Modern Aspects of Electrochemistry Volume 18
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Brian E. Conway, Ralph E. White (Eds.)
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Modern Aspects of Electrochemistry Volume 18
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Kluwer Academic Publishers
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9780306476044
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1
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CHF 92.30
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Naturwissenschaft
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English
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345
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Modern Aspects of Electrochemistry
Topic from Modern Aspects of Electrochemistry, No. 35 include:
Impedanc spectroscopy with specific applications to electrode processes involving hydrogen.
Fundamentals and contemporary applications of electroless metal deposition.
The development of computational electrochemistry and its application to electrochemical kinetics.
Transition of properties of molten salts to those of aqueous solutions.
Limitations of the Born Theory in applications to solvent polarization by ions and its extensions to treatment of kinetics of ionic reactions.
4 Thermodynamic and Transport Properties of Bridging Electrolyte-Water Systems
(p. 197-198)
Maurice Abraham and Marie-Christine Abraham
Département de Chimie, Université de Montréal, Montréal, Canada
I. INTRODUCTION
For a long time, most efforts in the physical chemistry of solutions were made to obtain information on the structure of aqueous electrolytic solutions. But, at the same time as our knowledge of these solutions was expanding, especially regarding dilute solutions, another field of research attracted attention, the physical chemistry of molten salts, with increasing interest in new technologies. Due to various reasons of scientific, technological and even historical nature, most investigations in these two fields of research were made almost independently. According to Braunstein classification, 1,2 between dilute aqueous solutions and molten salts lie the hydrates, with complete or incomplete water shells around the ions, covering a very large water mole fraction range, from about 0 to 0.9. Obviously, investigations on hydrates are very important for the knowledge of transition properties between dilute aqueous solutions and molten electrolytes.
As a matter of fact, these electrolyte- water systems became gradually the object of intense attention and their study is now seriously expanding as much for technical applications as for theoretical reasons. Hydrates are used, or planned to be, in technologies such as ore leaching and extraction processes, waste-water treatment, chemical and electrochemical manufacturing, absorption-type refrigeration machines. Due to concern about pollution and security problems, areas of technological interest include energy storage and generation. For example, solar energy storage, exploitation of geothermal energy sources, molten salts based fluids in nuclear reactors which could contain more or less water, deliberately introduced or not. The knowledge of thermodynamic and transport properties, for example water vapor pressure, heat of vaporization, viscosity, electrical conductance..., as well as the influence of water concentration, temperature... on these properties, over the ranges of anticipated operating conditions, are essential in the design and operation of technical systems in which they are utilized.
With regard to scientific interest, the suggestion was made, now and then,1-8 that more progress in the understanding of very concentrated aqueous solutions could come from the consideration of solutions obtained by adding water to fused electrolytes rather than concentrating dilute aqueous solutions. Reciprocally, one would expect the structure of solutions where water plays the role of the solute, its mole fraction being less than about 0.5, be akin to that of the anhydrous molten electrolytes so that in the limit of vanishing water mole fraction the properties of the solutions would tend to those of the anhydrous electrolytes. From this point of view, any theoretical bringing-in regarding those solutions could contribute to more progress concerning the anhydrous electrolytes themselves.
Recently, electrolyte-water systems were investigated in the liquid phase over practically the whole water concentration range. Since these systems bridge the gap between anhydrous electrolytes and dilute aqueous solutions, they are designated by the expression"bridging electrolytewater systems", the electrolyte being a single one or a mixture of several components. Bridging systems lie at the heart of the present chapter. Electrolyte-water systems which do not cover the entire concentration range will also be examined or taken into account inasmuch as they cover a sufficiently large water mole fraction region, starting especially near the anhydrous electrolyte, so that they can give information on the transition of properties between those at the two extremes of the concentration scale.
An Appreciation
7
Preface
11
CONTENTS
15
Applications of Electrochemical Impedance Spectroscopy to Hydrogen Adsorption, Evolution and Absorption into Metals
20
I. INTRODUCTION
20
II. DETERMINATION OF IMPEDANCES
21
III. HYDROGEN UPD
25
IV. THE HYDROGEN EVOLUTION REACTION
32
V. HYDROGEN ABSORPTION INTO METAL ELECTRODES
41
Electroless Deposition of Metals and Alloys
69
I. INTRODUCTION
69
III. BASIC DEFINITIONS, SIMILARITIES AND DIFFERENCES AMONG ELECTROLESS PROCESSES
72
V. DEPOSITION KINETICS AND EMPRICAL RATE LAWS
98
VII. RECENT DEVELOPMENTS
125
REFERENCES
142
Towards Computational Electrochemistry - a Kineticist’s Perspective
152
I. INTRODUCTION
152
II. THE ROLE OF COMPUTERS IN NATURAL SCIENCES
154
III. THE ROLE OF COMPUTERS IN ELECTROCHEMICAL KINETICS
168
IV. THE PRESENT APPROACH
176
V. CONCLUSIONS
201
VI. ACKNOWLEDGEMENTS
203
VII. REFERENCES
204
Thermodynamic and Transport Properties of Bridging Electrolyte- Water Systems
213
I. INTRODUCTION
213
II. THERMODYNAMIC PROPERTIES
215
III. TRANSPORT PROPERTIES
259
REFERENCES
305
Factors Limiting Applications of the Historically Significant Born Equation: a Critical Review
311
I. GENERAL INTRODUCTION
311
II. HISTORICAL INTRODUCTION
312
III. BASIS OF THE DERIVATION OF THE BORN EQUATION FOR EVALUATION OF ENERGIES OF ION SOLVATION
314
IV. CHANGE OF RADIUS OF AN ION UPON ENTRY INTO SOLUTION
319
V. CHANGE OF RADIUS OF A PARTICLE UPON CHARGING
321
VI. COMPARISON OF THE GAS- PHASE AND SOLUTION- PHASE CHARGING ENERGIES IN THE BORN EQUATION
322
VII. STRUCTURE AND VOLUME FACTORS IN THE SOLVENT CO- SPHERE AROUND AN ION
323
VIII. CASES OF HYDRATION OF THE PROTON AND THE ELECTRON
327
IX. RELATION TO MOLECULAR MODELING THROUGH ION- DIPOLE INTERACTIONS
330
X. BORN EQUATION AS A BASIS FOR PLOTTING PROCEDURES FOR EVALUATION OF IONIC SOLVATION ENERGIES
331
XI. RELATION TO IONIZATION PROCESSES IN SOLUTION
332
XII. DIELECTRIC POLARIZATION EFFECTS IN KINETICS OF REACTIONS INVOLVING CHARGED TRANSITION STATES
335
REFERENCES
337
Index
340
