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PRINCIPLES OF, INORGANIC CHEMISTRY, PRINCIPLES OF, Inorganic, Chemistry, A TEXT BOOK, for, B.Sc., B.Şc. (Hons.) & M.Sc. Students of Indian Universities as also for, Candidates appearing for Various Competitive Examinations, LATE B.R. PURI, . M.Sc., Ph.D., F.R.I.C., F.N.A.,, Formerly, Prof. of Physical Chemistry,, Panjab University, Chandigarh, LR. SHARMA, M.Sc., Ph.D., F.R.I.C. (London),, Formely, Prof. of Physical Chemistry,, Department of, Chemical Engineering &Technology,, Panjab University, Chandigarh, К.С. КALIA, M.Sc., Ph.D., (L.I.T., Kanpurj, Formerly, Prof. of Inorganic Chemistry,, Department of Chemistry,, Punjabi Univeršity, Patiala, te, MILEST ONE, PUBLISHERS & DISTRIBUTORS, 4271/XI, 3-Ansari Róad, Daryaganj,, DELHI-110 002 (INDIA), Puri Sharma, Kalia

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Published by:, MILESTONE, PUBLISHERS & DISTRIBUTORS, 4271/XI, 3nsari Road, Daryaganj,, DELH 110 002 (INDIA), Ph.011-23260206, Mob. : 9417 32295, 94172-72293, E-mail : [email protected], PREFACE TO THE THIRTY FIRST EDITION, The authors take pleasure in presenting the thirty first edition of their prestigious publication, Principles of Inorganic Chemistry. The entire text has been thoroughly revised and updated, in every respect. While minor but otherwise essentia! additions have been made in all the, chapters dealing with representative elements, transition elements and.inner transition elements,, some important additions have been made in chapters covering group theory, organometallic, compounds and inorganic polymers. The additions to group theory include additional applications, of group theory covering relaxation of selection rules for electronic transitions, study of the method, of descending symmetry and the study of electron absorption spectra using plane polarised light., ©Copyright Resetved, 2013-14, Character tables for important symmetry groups have also been given in this chapter. A, significant addition to the present edition is a new chapter describing the quantitative treatment, This book, or any part thereof, may nobbe reproduced in any form, without the written permission of the publishers and the authors., of crystal field theory. Mathematical expressions have been derived for calculating Vocts, Vietragonal, Viet and Dq values. The fact that in an octahedral ligand field potential, the energy, orbitals increases by 6 Dq while that of t2g orbitals decreases by 4 Dq, has been, eštablished mathematically., The book now adequately covers almost all the modern topics in inorganic chemistry. The, publication, therefore, can be rightly called modern Inorganic chemistry., We take this opportunity to express our sincere thanks to all the students and fellow téachers, who took pains to send us their valuable suggestions and criticism for further improvement of., * 595-00 (for Punjab and Delli, { 610-00 (for other States), 1200-00 (Library/International Edition), the text., The authors sincerely hope that the present revised and improved edition of the book will, be warmly received by the students and the teachers alike. Any suggestions for further, improvement of the text would be most welcome., AUTHORS,, Printed at :, Instant Printers, Jalandhar

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CONTENTS, Chap., Description, Page, Chap., Description, Page, 1. WAVE MECHANICAL CONCEPTS OF, ATOMIC STRUCTURE, Atomic properties (63), Covalent radius (64), Periodic trends incovalent radi (66), Van der Waals radius (67), lonic radius (67), Periodic trends in lonic radi (69), lonization energy (69), Factors determining ionization energies (71), Variation of ionization energy in the Periodic table (72), Electron affinity (73), Variation of electron afinity in the Periodic table (74), Successive olectron affinities (74), Electrónegativity (75), Pauling's approach (75); Table (75), Aflred and Rochow's approach (76), Mulliken's approach (76), Factors determining electronegativity (77), Applications of electronegativities (78), 1-57, Rutherford's nuclear model of the atom (1), Planck's quantum theory of radiation (2), Photoelectric effect and quantum theory (2), Bohr's model of the atom (3), Bohr's equation for the anergy of electron in hydrogen, atom (3), Bohr's theory and the origin of hydro, Sommerfeld's extension of Bohr's theory (8), Particle and wave character of electron. The de Broglie, equation (9), Experimental verification of de Broglie equation (10), Davisson and Germer experiment (10), Heinsenberg's uncertainty principle (12), Compton effect (13), Quantum mechanics or wave mechanics (14)., Postulates of quantum mechanics or wave mechanics (15), Schrodinger wave equation (16), Fomulation of Schrodinger wave equation (18), Probability density and significance of y (20), Solutions of Schrodinger wave equation for simple systems, spectrum (5), 3. MOLECULAR SYMMETRY AND GROUP, THEORY, 83-136, Symmetry operations and symmetry elements (83), (22), Equivalent symmetry elements and equivalent atoms (86), Particle in a one-dimensional box (22), Particle in a three- dimensional box (23), Schrodinger wave equation for hydrogen atom (24), Energy of electron in hydrogen and hydrogen-liko atoms, General relations amongst symmetry elements and ., symmetry operations (87), Symmetry elements and symmetry operations in molecules, of special symmetry (88), Symmetry classification of molecules (90), A complete set of symmetry operations as a mathematical, group (92), Classes of symmetry operations (94), Representațion of symmetry operations by matrices (95), Character tables (102), *. Wave functions aş basis of Ireducible representations (103), Direct product of matrices (105), Applications of group theory (105):, 1. Evaluation of Integrals (106), 2. Explanation of allowed and forbldden electronic, transilons (106)., 3. Hybridisation (107), 4. (A) Nature of bondingin octahedralcomplexes.(110), (b) Nature of bonding In tetrahedralcomplexes (110), (26), Radial wave function (26), Angular wave function (29), Angular wave functions and shapes of orbitals (30), Quantum numbers (35), Zeeman effect (37), Paull's exclusion principle (38), Energy level diagram of a multi-electron atom (40), The Siater's rule (41), Applications of Slater's rules (43), Electronic configurations of atoms (45), Elements beyond atomic number 103 7), Electronic configuration of elements. Tables (48-49), Extra stability of hal-filled and completefy filled orbitals (51), Hund's rule - its basis and applications (52), 2. PERIODIC TÁBLE AND ATOMIC, PROPERTIES, 5. Energy terms of strong fleid configuration of octahedral, complexes (111), 58-82, 6. Splitting of orbitals and terms inachemical environment, (112), The long form periodic table (58), Cause of periodicity (60), Cause of recurrencé of properties (61), Division of elements into s,p,dand /blocks (62), 7. Relaxation of selection rules for electronic transitions, (120), 8. Establishing state of symmetry by the method of, desconding symmetry (120), (i)

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(1), Chap., Page, (1), Chap., Description, Page, Chap., Description, Page, Chap., Descriptlon, Description, 9. Study of electron absorption spectra using plane, polarised light (125), Character tables for important symmetry groups (130-135), Walsh diagrams for AH2 molecules (185), Carbon dioxide molecule (187), molecularorbitals involved (188), Ammonia molecule (189), Comparison betweeen VBT and MOT (189), Metallic bond (190), Electron sea model for metals andexplanation of metailic, properties (190-191), The valehoe bond model (192), The band model. MOapproach (192), Hydrogen bond (194), Consequences of hydrogen bonding (195), Intermolecular forces (197), London forces (198), Basis for hard-hard and soft-soft interactions (310), ZnS crystal (zinc blende and wurtzite structures) (259), CsCl crystal (260), CaF2 crystal (261), TiO2 crystal (261), CaC2 crystal (261), Cd!2 crystal (262), Lattice energy of an ionic crystal (262), Calculation of lattice energies of ionic solids (263), Bomequation, its applícations (264), Experimental determination of lattice energy (266), The Bom-Haber cycle (266), Defect structures of crystals (268), Schóttky defect, Frenkef defect, metal excess defects, metal, deficiency defects, thermal defects (268-71), Semiconductors (272), Fabrication of transístors (272), 9. OXIDATION AND REDUCTION, 313-327, Oxidation number (313), Galvanic cells (314), Single electrode potential (315), Sign of electrode potential (315), Standard electrode potentials. Eloctrochemical series (316), Nemstequation (317), Applications of electrochemical series (318), Source of electricai energy in a galvanic cell (318), Hydrogen over voltage (319), Oxygen overvoltage (320), Redox stability in water (320), Oxidation by atmospheric oxygen (321), Latimer diagrams (322), Frost diagrams (324), Pourbaix diagrams (326), 4. ÇHEMICAL BONDING, 137-200, lonic bond (137), Docrease in energy in the formation of sodium chloride, (137), Variable valericy of cations (140), Covalent bond (141), Decrease of energy in formation of hydrogen molecule (141), *: Atomic orbital overlap concept of covalency (142), Variable covalency. Maximum covalency (144), Coordinate covalent bond. Dative bond (145)., Polarity in covalent bond (146), Covalent character of ionic bond. Polarization of ions (146), Fajan's rules (146), Effects of polarization (147), Percent ionic character of a polar covalent bond (147), Dipole moment and per cent ionic character (147), Dipole moment and structure of molecules (148), Some important bond characteristics (149), Bond iength, bondangle, bond energy (149-150), Wave Mechanical Treatment of Covalent Bond (150), Approximate solution of Schrodinger wave equation (151), The variation principle (151), Ritz linear combination method (152), Valence bond theory (152), 1 Singlet and triplet wave functions (156), Concept of resonance (157), Resonance energy (157), Linnet double quartet approach (159), Molecular orbital theory (160), Linear combination of atomic orbitals-LCAO (161), 'MO treatment of fH2* ion (161), Bonding and antibonding molecular orbitals (163), Construction of MO and VB wave functions (164), Electron charge densities in mblecular orbitals of H2+ ion, 5. HYBRIDISATION AND SHAPES OF, COVALENT MOLECULES, 201-233, 7. NON-AQUEOUS SOLVENTS, 275-294, Hybridisation (201), Salient features of phenomenon of hybridisation (205), Wave functions for hybrid orbitals (206), Orientation of hybrid orbitals in space (210), VSPER theory (213), Geometry of molecules containing only bond pairs of, electrons (BeF2, BF3, CH4, PF5, SF6, IF7 molecules), Classification of solvents (275), Characteristic properties of a solvent (275), Liquid'ammonia (277), Chemical reactions in liquid-ammonla (278), Solutions of alkai metals in liquid ammonia (283), Liquid hydrogen fluoride (283), Chemical reactions in liquid hydrogen fluoride (284), Sulphuric acid (285), Chemical reactions of sulphuric acid (285), Liquid dinitragen totroxide (286), Liquid sulphur dioxide (288), Reactions in iquid sulphur dioxide (289), Molten salts as non-aqueous solvents (292), 10. METALS AND METALLURGY, Occurrenca of metals (328), Various steps involved in metallurglcal processes (329), Concentratlon of ore (329), Calcination (330), Roasting. Reduction to free metal (332), Electrometallurgy (333), Thermodynamics of the oxidation of metals to metal oxides., The Ellingham diagram (333), Hydrometallurgy (336), Refining or purification (336), Zone refining (338), 328-339, (215-219), Geometry of molecules containing bond pairs as well as, lone pairs of electrons (SnCl2, NH3, H20, SF4, CIF3,, Xef2, XeF4. IF5 molecules) (219-223), Structure of CO2 molecule (226), Geometry of some ions (CO32, NO3, SO42-, CIO4",, CIO3 ions) (227-233), 6. THE STRUCTURE OF SOLIDS, 234-274, 8. ACIDS AND BASES, 294-312, 11. HYDROGEN, 339-356, Crystalline and amorphous solids (234), Size and shape of crystals (235), Interfacial angles (235), Symmetry in crystals (235), Plane, axis and centre of symmetry (236-37), Elements of symmetry of a crystal (237), (991), Space lattice and unit cell (238), Bravais lattices (239), Seven basic crystał systems (241), Millerindices (242), Types of crystals (244)., Structure of diamond (244), Close packing of ldentical solid spheres (246), Interstitial sites in close packing of spheres (249), Limiting radius ratio (250), Radius ratio rule and the shape of an ionic crystal (254), Structures of metallic crystals (256), Structures of ionic crystals (257), NaCi crysta! (258), Arrhenius concept (294), Proton transfer theory. Concept of Lowry and, Bronsted (294), Lux-Flood concept (296), The solvent-system.concept (296), The Lewis concepf (299), Relative strengths of acids and bases (300)., effect of solvent (300), ievelling effect (300), effect of polarity and dielectric constant (303), effect of substituents (303), Additional factors infiuencing relative strengths of acids and, bases (304), Measurement of acid-base strength in gas phase (307), Enthaipies of acid-base reactions from empirical parameters, Position in periodic table (339), Resemblance with alkali metals (339), Resemblance with the halogens (339), Preparation, properties and uses (340-41), Nascent hydrogen (341), Actfve hydrogen (342), Alomic hydrogen (342), Ortho and para hydrogen (344)., Hydrides (346), Heavyhydrogen or deuterium (350), Tritium (350), Heavy water (350), Pieterial reprasentation ol.combination of atomic orbitals to, form molecular orbitals (168), Conditions for the combination of atomic orbitals to form, molecular orbitals (171), Energy level dlagram for molecular orbitals (171), Mixing of orbitals (172), Electronic configurations of homonuclear diatomic molecules, 12. THE MAIN GROUP ELEMENTS. THE, GENERAL CHARACTERISTICS, (175), 357-373, Electronic configurations of heteronuclear diatomic, molecuies (179), Tem symbols for diatomic molecules (182), Molecular orbitals of polyatomic species (183), Walsh diagrams (184), (307) Mętallic character (357), Hard and soft acids and bases. Pearson's concept (308) Polarising power and polarizability (358), Bonding in hard-hard and solt-soft combinations (309), HSAB principle and its applications (309), Oxidising and reducing properties (361), Electropositive character. Electrodepotentials (361)

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(iv), (v), Chap., Description, Page, Chap., Description, Page, Chap., Description, Page, Chap., Description, Page, Complexes of beryllium (410), Chiorophyl! (411), Portland cement (412), Role of Mg2+ and Ca2+ jons in biological systems (414), Oxidation states (362), Sulphides (521), Nitrides (521), Hydrazine (524), Hydrazoic acid (525), Hydroxylamine (526), Nitrogen trifluoride, nitrogen difluoride, nitrogen tetrafluoride, Difference between tetrahalides of carbon and tetrahalides, Diagonal relationship (363), Compounds of main group elements (365), Some special characteristics of pblock.elemsnts (366), Reluctance of heavierpblock elements to show maximum, oxidation state (368), Reluctance of heavier pblock elements to involve porbitals, for pi bonding (368), Parlicipation of dorbitals in sigma bonding (369), Participation of dortbitals in n bonding (370), Electrohega!ivities (371), of other elements (460), Metal carbonyls, structure, preparation and properties, (464-66), Metal carbides (salt-like, covatent, interstitial, iron-type), (468), 15.THE ELEMENTS OF GROUP 13, 416-447, General characteristics (416), lonization energles (417), Oxidation states (417), Electropositive character (417), Tendency to form ionic compounds (417), Tendency to form covalent compounds (418), Açtion of air and water (418), Applications of carbides in industry (470), Intercalation compounds of graphite (473), Silicides (475), Silica (476), Glass, manufacture, varieties (478), Silicates (480), (527-528), Trisilyamine (529), Hexamine (urotropine) (529), Phosphazines (529), Hexachlorocyolotriphosphazine (529), Fertilizers (531)., 13.THE ELEMENTS OF GROUP 1, 374-395, Types of silicates (481), Orthosilicates (481), Pyrosilicates (481), Chain silicates (481), Cyclic silicates (482), Sheet silicates (482), Three-dimensional silicates (483), Mica, Clay, Fuler's earth (483), Zeolitos (484), Zeolites as molecular sieves (484), Silicones (484), Lead pigments (486)., General characteristics (374), Atomic and ionic radi (375), lonization energies (376), Eiectroposítive character (376), Formation of univalent positive ions (376), 536-565, Diagonal relationship between boron and silicon (418), Extraction of elements (419), Properties of Elements (420), Compounds of Group 13 elements (422), Acidic, amphoteric and basic character of oxides and, hydroxides (424), Relative strengths of trihalides as Lewis acids. Effect of, back bonding (426), 18.THE ELEMENTS OF GROUP 16, General characteristics (536), Oxidation states (537), Molecular structure (537), Extraction of the elements (538), Properties of elements of Group 16 (540), Anomalous behaviour af oxygen (540), Ozone (542), Structure of ozone (542), Allotropes of sulphur (544), Role of selenium In xeroxography (546), Compounds of elements of Group 16 (548), Hydrides (548), Halides (550) --, Oxides (552), Oxoacids (555), Sulphurous acid (555), Sulphuric acid (556), Peroxosulphuric acids (558), Caros's acid (559), Marshall's acid (559), Hydration of ions (376), Reducing properties. Oxidation potentials (377), Characteristic flame çolouration (378), Lattice energies (378), Chemical properties (379), Complexes of alkali metals (381), The wrap around' complexes (382), Comparison of lithium with other members of the family, Characteristic difference in the structures of trihalides of, boron and aluminium (428), Borides (430), Boron hydrides. Boranes (431), Diborane -Preparation, properties and structure, (383), 17.THE ELEMENTS OF GROUP 15, 489-535, (432-434), Resemblance of ithium and magnesium (385), Uses of alkali metals (385), Extraction of Alkali Metais (386), Properties of alkali metals and their uses (387), Compounds of elements of Group I (388-94), Role of Nat and K* ions in biological systems (394), Sodium pump (394), Bonding in boranes (434), Carboranes (440), Wade's rules (441), Compounds of boron with nitrogen (442), Borazine or borazole (443), Boric acid (443), Ultrmarine (446), General characteristics (490), Metallic and non-metallic charactor (490), Variation in physical state (490), Positive oxidation states (491), Negative oxidation states (491), Catenation or self-linkage (491), Allotropy (491), Chemical reactivity (492), Đifference between nitrogen and the rest of the family Oxohalides of sulphur (562), members (42), Extraction of eleients (493), Properties of elements of Group 15 (494), Allotropic forms of phosphorus (495), Chemical Properties of Phosphorus (4, Propertles of arsenic (498), Marsh test (499), Gutzelt test (499), Compounds of Group 15 elements -a comparative etudy, 396-415, 14.THE ELEMENTS OF GROUP 2, General characteristics (396), Atomio and ionic radii (397), onization energles (397), Reducing propertles: Oxidation potentials (399), Flame coleurationA(399), Chemical properties (400), Gradation in properties (400), Comparison of beryllium with other elements of Group 2, 16. THE ELEMENTS OF GROUP 14, 448-488, General Characteristics (448), tonization energy (449), Metallic and non-metalic character (449), Nature of bonds in compounds (449), Tendeney to ferm chains. Catenation (450), Extraction of elements (451), Artificial diamonds (451), Artificial graphite (451), Properties of Elements (452), Structure of Diamond (452), Structure of graphite (453), Fullerenes (454), Properties of Group 14 elements (454-458), Compounds of Group 14 eiements (458-459), Nitrides of sulphur (563), Organometallic compounds (564), 19.THE ELEMENTS OF GROUP 17, 566-610, General characteristics (566), Non-metallo character (567), Colour (567), Electron afinity (567), Oxidation states (568), Oxidising power (568), Combination with metais and non-metals (570), Reaction with water (570), Reaction with hydrocarbons (570), Preparation of Elements of Group 17570), (401), (501), Uses of alkaline earth metals (402), Extractlon of elements (402), Properties and uses ofalkallne earth metals (404), Compounds of alkaline earth metals (405-414), Comparison of solubility products of. hydroxides and, sulphates (406), Hydrides (501), Halides (504)-, Oxohalides (506)., Oxides (507) -, Oxoacids (512)