Analytical And Physical Electrochemistry

by Girault; Hubert H.

• ISBN13: 9780824753573
• ISBN10: 0824753577
• Format: Hardcover
• Copyright: 2004-10-25
• Publisher: EFPL Press

Summary

The study of electrochemistry is pertinent to a wide variety of fields, including bioenergetics, environmental sciences, and engineering sciences. In addition, electrochemistry plays a fundamental role in specific applications as diverse as the conversion and storage of energy and the sequencing of DNA. Intended both as a basic course for undergraduate students and as a reference work for graduates and researchers, Analytical and Physical Electrochemistry covers two fundamental aspects of electrochemistry: electrochemistry in solution and interfacial electrochemistry. By bringing these two subjects together into a single volume, the author clearly establishes the links between the physical foundation and the analytical applications of electrochemistry. The philosophy of Analytical and Physical Electrochemistry has been to publish all the mathematical derivations in detail, allowing you, if you so desire, to follow the calculations that lead to the main results. With this rigorous approach, the author has provided a book of reference constructed from first principles. In this respect, the nomenclature and standards of the IUPAC (International Union of Pure and Applied Chemistry) are observed.

Author Biography

Professor Hubert H. Girault, a graduate of the ENSEE Grenoble (France), obtained his doctorate in Electrochemistry at the University of Southampton (England)

Table of Contents

Preface	vii
Preface to the Original French Version	viii
Electrochemical Potential	1	(32)
Electrochemical potential of ions	1	(22)
Electrochemical potential of electrons	23	(10)
Electrochemical Equilibria	33	(50)
Redox reactions at metallic electrodes	33	(17)
Cells and accumulators	50	(4)
Pourbaix diagrams	54	(3)
Electrochemical equilibria at the interface between two electrolytes	57	(6)
Analytical applications of potentiometry	63	(15)
Ion exchange membranes	78	(5)
Appendix: The respiratory chain	82	(1)
Electrolyte Solutions	83	(50)
Liquids	83	(2)
Thermodynamic aspects of solvation	85	(15)
Structural aspects of ionic solvation	100	(5)
Ion-ion interactions	105	(18)
Ion pairs	123	(6)
Computational methods	129	(4)
Appendix	131	(2)
Transport in Solution	133	(44)
Transport in electrolyte solutions	133	(5)
Conductivity of electrolyte solutions	138	(7)
Influence of concentration on conductivity	145	(7)
Dielectric friction	152	(8)
Thermodynamics of irreversible systems	160	(3)
Statistical aspects of diffusion	163	(14)
Appendix: Elements of fluid mechanics	171	(6)
Electrified Interfaces	177	(44)
Interfacial tension	177	(3)
Interfacial thermodynamics	180	(4)
Thermodynamics of electrified interfaces	184	(10)
Spatial distribution of polarisation charges	194	(21)
Structure of electrochemical interfaces	215	(6)
Electrokinetic Phenomena and Electrochemical Separation Methods	221	(44)
Electrokinetic phenomena	221	(8)
Capillary electrophoresis	229	(10)
Electrophoretic methods of analytical separation	239	(5)
Electrophoretic separation of biopolymers	244	(12)
Ion chromatography	256	(5)
Industrial methods of electrochemical separation	261	(4)
Steady State Amperometry	265	(36)
Electrochemical kinetics	265	(3)
Current controlled by the kinetics of the redox reactions	268	(7)
Reversible systems: Current limited by diffusion	275	(5)
Electrodes with a diffusion layer of controlled thickness	280	(8)
Quasi-reversible systems: Current limited by kinetics and diffusion	288	(6)
Irreversible systems: Current limited by kinetics and diffusion	294	(1)
Quasi-reversible systems: Current limited by diffusion, migration and kinetics	295	(1)
Experimental aspects of amperometry	296	(5)
Pulse Voltammetry	301	(38)
Chronoamperometry following a potential step	301	(10)
Polarography	311	(8)
Square wave voltammetry	319	(14)
Stripping voltammetry
Thin layer voltammetry	333	(4)
Amperometric detectors for chromatograpy	337	(2)
Electrochemical Impedance	339	(36)
Transfer function	339	(4)
Elementary circuits	343	(8)
Impedance of an electrochemical system	351	(17)
AC voltammetry	368	(7)
Cyclic Voltammetry	375	(36)
Electrochemically reversible reactions with semi-infinite linear diffusion	375	(7)
Influence of the kinetics	382	(3)
EC reactions	385	(11)
Electron transfer at liquid | liquid interfaces	396	(3)
Assisted ion transfer at liquid | liquid interfaces	399	(3)
Surface reactions	402	(2)
Hemi-spherical diffusion	404	(3)
Voltabsorptometry	407	(1)
Semi-integration	408	(3)
ANNEX A VECTOR ANALYSIS	411	(6)
Coordinate systems	411	(1)
Circulation of the field vector	412	(1)
The vector gradient	413	(1)
Flux of the field vector	414	(1)
The Green-Ostrogradski theorem	414	(3)
ANNEX B Work functions and standard redox potentials	417	(8)
Symbols	425	(4)
Index	429