entropy (continued)
in crystals, 644
derivation from partition functions, 638–639
description, 66
disorder concept, 602–603
in ionic solutions, 228–230
isentropic processes, 90–91
of mixing, 78–79
natural variable equations, 96–99
in nonstandard chemical reactions, 220–221
order, 79–81, 602
for phase transitions, 147–148, 160
second law of thermodynamics, 72–79, 81–85, 602
spontaneity determination, 90
statistical thermodynamics, 601–603, 610–611
third law of thermodynamics, 81–85, 602–604
enzyme-catalyzed reactions, steady-state approximation,
713–714
equations of state, 5–9, 11, 100–101, 105,see also specific
states
equilibria
chemical equilibrium,seechemical equilibrium
chemical potential, 159–162
Clapeyron equation, 148–152
Clausius-Clapeyron equation, 152–155
description, 119–121
dynamic equilibrium, 120, 125
electrochemical equilibrium, 211–215
equilibrium constants, 125–129, 132–135, 218–225,
642–644, 696
Gibbs phase rule,seeGibbs phase rule
kinetics, 694–696
in multiple-component systems, 166–205
natural variables, 159–162
overview, 141, 162
partition functions, 640–644
phase diagrams, 154–159, 174–175
phase transitions, 143, 145–148
in single-component systems, 141–165
static equilibrium, 120
statistical thermodynamics, 640–644
thermal equilibrium, 4, 553
ethylene, Hückel approximation, 545
Euler’s theorem, 335
eutectic composition, in solid/solid solutions, 190–192
exact differentials, 35, 100
excitation, 548
exothermic processes
description, 38, 51, 53
phase transitions, 147
expansion coefficient
gases, 20
in perturbation theory, 391–392
experiment, 5, 708,see also specific experiments
explosions, kinetics, 717
extensive variables, 216
Eyring, Henry, 722
Eyring equation, 722–723F
Faraday, Michael, 46
Faraday’s constant, 210–212
fermions, 379, 631–632
Fick’s first law of diffusion, 674, 676
films, 766, 777–778
fingerprint regions, in vibrational spectroscopy, 504–506
first Bohr radius, 264, 361
first law of thermodynamics
chemical changes, 53–58
enthalpy,seeenthalpy
Gibbs free energy, 93
heat capacities, 31, 39–41, 46–50
internal energy,seeinternal energy
Joule-Thomson coefficients, 42–46, 103–104
limitations, 66–68
overview, 24, 62
phase changes, 50–53
state functions, 33–36, 38–42
temperature change, 58–60
work-heat relationship, 24–32
first-order reactions, rate laws, 686–694
fluorescence, 548–550
forbidden transition, 463
force
bending force constants, 496
charged particles, 207–209
electromotive force, 212–213, 215, 219–221
hydrogen atom central force problem, 352–353, 365
Newton’s second law of motion, 242–243, 653–654
work relationship, 24–25
force constant, 316, 484
formation reactions, 54–55
Fourier transform, in nuclear magnetic resonance, 581
fractional distillation
of azeotropes, 181
description, 176–178
Franck, James, 539–540
Franck-Condon principle, 539–541
Franklin, Benjamin, 207
free energy,seeGibbs free energy
free energy of formation, 95
free induction decay, 581
free radicals, 707, 714–715
freezing
description, 143
freezing point depression, 194–195
frequency
Bohr frequency condition, 462
Debye frequency, 646–648
description, 465824 INDEX