Ebook
Physical Chemistry: How Chemistry WorksISBN: 9781118751206
744 pages
October 2016

Description
Much of chemistry is motivated by asking 'How'? How do I make a primary alcohol? React a Grignard reagent with formaldehyde. Physical chemistry is motivated by asking 'Why'? The Grignard reagent and formaldehyde follow a molecular dance known as a reaction mechanism in which stronger bonds are made at the expense of weaker bonds. If you are interested in asking 'why' and not just 'how', then you need to understand physical chemistry.
Physical Chemistry: How Chemistry Works takes a fresh approach to teaching in physical chemistry. This modern textbook is designed to excite and engage undergraduate chemistry students and prepare them for how they will employ physical chemistry in real life. The studentfriendly approach and practical, contemporary examples facilitate an understanding of the physical chemical aspects of any system, allowing students of inorganic chemistry, organic chemistry, analytical chemistry and biochemistry to be fluent in the essentials of physical chemistry in order to understand synthesis, intermolecular interactions and materials properties. For students who are deeply interested in the subject of physical chemistry, the textbook facilitates further study by connecting them to the frontiers of research.
 Provides students with the physical and mathematical machinery to understand the physical chemical aspects of any system.
 Integrates regular examples drawn from the literature, from contemporary issues and research, to engage students with relevant and illustrative details.
 Important topics are introduced and returned to in later chapters: key concepts are reinforced and discussed in more depth as students acquire more tools.
 Chapters begin with a preview of important concepts and conclude with a summary of important equations.
 Each chapter includes worked examples and exercises: discussion questions, simple equation manipulation questions, and problemsolving exercises.
 Accompanied by supplementary online material: worked examples for students and a solutions manual for instructors.
 Written by an experienced instructor, researcher and author in physical chemistry, with a voice and perspective that is pedagogical and engaging.
Table of Contents
Preface xv
About the companion website xvii
1 Introduction 1
1.1 Atoms and molecules 1
1.2 Phases 2
1.3 Energy 3
1.4 Chemical reactions 4
1.5 Problem solving 5
1.6 Some conventions 7
Exercises 11
Further reading 14
2 Ideal gases 15
2.1 Ideal gas equation of state 16
2.2 Molecular degrees of freedom 18
2.3 Translational energy: Distribution and relation to pressure 21
2.4 Maxwell distribution of molecular speeds 23
2.5 Principle of equipartition of energy 24
2.6 Temperature and the zeroth law of thermodynamics 25
2.7 Mixtures of gases 27
2.8 Molecular collisions 27
Exercises 29
Further reading 30
3 Nonideal gases and intermolecular interactions 31
3.1 Nonideal behavior 31
3.2 Interactions of matter with matter 32
3.3 Intermolecular interactions 34
3.4 Real gases 39
3.5 Corresponding states 42
3.6 Supercritical fluids 43
Exercises 43
Further reading 44
4 Liquids, liquid crystals, and ionic liquids 45
4.1 Liquid formation 45
4.2 Properties of liquids 45
4.3 Intermolecular interaction in liquids 47
4.4 Structure of liquids 50
4.5 Internal energy and equation of state of a rigid sphere liquid 52
4.6 Concentration units 53
4.7 Diffusion 55
4.8 Viscosity 57
4.9 Migration 59
4.10 Interface formation 60
4.11 Liquid crystals 62
4.12 Ionic liquids 64
Exercises 66
Further reading 67
5 Solids, nanoparticles, and interfaces 68
5.1 Solid formation 68
5.2 Electronic structure of solids 70
5.3 Geometrical structure of solids 72
5.4 Interface formation 76
5.5 Glass formation 78
5.6 Clusters and nanoparticles 78
5.7 The carbon family: Diamond, graphite, graphene, fullerenes, and carbon nanotubes 80
5.8 Porous solids 83
5.9 Polymers and macromolecules 84
Exercises 86
Endnotes 86
Further reading 86
6 Statistical mechanics 87
6.1 The initial state of the universe 88
6.2 Microstates and macrostates of molecules 89
6.3 The connection of entropy to microstates 91
6.4 The constant α: Introducing the partition function 93
6.5 Using the partition function to derive thermodynamic functions 94
6.6 Distribution functions for gases 96
6.7 Quantum statistics for particle distributions 98
6.8 The Maxwell–Boltzmann speed distribution 102
6.9 Derivation of the ideal gas law 103
6.10 Deriving the Sackur–Tetrode equation for entropy of a monatomic gas 104
6.11 The partition function of a diatomic molecule 106
6.12 Contributions of each degree of freedom to thermodynamic functions 106
6.13 The total partition function and thermodynamic functions 111
6.14 Polyatomic molecules 113
Exercises 115
Endnotes 116
Further reading 116
7 First law of thermodynamics 117
7.1 Some definitions and fundamental concepts in thermodynamics 118
7.2 Laws of thermodynamics 118
7.3 Internal energy and the first law 119
7.4 Work 121
7.5 Intensive and extensive variables 123
7.6 Heat 124
7.7 Nonideal behavior changes the work 125
7.8 Heat capacity 126
7.9 Temperature dependence of Cp 127
7.10 Internal energy change at constant volume 129
7.11 Enthalpy 130
7.12 Relationship between CV and Cp and partial differentials 131
7.13 Reversible adiabatic expansion/compression 133
Exercises 136
Endnotes 138
Further reading 138
8 Second law of thermodynamics 139
8.1 The second law of thermodynamics 140
8.2 Thermodynamics of a hurricane 141
8.3 Heat engines, refrigeration, and heat pumps 145
8.4 Definition of entropy 148
8.5 Calculating changes in entropy 150
8.6 Maxwell's relations 152
8.7 Calculating the natural direction of change 154
Exercises 157
Endnotes 159
Further reading 159
9 Third law of thermodynamics and temperature dependence of heat capacity, enthalpy and entropy 160
9.1 When and why does a system change? 160
9.2 Natural variables of internal energy 161
9.3 Helmholtz and Gibbs energies 162
9.4 Standard molar Gibbs energies 163
9.5 Properties of the Gibbs energy 164
9.6 The temperature dependence of ΔrCp and H 168
9.7 Third law of thermodynamics 170
9.8 The unattainability of absolute zero 171
9.9 Absolute entropies 172
9.10 Entropy changes in chemical reactions 173
9.11 Calculating ΔrS· at any temperature 175
Exercises 177
Further reading 180
10 Thermochemistry: The role of heat in chemical and physical changes 181
10.1 Stoichiometry and extent of reaction 181
10.2 Standard enthalpy change 182
10.3 Calorimetry 184
10.4 Phase transitions 187
10.5 Bond dissociation and atomization 190
10.6 Solution 191
10.7 Enthalpy of formation 192
10.8 Hess's law 192
10.9 Reaction enthalpy from enthalpies of formation 193
10.10 Calculating enthalpy of reaction from enthalpies of combustion 194
10.11 The magnitude of reaction enthalpy 195
Exercises 196
Further reading 200
11 Chemical equilibrium 201
11.1 Chemical potential and Gibbs energy of a reaction mixture 201
11.2 The Gibbs energy and equilibrium composition 202
11.3 The response of equilibria to change 204
11.4 Equilibrium constants and associated calculations 209
11.5 Acid–base equilibria 212
11.6 Dissolution and precipitation of salts 216
11.7 Formation constants of complexes 219
11.8 Thermodynamics of selfassembly 222
Exercises 224
Endnote 228
Further reading 228
12 Phase stability and phase transitions 229
12.1 Phase diagrams and the relative stability of solids, liquids, and gases 229
12.2 What determines relative phase stability? 232
12.3 The p–T phase diagram 234
12.4 The Gibbs phase rule 237
12.5 Theoretical basis for the p–T phase diagram 238
12.6 Clausius–Clapeyron equation 240
12.7 Surface tension 242
12.8 Nucleation 246
12.9 Construction of a liquid–vapor phase diagram at constant pressure 250
12.10 Polymers: Phase separation and the glass transition 252
Exercises 254
Endnotes 255
Further reading 256
13 Solutions and mixtures: Nonelectrolytes 257
13.1 Ideal solution and the standard state 258
13.2 Partial molar volume 258
13.3 Partial molar Gibbs energy = chemical potential 259
13.4 The chemical potential of a mixture and ΔmixG 261
13.5 Activity 263
13.6 Measurement of activity 264
13.7 Classes of solutions and their properties 269
13.8 Colligative properties 273
13.9 Solubility of polymers 277
13.10 Supercritical CO2 279
Exercises 281
Endnote 282
Further reading 282
14 Solutions of electrolytes 283
14.1 Why salts dissolve 283
14.2 Ions in solution 284
14.3 The thermodynamic properties of ions in solution 287
14.4 The activity of ions in solution 289
14.5 Debye–Hückel theory 290
14.6 Use of activities in equilibrium calculations 292
14.7 Charge transport 295
Exercises 298
Further reading 299
15 Electrochemistry: The chemistry of free charge exchange 300
15.1 Introduction to electrochemistry 301
15.2 The electrochemical potential 306
15.3 Electrochemical cells 310
15.4 Potential difference of an electrochemical cell 312
15.5 Surface charge and potential 318
15.6 Relating work functions to the electrochemical series 319
15.7 Applications of standard potentials 321
15.8 Biological oxidation and protoncoupled electron transfer 326
Exercises 329
Endnotes 331
Further reading 332
16 Empirical chemical kinetics 333
16.1 What is chemical kinetics? 333
16.2 Rates of reaction and rate equations 335
16.3 Elementary versus composite reactions 336
16.4 Kinetics and thermodynamics 337
16.5 Kinetics of specific orders 338
16.6 Reaction rate determination 345
16.7 Methods of determining reaction order 346
16.8 Reversible reactions and the connection of rate constants to equilibrium constants 348
16.9 Temperature dependence of rates and the rate constant 350
16.10 Microscopic reversibility and detailed balance 353
16.11 Ratedetermining step (RDS) 354
Exercises 355
Endnotes 359
Further reading 359
17 Reaction dynamics I: Mechanisms and rates 360
17.1 Linking empirical kinetics to reaction dynamics 360
17.2 Hardsphere collision theory 361
17.3 Activation energy and the transition state 364
17.4 Transitionstate theory (TST) 366
17.5 Composite reactions and mechanisms 368
17.6 The rate of unimolecular reactions 372
17.7 Desorption kinetics 374
17.8 Langmuir (direct) adsorption 378
17.9 Precursormediated adsorption 380
17.10 Adsorption isotherms 381
17.11 Surmounting activation barriers 382
Exercises 386
Endnotes 389
Further reading 390
18 Reaction dynamics II: Catalysis, photochemistry and charge transfer 391
18.1 Catalysis 392
18.2 Heterogeneous catalysis 393
18.3 Acid–base catalysis 402
18.4 Enzyme catalysis 403
18.5 Chain reactions 407
18.6 Explosions 410
18.7 Photochemical reactions 411
18.8 Charge transfer and electrochemical dynamics 415
Exercises 428
Endnotes 431
Further reading 431
19 Developing quantum mechanical intuition 433
19.1 Classical electromagnetic waves 434
19.2 Classical mechanics to quantum mechanics 443
19.3 Necessity for an understanding of quantum mechanics 444
19.4 Quantum nature of light 448
19.5 Wave–particle duality 449
19.6 The Bohr atom 453
Exercises 458
Endnotes 460
Further reading 461
20 The quantum mechanical description of nature 462
20.1 What determines if a quantum description is necessary? 463
20.2 The postulates of quantum mechanics 463
20.3 Wavefunctions 464
20.4 The Schrödinger equation 467
20.5 Operators and eigenvalues 469
20.6 Solving the Schrödinger equation 471
20.7 Expectation values 475
20.8 Orthonormality and superposition 477
20.9 Dirac notation 480
20.10 Developing quantum intuition 481
Exercises 486
Endnotes 488
Further reading 488
21 Model quantum systems 489
21.1 Particle in a box 490
21.2 Quantum tunneling 495
21.3 Vibrational motion 497
21.4 Angular momentum 500
Exercises 511
Endnotes 513
Further reading 513
22 Atomic structure 514
22.1 The hydrogenl atom 515
22.2 How do you make it better? the Dirac equation 518
22.3 Atomic orbitals 520
22.4 Manyelectron atoms 524
22.5 Ground and excited states of He 528
22.6 Slater–Condon theory for approximating atomic energy levels 530
22.7 Electron configurations 533
Exercises 536
Endnotes 538
Further reading 538
23 Introduction to spectroscopy and atomic spectroscopy 539
23.1 Fundamentals of spectroscopy 540
23.2 Timedependent perturbation theory and spectral transitions 544
23.3 The Beer–Lambert law 547
23.4 Electronic spectra of atoms 550
23.5 Spin–orbit coupling 551
23.6 Russell–Saunders (LS) coupling 554
23.7 jjcoupling 559
23.8 Selection rules for atomic spectroscopy 560
23.9 Photoelectron spectroscopy 561
Exercises 566
Endnotes 569
Further reading 569
24 Molecular bonding and structure 570
24.1 Born–Oppenheimer approximation 571
24.2 Valence bond theory 573
24.3 Molecular orbital theory 576
24.4 The hydrogen molecular ion H+2 577
24.5 Solving the H2 Schrödinger equation 580
24.6 Homonuclear diatomic molecules 585
24.7 Heteronuclear diatomic molecules 588
24.8 The variational principle in molecular orbital calculations 591
24.9 Polyatomic molecules: The Hückel approximation 593
24.10 Density functional theory (DFT) 597
Exercises 598
Endnotes 601
Further reading 601
25 Molecular spectroscopy and excitedstate dynamics: Diatomics 602
25.1 Introduction to molecular spectroscopy 603
25.2 Pure rotational spectra of molecules 604
25.3 Rovibrational spectra of molecules 609
25.4 Raman spectroscopy 614
25.5 Electronic spectra of molecules 617
25.6 Excitedstate population dynamics 622
25.7 Electron collisions with molecules 628
Exercises 629
Endnotes 632
Further reading 633
26 Polyatomic molecules and group theory 634
26.1 Absorption and emission by polyatomics 635
26.2 Electronic and vibronic selection rules 637
26.3 Molecular symmetry 641
26.4 Point groups 645
26.5 Character tables 647
26.6 Dipole moments 650
26.7 Rovibrational spectroscopy of polyatomic molecules 652
26.8 Excitedstate dynamics 656
Exercises 665
Endnotes 667
Further reading 667
27 Light–matter interactions: Lasers, laser spectroscopy, and photodynamics 668
27.1 Lasers 669
27.2 Harmonic generation (SHG and SFG) 673
27.3 Multiphoton absorption spectroscopy 675
27.4 Cavity ringdown spectroscopy 682
27.5 Femtochemistry 685
27.6 Beyond perturbation theory limit: High harmonic generation 688
27.7 Attosecond physics 690
27.8 Photosynthesis 691
27.9 Color and vision 694
Exercises 697
Endnotes 698
Further reading 699
Appendix 1 Basic calculus and trigonometry 700
Appendix 2 The method of undetermined multipliers 703
Appendix 3 Stirling's theorem 705
Appendix 4 Density of states of a particle in a box 706
Appendix 5 Blackbody radiation: Treating radiation as a photon gas 708
Appendix 6 Definitions of symbols used in quantum mechanics and quantum chemistry 710
Appendix 7 Character tables 712
Appendix 8 Periodic behavior 714
Appendix 9 Thermodynamic parameters 717
Index 719
Author Information
Professor Kurt W. Kolasinski, West Chester University, Pennsylvania, USA
Kurt Kolasinski has been an Associate Professor of physical chemistry at West Chester University since 2011 having joined the faculty in 2006. He has held faculty positions at the University of Virginia (2004  2006), Queen Mary University of London (2001–2004), and the University of Birmingham (UK) (1995  2001). His research focuses on surface science, laser/surface interactions and nanoscience. A particular area of expertise is the formation of nanostructures in silicon and porous silicon using a variety of chemical and laserbased techniques. He is the author of over 90 scholarly publications as well as the widely used textbook Surface Science: Foundations of Catalysis and Nanoscience, which appeared in its third edition in 2012.