INORGANIC CHEMISTRY-III
Unit-I Coordination Chemistry: Werner’s theory, valence bond theory (inner and outer orbital complexes), electroneutrality principle and back bonding. IUPAC nomenclature of coordination compounds, isomerism in coordination compounds. Stereochemistry of complexes with 4 and 6 coordination numbers. Chelate effect, Labile and inert complexes. Crystal field theory, measurement of CFSE weak and strong fields, pairing energies, factors affecting the magnitude of 10 Dq in octahedral vs. tetrahedral coordination, tetragonal distortions from octahedral geometry, Jahn-Teller theorem, square planar geometry. Qualitative aspect of ligand field and MO Theory.
Unit-II Transition Elements-I: General group trends with special reference to electronic configuration, colour, variable valency, magnetic and catalytic properties, and ability to form complexes. Stability of various oxidation states and e.m.f. (Latimer & Ebsworth diagrams). Difference between the first, second and third transition series.
Unit-III Transition Elements-II: Chemistry of Ti, V, Cr, Mn, Fe and Co in various oxidation states (excluding their metallurgy). Lanthanoids and Actinoids Electronic configuration, oxidation states, colour, spectral and magnetic properties,lanthanide contraction, separation of lanthanides (ion-exchange method only).
General features of actinoids, separation of Np, Pm, Am from U.
Unit-IV Bioinorganic Chemistry: Metal ions present in biological systems, classification of elements according to their action in biological system. Na/K-pump, carbonic anhydrase and carboxypeptidase. Excess and deficiency of some trace metals. Toxicity of metal ions (Hg, Pb, Cd and As), reasons for toxicity, Use of
chelating agents in medicine. Iron and its application in bio-systems, Haemoglobin and myoglobin.
Recommended Text Books:
1. Lee J. D., Concise Inorganic Chemistry, Wiley India, 5th Edn., 2008.
2. Huheey J. E., Keiter E. A. and Keiter R. L., Inorganic Chemistry – Principles of structure and reactivity, , Pearson Education, 4th Ed. 2002.
3. Puri, Sharma, Kalia, Principles of Inorganic Chemistry, Vishal Pub. Co., 33rd ed., 2017.
4. Shriver D. E. Atkins P. W., Inorganic Chemistry, Oxford University Press, 5 th Edn..
Reference books
1. Das Asim K., Fundamentals of Inorganic Chemistry, Vol. II, CBS Publications, 2nd Ed. 2010.
2. Bioinorganic Chemistry, Asim Kumar Das, Books & Allied (P) Ltd. 1st Ed. 2015.
3. Selected Topic in Inorganic Chemistry, Mallick, Madan and Tuli, S. Chand Publisher. 17th Ed. 2010.
4. Pradeep’s Inorganic Chemistry, Vol. I & II, Universal Book seller, 14th Ed. 2017.
Organic Chemistry-III
Unit-I Nitrogen Containing Functional Groups Preparation and important reactions of nitro and compounds, nitriles. Amines: Effect of substituent and solvent on basicity; Preparation and properties: Gabriel phthalimide synthesis, Carbylamine reaction, Mannich reaction, Hoffmann’s exhaustive methylation, Hofmann elimination reaction; Distinction between 1°, 2° and 3° amines with Hinsberg reagent and nitrous acid.
Unit-II Diazonium Salts Preparation and their synthetic applications. Polynuclear Hydrocarbons Reactions of naphthalene and anthracene Structure, Preparation and structure elucidation and important derivatives of naphthalene and anthracene. Polynuclear hydrocarbons.
Unit-III Heterocyclic Compounds Classification and nomenclature, Structure, aromaticity in 5-numbered and 6-membered rings containing one heteroatom; Synthesis, reactions and mechanism of substitution reactions of: Furan, Pyrrole (Paal-Knorr synthesis, Knorr pyrrole synthesis, Hantzsch synthesis), Thiophene, Pyridine (Hantzsch synthesis), Pyrimidine. Fischer indole synthesis and Madelung synthesis, Derivatives of furan: Furfural and furoic acid (preparation only).
Unit-IV Alkaloids Natural occurrence, General structural features, Isolation and their physiological action. Hoffmann’s exhaustive methylation, Emde’s modification, Structure elucidation and synthesis of Hygrine and Nicotine. Medicinal importance of Nicotine, Hygrine, Quinine, Morphine, Cocaine, and Reserpine. Terpenes Occurrence, classification, isoprene rule; Elucidation of structure and synthesis of Citral, Neral and α- terpineol.
Recommended Text Books:
1. Morrison, R. N. & Boyd, R. N., Organic Chemistry, Dorling Kindersley (India) Pvt. Ltd. (Pearson Education).
2. Advanced Organic Chemistry, 2nd Edition, Arun Bahl & B S Bahl, S. Chand Publisher, 2012.
Reference Books:
1. Graham Solomons T. W., Fryhle, Craig B., Snyder Scott A, Organic Chemistry, Wiley Student Ed, 11th Edition (2013)
2. Jonathan Clayden, Nick Greeves, Stuart Warren, Organic Chemistry, 2nd Edition, Oxford Publisher, 2014.
3. Dhawan, S.N., Pradeep’s Organic Chemistry, (Vol. I and II), Pradeep Publications
PHYSICAL CHEMISTRY-IV
Unit-I: Conductance-I
Arrhenius theory of electrolytic dissociation. Conductivity, equivalent and molar conductivity and their variation with dilution for weak and strong electrolytes. Molar conductivity at infinite dilution. Kohlrausch law of independent migration of ions. Debye-Hückel-Onsager equation, Wien effect, Debye-Falkenhagen effect, Walden’s rules.
Unit-II: Conductance-II
Ionic velocities, mobilities and their determinations, transference numbers and their relation to ionic mobilities, determination of transference numbers using Hittorf and Moving Boundary methods. Applications of conductance measurement: (i) degree of dissociation of weak electrolytes, (ii) ionic product of water (iii) solubility and solubility product of sparingly soluble salts, (iv) conductometric titrations, and (v) hydrolysis constants of salts.
Unit-III: Electrochemistry-I
Quantitative aspects of Faraday’s laws of electrolysis, rules of oxidation/reduction of ions based on half-cell potentials, applications of electrolysis in metallurgy and industry. Chemical cells, reversible and irreversible cells with examples. Electromotive force of a cell and its measurement, Nernst equation; Standard electrode (reduction) potential and its application to different kinds of half-cells. Application of EMF measurements in determining free energy, enthalpy and entropy of a cell reaction, (ii) equilibrium constants, and (iii) pH values, using hydrogen, quinone-hydroquinone, glass electrodes.
Unit-IV: Electrochemistry-II
Concentration cells with and without transference, liquid junction potential; determination of activity coefficients and transference numbers. Qualitative discussion of potentiometric titrations (acid-base, redox, precipitation). Electrical properties of atoms and molecules
Basic ideas of electrostatics, Electrostatics of dielectric media. Clausius-Mosotti equation and Lorenz-Laurentz equation (no derivation), Dipole moment and molecular polarizabilities and their measurements.