**SEMESTER 1**

**AP1C01 ORGANOMETALLICS AND NUCLEAR CHEMISTRY**

**Credit: 4 Contact Lecture Hours: 72**

**Unit 1: Organometallic Compounds- Synthesis, Structure and Bonding (18 Hours)**

Organometallic compounds with linear pi donor ligands-olefins, acetylenes, dienes and allyl complexes-synthesis, structure and bonding.

Complexes with cyclic pi donors-metallocenes and cyclic arene complexes-structure and bonding. Hapto nomenclature. Carbene and carbyne complexes.

Preparation, properties, structure and bonding of simple mono and binuclear metal carbonyls, metal nitrosyls, metal cyanides and dinitrogen complexes. Polynuclear metal carbonyls with and without bridging. Carbonyl clusters-LNCCS and HNCCS, Isoelectronic and isolobal analogy, Wade-Mingos rules, cluster valence electrons.

**Unit 2: Reactions of Organometallic Compounds (9 Hrs)**

Substitution reactions-nucleophilic ligand substitution, nucleophilic and electrophilic attack on coordinated ligands.

Addition and elimination reactions-1,2 additions to double bonds, carbonylation and decarbonylation, oxidative addition and reductive elimination, insertion (migration) and elimination reactions.

Rearrangement reactions, redistribution reactions, fluxional isomerism.

**Unit 3: Catalysis by Organometallic Compounds (9 Hrs)**

Homogeneous and heterogeneous organometallic catalysis-alkene hydrogenation using Wilkinson catalyst, Tolman catalytic loops.

Reactions of carbon monoxide and hydrogen-the water gas shift reaction, the Fischer-Tropsch reaction(synthesis of gasoline).

Hydroformylation of olefins using cobalt or rhodium catalyst.

Polymerization by organometallic initiators and templates for chain propagation-Ziegler Natta catalysts.

Carbonylation reactions-Monsanto acetic acid process, carbonylation of butadiene using Co2(CO)8 catalyst in adipic ester synthesis.

Olefin methathesis-synthesis gas based reactions, photodehydrogenation catalyst (“Platinum Pop”). Palladium catalysed oxidation of ethylene-the Wacker process.

**Unit 4: Organometallic Polymers (9 Hrs)**

Polymers with organometallic moieties as pendant groups, polymers with organometallic moieties in the main chain, condensation polymers based on ferrocene and on rigid rod polyynes, polymers prepared by ring opening polymerization, organometallic dendrimers.

**Unit 5: Bioinorganic Compounds (18 Hrs)**

Essential and trace elements in biological systems, structure and functions of biological membranes, mechanism of ion transport across membranes, sodium pump, ionophores, valinomycin and crown ether complexes of Na+ and K+, ATP and ADP. Photosynthesis-chlorophyll a, PS I and PS II. Role of calcium in muscle contraction, blood clotting mechanism and biological calcification.

Oxygen carriers and oxygen transport proteins-haemoglobins, myoglobins and haemocyanin, haemerythrins and haemevanadins, cooperativity in haemoglobin. Iron storage and transport in biological systems-ferritin and transferrin. Redox metalloenzymes-cytochromes, peroxidases and superoxide dismutase and catalases. Nonredox metalloenzymes-CarboxypeptidaseA-structure and functions. Nitrogen Fixation-nitrogenase, vitamin B12 and the vitamin B12 coenzymes.

Metals in medicine-therapeutic applications of cis-platin, radio-isotopes and MRI agents. Toxic effects of metals(Cd, Hg, Cr and Pb).

**Unit 6: Nuclear Chemistry (9 Hrs)**

Fission products and fission yield. Neutron capture cross section and critical size. Nuclear fusion reactions and their applications. Chemical effects of nuclear transformations. Positron annihilation and autoradiography. Principles of counting technique such as G.M. counter, proportional, ionization and scintillation counters. Cloud chamber.

Synthesis of transuranic elements such as Neptunium, Plutonium, Curium, Berkelium, Einsteinium, Mendelevium, Nobelium, Lawrencium and elements with atomic numbers 104 to 109.

Analytical applications of radioisotopes-radiometric titrations, kinetics of exchange reactions, measurement of physical constants including diffusion constants, Radioanalysis, Neutron Activation Analysis, Prompt Gama Neutron Activation Analysis and Neutron Absorptiometry.

Applications of radio isotopes in industry, medicine, autoradiography, radiopharmacology, radiation safety precaution, nuclear waste disposal. Radiation chemistry of water and aqueous solutions.

Measurement of radiation doses. Relevance of radiation chemistry in biology, organic compounds and radiation polymerization.

**References**

J.E. Huheey, E.A. Keiter, R.L. Keiter, Inorganic Chemistry Principles of Structure and Reactivity, 4th Edn., Harper Collins College Publishers,1993.

F.A. Cotton, G. Wilkinson, C.A. Murillo, M. Bochmann, Advanced Inorganic Chemistry, 6th edition, Wiley-Interscience, 1999.

K.F. Purcell, J. C. Kotz, Inorganic Chemistry, Holt-Saunders, 1977.

P. Powell, Principles of Organometallic Chemistry, 2nd Edn., Chapman and Hall, 1988.

B.E. Douglas, D.H. McDaniel, J. J. Alexander, Concepts and Models of Inorganic Chemistry, 3rd Edn., Wiley-India, 2007.

B.D. Guptha, A.J. Elias, Basic Organometallic Chemistry, Universities Press, 2010.

R.W. Hay, Bio Inorganic Chemistry, Ellis Horwood, 1984.

H.J. Amikar, Essentials of Nuclear Chemistry, Wiley Eastern, 1982.

S.N. Goshal, Nuclear Physics, S. Chand and Company, 2006.

**AP1C02 STRUCTURAL AND MOLECULAR ORGANIC ****CHEMISTRY**

**Credit: 4 Contact Lecture Hours: 72****Unit 1: Basic Concepts in Organic Chemistry (18 Hrs)**

Review of basic concepts in organic chemistry: bonding, hybridisation, MO picture, inductive effect, electromeric effect, resonance effect, hyperconjugation, steric effect. Bonding weaker than covalent bonds.

The formalism of curved arrow mechanisms. Practicing of line diagram drawing.

Concept of aromaticity: delocalization of electrons – Hückel’s rule, criteria for aromaticity, examples of neutral and charged aromatic systems – annulenes. NMR as a tool for aromaticity. Anti-and homo-aromatic systems – Fullerenes, Carbon nanotubes and Graphene.

Mechanism of electrophilic and nucleophilic aromatic substitution reactions with examples. Arenium ion intermediates. SN1, SNAr, SRN1 and Benzyne mechanisms.

**Unit 2: Physical Organic Chemistry and Photochemistry (18 Hrs)**

Energy profiles. Kinetic versus thermodynamic control of product formation,Hammond postulate, kinetic isotope effects with examples, Hammet equation, Taft equation. Linear free energy relationships.

Catalysis by acids and bases and nucleophiles with examples from acetal, cyanhydrin and ester formation and hydrolysis reactions-AAC2, AAC1, AAL1, BAC2and BAL1 mechanisms. Solvent effect. Bulk and specific solvent effects. Introduction to carbon acids – pKa of weak acids, kinetic and thermodynamic acidity. Hard and soft acids and bases – HSAB principle and its applications.

Photoreactions of carbonyl compounds: Norrish reactions of ketones. Patterno-Buchi reaction. Barton, Di-π-methane and photo Fries rearrangements. Photochemistry of nitro and azo groups.

**Unit 3: Stereochemistry of Organic Compounds (18 Hrs)**

Introduction to molecular symmetry and chirality: examples from common objects to molecules. Axis, plane, center, alternating axis of symmetry.

Center of chirality: molecules with C, N, S based chiral centers, absolute configuration, enantiomers, racemic modifications, R and S nomenclature using Cahn-Ingold-Prelog rules, molecules with a chiral center and Cn, molecules with more than one center of chirality, definition of diastereoisomers, constitutionally symmetrical and unsymmetrical chiral molecules, erythro, threo nomenclature.

Axial, planar and helical chirality with examples, stereochemistry and absolute configuration of allenes, biphenyls and binaphthyls, ansa and cyclophanic compounds, spiranes, exo-cyclic alkylidenecycloalkanes.

Topicity and prostereoisomerism, topicity of ligands and faces as well as their nomenclature. NMR distinction of enantiotopic/diastereotopic ligands.

Stereoisomerism: definition based on symmetry and energy criteria, configuration and conformational stereoisomers.

Geometrical isomerism: nomenclature, E-Z notation, methods of determination of geometrical isomers. Interconversion of geometrical isomers.

**Unit 4: Conformational Analysis (18 Hrs)**

Conformational descriptors – factors affecting conformational stability of molecules. Conformational analysis of acyclic and cyclic systems: substituted ethanes, cyclohexane and its derivatives, decalins, adamantane, congressane, sucrose and lactose. Fused and bridged bicyclic systems. Conformation and reactivity of elimination (dehalogenation, dehydrohalogenation, semipinacolic deamination and pyrolytic elimination-Saytzeff and Hofmann eliminations), substitution and oxidation of 20 alcohols. Chemical consequence of conformational equilibrium -Curtin Hammett principle.

**References**

R. Bruckner, Advanced Organic Chemistry: Reaction Mechanisms, Academic Press, 2002.

F.A. Carey, R.A. Sundberg, Advanced Organic Chemistry, Part A: Structure and Mechanisms, 5th Edn., Springer, 2007.

J. Clayden, N. Greeves, S. Warren, P. Wothers, Organic Chemistry, Oxford University Press, 2004.

T.H. Lowry, K.S. Richardson, Mechanism and Theory in Organic Chemistry, 2nd Edn., Harper & Row, 1981.

N.S. Isaacs, Physical Organic Chemistry, ELBS/Longman, 1987.

D. Nasipuri, Stereochemistry of Organic Compounds: Principles and Applications, 3rd Edn., New Age Pub., 2010.

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D.G. Morris, Stereochemistry, RSC, 2001.

E.L. Eliel and S.H. Wilen, Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.

N.J. Turro, V. Ramamurthy, J.C. Scaiano, Principles of Molecular Photochemistry: An Introduction, University Science books, 2009.

N.J. Turro, Modern Molecular Photochemistry, Benjamin Cummings, 1978.

K.K.R. Mukherjee, Fundamentals of Photochemistry, New Age Pub., 1978.

**AP1C03 QUANTUM CHEMISTRY AND GROUP THEORY**

**Credit: 4 Contact Lecture Hours: 72****Unit 1: Postulates of Quantum Mechanics (9 Hrs)**

State function or wave function postulate: Born interpretation of the wave function, well behaved functions, orthonormality of wave functions.

Operator postulate: operator algebra, linear and nonlinear operators, Laplacian operator, commuting and noncommuting operators, Hermitian operators and their properties, eigen functions and eigen values of an operator.

Eigen value postulate: eigen value equation, eigen functions of commuting operators.

Expectation value postulate.

Postulate of time-dependent Schrödinger equation, conservative systems and time-independent Schrödinger equation.

**Unit 2: Application to Exactly Solvable Model Problems (18 Hrs)**

Translational motion: free particle in one-dimension, particle in a one-dimensional box with infinite potential walls, particle in a one-dimensional box with finite potential walls-tunneling, particle in a three dimensional box-separation of variables, degeneracy.

Vibrational motion: one-dimensional harmonic oscillator (complete treatment), Hermite equation(solving by method of power series), Hermite polynomials, recursion relation, wave functions and energies-important features, Harmonic oscillator model and molecular vibrations.

Rotational motion: co-ordinate systems, cartesian, cylindrical polar and spherical polar coordinates and their relationships. The wave equation in spherical polar coordinates-particle on a ring, the phi equation and its solution, wave functions in the real form. Non-planar rigid rotor (or particle on a sphere)-separation of variables, the phi and the theta equations and their solutions, Legendre and associated Legendre equations, Legendre and associated Legendre polynomials. Spherical harmonics (imaginary and real forms)-polar diagrams of spherical harmonics.

Quantization of angular momentum, quantum mechanical operators corresponding to angular momenta ( Lx, Ly, Lz and L2)-commutation relations between these operators. Spherical harmonics as eigen functions of angular momentum operators Lz and L2. Ladder operator method for angular momentum. Space quantization.

**Unit 3: Quantum Mechanics of Hydrogen-like Atoms (9 Hrs)**

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Potential energy of hydrogen-like systems. The wave equation in spherical polar coordinates: separation of variables-R, theta and phi equations and their solutions, wave functions and energies of hydrogen-like atoms. Orbitals-radial functions, radial distribution functions, angular functions and their plots.

The postulate of spin by Uhlenbeck and Goudsmith, discovery of spin-Stern Gerlach experiment. Spin orbitals-construction of spin orbitals from orbitals and spin functions.

**Unit 4: Symmetry and Groups (9 Hrs)**

Symmetry elements, symmetry operations, point groups and their symbols, sub groups, classes, abelian and cyclic groups, group multiplication tables-classes in a group and similarity transformation.

Symmetry in crystals-32 crystallographic point groups (no derivation), Hermann-Mauguin symbols. Screw axis-pitch and fold of screw axis. Glide planes. Space groups-determination of space group symbols of triclinic and monoclinic systems.

**Unit 5: Theory of Molecular Symmetry (18 Hrs)**

Matrices: addition and multiplication of matrices, inverse and orthogonal matrices, character of a matrix, block diagonalisation, matrix representation of symmetry operations, representation of groups by matrices, construction of representation using vectors and atomic orbitals as basis, representation generated by cartesian coordinates positioned on the atoms of a molecule (H2O and SO2 as examples).

Reducible and irreducible representations-construction of irreducible representation by standard reduction formula. Statement of Great Orthogonality Theorem (GOT). Properties of irreducible representations. Construction of irreducible representation using GOT-construction of character tables for C2v, C2h, C3v and C4v. Direct product of representations.

Molecular dissymmetry and optical activity.

**Unit 6: Application of Group Theory in Spectroscopy (9 Hrs)**

Applications in vibrational spectra: transition moment integral, vanishing of integrals, symmetry aspects of molecular vibrations, vibrations of polyatomic molecules-selection rules for vibrational absorption. Determination of the symmetry of normal modes of H2O, Trans N2F2 and NH3 using Cartesian coordinates and internal coordinates. Complementary character of IR and Raman spectra-determination of the number of active IR and Raman lines.

Application in electronic spectra: selection rules for electronic transition, electronic transitions due to the carbonyl chromophore in formaldehyde.

**References**

I.N. Levine, Quantum Chemistry, 6th Edn., Pearson Education Inc., 2009.

P.W. Atkins, R.S. Friedman, Molecular Quantum Mechanics, 4th Edn., Oxford University Press, 2005.

D.A. McQuarrie, Quantum Chemistry, University Science Books, 2008.

J.P. Lowe, K Peterson, Quantum Chemistry, 3rd Edn., Academic Press, 2006.

R. Anatharaman, Fundamentals of Quantum Chemistry, Macmillan India, 2001.

R.K. Prasad, Quantum Chemistry, 3rd Edn., New Age International, 2006.

T. Engel, Quantum Chemistry and Spectroscopy, Pearson Education, 2006.

H. Metiu, Physical Chemistry:Quantum Mechanics, Taylor & Francis, 2006.

L. Pauling, E.B. Wilson, Introduction to Quantum Mechanics, McGraw-Hill, 1935.

M.S. Pathania, Quantum Chemistry and Spectroscopy (Problems & Solutions), Vishal Publications, 1984.

F.A. Cotton, Chemical Applications of Group Theory, 3rd Edn., Wiley Eastern, 1990.

L.H. Hall, Group Theory and Symmetry in Chemistry, McGraw Hill,1969

V. Ramakrishnan, M.S. Gopinathan, Group Theory in Chemistry, Vishal Publications, 1992.

S. Swarnalakshmi, T. Saroja, R.M. Ezhilarasi, A Simple Approach to Group Theory in Chemistry, Universities Press, 2008.

S.F.A. Kettle, Symmetry and Structure: Readable Group Theory for Chemists, 3rd Edn., Wiley, 2007.

A. Vincent, Molecular Symmetry and Group Theory: A Programmed Introduction to Chemical Applications, 2nd Edn., Wiley, 2000.

A.S. Kunju, G. Krishnan, Group Theory and its Applications in Chemistry, PHI Learning, 2010

**AP1C04 CLASSICAL AND STATISTICAL THERMODYNAMICS**

**Credit: 3 Contact Lecture Hours- 54****Unit 1: Classical Thermodynamics (27 Hrs)**

Entropy, dependence of entropy on variables of a system (S,T and V; S,T and P). Thermodynamic equations of state. Irreversible processes – Clausius inequality.

Free energy, Maxwell relations and significance, temperature dependence of free energy – Gibbs Helmholtz equation, applications of Gibbs Helmholtz equation.

Partial molar quantities, chemical potential and Gibbs-Duhem equations, determination of partial molar volume and enthalpy.

Fugacity, relation between fugacity and pressure, determination of fugacity of a real gas, variation of fugacity with temperature and pressure. Activity, dependence of activity on temperature and pressure.

Thermodynamics of mixing, Gibbs-Duhem-Margules equation, Konowaloff’s rule, Henry’s law, excess thermodynamic functions-free energy, enthalpy, entropy and volume. Determination of excess enthalpy and volume.

Chemical affinity and thermodynamic functions, effect of temperature and pressure on chemical equilibrium- vant Hoff reaction isochore and isotherm.

Third law of thermodynamics, Nernst heat theorem, determination of absolute entropies using third law, entropy changes in chemical reactions.

Three component systems-graphical representation. Solid-liquid equilibria-ternary solutions with common ions, hydrate formation, compound formation. Liquid-liquid equilibria-one pair of partially miscible liquids, two pairs of partially miscible liquids, three pairs of partially miscible liquids.

Thermodynamics of irreversible processes with simple examples. Uncompensated heat and its physical significance. Entropy production- rate of entropy production, entropy production in chemical reactions, the phenomenological relations. The principle of microscopic reversibility, the Onsager reciprocal relations. Thermal osmosis. Thermoelectric phenomena.

Bioenergetics: coupled reactions, ATP and its role in bioenergetics, high energy bond, free energy and entropy change in ATP hydrolysis, thermodynamic aspects of metabolism and respiration, glycolysis, biological redox reactions.

**Unit 2: Statistical Thermodynamics (27 Hrs)**

Permutation, probability, apriori and thermodynamic probability, Stirlings approximation, macrostates and microstates, Boltzmann distribution law, partition function and its physical significance, phase space, different ensembles, canonical partition function, distinguishable and indistinguishable molecules, partition function and thermodynamic functions, separation of partition function-translational, rotational, vibrational and electronic partition functions. Thermal de-Broglie wavelength.

Calculation of thermodynamic functions and equilibrium constants, statistical interpretation of work and heat, Sakur-Tetrode equation, statistical formulation of third law of thermodynamics, thermodynamic probability and entropy, residual

entropy, heat capacity of gases – classical and quantum theories, heat capacity of hydrogen.

Need for quantum statistics, Bose-Einstein statistics: Bose-Einstein distribution, example of particles, Bose-Einstein condensation, difference between first order and higher order phase transitions, liquid helium, supercooled liquids. Fermi-Dirac distribution: examples of particles, application in electron gas, thermionic emission. Comparison of three statistics.

Heat capacity of solids- the vibrational properties of solids, Einsteins theory and its limitations, Debye theory and its limitations.

**References**

R.P. Rastogi, R.R. Misra, An Introduction to Chemical Thermodynamics, Vikas Publishing House, 1996.

J. Rajaram, J.C. Kuriakose, Thermodynamics, S Chand and Co., 1999.

M.C. Gupta, Statistical Thermodynamics, New age international, 2007.

M.W. Zemansky, R.H. Dittman, Heat and Thermodynamics, Tata McGraw Hill, 1981.

P.W. Atkins, Physical Chemistry, ELBS, 1994.

K.J. Laidler, J.H. Meiser, B.C. Sanctuary, Physical Chemistry, 4th Edn., Houghton Mifflin, 2003.

L.K. Nash, Elements of Classical and Statistical Mechanics, 2nd Edn., Addison Wesley, 1972.

D.A. McQuarrie, J.D. Simon, Physiacl chemistry: A Molecular Approach, University Science Books,1997

C. Kalidas, M.V. Sangaranarayanan, Non-equilibrium Thermodynamics, Macmillan India, 2002.

R.K. Murray, D.K. Granner, P. A. Mayes, V.W. Rodwell, Harper’s Biochemistry, Tata McGraw Hill,1999.

I. Tinoco, K. Sauer, J.C. Wang, J.D. Puglisi, Physical Chemistry: Principles and Applications in Biological Science, Prentice Hall,2002

F.W. Sears, G.L. Salinger, Thermodynamics, Kinetic Theory and Statistical Thermodynamics, Addison Wesley, 1975.

J. Kestin, J.R. Dorfman, A Course in Statistical Thermodynamics, Academic Press, 1971.