A Life Scientist's Guide to Physical Chemistry

A Life Scientist\'s Guide to Physical Chemistry......Page 1
Contents......Page 7
Preface......Page 11
1 Orientation: What is physical chemistry about?......Page 15
A note on graph axis labels and table headings......Page 17
Part One Quantum mechanics and spectroscopy......Page 19
2.1 Light......Page 21
2.2 Wave properties of matter......Page 27
2.3 Probability waves......Page 29
2.4 Quantization of energy......Page 30
2.5 A first look at spectroscopy......Page 33
Key ideas and equations......Page 35
3.1 Molecular energy......Page 37
3.2 The Boltzmann distribution......Page 39
3.3 Classes of spectroscopy experiments......Page 45
3.4 Absorption spectroscopy......Page 46
3.5 Fluorescence......Page 60
Key ideas and equations......Page 66
Part Two Thermodynamics......Page 69
4.1 The domain of classical thermodynamics......Page 71
4.2 Temperature, heat and thermometers......Page 72
4.3 Sign convention......Page 73
4.4 Molar, specific and “total” quantities......Page 74
Key ideas and equations......Page 75
5.1 Differentials......Page 76
5.2 Pressure–volume work......Page 78
5.3 The First Law of Thermodynamics......Page 82
5.4 Calculus of differentials......Page 83
5.5 Heat and enthalpy......Page 84
5.6 Heat capacity......Page 85
5.7 Phase transitions......Page 92
5.8 Standard states and enthalpies of formation......Page 96
5.9 More on the relationship between internal energy and enthalpy......Page 104
5.10 The dependence of energy and enthalpy changes on temperature......Page 110
5.11 Measuring the energy requirements of living organisms......Page 112
Key ideas and equations......Page 119
6.1 The Second Law of Thermodynamics......Page 123
6.2 Intensive and extensive properties......Page 124
6.3 Reversible processes and entropy......Page 125
6.4 The Second Law of Thermodynamics and entropy......Page 127
6.5 A microscopic picture of entropy......Page 132
6.6 Entropy and evolution......Page 140
6.7 The Third Law of Thermodynamics......Page 142
6.8 Heat engines and the Carnot cycle......Page 146
6.9 Refrigerators......Page 150
6.10 Thermodynamics: the cynic’s view......Page 152
Key ideas and equations......Page 153
7.1 The Clausius inequality......Page 155
7.2 Free energy functions......Page 156
7.3 Free energy as maximum work......Page 158
7.4 Standard states and tabulated values of the state functions......Page 159
7.5 Activity: expressing the dependence of Gibbs free energy on concentration......Page 162
7.6 Adjusting G to different temperatures......Page 166
Key ideas and equations......Page 168
8.1 What does rGm mean?......Page 171
8.2 Free energy and equilibrium......Page 173
8.3 Catalysts and equilibrium......Page 178
8.4 Coupled reactions......Page 179
8.5 Active transport......Page 183
8.6 Temperature and equilibrium......Page 187
Key ideas and equations......Page 194
9 Non-ideal behavior......Page 199
9.1 Activity coefficients......Page 200
9.2 Electrolyte solutions......Page 203
9.3 The solubility of ionic compounds in aqueous solution......Page 210
9.4 Beyond the limiting law......Page 212
Key ideas and equations......Page 213
10.1 Free energy and electromotive force......Page 216
10.2 Reduction and oxidation......Page 218
10.3 Voltaic cells......Page 220
10.4 Standard reduction potentials......Page 222
10.5 Other types of cells......Page 226
Key ideas and equations......Page 232
Part Three Kinetics......Page 235
11.1 The business of kinetics......Page 237
11.2 Subtleties of the rate concept......Page 238
11.3 Kinetics experiments......Page 239
11.4 Elementary and complex reactions......Page 240
11.5 The law of mass action......Page 242
11.6 Microscopic reversibility and chemical equilibrium......Page 244
Key ideas and equations......Page 246
12.1 Initial rate studies......Page 248
12.2 Simple empirical rate laws......Page 249
12.3 The van’t Hoff method......Page 253
Key ideas and equations......Page 257
13.1 First-order reactions......Page 258
13.2 Reactions of other orders......Page 269
13.3 Two-reactant reactions......Page 276
13.4 Reversible elementary reactions......Page 278
13.5 Fluorescence kinetics......Page 281
Key ideas and equations......Page 284
14.1 Two-step mechanisms......Page 288
14.2 Chain reactions......Page 292
14.3 Deriving rate laws of complex mechanisms......Page 294
14.4 Equilibria in complex reactions......Page 297
Key ideas and equations......Page 299
15.1 Properties of enzymes......Page 301
15.2 The Michaelis–Menten mechanism......Page 302
15.3 Enzyme inhibition......Page 312
Key ideas and equations......Page 324
16.1 Flow methods......Page 328
16.2 Flash photolysis......Page 331
16.3 Relaxation methods......Page 334
Key ideas and equations......Page 343
17.1 A simple picture of elementary reactions......Page 344
17.2 The Arrhenius equation......Page 348
17.3 Transition-state theory......Page 353
17.4 Ionic strength......Page 365
Key ideas and equations......Page 369
18.1 Diffusion......Page 373
18.2 A peculiar theory for diffusion coefficients in solution......Page 376
18.3 Bimolecular reactions in solution......Page 378
Key ideas and equations......Page 388
A.1 Enthalpy, free energy and heat capacity data......Page 389
A.2 Standard entropies......Page 392
Appendix B Standard reduction potentials at 298.15 K......Page 393
Appendix C Physical properties of water......Page 394
Appendix D The SI system of units......Page 395
D.1 Calculations in SI units......Page 396
Appendix E Universal constants and conversion factors......Page 398
Appendix F Periodic table of the elements, with molar masses......Page 400
Appendix G Selected isotopic masses and abundances......Page 401
Appendix H Properties of exponentials and logarithmic functions......Page 402
Appendix I Review of integral calculus......Page 403
I.1 Table of integrals......Page 405
Appendix J End-of-term review problems......Page 406
Appendix K Answers to exercises......Page 422
Index......Page 450