SUBJECT INDEX
Many subjects are listed both under their name(s) and under the general category to which they belong. Thus, all material relating to crystals is collected under Crystalline state; and all types of potential are listed under Potential. The Index therefore provides summaries of related subjects as well as the locations of specific items by name. Tables are indicated by page numbers followed by (T).
A Abbreviations, glossary, 841 Absolute rate theory, see Theory Absolute temperature, 3 Absolute zero, 6
attainment of, 209 Absorbance, 77 Absorption
of charged particles, 937 coefficient, see Coefficients) critical, 939
of electromagnetic radiation, 76, 827, 937 resonance, 947
Acceptor (in photosensitization), 803 Acetic acid
dimer, 262 dissociation, 458(T) Acid(s),478
Br0nsted, 480 conjugate, 480
dissociation constants, 468(T) hard (soft), 481
Lewis, 481, 911 weak, 470, 489
Acid—base reactions, see Reaction(s) Actinium series, 948
Activated complex, 573, see also Theory Activation energy, 563, 566
Activation parameters, 572(T) Activity, 317
absolute, 336 calculation, 321 conventions, 362, 379 of electrolytes, 453 mean, 455 rational, 245,336 of solutions, 319
Activity coefficient, 216, 317 calculation, 321
chemical equilibrium and, 243 conventions, 362, 379 determination, 458, 508 of electrolytes, 453, 460(T), 476 of gases, 316
mean, 455
reaction rate and, 626 from solubility, 456 of solutions, 319 Additive property, 75
kinetic studies and, 551 Adiabatic calorimeter, 148 Adiabatic demagnetization, 210 Adiabatic process, 112 Adsorption, 588
chemical, see Chemisorption Gibbs equation, 208, 342 Langmuir equation, 588 I I
Adsorption (cont.) negative, 334 physical, 588 Aerosol, 301 Age dating, 948
Alkali metal halides, see Crystalline state Alpha helix, 915
Alpha particle emission, 943 Amagat's law, 10
Ampere (unit), 88, 430, 432
Angular quantum number, see Quantum number
Anharmonic oscillator, 137, 646 Anisotropy factor, 838
Annihilation radiation, 938 Anode, 430, 500
Anomalous water, 285 Anthracene structure, 875 Antibonding, see Orbital(s) Antimatter, 945
Appearance potential, 583 Aromaticity rule, 782 Arrhenius equation, 563 Arrhenius parameters, 568(T) Associative law, 728 Athermal solution, 335 Atmosphere, ion, 463 Atomic bomb, 931, 944 Atomic energy states, 703 Atomic number, 927 Atomic unit of energy, 661
Atoms, enthalpies of formation of, 165(T) Aufbau, building up, 773
Auger effect, 939 Austenite, 417
Average quantities, 49, 372 Avogadro hypothesis, 8, 66 Avogadro number, 66, 430 Azeotropic mixture, 327
Azimuthal quantum number, see Quantum number
Β Balmer series, 658 Barn (unit), 936 Barometric equation, 10 Baryon, 945
Base, 478 Br0nsted, 480 conjugate, 480
dissociation constants, 468(T)
hard (soft), 481 Lewis, 481 weak, 470
Battery, see Electrochemical cell Beattie-Bridgman equation, 26 Benson-Golding equation, 26 Benzene, resonance energy, 164, 779 Berthelot equation, 26
Beta emission, 931, 943
Bimolecular collision frequency, 54 Bimolecular reaction, see Reaction(s) Binary, see Phase diagram, two-component Binding energy of nuclei, 933
Bingham plastic, 908 Biot (unit), 834
Blackbody radiation, 708 Bohr orbit, radius of, 661 Bohr magneton, 94, 815 Bohr theory, 659 Boiling point
apparatus, 358 diagrams, 324 elevation, 354, 359(T) normal, 253
critical temperature and, 258 Bolometer, 148
Boltzmann distribution, 40, 64 of nuclear spin states, 816 verification, 65
Boltzmann principle, see Principle(s) Bond (chemical), 694, 744, 759
as basis for representation, 744 coordinate, 581
dipole moment, 86(T) force constant, 810(T) hydrophobic, 916 pi, 748, 769, 775 sigma, 744, 769, 771 strength, 161, 165(T) Born—Haber cycle, 892
Born—Oppenheimer approximation, 760, 796 Bose—Einstein statistics, 946
Boson, 946
Boyle temperature, 14, 20 Boyle's law, 3, 4
Box, particle in, 127, 669, 801 Bragg equation, 869
Bravais lattice, see Crystalline state Brillouin zone, 881
Br0nsted acid and base, 480 Br0nsted equation, 622, 624 Buffer, 472
Bulk modulus, 906 Burgers vector, 883
SUBJECT INDEX 13
C of diffusion, 59, 365, 370(T)
mutual, 61 self-, 384 extinction, 77, 828 friction, 364, 917 Joule, 136
Joule-Thomson, 137, 214 sedimentation, 365, 370(T) temperature, 563
thermal conductivity, 61
thermal expansion, 17, 214, 282(T) transfer, 531
virial, 17,31
viscosity, see also Viscosity, 57 Cofactor, 635
Colligative properties, 353, 354(T), 357, 373 Collision
versus encounter, 615 frequency
bimolecular, 54 in mixtures, 71 surface, 50 theory, 567, 614
Colloids, 301, 448, 899, see also Detergent association, 905
flocculation, 903, 917 lyophilic, 899 lyophobic, 899 as phase, 413
Combustion, enthalpy of, 150(T) Communal entropy, 336 Commutative law, 728 Complex ions, 447, 486, 823 Component, 302, 393, 413 Composition units, 302 Compound
eutectic, 396
in freezing point diagram, 398 Compressibility
coefficient, 16, 282(T) factor, 13,215 Compton effect, 938
Concentration cell, see Electrochemical cell Condensation, 14, 22
Conductance, 434, 917, see also Conductivity Conductivity
equivalent, 433, 437(T), 453(T) metallic, 880
photo-, 881 specific, 432 thermal, 61
Congruent melting, 398 Consecutive reactions, 639 Consolute temperature, 330, 419 Cage, solvent, 2 5 2 , 2 9 1 , 6 1 2
Calomel electrode, 507 Caloric, 103, 179 Calorimetry, 147 Canonical ensemble, 209 Capillary
constant, 274 rise method, 273 Carnot cycle, 177
Carnot, S. (biography), 177 Cartesian coordinates, 666 Cast iron, 418
Catalysis
acid-base, 622
chemical equilibrium and, 241 enzyme, 634
heterogeneous, 551, 587 Catalytic constant, 635 Cathode, 430, 500 Cathode ray, 925 Cavitation, 26
Cell, see Electrochemical cell Cementite, 417
Chain reaction, 560, 586 Character table, 737(T)
Charge, molecular distribution of, 89 Charge transfer transition, 800 Chemical equilibrium, 227 Chemical kinetics, 543, 603 Chemical potential, 312 Chemical shift, 817 Chemisorption, 587 Chirality, 838 Cholesteric phase, 909 Chromophore, 78, 798(T)
Circular dichroism, see Optical activity Clapeyron equation, 253, 263
Clausius equation, 26
Clausius-Clapeyron equation, see Equation(s)
Closed shell, 692 Cloud chamber, 927 Clusters (in water), 284, 448 CNDO method, 783 Cobalamin, 878 Coefficient(s)
of absorption, 76 absolute, 827 Einstein, 828 activity, see Activity
of compressibility, 16, 214, 282(T) of dichroic absorption, 838
Constant(s) Crystal field, 751, 784 boiling point elevation, 356 Crystalline state, 849
Boltzmann, 12, 53 of alkali metal halides, 859
capillary, 274 of anthracene, 875
Faraday, 430 basis of unit cell, 853, 885
force, 81 OCT) ofbenzene, 861
freezing point depression, 356 of biological molecules, 878
gas,6(T) Born-Haber cycle and, 892
Hamaker, 900 Bragg equation, 869
Henry's law, 307, 311 Bravais lattices, 850, 852(T)
Madelung, 891(T) Brillouin zones, 881
mass action equilibrium, 228 Burgers vector, 883
Pascal, 93, 94(T) cleavage, 867
Planck, 656, 710 cohesive energy, 889
reproduction, 944 coordination number, 861
rotational, 812, 840 of covalent solids, 862
Rydberg, 658 crystal planes, 854
screening, 664, 683, 702, 817 cubic close packing, 857
crystal radii and, 893 defects, 881
Stefan-Boltzmann, 710 of diamond, 862
Constituent, 302 diffraction, 870
Cooling curve, 396 dislocations, 882
Coordinates double repulsion, 894
Cartesian, 666 electron density projections, 875
elliptical, 763 electron diffraction, 876
polar, 677 face centered cubic, 859
Coordination compounds, 447, 486, 823 Fourier series representation, 875
emission from, 822 geometric calculations, 865
Coordination number, see Crystalline state of graphite, 862
Correlation diagram, 769 habit of, 855
Corresponding state, 17, 24, 31, 258 heat capacity, 138
Cosmic radiation, 940 of hemoglobin, 879
Cotton (unit), 834 hexagonal close packing, 857
Cotton effect, 839 hydrogen bonded structures, 864
Cottrell boiling point apparatus, 357 of ice, 864
Coulomb, 88,432 interplanar distances, 866
Coulomb integral, 763, 776 of ionic crystals, 859
Coulomb's law, 88, 287 ionic radius, 893(T)
Coulometer, 485 lattice energy, 889
Critical absorption, 939 lattice types, 849
Critical behavior, 13 layer structures, 862
Critical constants, 15, 18(T) of metals, 880 Critical opalescence, 27 Miller indices, 854 Critical phenomena, 24 of molecular solids, 863
Critical point, 15, 27 mosaics and, 850
in ternary systems, 419 of MX compounds, 859
Critical temperature, 15 of MX2 compounds, 861
of miscibility, 312 nearest neighbors, 861
normal boiling point and, 258 neutron diffraction, 876 in ternary systems, 419 point groups, 851
Crookes tube, 867, 925 powder patterns ,871
Cross-differential, 111, 196, 213 precession method, 874 Cross section (nuclear), 936 of rare gases, 889
Cryohydric point, 401 repeating unit, 852, 888
SUBJECT INDEX rotation-oscillation method, 874
of semiconductors, 879 space groups, 851 of spheres, 857 stoichiometry, 861
structure determination, 873 structure factors, 888 surface density in planes, 867 symmetry notation, 885 type planes, 866 unit cell, 850
Weissenberg method, 874 x-ray diffraction, 867, 887 Crystals, see Crystalline state Cubic close packing, 857 Curie (unit), 940 Cyclic voltammetry, 536 Cyclotron, 930
D Dalton's law, 9, 301 Daniell cell, 501
de Broglie principle, 657, 664 Debye (unit), 79
Debye equation (polarization), 83
Debye-Huckel theory, 461, 476, 626, 902 Debye theory of heat capacity, 139, 211 Defects, 881
Degeneracy, 125, 201, 673, 777 Degree of freedom, 123, 392 Derealization, 778 Del squared operator, 666 Demagnetization (adiabatic), 210 Denaturation, 916
Desalination, 377 Detachment methods, 276
Detailed balancing, see Microscopic reversibility
Detergent
critical micelle concentration, 906 Kraft temperature, 905
surface tension of solutions, 333 Deviation, standard, 64, 949 Diamagnetism, 92
Diameter, molecular, 66(T) Diamond structure, 862 Dielectric constant, 88 Dieterici equation, 26 Differential
exact, 107 partial, 109
Differential heat of solution, 339 Diffraction, see Crystalline state Diffuse double layer, 901
Diffusion, 59, 365, 370(T), 384, 449 controlled reaction, 618(T) current, 535
Einstein equation, 59 of gases, 59 of ions, 481 potential, 482
theory of, in solution, 384 Dilatancy, 907
Dilatometer, 608
Dilution, heat of, 149,341
Dipole moment, 80, 85(T), 86(T), 91, 287 intermolecular forces and, 286
of transition, 828 Direct product, 753, 830 Dislocation, see Crystalline state Dispersion force, 289, 890, 900 Dissociation
calculation of, 439, 514 constants, 468(T) Dissymmetry factor, 838 Distillation, 327
steam, 329 Distribution
Boltzmann, 40, 64 radial, 252
Domain, 692, see also Orbital(s) Donnan equilibrium, 469 Donor, in photosensitization, 803 Doppler effect, 947
Dosimetry, 935 Double layer, 901
shear plane, 916 Drop weight method, 275 Duhem—Margules equation, 380 Dulong and Petit law, 138 du Nouy tensiometer, 277
Ε Effect(s)
Auger, 939 Compton, 938 Cotton, 839 Donnan, 469 Doppler, 947 electrokinetic, 916 electrophoretic, 483 Joule, 136
Effect(s) (cont.) Joule—Thompson, 137 Kelvin, 274
Môssbauer, 947 photoelectric, 656, 938 relaxation, 483 Stark, 813 tunnel, 944 Zeeman, 662
Efficiency of heat engine, 181 Effusion, 52
Eigenfunction, 680 Eigenvalue, 680 Einstein (unit), 656, 805 Einstein, A. (biography), 648 Einstein absorption coefficient, 828 Einstein diffusion equation, 59 Einstein heat capacity law, 138 Einstein relativity equation, 933 Elastic body, 906
Electrical definitions, 434(T) Electrical nature of matter, 925 Electricity, galvanic, 429 Electrocapillarity, 526
Electrochemical cell, 499, see also Electrode(s) calomel, 507
concentration, 514 with liquid junction, 528 Daniell, 501
diagram, 500
dissociation constants and, 514 fuel, 524
galvanic, 429 Jungner, 524 Leclanché, 524 primary, 523 secondary, 523
solubility product and, 513 standard, 506
storage, 523
thermodynamics, 503 Weston, 506
Electrochemical mobility, 443 Electrode(s)
calomel, 507
dropping mercury, 535 glass, 519
hydrogen, 500, 508,519 kinetics, 521
polarized, 521
potential, standard, 508, 511(T) process, irreversible, 520 quinhydrone, 519 reference, 507
Electrodeposition, 520 Electrokinetic effect, 916 Electrolyte(s)
activity, 453
activity coefficient, 453, 460(T), 476 colloidal, 905
dissociation, 475 solution, 429
surface tension of, 333 strong, 437
swamping, 467 weak, 438 Electron(s)
affinity, 892 capture, 931
charge to mass ratio, 925 diffraction, 876 magnetism, 94 naming of, 430 pair formation, 938 solvated, 800 spin
function for, 692 resonance, 821 volt, 502, 660 Electronegativity, 85
Electronic transition, see Transition(s) degenerate, 201
Electroosmosis, 916
Electrophoresis, 449, 917, 933 Electrophoretic effect, 483 Electroscope, 946 Elliptical coordinates, 763 Elliptically polarized light, 838 Emission, 802, see also State, excited
effect of pressure on, 823 resonance, 797
stimulated, 829, 831 Emissive power, 709 Emulsion, 301 Encounter, 612
charge effect on, 619 complex, 617
Endothermic reaction, 147 Energy
of activation, see Activation atomic unit, 661
binding, of nuclei, 933 delocalization, 778 dissociation, 892 versus enthalpy, 146 exchange,763 first law and, 104 function, 164
SUBJECT INDEX 17 ofhydration,447,476
internal, 105 ionization, 663(T) lattice, 476, 889 mass equivalent, 933 resonance, 164, 778
temperature dependence, 155 threshold, for nuclear reaction, 935 units, 660
zero point, 131,595,676 Ensembles, 209
Enthalpy, 115, see also Heat of chemical reaction, 146 of combustion, 151(T) of dilution, 149
versus energy of reaction, 146 of formation, 154(T)
of aqueous solutes, 156(T) of atoms, 165(T)
of ions, 156(T) function, 164,217,244 of fusion, 259(T) of hydrogénation, 151 (Τ) of mixing, 3 1 8 - 3 2 0 of solution, 149, 151(T),339
integral, 151 relative, 840 of sublimation, 266 surface, 271
temperature dependence of, 155 of vaporization, 259(T) Entropy, 176
calculations of changes in, 185 communal, 336
of formation, 240 of ice, 212
for irreversible processes, 188 of mixing, 3 1 8 - 3 2 0
for phase changes, 188 probability and, 196 production, 632
for reversible processes, 185 as state function, 185
statistical thermodynamic, 210(T) surface, 271
thirdlaw,210(T) translational, 204 unit, 185
of vaporization, 259(T) Enzyme catalysis, 624 Eôtvôs equation, 278 Equation(s)
Arrhenius, 563 barometric, 10
Beattie-Bridgman, 26 Benson—Golding, 26 Berthelot, 26
Boltzman, 40, 53,946 Bragg, 869
Br0nsted, 621, 624 Clapeyron,253,263 Clausius, for gases, 26
Clausius-Clapeytron, 254, 323, 393, 590 colligative property, 354(T)
Debye (polarization), 83 Dieterici, 26
Donnan, 469
Duhem—Margules, 380 Einstein
diffusion, 59 heat capacity, 138 relativity, 933 viscosity, 912 Eôtvôs, 278 Fourier, 61 Gibbs
adsorption, 316, 342 phase rule, 393
Gibbs-Duhem, 316, 320, 337, 363, 379, 454, 458
Gibbs-Helmholtz, 503 Hermite, 674
Kelvin, 23, 279
definition of phase and, 413 Langmuir adsorption, 588 Laplace, 271
Margules, 310 Nernst, 504
diffusion, 482 phenomenological, 3 Planck—Einstein, 656 Poiseuille,57,280,290,919 Poisson, 462, 902
Poisson-Boltzmann, 462, 902 Rayleigh-Jeans, 710
Ritz, 658
Sackur-Tetrode, 204, 211, 262, 577 Schrôdinger, 664, see also Wave mechanics
free particle, 668 harmonic oscillator, 673 hydrogen atom, 677 particle in box, 669 rigid rotator, 706 secular, 697, 776 Smoluchowski, 619 of state, 2, 17,26
reduced,17
thermodynamic, 214
Equation(s) (cont.) Staudinger, 913 Stirling, 42, 201 Sutherland, 68 Tafel, 522, 530
van der Waals, 17, 24, 254, 288 two-dimensional, 345 van't Hoff, 235,258 virial, 1 3 , 2 0 Young's, 272 Equilibrium
chemical, 227 emf and, 512 second law and, 241 criteria for, 192 Donnan, 469 heterogeneous, 391 inert gas effect, 232 ionic, 466, 487 isopiestic, 358
kinetics of perturbation from, 607 N2O4 dissociation, 9
osmotic, 359
oxidation—reduction, 512 PCI5 dissociation, 236 phase, 251
criterion for, 315 at high pressure, 264 pressure effect, 243 secular, 942 sedimentation, 369 solid-gas, 237
statistical thermodynamics, 244, 593 transient, 640, 942
Equilibrium constant determination, 231 mass action, 228 rate constants and, 630 temperature variation, 234 thermodynamic, 229 Equipartition
energy, 124, 581 principle, 122
Equivalent conductivity, see Conductivity Error function, 64, 949
Eulerrelationships, 111, 196,213 Euler theorem, 337
Eutectic
in boiling point diagrams, 396 in freezing point diagrams, 395 mixture, 398
in ternary systems, 409 Exact differential, 107
Excess thermodynamic quantities, 320
Exchange rate law, 643 Exchange reaction, 557 Excited state, see State Excluded volume, 19
Exclusion principle, 663, 694, 703, 765, 946 Existence rules, 931
Exothermic relactions, 147 Explosions, 159, 586
Extinction coefficient, 77, 828
F Fallout, 940
Faraday constant, 430 Fast reactions, see Reaction(s) Fermi-Dirac statistics, 946 Fermion, 946
Fick's law, 59, 365,696 Filled shell, 692 Film pressure, 345
First law of thermodynamics, 101 statements, 107, 207
statistical thermodynamic treatment, 125, 134
First order reaction, see Rate law Fischer—Tropsch reaction, 587
Fission, 935, 944, see also Nuclear process Flames, thermochemistry of, 159
Flash photolysis, 557 Flickering clusters, 284, 448 Flocculation, 900, 903, 917(T) Flow, see also Viscosity
Knudsen, 52 Newtonian, 57
Fluidity, 57, 282, see also Viscosity Fluorescence, 802, 822
quenching, 803 yield, 805
Forbidden transition, 676, 830, see also Transition
Force
dispersion, 289, 890, 900 intermolecular, 286 Keesom, 288
London, 289, see also Force, dispersion long range, 900
newton as unit of, 87 orientation, 288
van der Waals, 259, 286, 900
Force constant, 810(T), see also Vibrational Formal concentration, 434
Formaldehyde excited states, 799
SUBJECT INDEX Formality, 302
Formation
enthalpy, 154(T)
free energy and entropy, 240 Fourier series, 875
Fourier thermal conductivity law, 61 Fractional distillation, 218
Franck-Condon principle, 795 Free electron model, 672 Free energy, 191
calculation, 194 of elements, 218 of formation, 240
function, 217, 218(T), 244 Gibbs, 191
Helmholtz, 191 of ions (aqueous), 525 linear relationships, 620, 624 of liquid and its vapor, 268 ofmixing,318,320 surface, 271 Free particle, 668 Free radical, 583
Freedom, degrees of, 123, 392 Freezing point
depression of, 356, 359(T) solubility and, 375 Freezing point diagrams, 395
with compound formation, 398 cryohydric point in, 401
with immiscible components, 395 with partial miscibility, 414 quadruple point in, 403 ternary, 405
unstable compound formation in, 398 Frenkel defect, 882
Frequency factor, 563, see also Kinetics, Reaction(s)
Fresnel rhomb, 839
Friction coefficient, 364, 917 Fuel cell, 524
Fugacity, 214, 243 Fundamental particles, 945 Fusion, 259(T), 931
G
g factor, 816
Galvanic cell, see Electrochemical cell Galvanic electricity, 429, see also Potential Galvanometer, 429, 434
Gamma function, 49
Gamma radiation, 938, see also Radiation Gas
constant, 6(T) diffusion, 59 ideal, 1
entropy changes for, 186 law first and, 116 mixtures of, 8, 316 partition function for, 127 statistical thermodynamics of, 203 two-dimensional, 204, 345 kinetic molecular theory, 39 liquefaction, 138
molecular weight, 7 nonideal, 1, 13
fugacity of, 214, 243 self-diffusion in, 59, 62(T) solubility, 307
thermal conductivity, 61, 62(T) transport properties, 62(T) viscosity, 56, 62(T), 69 Geiger counter, 947 Gel, 906
Gerade, 744, 769
Gibbs, J. W. (biography), 208
Gibbs-Duhem equation, see Equation(s) Gibbs equation, see Equation(s)
Gibbs free energy, 191
Gibbs—Helmholtz equation, 503 Gibbs monolayers, 345
Gibbs phase rule, 391 Glan prism, 839 Glass elctrode, 519 Glide plane, 886 Gouy balance, 92 Graham's law, 52
Grand canonical ensemble, 209 Graphite, 863
Grotthus mechanism, 448, 475, 618 Group theory, 718, see also Symmetry
H Habit, see Crystalline state Half-cell, 509, see also Electrode Half-life, 546, 940, see also Rate law Half-wave potential, 535, see also Potential Hamaker constant, 900
Hamiltonian operator, 666
Hard acid (base), 481, see also Acid Hard sphere model, 30, 54
Harmonic oscillator, 135, 673, see also Oscillator
Hartree (unit), 661 Hartree-Fock method, 702 Heat, see also Enthalpy
capacity, 112, 157(T) Debye theory of, 139, 211 difference, 282(T) Einstein theory of, 138 molecular basis for, 122 rotational, 130 of solids, 138
temperature dependence of, 157(T) vibrational, 132
of dilution, 149, 341 latent, 105
machines, 177
mechanical equivalent, 103 of mixing, 319
pump, 183
of solution, 149, 339 specific, 112
theorem (of Nernst), 207, 209 Heisenberg principle, 657, 700 Helium atom, 701
Helmholtz free energy, 191, see also Free energy
Hemoglobin, 879 Henry's law, 306, 363 Hermite polynomials, 674 Heterogeneous catalysis, 551, 587 Heterogeneous equilibrium, 391, see also
Phase
Hexagonal close packing, 857, see also Crystalline state
Hittorf method, 451, 483 Huckel method, 775 Hund's rule, 706, 752, 778
Hybrid orbital, 694, see also Orbital(s) Hydration energy, 447, 476, see also Energy,
Enthalpy Hydrogen
atom
energy levels, 662 wave equation for, 677 bomb, 931
bond,262
electrode, 500, 508,518 iodide excited states, 794 molecule, 761
excited states, 791 molecule ion, 765, 791
Hydrogeneration enthalpies, 151 (T) Hydrogen-like atom, 661, 683, 691
Hydrolysis, 472
Hydrophobic bonding, 916 Hydrostatic pressure, 10 Hypercharge, 945
Hypothesis, see Principle(s)
I Ice, see also Crystalline state
calorimeter, 148 entropy, 212 structure, 283, 864 Iceberg model for water, 284 Ideal gas, see Gas
thermometer, 6
Ideal solution, 304, 318, 335 Identity operation, 718
Immiscible liquids, distillation of, 328 Impact parameter, 69
Improper rotation axis, 721 Incongruent melting, 398
Indeterminancy principle, 657, 700 Index of refraction, 78
Induced attraction, 288 Inertia, moment of, 134, 812 Infrared absorption, 807
Inhibition, 561, see also Kinetics Integrals
Coulomb, 763, 776 overlap, 763
resonance, 763, 772, 776
Interfacial tension, see Surface tension Interionic attraction, 441, see Debye-Huckel
theory
Intermolecular forces, 286, 290(T) Internal conversion, 802, 943 Internal energy function, 164 Internal pressure, 133,282(T) Intersystem crossing, 802
Intrinsic viscosity, 912, see also Viscosity Inversion point, 137
Iodine molecule, 796—797 Ionic character, 85
Ionic crystals, see Crystalline state Ionic diffusion, 481
Ionic equilibrium, 466, 486 Ionic radii, 893
Ionic reactions, see Reaction Ionic strength, 458
effect of, on reaction rate, 627 Ionization, see Energy, Potential
SUBJECT INDEX 111
Ions
association of, 430,477 atmosphere of, 463 complex, 447, 486, 823
enthalpies of formation of, 156(T) free energy of, 525
hydration of, 447, 476 mobility of, 442,446(T) pairing of, 477, see also Mobility thermodynamics of aqueous, 524, 525(T) Iron, cast, 418
Irreversible process, 108, 175 entropy change, 188 Isobar, 16
Isobaric process, 112 Isochoric process, 112 Isolated system, 187 Isolation method, 554 Isomeric transition, 943 Isometric, 16, see also Isostere Isopiestic equilibrium, 358 Isostere, 16
Isotactic, 911 Isotensiscope, 254
Isotherm, 16, 588, see also Adsorption Isothermal Joule—Thomson effect, 144 Isotone, 931
Isotonic, 376 Isotope, 931
effect, 601 mass, 929(T)
J Joule coefficient, 136 Joule effect, 136 Joule experiment, 116
Joule—Thomson coefficient, 137, 214 isothermal, 144
Joule—Thomson effect, 137 Junction
liquid, 5 0 1 , 5 0 7 , 5 2 7 potential, 507, 519, 529 Jungner battery, 524
Κ Kayser (unit), 660
Kekulé structure of benzene, 164, 779 Kelvin effect, 279, 885
Kelvin equation, see Equation(s)
Kinetic molecular theory, 39 summary, 62(T)
Kinetics, 543, 603
of excited state processes, 805 experimental methods, 551, 608 flash photolysis, 557
gas phase, 543
of heterogeneous catalysis, 587 inhibition in, 561
of nuclear disintegration, 940 shock tube method in, 557 of small perturbation, 607 of solution reactions, 603 stoichiometry and, 555, 558 Knudsen flow, 52
Kraft temperature, 905
L
Lagrange method of undetermined multipliers, 4 2 , 4 3
Laguerre polynomials, 681 Lambert's law, 76 Lande splitting factor, 821
Langmuir equation, 588, see also Adsorption Laplace equation, 271
Laplace operator, 666 Larmor precession, 820 Lasers, 808, 831
mode-locked, 833 Q-switched, 832 Latent heat, 105
Lattice, see Crystalline state, Energy Law(s)
Amagat, 10 associative, 728 Beer, 77
Beer-Lambert, 77, 938
Boltzmann distribution, 40, 65, see also Principle(s)
Boyle, 3 , 4 Charles, 3 commutative, 728
of constant heat summation ,151 Coulomb, 88, 286
Dalton, 9, 301
Debye-Huckel, 461, 476, 626, 902 Dulong and Petit, 138
of electrode kinetics, 521 Fick, 59, 365
first, of thermodynamics, 101, 107 statistical treatment of, 125, 134
Law(s) (cont.) Fourier, 61 Graham, 52
Henry, 303, 306, 363 Hess's, 151
ideal gas, 3, 53 Lambert, 76 of mass action, 227 Newton, 87 Ohm, 432
Ostwald dilution, 439, 475 of photochemical equivalence, 656 Raoult, 3 0 3 , 3 0 4 , 3 3 6
of rational intercepts, 855 of rectilinear diameter, 27, 262 second, of thermodynamics, 173
chemical equilibrium and, 241 statistical treatment of, 199 Stokes, 364, 443, 446, 917 Tate, 276
third, of thermodynamics, 173, 196, 209 Le Châtelier's principle, 239
Leclanché cell, 524 Legendre polynomial, 680
Lennard-Jones potential, 30, 68, 890 Lepton, 945
Lever principle, 309, 327, 331 in ternary diagrams, 404 Lewis acid (base), 481, 911 Lifetime, 805
Ligand field theory, 784 Light, absorption of, 76 Light scattering, 370
Lindemann—Christiansen mechanism, 570, 573, 576, 581, see also Reaction(s) Linear combinatin of atomic orbitals, 772 Linear free energy relationships, 624 Liquefaction of gases, 138
Liquid crystals, 908 Liquid junction, 501, 527
Liquid—solid phase diagrams, 263, see also Phase diagram(s)
Liquids
immiscible, distillation of, 329 phase equilibria of, 251
statistical thermodynamics of, 262, 336 surface tension of, 264, 278(T) thermodynamic coefficients of, 282(T) vapor pressure of, 253
viscosities of, 280, 281(T), 290 Logarithmic diagrams, 486 London force, see Force Lyman series, 658
Lyophilic, lyophobic, see Colloids
M McLeod gauge, 35
Macromolecules, see Polymers Madelung constant, 891(T) Magnetic balance, Gouy, 92 Magnetic moment, spin, 94 Magnetic permeability, 88 Magnetic properties of matter, 92 Magnetic quantum number, 662, see also
Quantum number Magnetic resonance
electron spin, 821 nuclear, 815 proton, 818
Magnetic susceptibility, 94 Magnetism, 93
Magneton
Bohr, 9 4 , 8 1 5 , 8 2 1 nuclear, 815 Margules equation, 310 Mass action law, 227 Mass
defect, 933
energy equivalent, 933 number, 927
reduced, 55, 659, 675 rest, 933
spectroscopy, 926 Matrix notation, 730
Maximum boiling point diagram, 326 Maximum vapor pressure diagram, 309 Maxwell-Boltzmann principle, see
Principle(s) Mean free path, 55, 63
in mixtures, 71 Mean life, 547
Mechanical equivalent of heat, 103 Mechanism of reaction, see Reaction(s) Melting point, see also Freezing point
congruent, 398 incongruent, 398
Membrane, semipermeable, 359, 469 Meson, 945
Mesophase, 908
Metals, see also Crystalline state conductance of, 880
ductility of, 859
Metastable phase equilibria, 267 Metastable state, 190
Method
capillary rise, 273 CNDO, 783 drop weight, 275
SUBJECT INDEX 113
Hartree-Fock, 702 Huckel, 775 isolation, 554 molecular orbital, 765 perturbation, 707 scientific, 6 stop flow, 609 temperature jump, 609 undetermined multiplier, 42, 43 valence bond, 761
variation, 646, 775 Wilhelmy slide, 277, 345 Micelle, 413, 906
Michaelis-Menten mechanism, 634 Microcanonical ensemble, 209
Microscopic reversibility, 242, 565, 580, 582 Microtome, 344
Microwave spectroscopy, 812, see also Spectroscopy
Miller index, 854, see also Crystalline state Minimum boiling point diagram, 326 Minimum vapor pressure diagram, 309 Miscibility
critical temperature for, 312 gap, 419
partial, 329, 342
Mixing, excess thermodynamic quantities for, 320
Mixtures of ideal gases, 8,316 Mobility, 442
electrochemical, 443 of electrons, 880 ionic, 442, 446(T) Model
band, of solids, 879 Bohr, 659
free electron, 762 Modulus, 906 Molality (unit), 302
mean, 455 Molar absorption, 77 Molar polarization, 81 Molar refraction, 78 Molarity (unit), 302 Molecular beam, 583 Molecular bonding, 759
Molecular charge distribution, 89
Molecular crystals, 863, see also Crystalline state
Molecular diameter, 66
Molecular orbital, 761, 768, see also Orbital(s)
Molecular size, 368 Molecular spectroscopy, 789
Molecular weight average, 372 determination of, 364 of gases, 7
of polymers, see Polymers Molecules
excited states of, 790
geometry of ground and excited states of, 812,821
molecular orbital method for, 765, 782 rotational spectra of, 812, 839 vibrational spectra of, 807, 839 Moment
dipole, 79, 80, 85(T) of inertia, 129, 134,812 quadrupole, 91(T) Monolayers, Gibbs, 345 Monomer, 910
Monomolecular films, see Monolayers Mossbauer effect, 947
Mosaics, 850
Moving boundary method, 445 Mu particle, 945
Multiplication table, see Symmetry element Multiplicity, 703, 765
Mutual diffusion coefficient, 61
Ν
Natural disintegration series, 948 Nematic phase, 909
Nernst equation, see Equation(s) Nernst heat theorem, 207, 209 Neutrino, 938,945
Neutron, 928 diffraction, 876 flux, 936 Newton (unit), 7, 87 Newton's first law, 87 Newton's viscosity law, 57 Nicol prism, 839
Nitrogenase, 635
NO2—N2O4 equilibrium, 9 Nonbonding, see Orbital(s) Noncrossing rule, 769 Nonelectrolytes, 301 Nonideal gases, 13
fugacity of, 214, 243
Nonideal solutions, 310, 317, 373 Normal boiling point, 255
Normal mode (of vibration), 133, 808 Normalization, 44, 671
Nuclear binding energy, 933 Nuclearbomb,931,944 Nuclear chemistry, 945 Nuclear disintegration
kinetics of, 940 modes of, 931 theories of, 943 Nuclear energetics, 931 Nuclear existence rules, 931 Nuclear g factor, 816
Nuclear magnetic resonance, 815 Nuclear magneton, 815
Nuclear process alpha emission, 943 annihilation, 938 beta emission, 931, 943 Compton effect, 938 electron capture, 931 fission, 935, 944 fusion, 931
internal conversion, 943 isomeric transition, 943 pair formation, 938 photoelectric effect, 938 positron emission, 93 J spallation, 935 Nuclear reactions, 934
cross section for, 936 Rutherford type, 934 Nuclear reactor, 944 Nucleation, 279
Nucleic acids, 364, 878, 915 Nucléon, 931
Number average molecular weight, 373 Nutrition, thermochemistry of, 160 Nylon, 911
Ο
Octahedron, 724, see also Symmetry Ohm's law, 432
One-component systems, 392—393 Opal, 280
Open system, 312
Operational definition, 6, 67 Operators, 667
Optical activity, 834 chirality, 838
circular dichroism, 837 circular polarization, 835
coefficient of dichroic absorption, 838
dextrorotatory, 834 dissymmetry factor, 838 instrumentation, 839 levorotatory, 835 molar rotation, 834 rotatory dispersion, 837 theory, 835
units, 834 Optical density, 77 Orbital(s), 683
antibonding, 769
as basis for representation, 736 domain representation, 692 hybrid, 694
hydrogen-like, 683
linear combination of atomic, 772 molecular, 768
excited states and, 789 nonbonding, 745, 771 overlap, 764
Orientation force, 288 Orthogonal, 772 Orthonormal, 680 Oscillator
anharmonic, 135, 676 harmonic, 135,673, 807 strength, 828
Osmosis, reverse, 378 Osmotic
effect, 359, 454, 469 pressure, 360, 376 and solvent tension, 377 Ostwald dilution law, 439, 475 Ostwald viscometer, 280
Overlap, 764, 772, see also Integrals, Orbital(s)
Overvoltage, 521, see also Potential Oxidation potential, 511(T), 517(T), see also
Potential
Oxidation—reduction reaction, 516, see also Reaction(s)
Oxide donor (acceptor), 481 Oxygen
excited states, 793 singlet, 824
Ρ Pair formation, 938 Parachor, 99 Paramagnetism, 92 Partial differential, 109
SUBJECT INDEX 115 Partial miscibility, 329, 342, 419
Partial molal quantities, 314, 337 Partial molal volume, 332, 338 Partial pressure, 8
Partial volume, 10 Particle
in box, 127,669,801 alpha emission and, 943 free, 668
Partition function, 125, 166, 199 electronic, 127
internal, 129 rotation, 129, 134 translation, 127 vibration, 131 Pascal constant, 94(T) Pascal (unit), 7 Paschen series, 658
Pauli principle, see Exclusion principle Peritectic, 401, 415
Permeability, magnetic, 88 Permittivity (of vacuum), 89 Perpetual motion machine
first kind, 106 second kind, 174, 242 Perturbation theory, 707 pH meter, 518
Phase
colloidal suspension as, 413 definition, 391,412 change, entropy of, 188, 258 equilibrium, 263, 315
metastable, 267 map, see Phase diagram(s) micelles as, 413
reaction, 396 rule, 391 Phase diagram(s)
acetone-chloroform, 305, 321 acetone—phenol-water, 418 A u - S i , 398
benzene, 264
benzene-ethanol, 310 benzene—toluene, 304 B i - P b - S n , 4 0 8 C a C h - C a F 2 , 4 0 4 carbon dioxide, 257 construction rules, 401 detergent, 905 F e - A u , 4 1 6 F e - C , 4 1 8 FeCh-water, 404 K C l - N a C l - w a t e r , 4 1 0
lever principle, 309, 327, 331, 409
liquid-solid, 263 liquid—vapor, 307
Li2S04-(NH4)2S04-water, 412 N a C l - N a2S 04- w a t e r , 411 Na2S04-water, 402 NH4NO3, 394 P b - B i , 4 1 6 peritectic, 416
phenol—/?-toluidine, 404 phosphorus, 394
quadruple point, 403, 406 sulfur, 266
solid-solid, 263
three-component, 405, 410 triangular graph paper for, 405 two-component, 394
water, 264, 266
Phenomenological equations, 3 Phonon,629
Phosphorescence, 802, 822 Photochemistry, 789
processes, 803, 805 Photochromism, 825 Photoconductivity, 881 Photoelectric effect, 656, 938
Photographic detection of radiation, 946 Photolysis, flash, 557
Photoreversibility, 8 0 5 - 8 0 7 , 825 Photosensitization, 803
Physical adsorption, see Adsorption Pi bond, 748, see also Bond Planck—Einstein equation, 656 Plasmolysis, 376
PLAWM trough, 345 Point defect, 882
Point group, see Crystalline state, Symmetry Poise (unit), 57
Poiseuille equation, 57, 200, 290, 919 Poisson equation, 462, 902
Polar coordinates, 677 Polarimeter, 834
Polarizability, 79, 85(T), 696, 900 intermolecular forces and, 288, 900 Polarization
activation, 522 concentration, 522, 532 at electrodes, 530 molar, 81 residual, 521
Polarography, 520, 530, 534 Polonium, 927
Polymers, 909 isotactic, 911
kinetics of formation, 910
Polymers (cont.) molecular weight, 912 secondary structure, 914 thermodynamics, 914 viscosity, 912 Positron, 928 Potential
absolute, 526 appearance, 583 decomposition, 521 diffusion, 482 Donnan, 470
electrochemical, and equilibrium, 512 electrode (absolute), 526
galvanic, 429, 527 half-wave, 535 ionization, 892 junction, 507, 509, 529
over-, 521 rational, 526 sedimentation, 916
standard electrode, 510, 511(T), 522 standard oxidation, 508, 511(T), 522 streaming, 919
zeta, 916
Potential energy function hard sphere, 30
Lennard-Jones, 30, 68, 890 oscillator, 135, 673
Potentiometer, 505
Powder pattern, see Crystalline state Precession, 819
Precession method, 874, see also Crystalline state
Predissociation, 797
Preexponential factor, 563, see also Kinetics, Reaction(s)
Pressure critical, 15 effect
on chemical equilibrium, 243 on emission, 823
on phase equilibrium, 264 on reaction rate, 646 on vapor pressure, 269 hydrostatic, 10
internal, 133,282(T) osmotic, 360, 376 partial, 8 reduced,17 surface, 345
two-dimensional, 345
Principal axis, 721, see also Symmetry Principal quantum number, 658, 661, 681
Principle(s) Avogadro, 8
Boltzmann, 2, 12, 40, 197, 462, 882, 901 corresponding states, 17, 24, 258 de Broglie, 657, 664
detailed balancing, see Microscopic reversibility
equipartition, 122, 808
exclusion, see Exclusion principle Franck-Condon, 795
Heisenberg uncertainty, 657, 700 ionic strength, 458
Le Châtelier, 239 lever, 3 0 9 , 3 2 7 , 3 3 1 , 4 0 4
Maxwell -Boltzmann, see Boltzmann principle
microscopic reversibility, 242
Pauli exclusion, see Exclusion principle Planck—Einstein, 656
uncertainty, see Heisenberg principle Probability
entropy and, 196 thermodynamic, 201 weight, 197 Protein
electrophoresis, 450 molecular weight, 364 structure, 879, 915 Proton
donor (acceptor), 480 magnetic resonance, 818
transfer reactions, 619(T), see also Reaction(s)
Pseudoplastic, 907 Pulse amplifier, 946 Pyrolysis, 561
Q Q-switching, 832 Quadruple point, 403, 406 Quadrupole moment, 91(T) Quantum number
angular (or azimuthal), 662, 767 magnetic, 662
principal, 658, 661, 681 rotational, 706
spin, 662 vibrational, 675 Quantum statistics, 746 Quantum yield, 551, 805
SUBJECT INDEX 117 Quenching (of fluorescence), 803
Quinhydrone, 519
R Rad (unit), 939 Radar, 812
Radial distribution, 252 Radiation
absorption of, 76, 827, 937 annihilation, 938
blackbody, 708 chemistry, 940 cosmic, 940 detection, 946 dosage, 939 emission, 797, 827 gamma, 938 x , 9 3 9
Radiationless deactivation, 803 Radical, 583
Radioactivity, 927
Raman spectroscopy, 807, 831 Random coil, 913
Random walk, 59 Range, 937
Raoult's law, 303, 304, 336 Rare gas crystals, 889
Rate, see also Kinetics, Rate law, Reaction(s) constant, 544
equilibrium constant and, 630 ionic strength dependence, 627 pressure dependence, 646 temperature dependence, 562 initial, 555
Rate law, 545, 550 first order, 545
branching, 637 pseudo, 549 reversible, 604 sequential, 639 isotope exchange, 643 order of, 545
reaction mechanism and, 557 second order, 547
reversible, 642 in solution, 614(T) zero order, 550 Rational activity, 245, 336 Rational potential, 526
Reaction(s), see also Kinetics, Rate, Rate law acid—base, 620
association, 557 bimolecular, 544 chain, 560, 586 coordinate, 575 decomposition, 557
degree of advancement, 575, 633 diffusion controlled, 618(T) elementary, 544, 557 entropy production, 632 exchange, 557
fast, 556, 609, 619(T) first order, see Rate law Fischer-Tropsch, 587 of ions, 826
mechanisms, 544, 545
in heterogeneous catalysis, 587 intimate, 573
Lindemann-Christiansen, 570, 573, 576,581
Michaelis-Menten, 634 rate laws and, 557 nuclear, 934
oxidation—reduction, 516 phase, 396
profile, 573
proton transfer, 619(T) pyrolysis, 501 rate, see Rate, Rate law reversible, 604, 642 second, order, see Rate law simple, 558(T)
spallation, 935 surface, 587 termolecular, 579 trajectory, 583
unimolecular, 544, 569, 572(T) Reactor (nuclear), 944
Rectilinear diameter law, 27, 262 Reduced mass, 55, 659, 675 Reduced variables, 17 Reduced viscosity, 912
Reference electrode, 507, see also Electrode Reference state, see Standard state
Refraction index of, 78 molar, 78 Refrigerator, 183 Regular solution, 335 Relative viscosity, 912 Relativity, 656, 933 Relaxation
effect, 483 longitudinal, 820 methods, 609
Relaxation (cont.) spin-lattice, 816, 820 time, 607
transverse, 821 Rem (unit), 939
Repeating unit, 852, 888, see also Crystalline state
Representation, see Symmetry group Reproduction constant, 944 Resistance, 432
Resonance, 765 absorption, 944 emission, 797 energy, 164, 778 integral, 763, 772, 776 Rest mass, 933
Retrograde solubility, 412 Reverse osmosis, 378 Reversible process, 114, 175
entropy change, 185 rate law, 604, 642 Reversible work, 113 Rheology, 906 Rheopexy, 908 Rigid rotator, 706 Rochan prism, 839
Rockets, thermochemistry of, 159 Roentgen (unit), 939
Rotation
optical, see Optical activity partition function, 129, 134 representations, 809 symmetry number, 134 wave mechanics, 706 Rotational constant, 812, 840 Rotational degree of freedom, 123 Rotational temperature, 130, 206 Rotational transition, 795
Rotatory dispersion, 837, see also Optical activity
Rubber, 910 Rule(s)
aromaticity, 782 Hund,706, 752, 778 noncrossing, 769 phase, 391
phase diagram construction, 401 Schulze-Hardy, 904
selection, 792, 830 Trouton,259(T),261 Walden, 368, 385
Russell—Saunders coupling, 703 Rydberg (unit), 661
Rydberg constant, 658 Rydberg progression, 790
S
Sackur-Tetrode equation, 204, 211, 262, 577 Salt bridge, 507
Saturation activity, 941 Scattering
factor, 888 light, 370 reactive, 584
Schoenflies symbol, 722, 885, see also Symmetry group
Schottky defect, 882
Schrôdinger equation, see Equation(s) Schulze-Hardy rule, 904
Scientific method, 6 Scintillation counter, 947
Screening constant, see Constant(s) Screw axis, 884
Sea water, 377
Second law of thermodynamics, 173 chemical equilibrium and, 241 emf and, 503
statements, 177, 207
Second order reaction, see Rate law Secular equation, 697, 776 Secular equilibrium, 942 Sedimentation
coefficient, 365,370(T) equilibrium, 369 potential, 916 velocity, 364 Selection rule, 792, 830 Self-consistent field, 702 Self-diffusion
coefficent, 384 of gases, 59 of ions, 481 Semiconductors, 879
intrinsic, 881
as radiation detectors, 947 Semipermeable membrane, 359 Shear rate, 907
Shell (closed or filled), 692 Shock tube, 557
SI (system of units), 87 Siemens (unit), 434
Sigma bond, 744, 771, see also Bond Similarity transformation, 729 Simple reaction, 558(T) Simple solution, 335 Singlet state, 765 Size, molecular, 54, 364 Slip plane, 882
Smectic phase, 909 Soap, see Detergent
SUBJECT INDEX 119 Soft acid (base), 481, see also Acid(s)
Sol, 280, 899 flocculation, 919 Solar energy, 824
Solid state, see Crystalline state Solid—solid phase diagrams, 263 Solubility
activity coefficients from, 456 diagrams, three-component, 410 equilibria, 468
freezing point depression and, 375 of gases, 307
product, 442, 456, 468(T), 513 retrograde, 412
Solute (definition), 375 Solution, see also Mixing
enthalpy of, 149, 151(T),339 entropy of, 319
free energy of, 319 heat of, 149
Solutions, 301, 353, 429 athermal, 335 definition of, 301 diffusion in, 334
electrolyte, see Electrolyte(s) ideal, 303, 317, 335
molar volume, 332 nonelectrolyte, 301, 353 nonideal, 310, 319, 373 polarization of, 84 polymer, see Polymers properties of, 332 regular, 335 simple, 335
statistical thermodynamics of, 336 surface tension of, 334, 342 vapor pressure of, 303, 323 viscosity of, 333
Solvay conferences, 699 Solvent cage, 252, 291, 612 Sound absorption of, 611
Space group, see Crystalline state, Symmetry Space suits, 162
Spallation reaction, 935
Specific conductivity, 432, see also Conductivity
Specific heat, 112 Specific resistance, 432 Specific viscosity, 912
Spectroscopic constants, 206(T) Spectroscopy
mass, 926 microwave, 812
magnetic resonance, see Magnetic resonance
molecular, 789 Raman, 807,831 vibration—rotational, 839 vibrational, 807
Sphere(s)
close packing of, 857 hard, 30, 54
Spherical harmonics, 692 Spin
conservation, 945
electron, 692, see also Electron -lattice relaxation, 816, 820 magnetic moment, 94 nuclear, 815
quantum number, 662 Square terms, 581 Square well potential, 30
Standard cell, 506, see also Electrochemical cell
Standard deviation, 64, 949
Standard state, 153, 317, see also Activity Standing wave, 660, 665, 667, 679 Stark effect, 813
State(s) atomic, 703
corresponding, 17, 24, 31, 258 delocalized, 801
excited, 789 chemistry of, 821 emission from, 827 of formaldehyde, 799 geometry of, 821 of hydrogen atom, 662 of hydrogen iodide, 794 of hydrogen molecule, 791 of hydrogen molecule ion, 765, 791 of iodine molecule, 796, 797 of oxygen molecule, 793 processes of, 801 structure of, 821 of sulfur molecule, 743 thermal equilibration of, 803 functions, 107
multiplicity of, 765 reference, see Standard state singlet, 765, 802
standard, see Standard state of system, 106
thexi, 802 triplet, 765, 802
Stationary state approximation, 559 Statistical thermodynamics
equilibrium and, 244, 593 first law quantities, 125, 134 J.W. Gibbs and, 208
Statistical thermodynamic s (cont.) ideal gas , 20 3
liquids, 262 , 33 6 nature of , 10 2
reaction rate s and , 577 , 59 3 second la w quantities , 19 9 solutions, 33 6
transition stat e theory , 59 3 Statistical weight , 41 , 12 5 Statistics
nuclear disintegration , 94 9 quantum, 94 6
Steady stat e approximation , 55 9 Steam distillation , 32 9
Steam engines , 17 8 Steel, 41 7
Stefan—Boltzmann constant , 71 0 Stereographic projection , 725(T) , see also
Symmetry Steric factor , 56 9
Stimulated emission , 829 , 83 1 Stirling's formula , 42 , 20 1 Stoichiometry
of chemica l equations , 14 5 in crystals , 86 1
in kinetics , 55 8
Stokes law , 364 , 443 , 446 , 91 7 Stokes shift , 79 8
Stop flo w method , 60 9 Strain, 90 7
Strangeness, 94 5 Streaming potential , 91 9 Stress, 90 7
Stripping, 58 5 Structure factor , 88 8 Sublimation, 26 6
Sulfur molecul e excite d states , 74 3 Supercooling, 27 9
Supersaturation, 2 3 Surface
collision frequency , 5 0
concentration o n crysta l planes , 86 7 pressure, 34 5
tension, 264 , 272 , 278(T ) measurement of , 27 2 Parachor and , 9 9 of solutions , 334 , 34 2
Surfactants, 334 , see also Detergent s Susceptibility, magnetic , 9 4 Suspension (definition) , 30 1 Sutherland equation , 6 8 Swamping electrolyte , 46 7 Symmetric top , 813(T ) Symmetry, 75 9
of crystals , see Crystallin e stat e
elements, 71 8
associative multiplicatio n la w for , 72 8 class of , 72 9
commutative multiplicatio n la w for , 72 8 multiplication tabl e for , 72 7
octahedron, 72 4 reciprocal, 72 8 tetrahedron, 72 3 group, 725(T )
bonds a s basi s for , 74 4 C3 v, 73 0
C4 v, direc t produc t for , 75 3 character tabl e for , 737(T ) definition, 72 7
irreducible representatio n of , 73 5 naming, 72 2
orbitals a s basi s for , 73 6 order of , 72 8
properties of , 72 8
reducible representation s of , 73 5 representation of , 729 , 73 5 Schoenflies' symbol s for , 722 , 88 5 stereographic projection , 719 , 725(T ) trace o f representatio n of , 73 4 Huckel theor y and , 78 1 notation fo r crystals , 88 5 number, 13 4
operations, 71 8 direct product , 75 3 horizontal plane , 72 1 identity, 71 8 improper axis , 72 1 principal axis , 72 1 secondary axis , 72 1 vertical plane , 72 1
point group , see Symmetry , grou p space groups , 722 , 88 6
transformation, matri x notatio n for , 73 0 System (open) , 31 2
Système Internationa l d'Unités , 8 7
Τ Tafel equation, 522, 530 Tate's law, 276 Teflon, 909 Temperature absolute, 3 Boyle, 14, 20 coefficient, 563, 566 consolute, 330,419 critical, 15
in ternary systems, 419
SUBJECT INDEX 121 dependence
of equilibrium constants, 234 of heat capacity, 157(T) of rate constants, 562 eutectic, 395
jump method, 609 reduced, 17 rotational, 130 vibrational, 131 Tensile strength, 23, 26 Tensiometer, 277
Termolecular reactions, 579
Ternary, see Three-component systems Tetrahedron, 723, see also Symmetry Theory
absolute rate, see Theory, transition state Bohr, 658
caloric, 103, 179 collision, 544, 567, 614 crystal field, 751
Debye-Hiickel, 461, 476, 626, 902 encounter, 628
kinetic molecular, 39, 63(T) ligand field, 784
nuclear disintegration, 943 overvoltage, 521
relativity, 656, 933 transition state, 573, 628
for solutions, 619
statistical thermodynamics of, 577, 593 Thermal analysis, 396
Thermal conductivity, 61 Thermal equilibration, 802 Thermal expansion, 17, 282(T) Thermochemistry, 145
Thermodynamic equation of state, 214 Thermodynamic equilibrium constant, 229 Thermodynamic probability, 201
Thermodynamic properties of liquids, 282(T) Thermodynamic relationships (summary), 212 Thermodynamics, see also First, Second,
Third laws of thermodynamics of aqueous ions, 524, 525(T) first law, 101
laws, 207 of polymers, 914 second law, 173, 177 statistical, 125, 199
chemical equilibrium and, 244, 593 nature of, 102
of surfaces, 270 Thermometer (ideal gas), 3 Thexi state, 802
Third law of thermodynamics, 173, 196, 207, 209
verification of, 210(T) Thixotropy, 908
Thompson, B. (biography), 103 Thorium series, 948
Three-component systems, 405 critical temperature, 419 lever principle, 409 partial miscibility, 419 solubility, 410 Tie-line, 309 Titration
conductimetric, 473 curves, 472, 490 Top, symmetric, 813(T) Total differential, 107
Trace, 734, see also Symmetry group Transfer coefficient, 531
Transference number, 446, 449, 451(T) Hittorf method for, 451, 483 Transient equilibrium, 640, 942 Transition
allowed, 828,830 charge transfer, 800 electronic, 795 forbidden, 676, 828 internal conversion, 802 intersystem crossing, 802 moment, 828
parity forbidden, 830 phosphorescent, 803
radiationless deactivation, 803 rotational, 795
selection rules, 830 vertical, 796 vibrational, 795
Transition state theory, see Theory Translation
degree of freedom, 123
entropy, 204, see also Sackur-Tetrode equation
partition function, 127
Transport number, see Transference number Transport properties of gases, 56, 63(T) Triatomic molecules, 774
Triboluminescence, 822 Triple point, 266, 394 Triplet state, 765
Trouton's rule, 259(T), 261 Tunnel effect, 944 Turbidity, 372 Turnover number, 635
Two-component systems, 392, 394, see also Freezing point
Two-dimensional gas, 204
Two-dimensional particle in box, 672
U Ultracentrifuge, 365 Ultraviolet catastrophe, 710 Uncertainty principle, 657, 700 Undetermined multipliers, 42, 43 Ungerade, 744, 769
Unimolecular reaction, 544, 569, 572(T), see also Reaction rate
United atom, 769 Units
of energy, 661 SI system of, 87 Unsold's theorem, 691 Uranium series, 948
V Valence bond method, 761 Van der Waals constants, 25(T) Van der Waals equation, see Equation(s) Van der Waals forces, 259, 286 Van't Hoff equation, 235, 258 Van't Hoff / factor, 374, 455 Vapor, 15
composition diagrams, 307 free energy, 268
Vapor pressure, 14, 251 diagrams, 303, 304 lowering, 354 pressure effect on, 264
temperature dependence of, 254, 323 Vaporization, enthalpy and entropy of, 259(T) Variation method, 696, 760
Velocity
averages, 49, 50 probable, 48 selector, 65 Vertical transition, 795
Vibrational degree of freedom, 124 Vibrational force constant, 675, 810(T) Vibrational heat capacity, 132 Vibrational normal mode, 133, 808 Vibrational partition function, 131 Vibrational quantum number, 675 Vibrational-rotational transitions, 840 Vibrational spectroscopy, 807 Vibrational temperature, 131 Vibrational transitions, 795 Virial coefficient, 13,31 Virial equation, 13, 20 Viscometer, 280
Viscosity
coefficient, 56, 912 gas, 56, 62(CT) intrinsic, 919
liquid, 280, 281 (T), 290 Newtonian, 56, 906 number, 912 polymer solution, 913 ratio, 912
reduced, 912 relative, 912 solution, 333, 912 specific, 912 Vitamin Β i 2 , 878 Volt (unit), 432 Voltaic pile, 429 Voltammetry, 536 Volume
excluded, 19 partial, of gases, 10 partial molal, 332, 338 reduced,17
w Walden inversion, 645 Walden's rule, 368, 447 Walsh diagram, 774 Water
anomalous, 285 conductivity, 441 desalination, 377 dissociation, 441 repellency, 275 structure, 283, 448 Wave mechanics, 655
alpha emission, 943 free particle, 668 harmonic oscillator, 673 hydrogen atom, 677 nature of, 667 particle in box, 669 postulates of, 667 rigid rotator, 706 Wavenumber, 658, 660
Weak electrolyte, 438, see also Acid(s), Electrolyte(s)
Weight average molecular weight, 373 Weissenberg method, 874
Weston cell, 506, see also Electrochemical cell Wheatstone bridge, 435
Wilhelmy slide method, 277, 345 Work (reversible), 113,503
χ
Χ radiation, 927, see also Radiation X rays
diffraction, 867, 887, see also Crystalline state
Y Yield (of nuclear reaction), 936 Yield point, 908
SUBJECT INDEX
Ζ Zeeman effect, 662
Zero point energy, 131, 595, 676 Zeta potential, 916
Zetameter, 449, 916 Zimm plot, 372 Zwitterion, 479
ο ι
Young's equation, 272 Young's modulus, 906
