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

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. INDICE: 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

• ISBN: 978-3-527-33322-6
• Editorial: Wiley VCH
• Encuadernacion: Cartoné
• Páginas: 560
• Fecha Publicación: 14/08/2013
• Nº Volúmenes: 1
• Idioma: Inglés