1382 Index
Subshell configuration
Aufbau principle and, 809–810f,
809–812, 811t
orbital wave functions, 772
Subshells, 742
Sum of two operators, 685
Superconductivity, 1183–1184
Supercooled systems
entropy changes of, 127–128
phase transitions in, 215–216, 215–216f
Supercritical fluids, 28
Superheated systems
cavity vapor pressure in, 229
entropy changes of, 127–128
phase transitions in, 215–216, 215–216f
Surface concentration, 233
Surface entropy, 232
Surface excess, 231
Surface Gibbs energy, 232, 235
Surface tension
in multicomponent system, 232–233
in one-component system, 224–227,
225–226f
Surfaces
in multicomponent systems, 230–234
in one-component system, 222–229
energy attributed to, 222–224
Laplace equation, 227–229
tension of, 224–227, 225–226f
one-componentvs. two-component systems,
230–231, 231f
Surfactant, 233
Surroundings, 13
Svedburg, 472
Svedburg, Theodor, 472
Symmetric matrix, 1251
Symmetric spin factor, 812
Symmetric stretch, 939
Symmetric top, 934
Symmetry element, 828
Symmetry number, 936, 1068
Symmetry operations, 897
on wave functions, 930–932
Symmetry operators, 897
function operation of, 830–832
group theory, 898–899
elementary applications of, 902–903
for molecular orbitals, 827–829, 829f,
894–895, 895t
point groups and Schoenflies symbols,
899–902, 901t, 902f
potential energy and, 897
for water, 899, 899t
Symmetry species, 1299
Symmetry-adapted basis functions, 1299
System(s), 4
closed fluid, work done on, 41–43
in physical chemistry, 12–19, 13f
simple, description of, 42
state of, 13–14
in classical mechanics, 621
measurements and determination,
717–720
work and, 40–50
thermodynamics of, 151–196
types of, 12–13Tafel equation, for overpotential, 607
Taylor series, for freezing point depression,
293–294
Temperature
Carnot cycle and, 111
cell voltage dependence on, 368–369
chemical equilibrium dependence on,
335–340
chemical reactions dependence on,
485, 524–525
nonelementary, 553
diffusion dependence on, 470–472
gas-phase reaction dependence on, 523
Gibbs energy dependence on, 178–180,
220–221
gradient, for heat conduction, 445
heat transfer during change of, 51–53
molar concentration, molality and, 254
pressurevs. molar volume and, 29, 30f,
32–33, 33f
rate constant dependence on, 487, 533–539
reduced, 34
thermodynamic, 110–113
viscosity dependence on, 470–472
Temperature-composition phase diagrams
of ideal solutions, 245–246, 245–246f
of nonideal mixtures
liquid-vapor, 282–283, 282–284f
solid-liquid, 285–286, 285–286f, 288,
288f
solid-liquid with compounds, 288–289,
288–289f
Temperature-jump method, for fast reaction
experimental, 516–520, 518f
Tension force, 1201Term symbols, for homonuclear diatomic
molecules, 847–848
Terminals, of electrochemical cells, 354
Termolecular process, 524
gas-phase reactions, 527
liquids, 532
Tesla, Nikola, 1002
Tetrahedral angle, 874, 874f
Tetramethyl silane, for NMR, 1016
Theorem of equipartition of energy,
1142–1143
Theoretical plate, of still, 246, 246f
Thermal conduction, in hard-sphere gas,
464–465
Thermal conductivity, 445
Thermal equilibrium, 204
Thermodynamic control, for competing
reactions, 514
Thermodynamic energy.SeeInternal energy
Thermodynamic entropy, statistical entropy
and, 136–137, 1117–1118
Thermodynamic equation of state
heat capacity and, 170
Maxwell relations, 167
Thermodynamic functions
in canonical ensembles, 1128–1130
classical, 1141–1146
of nonideal solutions, 275–280
Thermodynamic limit, 1048–1049
Thermodynamic probability, of macrostates,
133–134, 1082
Thermodynamic temperature, 111
ideal gas temperaturevs., 111–112
zeroeth law and, 110–113
Thermodynamics, 39
chemical equilibrium, 303–348
of electrochemical systems, 351–378
activities and activity coefficients of
electrolytes, 371–374
chemical potential and electric potential,
352–353
electrochemical cells, 354–361
half-cell potentials and cell potentials,
361–369
summary for, 378
thermodynamic information from
electrochemistry, 374–376
first law of, 39–102
for closed simple systems, 158
energy change calculations with chemical
reactions, 94–100