Essentials of physical chemistry by b s bahl

Preface The Essentials of Physical Chemistry has been written for BSc students It has been national best-seller for more than 65 years It has been used by more than million students It is 26 editions old It really has been that long A lot of things have changed since then We also changed with every edition so that you could get the best In this new edition we have retained all those features that made it a classic Recent reviews from some teachers are reproduced These sum up book’s high-quality and study-approach : The Essentials of Physical Chemistry is best summarised by “classic text, modern presentation” This simple phrase underlines its strong emphasis on fundamental skills and concepts As in previous editions, clearly explained step-by-step problem-solving strategies continue to be the strength of this student-friendly text This revision builds on its highly praised style that has earned this text a reputation as the voice of authority in Physical Chemistry The authors have built four colour art program that has yet to be seen in India ! The acknowledged leader and standard in Physical Chemistry, this book maintains its effective and proven features – clear and friendly writing style, scientific accuracy, strong exercises, step-by-step solved problems, modern approach and design The organisation and presentation are done with marvelous clarity The book is visually beautiful and the authors communicate their enthusiasm and enjoyment of the subject in every chapter This textbook is currently in use at hundreds of colleges and universities throughout the country and is a national best-seller In this edition, the authors continue to what they best, focus on the important material of the course and explain it in a concise, clear way I have found this book to be very easy to follow There are hundreds of computer-generated coloured diagrams, graphs, photos and tables which aid in understanding the text The book goes step-by-step, so you don’t get lost No wonder it is a market-leader ! STUDENT FRIENDLY Many BSc students not have a good background in Physical Chemistry This examinationoriented text is written with these students in mind The language is simple, explanations clear, and presentation very systematic Our commitment to simplicity is total ! Concept-density per page has been kept low We feel that this is a big time saver and essential to quick-learning and retention of the subject matter STRESS IS ON UNDERSTANDING This book will help you overcome the fear of Physical Chemistry Stress is on understanding and not on memorisation Topics which usually confuse the students are explained in greater detail than commonly done This text will help you learn Physical Chemistry faster and enjoy it more ! USEFUL FOR ENTRANCE TESTS This is an important textbook for the Medical and Engineering College Entrance Exams Your choice of a book can mean success or failure Because today you need a book that can help you streak ahead of competition and succeed No-one knows more about your needs than us It is a tall claim, but it is true ! NEW IN THIS EDITION The new edition of Essentials of Physical Chemistry contains numerous discussions, illustrations, and exercises aimed at overcoming common misconceptions It has become increasingly clear from our own teaching experience that students often struggle with Physical Chemistry because they misunderstand many of the fundamental concepts In this text, we have gone to great lengths to provide illustrations and explanations aimed at giving students more accurate pictures of the fundamental ideas of chemistry In this New Edition we have retained all that was judged good in the previous edition However, a number of changes have been made in this new edition Subject matter has been updated This edition provides quick access to the important facts and concepts It includes every important principle, equation, theorem, and concept The new syllabus recommended by the University Grants Commission has been our model This edition now includes two new chapters : Mathematical Concepts (Chapter 32), and Introduction to Computers (Chapter 33) VALUE ADDITION Problem-Solving To a great extent, a student’s understanding of chemistry depends on his or her ability to solve and analyse problems We have structured this book with the idea of weaving the techniques of problem-solving throughout the content, so that the student is systematically guided and challenged to view chemistry as a series of solvable problems Question-style has changed over the years Latest university questions are given at the end of each chapter to show these trends Step-by-step answers are provided for the in-chapter problems This book contains more than 1600 latest university questions It also contains more than 1600 multiple-choice questions By solving these problems you can precisely know your own success-level This is the book which the examiners use ! Four-Colour Art Program One of the distinctive features of the text is its visual impact This is the first Indian Physical Chemistry textbook to be completely done in four-colour and on computer Colour graphics, illustrations, and real pictures have been extensively used to highlight and reinforce the important points Colour has also been used to highlight change and concepts Guidelines are provided to help you understand concepts that are considered difficult and catch careless mistakes before exams Scientific Accuracy has been checked and rechecked Subject matter is modern and error-free Extensive Index has been provided for quick cross-reference WE WISH YOU SUCCESS ! Yes, we think you will appreciate the thought and care that has gone into the making of this text If you have the will, this book will show the way We urge you to study regularly, and hope that this error-free book will make it easier for you to so You can depend on this book ! The book has everything you want to have in your Physical Chemistry text In case you find something missing, please write at the following address : Mail : # 590, Sector 18-B, Chandigarh - 160018 e-mail : arunbahl2000@gmail.com We would be glad to receive suggestions and comments for further improvements Authors Highlights of Colour Edition Chapter openers include a half-page photograph related to the chapter material The Contents give students an overview of the topics to come The Artwork has been completely revised This has made the subject come alive ! New colour drawings and photographs make the artwork more realistic and easier to understand Flowcharts, important rules walk students through chemical processes in a simple, straight forward manner Special-interest boxes describe current applications of the subject Solved problems are located throughout the text These solved problems emphasise step-by-step approach to solving problems Brief Contents 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 Structure of Atom–Classical Mechanics .1 Structure of Atom–Wave Mechanical Approach .43 Isotopes, Isobars and Isotones .85 Nuclear Chemistry .103 Chemical Bonding–Lewis Theory .151 Chemical Bonding–Orbital Concept .193 First Law of Thermodynamics 236 Thermochemistry .271 Second Law of Thermodynamics .303 Gaseous State .355 Liquid State .415 Solid State .447 Physical Properties and Chemical Constitution .482 Solutions .528 Theory of Dilute Solutions .559 Osmosis and Osmotic Pressure .592 Chemical Equilibrium .621 Distribution Law .672 Phase Rule .697 Chemical Kinetics .731 Catalysis .781 Colloids .807 Adsorption .843 Electrolysis and Electrical Conductance .860 Theory of Electrolytic Dissociation .883 Ionic Equilibria–Solubility Product .909 Acids and Bases .932 Salt Hydrolysis .976 Electromotive Force .996 Photochemistry .1043 SI Units .1063 Mathematical Concepts .1069 Introduction To Computers .1099 Appendix .1132 Index .1136 Contents Pages STRUCTURE OF ATOM–CLASSICAL MECHANICS Discovery of Electron Measurement of e/m for Electrons Determination of the Charge on an Electron Positive Rays Protons Neutrons Subatomic Particles Alpha Particles Rutherford’s Atomic Model Mosley’s Determination of Atomic Number Mass Number Quantum Theory and Bohr Atom STRUCTURE OF ATOM–WAVE MECHANICAL APPROACH Wave Mechanical Concept of Atom de Broglie’s Equation Heisenberg’s Uncertainty Principle Schrödinger’s Wave Equation Charge Cloud Concept and Orbitals Quantum Numbers Pauli’s Exclusion Principle Energy Distribution and Orbitals Distribution of Electrons in Orbitals Representation of Electron Configuration Ground-state Electron Configuration of Elements Ionisation Energy Measurement of Ionisation Energies Electron Affinity Electronegativity ISOTOPES, ISOBARS AND ISOTONES Isotopes Representation of Isotopes Identification of Isotopes Aston’s Mass Spectrograph Dempster’s Mass Spectrograph Separation of Isotopes Gaseous Diffusion Thermal Diffusion Distillation Ultra centrifuge Electro-magnetic Separation Fractional Electrolysis Laser Separation Isotopes of Hydrogen Isotopes of Neon Isotopes of Oxygen Isotopes of Chlorine Isotopes of Uranium Isotopes of Carbon Isotopic Effects Isobars Isotones NUCLEAR CHEMISTRY Radioactivity Types of Radiations Properties of Radiations Detection and Measurement of Radioactivity Types of Radioactive Decay The Group Displacement Law Radioactive Disintegration Series Rate of Radioactive Decay Half-life Radioactive Dating Nuclear Reactions Nuclear Fission Nuclear Fusion Reactions Nuclear Equations Reactions Artificial Radioactivity Nuclear Isomerism Mass Defect Nuclear Binding Energy Nuclear Fission Process Nuclear Chain Reaction Nuclear Energy Nuclear Reactor Nuclear Fusion Process Solar Energy Fusion as a Source of Energy in 21st Century 43 85 103 CHEMICAL BONDING–LEWIS THEORY Electronic Theory of Valence Ionic Bond Characteristics of Ionic Compounds Covalent Bond Conditions for Formation of Characteristics of Covalent Compounds Covalent Bonds Co-ordinate Covalent Bond Differences Between Ionic and Covalent Bonds Polar Covalent Bonds Hydrogen Bonding (H-bonding) Examples of Hydrogen-bonded Compounds Characteristics of Hydrogen-bond Compounds Exceptions to the Octet Rule Variable Valence Metallic Bonding Geometries of Molecules VSEPR Theory CHEMICAL BONDING–ORBITAL CONCEPT Valence Bond Theory Nature of Covalent Bond Sigma (σ) Bond Pi (π) Bond Orbital Representation of Molecules Concept of Hybridization Types of Hybridization Hybridization involving d orbitals Hybridization and Shapes of Molecules sp3 Hybridization of Carbon sp2 Hybridization of Carbon sp Hybridization of Carbon Shape of H2O molecule Shape of PCl5 Molecule Shape of SF6 Molecule Molecular Orbital Theory Linear Combination of Atomic Orbitals (LCAO Method) Bond Order Homonuclear Diatomic Molecules FIRST LAW OF THERMODYNAMICS Thermodynamic Terms : System, Boundary, Surroundings Homogeneous and Heterogeneous Systems Types of Thermodynamic Systems Intensive and Extensive Properties State of a System Equilibrium and Nonequilibrium States Thermodynamic Processes Reversible and Irreversible Nature of Heat and Work Internal Energy Processes Units of Internal Energy First Law of Thermodynamics Enthalpy of a System Molar Heat Capacities JouleThomson Effect Adiabatic Expansion of an Ideal Gas Work Done In Adiabatic Reversible Expansion THERMOCHEMISTRY Enthalpy of a Reaction Exothermic and Endothermic Reactions Thermochemical Equations Heat of Reaction or Enthalpy of Reaction Heat of Combustion Heat of Solution Heat of Neutralisation Energy Changes During Transitions or Phase Changes Heat of Fusion Heat of Vaporisation Heat of Sublimation Heat of Transition Hess’s Law of Constant Heat Applications of Hess’s Law Bond Energy Summation Measurement of the Heat of Reaction SECOND LAW OF THERMODYNAMICS Spontaneous Processes Entropy Third Law of Thermodynamics Numerical Definition of Entropy Units of Entropy Standard Standard Entropy of Formation Carnot Cycle Entropy 151 193 236 271 303 INTRODUCTION TO COMPUTERS 18 19 20 21 22 23 24 25 (a) 500 MB (b) 500 GB (c) 700 MB (d) 700 GB (e) None of these Answer (c) Which of the following is not a GUI based software ? (a) Windows (b) UNIX (c) MS-Office (d) Corel Draw (e) Pagemaker Answer (b) The number of digits used in a number system is known as its (a) Power (b) Weight (c) Radix (d) Base (e) Either (c) or (d) Answer (e) Number System is used by the computer systems (a) Decimal (b) Binary (c) Octal (d) Hexadecimal (e) None of the these Answer (b) Hexadecimal Number System has a base of _ (a) (b) (c) (d) 10 (e) 16 Answer (e) Number System has a base of (a) Binary (b) Decimal (c) Octal (d) Hexadecimal (e) None of the these Answer (c) The octal equivalent of (111)2 is (a) (b) (c) (d) (e) None of the these Answer (d) The hexadecimal equivalent of (1111)2 is (a) (b) A (c) C (d) F (e) None of the these Answer (d) In Binary Addition, + is equal to _ (a) (b) (d) with carry (c) with carry (e) None of the these Answer (c) 1131 Appendix A Physical Constants Quantity Symbol Traditional units SI units th Atomic mass unit ( 12 mass of 12C atom) amu 1.6606 × 10–2 g 1.6606 × 10–27 kg Avogadro’s number N 6.022 × 1023 6.022 × 1023 particles/mol particles/mol Bohr radius a0 0.52918 Å 5.2918 × 10–13 m Boltzmann constant k 1.3807 × 10–16 erg/K 1.3807 × 10–23 J/K Charge-to-mass ratio of electron e/m 1.7588 × 108 Coulomb/g 1.7588 × 1011 C/kg Electron rest mass me 9.1095 × 10–28 g 9.1095 × 10–31 kg 0.00054859 amu Faraday constant F 96,487 coulombs/mole–1 96,487 J/V mol–1 Gas constant R 0.08206 Gravitational acceleration g 980.6 cm/s 9.906 m/s Molar volume (STP) Vm 22.414 L/mol 22.414 × 10–3 m3/mol Neutron rest mass mn 1.67495 × 10–24 g 1.67495 × 10–27 kg L atm mol K 8.3145 Pa dm3 mol K 1.008665 amu Planck’s constant h 6.6262 × 10–27 erg sec 6.6262 × 10–27 Proton rest mass mp 1.6726 × 10–27 erg sec 1.6726 × 10–27 kg 1.0077277 amu Velocity of ligh (in vaccum) c 2.9979 × 1010 cm/s 186,281 miles/s 2.9979 × 108 m/s Rydberg constant Rz 3.289 × 1015 cycles/s 1.0974 × 107 m–1 2.1799 × 10–11 erg 2.1799 × 10–18 J 1132 Appendix B Conversion Factors cm in in 2.54 cm cm3 in3 in3 2.54 cm3 cm in ft ft 12 in in 2.54 cm in cm 2.54 cm in in2 cm2 (2.54 cm)2 (1 in)2 km m2 (1000)2 (1 km)2 km mi 0.6214 m km km mi 0.6214 mi km laps lap 0.250 mi m mm ft in 12 in 1ft mm 0.001 m m 1m 39.37 in in cm dm3 m3 2.54 cm in cm3 in3 (0.1 m)3 (1 cm)3 (1 in)3 (1 dm)3 (0.01 m)3 (2.54 cm)3 1133 Appendix B L qt cu cu qt 1.057 qt 1L g mL L mL 0.84 g 1L 1000 mL cm3 g mL cm3 mL cm3 1.32 g kg g cm3 cm3 0.752 1000 g kg kg g 1000 g kg cm3 cm3 mL mL 1cm3 0.789g K °C K = °C + 273 °C K K = °C + 273 °F °C °C = [°F – 32] 1.8 °C °F °C = [°F – 32] 1.8 K °C K = °C + 273 d Cal cal 1000 cal Cal °F [°F – 32] 1.8 m d = v °C = m, V J 4.184J cal 1134 L 1L 100 mL Appendix C Dissociation constants of acids at 25ºC Name Formula Ka1 Ka2 Acetic acid CH3COOH 1.8 × 10–5 Arsenic acid H3AsO4 5.6 × 10–3 Arsenious acid H3AsO3 6.0 × 10–10 Benzoic acid C6H5COOH 6.5 × 10–5 Boric acid H3BO3 5.8 × 10–10 Carbonic acid H2CO3 4.3 × 10–7 Chloroacetic acid CICH2COOH 1.4 × 10–3 Formic acid HCOOH 1.8 × 10–4 Hydrocyanic acid HCN 4.9 × 10–10 Hydrofluoric acid HF 6.8 × 10–4 Hydrogen peroxide H2O2 2.4 × 10–12 Hydrogen sulphate ion HSO−4 1.2 × 10–2 Hydrogen sulphide H2S 5.7 × 10–8 Hypobromous acid HBrO 2.0 × 10–9 Hypochlorous acid HClO 3.0 × 10–8 Hypoiodous acid HIO 2.0 × 10–11 Lactic acid CH3(OH)COOH 1.4 × 10–4 Malonic acid CH3(OH)COOH 1.4 × 10–4 Malonic acid CH2(COOH)2 1.5 × 10–3 Nitrous acid HNO2 4.5 × 10–4 Oxalic acid (COOH)2 5.9 × 10–2 Phenol C6H5OH 1.3 × 10–10 Phosphoric acid H3PO4 7.5 × 10–3 Propionic acid CH3CH2COOH 1.3 × 10–5 Sulphuric acid H2SO4 strong acid 1.2 × 10–2 Sulphurous acid H2SO3 1.7 × 10–2 6.4 × 10–8 Tartaric acid (CHOHCOOH)2 1.0 × 10–3 4.6 × 10–5 1135 1.0 × 10–7 Ka3 3.0 × 10–12 5.6 × 10–11 2.0 × 10–6 6.4 × 10–5 6.2 × 10–8 4.2 × 10–13 1136 PHYSICAL CHEMISTRY Index Abbe refractometer, 436 Anisotropy, 448 Bar code reader, 1105 Anode compartment, 99 Barometric method, 564 Absolute zero, 1065 Anode, 999 Base peak, 514 Absorption coefficient, 1045 Antibonding orbitals, 219 Bases, 932 Absorption Antilogarithm, 1071 Beckmann thermometer, 572 Applications of Beckmann’s method, 576 spectrophotometer, 500 adsorption, 850 Becquerel, 115 Absorption, 844 colloids, 828 Acid rain, 953 ion-exchange adsorption, 852 Berkeley and Hartley’s method, 598 spectrum, 17, 497 Acid-base indicators, 963 Beryllium chloride, 180 Acid-base titrations, 1023 Arrhenius concept, 932 Beta rays, 104 Acids, 932 Arrhenius equation, 757 Binary Actinium series, 111 Arrhenius theory of ionisation, 883 addition, 1125 Artificial kidney machine, 830 digits, 1107 Associated colloids, 825 division, 1127 Aston’s mass spectrograph, 85 multiplication, 1126 Asymmetry effect, 913 number system, 1114 Activation energy, 767, 789 Adiabatic expansion, 258 process, 241 reversible compression, 312 reversible expansion, 260 reversible expansion, 312 systems, 239 Adsorption isotherms, 846 Adsorption theory, 792 Adsorption, 843 Aggregation methods, 813 Algorithm, 1113 Alpha particles, Alpha rays, 104 Aluminium chloride, 165 Aluminium oxide, 158 Ammonia, 161, 170 Ammonium ion, 164, 182 Amorphous solid, 448 Atomic subtraction, 1125 bomb, 133 Binding energy, 126 number, 11 Birkeland-Eyde process, 658 parachors, 483 BIT, 1107 spectra, 17 Body-centred cubic structure, 469 Aufbau principle, 65 Andrews isotherms, 395 Anionic exchange, 852 Bohr Autocatalysis, 788 atom, 12 Auto-ionisation of water, 940 atom, 23 Average life, 118 radius, 26 Average velocity, 375 Bohr’s theory, 23 Avogadro’s law, 362 Bohr-Bury scheme, 33 Avogadro-van’t Hoff law, 605 Boiling-point elevation, 570 Axis of symmetry, 450 Bomb calorimeter, 292 Azeotropes, 540 Bond Azimuthal quantum number, 54 energy, 195, 290 formation, 195 Ampere, 862 Analog computers, 1100 arithmetic, 1125 Balmer equation, 18 Balmer series, 18 1136 moment, 487 order, 220 Bonding electrons, 152 INDEX Born-Haber cycle, 462 catalytic reactions, 784 Colloids, 807 Boron trifluoride, 180 covalent compounds, 162 Combined gas law, 361 Boyle’s law, 358, 373 Compton effect, 23 Boyle-van’t Hoff law, 603 hydrogen-bonded compounds, 172 Bragg’s equation, 456 ionic compounds, 158 Concentration cells, 1027 1137 Common-ion effect, 915 Bravais unit cells, 452 Charles’ law, 373, 359 Concentration of solution, 528 Bredig’s are method, 811 Charles-van’t Hoff law, 604 Bronsted-Lowry concept, 934, 977 Chemical Conditions for hydrogen bonding, 169 Conductance Brownian movement, 817 actinometer, 1046 Bubble pressure method, 430 adsorption, 845 cell, 871 Buckminsterfullerene, 466 bond, 151 equation, 913 Bucky balls, 466 bonding, 151, 193 measurement, 872 Buffer solution, 953 equilibrium, 241, 621, 623 of electrolytes, 865 kinetics, 731 titrations, 898, 901 potential, 341 Congruent melting point, 717 shifts, 508 Conjugate acid-base pairs, 935 Cache memory, 1108 Calcium oxide, 157 Chemiluminescence, 1055 Consecutive reactions, 760 Calomel electrode, 1014 Chemiluminescent reaction, 1055 Constant of integration, 1086 Capillary-rise method, 425 Chemisorption, 845, 846 Contact process, 658 Carbon dioxide, 162, 180 Chiral, 492 Coordinate bond, 163 Carbon monoxide, 166 Chirality, 493 Coordination number, 456 Carbon-12, 94 Chloesteric liquid crystals, 473 Cottrell smoke precipitator, 829 Carbon-13, 94 Chlorine, 161 Cottrell’s method, 572 Carbon-14, 94 cis and trans isomers, 489 Coulomb, 862 Carnot cycle, 311, 316 Clapeyron equation, 330 Covalent bond, 160 Carnot theorem, 314 Classification of crystals, 459 Criteria for equilibrium, 241 Catalysis, 767, 781, 789 Claude’s method, 403 Criteria of spontaneity, 304 Catalytic poisoning, 787 Clausius-Clapeyron equation, 331 Cathode compartment, 999 Cleansing action of soap, 826 Criterion for spontaneous process, 328 Cathode rays, Closed system, 239 Critical Cathode, 999 Cloud chamber, 106 constants, 398 Cationic exchange, 851 Coagulation, 821 density, 399 CD-R, 1110 Coefficient of viscosity, 431 phenomenon, 395 CD-ROM, 1109 Cold light, 1055 state, 395 CD-RW, 1110 Cold packs, 277 temperature, 399 Cell potential, 1000 Colligative properties, 559 Cell reaction, 1000 Collision volume, 399 Crystal Celsius scale, 1065 diameter, 382 defects, 469 Centipoise, 432 frequency, 383 lattice, 452 Centre of symmetry, 450 properties, 380 Cesium chloride crystal, 462 Characteristics of theory of reactions rates, 756 Colloid mill, 811 structure, 451 Crystalline solid, 447 Cubic close-packed structure, 468 1138 PHYSICAL CHEMISTRY Cubic unit cells, 453, 454 Displacement-time graphs, 1073 Curie, 115 Dissociation constant method, 986 affinity, 73, 155 Dissolution, 547 microscope, 816 Distribution law, 672, 673, 675 sea model, 176 Cyclic process, 242 Dalton’s law, 364 Electron configuration, 63 Distribution of electrons, 61 Electronegativity values, 75 Daniel cell, 999 DOS, 1111 Electronegativity, 74 Davison experiment, 45 Dosimeter, 107 Electronic energy, 499 de Broglie’s equation, 44 Dot matrix printers, 1105 Electronic spectra, 500 de Broglie’s wavelength, 44 Downfield shift, 512 Electron-pair bond, 160 Debye-Huckel theory, 912 Drop-number method, 428 Electroosmosis, 820 Decimal number system, 1114 du Nouy tensiometer, 429 Electrophoresis, 819 Degree of dissociation, 579, 638, 914, 916 Dunstan rule, 485 Electrophoretic effect, 913 DVD drive, 1110 Electrovalent compounds, 154 Degree of hydrolysis, 979, 986 DVD-ROM, 1110 Emf, 1000 Deionization of water, 852 Dyanmic Emission spectra, 17 Demineralized water, 852 allotropy, 705 Emulsification, 827 Dempster’s mass spectrograph, 85 equilibrium, 623 Emulsifier, 827 method, 422 Emulsions, 826 Derivation of pH, 980 Derivation of Raoult’s law, 611 Enantiomers, 492 Desalination of sea water, 602 Egg experiment, 594 Enantiotropy, 704 Desilverization of lead, 688 Eigen-functions, 52 Determination of Endothermic reaction, 273 Eigen-values, 52 Endothermic processes, 274 association, 689 Einstein, 1051 Enthalpy of a reaction, 272, 278, 281 dipole moment, 486 Einstein’s equation, 125 Enthalpy of a system, 272 dissociation, 689 Electrical double layer, 819 Entropy of formation, 310 emf of a half-cell, 1006 Electrical properties of sols, 818 Entropy, 305, 306 molecular mass, 562 Electrical units, 861 Enzyme catalysis, 797 molecular weights, 833 Electrochemical cells, 997 Equilibrium concentrations, 634 osmotic pressure, 597 Electrode, 999 Equilibrium constant, 627 pH, 1017 Electrodialysis, 814 Equivalent conductance, 866 solubility, 549, 689 Electrical conductance, 860 Equivalent protons, 509 surface tension, 425 Electrolysis, 860 Eutectic system, 711 transport number, 889 Electrolyte, 999 Examples of Dialysis, 814 Electrolytes, 860 adsorption, 844 Diamagnetic substances, 494 Electrolytic cell, 860 colloids, 808 Differentiation, 1080 Electromagnetic emulsions, 827 Digital computers, 1100 radiations, 13, 498 first order reaction, 740 Dipole moment, 486 separation, 90 Dipole-dipole attractions, 416 spectrum, 15 hydrogen-bonded compounds, 170 Dipping calomel electrode, 1015 spectrum, 497 hydrolysis, 977 Dispersion methods, 811 isotopes, 91 INDEX Heterogeneous polar covalent bonds, 168 Geiger-Muller counter, 107 second order reaction, 744 Gels, 828 catalysis, 783 third order reactions, 745 Geometries of molecules, 179 equilibria, 650 Exothermic processes, 274 Ghosh’s formula, 911 Exothermic reaction, 273 Gibb’s Helmholtz equations, 326 Exponential functions, 1072 Gibbs Duhem equation, 342 Expressing concentration, 529 Glass electrode, 1016 Extensive properties, 239 Gold number, 822 Gouy balance, 494 1139 systems, 237 Heteronuclear diatomic molecules, 225 Hexagonal close-packed structure, 468 Hittorf’s method, 889 Homogeneous catalysis, 782 Factorial of an integer, 1088 Gradient of a line, 1078 Fahrenheit scale, 1066 Graphical method, 753 Faraday’s laws of electrolysis, 862 Grothus-Draper law, 1047 Homonuclear diatomic molecules, 221 Group displacement law, 111 Hot packs, 277 Graham’s law, 366, 374 Faraday’s method, 402 Fingerprint region, 505 First law of thermodynamics, 236, 249 First order reactions, 739 Floppy disk, 1109 Fluorescence, 1053 Fluoroborate ion, 164 Formation of ionic bond, 154 Fractional distillation, 540 Fractional electrolysis, 91 Fractionating columns, 541 Freezing mixtures, 716 Haber process, 656, 785 Homogeneous system, 237 Homogenizer, 827 How to determine the order of a reaction, 752 HTML, 1112 Habit of a crystal, 449 Hund’s rule, 61 Half reactions, 996 Hybrid computers, 1100 Half-cell, 999 Hybridization, 200 Half-life, 114, 746 Hydrogen Hard disk, 1109 bomb, 137, 138 Heat engines, 311 bonding, 169 Heat of bonding, 417 combustion, 283 fluoride, 170 formation, 281 spectrum, 28 fusion, 286 Hydrogen, 160 neutralisation, 284 Hydrogenation of ethene, 792 reaction, 278, 281 Hydrolysis constant, 978, 979 solution, 284 Hydrolysis, 976 Froth flotation process, 850 sublimation, 286 Hydronium ion, 164 Fugacity, 339 transition, 286, 289 Fundamental particles, vapourisation, 286 Fuos-mead osmometer, 833 adsorption, 845 Freezing-point depression, 573 Frequency, 13 Freundlich adsorption isotherm, 847 Fusion reaction, 137 Galvanic cell, 998 Ideal gas equation, 363 Heisenberg’s uncertainty principle, 48 Infrared spectroscopy, 504 Helmholtz double layer, 819 Integration, 1086 Henderson-Hasselbalch equation, 956 Intensive properties, 239 Gamma rays, 105 Henry’s constant, 678 Gas laws, 358 Henry’s law equation, 678 Gaseous state, 355 Henry’s law, 534, 677 Gay Lussac’s law, 361 Hess’s law, 286 Ink jet printers, 1106 Interfacial angles, 449 Intermolecular forces, 415, 419 Intermolecular hydrogen bonding, 171 1140 PHYSICAL CHEMISTRY Internal energy, 248, 271 experiment, 257 Interstitial defect, 469 Intramolecular hydrogen bonding, 172 Kelvin scale, 1065 Intrinsic energy, 271 Kidney dialysis, 597 Ion-exchange adsorption, 851 Kinetic Ionic gas equation, 369 bond, 153 molecular theory , 367 character, 490 properties of sols, 817 crystals, 459 Kirchoff’s equations, 278 equilibria, 909 Kohlrausch’s law, 894 Ionisation chamber, 106 energy, 155, 69 Irreversible Lamber law, 1045 Lamber-Beer law, 1045 expansion, 247 Landsberger-Walker method, 571 processes, 242, 243 Isobaric processes, 241 Langmuir adsorption isotherm, 847 Isobars, 96 Langmuir scheme, 31 Liquid-liquid chromatography, 687 Liquids, 415 Lodge’s moving boundary experiment, 884 Logarithmic functions, 1069 Logarithms, 1070 London dispersion forces, 417 Lyophilic sols, 810, 811 Macromolecules, 831 Magnesium chloride, 157 Magnetic balance, 494 disk, 1108 properties, 494 quantum number, 55 tape, 1108 Isochoric processes, 242 Laplacian operator, 52 Manometric method, 564 Isolated system, 238 Laser printers, 1106 Mantissa, 1070 Isothermal processes, 241 Laser separation, 91 Manufacture of Isothermal reversible compression, 312 Lattice energy, 155, 462 nitric acid, 658 Law of corresponding states, 400 sulphuric acid, 658 Isothermal reversible expansion, 312 Law of mass action, 626 Isotones, 96 Isotonic solutions, 600 Isotopes of chlorine, 93 hydrogen, 92 Neon, 92 oxygen, 93 uranium, 93 Isotopes, 85 Isotopic effects, 95 Isotropy, 448 Laws of osmotic pressure, 603 defect, 126 LCAO method, 213 number, 11 Le Chatelier’s principle, 652 of electron, Lewis concept, 938 spectrometer, 515 Lewis symbols, 152 spectroscopy, 514 Ligand, 164 Mathematical concepts, 1069 Linde’s method, 403 Maxima, 1084 Lindeman’s theory, 767 Mean free path, 380 Linear Measurement of equations, 1077 electrolytic conductance, 871 hybrid, 201 emf, 1002 molecules, 180 Linus Pauling, 154 Joule-Kelvin effect, 257 Joule-Thomson coefficient, 258 effect, 257 Mass pH, 945, 946 Mechanical Linux, 1112 dispersion, 811 Liquefaction of gases, 395 equilibrium, 241 Liquid crystals, 472 Liquid systems, 648 Mechanism of adsorption, 844 electrolysis, 861 INDEX 1141 Memory stick, 1110 Negative catalysis, 789 Orbitals, 201 Meso form, 493 Nematic liquid crystals, 473 Order of a reaction, 734, 737 Metal alloys, 470 Neptunium series, 112 Order of filling of electrons, 62 Metallic bonding, 176 Nernst equation, 1011 Osmometer, 599 Metallic crystals, 465 Nernst’s partition law, 673 Osmosis, 592 Methane, 161, 181 Neutrons, Osmotic pressure method, 833 Milikan’s oil-drop experiment, Nicotine-water system, 538 Osmotic pressure, 596, 607, 611 Miller indices, 450 Nitrogen, 162 Ostwald method, 432 Millipoise, 432 Nitromethane, 165 Minima, 1084 Nitrophenol, 171 Ostwald and Walker’s dynamic method, 564 Molal depression constant, 335 Nonbonding electrons, 152 Ostwald viscometer, 433 Molality, 532 Non-equivalent protons, 509 Ostwald’s dilution law, 909 Molar Normality, 533 Output devices, 1105 Nuclear Overpotential, 1026 concentration, 869 heat capacities, 254, 255 binding energy, 126 Overvoltage, 1026 refraction, 436, 490 chain reaction, 131 Oxidation-reduction reaction, 996 viscosity, 485 chemistry, 103 Oxidation-reduction titrations, 1024 Molarity, 530 energy, 131 Mole fraction, 530 equations, 123, 122 Molecular fission process, 130 Oxygen, 162 Ozone, 166 collision theory, 626 fission reactions, 120 crystals, 464 fusion process, 136 energy levels, 498 fusion reactions, 121 ion, 515 isomerism, 125 orbital theory, 213 sieve theory, 600 magnetic resonance (NMR) spectroscopy, 508 spectra, 496 power plant, 135 Partial differentiation, 1083 velocities, 374, 377 reactions, 120 Partition chromatography, 687, 688 weight, 515, 831 reactor, 135 Partition law, 673 system, 1114 Parts of a computer, 1101 Molecularity of reaction, 735 Monoisotopic, 94 Paramagnetic substances, 494 Parameters of a gas, 356 Parke’s process, 688 Pauli’s exclusion principle, 58 Molecularity, 737 Monitor, 1106 Parachors, 483 Octahedral hybridization, 203 Peak area, 511 Peak splitting, 512 Monoprotic acids, 937 Octal number system, 1117 Pen drive, 1110 Monoprotic bases, 937 Octet rule, 153, 174 Peptization, 811 Monotropy, 704 Ohm, 862 Peptizing agent, 811 Mouse, 1103 One-component system, 702 Periodic table, 68 Moving boundary method, 892 Open system, 239 MRI, 513 Opposing reactions, 760 Permutations and combinations, 1088 Multiple extraction, 681 Optical activity, 438, 492 Nanotube membranes, 603 mouse, 1103 properties of sols, 815 Pfeffer’s method, 597 pH of solutions, 944 pH range of indicators, 963 pH scale, 946, 948 1142 PHYSICAL CHEMISTRY Relative pH values, 948 Protons, Phase diagrams, 702 Pseudo-first order, 738 speed of ions, 886 Phase rule, 697 Purification of sols, 813 strength of acids, 940 Phenol-water system, 537 Pyramidal molecules, 182 strength of bases, 943 viscosity, 432 Phosphorescence, 1054 Phosphorus trichloride, 183 Photochemical reactions, 1043, 1044 Quantum efficiency, 1048 Relaxation effect, 912, 913 Reverse osmosis, 602 Reversible Photochemistry, 1043 numbers, 53 cells, 1003 Photoelectric cell, 1046 theory 12 expansion, 247 Photoelectric effect, 20 theory, 19 process, 242, 243 Photoelectrons, 20 yield, 1048 reactions, 621, 760 Photo-ionisation, 70 Quinhydrone electrode, 1016 Rheochor, 485 Photons, 19 Racemate, 492 Ring-detachment method, 429 Photophysical processes, 1053 Racemic mixture, 492 Role of emulsifier, 827 Photosenitized reactions, 1053 Radioactive ROM, 1108 Physical adsorption, 845, 846 dating, 118 Root mean square velocity, 375 Pi(π) bond, 197 decay series, 111 Rotating crystal method, 458 Pioseulle’s equation, 432 disintegration series, 111 Rotational energy, 498 Plane of symmetry, 449 equilibrium, 118 Rotational spectra, 500, 501 Plasma, 137 series, 111 Rutherford’s model, Polar covalent bonds, 167 Radioactivity, 103 Rydberg constant, 29 Polarimeter, 439 Radix, 1114 Rydberg’s constant, 29 Polymorphism, 704 RAM, 1108 Polynomial, 1073 Raman Polyprotic acids, 937 effect, 516 Salt bridge, 997 Polyprotic bases, 937 frequency, 517 Salt hydrolysis, 976 Positive rays, lines, 516 Scanners, 1104 Potentiometric titrations, 1023 scattering, 516 Schrodinger’s wave equation, 50 Powder method, 459 spectra, 516 Scintillation counter, 108 Preparation of emulsions, 827 spectrum, 516 Scroll mouse, 1103 Preparation of sols, 811 Random access memory, 1108 Primary memory, 1107 Raoult’s law, 560 Second law of thermodynamics, 303, 307 Principal quantum number, 24, 54 Rast’s Camphor method, 577 Second order reactions, 743 Printers, 1105 Rate laws, 734 Secondary memory, 1108 Probability, 1090, 1091 Rate of radioactive decay, 113 Selective precipitation, 922 Programming languages, 1113 Rayleigh line, 516 Semiconductors, 471 Promoters, 786 Rayleigh scattering, 516 Semipermeable membranes, 595 Properties of Reaction rate, 732 Separation of isotopes, 89 emulsions, 827 Read only memory, 1108 Shape of gels, 828 Recrystallisation, 547 ammonia molecule, 208 sols, 815 Redox reaction, 996 Proton number, 11 Refractive index, 435 phosophorus pentachloride molecule, 211 INDEX sulphur hexafluoride molecules, 212 sp3 hybridization of carbon, 206 sp3 hybridization, 202 Surface tension, 423, 483 water molecule, 210 sp3d2 hybrid orbitals, 203 Symmetry of crystals, 449 molecules, 184 Specific Syneresis, 828 SHE, 1006 conductance, 865 SI units, 1063 heat ratio, 384 SI unit of heat, 384 1143 Svedberg’s method, 834 Synthesis of ammonia, 656 temperature, 1065 refraction, 436 Tau scales, 509 length, 1064 resistance, 865 Tetrahedral hybridization, 202 rotation, 439 Tetramethylsilane, 509 volume, 1064 Sigma (σ) bond, 197 Spectroscope, 18 Theories of catalysis, 790 Sign convention of Spin quantum number, 57 Theories of osmosis, 600 heat, 244 Spin-spin coupling, 512 Theory of work, 244 Spontaneous processes, 303 dilute solutions, 559 Significance of entropy, 318 Spontaneous reactions, 731 electrolytic dissociation, 883 Silica garden, 594 Square planar hybridization, 203 strong electrolytes, 911 Silver-silver electrode, 1014 Stabilisation energy, 195 valence, 153 Simultaneous reactions, 760 Stability of sols, 824 Thermal equilibrium, 241 Single electrode potential, 1005 Stalagmometer, 428 Thermochemical equations, 277 Slope of a line, 1078 Standard emf of a cell, 1005 Thermochemical reactions, 1044 Smectic liquid crystals, 473 Standard entropy, 309 Thermochemistry, 271 Sodium chloride crystal, 460 Standard heat of Thermodynamic equilibrium, 240 Sodium chloride, 156 formation, 281 Thermonuclear reactions, 137 Solar cell, 472 reaction, 281 Thermopile, 1045 Solar energy, 137 Stark effect, 54 Solid state, 447 Stark-Einstein law, 1047 Third law of thermodynamics, 308, 318 Solubility State functions, 240 Third order reactions, 745 curves, 549 State method, 421 Thixotropic paints, 829 equilibria, 917 State variables, 240 Thixotropy, 828 product, 909, 917 Steam distillation, 543 Thorium series, 111 Solutions, 528 Strong electrolytes, 871 Time’s arrow, 344 Solvation, 810 Structural parachors, 483 Transition state theory, 765 Solvent extraction, 687 Structure of Transport number, 888 Trends in Sommerfeld orbits, 31 atom, 43 Sommerfeld’s modification, 30 benzene, 484 electronegativities, 75 sp hybrid orbitals, 201 diamond, 465 electron affinities, 74 sp hybridization, 201, 208 sp2 hybrid orbitals, 202 metal crystals, 467 nitro group, 484 Triethylamine-water system, 538 sp2 hybridization of carbon, 207 sp2 hybridization, 202 quinone, 484 Trigonal hybridization, 202 sp2d hybridization, 203 sp3d hybridization, 203 sp3 hybrid orbitals, 202 ionisation energies, 71 Subatomic particles, Trigonal planar molecules, 180 Sulphate ion, 165 Trigonometric functions, 1079 Sulphur dioxide, 165, 184 Triple point, 703 Sulphur trioxide, 181 Two-component systems, 710 1144 PHYSICAL CHEMISTRY Tyndall effect, 815 surface tension, 424 Weak electrolytes, 871 Types of third order rate constant, 746 Web camera, 1104 adsorption, 845 viscosity, 432 Weston standard cell, 1002 catalysis, 782 work and heat energy, 1067 Wheatstone bridge, 871 colloidal systems, 809 work, 244 Windows, 1111 zero order rate constant, 746 Work function, 336 computers, 1100 gels, 828 Uranium series, 111 hybridization, 201 hydrogen-bonding, 171 X-ray crystallography, 456 molecular spectra, 500 Vacancy defect, 469 radiations, 104 Valence bond theory, 195 radioactive decay, 108 Valence electrons, 152 Zeeman effect, 34 solutions, 529 Valence, 151 Zeeman effect, 54 thermodynamic systems, 238 van der Walls equation, 388, 390 Zeotropic mixtures, 540 van der Walls forces, 415 Zero order reaction, 735, 739 van’t Hoff equation, 604 Zeroth law of thermodynamics, 344 Ultrafiltration, 815 factor, 581 Zeta potential, 819 Ultramicroscope, 816 isochore, 338 Zinc electrode, 1007 Ultraviolet-visible spectroscopy, 506 isotherm, 336 Zip disk, 1109 Unit of dipole moment, 486 reaction, 646 Unit of equivalent conductance, 867 theory of dilute solutions, 605 Ultracentrifuge, 90 reaction isotherm, 643 Unit cells, 452 Vapour pressure, 420 Units of Variable valence, 175 density, 1068 Velocity-time graphs, 1075 energy changes, 272 Vibrational energy, 498 entropy, 309 Vibrational spectra, 500, 502 equilibrium constant, 642 Virial theorem, 194 first order rate constant, 746 Viscosity method, 834 force, 1067 Viscosity, 431, 485 heat capacity, 254 Volt, 862 heat, 244 Voltaic cells, 998 internal energy, 249 Volumetric titrations, 901 mass and weight, 1066 VSEPR theory, 179 pressure, 1068 radioactivity, 113 rate constant, 745 Water calorimeter, 292 rate, 732 Water softening, 852 second order rate constant, 746 Water, 161, 170 specific conductance, 866 Wave number, 14 Wavelength, 13 ... Electronegativity ISOTOPES, ISOBARS AND ISOTONES Isotopes Representation of Isotopes Identification of Isotopes Aston? ?s Mass Spectrograph Dempster? ?s Mass Spectrograph Separation of Isotopes Gaseous Diffusion... Hydrolysis Acids and Weak Bases Salts of a Weak Acid and Strong Base Relation Between Hydrolysis Constant and Degree of Hydrolysis Salts of Weak Bases and Strong Acids Salts of Weak Acids and Weak Bases... What Is Hydrolysis Bronsted-Lowry Concept of Hydrolysis Why NaCl Solution is Neutral Salts of Weak Acids and Strong Bases Salts of Weak Bases and Strong Acids Salts of Weak Quantitative Aspect of