Principles of Polarography is a revised and extended version of an original Czech edition that appeared in 1962 at the Publishing House of the Czechoslovak Academy of Sciences in Prague. Based on a one-term course of lectures for third-year students of chemistry at the Charles University it brings the fundamental results of more than forty years' research in the field of polarography. The book contains 22 chapters and opens with a discussion of the principles of polarography. This is followed by separate chapters on polarizable electrodes used in polarography; charging current; influence of the resistance of the electrolyte on polarographic curves; migration and diffusion-controlled currents; and equation of a reversible polarographic wave. Subsequent chapters deal with reversible processes controlled by diffusion of complex ions; reversible reduction of organic substances; deposition of mercury ions; irreversible electrode processes; applications of limiting currents; polarographic curves for the formation of semiquinones and dimers; and catalytic hydrogen currents.
Inhalt
I. Principles of Polarography
1. The Origin of Polarography
Electrocapillarity
2. A Simple Measuring Circuit
Influence of the Resistance of the Potentiometer
3. Polarization of the Dropping Mercury Electrode and Depolarization Processes
4. Current-Potential Curves without Concentration Polarization. The Exponential Form of Polarographic Curves
5. The Polarograph
Literature
II. Polarizable Electrodes Used in Polarography
A. Mercury Capillary Electrodes
1. The Dropping Mercury Electrode
2. Streaming Mercury Electrode (Mercury Jet Electrode)
B. Stationary Mercury Electrodes
C. Solid Electrodes
Literature
III. Charging Current
Integral and Differential Capacity of the Electrode Double-Layer
Literature
IV. Influence of the Resistance of the Electrolyte on Polarographic Curves
Literature
V. Migration Currents
A. Influence of Concentration of Indifferent Electrolyte
1. Reduction of Cations
2. Reduction of Anions
3. Oxidation of Cations
4. Anodic Depolarization of Anions
B. "Exaltation" of the Migration Current
Literature
VI. Diffusion-Controlled Current
Introduction
1. Diffusion to Stationary Electrodes
Linear Diffusion
Spherical Diffusion
2. Linear Diffusion to a Growing Dropping Electrode - the Ilkovic Equation
3. Consequences of the Ilkovic Equation
a) Dependence on Concentration
b) Dependence on the Height of the Mercury Head, Capillary Characteristics and Potential
4. Influence of Temperature on the Diffusion Current
5. Correction for Spherical Diffusion in the Ilkovic Equation
6. Comparison of Experimental Results Obtained with the Simple Ilkovic
Equation and with the Equation Corrected for Spherical Diffusion
A. Assumptions made in Deriving a Diffusion Current Equation
B. Survey of Experimental Verifications of Diffusion Current Equations
7. Dropping Mercury Amalgam Electrode
8. Diffusion Coefficients
9. Influence of Viscosity and of Complex Formation on Diffusion Current
10. Diffusion Current at a Streaming Electrode
11. Rotated Disc Electrode
12. Rotated Dropping Mercury Electrode
Literature
VII. Equation of a Reversible Polarographic Wave
1. Equation of a Cathodic Wave
2. Equation of an Anodic Wave
3. Equation of an Cathodic-Anodic Wave
4. Analysis of Reversible Polarographic Waves
5. Derivative Polarographic Curves
6. Significance of Half-Wave Potentials
7. Influence of Ionic Strength on Half-Wave Potentials
8. Equation of a Polarographic Wave Corrected for Spherical Diffusion
9. i-t-Curves on the Rising Portion of a Reversible Polarographic Wave
10. Equation of a Reversible Process at the Hanging Mercury Drop Electrode
Literature
VIII. Reversible Processes Controlled by Diffusion of Complex Ions
1. Reversible Reduction of Complexes to Metals
2. Consecutive Complex Formation in which the Reduction Product Forms an Amalgam
3. Determination of the Mean Diffusion Coefficient
4. Reduction of Complexes to a Lower Valency
5. Successive Reduction of Complexes
Literature
IX. Reversible Reduction of Organic Substances
Literature
X. Deposition of Mercury Ions Formation of Salts and Complexes with Mercury
1. Reduction of Mercurous and Mercuric Ions
2. Reduction of Mercury Complexes
3. Anodic Dissolution of Mercury
4. Formation of Insoluble Salts with Mercury
5. Formation of Complexes with Mercury
Literature
XI. Polarographic Curves for the Formation of Semiquinones and Dimers
1. The Current-Voltage Curve for the Formation of Semiquinones
2. The Current-Voltage for the Complete Dimerization of a Semiquinone
Literature
XII. Diffusion Currents in Unbuffered Media and in Solutions with Insufficient Concentration of Complex-Forming Agents
1. Diffusion Currents in Unbuffered and Insufficiently Buffered Media
a) Unbuffered Solutions
b) Diffusion Currents in Poorly Buffered Media
2. Diffusion Currents for Complexes with an Insufficient Concentration of the Complex-Forming Agent
3. Reaction of Depolarization Products with Another Depolarizer
Literature
XIII. Mixed Currents. Simultaneous Oxidation and Reduction Processes
Literature
XIV. Irreversible Electrode Processes
1. An Approximate Treatment of a Slow Electrode Process
2. A Rigorous Treatment of a Slow Electrode Process
3. Polarographic Curves for Irreversible Processes at a Hanging Mercury Drop
4. Irreversible Reduction of Complexes
Complexes and the Rate of Electrode Processes
5. Determination of Activation Energy for an Irreversible Electrode Process
6. The Electrode Double Layer and the Rate of the Electrode Process
a) Properties of the Electrode Double Layer
b) Influence of Structure of the Electrode Double Layer on the Rate of an Irreversible Process
7. Reduction of Cations
A. Reduction of Hydrogen Ions and Hydrogen Overvoltage
B. Further Examples
8. Reduction of Anions and the Discontinuity on Their Polarographic Curves
a) Influence of Electrolytes on the Reduction and Half-Wave Potentials of Anions
b) Limiting Currents for Anions
c) Interpretation of the Reduction of Anions
d) Reduction of Nitrate Ions and Discontinuity on Polarographic Curves
e) Non-Reducible Anions
9. Polarography of Organic Substances
Correlations between Half-Wave Potentials and the Constitution of Organic Substances
Literature
XV. Applications of Limiting Currents
A. Limiting Current Titrations (Amperometric or Polarometric Titrations)
Types of Titrations
Apparatus
B. Polarographic Coulometry
1. Determination of the Number of Elect…