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Transport, Relaxation and Kinetic Processes in Electrolyte Solutions : Lecture Notes in Chemistry - Pierre Turq

Transport, Relaxation and Kinetic Processes in Electrolyte Solutions

Lecture Notes in Chemistry

Paperback ISBN: 9783540550020
Number Of Pages: 206

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The subject of this book is the treatment of transport phenomena in electrolyte solutions and their natural coupling with ionic reactions. The topic is treated at the level of lectures for 3rd year undergraduate students in physical chemistry. The knowledge in statistical mechanics, hydrodynamics and electrodynamics needed for the understanding of the book as well as the necessary mathematical techniques are introduced in a simple and concise way. Treatment of coupled transport and kinetic processes is introduced with normal modes analysis yielding a clear separation of relaxation and propagative modes. The book is conceived at the level of one-particle hydrodynamic continuity equations. Extensions beyond the ideal multicomponent systems are given at the level of chemical model (CM) and mean spherical approximation (MSA) calculations.

I: Basic Concepts.- 1.1 Introduction.- 1.1.1 Ions in solution.- 1.1.2 Diffusion current.- 1.1.3 Electric current.- 1.2 Systems in Thermodynamic Equilibrium.- 1.2.1 Equilibrium conditions.- 1.2.2 Chemical potential.- 1.2.3 Chemical equilibrium.- 1.3 Electrolyte Solutions.- 1.3.1 Mean concentration and mean activity coefficient.- 1.3.2 Electrochemical potential.- 1.3.3 Ionic equilibria in solutions.- 1.4 Preliminary Remarks on Transport Processes.- II: Coupled Processes and Chemical Reactions in Solutions.- 2.1 Continuity Equations.- 2.2 Mass Conservation.- 2.3 Constitutive Equations.- 2.4 Solutions of the Basic Transport Equations.- 2.5 Normal Modes.- 2.5.1 Relaxation modes.- 2.5.2 Migration modes.- 2.5.3 Diffusion modes.- 2.5.4 Series expansion of normal modes.- 2.5.5 Mutual diffusion.- 2.6 Coupled Diffusion.- 2.6.1 Diffusion coefficients.- 2.6.2 Coupled diffusion.- 2.6.3 Normal mode analysis without ion pairing.- III: Hydrodynamic Properties.- 3.1 Introduction.- 3.2 General Aspects of Hydrodynamics.- 3.3 Inviscid Fluids.- 3.3.1 Time derivative of velocity.- 3.3.2 Euler's equation.- 3.3.3 Bernoulli's relation.- 3.3.4 Vorticity.- 3.4 Viscous Incompressible Fluids.- 3.4.1 Preliminary remarks.- 3.4.2 Microscopic origin of viscosity.- 3.4.3 Equation of motion of a viscous liquid.- 3.4.4 Dynamic similarity and Reynolds number.- 3.5 Stokes Approximation.- 3.5.1 Flow due to a moving sphere at small Reynolds numbers.- 3.5.2 Velocity field around a sphere.- 3.6 Hydrodynamic Interactions of Moving Spheres.- IV: Excess Quantities.- 4.1 Distribution and Correlation Functions.- 4.2 Debye-Huckel Limiting Law.- 4.3 Activity Coefficients.- 4.3.1 System of hard spheres.- 4.3.2 Ions in solution.- 4.4 Chemical Model.- 4.5 Electrolyte Solutions at Moderate to High Concentrations.- 4.5.1 Cluster expansion of the pair-correlation function.- 4.5.2 Ornstein-Zernike equation.- 4.5.3 Integral equation methods.- 4.5.4 Mean spherical approximation.- 4.6 Hydrodynamic Interactions.- V: The Role of Ion Aggregation and Micelle Formation Kinetics in Diffusional Transport of Binary Solutions.- 5.1 Diffusional Transport of Symmetrical Electrolytes.- 5.2 Some Remarks on the Diffusional Transport of Symmetrical Electrolytes.- 5.2.1 Role of activity coefficients.- 5.2.2 Relaxation to local equilibrium.- 5.2.3 Relaxation to local electroneutrality.- 5.2.4 Relaxation of an electroneutral fluctuation of electrolyte concentration.- 5.3 Diffusional Transport of Unsymmetrical Electrolytes.- 5.3.1 Continuity equations and their transformations.- 5.3.2 Case of one ionic complex and no solvation-desolvation process.- 5.3.3 Case of two ionic complexes and one solvation-desolvation process.- 5.3.4 Three ionic complexes and two solvation-desolvation processes.- 5.4 Monomer-Micelle Exchange in Micelle Diffusion.- 5.5 Concluding Remarks.- VI: Diffusion, Migration and Chemical Reactions in Electrolyte Solutions beyond Ideality.- 6.1 Introduction.- 6.2 Electrolyte Conductance.- 6.3 Apparent Ionic Charge.- 6.3.1 Electrolyte conductance and self-diffusion.- 6.3.2 Relaxation effect.- 6.3.3 Electrophoretic effect.- 6.3.4 Apparent charge at Debye-Huckel and CM level.- 6.3.5 Apparent charge at MSA level.- 6.4 Experimental Contributions to the Apparent Charge Concept.- 6.4.1 Solutions of completely dissociated electrolytes.- 6.4.2 Solutions of associated electrolytes.- 6.4.3 Polyelectrolyte solutions.- 6.4.4 Coupled diffusion of polyelectrolytes.- 6.5 Solutions of Complex Electrolytes.- 6.5.1 Fast exchange reactions.- 6.5.2 Slow exchange reactions.- 6.6 Electrophoretic Transport and Exchange Reactions.- 6.6.1 Transport equations.- 6.6.2 Data analysis.- 6.6.3 Electrophoretic transport pattern.- VII: Relaxation. Processes in High Frequency Electromagnetic Fields.- 7.1 Fundamental Equations.- 7.2 Electric Polarization.- 7.2.1 Electric polarization of nonconducting liquids at low frequencies.- 7.2.2 Electric polarization of nonconducting liquids at high frequencies.- 7.2.3 Polarization at optical frequencies.- 7.3 Response Functions and Relaxation Times.- 7.3.1 Step-response function and pulse-response function.- 7.3.2 Molecular response function.- 7.3.3 Relaxation times and relaxation time distributions.- 7.4 Relaxation Processes in Solvents and Their Electrolyte Solutions.- 7.4.1 Relaxation processes in pure solvents and solvent mixtures.- 7.4.2 Influence of ions on solvent relaxation times.- 7.4.3 Relaxation processes of ion pairs.

ISBN: 9783540550020
ISBN-10: 354055002X
Series: Lecture Notes in Chemistry
Audience: General
Format: Paperback
Language: English
Number Of Pages: 206
Publisher: Springer-Verlag Berlin and Heidelberg Gmbh & Co. Kg
Country of Publication: DE
Dimensions (cm): 24.41 x 16.99  x 1.22
Weight (kg): 0.37