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3 1 . The Solid State 1165-1212 32. The Colloidal State 121 3-12 50
Difference between crystalline and amorphous The colloidal systems (1213)
solids (1165) Preparation of lyophobic colloidal solutions (1213)
Symmetry in crystal systems (1166) A. Dispersion methods (1213)
Point groups and space groups (1168) B. Condensation methods (1215)
Space lattice and the unit cell (1169) Purification of colloidal solutions (1216)
Bravais lattices (1169) Properties of colloidal systems (1216)
Seven crystal systems (1170) Properties of hydrophobic colloidal systems
Lattice energy of an ionic crystal (1173) (1218)
Born-Lande equation and the Born-Haber I. Electrical properties (1218)
cycle (1174) Charge on colloidal particles (1218)
Law of rational indices (1175) The electrical double layer (1219)
Miller indices (1175) DLVO theory of the stability of lyophobic
Interplanar spacing in a crystal system (1175) colloids (1221)
Xray diffraction (1176) Coagulation of colloidal solutions (1222)
The Bragg equation (1176) II. Electrokinetic properties (1224)
Experimental methods : The rotating crystal and Electrophoresis (1224)
the powder (The Debye-Scherrer) techniques (1177) Electroosmosis (1225)
X-ray diffraction pattern for a cubic system Determination of size of colloidal particles (1225)
(1180) Surfactants (Surface-active agents) (1226)
X-ray diffration pattern for tungsten crystal (1181)
Hydrophile-Lipophile balance (HLB) (1228)
Fourier synthesis of electron density in a crystal
Micelle formation (1229)
(1183)
The mass action model and the phase
Patterson synthesis (1184)
separation model (1229)
Electron diffraction (1186)
Shape and structure of micelles (1231)
Neutron diffraction (1187)
Micellar aggregation numbers (1232)
Types of crystals (1188)
Critical micelle concentration (CMC) (1233)
Molecular crystals (1188)
Factors affecting CMC in aqueous media
Covalent crystals (1189)
(1234)
Ionic crystals (1189)
Thermodynamic approach to CMC (1236)
Characteristic structures of ionic crystals (1190)
Thermodynamics of micellization (1237)
Metallic crystals (1193)
Solubilization (1238)
Free electron model of metals (1194)
Location of solubilizates in micelles (1239)
Band theory of solids (1197)
The phase rule of solubilization (1240)
Energy band theory of conductors, semiconductors
and insulators (1199) Micellar catalysis (1240)
Superconductivity (1202) Emulsification by surfactants (1242)
LTSC and HTSC (1202) Macroemulsions (1242)
Imperfections in a crystal (1204) Factors determining stability of emulsions (1243)
Point defects (1204) Microemulsions (1245)
Schottky defects (1204) Theories of emulsions (1246)
Frenkel defects (1206) The selection of surfactants as emulsifying agents
Colour centres (1207) (1246)
Chapters 136
A Amphipathy 1226 Avogadros law 452
ab initio calculations 232 Amphiphile 1226 Axis of rotation
ABMO 174 Angular functions 65 improper 248
Absolute activity 1293 Angular momentum 87,141,165 proper 247
Absolute entropies 610 Addition of 169 Azeotropic mixtures 766
determination of 610 Matrices 165
standard 613 Angular momentum operators 141 B
Absorption spectrum 302 Anharmonicity constant 317 Balmer series 30
AcidBase catalysis 1148 Anilinehexane system 772 Bancroft rule 1242
indicators 733 Anisotropy 516 Band spectra 305
titrations 735 Antibodies 1238 Band theory 1197
Acids and Bases 706 Antiferromagnetism 448 Barometric formula 477
Arrhenius concept 706 Anthrancene reaction 1128 Base pairing in DNA 1320
Bronsted-Lowry concept 706 Anti-Stokes Raman spectroscopy Basis set 232
Lewis concept 710 334 Bathochromic shift 339
Actin 1312 Apparent equilibrium constant 655 BBGKY equations 514
Actinometer 1120 Apparent standard reaction BeerLambert law 1115
Activated complex theory 1063 Gibbs energy 656 Berthelot equation 485
Activation energy 1058 Appearance potentials 1332 BET adsorption isotherm 1259
Activity 605 Associated Legendre polynomials 67 BET equation 1261
coefficient 606 Arrhenius equation 1058 Binding and antibinding regions 232
Activity coefficients 827 Arrhenius frequency factor 1058 Bipolaron 1308
Addition polymerization 1301 Arrhenius parameters 1058 BPP theory of relaxation
Adhesion 505 Arrhenius activation energy 1058 processes 372
Adiabatic demagnetization 496 Asymmetric top molecules 314 Biochemical equilibria 654
Adiabatic expansion 538 Asymmetry parameter 421 Bioelectrochemistry 930
Adsorption 1251 Atactic polymers 1275 Biological electrochemical cell 930
applications of 1252 Atomic populations 238 Bjerrum theory of ion association 887
BET theory 1259 Atomic states and term symbols 149 Bismuthcadmium system
heat of 1253 Atomic number 23 (phase rule) 683
isobar 1254 Atomic spectra 154 Black body radiation 24
isostere 1254 fine structure 155 and BE statistics 960
isotherms 1263 hyperfine structure 162 Bloch function 1197
multilayer 1259 Stark effect 162 Blue shift 339
from solution 1264 Zeeman effect 159 BMO 177
Langmuir 1256 Aufbau principle 87 BCS theory 1202
Adenosine diphosphate (ADP) 655 Auger electron spectroscopy Bohrs correspondence principle 109
Adenosine triphosphate (ATP) 654 (AES) 1270 Bohr frequency condition 355
Affinity 1279 Austin Model 1 237 Bohrs theory 26
Allotropy 672 Autocatalysis 1161 Bohr radius 28
Amperometric titrations 929 Auxochrome 339 BohrSommerfeld theory 31
(i)
GENERAL
BIBLIOGRAPHY3GENERAL
1368 BIBLIOGRAPHY PRINCIPLES OF PHYSICAL CHEMISTRY
(ii)
Boiling point elevation 788 Chandrasekhar limit 976 classification 1213
and molar mass 790 Character 252 coagulation 1221
Boltzmann constant 453 Character tables 255 origin of charge 1218
Boltzmann population 311 Characteristic rotational peptization 1214
Boltzmann factor 311 temperature 945 preparation 1213
Boltzons 935 Characteristic vibrational properties 1216
Boltzmann entropy equation 618 temperature 947 protective 1222
Bomb calorimeter 565 Charge-Coupled device (CCD) Combination bands 322
Bond energies 563 sensor 1209 Combustion, enthalpy of 555
Bond length 260 Charge transfer bands 344 Common ion effect 719
Bond moments 440 Chargetransfer spectra 340 Commutation relations 141
Bond order 186 Charles law 452 Commutator 141
Born-Haber cycle 1174 Chemical affinity 629 Complex NMR spectra 385
Borns interpretation 42 Chemical equilibrium 620 Complex reactions,
BornOppenheimer approximation174 law of 624 mechanism of 1053
BornLande equation 1174 Chemical shift 358 Components, phase rule 661
Bose-Einstein condensation 964 Chemical shift reagents 386 Compound triplet 158
Bose-Einstein distribution 963 Chemical isomer shift 414 Compressibility 460
BoseEinstein statistics 936 Chemical kinetics 1033 Compressibility factor 479
and ideal photon gas 960 Chemical potential 592 Compton effect 36
Bose gas 962 Chemiluminescence 1134 Compton shift 36
Bosons 936 Chemisorption 1251 Compton wave length 37
Bound state 438 Chlorine electrode 837 Computational quantum
Boyle temperature 484 Cholesteric liquid crystals 521 chemistry 232
BZ reaction 1161 Chromophores 338 Computer-assisted tomography
Brackett series 29 Circular dichroism (CD) 512 (CAT) 391
Bragg equation 1176 CIDNP 388 Computer programs 238
Branched chain reaction 1085 Clapeyron equation 597 Computer simulation of liquids 512
Bravais lattices 1169 ClapeyronClausius equation 598 Concentration cells 853
Brillouin zone 1198 Class 250 with transference 859
Brownian movement 1218 Classical and quantum limits of without transference 857
Buffer solutions 720 statistical mechanics 1001 Concentration polarisation 919
capacity and buffer index 721 Classical canonical distribution 1005 CNDO 238
Butler-Volmer equation 914 Classical stastistical mechanics 989 Conductance, electrolytic 801
Claudes process 496 equivalent 801
C Clausius equation 485 molar 802
Cage effect 1054 ClausiusMosotti equation 432 specific 801
Calomel electrode, saturated ClebschGordon coefficients 170 Condensation polymerization 1303
(SCE) 837 ClebschGordon series 170 Conductometric titrations 821
Canonical commutation relation 138 Cluster expansion 1027 Configurational integral 1026
Canonical ensemble 1004 Coagulation of colloidal solutions Configuration interaction 236
Canonical partition function 1006 1221 Conductors, semiconductors 1199
Canonical structures 196 Coefficient of viscosity 508 and insulators
Capillary-active and inactive 1266 Coefficients of hybridization 200 Conformations of polymers 1296
Capillary condensation 1264 Coherence length 1142 Congruent melting point 686
Capillary electrophoresis 1325 Coherent anti-Stokes Conjugate elements 250
Carbon dioxide system Raman spectroscopy (CARS) 334 Conjugate acids and bases 707
(phase rule) 679 Cohesion 505 Conjugate solutions 772
Carbon dioxide laser 1145 Collagen 1312 Conjugated molecules 345
Carnot, cycle 572 Colligative properties of dilute Conservation of energy 528
theorem 574 solutions 778 Conservation of mass and
Catalysis 1147 Collisions and encounters 1087 energy 1345
acidbase 1149 Collision broadening 304 Conservative forces 461
auto 1161 Collision parameters 461 Consolute temperature 771
characteristics of 1148 Collision cross-section 461 Constrained chain 1300
enzyme 1150 Collision diameter 461 Constructive interference 1199
heterogeneous 1157 Collision frequency 462 Contact shift 387
homogeneous 1148 Collision number 461 Continuity of state 490
Cathode rays 21 Collision theory 1060 Contour length 1296
Cell constant 802 Colour centres 1207 Cooling curves 681
Cells, concentration 853 Colloidal particles 1213 Cooper pairs 1202
fuel 862 Colloidal state 1213 Cooperativity 658
Chain reactions in kinectics 1082 applications 1177 Corey-Pauling rules 1313
INDEX 1369
(iii)
Correct Bolzmann counting 996 Degree of association 796 Ebullioscopic constant 790
Correlation diagram 225 Degree of dissociation 632,797 Echo planar imaging (EPI) 391
Correlation energy 233 Degrees of freedom 472 Eckarts inequality 149
Correlation spectroscopy rotational 472 Effective Fock operator 235
(COSY) 384 translational 472 Efficiency, of heat engine 572
Corresponding states, principle vibrational 473 Eigenvalue equation 39
of 493 Degrees of freedom (phase rule) 663 Eigenfunctions and eigenvalues 141
Corrosion of metals 918 Degree of hydrolysis 726 Einsteins photoelectric equation 25
Coulomb operator 234 Degree of polymerization 1275 Einstein-Smoluchowski equation
Counter ions 1220 Delocalization energy 208 1294
Coupled flows 1344 Detergents 507 Einstein theory of heat capacity 982
Coupled reactions 1351 Density functional theory (DFT) 239 Electric field gradient (EFG) 420
Covalent bond 173 Density of states (DOS) 245,1195 Electric properties of molecules 431
Criteria for reversible Density matrix (statistical matrix) 997 Electrical capacitance 895
and irreversible processes 589 Destructive interference 1199 Electrical double layer 1219
Critical constants of a gas 489 Deviations from ideality 480 Electrical energy 840
Critical micelle concentration Diamagnetism 444 Electrified interfaces 892
(CMC) 1233 Diamond, structure of 1189 Electrocapillary measurements 891
Critical phenomena 489 Diatomic rotor 307 Electrocatalysis 909
Critical solution temperature Dieterici equation 484 Electrochemical series 847
(CST) 771 Difference bands 322 Electrode potential 838
Critical temperature 490 Diffraction, electron 1186 Electrode reactions, kinetiecs of 911
Critical volume 489 neutron 1187 Electrokinetic properties 1224
Cryosopic constant 794 Diffusion 470,1293 Electrolytic cell 836
Crystal imperfections 1204 Diffusion coefficient 1293 Electrolytic conductance 801
Crystals, covalent 1189 Diffusion-controlled reactions 1087 Electron correlation 233
ionic 1189 Diffusion layer 920 Electron diffraction 1186
metallic 1193 Diffusion overpotential 916 e/m ratio 21
molecular 1188 Dipole-dipole interaction 487 Electron mass 22
Crystallographic symmetry 261 Dipole moments and Electron spectrocopy for
Crystal systems 262 molecular structure 440 chemical analysis (ESCA) 417
Curie temperature 448 Dirac delta function 994 Electron spin resonance
Curved Hammett plots 653 Diracs bra and ket notation 996 (ESR) spectra 392
Cyclic rule 8,532 Diracs relativistic quantum Electron tunnelling in Marcus theory
Cyclic process 872 mechanics 37 1107
Direct product 275 Electronic spectra 335
D Discshaped liquid crystals 522 of conjugated molecules 345
Daltons law 453 Dislocations 1208 of transition metal complexes 341
Daniell cell 835 Dissociation constants 712 Electronically conducting
Davisson-Germer experiment 35 Dissociation energy 265 polymers 1306
d-d bands 343 Distillation, fractional 768 Electron-molecule collisions 1331
de Broglies equation 33 of immiscible liquids 768 Electron transfer reactions
experimental verification of 34 steam 769 Marcus theory 1105
de Donders treatment 628 Distribution law (Nernsts) 697 Electron tunnelling 1107
Debye equation 433 applications of 701 Electro-osmosis 1357
Debyes T3 Law 986 thermodynamic derivation of 698 Electro-osmotic pressure
Debye-Falkenhagen effect 826 DLVO theory 1221 (EOP) 1357
DebyeHckel limiting law 832 DNA double helix 1321 Electrophoretic mobility 1225
DebyeHckel theory, DNA denaturation 1322 Electrophoresis 1224
of strong electrolytes 824, 882 DNA renaturation 1323 capillary, gel, pulsed field 1324
of mean activity coefficients Donnan membrane equilibrium 1283 ELDOR 406
830,882 Doping in semiconductors 1201 ENDOR 406
Debye-Hckel-Onsager equation826 Doppler Broadening 304 EMF of galvanic cells 848
Debye length 831 Double helix (DNA) 1321 EMF measurements, applications
DebyeScherrer method 1178 Double resonance 381 865
DebyeSmoluchowski equation 1087 DPM 387 Emission spectrum 302
Debye theory of heat capacity 983 DPPH 397 Emulsifiers 1246
Debye temperature 986 Dropping mercury electrode Emulsions 1242
Defects in crystals 1204 (DME) 922 Enantiotropic transitions 523
Degeneracy 53 Dye lasers 1144 Endergonic reactions 655
Degeneracy temperature 966 Endothermic reactions 552
Degenerate BE gas 966 E Energy barrier 1057
Degree of advancement 628 Eadie-Hofstee method 1153 Energy transfer 1131
GENERAL
BIBLIOGRAPHY3GENERAL
1370 BIBLIOGRAPHY PRINCIPLES OF PHYSICAL CHEMISTRY
(iv)
Ensemble average 991 Extremum principle 1360 Free energy of a spontaneous
Ensemble theory 989 Eulers relation 64 reaction 620
Enthalpy 533 Eutectic point 680 Free induction decay (FID) 371
Enthalpy change 552 Eutectic systems 679 Free path phenomena 471
of combustion 555 Explosion temperature 562 Free volume 500
of formation 557 Eyring equation 1065 Freely jointed chain 1296
of neutralization 555 Freezing mixtures 685
of reaction 555 F Freezing point depression 792
of solution 556 Fast atom bombardment (FAB) 1330 and molar mass 794
Entropy 575 Fcentres 1207 Frenkel defects 1204
absolute values 610 FEMO theory 204 Freons (chlorofluorocarbons) 1131
and probability 618 Femtochemistry 1034 Freundlich adsorption isotherm 1253
change in reversible and Femtosecond transition state Frictional coefficient 1294
irreversible processes 577 spectrocopy 1145 Frontier molecular orbitals 337
of mixing of gases 582 f-f bands 345 Fuel cells 862
of vaporization 578 Fermi contact interaction 367 Fugacity 601,1013
physical significance of 584 Fermi-Dirac distribution 969 determination of 602
Entropy change of mixing of an Fermi-Dirac gas 969 Full rotation group 257
ideal solution 761 FermiDirac statistics 939 Functional derivative 241
Entropy production and entropy Fermions 936 Functional MRI 390
flow in open systems 1352 Fermi energy 970 Fundamental vibrational
Entropy production due to heat Fermis golden rule 245 frequency 316
flow 1348 Fermi Level 970
Entropy production in chemical Fermi momentum 971 G
reactions 1349 Fermi resonance 323 g-factor in ESR 396
Entropy production per unit time1351 Fermi surface 1198 Galvanic cells 835
Entropy, residual 618 Fermi temperature 972 Gamma function 961
Enzyme catalysis 1150 Ferretin 1312 Garrett-Brattain space charge 905
Equations of state 481 Ferromagnetism 448 Gas electrodes 836
The Euler reciprocal relation 531 Ficks first law of diffusion 1293 Gas lasers 1144
Equilibrium approximation 1054 Fictitious reference system 239 Gas laws, derivation of 451
Equilibrium constant 624 Field desorption (FD) 1330 Avogadros law 452
pressure dependence 640 Field ionization (FI) 1330 Boyles law 451
temperature dependence 637 Fifth state of matter 967 Charless law 452
Equipartition of energy 474 Fine structure 87, 155 Daltons law 453
Ergodic hypothesis 991 Fine structure constant 127 Grahams law 453
ESCA 417 Fingerprint region 324 Gases, kinetic theory of 450
ESI (electrospray ionization) 1331 First law of thermodynamics 528 Gas-liquid chromatography GLC 1338
Even-even rule 1335 Firstorder reactions 1035 Gaussian type orbitals (GTOs) 232
EXAFS 1270 Flame temperature 562 Gel electrophoresis 1324
Excimer lasers 1144 Flash photolysis 1096 Gels 1247
Excess population 372 Flocculation values 1223 Generalized angular momentum 149
Excluded volume 481 Flory-Huggins equation 1311 Generalized gradient approximation
Excited states 1138 Flory-Huggins theory 1309 (GGA) 242
Expansion of an ideal gas 535 Flow methods for fast reactions 1095 Generating operators 292
adiabatic 538 Fluctuations in ensembles 1015 Giant magnetoresistance (GMR)
isothermal 535 Fluidity 509 1209
Exact and inexact differentials 530 Fluorescence 1115 Gibbs adsorption isotherm 1264
Excess pressure in a drop 506 quenching of 1133 GibbsDuhem equation 592
Exchange-correlation energy Fluxes and forces 464,1343 GibbsDuhemMargules equation
functional 240 Force constant 54 758
Exchange energy 151 Fourier synthesis of electron Gibbs free energy 586
Exchange operator 234 density 1183 Gibbs free energy change of
Excited states, geometry 1138 Fourier transform NMR mixing for an ideal solution 759
Exciton 1209 spectroscopy 370 GibbsHelmholtz equation 590
Exergonic reactions 655 Fourier transform spectroscopy 303 Gibbs paradox 995
Exothermic reactions 552 Fractional distillation 768 Gibbs phase rule 665
Expansivity 460 Fragmentation in mass Glass electrode 871
Explosion limits of chain reactions spectrometry 1333 Glide plane 264
1086 Franck-Condon principle 335 Glycolysis 656
Extended Hckel theory (EHT) 236 Franck-Hertz experiment 28 Gold number 1222
Extinction (absorption) Franck-Rabinovich effect 1054 Good solvent 1299
coefficient, molar 1116 Free electron model 1194 Gouy balance 447
INDEX 1371
(v)
Gouy-Chapman model 900 spectra 383 zeroorder reactions 1047
Graft copolymers 1276 Heterogeneous equilibria 642 Interfacial tension 507
Grand canonical ensemble 993 High energy phosphate ester Interionic effect 824
Grand canonical partition function bonds 655 Intramolecular energy transfer 1079
1013 High pressrue phase diagrams 678 Internal pressure 482
Grand potential 1013 Hindered rotation 373 Intensity of spectral lines 304
Grand/Great orthogonality Hinshelwood theory 1073 Intermediate neglect of
theorem (G.O.T.) 253 Hittorfs theoretical device 805 differential overlap (INDO) 238
Graphite, structure of 1189 Hohenberg-Kohn theorem 239 Intermolecular energy transfer 1136
Grotrian diagram 155 Holes in semiconductors 1200 Intermolecular forces 487
GrotthusDraper law 1118 Homogeneous equilibria 630 Internal conversion 1114
Grotthus mechanism 805 Homonuclear 2D J-resolved Internal energy 529
Group moments 441 spectra 383 Internal rotation 314
Group postulates 249 HOMO-LUMO transition 340 Internuclear distance 309
Group theory 247 Hookes law potential 54 Internuclear double resonance
and normal modes of vibration 268 Hckel molecular orbital theory 205 (INDOR) 385
direct porduct of irreducible Hckels rule of aromaticity 210 Intersystem crossing (ISC) 1114
representations 275 Hund's rule 87 Intramolecular photophysical
use in determining selection Hunds rules 151 processes 1135
rules in transitions 279 Hybrid functional 242 Inverse anti-Stokes Raman
use in factoring the secular Hybridization 197 scattering 334
equation in MOT 285 coefficients of 200 Inverse-Stokes Raman scattering
Group velocity 134 Hydration number 886 334
Hydrogenbromine reaction Inversion doubling 323
H Inversion temperature 548
(photochemical) 1126
Halflife time 1047 Inversion spectrum 315
Hydrogenchlorine reaction
Halfwave potential 925 Ionic atmosphere 825
(photochemical) 1125
Hamiltonian operator 42 Ionization potentials 1332
Hydrogen electrode 836
Hammett equation 648 Ionic, bond 173
Hydrogen-oxygen fuel cell 862
Hammett constants 648 mobility 804,814
Hydrogen spectrum 28
Hammett plot 650 product of water 715
Hydrolysis of salts 724
Hard-sphere potential 1029 Ionic crystals, structures of 1190
Hydronium ion 706
HartreeFock selfconsistent Ionic doublets 824
Hydrophile-Lipophile balance
field method 128 Ionic strength 829
(HLB) 1228
Hartree-Fock-Roothaan SCF method Ionization efficiency curve 1332
Hydrophobic interaction 1314
234 Ionization potentials 1332
Hyperchromic effect 1322
Heat capacities of monatomic Isenthalpic process 546
Hyperfine structure in atomic
crystals 982
spectra 162 Isentropic process 582
The Debye theory 983
Hyperfine structure in ESR 393 Irreversible processes 577
The Einstein theory 982
Hypsochromic shift 339 Irreversible thermodynamics 1343
Heat capacity 534
Isoelectric focusing 1324
Heat capacities at constant I Isoelectric point (pI) 1324
pressure and constant volume 535 Icosahedral symmetry 1209 Isomorphism 297
Heisenbergs uncertainty principle 36 Ideal gas equation 452 Isosteric enthalpy of adsorption 1185
-helix 1313 Ideal solution 756 Isotactic polymers 1275
Helix-coil transitions 1312 Idempotent matrix 998 Isothermal expansion 535
Hellmann-Feynman theorem 229 Identical particles 1002 work done in 535
Heitler-London-Slater-Pauling Impact parameter 1103 Isotope peaks 1329
(HLSP) theory 192
Imperfections in crystals 1209 Isotope separation 1144
Helmholtz free energy 585
Incongruent melting point 687 Isotopic substitution 312
Helmholtz-Perrin model 899
Index of hydrogen deficiency 1336 Isotropy 516
Hemoglobin, binding of oxygen 658 Isothermal expansion 535 Iteration 128
Henderson-Hasselbalch
Ilkovic equation 923
equation 722 J
derivation 923
Henrys law 774 Jablonski diagram 1113
Indicators, acidbase 733
Henrys law and Raoults law 775 Jahn-Teller distortion 343
theory of 733
Hermite equation 55 Jahn-Teller Theorem 109
Inorganic phosphate 655
Hermite polynomials 56 j.j. coupling 153
Insulators 1201
Hermitian operators 106 Joule-Thomson coefficient 546
Integrated absorption coefficient1137
Hess law 563 Joule-Thomson effect 545
Integration of rate expressions
applications of 564
first-order reactions 1038
Heterogeneous catalysis 1155 K
secondorder reactions 1042
Heteronuclear 2D J-resolved Karplus relation in NMR 368
thirdorder reactions 1045
GENERAL
BIBLIOGRAPHY3GENERAL
1372
(vi) BIBLIOGRAPHY PRINCIPLES OF PHYSICAL CHEMISTRY
Kelvin equation 506 BeerLambert 1115 Magnetic properties of molecules442
Kinetic energy and temperature 453 Boyles 451 permeability 442
Kinetic gas equation 451 Charles 452 susceptibility 443
Kinetic theory of gases 450 Curies 445 Magnetic polarizability
and gas laws 451 of chemical equilibrium 625 (magnetizability) 445
Kinectics of of conservation of energy 528 Magnetic resonance imaging
acidbase catalysed reactions of corresponding states 493 (MRI) 390
1149 Daltons 453 Magnetic resonance spectroscopy
branchedchain reactions 1085 distribution (Nernst) 697 299
chain reactions 1082 equipartition of energy 474 Magnetogyric ratio 303
complex reactions 1079 Henrys 774 MALDI 1330
consecutive reactions 1081 Hesss 563 MALDI-TOF mass spectrometry
diffusioncontrolled reactions 1087 of mass action 625 1330
electrode reactions 912 of photochemical equivalence1118 Marcus cross relation 1109
enzymecatalysed reactions 1150 of rational indices 1175 Marcus theory of electron transfer
fast reactions 1093 LCAO-MO approximation 174 reactions 1105
polymerization 1301 LCDs 519 MarkHouwink equation 1279
reactions in solution 1086 Le Chateliers principle 646 Mass number 23
reversible reactions 1079 Leadsilver system (phase rule) 682 Mass spectrometry 1327
surface reactions 1155 LEED 1269 Mathematical probability 618
Kirchhoff equation 560 LennardJones (6, 12) potential Matrix element 112,175
Knudsen cell 1332 488,1030 Matrix mechanics 37
Knudsen effect 1359 Lever rule 768 Matter waves 34
Knudsen gas 462 Levitation 1202 Maximum work 537
Kohlrausch law 810 Lewis concept of acids and bases MaxwellBoltzmann statistics 935
applications 815 710 Maxwells distribution of molecular
Kohn-Sham method 239 Light scattering 1289 energies 455
Koopmanns theorem 108,417 Limiting current density 921 Maxwells distribution of molecular
Kramers degeneracy 109 Limiting diffusion current 921 velocities 454
Kramers theorem 109,401 Lindemanns theory of unimolecular Maxwells relation 437
Kronecker delta 42 reactions 1070 Maxwells relations in
k-space 1197 Line defects : Dislocations 1208 thermodynamics 587
Line spectra 305 Mayer f-function 1026
L Linear free energy relationships McBain micelles 1231
Ladder operators 143 (LFERs) 648 McConnell equation 398
Lambda temperature 1018 Linear rotor 313 McLafferty rearrangement 1335
Lambda transition 1018 Lineweaver-Burk method 1152 Mean ionic activity 852
Laminar flow 508 Lippmann equation 894 Mean free path 462
Langmuir-Hinshelwood mechanism Liquefaction of gases 495 Mechanisms of complex reactions
1155 Liquid crystals 516 1053
Lagranges equations of motion 321 classification of 520 Melting curves of DNA 1322
Lagranges undetermined molecular arrangements in 524 Meritectic (or peritectic)
multipliers 937 Liouville theorem 992 temperature 687
Landau theory of liquid helium-II 1022 Liquid helium system 678,1018 Meissner effect 1202
Lande interval rule 159 Liquidjunction potential 860 Membranes, biochemical 930
Lande g-factor 159 Liquid state 499 Membrane potentials 930
Langevin function 434 Local density approximation (LDA) Mesomorphic state 516
Langmuir's adsorption isotherm 1256 242 Mesomorphism
Langmuirs theory of adsorption 1256 London forces 487 lyotropic 516
Lanthanide shift reagents 386 London-Tisza theory 1019 Thermotropic 516
Laplace equation 421 Lorentz-Lorenz equation 437 Metabolism : anaerobic and
Laplacian operator 42 Lotka-Volterra mechanism 1162 aerobic 656
Laporte rule 343 Lowering of vapour pressure 778 Metal deficiency defects 1207
Larmor frequency 357 l-type doubling 323 Metallic crystals 1193
Larmor precession 357 Lyman series 29 free electron model of 1194
Laser 1139 Metallic properties 1193
Laser Raman spectroscopy 1143 M Metal-metal transitions 343
Lattice energy 1173 Macroemulsions 1242 Metastable equilibrium 674
Lattice model of polymer solution Macromolecules 1273 Metastable peaks 1329
1309 conformations of 1296 MichaelisMenten equation 1151
LCST 771 molar masses of 1277 Micellar aggregation numbers 1232
Law Madelung constant 1173 Micellar catalysis 1240
Avogadros 452 Magic angle spinning (MAS) 381 Micelle formation 1229
INDEX (vii)
1373
Mass action model 1229 N Orbitals, filling of 87
Phase separation model 1229 Natural linewidth 304 Orbital exponent 232
Microcanonical enemble 993 Neel point 443 Order parameter 523
Microemulsions 1245 Nematic liquid crystals 521 Order of a reaction 1035
Microscopy far-field confocal 1144 Nernst Distribution law 697 methods of determination 1051
near-field optical 1144 Nernst, equation 844 Order and molecularity of simple
Microstates 936 heat theorem 609 reactions 1052
Microwave oven 313 Nervous system 931 Order and molecularity of complex
Microwave spectra 307 Neutron 23 reactions 1053
Milikans oil drop technique 21 Neutron diffraction 1187 Order of a group 250
Miller indices 1175 Nicotinewater system 773 Orthonormal set of wave functions
MINDO 238 Nitrogenous bases in DNA and 42
Mode locking 1142 RNA 1319 Orgel diagrams 344
Mobility, ionic 804 Nonlinear thermodynamics of Ortho and para hydrogen 958
determination of 814 irreversible processes 1361 Oscillator strength 1138
Molal boiling point elevation Non-Newtonian liquids 508 Oscillatory reactions 1161
constant 790 Nonradrative transitions 1114 Osmometry 1281
Molal freezing point depression Normal coordinate analysis 321 Osmosis 781
constant 794 Normal coordinates 269 osmotic pressure 781
Molar absorption coefficient 1116 Normal mode of vibration 268, 320 Osmotic pressure and molar mass
Molar conductance 802 Normalization of wave function 47 783
Molar extinction coefficient 1116 NRF spectroscopy 412 Osmotic pressure and vapour
Molar ionic conductance at Nuclear magnetic double pressure lowering 784
infinite dilution 803 resonance (NMDR) 374 Ostwalds dilution law 822
and ionic mobility 812 Nuclear magnetic resonance Outer Helmholtz plane (OHP) 898
Molar polarization 432 (NMR) 353 Overtones 322
Molar mass determination by Nuclear spin and rotational Overpotential 912
mass spectrometry 1337 partition function 956 Overvoltage 917
Molar mass distribution in Nuclear Overhauser effect applications of 917
condensation polymerization 1303 (NOE) 381 Oxidation potential 838
Molar refraction 437 Nuclear spin-spin interaction 362 Oxidationreduction indicators 879
Molecular beam methods 1097 Nucleic acids (DNA and RNA) 1319 Oxidationreduction electrodes 838
Molecular dynamics (MD) method NMR of AB spin system 375 Ozone hole 1131
513 NMR, 2-dimensional 380 Ozone layer 1129
Molecular ion 1336 NMR of liquid crystals 389
Molecular orbital theory (MOT) 174 NMR of paramagnetic compounds P
Molecular orbitals 174 387 PV isotherms of carbon dioxide
antibonding 174 NMR of solids 380 gas 490
bonding 174 Non-trivial solution 176 Parallel bands 324
Molecular orbitals Nuclear quadrupole resonance Paramagnetism 444
for homonuclear diatomic (NQR) spectroscopy 420 Parity 260
molecules 186 Nylon 66 1277 Pariser-Parr-Pople (PPP)
for heteronuclear diatomic approximation 235
O Partial molar properties 591, 595
molecules 188
Off-resonance proton decoupling382 Particles
Molecular partition function 942
Onedimensional simple indistinguishable 1002
Molecular reaction dynamics 1097
harmonic oscillator 54 distinguishable 1002
Molecular symmetry 247
Open systems 591 Partition function,
Molecularity of a reaction 1052
Onsagers phenomenological canonical 976
Moment of inertia 308 coefficients 1274
Monochromatic radiation 1066 electronic 948
Onsagers reciprocal relations,
Monte Carlo (MC) procedure 1103 nuclear 951
verification of 1345,1355
Morse potential 317 rotational 945
Opacity function 1103
Mssbauer spectroscopy 412 translational 943
Operand 43
Moving boundary method 809 vibrational 946
Operators in quantum mechanics 43
Mutual exclusion rule 330 Pascals constants 444
Optical activity 511
Mulliken population analysis Pascals triangle 363, 396
Optical pumping 1141
(MPA) 238 Paschen series 29
Optical rotatory dispersion
Multicentre integrals 238 Paschen-Back effect 162
(ORD) 512
Multiphoton spectroscopy 1143 Patterson synthesis 1184
Optimal pH point 1161
Multiplication table in group theory Paulis exclusion principle 85
Orbital and spin angular
250 momentum operators 147 Pauli spin matrices 167
Myoglobin, binding of oxygen 657 Orbital energies of multielectron Penrose tiling pattern 1210
Myosin 1312 atoms 87 Perfect pairing approximation 144
Perpendicular bands 324
GENERAL
BIBLIOGRAPHY3GENERAL
(viii)
1374 BIBLIOGRAPHY PRINCIPLES OF PHYSICAL CHEMISTRY
Perturbation Theory 111 Polarography 919 Quenching of fluorescence 1133
Degenerate 117 applications of 926 Quenching of orbital angular
first order 115 Polaron 1308 momentum 446
second order 113 Polyacetylene 1307 Q-switching 1142
Non degenerate 112 Polyethylene (LDPE and HDPE)1274 Quinhydrone electrode 838
time-dependent 242 Poly(para-phenylene) 1308
time-independent 111 Poly(sulphur nitride) 1306 R
application to helium 115 Polymerase chain reaction Racah parameters 151
Perovskite structure 1203 (PCR) 1323 Radial distribution function 512
PET (polyethylene terephthalate) Polymers, classification 1275 Radiative transitions 1045
1277 Polymer liquid crystals 522 Radius of gyration 1298
Pfund series 29 Polymorphism 672 Radius of the ion sphere 831
pH scale 716 Polymorphism in liquid crystals 522 Raising and lowering operators 143
pH, determination of 869 PMMA 1274 Ramachandran diagram 1314
Phase problem in crystallography Polydispersity index (PDI) 1278 Raman shift 327
1184 Polynucleotides 1319 Raman spectroscopy 326
Phase equilibria 661 Polystyrene 1274 Ramsay-Shields equation 504
Phase 661 Population inversion 1141 Raoults law 752
Phase rule (Gibbs) 665 Potassium iodidewater system of vapour pressure lowering 779
derivation of 665 (phase rule) 683 Rate constant 1035
Phase rule, application to Potential energy surfaces 1099 statistical mechanical derivation
onecomponent systems 667 Potentiometric titrations 872 of 1067
twocomponent systems 679 Pressure of an ideal gas 450 Rate of Reactions 1034
threecomponent systems 690 Pressure-induced polymorphism 523 Rate expressions, integrations of
Phase transitions, Ehrenfest Primary process 1122 1038,1042,1045,1047
classification 692 Principal axis system 421 Rational indices, law of 1175
Phenolwater system (phase rule) Prigogines principle of Rayleigh-Jeans law 961
772 minimum entropy production 1360 Rayleigh ratio 1291
Phenomenological laws 1343 Principle of microrcopic reversibility Rayleigh scattering 326
Phonon 1209 1354 Reaction coordinate 1054
Phosphorescence 1115 Probe and pump pulses 1145 Reaction cross-section 1103
Photochemical rate law 1124 Projection operators 292 Reaction rate, effect of temperature
Photobiology 1112 Proteins, structure of 1312 1056
Photochemical reactions 1123 denaturation of 1315 Reaction rates, theories of 1060
kinetics of 1125 Protein folding 1315 Reactions in flow systems 1090
Photochemistry 1112 Pseudo-contact shift 387 Rearrangements 1335
Photodissociation coefficient 1130 Pseudmonomolecular reactions 1052 Real gases 479
Photoelectric effect 24 Pulse radiolysis 1097 deviation from ideal behaviour 479
Photoelectron spectroscopy PVC 1274 Rectifier 1201
(PES) 416 Red shift 339
appilications of 417 Q RedlichKwong equation 485
Photon 25 Quantal canonical distribution 1010 Redox titrations 875
Photosensitization 1131 Quantal grand canonical Reduced osmotic pressure 1282
Photosynthesis in plants 1132 distribution 1014 Reducible and irreducible
Pierls distortion 1307 Quantal microcanonical ensemble representations 252
Plancks constant 24 998 Reduced phase rule equation 679
Phanck's law 961 Quantization of phase space 1000 Reduced plack's constant 46
Plait point 691 Quantum chemistry programs 238 Reduction potential 838
Plasmolysis 786 Quantum concentration 1293 Refractive index 510
-pleated sheet 1313 Quantum electrodynamics Refraction, molar 510
Pockels cell 1142 (QED) 227 Relativistic quantum mechanics 37
Point defects 1204 Quantum mechanical tunnelling 133 Relaxation methods in kinetics 1093
Point groups 250 Quantum mechanics 37 Relaxation processes in NMR 371
character tables for 254 postulates of 39 Residual entropy 618
representations of 251 Quantum numbers 83 Resonance energy 569
Poisseuilles equation 509 azimuthal 83 Resonance Raman spectroscopy
Poisson equation 882 magnetic 83 331
Poisson-Boltzmann equation 883 principal 83 Rest mass 22
Polar, resonance and steric spin 84 Reverse osmosis 786
effects 653 Quantum statistical mechanics 996 Reversible and irreversible
Polarisation of a molecule in an Quantum theory of radiation 24 processes : criteria for 589
electric field 431 Quantum yield 1118 Reversible electrodes 836
Polarizability 431 Quasicrystals 1209 Reversible isothermal expansion
Polarizability volume 435 Quasiparticles 1022 of a real gas 543
INDEX (ix)
1375
Reynolds number 509 Lamb's formula 360 Standard hydrogen electrode
Rhodopsin 1312 Sigmoid binding curve 658 (SHE) 836
Ribosomes 1319 Simple harmonic oscillator (SHO) 54 Standard state 606
Rice-Herzfeld mechanism 1083 Algebraic technique for solving Standard reduction formula 268
Riemann zeta function 961 the schrdinger equation 137 Stark effect 162
Root mean square velocity 457 Single electrode potential 839 Stark effect in microwave spectra
Rotational quantum number 64 Single-molecule spectroscopy 1144 314
Rotational constant 308 Singlet state 113 StarkEinstein law 1118
Rotational spectra 307 Slater determinant 76, 1003 State of a system 526
Rotational term 308 Slater type orbitals (STOs) 232 Statee
Rotationvibration spectra 319 Slaters rules 131 mixed 997
Rotons 1022 Slater sum 1011 pure 997
RRK theory 1074 Slope-intercept method 595 State variables 526
RRKM theory 1077 Smectic liquid crystals 521 Stationary nonequilibrium states1359
Russell-Saunders coupling 132 Soft Laser Desorption (SLD) 1331 Statistical averaging 996
Rutherfords atomic model 23 Solid state laser 1144 Statistics, types of 935
Rydberg constant 30 Soliton 1308 BoseEinstein 935
Soliton pair 1308 FermiDirac 935
S
Solubility of partially miscible MaxwellBoltzmann 935
Sackur-Tetrode equation 954
liquids 770 Statistical entropy 619
Saddle point 1101
Solubility product 740 Statistical thermodynamics 935
SALCs 286
applications of 742 Staudinger index 1279
Salt bridge 861
Solubilization 1238 STM (Scanning tunnelling
Salt effects on reaction rates 1088
Solutions of nonelectrolytes 750 microscopy) 1270
Saturated calomel electrode
Solutions of gases in liquids 773 STO-3G basis set 233
(SCE) 839
Solutions of liquids in liquids 750 Steady-state approximation 1054
Saxons relation 1358
Solvent extraction 702 Steam distillation 769
Schottky defects 1204
Sommerfeld extension of Bohr Stephen-Boltzmann law 961
Scattering factor 1183
theory 31 Sternheimer effect 427
Schrdinger wave equation,
Space groups 263 Stereoregular polymers 1276
solutions of 40,45-83
Space lattice 263,1169 Stern-Gerlach experiment 84
particle in a one-dimensional
box 45 Spectra, Stern Model 902
particle in a three-dimensional charge transfer 340 Stern-Volmer equation 1137
box 52 electronic 335 Stimulated Raman scattering
rigid diatomic rotor 63 electron spin resonance 392 (SRS) 332,1143
simple harmonic oscillator 54 hydrogen 28 Stirling approximation 937
hydrogen atom 65 molecular 305 Stirred flow reactor 1091
many-electron atoms 111 Raman 326 Stokes and anti-Stokes lines 326
Screw axis 264 rotational 307,313 Stokes-Einstein equation 1294
Screw dislocation 1208 vibrational 315,320 Streaming current (SC) 1358
Secondorder reactions 1042 Spectroscopic transition 302 Streaming potential (SP) 1358
Second law of thermodynamics 571 Spectroscopy 302 Structure factor 1184
Second sound 1020 Spherical harmonics 64 Structure of liquids 512
Second virial coefficient 486 Spherical wave 1270 Subgroup 250
Secondary process 1122 Spherical top molecules 324 Sulphur system (phase rule) 672
Secular determinant 176 Spin Hamiltonian in ESR 410 Supercoiled DNA 1321
Secular equation 176 Spin labels 397 Superconductivity 1202
Sedimentation equilibrium method Spin multiplicity 1113 LTSC and HTSC 1202
1288 Spinors 169 Superfluidity 1018
Sedimentation velocity method 1285 Spin-lattice relaxation in NMR 372 Supermolecule 1100
Selection rules 303 Spin-lattice relaxation time 372 Supertwist 1322
Semiconductors 1200 Spin-orbit coupling 153 Surface energy 503
Semiconductor interfaces 904 Spin quantum number 84 Surface excess 1266
Semi-empirical methods 236 Spin-spin coupling constant 363 Surface films on liquids 1267
Semipermeable membrane Spin-spin interaction in NMR 362 Surface reactions 1085
(SPM) 781 Spin vectors 168 Surface structure techniques
Semipermeability, theories of 785 Spontaneous processes 571 (EXAFS and SEXAFS) 1270
Seven segment cell 518 Spontaneous reactions 620 Surface tension 502
Shirakawa technique 1307 free energy of 620 Surfactants 1226
Similarity transformation 250 Square-well potential 1029 Svedberg equation 1286
Shielding constant 131,358 SQUID 447 Symmetric and antisymmetric wave
Shielding mechanisms in NMR 360 Standard electrode potentials 846 functions 1003
Standard enthalpies 555 Symmetric top molecules 324
GENERAL
BIBLIOGRAPHY3GENERAL
1376 BIBLIOGRAPHY PRINCIPLES OF PHYSICAL CHEMISTRY
(x)
Symmetry, in crystal systems 1166 Transition state theory 1063 Variation method 120
axis of 1166 Transmission coefficient 1068 Application to helium 121
centre of 1167 Transmission probability 135 Variation theorem 148
elements of 1167 Transitions (allowed and forbidden) Velocity,
operations 1167 303 average 457
plane of 1167 Transitions most probable 453
Symmetry of molecular orbitals 185 electric dipole 154 root-mean-square 457
Symmetry of wave functions 1003 magnetic dipole 154 Vibrational quantum number 316
Syndiotactic polymers 1275 Transistors 1201 Vibrational spectra 315
System of identical particles 1002 Transmittance 1116 of polyatomic molecules 320
Transport number 806 Vibrational term 316
T
determination of 807 Virial coefficients 486
Tafel equations 914
Transport properties in gases 463 Virial equation of state 486,1028
Tafel plot 915
Transverse relaxation time 372 Virial theorem 108
Taft equation 654
Trial wave function 121 Virtual orbitals 236
Tanabe-Sugano diagrams 344
Triethylaminewater system Viscometry 1279
Temperature coefficient 1056
(phase rule) 772 Viscosity of gases 467
Temperaturedependence Triple point 669
of equilibrium constant 637 Viscosity of liquids 508
Triplet state 1114 Volcanoes 910
TEMPOL 397
Troutons rule 502 Volume change and enthalpy
Term symbols for diatomic
Turbidity 1292 change of mixing for an ideal
molecules 184
Turnover number 1152 solution 760
Tetramethylsilane (TMS) 359
Two-dimensional NMR 380 VSEPR theory 226
Theorems of quantum mechanics 107
Tyndall effect 1289
Theoretical plate 768 W
Thermal analysis, phase rule 681 U Waldens rule 817
Thermal conductivity 465 UCST 771 Walsh diagrams 225
Thermochemistry 552 Ultracentrifugation 1285 Water system (phase rule) 668
Thermodynamic equilibrium 526 Ultramicroscope 1217 Watson-Crick model 1320
Thermodynamic potentials 630 Unimolecular reactions, theories Wave-particle duality of electron 33
Thermodynamic probability 618 of 1070 Wave mechanics 37
Thermodynamic processes 527 Hinshelwood theory 1073 Width of spectral lines 304
Thermodynamics of CMC 1236 Lindemann theory 1070 Wiens displacement law 24, 961
Thermodynamics of ideal RRK theory 1074 Wien effect 827
solutions 759 RRKM theory 1077 Wierl equation 1186
Thermodynamics, laws of 525 Unimolecular surface reactions 1155 Wigner coefficients 170
Thermography 518 Unit cell 1169 Wiger-Seitz cell 1199
Thermomechanical effect 1358 Unsolds theorem 108 Work function 25
Thermomolecular pressure UPES (Ultraviolet photoelectron
difference (TPD) 1358 spectroscopy) 416 X
Thermo-osmosis 1359 Upper bound 175 Xray diffraction 1176
Third law of thermodynamics 609 X-ray diffraction pattern of a
V cubic system 1180
experimental verification of 615
Vacancy theory of liquids 499 Xray diffractometer 1177
Thirdorder reactions 1045
Valence bond theory (VBT) 192
Thomas-Fermi equation 164 Y
Valence state ionization
Thomas-Fermi model 163 potentials 233 Young-Laplace equation 507
Threshold energy 1056 van der Waals constants 482
Threshold frequency 25 Z
van der Waals equation 481 Zeeman effect 84, 159
Threecomponent systems 690 and critical phenomena 491
Tie line 768 Normal and anomalous 159
van der Waals forces 433 Zeeman effect in NQR 425
Time-dependent perturbation vant Hoff equation 637
theory (TDPT) 242 Zero differential overlap (ZDO) 238
vant Hoff osmotic pressure Zeroorder reactions 1049
Time-dependent Schrdinger equation 782
equation (TDSE) 242 Zeroeth law of thermodynamics 549
reaction isotherm 626
Time-independent perturbation Zeroeth law and temperature
vant Hoff factor 796 scale 549
theory (TIPT) 111
Vapour pressure of liquids 500 Zero-point energy (ZPE) 56
Time-independent Schrdinger
Vapour pressure lowering 778 Zero-field splitting (ZFS) 109,401
equation (TISE) 42
Vapour pressure lowering and Zeta potential 1221
Time-resolved spectroscopy 1143
molar mass 779 Ziegler-Natta catalyst 1276
Townes-Dailey theory 426
Vapour pressures of ideal
Trace of a matrix 997 Zimm equation 1292
solutions 753
Transfer coefficient in electrode Zimm plot 1292
Vapour pressures of nonideal
kinetics 913 Zinc-air fuel cell (ZAFC) 864
solutions 763
Zwitterion 1324