Physical Chemistry Third Edition

Index 1363

normalization, 697–698
position measurements, 699–700
predictable case and statistical case,
698–699
probabilities and probability densities,
700–705, 701–704f
wave functions not energy eigenfunctions,
707–710
Fourth-order bonds, 880
Fowler, Ralph H., 111
Franck–Condon factor, 974
Franck–Condon principle
for electronic transition, 973–974, 974f, 978
photoelectron spectroscopy, 992
Franklin, Benjamin, 475, 1002
Free energy.SeeGibbs energy;
Helmholtz energy
Free enthalpy.SeeGibbs energy
Free induction decay (FID), 1025, 1026f
Free particle, uncertainty product of, 714–715
Free-electron molecular orbital method
(FEMO), 892–893
Free-electron theory, of crystalline solid
electronic structure, 1175–1179, 1176f
Freely jointed chain, polymers, 1194–1197
Freezing, 27–28, 27f.See alsoPhase
transitions
latent heat of, 54
Freezing point depression, 292–295
Freezing point depression constant, 294
Frequency
of classical waves, 629
of flexible string, 634, 635f
of oscillations, 626
of traveling waves, 637–638
Frequency distribution, 1166
Friction coefficient, 468, 482
in electrolyte solution, 477–479
Frictional force, 468, 482
electrical force and, 477
Fugacity, 176
in Gibbs energy calculation, 176–177
of nonideal gas mixture, 187
Fugacity coefficient.SeeActivity coefficient
Functions, 5–7, 7f
basis and expanded, 694
complex conjugates, 692
expansion coefficients of, 694
orthogonal, 693
Fundamental band
of vibrational spectra, 976, 997

of vibration-rotation spectra, 965–966,

966f, 968f, 997

Fundamental relation of chemical

thermodynamics.SeeGibbs

equation

Fundamental wave, 634, 635f

Fusion.SeeFreezing

G.SeeGibbs energy

Galilei, Galileo, 4

Galvani, Luigi, 354

Galvanic cell, 354, 378

Gas kinetic theory, 383–437

classical mechanics, 387

dilute gas pressure, 411–415

mixture of gases, 415

Newton’s third law, 412

in prism, 413–414, 414f

trajectory of, 412, 412f

effusion and wall collisions, 416–417

hard-sphere gas, 422–433

excluded volume of, 423, 423f

hard-sphere potential, 422–423, 423f

molecular collisions in, 426–430

overview of, 423

pressure of, 424

transport processes, 460–466

macroscopic system states, 384–386

averages, 384

general postulate, 384

probability distributions, 384–386

mathematical analysis of, 383

mean values of mechanical variables,

392–393

microscopic states of, 390–391f, 390–392

molecular speed distribution, 405–410

molecular structure of liquids, 434–436

Newton’s laws of motion, 387–389, 388f

potential energy, 389, 418–421

intermolecular forces, 420–421,

420–421f

one-body forces, 419–420

summary for, 436–437

of transport processes, 460–466, 482

self-diffusion, 460–464, 461f

thermal conduction, 464–465

viscosity, 465–466

velocity probability distribution, 394–404

derivation of, 395–397, 395f

identification of parameter b, 398–404,

399f, 404f

Gases.See alsoDense gases; Dilute gas;

Ideal gas(es)

behavior of, 3–38

introduction to, 3–11

real gases, 21–25

summary of, 35–36

systems and states, 12–19, 13f

volumetric, 6

chemical reactions, involving pure solids

or liquids, 310–313

heat capacities of, 52–53

internal energy of, 58–59

molecular dynamics for, 425

reaction mechanism and elementary

processes, 523–527

collision theory of bimolecular processes,

523–526

collision theory of termolecular

gas-phase reactions, 527

collision theory of unimolecular

processes, 527

general statement for, 527

real, 21–25

solubility in liquid, 255–256

standard state of, 87

volumetric data graphical representation for,

24–25, 24f

Gas-phase reaction

energy change for, 99–100

homogenous catalysis of, 573–574

principle of Le Châtelier, 338

rate law for, 489–490

temperature dependence of, 523

Gauss, 1002

Gauss, Johann Carl Friedrich, 400, 706

Gaussian distribution, 399–400, 399f, 706

in Fick’s second law of diffusion,

450, 451f

harmonic oscillator probability density, 706

with Hartree–Fock–Roothaan method, 798

probability integral for, 401

uncertainty product, 713

Gaussian orbitals, computation of, 907

General solution, of differential equation, 624

Generalized Gibbs–Duhem relation, 190, 196

Geometric means, 269

Geometric progression, 1069

Gerade, eigenfunction, 832

Giauque, William Francis, 139

Gibbons–Laughton equation of state, 23, 23t

for fluid surface, 30f, 31