thermodynamics (continued)
partition functions, 586, 596–600, 604–613, 617–623,
636–637
phase changes, 50–53
property derivation, 600–604
rotations, 628–636
second law of thermodynamics, 66–88
state, 2–3
state functions, 33–36, 38–42, 608–613
statistical thermodynamics, 586–650
surroundings, 2–3
system, 2–3
temperature change, 58–60
third law of thermodynamics, 66–88
vibrations, 623–628
work-heat relationship, 24–32
zeroth law of thermodynamics, 1–23
third law of thermodynamics
Carnot cycle, 68–73, 94
entropy, 81–85, 602–604
order, 79–81, 602
overview, 66
Thompson, Benjamin, 30
Thomson, G. P., 268
Thomson, Joseph J., 251, 268
Thomson, William, 7
threshold frequency, 253
tie line
description, 176
in nonideal two-component liquid solutions, 180
torr, units of measure, 3
total power flux, 259
Townes, Charles, 554
transition moment
description, 462, 489–490
for electronic transitions, 520
for magnetic transitions, 565–566
transition-state theory, 719–725
transport properties, 674
triple point, 155–156
Trouton’s rule, 148
tunneling, quantum mechanics, 296–299
tunneling microscopy, 298–299
two-component systems,seemulticomponent systems
U
ultrahigh vacuums, 781–782
ultraviolet catastrophe, 256
ultraviolet radiation
characteristics, 464–465
electronic transitions for polyatomic molecules, 542
uncertainty principle, 279–281
unexplainable phenomena, classical mechanics, 248
unit cell
description, 733–738
rationalizing, 752–755V
valence bond theory, symmetry, 446–450
van der Waals, Johannes, 13
van der Waals constants, 13–14
van der Waals equation, 13–14, 16, 102
van’t Hoff, Jacobus, 198
van’t Hoff equation, 133, 198, 201, 702
vaporization
Clapeyron equation, 151
description, 51–53, 143
heat of vaporization, 51–53, 146
vapor-phase mole fractions, 173–174
vapor pressure
description, 153–154
in liquid/liquid systems, 169–179, 193
negative deviation, 179
in nonideal two-component liquid solutions, 179–183
phase diagrams, 154–159, 174–175
positive deviation, 179
variation theory
linear variation theory, 398–402
perturbation theory compared, 402–403
in quantum mechanics, 394–397, 402–403
varying dipole moment, 488
velocity, kinetic theory of gases, 656–666
vibrational spectroscopy,see alsoelectronic spectroscopy;
lasers; rotational spectroscopy
fingerprint regions, 504–506
Franck-Condon principle, 539–541
mechanisms, 487–504
molecule vibration, 481–484
nonallowed transitions, 503–504
nonfundamental transitions, 503–504
normal vibration modes, 483–484
overview, 461–462, 514
quantum-mechanical treatment, 484–487
rotational-vibrational spectroscopy, 506–511
symmetry considerations, 494–498
vibrational degrees of freedom, 482–483, 500, 541
vibrational temperature, 625–627
virial coefficients, 11–12
virial equation, 11
visible light, 464
volt, 209
Volta, Alessandro, 209
voltaic cell, 215, 220–221
volume
Clausius-Clapeyron equation, 152–155
common units, 3
equations of state, 5–9
molar volume, 10836 INDEX