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Liquid-State Physical Chemistry: Fundamentals, Modeling, and Applications

ISBN: 978-3-527-33322-6
560 pages
September 2013
Liquid-State Physical Chemistry: Fundamentals, Modeling, and Applications  (3527333223) cover image

Description

For many processes and applications in science and technology a basic knowledge of liquids and solutions is a must. Gaining a better understanding of the behavior and properties of pure liquids and solutions will help to improve many processes and to advance research in many different areas. This book provides a comprehensive, self-contained and integrated survey of this topic and is a must-have for many chemists, chemical engineers and material scientists, ranging from newcomers in the field to more experienced researchers. The author
offers a clear, well-structured didactic approach and provides an overview of the most important types of liquids and solutions. Special topics include chemical reactions, surfaces and phase transitions. Suitable both for introductory as well as intermediate level as more advanced parts are clearly marked. Includes also problems and solutions.
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Table of Contents

Preface XV

Acknowledgments XIX

List of Important Symbols and Abbreviations XXV

1 Introduction 1

1.1 The Importance of Liquids 1

1.2 Solids, Gases, and Liquids 2

1.3 Outline and Approach 5

1.4 Notation 8

References 9

Further Reading 9

2 Basic Macroscopic and Microscopic Concepts: Thermodynamics, Classical, and Quantum Mechanics 11

2.1 Thermodynamics 11

2.2 Classical Mechanics 26

2.3 Quantum Concepts 35

2.4 Approximate Solutions 44

References 51

Further Reading 51

3 Basic Energetics: Intermolecular Interactions 53

3.1 Preliminaries 53

3.2 Electrostatic Interaction 55

3.3 Induction Interaction 59

3.4 Dispersion Interaction 60

3.5 The Total Interaction 63

3.6 Model Potentials 65

3.7 Refinements 68

3.8 The Virial Theorem 72

References 72

Further Reading 73

4 Describing Liquids: Phenomenological Behavior 75

4.1 Phase Behavior 75

4.2 Equations of State 76

4.3 Corresponding States 79

References 86

Further Reading 87

5 The Transition from Microscopic to Macroscopic: Statistical Thermodynamics 89

5.1 Statistical Thermodynamics 89

5.2 Perfect Gases 101

5.3 The Semi-Classical Approximation 104

5.4 A Few General Aspects 110

5.5 Internal Contributions 112

5.6 Real Gases 118

References 126

Further Reading 127

6 Describing Liquids: Structure and Energetics 129

6.1 The Structure of Solids 129

6.2 The Meaning of Structure for Liquids 132

6.3 The Experimental Determination of g(r) 138

6.4 The Structure of Liquids 140

6.5 Energetics 146

6.6 The Potential of Mean Force 150

References 154

Further Reading 154

7 Modeling the Structure of Liquids: The Integral Equation Approach 155

7.1 The Vital Role of the Correlation Function 155

7.2 Integral Equations 156

7.3 Hard-Sphere Results 165

7.4 Perturbation Theory 168

7.5 Molecular Fluids 174

7.6 Final Remarks 174

References 175

Further Reading 175

8 Modeling the Structure of Liquids: The Physical Model Approach 177

8.1 Preliminaries 177

8.2 Cell Models 178

8.3 Hole Models 187

8.4 Significant Liquid Structures 194

8.5 Scaled-Particle Theory 200

References 202

Further Reading 202

9 Modeling the Structure of Liquids: The Simulation Approach 203

9.1 Preliminaries 203

9.2 Molecular Dynamics 205

9.3 The Monte Carlo Method 211

9.4 An Example: Ammonia 214

References 218

Further Reading 219

10 Describing the Behavior of Liquids: Polar Liquids 221

10.1 Basic Aspects 221

10.2 Towards a Microscopic Interpretation 223

10.3 Dielectric Behavior of Gases 224

10.4 Dielectric Behavior of Liquids 231

10.5 Water 238

References 249

Further Reading 250

11 Mixing Liquids: Molecular Solutions 251

11.1 Basic Aspects 251

11.2 Ideal and Real Solutions 256

11.3 Colligative Properties 260

11.4 Ideal Behavior in Statistical Terms 262

11.5 The Regular Solution Model 265

11.6 A Slightly Different Approach 272

11.7 The Activity Coefficient for Other Composition Measures 277

11.8 Empirical Improvements 278

11.9 Theoretical Improvements 281

References 283

Further Reading 284

12 Mixing Liquids: Ionic Solutions 285

12.1 Ions in Solution 285

12.2 The Born Model and Some Extensions 289

12.3 Hydration Structure 293

12.4 Strong and Weak Electrolytes 300

12.5 Debye–Hückel Theory 303

12.6 Structure and Thermodynamics 308

12.7 Conductivity 311

12.8 Conductivity Continued 317

12.9 Final Remarks 323

References 323

Further Reading 324

13 Mixing Liquids: Polymeric Solutions 325

13.1 Polymer Configurations 325

13.2 Real Chains in Solution 333

13.3 The Florry–Huggins Model 339

13.4 Solubility Theory 347

13.5 EoS Theories 352

13.6 The SAFT Approach 361

References 368

Further Reading 369

14 Some Special Topics: Reactions in Solutions 371

14.1 Kinetics Basics 371

14.2 Transition State Theory 373

14.3 Solvent Effects 379

14.4 Diffusion Control 381

14.5 Reaction Control 384

14.6 Neutral Molecules 385

14.7 Ionic Solutions 387

14.8 Final Remarks 392

References 393

Further Reading 393

15 Some Special Topics: Surfaces of Liquids and Solutions 395

15.1 Thermodynamics of Surfaces 395

15.2 One-Component Liquid Surfaces 402

15.3 Gradient Theory 409

15.4 Two-Component Liquid Surfaces 413

15.5 Statistics of Adsorption 415

15.6 Characteristic Adsorption Behavior 417

15.7 Final Remarks 425

References 425

Further Reading 427

16 Some Special Topics: Phase Transitions 429

16.1 Some General Considerations 429

16.2 Discontinuous Transitions 434

16.3 Continuous Transitions and the Critical Point 437

16.4 Scaling 447

16.5 Renormalization 451

16.6 Final Remarks 457

References 457

Further Reading 458

Appendix A Units, Physical Constants, and Conversion Factors 459

Basic and Derived SI Units 459

Physical Constants 460

Conversion Factors for Non-SI Units 460

Prefixes 460

Greek Alphabet 461

Standard Values 461

Appendix B Some Useful Mathematics 463

B.1 Symbols and Conventions 463

B.2 Partial Derivatives 463

B.3 Composite, Implicit, and Homogeneous Functions 465

B.4 Extremes and Lagrange Multipliers 467

B.5 Legendre Transforms 468

B.6 Matrices and Determinants 469

B.7 Change of Variables 471

B.8 Scalars, Vectors, and Tensors 473

B.9 Tensor Analysis 477

B.10 Calculus of Variations 480

B.11 Gamma Function 481

B.12 Dirac and Heaviside Function 482

B.13 Laplace and Fourier Transforms 482

B.14 Some Useful Integrals and Expansions 484

Further Reading 486

Appendix C The Lattice Gas Model 487

C.1 The Lattice Gas Model 487

C.2 The Zeroth Approximation or Mean Field Solution 488

C.3 The First Approximation or Quasi-Chemical Solution 490

C.3.1 Pair Distributions 491

C.3.2 The Helmholtz Energy 492

C.3.3 Critical Mixing 493

C.4 Final Remarks 494

References 494

Appendix D Elements of Electrostatics 495

D.1 Coulomb, Gauss, Poisson, and Laplace 495

D.2 A Dielectric Sphere in a Dielectric Matrix 498

D.3 A Dipole in a Spherical Cavity 500

Further Reading 501

Appendix E Data 503

References 512

Appendix F Numerical Answers to Selected Problems 513

Index 515

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Author Information

Gijsbertus de With is full professor in materials science. He graduated from Utrecht State University and received his PhD in 1977 from the
University of Twente on the 'Structure and charge distribution of molecular crystals'. In the same year he joined Philips Research
Laboratories, Eindhoven. In 1985 he was appointed part-time professor and in 1996 he became full professor at the Eindhoven University
of Technology. Since 2006 he is also chairman of the Soft Matter CryoTEM Research Unit. His research interests cover structural and
interfacial phenomena in relation to the processing and behavior of multi-phase materials. He has (co)-authored more than 250 research
papers and holds about 20 patents. He is a member of the Advisory board of the J. Eur. Ceram. Soc. and is presently co-organizer of the
annual Coatings Science International conferences. In 2006 his twovolume monograph Structure, Deformation, and Integrity of Materials
was published.
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