## Modern Aspects of Electrochemistry No. 6, Issue 6In the last decade, the evolution of electrochemistry away from concern with the physical chemistry of solutions to its more fruitful goal in the study of the widespread consequences of the transfer of electric charges across interphases has come to fruition. The turning of technology away from an onward rush, regardless, to progress which takes into account repercussions of techno logical activity on the environment, and the consequent need for a reduction and then termination of the injection of CO into 2 the atmosphere (greenhouse effect), together with a reckoning with air and water pollution in general, ensures a long-term need for advances in a basic knowledge of electrochemical systems, an increased technological use of which seems to arise from the environmental necessities. But a mighty change in attitude needs to spread among electro chemists (indeed, among all surface chemists) concerning the terms and level in which their field is discussed. The treatment of charge transfer reactions has often been made too vaguely, in terms, it seemed, of atom transfer, with the electron-transfer step, the essence of electrochemistry, an implied accompaniment to the transfer of ions across electrical double layers. The treatment has been in terms of classical mechanics, only tenable while inadequate questions were asked concerning the behavior of the electron in the interfacial transfer. No process demands a more exclusively quantal discussion than does electron transfer. |

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### Contents

1 | |

2 | |

3 | |

5 | |

9 | |

Approximation Techniques | 14 |

Monte Carlo and Molecular Dynamic Methods | 16 |

Other Approximation Methods | 21 |

Conclusion | 237 |

tion | 246 |

Developments of the Quantum Mechanical Theory | 258 |

Absolute Reaction Rate Approach to ChargeTransfer | 275 |

Electrostatic Treatment of the Rate of Redox Reactions | 281 |

Ion Tunneling | 302 |

Concluding Remarks | 314 |

The Adiabatic Principle and Related Approxi | 320 |

MacMillanMayer Theory | 36 |

Thermodynamics | 44 |

Results Which Are Independent of the Model | 48 |

Properties of the Primitive Model | 53 |

Some Other Models with Discontinuous Potentials | 66 |

Models with Continuous Potential Functions | 73 |

Model Calculations in Some Related Areas | 82 |

Supplement | 84 |

Acknowledgment | 86 |

Definitions | 91 |

Surface Potential of Aqueous Solutions of Inorganic | 100 |

Ionized Monolayers | 121 |

Incompletely and Unionized Monolayers | 145 |

Notation | 153 |

Chapter 3 | 159 |

Convective Diffusion at Electrodes with Flowing Solu | 182 |

IV Electrodes under Free Convection | 197 |

ELECTROCHEMICAL PROCESSES IN GLOW DISCHARGE AT THE GAS SOLUTION INTERFACE A Hickling I Introduction | 329 |

History | 330 |

Experimental Technique | 331 |

Physical Features of GDE | 335 |

GlowDischarge Phenomena in Conventional Elec | 339 |

trolysis | 340 |

Chemical Results of GlowDischarge Electrolysis | 344 |

Aqueous Solutions of Oxidizable Substrates | 347 |

Other Inorganic Reactions in Water | 351 |

Nonadueous Reactions | 352 |

Chemical Effects of Other Discharges | 354 |

Mechanism of GlowDischarge Electrolysis | 356 |

GlowDischarge Electrolysis and Radiation Chemistry | 368 |

Applications of GlowDischarge Electrolysis | 370 |

References | 371 |

375 | |

### Other editions - View all

Modern Aspects of Electrochemistry, Issue 6 J. O'M. Bockris,B. E. Conway No preview available - 2012 |

### Common terms and phrases

1–1 electrolyte acid Acta activation adsorbed adsorption anode aqueous solutions assumed atom barrier Bockris boundary conditions calculated cathode charge transfer Chem chemical cluster expansion coefficients computed concentration configuration considered coordinates correlation functions corresponding cosphere current density curves Debye–Hückel dependence derived dielectric constant differential equation diffusion distance effect electrical electrochemical electrode potential electrolyte electrolyte solutions electron transfer electron tunneling equilibrium experimental expression factor Faraday Soc Figure flow free energy given Gurney Helmholtz free energy HNC equation hydrodynamic hydrogen integral equation interactions interface ionic solutions ionic systems ionization ions Kelbg kinetics Levich limiting law liquid McMillan-Mayer theory metal model potential molecular monolayers obtained osmotic overpotential pair potential parameters particles phase Phys potential-energy pressure primitive model properties proton proton tunneling quantum mechanical reactants real system solvent species surface potential temperature thermodynamic tion velocity virial virial coefficient water molecules Xu,o