1360 Index
Electronic structure (cont.)
of polyatomic molecules, 867–912
ammonia molecule, 875
applications of symmetry to molecular
orbitals, 894–895, 895t
beryllium hydride andsphybrid orbitals,
867–912
boron hydride andsp^2 hybrid orbitals,
871–872, 872f
computational chemistry, 904–911
delocalized bonding, 885–890
free-electron molecular orbital method,
892–893
groups of symmetry operators, 896–903
methane molecule, 873–875, 874f
multiple bonds, 878–880
summary for, 912
valence-bond description, 881–884
water molecule, 875–876f, 875–878
Electronic transitions
bands of, 973
fluorescence, 978
Franck–Condon principle, 973–974, 974f
phosphorescence, 978
spectroscopy of, 949
Electronic wave functions
of homonuclear diatomic molecules, 823
transitions, 974
Electrons
indistinguishability of, 766–768
shell of, 742
Electrophoretic effect, in electrolyte
solutions, 479
Electrostatic factor, in bimolecular
processes, 530
Electrostatic force (F), 352
Electrostatic theory, ion atmosphere and, 271
Electrostatics, Poisson equation of, 597
Elementary processes
of chemical reactions, 523–524
molecularity of, 523–524
Elements, of matrix, 1249
Ellipsoid of polarizability, 987
Emission, of radiation
spontaneous, 953
stimulated, 953
Emission spectroscopy, 954–955, 954–955f
of hydrogen atom, 954, 955f
observation by, 953–954
quantum mechanics of spectroscopic
transitions, 951–955, 954–955f
Enantiomorph, 903
End-centered lattice, 1155t, 1156, 1156f
Endothermic reaction, 86
Energy.See alsoInternal energy
calculation of change in, 60–72
of chemical reactions, 94–100
ideal gas for, 61–63
irreversible adiabatic processes, 71–72
Joule experiment, 63–67, 63f, 66f
reversible adiabatic processes, 67–71, 68f
chemical reactions and, 94–100
average bond energies, 99–100
calorimetry, 96–99, 97f
of dilute gas, 398–399
in gas kinetic theory, 392
of harmonic oscillator, 627
heat transferal of, 39
internal, 55–59
law of conservation of, 101–102
of molecule, 742
uncertainty relation of, 715–716
Energy changes of formation, calculation
of, 94–96
Energy eigenfunctions, 662
for central-force system, 730, 736–737
electronic, 831
of hydrogen atom, 742, 743t, 744f, 760,
1280–1281
radial factors, 740, 740t, 744f
of particle in a one-dimension box, 665,
666f, 892
of particle in a three-dimension box,
669–670
probability density of, 703–704, 703–704f
of quantum harmonic oscillator,
677–678, 678f
wave functions not, 707–710
Energy eigenvalues, 662
of free particle in three dimensions,
665, 666f
of particle in one-dimensional box,
665, 666f
for relative motion, 725
states of, 738
zero-order, 799
Energy levels
of electrons, 649
emission/absorption spectroscopy
and, 950–958
quantum mechanics of spectroscopic
transitions, 951–955, 954–955fenergy eigenvalues and, 670
of hydrogen atom, 738–740, 739f
of multielectron atoms, 789
of particle in a one-dimension box, 892
of rigid rotor, 921, 921f
Ensembles, 1121–1151
canonical, 1122–1128, 1122f
classical statistical mechanics, 1133–1135
dilute gas in, 1130–1132, 1131f
thermodynamic functions in, 1128–1130
Enthalpy (H), 74–80, 101–102
calculation of
without chemical reactions, 81–85, 85f
of a class of chemical reactions, 86–93
chemical reactions and
adiabatic, 91–93, 92f
other than standard-state, 91
standard-state, 86–89
at various temperatures, 89–91, 90f
description of, 39, 74
of dilute gas, statistical thermodynamics,
1086
of electrochemical cells, 375–376
excess, 277
Gibbs energy and, 153
heat capacity at constant pressure, 75–77
Helmholtz energy and, 153
of ideal solution, 241
Joule–Thomson experiment, 77–80, 78f
maxwell relations, 160–161
of multicomponent systems, 183–184
standard-state reaction change of, 87
temperature and, 336–337
Enthalpy change of formation
calorimetry for, 96–99, 97f
of solutes, 279
standard-state, 87–89
Enthalpy change of fusion, of solvent, 293
Enthalpy change of mixing, expression of, 278
Enthalpy change of solution, enthalpy change
of mixing for, 278
Entropy (S)
absolute, 140–141
calculation of, 140–141
definition of, 140
phase change and, 141
Boltzmann definition of, 105
in classical canonical ensemble, 1141–1142
dilute gas, 1144–1146
definition of, 105, 114, 137
derivation of, 163–165