Liquids, solutions, and interfaces : from classical macroscopic descriptions to modern microscopic details / W. Ronald Fawcett.

Format:

Book

Author/Creator:

Fawcett, W. Ronald.

Language:

English

Subjects (All):

Solution (Chemistry).

Interfaces (Physical sciences).

Physical Description:

xvi, 621 pages : illustrations ; 25 cm

Place of Publication:

Oxford ; New York : Oxford University Press, 2004.

Summary:

Fifty years ago solution chemistry occupied a major fraction of physical chemistry textbooks, and dealt mainly with classical thermodynamics, phase equilibria, and non-equilibrium phenomena, especially those related to electrochemistry. Much has happened in the intervening period, with tremendous advances in theory and the development of important new experimental techniques. This book brings the reader through the developments from classical macroscopic descriptions to more modern microscopic details.

Contents:

Fundamental Constants xvi

1. The Thermodynamics of Liquid Solutions 3

1.1 Most Liquid Solutions Are Not Ideal 3

1.2 Concentration Units 4

1.3 Thermodynamic Quantities 6

1.4 Partial Molar Quantities 9

1.5 Ideal Solutions

Raoult's Law 15

1.6 Thermodynamics of Ideal Solutions 16

1.7 Non-Ideal Solutions 18

1.8 Thermodynamics of Non-Ideal Solutions 21

1.9 Regular Solutions 24

1.10 An Empirical Approach to Non-Ideal Solutions 30

1.11 Ideally Dilute Solutions 33

1.12 Thermodynamics of Ideally Dilute Solutions 34

1.13 Experimental Determination of Solution Activities 38

2. The Structure of Liquids 45

2.2 The Statistical Thermodynamics of Liquids 47

2.3 Intermolecular Forces 52

2.4 Distribution and Correlation Functions 61

2.5 The Experimental Study of Liquid Structure 65

2.6 The Direct Correlation Function and the Mean Spherical Approximation 70

2.7 Computer Simulations of Simple Liquids 73

2.8 Estimation of Thermodynamic Properties from the Pair Correlation Function 75

2.9 The Properties of a Hard-Sphere Fluid 79

2.10 The Structure of Water 84

2.11 Distribution Functions for Liquid Solutions 88

3. Electrolyte Solutions 95

3.1 Electrolyte Solutions Are Always Non-Ideal 95

3.2 Ionic Size in Solutions 97

3.3 The Thermodynamics of Ion-Solvent Interactions 100

3.4 Ion-Solvent Interactions According to the Born Model 102

3.5 Ion-Solvent Interactions According to the Mean Spherical Approximation 106

3.6 The Thermodynamics of Electrolyte Solutions 111

3.7 The Experimental Determination of Activity Coefficients for Electrolytes 116

3.8 Ion-Ion Interactions According to the Debye-Huckel Model 121

3.9 Ion-Ion Interactions According to the MSA 130

3.10 The Thermodynamics of Ion Association 135

3.11 Ion Association According to the MSA 140

4. Polar Solvents 148

4.1 What Constitutes a Polar Liquid? 148

4.2 Some Important Properties of Polar Solvents 149

4.3 The Static Solvent Permittivity on the Basis of Continuum Models 153

4.4 The Static Solvent Permittivity According to the MSA 162

4.5 Dielectric Relaxation Phenomena 169

4.6 The Permittivity of Electrolyte Solutions 176

4.7 The Dielectric Relaxation Parameters 180

4.8 Ion Solvation in Polar Solvents 184

4.9 Polar Solvents as Lewis Acids and Bases 191

5. Spectroscopic Studies of Liquid Structure and Solvation 204

5.1 What Spectroscopic Techniques Are Available? 205

5.2 X-Ray and Neutron Diffraction Experiments 206

5.3 Nuclear Magnetic Resonance Spectroscopy in Solutions 213

5.4 NMR Studies of Ion Solvation in Water 219

5.5 NMR Studies of Ion Solvation in Non-Aqueous Solvents 223

5.6 Vibrational Spectroscopy in Solutions 226

5.7 Infrared Spectroscopy of Polar Solvents 232

5.8 Infrared Spectroscopy of Non-Electrolyte Solutions 239

5.9 Infrared Spectroscopy of Electrolyte Solutions 242

5.10 Ultraviolet-Visible Spectroscopy and Solvatochromic Effects 245

6. Non-Equilibrium Phenomena in Liquids and Solutions 254

6.1 Non-Equilibrium Processes Are Usually Complex 254

6.2 The Thermodynamics of Irreversible Processes 255

6.3 The Viscosity of Liquids 259

6.4 Isothermal Diffusion in Solutions 264

6.5 Linear Diffusion from a Wall 266

6.6 The Electrochemical Potential 271

6.7 The Conductivity of Electrolyte Solutions 274

6.8 Experimental Studies of Conductivity 283

6.9 The Debye-Onsager Model for Conductivity 288

6.10 Transport Phenomena in Non-Aqueous Solutions 294

6.11 Proton Transport Phenomena 298

7. Chemical Reaction Kinetics in Solution 304

7.1 What Time Scales Are Involved for Chemical Reactions in Solution? 304

7.3 General Types of Solution Reactions 312

7.4 Temperature Effects and Transition State Theory 323

7.5 Diffusion-Controlled Rapid Reactions 329

7.6 Relaxation Techniques for Rapid Reactions 332

7.7 Laser Spectroscopy and Femtochemistry in Solutions 338

7.8 The Theory of Homogeneous Electron Transfer 346

7.9 NMR Spectroscopy and Chemical Exchange Reactions 358

7.10 Medium Effects in Solution Reactions 366

7.11 Linear Gibbs Energy Relationships 375

8. Liquids and Solutions at Interfaces 383

8.1 The Molecular Environment at the Interface Is Different than in the Bulk 383

8.2 The Interfacial Tension of Liquids 385

8.3 The Thermodynamics of Fluid Interfaces 390

8.4 The Electrical Aspects of Interfaces 395

8.5 The Work Function for Electrons in Metals 398

8.6 The Liquid[vertical bar]Gas Interface and the Adsorption Isotherm 401

8.7 Experimental Measurement of the Volta Potential Difference at Interfaces 408

8.8 The Metal[vertical bar]Solution Interface 422

8.9 The Liquid[vertical bar]Liquid Interface 426

8.10 Surface Films on Liquids 433

8.11 Spectroscopy at Liquid Interfaces 437

9. Charge Transfer Equilibria at Interfaces 447

9.1 Electrochemical Equilibria Occur at a Wide Variety of Interfaces 447

9.2 Electrochemical Cells 448

9.3 The Thermodynamic Basis of the Nernst Equation 456

9.4 The Absolute Electrode Potential 461

9.5 Experimental Studies of Electrochemical Cells 464

9.6 Electrochemical Cells for Electroanalysis 474

9.7 The Liquid Junction Potential 477

9.8 Membrane Potentials and the Donnan Effect 484

9.9 Ion-Selective Electrodes 494

9.10 p-Functions and the Definition of pH 502

10. The Electrical Double Layer 508

10.1 The Electrical Double Layer Is an Example of Electrostatic Equilibrium 508

10.2 The Thermodynamics of the Ideally Polarizable Interface 510

10.3 The Experimental Study of the Double Layer 516

10.4 The Structure of the Double Layer 530

10.5 The Potential of Zero Charge and the Role of the Metal 535

10.6 The Gouy-Chapman Model of the Diffuse Double Layer 542

10.7 The Structure of the Inner Layer in the Absence of Adsorption 552

10.8 The Specific Adsorption of Ions 558

10.9 The Adsorption of Molecules at Electrodes 569

A.1 Laplace Transforms 582

A.2 Fourier Transforms 584

A.3 Complex Numbers and Functions 585

A.4 Power Series 586

Appendix B. The Laws of Electricity and Magnetism 589

Appendix C. Numerical Methods of Data Analysis 595

C.1 The Principle of Least Squares 595

C.2 Linear Regression 599

C.3 Multiple Linear Regression 605

C.4 Numerical Methods 608

C.5 Numerical Interpolation 610

C.6 Numerical Integration 612

C.7 Numerical Differentiation 614.

Notes:

Includes bibliographical references and index.

ISBN:

0195094328

OCLC:

52509425