Statistical thermodynamics for chemists and biochemists:
Gespeichert in:
| 1. Verfasser: | |
|---|---|
| Format: | Buch |
| Sprache: | English |
| Veröffentlicht: |
New York [u.a.]
Plenum Press
1992
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| Schlagworte: | |
| Online-Zugang: | Inhaltsverzeichnis |
| Beschreibung: | XVIII, 697 S. graph. Darst. |
| ISBN: | 0306438488 |
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Datensatz im Suchindex
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|---|---|
| adam_text | Statistical
Th ermo dynamics
for Chemists and
Biochemists
Arieh Ben-Nairn
Department of Physical Chemistry
The Hebrew University of Jerusalem
Jerusalem, Israel
Plenum Press • New York and London
Contents
Chapter 1 The Fundamental Tools 1
1 1 Introduction 1
1 2 Notation 3
1 3 The Fundamental Equations of Statistical Thermodynamics 6
131 E, V,N Ensemble 6
132 T, V,N Ensemble 7
133 T, P, N Ensemble 10
134 T, V, n Ensemble 12
1 4 Some Average Quantities 15
1 5 Classical Statistical Thermodynamics 17
1 6 The Ideal Gas 21
1 7 Pair Potential and Pairwise Additivity 24
1 8 Virial Expansion and van der Waals Equation 30
Suggested Readings 35
Chapter 2 Simple Systems without Interactions 37
2 1 Introduction 37
2 2 The Chemical Potential of an Ideal Gas 37
2 3 Mixture of Ideal Gases 39
2 4 Chemical Equilibrium in an Ideal-Gas Mixture 42
241 Simple Isomerization Equilibrium 43
242 An Analogue of the Isomerization Equilibrium 47
243 Standard Thermodynamic Quantities of a Chemical Reaction 50
244 Generalizations 52
245 Heat Capacity of a System in Chemical Equilibrium 55
2 5 Ideal Gas in an External Electric Field 57
2 6 Ideal Gas in a Gravitational or Centrifugal Field 62
2 7 Noninteracting Magnetic Dipoles in a Magnetic Field 67
2 8 Simple Adsorption Isotherms 68
281 The Molecular Model and Its Solution 69
282 Thermodynamics and the Langmuir Isotherm 71
283 Rederivation of the Langmuir Isotherm Using the
Grand Partition Function 72
284 Occupation Probabilities and Free Energy of Cavity Formation 74
285 The Analogue of the Pseudochemical Potential 78
286 Mixture of Ligands 80
287 Two Kinds of Site 80
xii CONTENTS
2 9 Multiple Occupancy of the Sites 81
291 Thermodynamic Derivation 83
292 Indistinguishable Sites 85
2 10 Adsorption with Conformation Changes in the Adsorbent Molecules 86
2 10 1 The Model and Its Solution 86
2 10 2 The Adsorption Isotherm 91
2 10 3 Thermodynamics of the Adsorption Process 94
2 10 4;i Partial Molecular Thermodynamic Quantities in the
Mixture Model Formalism 99
Suggested Readings 103
Chapter 3 Simple Systems with Interactions 105
3 1 Two Identical Sites on a Polymer: Direct Interaction between the Ligands 105
311 The Binding Isotherm 106
312 Distribution Functions 108
313 Generalizations 110
314 Some Numerical Examples 110
3 2 Two Identical Sites on a Polymer Having Two Conformational States:
Direct and Indirect Correlations 113
321 The Model and Its Solution 113
322 Probabilities 114
323 Correlation Function 116
324 Binding Helmholtz Energies on First and Second Site, Cooperativity 118
325 Energy of Binding on First and Second Sites 121
326 Cooperativity and Induced Conformational Changes 123
327 The Binding Isotherm 126
3 3 Two Subunits Each Having One Site: Allosteric Effect 127
331 The Empty Polymer 127
332 Potential of Average Force between the Subunits 130
333 The Binding Isotherm 132
334 Probabilities 133
335 Binding Helmholtz Energies on First and Second Sites 134
336 Correlation Function and Cooperativity 136
337 Energy Change for Binding on First and Second Sites 141
338 Induced Conformational Changes in the Two Subunits 142
339 Two Limiting Cases 143
3 4 Three Identical Sites on a Polymer Having Two Conformational States:
Triplet Correlations 146
341 Binding Thermodynamics 147
342 Pair Correlation Functions 149
343 Triplet Correlation Function and Triplet Potential of Average Force 151
344 Superposition Approximation: Nonadditivity of the Triplet
Potential of Average Force 153
345 The Binding Helmholtz Energy on the Third Site 155
3 5 Three Subunits, Each of Which Can Be in One of Two Conformations 157
351 The Empty System 157
352 The System with Ligands 159
CONTENTS xiii
353 Further Examination of the Correlation Functions and
Nonadditivity Effect 162
354 Cooperativity 164
3 6 The Tetrahedral Tetramer: A Minimal Model for the Binding of Oxygen
to Hemoglobin 166
361 The Model 168
362 Some Special Cases 170
363 Binding- Thermodynamics and Correlation Functions 174
364 Comparison with the Square Model 177
365 The Requirement on the First Binding Constants 178
3 7 Regulatory Enzymes 179
371 Regulation by Competitive Binding 181
372 One Polymer with One Active and One Regulatory Site 183
373A Minimal Model for a Regulatory Enzyme 186
References 189
Suggested Reading 189
Chapter 4 One-Dimensional Models 191
4 1 Introduction 191
4 2 Simplest Ising Models 191
421 One-Dimensional Model of Interacting Spins 192
422 Lattice Gas 196
423 Lattice Model of a Two-Component Mixture 198
424 Two-State Equilibrium Modulated by an External Field 200
4 3 Molecular Distribution Functions in the Ising Model 202
431 Singlet Distribution Function 202
432 Pair Distribution Function 206
433 Triplet and Higher-Order Distribution Functions 211
434 Correlation Functions 213
435 Some Examples for the Lattice Gas 215
436 An Alternative Way to Obtain the Molecular Distribution
Functions from the Partition Function 218
4 4 Some Generalizations of the Ising Model 219
441 Lattice Gas Model of a Binary Mixture 219
442 Multiple but Degenerate States 220
443 Ising Model with Nearest- and Next-Nearest-Neighbor Interactions 223
4 5 One-Dimensional Fluids 227
451 The Model and Its Solution 227
452 Thermodynamics and the Equation of State 229
453 An Alternative Derivation for Hard Rods 231
454 One-Dimensional Water 233
455 One-Dimensional Mixture of Fluids 238
456 Solvation in a One-Dimensional System 242
4 6 Phase Transition in a One-Dimensional System 243
461 The Model and Its Solution 243
462 Thermodynamics 247
463 Phase Transition in the PV Diagram 249
xiv CONTENTS
4 7 Helix-Coil Transition in Proteins 251
471 The Problem of Protein Denaturation 251
472 The Helix-Coil Transition 253
473 The Partition Function 255
References 261
Suggested Readings 261
Chapter 5 Theory of Liquids 263
5 1 Introduction 263
5 2 Molecular Distribution Functions 263
521 The Singlet Distribution Function 264
522 Pair Distribution Function 269
523 Pair Correlation Function 271
5 3 Features of the Radial Distribution Function 274
531 Ideal Gas 275
532 Very Dilute Gas 276
533 Slightly Dense Gas 277
534 Lennard-Jones Particles at Moderately High Densities 280
5 4 Potential of Average Force 282
541 Hard Spheres and Lennard-Jones Particles 286
542 Potential of Average Force and Helmholtz Energy Changes 289
55A Brief Survey of the Methods of Evaluating g(R) 292
551 Experimental Methods 292
552 Theoretical Methods 294
553 Simulation Methods 295
5 6 Higher-Order Molecular Distribution Functions 299
5 7 Molecular Distribution Functions in the Grand Canonical Ensemble 300
5 8 Molecular Distribution Functions and Thermodynamics 302
581 Average Values of Pairwise Quantities 302
582 Internal Energy 305
583 The Pressure Equation 307
584 The Compressibility Equation 310
5 9 The Chemical Potential 314
591 The General Expression 315
592 Continuous Coupling of the Binding Energy 317
593 The Pseudochemical Potential 320
594 Building Up the Density of the System 321
595 First-Order Expansion of the Coupling Work 322
596 Some Generalizations 323
597 Other Ensembles 324
5 10 The Work Required to Form a Cavity in a Fluid 324
5 10 1 Spherical Cavity 325
5 10 2 Cavity Formation and the Pseudochemical Potential of a
Hard Sphere 327
5 10 3 Nonspherical Cavities 329
5 11 Elements of the Scaled-Particle Theory 331
5 12 Perturbation Theories of Liquids 337
CONTENTS xv
5 13 Generalized Molecular Distribution Functions 340
5 13 1 The Singlet Generalized Molecular Distribution Function 340
5 13 2 Coordination Number 341
5 13 3 Binding Energy 344
5 13 4 Volume of the Voronoi Polyhedron 344
5 13 5 Combination of Properties 346
5 13 6 Some Illustrative Examples 346
5 13 7 TheiMixture Model Approach to Liquids 349
5 13 8 General Relations between Thermodynamics and
Quasicomponent Distribution Functions 350
5 13 9 Reinterpretation of Some Thermodynamic Quantities Using the
Mixture Model Approach 352
5 13 10 Some Thermodynamic Identities in the Mixture Model Approach 354
References 356
Suggested Readings 357
Chapter 6 Theory of Solutions 359
6 1 Introduction 359
6 2 Molecular Distribution Functions in Mixtures: Definitions 359
6 3 Molecular Distribution Functions in Mixtures: Properties 362
6 4 Potential of Average Force in Mixtures 367
6 5 Mixtures of Very Similar Components 369
6 6 Very Dilute Solution of A in B 371
6 7 The Kirkwood-Buff Theory of Solutions 372
671 General Derivation 373
672 Two-Component Systems 377
673 Inversion of the Kirkwood-Buff Theory 380
6 8 Symmetric Ideal Solutions: Necessary and Sufficient Conditions 382
681 Necessary and Sufficient Conditions 383
682 Small Deviations from Symmetric Ideal (SI) Solutions 386
6 9 Dilute Ideal Solutions 387
691 Limiting Behavior of the Chemical Potential 387
692 Small Deviations from Dilute Ideal Solutions 390
6 10 A Completely Solvable Example 394
6 10 1 Ideal-Gas Mixture as a Reference System 396
6 10 2 Symmetric Ideal Solution as a Reference System 397
6 10 3 Dilute Ideal Solution as a Reference System 397
6 11 The McMillan-Mayer Theory of Solutions 398
6 11 1 Derivation 399
6 11 2 The Virial Expansion of the Osmotic Pressure 402
6 12 Electrolyte Solutions 405
6 12 1 Dissociation into Ions 406
6 12 2 Deviations from Ideality Due to Long-Range Interactions 407
6 12 3 The Debye-Huckel Theory 409
6 12 4 The Poisson-Boltzmann Equation 411
6 12 5 Calculation of the Activity Coefficient 416
xvi CONTENTS
6 12 6 The Concept of the Ionic Atmosphere 417
6 12 7 Excess Thermodynamic Quantities 419
6 12 8 The Debye Charging Process 420
6 13 Solvation Thermodynamics 421
6 13 1 Definition of the Solvation Process 421
6 13 2 Calculation of the Thermodynamic Quantities of Solvation from
Experimental Data 424
6 13 Jfj Solvation of Inert-Gas Molecules 430
6 14 Conditional Solvation and the Pair Correlation Function 433
6 14 1 Conditional Solvation Helmholtz Energy: Hard and Soft Parts 436
6 14 2 Conditional Solvation Helmholtz Energy: Group Additivity 438
6 15 The Solvation Helmholtz Energy of a Molecule Having Internal
Rotational Degrees of Freedom 440
6 16 Solvation Thermodynamics of Completely Dissociable Solutes 444
6 17 Preferential Solvation 448
6 17 1 Formulation of the Problem for a Three-Component System 450
6 17 2 Relation between Preferential Solvation and Measurable Quantities 452
6 17 3 Preferential Solvation in a Two-Component System 455
References 457
Suggested Readings 457
Chapter 7 Water and Aqueous Solutions 459
7 1 Introduction 459
7 2 Survey of Some Properties of Pure Water 461
7 3 The Radial Distribution Function of Water 465
7 4 Effective Pair Potential for Water 467
7 5 Second Virial Coefficients of Water 472
7 6 The Structure of Water and the Mixture Model Approach to the Theory
of Water 474
7 7 Solvation of Water in Pure Water 477
7 8 Distribution of Species of Water Molecules 482
7 9 Applications of the Mixture Model Approach 485
791 Construction of an Exact Two-Structure Model 485
792A Prototype of an Interstitial Lattice Model for Water 491
7 10 Aqueous Solutions of Simple Solutes: Properties 497
7 10 1 Survey of Some Properties of Simple Aqueous Solutions 498
7 10 2 Hydrophobicity and Conditional Hydrophobicity 502
7 11 Formal Statistical Mechanical Expressions for the Solvation Quantities
in Water 503
7 12 Application of the Mixture Model Approach to Aqueous Solutions of
Simple Solutes 508
7 12 1 Application of a Two-Structure Model 509
7 12 2 Application of an Interstitial Lattice Model 512
7 13 The Problem of Stabilization of the Structure of Water by Simple Solutes 516
7 13 1 An Argument Based on the Kirkwood-Buff Theory 518
7 13 2 An Exact Argument for a Hypothetical Solute 523
7 13 3 How Much Structural Change Is Induced by the Solute? 524
7 14 Solvent-Induced Interactions and Forces 525
CONTENTS xvii
7 15 Two Simple Nonpolar Solutes: Hydrophobic Interaction 530
7 16 Interaction between Two Hydrophilic Solvatons 537
7 16 1 Hcpl Interaction at R, « 2 76 A 539
7 16 2 H0I Interaction at R2 =45A 542
7 17 Mixed H0O-H0I Interactions 545
7 18 Generalization to Many Solutes 549
7 18 1 An Improved Approximate Measure of the H0O Interaction 550
7 18 2 H^Oflnteraction among Many Solute Particles Forming a
Compact Aggregate in Water 553
Reference 559
Suggested Readings 559
Chapter 8 Solvent Effects on Processes in Aqueous Solutions 561
8 1 Introduction 561
8 2 From Pair Potential to Potential of Average Force 562
8 3 Chemical Reaction 564
8 4 Simple Langmuir Isotherms in Solution 567
841 Langmuir Isotherm in Solution with No Conformational Changes 567
842 Langmuir Isotherm with Conformational Changes 569
8 5 Allosteric Systems in Solution 573
851 Ligand-Ligand Correlation Mediated by the Solvent 573
852 Ligand-Ligand Correlation Mediated by the Polymer and
the Solvent 577
8 6 One-Dimensional Models in a Solvent 579
861 The General Modification of the PF of a 1-D System in Solution 580
862 1-D Water in Liquid Water 585
863 The Helix-Coil Transition in a Solvent 588
8 7 Protein-Protein Association and Molecular Recognition 590
871 Formal Separation of the Solvent Effects 591
872 Classification of the Various Contributions to SG 594
873 Methods of Estimating the Various Contributions to SG 600
874 Selection of Specific Binding Site: Molecular Recognition 603
875 Averaging over All Conformations of P, L, and PL 612
876 Solvent-Induced Forces between Macromolecules 614
8 8 Protein Folding 618
881 Formal Separation of Solvent Effects 620
882 Methods of Estimating the Various Contributions to SG 623
883 Force in Protein Folding 625
884 The Solvent Effect on the Specificity of the Protein-Folding
Pathway 628
885 Possible Solvent-Induced Effects on the Formation of the a Helix 634
8 9 Aggregation and Self-Assembly in Aqueous Solutions 636
891 Formation of Micelles in Aqueous Solutions 636
892 Solubilization 643
893 Self-Assembly of Macromolecules 645
8 10 Solute Effects on Processes in Aqueous Solutions 647
8 10 1 Solubility 648
xviii CONTENTS
8 10 2 Solute Effect on the Solvation Gibbs Energy of a Molecule
with a Fixed Conformation 651
8 10 3 Solute Effect on the Solvation Gibbs Energy of a Molecule
Having Two Conformations 654
8 10 4 Conclusion 655
Suggested Readings 656
Appendix A Some Geometries Involving Hydrogen Bonding 657
Appendix B On the Extent of Independence of the Conditional Solvation Gibbs
Energies of the Four Arms of a Water Molecule 661
Appendix C Estimate of the Solvent-Induced Interactions between Two, Three,
and Four H j I Groups 665
Appendix D Local Densities of Water Molecules near H(j)I Groups Having a
Fixed Orientation 669
Appendix E The Chemical Potential in Various Ensembles 673
Appendix F Estimates of the PAVf Term for Some Simple Solvation Processes 675
Appendix G Transfer ability of the Conditional Solvation Gibbs Energy 6 7 7
Appendix H Selected Values of the Conditional Solvation Gibbs Energies
of Some Groups Attached to Small Model Compounds 683
Appendix I Correlation Functions in the Canonical and Grand
Canonical Ensembles 685
Appendix J A Simplified Expression for the Derivative of the Chemical
Potential with Respect to the Number of Particles 689
List of Abbreviations 693
Index 695
|
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| illustrated | Illustrated |
| indexdate | 2024-07-09T16:31:19Z |
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| isbn | 0306438488 |
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| publisher | Plenum Press |
| record_format | marc |
| spelling | Ben-Naim, Arieh 1934- Verfasser (DE-588)138575460 aut Statistical thermodynamics for chemists and biochemists Arieh Ben-Naim New York [u.a.] Plenum Press 1992 XVIII, 697 S. graph. Darst. txt rdacontent n rdamedia nc rdacarrier Chimie physique et théorique Chimie physique et théorique ram Thermodynamique statistique Thermodynamique statistique ram Chemie (DE-588)4009816-3 gnd rswk-swf Biochemie (DE-588)4006777-4 gnd rswk-swf Statistische Thermodynamik (DE-588)4126251-7 gnd rswk-swf Chemie (DE-588)4009816-3 s Statistische Thermodynamik (DE-588)4126251-7 s DE-604 Biochemie (DE-588)4006777-4 s HEBIS Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=003472300&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Ben-Naim, Arieh 1934- Statistical thermodynamics for chemists and biochemists Chimie physique et théorique Chimie physique et théorique ram Thermodynamique statistique Thermodynamique statistique ram Chemie (DE-588)4009816-3 gnd Biochemie (DE-588)4006777-4 gnd Statistische Thermodynamik (DE-588)4126251-7 gnd |
| subject_GND | (DE-588)4009816-3 (DE-588)4006777-4 (DE-588)4126251-7 |
| title | Statistical thermodynamics for chemists and biochemists |
| title_auth | Statistical thermodynamics for chemists and biochemists |
| title_exact_search | Statistical thermodynamics for chemists and biochemists |
| title_full | Statistical thermodynamics for chemists and biochemists Arieh Ben-Naim |
| title_fullStr | Statistical thermodynamics for chemists and biochemists Arieh Ben-Naim |
| title_full_unstemmed | Statistical thermodynamics for chemists and biochemists Arieh Ben-Naim |
| title_short | Statistical thermodynamics for chemists and biochemists |
| title_sort | statistical thermodynamics for chemists and biochemists |
| topic | Chimie physique et théorique Chimie physique et théorique ram Thermodynamique statistique Thermodynamique statistique ram Chemie (DE-588)4009816-3 gnd Biochemie (DE-588)4006777-4 gnd Statistische Thermodynamik (DE-588)4126251-7 gnd |
| topic_facet | Chimie physique et théorique Thermodynamique statistique Chemie Biochemie Statistische Thermodynamik |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=003472300&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
| work_keys_str_mv | AT bennaimarieh statisticalthermodynamicsforchemistsandbiochemists |