ELECTROCHEMISTRY

By H. CAKAK

CONTENTS SOME FUNDAMENTAL CONCEPTS INTRODUCTION OUTER, SURFACE, AND INNER POTENTIALS THERMODYNAMICS OF ELECTROCHEMICAL PROCESSES INTERFACE BETWEEN TWO METALS IN CONTACT ELECTROCHEMICAL POTENTIAL OF THE ELECTRON NERNST’S EQUATION AND STANDARD ELECTRODE POTENTIALS FORMAL ELECTRODE POTENTIALS ELECTRICAL DOUBLE LAYER MODELS FOR THE ELECTRICAL DOUBLE LAYER SPECI?C ADSORPTION KINETICS OF THE CHARGE TRANSFER THE BUTLER–VOLMER MODEL THE MARCUS–HUSH MODEL MASS TRANSPORT MINIMIZATION OF THE MIGRATION COMPONENT TEMPORAL EVOLUTION CONVECTION MASS TRANSPORT COEF?CIENT THREE-ELECTRODE SYSTEMS OHMIC DROP, RESISTANCE OF THE CELL, AND RC TIME CONSTANT PULSE VERSUS STEP REFERENCES SINGLE PULSE VOLTAMMETRY: REVERSIBLE ELECTROCHEMICAL REACTIONS REVERSIBLE ELECTRODE REACTION PLANAR ELECTRODES CONCENTRATION PRO?LES CURRENT–TIME CURVES (CHRONOAMPEROMETRY) AND CURRENT–POTENTIAL CURVES (VOLTAMMETRY) STOICHIOMETRIC COEF?CIENTS DIFFERENT FROM THE UNITY ION TRANSFER THROUGH LIQUID MEMBRANES ONE-POLARIZED INTERFACE SYSTEMS TWO-POLARIZED INTERFACES SYSTEMS ELECTRON TRANSFER AT THE LIQUID/LIQUID INTERFACE DROPPING MERCURY ELECTRODE (DME) DC POLAROGRAPHY NORMAL PULSE POLAROGRAPHY (NPP) SPHERICAL ELECTRODES UNEQUAL DIFFUSION COEF?CIENTS (DO 6¼ DR) EQUAL DIFFUSION COEF?CIENTS (DO ¼ DR) OTHER ELECTRODES GEOMETRIES MICROELECTRODES STEADY-STATE VOLTAMMETRY ROTATING DISC ELECTRODE THIN LAYER VOLTAMMETRY SINGLE PULSE VOLTAMMETRY: NON-REVERSIBLE AND COMPLEX ELECTROCHEMICAL REACTIONS QUASI-REVERSIBLE AND IRREVERSIBLE ELECTROCHEMICAL REACTIONS DROPPING MERCURY ELECTRODE SPHERICAL ELECTRODES AND MICROELECTRODES MICRODISCS STEADY-STATE VOLTAMMETRY GENERAL EXPRESSION FOR THE STATIONARY CURRENT–POTENTIAL RESPONSE AT MICROELECTRODES COMPARISON BETWEEN MARCUS–HUSH AND BUTLER–VOLMER KINETICS MULTI-ELECTRON ELECTROCHEMICAL REACTIONS TWO-ELECTRON ELECTROCHEMICAL REACTIONS AT PLANAR ELECTRODES TWO-ELECTRON ELECTROCHEMICAL REACTIONS AT DIFFERENT ELECTRODE GEOMETRIES NON-REVERSIBLE TWO-ELECTRON ELECTROCHEMICAL REACTIONS GENERAL SOLUTION FOR MULTI-ELECTRON ELECTROCHEMICAL REACTIONS FIRST-ORDER CHEMICAL REACTIONS COUPLED TO CHARGE TRANSFER PROCESSES CATALYTIC MECHANISM CE MECHANISM EC MECHANISM COMPARISON OF THE DISTURBED REGIONS BY CATALYTIC, CE, AND EC MECHANISMS COMPARISON BETWEEN THE CURRENT–POTENTIAL CURVES CORRESPONDING TO CATALYTIC, CE, AND EC MECHANISMS DETERMINATION OF KINETIC PARAMETERS ECE MECHANISM AND OTHER MORE COMPLEX REACTION SCHEMES CATALYTIC MECHANISM AT DISC ELECTRODES REVERSIBLE CHARGE TRANSFERS PRECEDED AND FOLLOWED BY SEVERAL COMPLEXATION REACTIONS IN EQUILIBRIUM (LADDER MECHANISM) DOUBLE PULSE VOLTAMMETRIES REVERSIBLE ELECTROCHEMICAL REACTIONS APPLICATION OF A DOUBLE POTENTIAL PULSE TO ELECTRODES AND MICROELECTRODES OF ANY GEOMETRY DOUBLE PULSE CHRONOAMPEROMETRY AND CHRONOCOULOMMETRY REVERSE PULSE VOLTAMMETRY DIFFERENTIAL DOUBLE PULSE VOLTAMMETRY DIFFERENTIAL NORMAL DOUBLE PULSE VOLTAMMETRY ADDITIVE DIFFERENTIAL DOUBLE PULSE VOLTAMMETRY NONREVERSIBLE ELECTROCHEMICAL REACTIONS APPLICATION OF A DOUBLE POTENTIAL PULSE TO PLANAR AND SPHERICAL ELECTRODES ADDITIVE DOUBLE DIFFERENTIAL PULSE VOLTAMMETRY APPLICATION OF A DOUBLE POTENTIAL PULSE TO ELECTRODES OF ANY GEOMETRY CATALYTIC MECHANISM AT DISC, SPHERICAL, AND PLANAR ELECTRODES CE AND EC MECHANISMS AT PLANAR ELECTRODES TRIPLE PULSE VOLTAMMETRIES REVERSE DIFFERENTIAL PULSE VOLTAMMETRY DOUBLE DIFFERENTIAL TRIPLE PULSE VOLTAMMETRY MULTIPULSE AND SWEEP VOLTAMMETRIES I APPLICATION OF A MULTIPULSE SEQUENCE TO ELECTRODES AND MICROELECTRODES OF ANY GEOMETRY MULTIPULSE CHRONOAMPEROMETRY CYCLIC STAIRCASE VOLTAMMETRY AND CYCLIC VOLTAMMETRY AT ELECTRODES AND MICROELECTRODES OF ANY GEOMETRY NON-REVERSIBLE ELECTROCHEMICAL REACTIONS REVERSIBILITY CRITERIA OTHER ELECTRODE GEOMETRIES: MICROELECTRODES AND STEADY-STATE VOLTAMMETRY MARCUS–HUSH KINETICS ADVANTAGES OF USING MICROELECTRODES REDUCTION OF OHMIC DROP AND CAPACITIVE EFFECTS NEGLECTING CONVECTION ULTRAFAST VOLTAMMETRY MICROELECTRODE ARRAYS NANOELECTRODES ION TRANSPORT THROUGH LIQUID MEMBRANES ONE POLARIZED INTERFACE TWO POLARIZED INTERFACES MICRO-ITIES AND ASYMMETRICAL DIFFUSION MULTIPULSE AND SWEEP VOLTAMMETRIES II FIRST-ORDER CHEMICAL REACTIONS COUPLED WITH THE CHARGE TRANSFER CE AND EC MECHANISMS ECE MECHANISM REVERSIBLE CHARGE TRANSFERS PRECEDED AND FOLLOWED BY SEVERAL COMPLEXATION REACTIONS IN EQUILIBRIUM AT ELECTRODES OF ANY GEOMETRY (“LADDER” MECHANISM) SURFACE-BOUND MOLECULES ONE-ELECTRON ELECTROCHEMICAL REACTIONS: STATEMENT OF THE PROBLEM ONE-ELECTRON ELECTROCHEMICAL REACTIONS: CYCLIC VOLTAMMETRY TWO-ELECTRON ELECTROCHEMICAL REACTIONS ELECTROCATALYTIC PROCESSES AT MODI?ED ELECTRODES DIFFERENTIAL MULTIPULSE AND SQUARE WAVE VOLTAMMETRIES REVERSIBLE ELECTROCHEMICAL REACTIONS AT ELECTRODES AND MICROELECTRODES OF ANY GEOMETRY DIFFERENTIAL STAIRCASE VOLTAMMETRY DIFFERENTIAL MULTIPULSE VOLTAMMETRY SQUARE WAVE VOLTAMMETRY FIRST-ORDER CHEMICAL REACTIONS COUPLED TO THE CHARGE TRANSFER REACTION LADDER MECHANISM ONE-ELECTRON ELECTROCHEMICAL REACTIONS ELECTROCATALYTIC REACTIONS AT MODI?ED ELECTRODES