Paper I: Inorganic Chemistry
Periodic table, group trends and periodic trends in physical properties. Classification of elements on the basis of electronic configuration. Modern IUPAC Periodic table. General characteristic of s, p, d and f block elements. Effective nuclear charges, screening effects, atomic radii, ionic radii, covalent radii. Ionization potential, electron affinity and electro-negativity. Group trends and periodic trends in these properties in respect of s-, p- and d-block elements. General trends of variation of electronic configuration, elemental forms, metallic nature, magnetic properties, catenation and catalytic properties, oxidation states, aqueous and redox chemistry in common oxidation states, properties and reactions of important compounds such hydrides, halides, oxides, oxy-acids, complex chemistry in respect of s-block and p-block elements.
Chemical Bonding and structure:
Ionic bonding: Size effects, radius ratio rules and their limitations. Packing of ions in crystals, lattice energy, Born-lande equation and its applications, Born-Haber cycle and its applications. Solvation energy, polarizing power and polarizability, ionic potential, Fazan's rules. Defects in solids. Covalent bonding: Lewis structures, formal charge. Valence Bond Theory, Molecular orbital Theory, hybridizations, VSEPR theory. Partial ionic Character of covalent bonds, bond moment, dipole moment and electro negativity differences. Concept of resonance, resonance energy, resonance structures. Schrodinger equation for the H-atom.
Coordinate bonding: Werner theory of coordination compounds, double salts and complex salts, Lewis acid-base. Ambidentate and polydentate ligands, chelate complexes. IUPAC nomenclature of coordination compounds. Coordination numbers, Geometrical isomerism. Stereoisomerism in square planar and octahedral complexes. Hydrogen bonding. Metallic bonding: qualitative idea of band theory, conducting, semi conduct ing and insulating properties.
Chemistry of coordination compounds:
Isomerism, reactivity and stability: Determination of configuration of cis- and trans- isomers by chemical methods. Labile and inert complexes, substitution reaction on square planer complexes, trans effect. Stability constants of coordination compounds and their importance in inorganic analysis. Structure and bonding: Elementary Crystal Field Theory: splitting of dn configurations in octahedral, square planar and tetrahedral fields, crystal field stabilization energy; pairing energy. Jahn- Teller distortion. Metal-lig and bonding, sigma and pi bonding in octahedral complexes and their effects on the oxidation states of transitional metals . Orbital and spin magnetic moments, spin only moments of and their correlation with effective magnetic moments, d-d transitions; L-S coupling, spectroscopic ground states, selection rules for electronic spectral transitions; spectro-chemical series of ligands; charge transfer spectra.
Acid-Base concept: Arrhenius concept, theory of solvent system, Bronsted-Lowry's concept, relative strength of acids, Pauling rules. Lewis concept. Acidbase equilibria in aqueous solution and pH. Acid-base neutralisation curves; indicator, choice of indicators.
Precipitation and Redox Reactions:
Solubility product principle, common ion effect. Ion-electron method of balancing equation of redox reaction. Standard redox potentials, Nernst equation. Influence on complex formation, precipitation and change of pH on redox potentials; formal potential. Feasibility of a redox titration, redox potential at the equivalence point, redox indicators. Redox potential diagram of common elements and their applications. Disproportionation and comproportionation reactions.
Organo metallic compounds:
18-electron rule and its applications to carbonyls, nitrosyls, cyanides, and nature of bonding involved therein. Simple examples of metal-metal bonded compounds and metal clusters. Metal-olefin complexes: zeises salt, Ferrocene.
Radioactive decay - General characteristics, decay kinetics, parent-daughter decay growth relationships, determination of half-lives, Nuclear models -shell model, liquid drop model, Fermi gas model, Collective model and optical model. Nuclear stability.
Decay theories. Nuclear reactions- fission, fusion and spallation reactions. Definition of curie and related calculations, preparation of artificial radionuclides by bombardment, radiochemical separation techniques. Experimental techniques in the assay of radioisotopes, gas filled detectors-ionization chamber, proportional and Geiger-Muller counters -G.M. Plateau, dead time, coincidence loss, determination of dead time, scintillation counters, solid state detectors.
Hydride, hydration energies, solvation and complexation tendencies of alkali and alkaline-earth metals, principle of metallurgical extraction, Chemistry of Li and Be, their anomalous behaviour and diagonal relationships, alkyls and aryls.
Comparative study of group 13 & 14 elements with respect to periodic properties. Compounds such as hydrides, halides, oxides and oxyacids; diagonal relationship; preparation, properties, bonding and structure of diborane, borazine and alkalimetal borohydrides. Preparation, properties and technical applications of carbides and fluorocarbons. Silicones and structural principles of silicates.
Chemistry of d- and f- block elements:
General comparison of 3d, 4d and 5d elements in term of electronic configuration, elemental forms, metallic nature, atomization energy, oxidation states, redox properties, coordination chemistry, spectral and magnetic properties. f-block elements: electronic configuration, ionization energies, oxidation states, variation in atomic and ionic (3+) radii, magnetic and spectral properties of lanthanides, comparison between lanthanide and actinides, separation of lanthanides (by ion-exchange method).
Chemistry of some representative compounds: K2Cr2O7, KMnO4, K4[Fe(CN)6], K2[Ni(CN)4], H2PtCl6, Na2[Fe(CN)5NO].