Principles of Polarography

Principles of Polarography

1st Edition - January 1, 1965

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  • Authors: Jaroslav Heyrovský, Jaroslav Kůta
  • eBook ISBN: 9781483264783

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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.

Table of Contents

  • I. Principles of Polarography

    1. The Origin of Polarography


    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


    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


    III. Charging Current

    Integral and Differential Capacity of the Electrode Double-Layer


    IV. Influence of the Resistance of the Electrolyte on Polarographic Curves


    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


    VI. Diffusion-Controlled Current


    1. Diffusion to Stationary Electrodes

    Linear Diffusion

    Spherical Diffusion

    2. Linear Diffusion to a Growing Dropping Electrode — the Ilkovič Equation

    3. Consequences of the Ilkovič 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 Ilkovič Equation

    6. Comparison of Experimental Results Obtained with the Simple Ilkovič

    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


    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


    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


    IX. Reversible Reduction of Organic Substances


    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


    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


    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


    XIII. Mixed Currents. Simultaneous Oxidation and Reduction Processes


    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


    XV. Applications of Limiting Currents

    A. Limiting Current Titrations (Amperometric or Polarometric Titrations)

    Types of Titrations


    B. Polarographic Coulometry

    1. Determination of the Number of Electrons n

    2. Coulometry in Polarographic Analysis

    C. Investigation of Kinetics of Homogeneous Reactions in Solution


    Fundamentals of the Measuring Technique

    Investigation of Fast Reactions



    XVI. Adsorption Effects at the Dropping Mercury Electrode

    A. Polarographic Currents Influenced by Adsorption of Electroactive Substances

    1. Reversible Processes

    2. Irreversible Processes

    B. Polarographic Currents Influenced by Adsorption of Electroinactive Substances

    1. Inhibition and Acceleration of the Electrode Process by Surface-Active Substances

    2. Classification of Surface-Active Substances

    3. Qualitative Interpretation of Effect of Surface-Active Substances on Electrode Processes

    4. Quantitative Theories of the Effect of Surface-active Substances on Electrode Processes


    XVII. Kinetic Currents


    Types of Chemical Reactions Affecting Polarographic Currents

    Methods for Computing Kinetic Currents

    A. Reactions Preceding the Electrode Process

    B. Reactions Parallel to the Electrode Process-Catalyzed Electrode Processes

    C. Reactions Subsequent to the Electrode Process


    XVIII. Catalytic Hydrogen Currents

    Catalysis by Platinum Metals

    Catalysis by Substances Present in the Solution

    1. Historical Introduction

    2. Influence of pH and Buffer Concentration on Catalytic Limiting Currents of Hydrogen

    3. Properties of Catalytic Currents

    4. Catalytically-Active Groups

    5. Interpretation of the Catalytic Evolution of Hydrogen

    6. Catalysis in Buffered Solutions in the Presence of Cobalt Salts


    XIX. Polarographic Maxima

    A. Maxima of the First Kind


    1. Occurrence and Properties

    2. Suppression of Maxima of the First Kind

    3. Polarity of Maxima of the First Kind

    4. Streaming of Electrolyte and Maxima of the First Kind

    5. Interpretation of Maxima of the First Kind

    Β. Maxima of the Second Kind


    1. Occurance and Properties

    2. Suppression of Maxima of the Second Kind

    3. Streaming of Electrolyte with Maxima of the Second Kind

    4. Interpretation of Maxima of the Second Kind

    C. Simultaneous Occurrence of Maxima of the First and the Second Kind

    D. Other Maxima

    E. Practical Application of Polarographic Maxima


    XX. Polarography in Non-Aqueous Solvents and Melts


    1. Reference Electrodes and the Influence of the iR Drop

    2. Frequently Used Solvents

    a) Alcohols

    b) Acetic Acid

    c) Sulphuric Acid

    d) Formic Acid

    e) Liquid Ammonia

    f) Acetonitrile

    g) Ethylenediamine

    h) Other Solvents

    3. Polarography in Melts


    XXI. The Kalousek Commutator (Switch) and Related Methods

    A. Mean Currents with Square Wave (Rectangular) Voltage


    1. Selection of the Commutated Voltage and the Character of the Recorded Current-Voltage Curves

    2. Later Modifications of the Commutator

    3. Experimental Results

    4. Calculation of Currents with a Periodically Changing Square-Wave Voltage

    B. Methods Related to the Kalousek Commutator


    XXII. Oscillographic Polarography


    Osciloscopic Investigation of Instantaneous Currents at Constant Potential

    Measurement of Half-Wave Potentials

    Oscillographic Polarography Proper

    A. Oscillographic Polarography with Applied Voltage

    B. Controlled-Current Oscillographic Polarography


    Tables of Half-wave Potentials

    List of Symbols

    Text—Books on Polarography


Product details

  • No. of pages: 582
  • Language: English
  • Copyright: © Academic Press 1965
  • Published: January 1, 1965
  • Imprint: Academic Press
  • eBook ISBN: 9781483264783

About the Authors

Jaroslav Heyrovský

Jaroslav Kůta

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