GRADUATE INORGANIC CHEMISTRY (VOLUME - I)

Transcription

1 GRADUATE INORGANIC CHEMISTRY (VOLUME - I) (for B.Sc. Ist year students of U.P. (Unified), GNDU, Panjab, Punjabi, MDU, KU, Himachal, Jammu, Kashmir and other Indian Universities) (Strictly as per new syllabus and UGC curriculum) B. R. PURI L.R. SHARMA M.Sc., Ph.D., F.R.I.C., F.N.A., Formerly, Prof. of Physical Chemistry, Panjab University, Chandigarh M.Sc., Ph.D., F.R.I.C. (London), Formely, Prof. of Physical Chemistry, SSB University Institute of Chemical Engineering &Technology, Panjab University, Chandigarh K. C. KALIA GEETANJLI KAUSHAL M.Sc., Ph.D. (I.I.T. Kanpur) M.Sc., M.Phil., Ph.D. Formerly, Prof. of Inorganic Chemistry, Post Graduate Department of Chemistry, Department of Chemistry, Lyallpur Khalsa College, Punjabi University, Patiala Jalandhar (Pb.) Future for WINNERS VISHAL PUBLISHING CO. JALANDHAR - DELHI

2 CONTENTS 1. ATOMIC STRUCTURE Introduction (1) 1.2. de Broglie Concept of Particle and Wave Character (Dual Character) of Electron (2) Derivation of de Broglie Equation (2) Derivation of The Bohr Angular Momentum Postulate From de Broglie s Relation (4) Bohr postulate (4) Experimental Verification of de Broglie s Relation (4) Davisson-Germer Experiment (4) 1.3. Heisenberg s Uncertainty Principle (6) 1.4. Schrödinger Wave Equation (7) Eigen wave functions (9) Schrödinger Wave Equation for Hydrogen Atom (9) Energy of Electron (11) 1.5. Significance of and 2 (11) 1.6. Radial and Angular Wave Functions(11) 1.7. Shapes of Orbitals and Relationship between Spherical Harmonics (12) Complete Wave Functions for s Orbitals and their Shapes (13) Complete Wave Functions for p Orbitals and their Shapes (14) Complete Wave Functions for d Orbitals and their Shapes (15) Shapes of f Orbitals (18) 1.8. Probability Distribution of Electrons Around The Nucleus / Concept of Atomic Orbitals (19) Probability Distribution Curves (20) 1.9. Quantum Numbers (22) Principal Quantum Number (22) Angular Momentum Quantum Number (22) Magnetic Quantum Number (22) Spin Quantum Number (24) The Zeeman Effect (24) Pauli s Exclusion Principle (24) Hund s Rule of Maximum Multiplicity (25) The Aufbau Principle (25) Electronic Configuration of The Elements (26) Anomalous Configurations of Chromium and Copper (29) Electronic Configuration of Ions (29) Extra Stability of Half-Filled and Completely-Filled Orbitals (32) Orbital Energies in Multielectron Atoms / Screening Effect (34) The Slater s Rules. The Concept of Effective Nuclear Charge (34) Applications of Slater s Rules (36) Summary (38) Questions (40) * 2. PERIODIC PROPERTIES Long Form Periodic Table (46) Position of Elements in The Periodic Table (46) Periods (46) Groups (48) Cause of Periodicity (48) Cause of Recurrence of Properties At Regular Intervals of Atomic Numbers (49) Division of Elements Into s, p, d and f Blocks (50) 2.2. Periodic Properties (51) Size of atoms and Ions (51) Covalent (Atomic*) Radius (51) Periodic Trends in Covalent Radii (53) Van der Waals Radius (55) Ionic Radius (55) Variation of Ionic Radii in Iso-electronic Ions (56) Periodic Trends in Ionic radii (57) Determination of Ionic radii (58) Ionisation Energy (IE) (58) Factors Determining Ionisation Energy (60) Variation of Ionisation Energy in the Periodic Table (61) Method of evaluation of Ionisation Energy (62) Electron Affinity (EA) (62) Variation of Electron Affinity in the Periodic Table (63) Measurement of Electron Affinities (64) Electonegativity (65) Pauling s Approach (65) Allred and Rochow s Approach (67) Mulliken s Approach (67) Factors Affecting the Magnitude of Electronegativity (68)

3 Predicition and Explanation of Chemical Behaviour - An Application of Electronegativity (69) Trends in Periodic Table (70) Summary (72) Questions (73) 3. CHEMICAL BONDING I (Covalent-Bond) Covalent Bond (80) Atomic Orbital Theory of Covalent Bond (81) Variable Covalency, Maximum Covalency (84) Some Important Characteristics of Covalent Bond (85) Bond Length (85) Bond Angle (85) Bond Strength (85) 3.2. Polarity in Covalent Bonds (86) Percent Ionic Character of A Polar Covalent Bond (86) Electronegativity Difference and Percent Ionic Character (86) Dipole Moment and Percent Ionic Character (86) Quantum Mechanical Treatment of the Covalent Bond (87) 3.3. Valence Bond Theory (VBT) (87) Limitations of Valence Bond Theory (92) 3.4. Resonance (93) 3.5. Hybridisation (96) 3.6. Valence Shell Electron Pair Repulsion Theory (VSEPR theory) (101) Geometry of Covalent Molecules (102) Regular and Irregular Geometry (103) Geometry of Molecules and Ions Containing only Bond Pairs of Electrons (104) Beryllium Fluoride (BeF 2 ) (104) Boron Trifluoride (BF 3 ) (104) Methane (CH 4 ) (105) Phosphorus Pentafluoride (PF 5 ) (105) Sulphur Hexafluoride (SF 6 ) (106) Iodine Heptafluoride (IF 7 ) (107) BF 4 ion (107) PF 6 ion (108) SnCl 6 2 ion (108) Sulphate Ion (SO 4 ) 2 (109) Perchlorate Ion (ClO 4 ) (109) Geometry of Molecules and Ions Containing Bond Pairs as well as Lone Pairs of Electrons (110) SnCl 2 (111) NH 3 (111) H 3 O + (112) H 2 O (112) SF 4 (113) CIF 3 (113) XeF 2 (114) XeF 4 (114) ICI 2 (115) Limitations of VSEPR Theory (116) 3.7. Molecular Orbital Theory (118) Conditions for the Combination of Atomic Orbitals (126) Electronic Configurations and Molecular Orbital Energy Level Diagrams of Homonuclear Diatomic Molecules (129) H 2 (129) H 2 + (129) He 2 (130) He 2 + (130) Li 2 (131) Be 2 (131) B 2 (131) C 2 (131) N 2 (132) O 2 (132) F 2 (133) Ne 2 (133) Molecular Orbital Energy Level Diagrams of Heteronuclear Diatomic Molecules (134) BO (134) CN (135) CN (135) CO (136) CO + (137) NO (137) NO + (138) HF (138) HCl (139) Comparison Between Valence Bond Theory (VBT) and Molecular Orbital Theory (MOT) (140) 3.8. Multicenter Bonding in Electron Deficient Molecules (141) Bonding in Boranes (141) Summary (143) Questions and Problems (146)

4 = 4. CHEMICAL BONDING II (Ionic Solids and Weak Interactions) 4.1. Solid State (153) Space Lattice and Unit Cell (155) Types of Crystals (158) 4.2. Ionic Bond (158) 4.3. Close Packing of Indentical Solid Spheres (160) Interstitial Sites in Close Packing of Spheres (164) Sizes of Interstitial Sites in Ionic Crystals, Limiting Radius Ratios (164) Radius Ratio Rule : Coordination Number and The Shape of Ionic Crystals (169) Limitations of Radius Ratio Rule (171) Structures of Ionic Crystals (171) Structure of Sodium Chloride (NaCl) (172) Structure of Zinc Sulphide (ZnS) (173) Zinc Blende Structure (173) Wurtzite Structure (174) Structure of Cesium Chloride (CsCl)(174) Structure of Calcium Fluoride (CaF 2 ).The fluorite structure (175) Structure of Sodium Oxide (Na 2 O). The antifluorite structure (175) Structure of Titanium Dioxide, TiO 2, The Rutile Structure (176) 4.4. Lattice Energy : Born Lande Equation (177) Experimental Determination of Lattice Energy, The Born-Haber Cycle (179) 4.5. Solvation Energy and Solubility of Ionic Solids (182) 4.6. Polarizing Power and Polarizability of Ions (182) Fajan s Rules (183) 4.7. Imperfections in a Crystal Lattice Defects (184) Schottky Defects (184) Frenkel Defects (185) Consequences of Schottky and Frenkel Defects (185) Metal Excess Defects (186) Metal Deficiency Defects (187) 4.8. Metallic Crystals (187) Free Electron Model (187) The Valence Bond Model (189) The Band Model (190) 4.9. Energy Band Theory of Conductors, Insulators and Semiconductors (192) Semiconductors (193) Weak Interactions (195) Hydrogen Bond (195) Consequences of Hydrogen Bonding (196) Van der Waals Forces / Intermolecular Forces (198) Summary (200) Questions (203) # 5. s-block ELEMENTS General Characteristics of Alkali Metals (209) Physical Properties (209) Chemical Properties (214) Comparison of Lithium with Other Members of The Family (217) 5.2. General Characteristics of Alkaline Earth Metals (218) Physical Properties (219) Chemical Properties (222) Comparison of Beryllium With Other Elements of Group 2 (223) 5.3. Diagonal Relationship (224) Resemblance of Lithium and Magnesium (225) Diagonal Relationship Between Beryllium and Aluminium (226) 5.4. Hydrides (226) 5.5. Tendency Towards Solvation (227) 5.6. Tendency to Form Complexes (229) The Wrap Around Complexes (230) 5.7. Function of s-block Elements (232) Role of Na + and K + ions in Biological Systems (232) Role of Mg 2+ and Ca 2+ Ions in Biological Systems (233) 5.8. Alkyls and Aryls of s-block Elements (233) Alkyls and Aryls of Alkali Metals (233) Alkyls and Aryls of Alkaline Earth Metals (235) Summary (236) Questions (237) # 6. CHEMISTRY OF NOBLE GASES Occurrence (243) Histroy of Discovery of Noble Gases (243) Isolation of Noble Gases from the Atmosphere (244) 6.2. Electronic Configuration of Noble Gases (246) 6.3. General Physical Properties (246) 6.4. Utility of Noble Gases (247) 6.5. Chemistry of Noble Gases (248) Hydrates of Noble Gases (249) Clathrates of Noble Gases (249) 6.6. Fluorides, Oxofluorides and Oxides of Xenon (250) Xenon (II) Compounds (250) Xenon Difluoride, XeF 2 (250) Xenon (IV) Compounds (252)

5 Xenon Tetrafluoride, XeF 4 (252) Xenon Oxodifluoride, XeOF 2 (253) Xenon (VI) Compounds (254) Xenon Hexafluoride, XeF 6 (254) Xenon Oxotetrafluoride, XeOF 4 (256) Xenon dioxodifluoride, XeO 2 F 2 (257) Xenon Trioxide, XeO 3 (258) Xenon (VIII) Compounds (259) 6.7. Fluorides of Krypton and Radon (260) Krypton difluoride, KrF 2 (260) Summary (261) Questions (262) 7. p- BLOCK ELEMENTS Metallic Character (265) Melting Points and Boiling Points (266) Oxidising and Reducing Properties (266) Electrode Potentials & Electropositive Character (267) Oxidation States (268) 7.1. The Elements of Group 13 (270) Diagonal Relationship Between Boron and Silicon (272) A Comparative Study of Chemistry of Group 13 Elements (273) Hydrides (273) Oxides and Hydroxides (274) Halides (276) Oxo-Compounds of Boron (281) Boron Hydrides, Boranes (283) Diborane, B 2 H 6 (284) Bonding in Boranes (287) Higher Boranes (289) Borohydrides (293) Compounds of Boron With Nitrogen (295) Boron Nitride, BN (295) Borazine or Borazole (296) 7.2. The Elements of Group 14 (297) Structure of Diamond (300) Structure of Graphite (300) Fullerenes (301) Comparison of Carbon With Silicon (302) A Comparative Study of Chemistry of Group 14 Elements (303) Hydrides (303) Halides (305) Oxides (307) Oxyacids (310) * Not meant for Punjabi University, Patiala = Not meant for Panjab University, Chandigarh # Not meant for GNDU, MDU, KU and HPU Carbides (310) Salt-like Carbides (310) Covalent Carbides (311) Interstitial Carbides (312) Silicates (312) 7.3. The Elements of Group 15 (317) A Comparative Study of Compounds of Group 15 Elements (322) Hydrides (322) Halides (329) Oxides (334) Oxoacids (339) 7.4. The Elements of Group 16 (351) A Comparative Study of Compounds of Group 16 Elements (358) Hydrides (358) Halides (360) Oxides (362) Oxoacids (365) Nitrides of Sulphur (373) Tetrasulphur Tetranitride, S 4 N 4 (373) Disulphur Dinitride, S 2 N 2 (374) 7.5. The Elements of Group 17 (375) Properties of Elements of Group 17 (379) A Comparative Study of Compounds of Group 17 Elements (383) Hydrides (Hydrogen Halides) (383) Oxides (385) Oxoacids (389) Interhalogen Compounds or Interhalogens (396) Interhalogen and Polyhalogen Anions and Cations or Polyhalides (403) Basic / Electropositive Character of Iodine (405) Fluorocarbons (406) 7.6. Inorganic Polymers (407) General Properties of Inorganic Polymers (408) Phosphazenes, (NPR 2 ) n (409) Chlorophosphazenes (411) Bonding in Triphosphazenes (412) Silicon-Based Polymers (413) Organosilicones or Organopolysiloxanes (413) Silicones (414) Summary (420) Questions (422)