Index 1361
differential of, 116
of dilute gas, statistical thermodynamics,
1082–1084, 1095–1098
of electrochemical cells, 375
excess, 277
of ideal solution, 241–242
interpretation of, 137–138
production, 129
standard state for, 142–143
statistical, 133–138
definition of, 133, 137–138
lattice gas and, 134, 134f
microstate coordination calculation,
134–135
third law of thermodynamics, 144–145
surface, 232
of universe, 151
Entropy change(s)
adiabatic processes and, 117–119, 118f
calculation of, 121–131, 148
irreversible processes, 126–128
isothermal reversible processes in closed
systems, 121–122
mixing ideal gases, 130–131, 130f
nonequilibrium steady states,
128–129, 129f
processes with no temperature
change, 123
reversible phase changes, 123–124
reversible temperature changes,
124–126
of chemical reactions, 141–142
standard state, 142–143
at various temperatures, 143–144
of mixing, 130
nonadiabatic processes, 120–121, 120f
Entropy production, 129
Enzyme catalysis, 575–580, 576f,
578–579f, 615
active site of, 576, 576f
description of, 566
examples of, 575–576
inhibition of, 580, 580f
Michaelis–Menten mechanisms,
577–580, 578–579f
specificity of, 576
Enzyme molecules
active site of, 345–346
principle of Le Châtelier and, 345
EPR.SeeElectron spin resonance
Equation of continuity, 447–448, 447f
Equation of motion
for harmonic oscillator, 624
Newton’s laws of motion, 1267
Equation of state
description of, 6, 23, 23t
fluid surface and, 30f, 31, 32–33, 33f
for hard-sphere fluid, 425
for ideal rubber, 1202
for nonideal gas, 424
van der Waals, 21
virial, 22
pressure, 22
Equilibrium
aspects of, 204
chemical, 303–348
of chemical reactions, 486–487, 487f
of phases, 199–235
fundamental fact of, 200–202
Gibbs energy and phase transitions,
215–221
Gibbs phase rule, 202–204
multicomponent system surfaces,
230–234
one-component system surfaces, 222–229
in one-component systems, 205–213
temperature and pressure at, 36
Equilibrium approximation
for oscillatory chemical reactions, 588
in rate-limiting approximation, 542
Equilibrium constant, 310, 348
for acetic acid, 325
for dilute gas, 1103–1105
electrochemical cells, 375
Gibbs energy changes and, 304–310
of ideal gases, 310–311, 348
of solids and liquids, 312–313
of solutes, 316, 348
of solvents, 316
for water ionization, 321–322
Equilibrium electrochemical cell, 354, 378
Equilibrium populations, of molecular states,
942–947
Equilibrium state
of closed simple system, 155–157, 155f
of nonsimple systems, 157
Equilibrium statistical mechanics
classical statistical mechanics, 1133–1140,
1150–1151
canonical ensemble, 1133–1135
canonical thermodynamic functions,
1141–1146classicalvs. quantum partition functions,
1137–1140, 1138f
of dense gases and liquids, 1147–1150
dilute gases in ensemble, 1135–1137
phase space, 1133
ensembles, 1121–1151, 1150–1151
canonical, 1122–1128, 1122f
dilute gas in canonical, 1130–1132, 1131f
thermodynamic functions in canonical,
1128–1130
quantum
molecular partition function calculation,
1064–1075
postulates of, 1042–1043
probability distribution and molecular
partition function, 1055–1063
probability distribution for dilute gas,
1047–1054
of simple model system, 1040–1046
summary for, 1077
thermodynamics, 1081–1118
activated complex theory, 1106–1115
dilute gas, 1082–1088
dilute gas chemical equilibrium,
1101–1105
dilute gas working equations, 1089–1100
miscellaneous topics, 1116–1118
summary for, 1118
Equilibrium system, intensive state of, 33
Error function, in Fick’s second law of
diffusion, 449–450, 450f
ESR.SeeElectron spin resonance
Euler, Leonhard, 16
Euler reciprocity relation, 16, 63
Maxwell relations and, 159–161, 185
Euler’s reciprocity relation, 1236–1237
Euler’s theorem
derivation of, 1263–1264
description of, 151, 188, 196
Gibbs–Duhem relation and, 188–194
mean molar quantity and, 189
multicomponent surfaces and, 232
Eutectic point, 286, 286f
peritectic pointvs., 289–290
Even function, 661
Even parity, 932
Exact Born–Oppenheimer molecular
orbitals, 825
Exact differential equations, 48,
1237–1238, 1245
inexactvs., 49–50