Atkins' physical chemistry:
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| Main Authors: | , |
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| Format: | Book |
| Language: | English |
| Published: |
Oxford
Oxford Univ. Press
2014
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| Edition: | 10. ed. |
| Subjects: | |
| Online Access: | Inhaltsverzeichnis |
| Physical Description: | XXV, 1008 S. Ill., graph. Darst. |
| ISBN: | 9780199697403 019969740X |
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| 084 | |a CHE 100f |2 stub | ||
| 100 | 1 | |a Atkins, Peter W. |d 1940- |e Verfasser |0 (DE-588)128437782 |4 aut | |
| 245 | 1 | 0 | |a Atkins' physical chemistry |c Peter Atkins ; Julio de Paula |
| 246 | 1 | 3 | |a Physical chemistry |
| 250 | |a 10. ed. | ||
| 264 | 1 | |a Oxford |b Oxford Univ. Press |c 2014 | |
| 300 | |a XXV, 1008 S. |b Ill., graph. Darst. | ||
| 336 | |b txt |2 rdacontent | ||
| 337 | |b n |2 rdamedia | ||
| 338 | |b nc |2 rdacarrier | ||
| 650 | 4 | |a Chemistry, Physical and theoretical | |
| 650 | 4 | |a Chemistry, Physical and theoretical / Problems, exercises, etc | |
| 650 | 0 | 7 | |a Theoretische Chemie |0 (DE-588)4185098-1 |2 gnd |9 rswk-swf |
| 650 | 0 | 7 | |a Physikalische Chemie |0 (DE-588)4045959-7 |2 gnd |9 rswk-swf |
| 655 | 7 | |0 (DE-588)4123623-3 |a Lehrbuch |2 gnd-content | |
| 689 | 0 | 0 | |a Physikalische Chemie |0 (DE-588)4045959-7 |D s |
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| 689 | 1 | 0 | |a Theoretische Chemie |0 (DE-588)4185098-1 |D s |
| 689 | 1 | |8 1\p |5 DE-604 | |
| 700 | 1 | |a de Paula, Julio |e Verfasser |0 (DE-588)132130599 |4 aut | |
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Record in the Search Index
| _version_ | 1804152021049147392 |
|---|---|
| adam_text | FULL CONTENTS
List of tables xxiv
List of chemist s toolkits xxvi
Foundations 1
A Matter 2
A.i Atoms 2
(a) The nuclear model 2
(b) The periodic table 2
(c) Ions 3
A.2 Molecules 3
(a) Lewis structures 3
(b) VSEPR theory 4
(c) Polar bonds 4
A. 3 Bulk matter 5
(a) Properties of bulk matter 5
(b) The perfect gas equation 6
Checklist of concepts 7
Checklist of equations 8
B Energy 9
B. l Force 9
(a) Momentum 9
(b) Newton s second law of motion 10
B.2 Energy: a first look 11
(a) Work 11
(b) The definition of energy 11
(c) The Coulomb potential energy 12
(d) Thermodynamics 14
B. 3 The relation between molecular and bulk properties 15
(a) The Boltzmann distribution 15
(b) Equipartition 17
Checklist of concepts 17
Checklist of equations 18
C Waves 19
C. 1 Harmonic waves 19
C.2 The electromagnetic field 20
Checklist of concepts 21
Checklist of equations 22
Discussion questions and exercises 23
PART 1 Thermodynamics 27
CHAPTER 1 The properties of gases 29
Topic 1A The perfect gas 30
1A.I Variables of state 30
(a) Pressure 30
(b) Temperature 31
IA. 2 Equations of state 32
(a) The empirical basis 32
(b) Mixtures of gases 35
Checklist of concepts 36
Checklist of equations 36
Topic 1B The kinetic model 37
IB. 1 The model 37
(a) Pressure and molecular speeds 37
(b) The Maxwell-Boltzmann distribution of speeds 39
(c) Mean values 40
IB. 2 Collisions 42
(a) The collision frequency 42
(b) The mean free path 43
Checklist of concepts 44
Checklist of equations 44
Topic 1C Real gases 45
IC. 1 Deviations from perfect behaviour 45
(a) The compression factor 46
(b) Virial coefficients 47
(c) Critical constants 48
1C.2 The van der Waals equation 48
(a) Formulation of the equation 48
(b) The features of the equation 50
(c) The principle of corresponding states 52
Checklist of concepts 53
Checklist of equations 53
Discussion questions, exercises, and problems 54
Mathematical background 1 Differentiation and integration 59
CHAPTER 2 The First Law 63
Topic 2A Internal energy 64
2A.1 Work, heat, and energy 65
(a) Operational definitions 65
(b) The molecular interpretation of heat and work 66
2A.2 The definition of internal energy 66
(a) Molecular interpretation of internal energy 67
(b) The formulation of the First Law 67
2A.3 Expansion work 68
(a) The general expression for work 68
(b) Expansion against constant pressure 69
(c) Reversible expansion 70
(d) Isothermal reversible expansion 70
XÎV Full contents
2A.4 Heat transactions 71
(a) Calorimetry 71
(b) Heat capacity 72
CheiUht of concepts 74
Checkfwi of eqiwtions 74
Topic 2B Enthalpy 75
2B.1 The definition of enthalpy 75
(a) Enthalpy change and heat transfer 75
(b) Calorimetry 76
2B.2 The variation of enthalpy with temperature 77
(a) Heat capacity at constant pressure 77
(b) The relation between heat capacities 79
Checklist of concepts 79
Checklist of equations 79
Topic 2C Thermochemistry 80
2C.1 Standard enthalpy changes 80
(a) Enthalpies of physical change 81
(b) Enthalpies of chemical change 82
(c) Hess s law 83
2C.2 Standard enthalpies of formation 84
(a) The reaction enthalpy in terms of enthalpies of formation 85
(b) Enthalpies of formation and molecular modelling 85
2C.3 The temperature dependence of reaction enthalpies 86
2C.4 Experimental techniques 87
(a) Differential scanning calorimetry 87
(b) Isothermal titration calorimetry 88
’f.hpck -viC iv-r !:
Topic 2D State functions and exact differentials 90
2D.1 Exact and inexact differentials 90
2D.2 Changes in internal energy 91
la) General considerations 91
(b) Changes in internal energy at constant pressure 93
2D.3 The Joule-Thomson effect 95
(a) Observation of the Joule-Thomson effect 95
(b) The molecular interpretation of the Joule-Thomson effect 98
Chedviisi of concepts 9«
Checklist of equations 99
Topic 2E Adiabatic changes 100
2E.1 The change in temperature 100
2E.2 The change in pressure 101
Checklist of concepts 102
Checklist of equations 10}
Discussion questions, exercises, and problems 103
fVlatbematica! background 2 bk4i;vc?riai‘? cHcyCi KC
CHAPTER 3 The Second and Third Laws 112
Topic 3A Entropy 113
3A.1 The Second Law 113
3A.2 The definition of entropy 115
¡a) The thermodynamic definition of entropy 115
(b) The statistical definition of entropy 116
3A.3 The entropy as a state function 117
(a) The Carnot cycle 118
(b) The thermodynamic temperature 120
(c) The Clausius inequality 120
3A.4 Entropy changes accompanying specific processes 121
(a) Expansion 121
(b) Phase transitions 122
(c) Heating 123
(d) Composite processes 124
Checklist of concepts 124
Checklist of equations 125
Topic 3B The measurement of entropy 126
3B.1 The calorimetric measurement of entropy 126
3B.2 The Third Law 127
(a) The Nernst heat theorem 127
(b) Third-Law entropies 129
Checklist of concepts 130
Checklist of equations 130
Topic 3C Concentrating on the system 131
3C.1 The Helmholtz and Gibbs energies 131
(a) Criteria of spontaneity 131
(b) Some remarks on the Helmholtz energy 133
(c) Maximum work 133
(d) Some remarks on the Gibbs energy 134
(e) Maximum non-expansion work 135
3C.2 Standard molar Gibbs energies 136
(a) Gibbs energies of formation 136
lb) The Born equation 137
Omiiki, «b eoitcepfs 138
Ote».Kfei: (if ¡38
Topic 3D Combining the First and Second Laws 140
3D.1 Properties of the internal energy 140
(a) The Maxwell relations 141
(b) The variation of internal energy with volume 141
30.2 Properties of the Gibbs energy 142
(a) General considerations 142
(b) The variation of the Gibbs energy with temperature 144
(c) The variation of the Gibbs energy with pressure 144
(d) Thefugacity 146
Checklist of concepts 148
Checklist of equations 148
Discussion questions, exercises, and problems 149
CHAPTER 4 Physical transformations of
pure substances 154
Topic 4A Phase diagrams of pure substances 155
4A.1 The stabilities of phases 155
la) The number of phases 155
(b) Phase transitions 156
(c) Thermodynamic criteria of phase stability 156
4A.2 Phase boundaries 157
(a) Characteristic properties related to phase transitions 157
(b) The phase rule 159
4A.3 Three representative phase diagrams 160
Full contents XV
(a) Carbon dioxide 160 5C.2 Temperature-composition diagrams 206
(b) Water 161 (a) The distillation of mixtures 206
(c) Helium 162 (b) Azeotropes 207
Checklist of concepts 162 (c) Immiscible liquids 208
Checklist of equations 163 5C.3 Liquid-liquid phase diagrams 208
(a) Phase separation 208
Topic 4B Thermodynamic aspects of phase transitions 164 (b) Critical solution temperatures 209
4B.i The dependence of stability on the conditions 164 (c) The distillation of partially miscible liquids 211
(a) The temperature dependence of phase stability 165 5C.4 Liquid-solid phase diagrams 212
(b) The response of melting to applied pressure 165 (a) Eutectics 212
(c) The vapour pressure of a liquid subjected to pressure 166 (b) Reacting systems 214
4B.2 The location of phase boundaries 167 (c) Incongruent melting 214
(a) The slopes of the phase boundaries 167 Checklist of concepts 2IS
(b) The solid-liquid boundary 168 Checklist of equations 215
(c) The liquid-vapour boundary 169
(d) The solid-vapour boundary 170 Topic 5D Phase diagrams of ternary systems 216
4B,3 The Ehrenfest classification of phase transitions 171 5D.1 Triangular phase diagrams 216
(a) The thermodynamic basis 171 SD.2 Ternary systems 217
(b) Molecular interpretation 172 (a) Partially miscible liquids 217
Checklist of concepts 173 (b) Ternary solids 218
Checklist of equations 173 Checklist of concepts 219
Discussion questions, exercises, and problems 174 Topic 5E Activities 220
5E.1 The solvent activity 220
CHAPTER 5 Simple mixtures 178 5E.2 The solute activity 221
Topic 5A The thermodynamic description of mixtures 180 (a) Ideal-dilute solutions 221
5A.1 Partial molar quantities 180 (b) Real solutes 221
(a) Partial molar volume 181 (c) Activities In terms of molalities 222
(b) Partial molar Gibbs energies 182 (d) The biological standard state 222
(c) The wider significance of the chemical potential 183 5E.3 The activities of regular solutions 223
(d) The Gibbs-Duhem equation 183 Cl tuck list of concepts 224
5A.2 The thermodynamics of mixing 184 Checklist of equations 22$
(a) The Gibbs energy of mixing of perfect gases 185
(b) Other thermodynamic mixing functions 186 Topic 5F The activities of ions 226
5A.3 The chemical potentials of liquids 187 SF.i Mean activity coefficients 226
(a) Ideal solutions 187 (a) The Debye-Hiickel limiting law in
lb] Ideal-dilute solutions 188 ibi Extensions of the limiting law 228
Checklist of concepts 190 5F.2 The Debye-Hiickel theory 229
Checklist of equations 190 la] The work of charging 229
(b) The potential due to the charge distribution 229
Topic 5B The properties of solutions 192 (c) The activity coefficient 230
5B.1 Liquid mixtures 192 Checklist of concepts 232
(a) Ideal solutions 192 Checklist of equations 232
(b! Excess functions and regular solutions 193
5B.2 Colligative properties 195 Discussion questions, exercises, and problems 233
la) The common features of colligative properties 195
lb] The elevation of boiling point 196 CHAPTER 6 Chemical equilibrium 244
(c) The depression of freezing point 197 Topic 6A The equilibrium constant 245
(d) Solubility 198 6A.1 The Gibbs energy minimum 245
lei Osmosis 199 la) The reaction Gibbs energy 245
Checklist of concepts ¡fl ; b: Exergonic and endergonic reactions 246
Checklist of equations 201 6A.2 The description of equilibrium 247
a; Perfect gas equilibria 247
Topic 5C Phase diagrams of binary systems 202 b The general case of a reaction 248
5C.i Vapour pressure diagrams 202 c. The relation between equilibrium constants 251
a The composition of the vapour 202 d Molecular interpretation of the equilibrium constant 251
b The interpretation of the diagrams 203 Check¥.v concepts 25 2
¡c The lever rule 205 Checklist of equations 252
XVI Full contents
Topic 6B The response of equilibria to the conditions 6B.1 The response to pressure 6B.2 The response to temperature
(a) The van t Hoff equation
(b) The value of K at different temperatures Checklist of concepts
Checklist of equations
Topic 6C Electrochemical cells 6C.1 Half-reactions and electrodes 6C.2 Varieties of cells
(a) Liquid junction potentials
(b) Notation
6C.3 The cell potential
(a) The Nernst equation
(b) Cells at equilibrium
6C.4 The determination of thermodynamic functions
Checklist of concepts Checklist of equations
Topic 6D Electrode potentials 6D.1 Standard potentials
(a) The measurement procedure
(b) Combining measured values 6D.2 Applications of standard potentials
(a) The electrochemical series
(b) The determination of activity coefficients
(c) The determination of equilibrium constants Checklist of concepts
Checklist of equations
Discussion questions, exercises, and problems
PART 2 Structure
CHAPTER 7 Introduction to quantum theory
Topic 7A The origins of quantum mechanics 7A.1 Energy quantization
(a) Black-body radiation
(b) Heat capacities
(c) Atomic and molecular spectra 7A.2 Wave-particle duality
(a) The particle character of electromagnetic radiation
(b) The wave character of particles
Checklist of concepts Checklist of equations
Topic 7B Dynamics of microscopic systems 7B.1 The Schrodinger equation 7B.2 The Born interpretation of the wavefunction (a) Normalization
(bl Constraints on the wavefunction (c! Quantization 7B.3 The probability density
Checklist of concepts Checklist of equations
Topic 7C The principles of quantum theory 299
70 Operators 299
(a) Eigenvalue equations 299
(b) The construction of operators 300
(c) Hermitian operators 302
(d) Orthogonality 303
7C.2 Superpositions and expectation values 304
7C.3 The uncertainty principle 305
7C.4 The postulates of quantum mechanics 308
Checklist of concepts 308
Checklist of equations 308
Discussion questions, exercises, and problems 310
Mathematical background 3 Complex numbers 314
CHAPTER 8 The quantum theory of motion 316
Topic 8A Translation 317
8A.1 Free motion in one dimension 317
8A.2 Confined motion in one dimension 318
(a) The acceptable solutions 318
(b) The properties of the wavefunctions 320
(c) The properties of observables 321
8A.3 Confined motion in two or more dimensions 322
(a) Separation of variables 322
(b) Degeneracy 324
8A.4 Tunnelling 324
Checklist of concepts 327
Checklist of equations 328
Topic 8B Vibrational motion 329
8B.1 The harmonic oscillator 329
(a) The energy levels 330
(b) The wavefunctions 331
8B.2 The properties of oscillators 333
(a) Mean values 334
(b) Tunnelling 335
Checklist of concepts 336
Checklist of equations 336
Topic 8C Rotational motion 337
8C.1 Rotation in two dimensions 337
(a) The qualitative origin of quantized rotation 337
(b) The solutions of the Schrodinger equation 338
(c) Quantization of angular momentum 340
8C.2 Rotation in three dimensions 342
(a) The wavefunctions 342
(b) The energies 344
(c) Angular momentum 345
(d) Space quantization 345
fe The vector model 346
Checklist of concepts 347
Checklist of equations 347
Discussion questions, exercises, and problems 349
Mathematical background 4 Differential equations 354
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Full contents XVÜ
CHAPTER 9 Atomic structure and spectra
Topic 9A Hydrogenic atoms
9A.1 The structure of hydrogenic atoms
(a) The separation of variables (b| The radial solutions 9A.2 Atomic orbitals and their energies
(a) The specification of orbitals
(b) The energy levels
(c) Ionization energies
(d) Shells and subshells
(e) s Orbitals
(f) Radial distribution functions
(g) p Orbitals
(h) d Orbitals Checklist of concepts Checklist of equations
Topic 9B Many-electron atoms 9B.1 The orbital approximation
(a) The helium atom
(b) Spin
(c) The Pauli principle
(d) Penetration and shielding 9B.2 The building-up principle
(a) Hund s rules
(b) Ionization energies and electron affinities 9B.3 Self-consistent field orbitals
Checklist of concepts Checklist of equations
Topic 9C Atomic spectra
9C.I The spectra of hydrogenic atoms 9C.2 The spectra of complex atoms tat Singlet and triplet states lb) Spin-orbit coupling (cl Term symbols id) Hund s rules le) Selection rules Checklist of concepts Checklist of equations
Discussion questions, exercises, and problems Mathematical background 5 Vectors
CHAPTER 10 Molecular structure
Topic 10A Valence-bond theory lOA.t Diatomic molecules
■a; The basic formulation b Resonance
10A.2 Polyatomic molecules a Promotion b Hybridization
Checklist of concepts Checklist of equations
Topic 10B Principles of molecular orbital theory 407
10B.1 Linear combinations of atomic orbitals 407
(a) The construction of linear combinations 407
(b) Bonding orbitals 409
(c) Antibonding orbitals 411
IOB. 2 Orbital notation 412
Checklist of concepts 412
Checklist of equations 412
Topic 10C Homonuclear diatomic molecules 413
IOC. 1 Electron configurations 413
(a) o Orbitals and k orbitals 413
(b) The overlap integral 415
(c) Period 2 diatomic molecules 416
IOC. 2 Photoelectron spectroscopy 418
Checklist of concepts 419
Checklist of equations 419
Topic 10D Heteronuclear diatomic molecules 420
IOD. 1 Polar bonds 420
(a) The molecular orbital formulation 420
(b) Electronegativity 421
IOD. 2 The variation principle 422
(a) The procedure 423
(b) The features of the solutions 424
Checklist of concepts 425
Checklist of equations 426
Topic 10E Polyatomic molecules 427
IOE. 1 The Hiickel approximation 427
la) An introduction to the method 428
(bi The matrix formulation of the method 428
10E.2 Applications 430
lai Butadiene and ji-electron binding energy 430
!b( Benzene and aromatic stability 431
10E.3 Computational chemistry 432
la) Semi-empirical and ab initio methods 433
fb) Density functional theory 434
io Graphical representations 434
Checklist of concepts 435
Checklist of equations 435
Discussion questions, exe-dses, and problems 436
Mathematical background 6 Matrices 443
CHAPTER 11 Molecular symmetry 446
Topic 11A Symmetry elements 447
11A.1 Symmetry operations and symmetry elements 448
nA.2 The symmetry classification of molecules 449
■a; The groups C„C„ and Cs 450
b The groups C„, C„„ and C„h 451
c ; The groups D„,0„h, and Dnd 452
id; The groups S„ 452
e; The cubic groups 453
f, The full rotation group 454
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xviii Full contents
11A.3 Some immediate consequences of symmetry 454 Checklist of concepts 494
(a) Polarity 454 Checklist of equations 494
(b) Chirality 455
Checklist of concepts 45S Topic 12C Rotational spectroscopy 495
Checklist of operations and elements 4S6 12C.1 Microwave spectroscopy 495
(a) Selection rules 495
Topic 11B Group theory 457 (b) The appearance of microwave spectra 497
11B.1 The elements of group theory 457 12C.2 Rotational Raman spectroscopy 498
11B.2 Matrix representations 458 12C.3 Nuclear statistics and rotational states 500
(a) Representatives of operations 459 Checklist of concepts 502
(b) The representation of a group 459 Checklist of equations 502
(c) Irreducible representations 459
(d) Characters and symmetry species 460 Topic 12D Vibrational spectroscopy of diatomic molecules 503
11B.3 Character tables 461 12D.1 Vibrational motion 503
(a) Character tables and orbital degeneracy 461 12D.2 Infrared spectroscopy 505
(b) The symmetry species of atomic orbitals 462 12D.3 Anharmonicity 506
(c) The symmetry species of linear combinations of orbitals 463 (a) The convergence of energy levels 506
Checklist of concepts 464 (b) The Birge -Sponer plot 508
Checklist of equations 464 12D.4 Vibration-rotation spectra 509
(a) Spectral branches 509
Topic TIC Applications of symmetry 465 (b) Combination differences 510
11C.1 Vanishing integrals 465 12D.5 Vibrational Raman spectra 511
(a) Integrals over the product of two functions 466 Checklist of concepts 512
(b) Decomposition of a direct product 467 Checklist of equations 512
(c) Integrals over products of three functions 467
11C.2 Applications to orbitals 468 Topic 12E Vibrational spectroscopy of polyatomic molecules 514
(a) Orbital overlap 468 12E.1 Normal modes 514
(b) Symmetry-adapted linear combinations 468 12E.2 Infrared absorption spectra 516
11C.3 Selection rules 469 12E.3 Vibrational Raman spectra 518
Checklist of concepts 470 (a) Depolarization 518
Checklist of equations 470 (b) Resonance Raman spectra 518
(c) Coherent anti-Stokes Raman spectroscopy 519
Discussion questions, exercises, and problems 471 12E.4 Symmetry aspects of molecular vibrations 520
(a) Infrared activity of normal modes 520
CHAPTER 12 Rotational and vibrational spectra 474 (b) Raman activity of normal modes 521
Topic 12A General features of molecular spectroscopy 476 Checklist of concepts 521
12A.1 The absorption and emission of radiation 477 Checklist of equations 522
(a) Stimulated and spontaneous radiative processes 477
(b) Selection rules and transition moments 478 Discussion questions, exercises, and problems 523
(c) The Beer-Lambert law 479 CHAPTER 13 Electronic transitions 531
12A.2 Spectral linewidths 480
(a) Doppler broadening 481 Topic 13A Electronic spectra 532
(b) Lifetime broadening 482 13A.1 Diatomic molecules 533
12A.3 Experimental techniques 482 (a) Term symbols 533
(a) Sources of radiation 482 (b) Selection rules 535
(b) Spectral analysis 483 (c) Vibrational structure 536
(c) Detectors 485 (d) Rotational structure 538
(d) Examples of spectrometers 485 13A.2 Polyatomic molecules 539
Checklist of concepts 486 (a) d-Metal complexes 539
Checklist of equations 487 (b) and it* ---n transitions 540
(c) Circular dichroism 541
Topic 12B Molecular rotation 488 Checklist of concepts 542
12B.1 Moments of inertia 488 Checklist of equations 542
12B.2 The rotational energy levels 490
(a) Spherical rotors 490 Topic 13B Decay of excited states 543
(b) Symmetric rotors 491 13B.1 Fluorescence and phosphorescence 543
(c! Linear rotors 493 13B.2 Dissociation and predissociation 545
id) Centrifugal distortion 493 Checklist of concepts 546
Full contents XÍX
Topic 13C Lasers 547
13C.1 Population inversion 547
13C.2 Cavity and mode characteristics 549
13C.3 Pulsed lasers 550
13C.4 Time-resolved spectroscopy 552
13C.5 Examples of practical lasers 552
(a) Gas lasers 553
(b) Exciplex lasers 554
(c) Dye lasers 554
(d) Vibronic lasers 554
Checklist of concepts 555
Checklist of equations 555
Discussion questions, exercises, and problems SSC
CHAPTER 14 Magnetic resonance 560
Topic 14A General principles 561
14A.1 Nuclear magnetic resonance 561
(a) The energies of nuclei in magnetic fields 561
|b) The NMR spectrometer 563
14A.2 Electron paramagnetic resonance 564
(a) The energies of electrons in magnetic fields 565
(b) The EPR spectrometer 566
C lu. i Must ot tuiu opts 567
t Itci Mist l equ.ihoiy, S( 7
Topic 14B Features of NMR spectra 568
I4B.1 The chemical shift 568
14B.2 The origin of shielding constants 570
(a I The local contribution 570
ib) Neighbouring group contributions 571
(0 The solvent contribution 573
14B.3 The fine structure 573
lai The appearance of the spectrum 573
(bl The magnitudes of coupling constants 575
(0 The origin of spin-spin coupling 576
id Equivalent nuclei 577
se Strongly coupled nuclei 579
14B.4 Conformational conversion and exchange processes 580
Checklist of concepts 581
Checklist of equations 581
Topic 14C Pulse techniques in NMR 582
14C.I The magnetization vector 582
¡at The effect of the radiofrequency field 583
b¡ Time-and frequency-domain signals 584
14C.2 Spin relaxation 585
ai Longitudinal and transverse relaxation 585
b The measurement of T, and T¡ 587
iJC.3 Spin decoupling 588
•JC.4 The nuclear Overhauser effect 589
14C.5 Two-dimensional NMR 590
54C,6 Solid-state NMR 592
i. « C K i: S t C1! C Is C i w’t Ch6ikil;t Cf füi: C ;
Topic 14D Electron paramagnetic resonance 594
?40.f Theg-value 594
14D.2 Hyperfine structure 595
(a) The effects of nuclear spin 595
(b) The McConnell equation 596
(c) The origin of the hyperfine interaction 597
Clb.’iMisi of concepts 598
Ch» klist of equations 598
Discussion questions, exercises, and problems 599
CHAPTER 15 Statistical thermodynamics 604
Topic 15A The Boltzmann distribution 605
15A.1 Configurations and weights 605
(a) Instantaneous configurations 605
(bl The most probable distribution 607
(c) The relative population of states 608
15A.2 The derivation of the Boltzmann distribution 608
(a) The role of constraints 609
(bj The values of the constants 610
Checklist ol concepts 611
Checklist ul equations 611
Topic 15B Molecular partition functions 612
15B.1 The significance of the partition function 612
15B.2 Contributions to the partition function ’ 614
(a) The translational contribution 615
(bl The rotational contribution 616
(cl The vibrational contribution 620
(d) The electronic contribution 621
( her Mis! ol concepts f ?2
C !)e kli .t o! i pc! son t)¿ J
Topic 15C Molecular energies 624
ISC.t The basic equations 624
)5C2 Contributionsofthefundamentalmodesofmotion 625
tai The translational contribution 625
Ib) The rotational contribution 625
(cl The vibrational contribution 626
id/ The electronic contribution 627
(ei The spin contribution 628
Check list of concepts 628
Checklist of equations 628
Topic 15D The canonical ensemble 630
15D.1 The concept of ensemble 630
(ai Dominating configurations 631
ib/ Fluctuations from the most probable distribution 631
15D.2 The mean energy of a system 632
15D.3 Independent molecules revisited 633
’5D4 The variation of energy with volume 633
£ ol concepts 635
C■cei t T -t ij* .«u.(oos 633
Topic 15E The internal energy and the entropy 636
15E.1 The internal energy 636
a The calculation of internal energy 636
b Heat capacity 637
SB,2 The entropy 638
a Entropy and the partition function 638
XX Full contents
(b) The translational contribution
(c) The rotational contribution
(d) The vibrational contribution
(e) Residual entropies
Checklist of concepts
Checklist of equations
Topic 15F Derived functions 15F.1 The derivations 15F.2 Equilibrium constants
(a) The relation between K and the partition function
(b) A dissociation equilibrium
(c) Contributions to the equilibrium constant
Checklist of concepts
Checklist of equations
Discussion questions, exercises, and problems
CHAPTER 16 Molecular interactions
Topic 16A Electric properties of molecules 16A.1 Electric dipole moments 16A.2 Polarizabilities 16A.3 Polarization
(a) The frequency dependence of the polarization
(b) Molar polarization
Checklist of concepts
Checklist of equations
Topic 16B Interactions between molecules
16B.1 Interactions between partial charges 16B.2 The Interactions of dipoles
(a) Charge-dipole interactions
(b) Dipole-dipole interactions
(c| Dipole-induced dipole interactions
(d) Induced dipole-induced dipole interactions 16B.3 Hydrogen bonding 16B.4 The hydrophobic interaction 16B.5 The total interaction
Checklist of concepts
Checklist of equations
Topic 16C Liquids
160 Molecular interactions in liquids
(a) The radial distribution function
(b) The calculation of g(r)
(c) The thermodynamic properties of liquids 16C.2 The liquid-vapour interface
(a) Surface tension
(b) Curved surfaces
(c) Capillary action 16C.3 Surface films
(a) Surface pressure
(b) The thermodynamics of surface layers 16C.4 Condensation
Checklist of concepts
Checklist of equations
Discussion questions, exercises, and problems
CHAPTER 17 Macromolecules and
self-assembly 696
Topic 17A The structures of macromolecules 697
17A.1 The different levels of structure 697
17A.2 Random colls 698
(a) Measures of size 699
(b) Constrained chains 702
(c) Partly rigid coils 702
17A.3 Biological macromolecules 703
(a) Proteins 704
(b) Nucleic adds 705
Checklist of concepts 706
Checklist of equations 706
Topic 17B Properties of macromolecules 708
17B.1 Mechanical properties 708
(a) Conformational entropy 708
(b) Elastomers 709
17B.2 Thermal properties 710
17B.3 Electrical properties 712
Checklist of concepts 712
Checklist of equations 713
Topic 17C Self-assembly 714
17C.1 Colloids 714
(a) Classification and preparation 714
(b) Structure and stability 715
(c) The electrical double layer 715
17C.2 Micelles and biological membranes 717
(a) Micelle formation 717
(b) Bilayers, vesicles, and membranes 719
(c) Self-assembled monolayers 720
Checklist of concepts 720
Checklist of equations 721
Topic 17D Determination of size and shape 722
17D.1 Mean molar masses 722
17D.2 The techniques 724
(a) Mass spectrometry 724
(b) Laser light scattering 725
(c) Sedimentation 726
(d) Viscosity 728
Checklist of concepts 730
Checklist of equations 730
Discussion questions, exercises, and problems 731
CHAPTER 18 Solids 736
Topic 18A Crystal structure 737
I8A.1 Periodic crystal lattices 737
I8A.2 The identification of lattice planes 740
(a) The Miller indices 740
(bl The separation of planes 741
18A.3 X-ray crystallography 742
(a) X-ray diffraction 742
(b) Bragg s law 744
(c) Scattering factors 745
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Full contents XXi
(d) The electron density
(e) Determination of the structure 18A.4 Neutron and electron diffraction
Checklist of concepts Checklist of equations
Topic 18B Bonding in solids
18B.1 Metallic solids
(a) Close packing
(b) Electronic structure of metals 18B.2 Ionic solids
(a) Structure
(b) Energetics
18B.3 Covalent and molecular solids Checklist of concepts Checklist of equations
Topic 18C Mechanical, electrical, and magnetic properties of solids
18C.1 Mechanical properties 18C.2 Electrical properties
(a) Conductors
(b) Insulators and semiconductors
(c) Superconductivity 18C.3 Magnetic properties
(a) Magnetic susceptibility
(b) Permanent and induced magnetic moments
(c) Magnetic properties of superconductors
Checklist of concepts
Checklist of equations
Topic 18D The optical properties of solids
180.1 Light absorption by excitons in molecular solids
180.2 Light absorption by metals and semiconductors 1803 Light-emitting diodes and diode lasers
18D.4 Nonlinear optical phenomena
Checklist of concepts
Discussion questions, exercises, and problems
Mathematical background 7 Fourier series and
Fourier transforms
PART 3 Change
CHAPTER 19 Molecules in motion
Topic 19A Transport in gases
19A.1 The phenomenological equations 19A.2 The transport parameters
(a) The diffusion coefficient
(b) Thermal conductivity
(c) Viscosity td) Effusion
Checklist of concepts Checklist of equations
Topic 19B Motion in liquids
19B.1 Experimental results
(a) Liquid viscosity 798
(b) Electrolyte solutions 799
19B.2 The mobilities of ions 800
(a) The drift speed 800
(b) Mobility and conductivity 802
(c) The Einstein relations 803
Checklist of concepts 804
Checklist of equations 804
Topic 19C Diffusion 805
19C.1 The thermodynamic view 805
19C.2 The diffusion equation 807
(a) Simple diffusion 807
(b) Diffusion with convection 808
(c) Solutions of the diffusion equation 809
19C.3 The statistical view 810
Checklist of concepts 811
Checklist of equations 811
Discussion questions, exercises, and problems 813
CHAPTER 20 Chemical kinetics 818
Topic 20A The rates of chemical reactions 820
20A.1 Monitoring the progress of a reaction 820
(a) General considerations 820
(b) Special techniques 821
20A.2 The rates of reactions 822
(a) The definition of rate 822
(b) Rate laws and rate constants 823
fc) Reaction order 824
(d) The determination of the rate law 824
Checklist of concepts 826
Checklist of equations 826
Topic 20B Integrated rate laws 827
20B.1 First-order reactions 827
20B.2 Second-order reactions 829
Checklist of concepts 831
Checklist of equations 832
Topic 20C Reactions approaching equilibrium 833
20C.1 First-order reactions approaching equilibrium 833
20C.2 Relaxation methods 834
Checklist of concepts 836
Checklist of equations 836
Topic 20D The Arrhenius equation 837
20D.1 The temperature dependence of reaction rates 837
20D.2 The interpretation of the Arrhenius parameters 839
(a) A first look at the energy requirements of reactions 839
ibi The effect of a catalyst on the activation energy 840
Checklist of concepts «41
Checklist of equations 841
Topic 20E Reaction mechanisms 842
2OE.1 Elementary reactions 842
2GE.2 Consecutive elementary reactions 843
2OE.3 The steady-state approximation 844
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XXii Full contents
20E.4 The rate-determining step 845
20E.5 Pre-equilibria 846
20E.6 Kinetic and thermodynamic control of reactions 847
Checklist of concepts 848
Checklist of equations 848
Topic 20F Examples of reaction mechanisms 849
20F.1 Unlmolecular reactions 849
20F.2 Polymerization kinetics 850
(a) Stepwise polymerization 851
(b) Chain polymerization 852
Checklist of concepts 854
Checklist of equations 854
Topic 20G Photochemistry 855
20G.1 Photochemical processes 855
20G.2 The primary quantum yield 856
20G.3 Mechanism of decay of excited singlet states 857
20G.4 Quenching 858
20G.5 Resonance energy transfer 860
Checklist of concepts 861
Checklist of equations 862
Topic 20H Enzymes 863
20H.1 Features of enzymes 863
20H.2 The Michaeiis-Menten mechanism 864
20H.3 The catalytic efficiency of enzymes 866
20H.4 Mechanisms of enzyme inhibition 866
Checklist of concept;. sew
f),.., ■i.vsini! ij.tt-si !i ST- *■ v«*. !•..*% tee fi-- h:vsi:c pV* *
CHAPTER 21 Reaction dynamics 879
Topic 21A Collision theory 881
21A.1 Reactive encounters 881
(a) Collision rates in gases 882
(b) The energy requirement 883
(c) The steric requirement 885
21A.2 The RRK model 886
Checklist of concepts 888
Checklist of equations 888
Topic 21B Diffusion-controlled reactions 889
21B.1 Reactions in solution 889
(a) Classes of reaction 889
tb! Diffusion and reaction 890
21B.2 The material-balance equation 891
(a) The formulation of the equation 891
(b) Solutions of the equation 892
concept-, a- ■ r. -a;....!;-:.. ,
Topic 21C Transition-state theory 894
21C.1 The Eyring equation 894
la! The formulation of the equation 894
ib The rate of decay of the activated complex 895
(cl The concentration of the activated complex 896
(d) The rate constant 896
(e) Observation and manipulation of the activated complex 897
21C.2 Thermodynamic aspects 899
(a) Activation parameters 899
(b) Reactions between ions 900
21C.3 The kinetic isotope effect 901
Checklist of concepts 903
Checklist of equations 903
Topic 21D The dynamics of molecular collisions 904
2101 Molecular beams 904
(a) Techniques 904
(b) Experimental results 905
21D.2 Reactive collisions 907
(a) Probes of reactive collisions 907
(b) State-to-state reaction dynamics 907
21D.3 Potential energy surfaces 908
21D.4 Some results from experiments and calculations 910
(a) The direction of attack and separation 910
(b) Attractive and repulsive surfaces 911
(c) Classical trajectories 912
(d) Quantum mechanical scattering theory 912
Checklist of concepts 913
Checklist of equations 913
Topic 21E Electron transfer in homogeneous systems 914
21E.1 The electron transfer rate law 914
21E.2 The rate constant 915
(a) The role of electron tunnelling 916
(b) The reorganization energy 917
CIllH kiist of »oik opts 919
ChtKU . - . Of equations 919
Topic 21F Processes at electrodes 920
21F.1 The electrode-solution interface 920
21F.2 The rate of electron transfer 921
(a) The Butler-Volmer equation 921
(b) Tafel plots 924
21F.3 Voltammetry 925
21F.4 Electrolysis 927
21F.5 Working galvanic cells 927
Checklist of concepts 928
Checklist of equations 929
Discussion questions, exercises, and problems 930
CHAPTER 22 Processes on solid surfaces 937
Topic 22A An introduction to solid surfaces 938
22A.1 Surface growth 938
22A.2 Physisorption and chemisorption 939
22A.3 Experimental techniques 940
¡a! Microscopy 940
tbi Ionization techniques 942
(ci Diffraction techniques 942
id) Determination of the extent and rates of adsorption
and desorption 944
Checklist of concepts 943
Checklist of equations 94s
Full contents XXÜi
Topic 22B Adsorption and desorption 946 (c) The Eley~Rideal mechanism 956
22B.1 Adsorption isotherms 946 22C.2 Catalytic activity at surfaces 957
(a) The Langmuir isotherm 946 Checklist of concepts 958
(b) The isosteric enthalpy of adsorption 948 Checklist of equations 958
(c) The BET isotherm 949
(d) TheTemkin and Freundlich isotherms 951 Discussion questions, exercises, and problems 959
22B.2 The rates of adsorption and desorption 951
(a) The precursor state 951 Resource section 963
(b) Adsorption and desorption at the molecular level 952 1 Common integrals 964
(c) Mobility on surfaces 953
Checklist of concepts 954 2 Units 965
Checklist of equations 954 3 Data 966
4 Character tables 996
Topic 22C Heterogeneous catalysis 955 Index
22C.1 Mechanisms of heterogeneous catalysis 955 999
(a) Unimolecular reactions 956
(b) The Langmuir-Hinshelwood mechanism 956
|
| any_adam_object | 1 |
| author | Atkins, Peter W. 1940- de Paula, Julio |
| author_GND | (DE-588)128437782 (DE-588)132130599 |
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| building | Verbundindex |
| bvnumber | BV041735392 |
| classification_rvk | VE 5000 VE 5010 |
| classification_tum | CHE 100f |
| ctrlnum | (OCoLC)870209700 (DE-599)BVBBV041735392 |
| dewey-full | 541 |
| dewey-hundreds | 500 - Natural sciences and mathematics |
| dewey-ones | 541 - Physical chemistry |
| dewey-raw | 541 |
| dewey-search | 541 |
| dewey-sort | 3541 |
| dewey-tens | 540 - Chemistry and allied sciences |
| discipline | Chemie / Pharmazie Physik Chemie |
| edition | 10. ed. |
| format | Book |
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| id | DE-604.BV041735392 |
| illustrated | Illustrated |
| indexdate | 2024-07-10T01:04:05Z |
| institution | BVB |
| isbn | 9780199697403 019969740X |
| language | English |
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| physical | XXV, 1008 S. Ill., graph. Darst. |
| publishDate | 2014 |
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| publisher | Oxford Univ. Press |
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| spelling | Atkins, Peter W. 1940- Verfasser (DE-588)128437782 aut Atkins' physical chemistry Peter Atkins ; Julio de Paula Physical chemistry 10. ed. Oxford Oxford Univ. Press 2014 XXV, 1008 S. Ill., graph. Darst. txt rdacontent n rdamedia nc rdacarrier Chemistry, Physical and theoretical Chemistry, Physical and theoretical / Problems, exercises, etc Theoretische Chemie (DE-588)4185098-1 gnd rswk-swf Physikalische Chemie (DE-588)4045959-7 gnd rswk-swf (DE-588)4123623-3 Lehrbuch gnd-content Physikalische Chemie (DE-588)4045959-7 s DE-604 Theoretische Chemie (DE-588)4185098-1 s 1\p DE-604 de Paula, Julio Verfasser (DE-588)132130599 aut Digitalisierung UB Regensburg - ADAM Catalogue Enrichment application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=027182103&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis 1\p cgwrk 20201028 DE-101 https://d-nb.info/provenance/plan#cgwrk |
| spellingShingle | Atkins, Peter W. 1940- de Paula, Julio Atkins' physical chemistry Chemistry, Physical and theoretical Chemistry, Physical and theoretical / Problems, exercises, etc Theoretische Chemie (DE-588)4185098-1 gnd Physikalische Chemie (DE-588)4045959-7 gnd |
| subject_GND | (DE-588)4185098-1 (DE-588)4045959-7 (DE-588)4123623-3 |
| title | Atkins' physical chemistry |
| title_alt | Physical chemistry |
| title_auth | Atkins' physical chemistry |
| title_exact_search | Atkins' physical chemistry |
| title_full | Atkins' physical chemistry Peter Atkins ; Julio de Paula |
| title_fullStr | Atkins' physical chemistry Peter Atkins ; Julio de Paula |
| title_full_unstemmed | Atkins' physical chemistry Peter Atkins ; Julio de Paula |
| title_short | Atkins' physical chemistry |
| title_sort | atkins physical chemistry |
| topic | Chemistry, Physical and theoretical Chemistry, Physical and theoretical / Problems, exercises, etc Theoretische Chemie (DE-588)4185098-1 gnd Physikalische Chemie (DE-588)4045959-7 gnd |
| topic_facet | Chemistry, Physical and theoretical Chemistry, Physical and theoretical / Problems, exercises, etc Theoretische Chemie Physikalische Chemie Lehrbuch |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=027182103&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
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