This publication is presented to you through Paradigm Publishing Services
University of California Press
Chapter
Licensed
Unlicensed
Requires Authentication
18. More general proof of the entropy theorem. Treatment of the equations corresponding to the stationary state
-
Ludwig Boltzmann
You are currently not able to access this content.
You are currently not able to access this content.
Chapters in this book
- Frontmatter I
- CONTENTS V
- Translator's Introduction 1
-
PART I THEORY OF GASES WITH MONATOMIC MOLECULES, WHOSE DIMENSIONS ABE NEGLIGIBLE COMPARED TO THE MEAN FREE PATH
- NOTE ON LITERATURE CITATIONS 20
- Foreword 21
- Introduction 23
- 1. Mechanical analogy for the behavior of a gas 23
- 2. Calculation of the pressure of a gas 30
- CHAPTER I THE MOLECULES ARE ELASTIC SPHERES. EXTERNAL FORCES AND VISIBLE MASS MOTION ABE ABSENT 36
- 3. Maxwell's proof of the velocity distribution law; frequency of collisions 36
- 4. Continuation; values of the variables after the collision; collisions of the opposite kind 43
- 5. Proof that Maxwell's velocity distribution is the only possible one 49
- 6. Mathematical meaning of the quantity H 55
- 7. The Boyle-Charles-Avogadro law. Expression for the heat supplied 62
- 8. Specific heat. Physical meaning of the quantity H 68
- 9. Number of collisions 75
- 10. Mean free path 82
- 11. Basic equation for the transport of any quantity by the molecular motion 87
- 12. Electrical conduction and viscosity of the gas 91
- 13. Heat conduction and diffusion of the gas 98
- 14. Two kinds of approximations; diffusion of two different gases 104
- CHAPTER II THE MOLECULES ABE CENTERS OF FORCE. CONSIDERATION OF EXTERNAL FORCES AND VISIBLE MOTIONS OF THE GAS 110
- 15. Development of partial differential equations for f and F 110
- 16. Continuation. Discussion of the effects of collisions 114
- 17. Time-derivatives of sums over all molecules in a region 123
- 18. More general proof of the entropy theorem. Treatment of the equations corresponding to the stationary state 131
- 19. Aerostatics. Entropy of a heavy gas whose motion does not violate Equations (147) 141
- 20. General form of the hydrodynamic equations 147
- CHAPTER III THE MOLECULES REPEL EACH OTHER WITH A FORCE INVERSELY PROPORTIONAL TO THE FIFTH POWER OF THEIR DISTANCE 161
- 21. Integration of the terms resulting from collisions 161
- 22. Relaxation time. Hydrodynamic equations corrected for viscosity. Calculation of Bb using spherical functions 172
- 23. Heat conduction. Second method of approximate calculations 182
- 24. Entropy for the case when Equations (147) are not satisfied. Diffusion 197
-
PART II VAN DER WAALS' THEORY; GASES WITH COMPOUND MOLECULES; GAS DISSOCIATION ; CONCLUDING REMARKS
- Foreword 215
- CHAPTER I FOUNDATIONS OF VAN DER WAALS' THEORY 217
- 1. General viewpoint of van der Waals 217
- 2. External and internal pressure 220
- 3. Number of collisions against the wall 221
- 4. Relation between molecular extension and collision number 222
- 5. Determination of the impulse imparted to the molecules 224
- 6. Limits of validity of the approximations made in §4 226
- 7. Determination of internal pressure 227
- 8. An ideal gas as a thermometric substance 230
- 9. Temperature-pressure coefficient. Determination of the constants of van der Waals' equation 231
- 10. Absolute temperature. Compression coefficient 234
- 11. Critical temperature, critical pressure, and critical volume 236
- 12. Geometric discussion of the isotherms 240
- 13. Special cases 243
- CHAPTER II PHYSICAL DISCUSSION OF THE VAN DER WAALS' THEORY 246
- 14. Stable and unstable states 246
- 15. Undercooling. Delayed evaporation 248
- 16. Stable coexistence of both phases 250
- 17. Geometric representation of the states in which two phases coexist 253
- 18. Definition of the concepts gas, vapor, and liquid 256
- 19. Arbitrariness of the definitions of the preceding section 257
- 20. Isopycnic changes of state 259
- 21. Calorimetry of a substance following van der Waals' law 261
- 22. Size of the molecule 264
- 23. Relations to capillarity 265
- 24. Work of separation of the molecules 268
- CHAPTER III PRINCIPLES OF GENERAL MECHANICS NEEDED FOR GAS THEORY 271
- 25. Conception of the molecule as a mechanical system characterized by generalized coordinates 271
- 26. Liouville's Theorem 274
- 27. On the introduction of new variables in a product of differentials 278
- 28. Application to the formulas of §26 283
- 29. Second proof of Liouville's theorem 285
- 30. Jacobi's theorem of the last multiplier 290
- 31. Introduction of the energy differential 294
- 32. Ergoden 297
- 33. Concept of the momentoid 300
- 34. Expression for the probability; average values 304
- 35. General relationship to temperature equilibrium 310
- CHAPTER IV GASES WITH COMPOUND MOLECULES 313
- 36. Special treatment of compound molecules 313
- 37. Application of Kirchhoff's method to gases with compound molecules 315
- 38. On the possibility that the states of a very large number of molecules can actually lie within very narrow limits 317
- 39. Treatment of collisions of two molecules 319
- 40. Proof that the distribution of states assumed in §37 will not be changed by collisions 323
- 41. Generalizations 325
- 42. Mean value of the kinetic energy corresponding to a momentoid 327
- 43. The ratio of specific heats, K 331
- 44. Value of k for special cases 332
- 45. Comparison with experiment 334
- 46. Other mean values 336
- 47. Treatment of directly interacting molecules 338
- CHAPTER V DERIVATION OF VAN DER WAALS' EQUATION BY MEANS OF THE VIRIAL CONCEPT 341
- 48. Specification of the point at which van der Waals' mode of reasoning requires improvement 341
- 49. More general concept of the virial 342
- 50. Virial of the external pressure acting on a gas 344
- 51. Probability of finding the centers of two molecules at a given distance 346
- 52. Contribution to the virial resulting from the finite extension of the molecules 350
- 53. Virial of the van der Waals cohesion force 352
- 54. Alternatives to van der Waals' formulas 354
- 55. Virial for any arbitrary law of repulsion of the molecules 356
- 56. The principle of Lorentz's method 358
- 57. Number of collisions 361
- 58. More exact value of the mean free path. Calculation of W/ according to Lorentz's method 364
- 59. More exact calculation of the space available for the center of a molecule 365
- 60. Calculation of the pressure of the saturated vapor from the laws of probability 367
- 61. Calculation of the entropy of a gas satisfying van der Waals' assumptions, using the calculus of probabilities 370
- CHAPTER VI THEORY OF DISSOCIATION 376
- 62. Mechanical picture of the chemical affinity of monovalent similar atoms 376
- 63. Probability of chemical binding of an atom with a similar one 379
- 64. Dependence of the degree of dissociation on pressure 383
- 65. Dependence of the degree of dissociation on temperature 385
- 66. Numerical calculations 389
- 67. Mechanical picture of the affinity of two dissimilar monovalent atoms 393
- 68. Dissociation of a molecule into two heterogeneous atoms 396
- 69. Dissociation of hydrogen iodide gas 398
- 70. Dissociation of water vapor 399
- 71. General theory of dissociation 402
- 72. Relation of this theory to that of Gibbs 406
- 73. The sensitive region is uniformly distributed around the entire atom 408
- CHAPTER VII SUPPLEMENTS TO THE LAWS OF THERMAL EQUILIBRIUM IN GASES WITH COMPOUND MOLECULES 412
- 74. Definition of the quantity H, which measures the probabilities of states 412
- 75. Change of the quantity H through intramolecular motion 414
- 76. Characterization of the first special case considered 415
- 77. Form of Liouville's theorem in the special case considered 417
- 78. Change of the quantity if as a consequence of collisions 419
- 79. Most general characterization of the collision of two molecules 422
- 80. Application of Liouville's theorem to collisions of the most general kind 424
- 81. Method of calculation with finite differences 427
- 82. Integral expression for the most general change of H by collisions 431
- 83. Detailed specification of the case now to be considered 432
- 84. Solution of the equation valid for each collision 433
- 85. Only the atoms of a single type collide with each other 435
- 86. Determination of the probability of a particular kind of central motion 437
- 87. Characterization of our assumption about the initial state 441
- 88. On the return of a system to a former state 443
- 89. Relation to the second law of thermodynamics 444
- 90. Application to the universe 446
- 91. Application of the probability calculus in molecular physics 448
- 92. Derivation of thermal equilibrium by reversal of the time direction 450
- 93. Proof for a cyclic series of a finite number of states 453
- BIBLIOGRAPHY 454
- INDEX 483
Chapters in this book
- Frontmatter I
- CONTENTS V
- Translator's Introduction 1
-
PART I THEORY OF GASES WITH MONATOMIC MOLECULES, WHOSE DIMENSIONS ABE NEGLIGIBLE COMPARED TO THE MEAN FREE PATH
- NOTE ON LITERATURE CITATIONS 20
- Foreword 21
- Introduction 23
- 1. Mechanical analogy for the behavior of a gas 23
- 2. Calculation of the pressure of a gas 30
- CHAPTER I THE MOLECULES ARE ELASTIC SPHERES. EXTERNAL FORCES AND VISIBLE MASS MOTION ABE ABSENT 36
- 3. Maxwell's proof of the velocity distribution law; frequency of collisions 36
- 4. Continuation; values of the variables after the collision; collisions of the opposite kind 43
- 5. Proof that Maxwell's velocity distribution is the only possible one 49
- 6. Mathematical meaning of the quantity H 55
- 7. The Boyle-Charles-Avogadro law. Expression for the heat supplied 62
- 8. Specific heat. Physical meaning of the quantity H 68
- 9. Number of collisions 75
- 10. Mean free path 82
- 11. Basic equation for the transport of any quantity by the molecular motion 87
- 12. Electrical conduction and viscosity of the gas 91
- 13. Heat conduction and diffusion of the gas 98
- 14. Two kinds of approximations; diffusion of two different gases 104
- CHAPTER II THE MOLECULES ABE CENTERS OF FORCE. CONSIDERATION OF EXTERNAL FORCES AND VISIBLE MOTIONS OF THE GAS 110
- 15. Development of partial differential equations for f and F 110
- 16. Continuation. Discussion of the effects of collisions 114
- 17. Time-derivatives of sums over all molecules in a region 123
- 18. More general proof of the entropy theorem. Treatment of the equations corresponding to the stationary state 131
- 19. Aerostatics. Entropy of a heavy gas whose motion does not violate Equations (147) 141
- 20. General form of the hydrodynamic equations 147
- CHAPTER III THE MOLECULES REPEL EACH OTHER WITH A FORCE INVERSELY PROPORTIONAL TO THE FIFTH POWER OF THEIR DISTANCE 161
- 21. Integration of the terms resulting from collisions 161
- 22. Relaxation time. Hydrodynamic equations corrected for viscosity. Calculation of Bb using spherical functions 172
- 23. Heat conduction. Second method of approximate calculations 182
- 24. Entropy for the case when Equations (147) are not satisfied. Diffusion 197
-
PART II VAN DER WAALS' THEORY; GASES WITH COMPOUND MOLECULES; GAS DISSOCIATION ; CONCLUDING REMARKS
- Foreword 215
- CHAPTER I FOUNDATIONS OF VAN DER WAALS' THEORY 217
- 1. General viewpoint of van der Waals 217
- 2. External and internal pressure 220
- 3. Number of collisions against the wall 221
- 4. Relation between molecular extension and collision number 222
- 5. Determination of the impulse imparted to the molecules 224
- 6. Limits of validity of the approximations made in §4 226
- 7. Determination of internal pressure 227
- 8. An ideal gas as a thermometric substance 230
- 9. Temperature-pressure coefficient. Determination of the constants of van der Waals' equation 231
- 10. Absolute temperature. Compression coefficient 234
- 11. Critical temperature, critical pressure, and critical volume 236
- 12. Geometric discussion of the isotherms 240
- 13. Special cases 243
- CHAPTER II PHYSICAL DISCUSSION OF THE VAN DER WAALS' THEORY 246
- 14. Stable and unstable states 246
- 15. Undercooling. Delayed evaporation 248
- 16. Stable coexistence of both phases 250
- 17. Geometric representation of the states in which two phases coexist 253
- 18. Definition of the concepts gas, vapor, and liquid 256
- 19. Arbitrariness of the definitions of the preceding section 257
- 20. Isopycnic changes of state 259
- 21. Calorimetry of a substance following van der Waals' law 261
- 22. Size of the molecule 264
- 23. Relations to capillarity 265
- 24. Work of separation of the molecules 268
- CHAPTER III PRINCIPLES OF GENERAL MECHANICS NEEDED FOR GAS THEORY 271
- 25. Conception of the molecule as a mechanical system characterized by generalized coordinates 271
- 26. Liouville's Theorem 274
- 27. On the introduction of new variables in a product of differentials 278
- 28. Application to the formulas of §26 283
- 29. Second proof of Liouville's theorem 285
- 30. Jacobi's theorem of the last multiplier 290
- 31. Introduction of the energy differential 294
- 32. Ergoden 297
- 33. Concept of the momentoid 300
- 34. Expression for the probability; average values 304
- 35. General relationship to temperature equilibrium 310
- CHAPTER IV GASES WITH COMPOUND MOLECULES 313
- 36. Special treatment of compound molecules 313
- 37. Application of Kirchhoff's method to gases with compound molecules 315
- 38. On the possibility that the states of a very large number of molecules can actually lie within very narrow limits 317
- 39. Treatment of collisions of two molecules 319
- 40. Proof that the distribution of states assumed in §37 will not be changed by collisions 323
- 41. Generalizations 325
- 42. Mean value of the kinetic energy corresponding to a momentoid 327
- 43. The ratio of specific heats, K 331
- 44. Value of k for special cases 332
- 45. Comparison with experiment 334
- 46. Other mean values 336
- 47. Treatment of directly interacting molecules 338
- CHAPTER V DERIVATION OF VAN DER WAALS' EQUATION BY MEANS OF THE VIRIAL CONCEPT 341
- 48. Specification of the point at which van der Waals' mode of reasoning requires improvement 341
- 49. More general concept of the virial 342
- 50. Virial of the external pressure acting on a gas 344
- 51. Probability of finding the centers of two molecules at a given distance 346
- 52. Contribution to the virial resulting from the finite extension of the molecules 350
- 53. Virial of the van der Waals cohesion force 352
- 54. Alternatives to van der Waals' formulas 354
- 55. Virial for any arbitrary law of repulsion of the molecules 356
- 56. The principle of Lorentz's method 358
- 57. Number of collisions 361
- 58. More exact value of the mean free path. Calculation of W/ according to Lorentz's method 364
- 59. More exact calculation of the space available for the center of a molecule 365
- 60. Calculation of the pressure of the saturated vapor from the laws of probability 367
- 61. Calculation of the entropy of a gas satisfying van der Waals' assumptions, using the calculus of probabilities 370
- CHAPTER VI THEORY OF DISSOCIATION 376
- 62. Mechanical picture of the chemical affinity of monovalent similar atoms 376
- 63. Probability of chemical binding of an atom with a similar one 379
- 64. Dependence of the degree of dissociation on pressure 383
- 65. Dependence of the degree of dissociation on temperature 385
- 66. Numerical calculations 389
- 67. Mechanical picture of the affinity of two dissimilar monovalent atoms 393
- 68. Dissociation of a molecule into two heterogeneous atoms 396
- 69. Dissociation of hydrogen iodide gas 398
- 70. Dissociation of water vapor 399
- 71. General theory of dissociation 402
- 72. Relation of this theory to that of Gibbs 406
- 73. The sensitive region is uniformly distributed around the entire atom 408
- CHAPTER VII SUPPLEMENTS TO THE LAWS OF THERMAL EQUILIBRIUM IN GASES WITH COMPOUND MOLECULES 412
- 74. Definition of the quantity H, which measures the probabilities of states 412
- 75. Change of the quantity H through intramolecular motion 414
- 76. Characterization of the first special case considered 415
- 77. Form of Liouville's theorem in the special case considered 417
- 78. Change of the quantity if as a consequence of collisions 419
- 79. Most general characterization of the collision of two molecules 422
- 80. Application of Liouville's theorem to collisions of the most general kind 424
- 81. Method of calculation with finite differences 427
- 82. Integral expression for the most general change of H by collisions 431
- 83. Detailed specification of the case now to be considered 432
- 84. Solution of the equation valid for each collision 433
- 85. Only the atoms of a single type collide with each other 435
- 86. Determination of the probability of a particular kind of central motion 437
- 87. Characterization of our assumption about the initial state 441
- 88. On the return of a system to a former state 443
- 89. Relation to the second law of thermodynamics 444
- 90. Application to the universe 446
- 91. Application of the probability calculus in molecular physics 448
- 92. Derivation of thermal equilibrium by reversal of the time direction 450
- 93. Proof for a cyclic series of a finite number of states 453
- BIBLIOGRAPHY 454
- INDEX 483