatization
13. Some Applications
14. Electrochemical Detectors and Capillary Electrophoresis
Appendices
A1. Voltage Measurements
A2. Obtention of the Butler–Volmer’s Equation
1. Generalities
2. Setting up the Butler–Volmer’s equation
A3. Laplace Transforms
1. Laplace Transforms in Brief
2. Laplace Transforms and Their Handling
3. Examples of Laplace Transforms
A4. Fick’s Laws of Diffusion
1. Supplementary Considerations About the Diffusion
2. Linear Diffusion-Fick’s Second Law Linear Diffusion Semi-Infinity
3. Fick\'s Second Law. Radial Diffusion
4. Beginning of Resolution of the Partial Differential Equation of the Second Order (3)
A5. Fresnel’s Rule
A6. Cottrell’s Equation and Extensions
1. Cottrell’s Equation
2. Extensions
A7. Polarography: Ilkowic’s Equation
1. Fast Electrochemical Systems
2. Lineary Dependence of the Limiting - Intensity with the Concentration of the Electroactive Substance in Conventional Polarography in the Case of a Slow System
A8. Quantitative Relationships in Pulse Differential Polarography
1. Second Pulse
2. First Pulse
A9. Electrochemical Methods of Analysis Grounded on the Linear Sweeping of Potential Equation of Randles–Sevcik
1. Reversible Systems
2. Irreversible and Quasi-Reversible Systems
A10. Elimination of the Migration Current
1. Principle of the Demonstration
2. Some Examples
3. Suppression of the Transport of an Ion by Migration by Addition of a Support Electrolyte
A11. Potential of Liquid Junction: Eisenmann–Nikolskii\'s Relation
1. Different Types of Liquid Junction
2. Calculation of the Potentials of Liquid Junction
3. Relation of Eisenmann-Nikolskii
A12. Henderson’s Equation
A13. Equation of Michaelis–Menten
A14. Quantitative Aspects Applying to the Amperometric and Potentiometric Enzymatic Biosensors
1. Theoretical Considerations Applicating to the Amperometric and Potentiometric Biosensors
2. Principle of Resolution of the Equations (1) and (2)
3. Amperometric Biocaptors
4. Potentiometric Biocaptors
General Bibliography
Glossary Electrochemical
Index