Page 11 - Modern physical chemistry

xii Contents

Problems 401 17.6 The Ideal Concentration Equilibrium
References 401 Constant 471
17.7 Basis for the Distribution Law 473
Chapter 15 17.S Black-Body Radiation 475
Phenomenonological Chemical Kinetics 405 17.9 Allowance for Particle Transfer 477
15.1 The Rate of a Reaction 405 17.10 Fenni-Dirac Statistics 479
15.2 Reaction Order and Molecularity 407 17.11 Bose-Einstein Statistics 482
15.3 Zero-Order Reactions 407 Questions 483
15.4 First-Order Reactions 408 Problems 484
15.5 Second-Order Reactions 408 References 485
15.6 Third-Order Reactions 410
15.7 Detennining the Differential Rate Law 412 Chapter 18
15.S Detennining Order from an Integrated Reaction Rate Theory 487
Form 414 IS.1 The Transition State 487
15.9 The Arrhenius Equation 416 IS.2 The Eyring Equation 489
15.10 Reversible First-Order Reactions 418 IS.3 The Kinetic Isotope Effect 492
15.11 First-Order Reaction Opposed by a IS.4 Static Nonideality 493
Second-Order Reaction 419 IS.5 Transition State Recrossings 494
15.12 Perturbation Experiments 420 IS.6 Thermodynamic Considerations 496
15.13 Reactions in High Pressure Gaseous and IS.7 Transition State Location 497
in Condensed Phases 421 IS.S Viscous Nonideality 498
15.14 The Encounter Rate Constants 422 18.9 Variation of the Rate Coefficients with
15.15 Solution Reaction Rates 424 Temperature 500
15.16 Dependence of the Specific Reaction Rate IS.10 Further Relationships 501
on Activity Coefficients 426 Questions 504
Questions 428 Problems 505
Problems 429 References 507
References 432
Chapter 19
Chapter 16 Photochemistry 509
Explanatory Mechanisms 485 19.1 Pertinent Wave Properties 509
16.1 Types of Elementary Reactions 435 19.2 Pertinent Particle Properties 510
16.2 Activation in Simple First-Order 19.3 Phenomenology of Absorption 512
Reactions 436 19.4 Absorption Intensities 514
16.3 Decomposition of Nitrogen 19.5 Electronic Transitions 515
Pentoxide 438 19.6 Reaction Possibilities 518
16.4 Hydrogen-Iodine Reactions 440 19.7 The Hydrogen-Iodine Reaction 519
16.5 Hydrogen-Bromine Reactions 442 19.5 The Hydrogen-Bromine Reaction 521
16.6 Hydrogen-Chlorine Reactions 444 19.9 The Hydrogen-Chlorine Reaction 521
16.7 Thermal Explosions 445 19.10 Photosensitization 522
16.S Hydrogen-Oxygen Reactions 448 19.11 Chemiluminescence 523
16.9 Decomposition of Ethane 451 19.12 The Carbon Monoxide-Oxygen
16.10 The Activity Coefficient Effect 452 Reaction 524
16.11 Conversion of Ammonium Cyanate to Questions 525
Urea 455 Problems 526
16.12 Nitration of Aromatic Compounds 456 References 527
Questions 458
Problems 459 Glossary 529
References 461
Appendix 1: Fundamental Units 581
Chapter 17
Statistical Thermodynamics 468 Appendix 2: Derived Units 582
17.1 Earlier Discussions 463
17.2 Relating Thermodynamic Properties to Appendix 3: Physical Constants 588
the Partition Function 463
17.3 Relating System Partition Functions to Appendix 4: Primitive Character Vectors and
Molecular Ones 466 Basis Functions for Important
17.4 Ideal Translational Entropy 468 Symmetry Groups 534
17.5 Energy and Entropy of a Vibrational
Mode 470 Index 543