Unit I: Chemistry of d and f block Elements
General characteristics of d-block elements with special reference to electronic configuration, oxidation states, variable valency, metallic character, colour, magnetic properties, catalytic properties and ability to form complexes.Comparison of the properties of second and third transition series with first transition series. Chemistry of lanthanides – electronic structure, oxidation states, lanthanide contraction, consequences of lanthanide contraction, magnetic properties, spectral properties and separation of lanthanides by ion exchange and solvent extraction methods (Brief study). Chemistry of actinides – electronic configuration, oxidation states, actinide contraction, position of actinides in the periodic table, comparison with lanthanides in terms of magnetic properties and spectral properties (Brief study). Extraction of Thorium, Uranium and Plutonium from burnt nuclear fuels.
Unit II: Coordination Compounds
Werner’s coordination theory and its experimental verification, nomenclature of coordination compounds, isomerism in coordination compounds, valence bond theory of transition metal complexes.Limitations of VBT. Elementary treatment of crystal field theory, splitting of d-orbitals in square planar, tetrahedral and octahedral complexes, factors affecting crystal field parameters, Explanation of magnetic behaviour and colour of complexes using CFT, effective atomic number concept. Metal carbonyl, 18 electron rule, Preparation, structure and reactions of Ni(CO)4, Fe(CO)5 and V(CO)6, nature of bonding in metal carbonyls.
Unit III: Metallurgy
Types of metallurgy: Pyrometallurgy - Extraction of Nickel from sulphide ore – general metallurgy followed by Mond’s process (purification), manganese from oxide ores – reduction by the Aluminothermite process – refining by electrolytic process. Hydrometallurgy: Extraction of gold from native ore by cyanide process and refining. Electrometallurgy: Extraction of lithium by fusion method followed by electrolysis of lithium chloride. Powder metallurgy: Importance, metal powder production and applications, production of tungsten powder. Extraction of (1) Thorium from monazite sand – purification by iodine method, (2) uranium from pitch blende – production of U3O8 by carbonate method, U3O8 to UO2 by reduction, UO2 to U by fluoride method.
Unit IV: Chemical Kinetics
Chemical kinetics and its scope, rate of a reaction, factors influencing the rate of a reaction – concentration, temperature, pressure, solvent, light, catalyst. Concentration dependence of rates, mathematical characteristics of simple chemical reactions – zero order, first order, second order, pseudo order, half life and mean life. Determination of the order of reaction – differential method, method of integration, method of half-life period and isolation method. Radioactive decay as a first order phenomenon.Effect of temperature on rate of reaction, Arrhenius equation, concept of activation energy.Simple collision theory based on hard sphere model, transition state theory (equilibrium hypothesis). Expression for the rate constant based on equilibrium constant and thermodynamic aspects.
Unit V: Spectroscopy
UV and Visible spectroscopy: Introduction, absorption laws, instrumentation, formation of absorption bands, types of electronic transitions, chromophores, auxochromes, absorption and intensity shifts, solvent effects, Woodward – Fieser rules for calculating absorption maximum in dienes and α,β-unsaturated carbonyl compounds. IR spectroscopy: Introduction, theory of molecular vibrations, vibrational frequency, factors influencing vibrational frequencies, finger print region and applications of IR spectroscopy. NMR spectroscopy: Introduction, instrumentation, number of signals, position of signals (Chemical shift),shielding and deshielding effects, factors influencing chemical shifts- inductive effect, anisotropic effect and hydrogen bonding. Splitting of signals, spin-spin coupling, chemical exchange and coupling constant. Structural determination of simple organic compounds using UV, IR and NMR spectral data.