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Unit - 1
INORGANIC Chemistry 1. Coordination Compounds - II Crystal filed theory (CFT) – Postulates of CFT, splitting patterns of d-orbitals in octahedral, tetrahedral, square planar with suitable examples. Crystal field stabilization energies and its calculations for various dn configurations in octahedral complexes. High Spin Low Spin complexes. Magnetic properties of transition metal complexes – para, dia, ferro, anti ferromagnetic properties, determination of magnetic susceptibility (Guoy method), spin only formula, calculations of magnetic moments. Electronic spectra of metal complexes – colour of transition metal aqua complexes – d-d transitions. Detection of complex formation – basic principles of various methods – change in chemical properties, solubility, colour, pH, conductivity, magnetic susceptibility. Thermodynamic and kinetic stability of transition of metal complexes. Stability of metal complexes – stepwise and overall stability constant and their relationship. Factors effecting the stability constants. Chelate effect, determination of composition of complex by Job’s method and mole ratio method. Applications of Coordination Compounds Applications of coordination compounds (a) in quantitative and qualitative analysis with suitable examples (b) in medicine for removal of toxic metal ions and cancer therapy (c) in industry as catalysts polymerization – Ziegler Natta catalyst (d) water softening. 2. Boranes and Carboranes Definition of clusters – Structures of boranes and carboranes – Wade’s rules, closo, nido arachno boranes and carboranes.
Unit - 2
Organic Chemistry 1. Amines, Cyanides and Isocyanides Amines: Nomenclature, classification into 10 , 20 , 30 Amines and Quarternary ammonium compounds. Preparative methods – 1. Ammonolysis of alkyl halides 2. Gabriel synthesis 3. Hoffman’s bromamide reaction (mechanism). Reduction of Amides and Schmidt reaction. Physical properties and basic character – Comparative basic strength of Ammonia, methyl amine, dimethyl amine, trimethyl amine and aniline – Comparative basic strength of aniline, N-methylaniline and N, N-dimentyl aniline (in aqueous and non-aqueous medium), steric effects and substituent effects. Use of amine salts as phase transfer catalysts. 4. Chemical Properties: (a) Alkylation (b) Acylation (c) Carbylamine reaction (d) Heinsberg separation. 5. Reaction with Nitrous acid of 1°, 2°, 3° (Aliphatic and aromatic amines). Electrophilic substitutions of Aromatic amines – Bromination and Nitration, oxidation of aryl and 3° Amines, diazotisation. 6. Diazonium salts : Preparation with mechanism. Synthetic importance – (a) Replacement of diazonium group by – OH, X(CI) – Sandmeyer and Gatterman reaction, by fluorine (Schiemann’s reaction), by iodine, CN, NO2 , H and aryl groups. Coupling Reaction of diazonium salts – (i) with phenols (ii) with anilines. Reduction to phenyl hydrazines. Syllabus Cyanides and Isocyanides Nomenclature (aliphatic and aromatic) structure – Preparation of cyanides from (a) Alkyl halides (b) from amides (c) from aldoximes – Preparation of isocyanides from Alkyl halides and Amines. 2. Properties of cyanides and isocyanides, (a) hydrolysis (b) addition of Grignard reagent (c) reduction (d) oxidation. 2. Heterocyclic Compounds Introduction and definition: Simple 5 membered ring compounds with one hetero atom Ex. Furan. Thiophene and pyrrole. Importance of ring systems – Presence in important natural products like hemoglobin and chlorophyll. Numbering the ring systems as per Greek letter and Numbers. Aromatic character – 6-electron system (four-electrons from two double bonds and a pair of nonbonded electrons from the hetero atom). Tendency to undergo substitution reactions. Resonance structures: Indicating electron surplus carbons and electron deficient hetero atom. Explanation of feebly acidic character of pyrrole, electrophilic substitution at 2 or 5 position, Halogenation, Nitration and Sulphonation under mild conditions – Reactivity of furan as 1, 3-diene, Diels Alder reactions (one example). Sulphonation of thiophene purification of Benzene obtained from coal tar. Preparation of furan, Pyrrole and thiophene from 1, 4, -dicarbonyl compounds only, Paul-Knorr synthesis, structure of pyridine, Basicity – Aromaticity – Comparison with pyrrole – one method of preparation and properties – Reactivity towards Nucleophilic substitution reaction – Chichibabin reaction.
Unit - 3
Physical Chemistry 1. Chemical Kinetics Introduction to chemical kinetics, rate of reaction, variation of concentration with time, rate laws and rate constant. Specific reaction rate. Factors influencing reaction rates : effect of concentration of reactants, effect of temperature, effect of pressure, effect of
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