University of Kerala Courses

M.Sc. (Chemistry)

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Duration: 2 Years

Eligibility: Graduation

Course Structure

Course Code	Course Title
Semester - I
CHE 511	Inorganic Chemistry‑I
CHE 512	Organic Chemistry‑I
CHE 513	Physical Chemistry‑I
CHE 514	Inorganic Chemistry Lab‑I
CHE 515	Organic Chemistry Lab-I
CHE 516	Physical Chemistry Lab‑I
Semester - II
CHE 521	Inorganic Chemistry‑II
CHE 522	Organic Chemistry‑II
CHE 523	Physical Chemistry‑II
CHE 524	Inorganic Chemistry Lab‑II
CHE 525	Organic Chemistry Lab‑II
CHE 526	Physical Chemistry Lab‑II
Semester - III
CHE 531	Inorganic Chemistry‑III
CHE 532	Organic Chemistry‑III
CHE 533	Physical Chemistry‑III
CHE 534	Inorganic Chemistry Lab‑III
CHE 535	Organic Chemistry Lab‑III
CHE 536	Physical Chemistry Lab‑III
Electives
CHE 501	Advanced Inorganic Chemistry‑I
CHE 502	Advanced Organic Chemistry‑I
CHE 503	Advanced Physical Chemistry‑I
Semester - IV
CHE 541	Analytical and Environmental Chemistry
CHE 542	Dissertation
Electives
CHE 504	Advanced Inorganic Chemistry‑II
CHE 505	Advanced Organic Chemistry‑II
CHE 506	Advanced Physical Chemistry‑II
CHE 507	Instrumental Methods
CHE 508	Computational Chemistry: Theory & Lab

 

Course Detail

Semester - I

CHE 511   Inorganic Chemistry‑I

Unit I  Main Group Elements

      Chemistry of the noble gases: Xenon fluorides and oxofluorides.  Xenon compounds with bonds to other elements.  Chemistry of Krypton and Radon.  Chemistry of halogens:  Halogens in positive oxidation states.  Interhalogen compounds, pseudohalogens and polyhalide ions.  Astatine.

Unit II  Sulphur, Nitrogen and Phosphorus Compounds

      Sulphur‑Nitrogen compounds: Tetrasulphur tetranitride, disulphur dinitride and polythiazyl. S_xN_y compounds. S-N cations and anions. Other S-N compounds. Sulphur‑phosphorus compounds: Molecular sulphides such as P₄S₃, P₄S₇, P₄S₉ and P₄S_10. Phosphorus-nitrogen compounds: Phosphazines. Cyclo and linear phosphazines. Other P-N compounds. 

Unit III  Boron Compounds

      Boron hydrides: Reactions of diborane, and its structure and bonding. Polyhedral boranes: Preparation, properties, and structure and bonding. The topological approach to boron hydride structure.  Styx numbers.  Wade’s rules. Carboranes: Closo, nido and arachno carboranes. Metallaboranes and metallacarboranes. Organoboron compounds and hydroboration. Boron-nitrogen compounds: Borazine, substituted borazines and boron nitride.

Unit IV Introduction to Coordination Chemistry  

      Types of ligands and complexes. Coordination number and geometry. Isomerism:  Geometrical, optical and structural isomerism. Stability of complex ions in aqueous solution: Formation constants. Stepwise and overall formation constants. Factors affecting stability of complexes. Determination of stability constants. Chelate and macrocyclic effects.

 

CHE 512  Organic Chemistry-I                                                                   

 Unit I  Organic Structure, Stereochemistry and Reactivity

      Effect of electronic and steric factors on the properties and reactivities of organic compounds. Aromaticity. Aromaticity of annulenes, mesoionic compounds, metallocenes, cyclic carbocations and carbanions. Fullerenes. Molecular chirality, stereochemical nomenclature, prostereoisomerism, stereotopicity and stereoprojections. Non-carbon chiral centres. Atropisomerism and its designation.  Stereoselectivity, enantiomeric excess and chiral separation methods. Conformational analysis of alkanes, cycloalkanes and biased systems.  Effect of conformation on reactivity of cyclohexane and decalin derivatives. 

Unit II  Reaction Mechanisms and Reactive Intermediates

      Types of organic reactions and mechanisms. Reaction profiles, kinetic and thermodynamic control. Hammond’s postulate.  Concerted and multistep reactions. Methods for the determination of reaction mechanisms. Intermediates in organic reactions. Structure, stability, formation and reactions of carbenes, nitrenes, carbon  radicals, carbocations and carbanions.

Unit III  Organic Reactions of  sp³ Carbon Systems

      Stereochemical and mechanistic aspects of S_N reactions. Effect of solvent, leaving group and substrate structure.  Neighbouring group participation. Nonclassical carbocations and ion pairs in S_N reactions. Ambident nucleophiles and substrates. S_N′ and S_Ni reactions. Elimination  reactions leading to C=C  bond formation. E1, E2 and E1cB mechanisms. Hoffman and Saytzeff modes of elimination. Effect of leaving group and substrate structure. Cis eliminations.

Unit IV  Organic Reactions of  sp² Carbon and Aromatic Systems

      Electrophilic addition to C=C: Reactions and their mechanistic and stereochemical aspects. C=O based and C=O activated reactions. Named reactions based on C=O group. Stereochemistry of addition to C=O systems.  Cram's rule.  Felkin-Anh Model.  Mechanism of esterification and ester hydrolysis. Aromatic electrophilic and  nucleophilic substitutions.  Electronic and steric effects of substituents.  S_N1, S_NAr, Benzyne and S_RN1mechanism and their evidences. Radical additions, substitutions and chain reactions.

 

CHE 513 Physical Chmistry-I                                                                                 

Unit I  Quantum Mechanics-I   

      Formulation of quantum mechanics: The wave nature of sub‑atomic particles. de Broglie relation and its experimental proof. Group velocities and phase velocities. The uncertainty principle and its consequences. The postulates of  quantum mechanics.  Setting up of the Schrodinger wave equation.  Concept of operators: Laplacian, Hamiltonian, linear and Hermitian operators. Angular momentum operators and their properties. Commutators. Eigen function and eigen values. Physical interpretation of wave function. Orthogonality theorem.  Orthonormality. Boundary conditions and well behaved functions.

      Applications of quantum mechanics to simple systems: Solutions of Schrodinger wave equations for a free particle, particle in 1D box and particle in 3D box. Harmonic oscillator. Energy of transition and spectral lines. Degeneracy. Rigid rotator. Hydrogen‑like atom. Space quantization. Spin of electron. Many electron atoms. Qualitative idea of self‑consistent field method. The exclusion principle. Vector atom model. Spin orbit coupling. Term symbols and explanation of spectral lines.     

Unit II  Quantum Mechanics-II

      Chemical bonding: Approximate methods. Perturbation theory. A set of successive corrections to an unperturbed problem.  The variation principle.  Secular equations.  MO theory of hydrogen molecule ion.  Electron density distribution and stability of H₂⁺ ion. MO and VB theories of H₂. Resonance. MO theory of homonuclear diatomic molecules. Bond order and stability. MO theory of simple heterogeneous diatomic molecules like HF, LiH, CO and NO.

      Directed valences: The hybridization. Expression for hybrid orbitals in terms of wave functions of s and p orbitals and explanation for directed valences of sp, sp² and sp³ hybrid orbitals. The p‑bonds and the treatment of delocalized electrons. Qualitative picture of butadiene and benzene.  Bonding and hybridization involving d‑orbitals. Introduction of ligand field theory and MO theory of bonding in transition metal complexes. Ionic bonding: Ionic bonding and potential energy field. Lattice energy. Born theory and Born‑Haber cycle. 

Unit III  Thermodynamics

       First and second laws of thermodynamics. Thermodynamic criteria for equilibrium and spontaneity. The third law of thermodynamics. Need for the third law. Nernst heat theorem. Apparent exceptions to third law. Applications of third law. Thermodynamics of irreversible processes: Simple examples of irreversible processes. General theory of nonequilibrium processes. Entropy production.  The phenomenological relations. Onsager reciprocal relations. Application to the theory of diffusion, thermal diffusion, thermoosmosis and thermomolecular pressure difference. Electrokinetic effects. The Glansdorf-Pregogine equation.

Unit V  Chemical Kinetics and Catalysis

      Order and molecularity of reactions.  Time dependency of order.  Complex reactions:  Reversible, consecutive, concurrent and branching reactions. Free radical and chain reactions. Steady state treatment. Reactions like H₂‑Cl and  H₂‑Br₂. Decomposition of ethane, acetaldehyde and N₂O₅. Rice‑Herzfeld mechanism.  Unimolecular reaction. Lindemann treatment.  Semenoff‑Hinshelword mechanism of chain reactions and explosion. Kinetics of fast reactions:  Relaxation method.  Relaxation spectrometry.  Flow method. Shock method. Fast mixing method. Field‑jump method. Pulse method. Flash photolysis. Catalysis: Mechanism and theories of homogeneous and heterogeneous catalysis. Acid‑base and enzyme catalysis. Bimolecular surface reactions. Langmuir‑Hinshelwood mechanism.          

    Note : At least 100 problems to be worked out from all the units put together. 30% of the questions for examination shall contain numerical problems

 

CHE 514   Inorganic Chemistry Lab-I  

Separation and identification of rare/less familiar metal ions such as Ti, W, Se, Mo, Ce, Th, Zr, V, U      and Li in their binary mixtures.  A student must analyse at least 6 samples.

Volumetric estimations using EDTA, ammonium vanadate, cerium(IV) sulphate, chloramine-T and        potassium iodate. A student must do at least 8 estimations.

 

CHE 515   Organic Chemistry Lab-I   

Quantitative wet chemistry separation of a mixture of two components by solvent extraction      [Assessment is based on % recovery].

Separation of binary mixtures of organic compounds using chromatographic       methods: TLC and       column chromatography. Identification using R_F values. [Assessment is based on quality of separation and/or % recovery].

 

CHE 516   Physical Chemistry Lab-I    

Distribution law: Partition of iodine, ammonia and aniline between water and organic solvents.  Association of benzoic acid. Equilibrium constants of tri-iodide and copper-ammonium complexes.            Enthalpy change for tri-iodide formation.

Refractometry: Refractive index and molar refraction of liquids. Atomic refractions. Composition of     solid solutes. Molecular and ionic radii from molar refraction. Study of the complex K₂[HgI₄].

Chemical kinetics: Acid hydrolysis of esters. Comparison of strengths of acids. Saponification of          esters. Persulphate-iodide second order reaction.Aactivation energy. Arrhenius parameters. Primary  salt effect.

Thermochemistry: Determination of water equivalent. Heat of neutralization and heat of ionization.       Integral and differential heats of solution. Thermometric titrations. Determination of concentrations         of strong acids.

Polarimetry: Inversion of cane sugar. Velocity constants for different acid strengths. Comparison of      strengths of two acids.

Adsorptoin: Verification of Langmuir and Freundlich isotherms for solute adsorption on solids.             Estimation of surface area. First order kinetics. Computation of adsorption thermodynamics.     Exothermic and endothermic reactions.

 

Semester - II

CHE 521 Inorganic Chemistry-II       

Unit I  Theories of Metal Complexes

      Valence bond theory and its limitations. Ligand field theory: Splitting of d orbitals in different ligand fields such as octahedral, tetragonal,  square planar, tetrahedral, trigonal bipyramidal and square pyramidal fields. Jahn‑Teller effect. LFSE and its calculation. Thermodynamic effects of LFSE.  Factors affecting the splitting  parameter. Spectrochemical series. Molecular orbital theory based on group theoretical approach and bonding in metal complexes. MO diagrams of complexes with and without p bonds. Effect of  p bond on the stability of s bond. Nephelauxetic series.

Unit II  Spectral and Magnetic Properties of Metal Complexes

      Spectral properties of complexes: Term symbols for d‑ions. Characteristics of d‑d transitions.  Selection rules for d‑d transitions. Orgel diagrams. Tanabe‑Sugano diagrams. Effects of Jahn‑Teller distortion and spin‑orbit coupling on spectra. Charge transfer spectra. Magnetic properties of metal complexes:  Types of magnetism shown by complexes.  Magnetic susceptibility measurements.  Gouy method. Spin‑only value. Orbital contribution to magnetic moment. Ferromagnetism and antiferromagnetism in complexes. Application of magnetic measurements to structure determination of transition metal complexes.

Unit III  Transition Metals   

      Survey of the transition elements. General characteristics of transition elements. Oxidation states.           Study of the following groups of elements and their compounds with peculiar structures and their chemistry:

                        Ti                     V                     Cr                    Mn

                        Zr                     Nb                   Mo                   Tc

                        Hf                    Ta                    W                     Re

      Polyacids: Isopoly and heteropoly acids of Mo and W. Structure and properties of refractory and ionic borides, carbides, nitrides and silicides. Silicates: Classification and structure. Silicones.

Unit IV  Lanthanides and Actinides  

Lanthanides: Characteristic properties. Electronic configuration and term symbols. Occurrence and extraction. Separation techniques. Oxidation states. Spectral and magnetic properties. Actinides:  Occurrence and general properties. Electronic configuration and term symbols. Oxidation states. Spectral and magnetic properties. Comparative properties of lanthanides and actinides. Trans‑uranium elements and their stabilities. Applications of lanthanides, actinides and their compounds. 

 

CHE 522  Organic Chemistry-II  

Unit I   Symmetry Controlled Reactions and Organic Rearrangements

      Symmetry properties of MOs.  Theory, mechanism and stereocourse of electrocyclic, cycloaddition and sigmatropic reactions, 1,3-dipolar cycloadditions, ene reactions, cheletropic reactions and thermal  eliminations. Woodward-Hoffmann selection rules. Fluxional molecules. Types of organic rearrangements. Anionotropic, cationotropic, prototropic, free radical, carbene, nitrene and long-range rearrangements. Migratory aptitude in rearrangements. Rearrangements involving C à C, C à N, C à O,  hetero atom à C migrations of H, alkyl, aryl, hetero atom and other groups. 

Unit II Organic Photochemistry

      Primary photoprocesses.  Photoreactions of C=O systems,  enes,  eneones, dienes and arenes.  Photoisomerisations, Norrish type I and II reactions. Patterno-Buchi and Barton reactions. Di-p-methane and aromatic photo rearrangements. Photochemical remote functionalisation and hydrogen abstraction reactions. Introduction to PET, chemi and bioluminescent reactions.  Chemistry of singlet oxygen. Photochemistry in nature. Photosynthesis. Introduction to organic applied photochemistry and femtochemistry.

Unit III  Organic NMR Spectroscopy

       ¹H and ¹³C NMR chemical shifts and coupling constants of organic compounds. Field and anisotropic factors. Coupled spin systems.  Structure implications of δ and J values.  Spin systems and their analysis. Tree diagram. Chemical exchange, double resonance, NOE and DEPT. Introduction to 2D NMR. Correlation, NOE and quantum correlation spectroscopy techniques.

Unit IV  Organic Structure by Spectroscopy

      UV-VIS spectra of enes, eneones, arenes and conjugated systems.  Solvent effect on absorption spectra. Characteristic IR bands of functional groups. Identification of functional groups and other structural features by IR. MS in organic structure analysis.  EI, CI, FAB, ES and MALDI ion production methods. Characteristic EIMS fragmentation modes and MS rearrangements. Spectral interpretation, structure identification and solving of structural problems using numerical and spectral data.

 

CHE 523 Physical Chemistry-II    

Unit I  Molecular Symmetry

      Symmetry and character tables: Symmetry elements and symmetry operations. Point groups.  Multiplication of operations. Conditions for a set of elements to form a group. Group multiplication table.  Similarity transformation and classification of symmetry operations.  Matrix representation of point group. Reducible and irreducible representations. Character of a matrix. Orthogonality theorem. Rules derived from orthogonality theorem (proof not required). Setting up of the character tables of simple groups such as C_2V and C_3V on the basis of the rules. The four areas of the character table.

      Basics of molecular spectroscopy: Origin of spectra. Energy levels in molecules. Origin of rotational, vibrational, electronic and Raman spectra. Intensity of absorption. Beer‑Lambert law. Selection rules for vibrational, electronic, rotational and Raman spectra.  Basic elements of practical spectroscopy:  Signal to noise ratio, width and intensity of spectral transitions. Born‑Oppeheimer approximation.

Unit II  Spectroscopy-I

      Spectra of diatomic molecules: Microwave spectroscopy. Rotation of diatomic molecules. Rotational spectrum. Intensity of spectral lines. Calculation of internuclear distance. Nonrigid rotors and centrifugal distortion. Introduction to instrumentation. Infrared spectroscopy: Vibrational spectra of harmonic and anharmonic diatomic molecules. Fundamental and overtones. Determination of force constants. Interaction of rotation and vibration. Different branches of spectrum. Symmetry of vibrational‑rotation spectrum.  Introduction to instrumentation and FT IR. 

      Raman spectra:  Scattering of light. Raman scattering. Polarizability and classical theory of Raman spectrum. Quantum theory of Raman spectrum. Rotational and vibrational Raman spectrum. Introduction to instrumentation. Laser Raman spectrum. Electronic spectra: Term symbols of molecules. Electronic spectra of diatomic molecules. Vibrational coarse structure and rotational fine structure of electronic spectrum. Franck‑Condon principle. Types of electronic transitions. Fortrat diagram. Predissociation. Morse function.  Calculation of heat of dissociation. Introduction to instrumentation.

Unit III  Spectroscopy-II

       Spectra of polyatomic molecules: Rotational spectra of polyatomic molecules. Linear and symmetric top molecules. Vibrational spectra of polyatomic molecules. Normal modes. Classification of vibrations. Overtones, combination and Fermi resonance. Group frequencies. Raman spectra of polyatomic molecules. Complementarity of Raman and IR spectra.

      Electronic spectra of polyatomic molecules: Electronic transitions and absorption frequencies. Effect of conjugation. Resonance spectroscopy:  Nuclear spin and interaction with an applied magnetic field. Nuclear resonance. Population of energy levels. ¹H NMR spectrum. Chemical shift. Spin‑spin coupling. Fine structure. NMR spectra of other nuclei.  Introduction to instrumentation. 

      Electron spin in molecules and its interaction with magnetic field. ESR spectrum. The g factor and its determination.  Fine structure and hyperfine structure.  Mossbauer spectroscopy:  Doppler effect. Chemical shift.  Quadrupole effect.

Unit IV  Statistical Thermodynamics

      Statistical thermodynamics: Mechanical description of molecular systems. Thermodynamic property and entropy. Microstates.  Canonical and grand canonical ensembles. Equation of state for ideal quantum gases. Maxwell‑Boltzman distribution. The partition functions. Partition function for free linear motion, for free motion in a shared space, for linear harmonic vibration.  Complex partition functions and partition functions for particles in different force fields. Langevins partition function and its use for the determination of dipole moments. Electrostatic energies. Molecular partition functions. Translational, rotational, vibrational and electronic partition functions. Total partition functions. Partition functions and thermodynamic properties. Heat capacity of gases. Equipartition principle and quantum theory of heat capacity.

            Quantum statistics: Bose‑Einstein statistics. Examples of particles. Theory of paramagnetism.  Bose‑Einstein condensation. Liquid helium. Super cooled liquid. Fermi‑Dirac statistics. Thermionic emission. Relations between Maxwell‑Boltzman, Bose‑Einstein and Fermi‑Dirac statistics. Heat capacity of solids. The vibrational properties of solids.  Einstein theory of heat capacity.  The spectrum of normal modes. The Debye theory. The electronic specific heat.

      Note : At least 100 problems to be worked out from all the units put together. 30% of the questions for Examination shall contain numerical problems

 

CHE 524  Inorganic Chemistry Lab -II     

• Colorimetric determinations of Cr, Fe, Mn, Ni, Ti, W and Cu.
• Estimation of simple binary mixtures of metal ions in solution (involving quantitative separation) by volumetric and gravimetric methods.
• Analysis of some typical alloys such as brass, bronze and type metal.

 

CHE 525  Organic Chemistry Lab-II     

Preparation of organic compounds by multi-step reactions involving nitration, halogenation,       acetylation and oxidation. [Assessement is based on yield and purity].

Spectral interpretation of organic compounds [simple as well as  prepared in lab as above}using UV-     VIS and IR. [Assessement is based on identification and interpretaion].

 

CHE 526  Physical Chemistry Lab -II     

Viscosity: Viscosities of liquids and mixtures of liquids. Verification of Kendall’s equation and             Jones-Dole equation. Viscosity of polymer solutions. Variation of viscosity with temperature. 

Surface tension: Surface tension and parachor of liquids by differential capillary and stalagmometer      methods. Variation of surface tension with concentration.  Determination of atomic parachor. 

Cryoscopy: Determination of molar freezing points. Depression constant and molecular mass using       solid and liquid solvents. Study of dissociation and association of solutes. Atomicity of substances     like sulphur.          

Phase equilibria: CST of phenol-water system. Determination of unknown concentrations of NaCl,        acetic and oxalic acid. Construction of phase diagrams of unknown mixtures. Three component           systems with one pair of partially miscible liquids. Construction of phase diagrams and tie lines.          Composition of homogeneous mixtures.     

Transition temperature: Transition temperature of sodium acetate.  K_f of sodium acetate. Molecular        mass of urea. Transition temperature of sodium thiosulphate.

 

Semester - III

CHE 531  Inorganic Chemistry-III      

Unit I   Crystalline State

       Crystal systems and lattice types. Bravais lattices. Crystal symmetry. Point groups and  space groups. Miller indices. Reciprocal lattice concept. Close packed structures: BCC, FCC and HCP. Voids. Coordination number. X‑Ray diffraction by crystals: Functions of crystals. Transmission grating and reflection grating. Braggs equation. Diffraction methods. Powder, rotating crystal, oscillation and Weisenberg methods.      Indexing and determination of lattice type and unit cell dimensions of cubic crystals. Structure factor. Fourier synthesis.

Unit II  Solid State Chemistry

      Binding forces in solids: Molecular, ionic, covalent, metallic and hydrogen bonded crystals. Free electron theory and band theory of solids. Conductors, insulators and semiconductors. Mobility of charge carriers. Hall effect. Crystal  defects: Point, line and plane defects. Electrons and holes. Imperfections  and nonstoichiometry (oxides and sulphides). Techniques of introducing imperfections in solids. 

Unit III   Properties of Solids

      Electrical properties of solids: Conductivity of pure metals. Superconductivity. Photoconductivity. Photovoltaic effect. Dielectric properties. Piezoelectricity and ferroelectricity. Magnetic properties of solids: Diamagnetism, paramagnetism, ferromagnetism, ferrimagnetism and antiferromagnetism. Lasers and their applications.

Unit IV  Reactions of Metal Complexes

      Kinetics and mechanism of reactions involving complexes in solution.  Inert and labile complexes.  Ligand displacement (substitution) reactions in octahedral and square planar complexes. The trans effect.  Ligand field effects on reaction rate. Influence of acid and base on reaction rate. Racemization and isomerization. Redox reactions in complexes: Electron transfer and electron exchange reactions.  Outer sphere and inner sphere mechanisms of redox reactions.

 

CHE 532  Organic Chemistry-III   

Unit I  Organic Synthesis

      Introduction to retrosynthetic analysis. Linear and convergent synthesis, Synthons, functional group equivalents and umpolung. Chemo, regio and stereoselectivity in synthesis. Classical and modern carbon-carbon and carbon-hetero atom bond forming reactions in organic synthesis. Baylis-Hilman, Sonogashira reaction. Glaser coupling, Shapiro, Peterson, Heck, Stille, McMurray, Wittig and related reactions. Functional group interconversions. Enol and enamine alkylation. Conversion of alkenes to diols. Organometallic [Mg, Cu Pd and Li] and organo-nonmetallic [Si, B, P and S] reagents in organic synthesis. Asymmetric synthesis: chemical and enzymatic Approaches.

Unit II  Reduction and Oxidation  in Organic Synthesis

      Catalytic hydrogenation and stereochemistry. Hydrogenation catalysts and their selectivity.  Homogeneous hydrogenations. Fe, Zn, Na and Li reductions. Reduction using LAH, NaBH₄ and NaCNBH₃. Birch reduction. Lindlar catalysts and Rosenmund reduction. Oxidations using SeO₂, lead tetraacetate, ozone, HIO₄, OsO₄ and peracids. Sommelet reaction. Dehydrogenation to aromatic compounds. Oppenauer oxidation.

Unit III  Natural Products Chemistry 

      Classes, typical examples and structures of secondary metabolites. Chemical, spectroscopic and chiroptical methods for establishing carbon skeleton, functional groups and stereochemistry of natural products. Structure elucidation of santonin, reserpine, quercetin; b-carotene; ascorbic acid. Biosynthesis of terpenoids: introduction.

Unit IV  Chemistry of  Biopolymers and Polymers

      Peptide bond formation methods, amino and carboxy protection in SPPS.  Synthesis of  A, G, C, T, U adenosine, ADP and ATP. Automated polypeptide and oligonucleotide synthesis. Structure organization of proteins and polynucleotides. Structure of polysaccharides including starch, cellulose, glycogen and chitin. Classes of polymers. Types and mechanisms of polymerization reactions. Methods of molecular mass and size distribution determination. Polymer structure and property characterisation. Synthesis of stereoregular polymers. Polymers in organic synthesis: supports, reagents and catalysts.

 

CHE 533 Physical Chemistry-III   

Unit I  Surface Chemistry

      Types of surfaces. Thermodynamics of surfaces. Measurements of surface pressure and surface potential. Surfactants and miscelles. The gas-solid interface. Types of adsorption. Heat of adsorption.  Adsorption isotherms. Gibb adsorption equation and its verification. Langmuir isotherm. Multilayer adsorption. Freundlich isotherm. BET isotherm. Solid-liquid interface. Influence of surface tension on adsorption. Measurements of surface area of solids. Harkin-Jure method.  Entropy and point B methods.  Use of Langmuir isotherm.  BET method.

Unit II  Kinetic Theory

      Brownian movement. Determination of Avogadro number. Distribution of molecular velocities.  Maxwells equation. Average and most probable velocities from Maxwells equation. Influence of temperature.  Mean free path. Collision diameter. Triple collision. Viscosity. Thermal conductivity and diffusion.  Determination of viscosity of gases.  Influence of temperature and pressure on transport properties.

Unit III  Photochemistry

      Laws of photochemistry. Quantum yield.  Radiative and non-radiative transitions. Fluorescence and phosphorescence. Intensity and concentration. Fluorescence indicators. Quenching of fluorescence.  Chemiluminescence.  Flash photolysis. Explosion reaction. Kinetics of photochemical reaction of H₂ and Cl₂, and H₂ and Br₂.

Unit IV Electrochemistry

      Ionic activity. Ion-solvent interaction. Strong electrolytes. Ion transport. Debye-Huckel treatment.  Onsagar equation. Types of electrodes. Electrochemical cells. Liquid junction potential. Evaluation of thermodynamics properties. Electrode-electrolyte interface. Electrokinetic phenomena. Current-potential curves. Over potential. Butler-Volmer equation. Tafel and Nernst equations. Corrosion and its control.  Introduction to solid state electrochemistry.

      Note : At least 100 problems to be worked out from all the units put together. 30% of the questions for Examination shall contain numerical problems

 

CHE 534  Inorganic Chemistry Lab-III      

• Analysis of fertilizers: Estimation of nitrogen in ammonium compounds. NPK estimations in      synthetic fertilizers.
• Analysis of some typical ores: Carbonate ore, sulfate ore, ilmenite and monazite.
• Ion exchange separation of binary mixtures: Zn & Mg and Co & Ni.
• Preparation and characterisation of complexes  by UV-VIS, IR, magnetic susceptibility and        electrical conductivity.
  

 

CHE 535  Organic Lab-III    

Estimation of esters, acids, reducing sugars, phenols, amines and ketones. [Assessement is based on % error]

Spectrophotometric estimation of cholesterol, ascorbic acid, glucose and ammonia. [Assessement is       based on % error]

 

CHE 536  Physical Chemistry Lab-III 

Conductance: Verification of Onsagar equation. Solubility of sparingly soluble substances.        Oswald’s dilution law. Basicity of acids. Dissociation constants of acids and bases. Conductometric     titrations involving acid-base and precipitation reactions. Equivalent conductance of solutions of          strong electrolytes and weak electrolytes.

Potentiometry: Single electrode potentials of hydrogen and glass electrodes. Quinhydron electrode.        Potentiometric titrations involving acid-base, redox and precipitation reactions. pH of buffer      solutions. Solubility of AgCl. Determination of dissociation constant.

Polarography: Polarographic estimation of cadmium, zinc and lead. Composition of mixtures.

Flame photometry: Estimation of Na⁺, K⁺, Li⁺, Ca²⁺ and Mg²⁺. Composition of the mixtures.

Karl-Fischer titrator: Estimation of water contents in pharmaceuticals, oils, fats and paints.

 

CHE 501   Advanced Inorganic Chemistry-I  

Unit I   Metal-Metal Bonds and Metal Clusters

      Metal‑metal bonds:  Metal carbonyl clusters. Anionic and hydrido clusters. LNCCs and HNCCs.   Isoelectronic and isolobal relationships. Hetero atoms in metal clusters: Carbide and nitride containing clusters. Electron counting  schemes for HNCCs.  Capping rule. Chalcogenide clusters. Chevrel phases.  Compounds with M‑M multiple bonds. Quadrupole bonds. Relation of clusters to multiple bonds. One‑dimensional solids.

Unit II   Organometallic Chemistry-I

       Metal carbonyls:  Preparation and reactions.  Bonding and structure.  Polynuclear carbonyls with and without bridging.  Vibrational spectra of metal carbonyls. Carbonylate anions and metal carbonyl halides.  Photochemical reactions of metal carbonyls.  Nucleophilic and electrophilic attacks on CO. Metal nitrosyls and cyanides: Synthesis, structure and bonding. Metal isocyanides.

Unit III   Organometallic Chemistry-II

      Organometallic compounds: Preparation and general properties. Structure and bonding. Metal alkyls and aryls. Complexes with chain p‑donor ligands: Allene, allyne, allyl and diene complexes.  Hapto nomenclature. Complexes with cyclic  p‑donors:  Cyclopentadiene, benzene, cycloheptatriene and cyclooctatetraene complexes. Characterization of organometallic compounds.  Oxidative addition and reductive elimination. Insertion and elimination. Fluxional molecules. Catalysis by organometallic compounds: Hydrogenation, hydroformylation, isomerization and polymerization reactions.

Unit IV Inorganic Polymers

            Types of inorganic polymers. Characteristics of polymers: Molecular masses and their distribution.  Structural features.  Chain statistics.  Solubility consideration.  Crystallinity.  Mechanical properties. Polyphosphazenes: Synthetic routes. Molecular structure of polyphosphazene.  Structure property relationship. Polysiloxanes and related polymers: Preparation and structural features.  Polysilanes and related polymers: Synthesis and chemical modification. Electrical conductivity and photoconductivity. Polysilanes as photoresists and photoinhibitors. Metal coordination polymers. Metalloporphyrin and phthalocyanine polymers.

 

CHE 502 Advanced Organic Chemistry-I

Unit I  Molecular Recognition and Supramolecular Chemistry

      Noncovalent interactions and their significance in molecular recognition.  Molecular  recognition in bioprocesses. Codon and anticodon recognition. Protein biosynthesis. Introduction to protein and dideoxy DNA sequencing and PCR. Supramolecular chemistry.  Host-Guest interaction. Molecular receptors. Calixarenes, cryptands, crowns and other molecular hosts. Self assembly of supramolecular structures. Introduction to MR based chemo and biosensors.  Molecular devices and nanochemistry.

Unit II  Green Chemistry

      Background, origin and principles of green chemistry. Atom economy and other metrics of greenness. Examples of green processes. Microwave and sonochemical synthesis. Synthesis using solventless or alternate media conditions:  fluorous and ionic liquid media.

Unit III  Medicinal Chemistry and the Chemistry of the Cell 

      Introduction to antibiotics and analgesics with examples. Drug action and its specificity. Classification, chemical composition and structural features of lipids. Structure of  biomembranes and their chemical models. Introduction to enzyme and coenzyme chemistry. Introduction to the chemistry of metabolism and metabolic cycles. Introductory bioenergetics. Introductory bioenergetics. Brief study of biosynthetic pathways leading to secondary metabolites.

Unit IV  Organic Analytical Chemistry

      Quantitative analysis of organic functional groups. Analysis of drugs, oils and fats. Characterization of oils. Principle of the analysis of milk and starch based food materials. Analysis and estimation of organic pollutants. Organic trace analysis using spectrophotometry and fluorimetry. Microreactors and Lab-on-Chips.

 

CHE 503  Advanced Physical Chemistry-I       

Unit I Symmetry and Character Tables

      Symmetry elements.  Symmetry operations.  Properties of a group.  Point groups.  Group multiplication table.  Abelian groups. Cyclic group.  Similarity transformation and classification of symmetry operation.  Matrix representation of symmetry operations.  Group representation.  Trace of a matrix.  Reducible and irreducible representations. Construction of character tables.  The four areas of the character table. Mullikans symbols. Transformation of dipole vectors.  Atomic orbitals and polarizability tensor. Reduction formula. Reduction of reducible representations to irreducible representations. Applications of character tables to spectroscopy. Transition moment operators.  Symmetry and selection rules of IR, Raman and electronic spectra. Identification of allowed and forbidden electronic transitions in carbonyl group. Application of character table to orbitals.  Construction of hybrid orbitals. Symmetry adapted LCAO. MO theory of conjugated hydrocarbons.  Huckel calculation of energy of ethylene, butadiene and benzene.

 

Unit II Applications of Schrodinger Wave Equation to Exactly Solvable Systems   

      The Schrodinger wave equation and the eigen value spectrum. Expansion theorem. Particle on a ring.  Complete solution of linear harmonic oscillator in one dimension.  Hermite polynomial. Recurrence formula and orthogonality. Introduction to three‑dimensional harmonic oscillator.  Schrodinger wave equation in polar coordinates. Rigid rotator.  Separation of variables and complete solutions of  q and  f equations. Legendre polynomial and associated Legendre function. The spherical harmonics. The hydrogen atom: Separation of variables and complete solution of the radial part, the Laguarre polynomial, total wave function of hydrogen atom. The wave functions for atomic orbitals and explanation of the shapes of orbitals.

Unit III Approximate Systems

      The variation method: Variation theorem and its proof. The variation integral and its properties. The normal state of helium. The more generalized variation method.  The WKG approximation. The perturbation theory: First order perturbation. Theory of nondegenerate level.  The normal helium atom.  First order perturbation of degenerate level. The hydrogen atom:  Second order perturbation theory and Stark effect.  The generalized perturbation theory.  Time dependent perturbation theory:  Variation in the state of a system with time. Emission and absorption of radiation. The Einstein transition probabilities and their calculations. Selection rule and intensity of harmonic oscillator, rigid rotator and hydrogen atom

Unit IV Many Electron Systems

      Many electron atoms: Slitters' treatment of complex atoms.  Exchange of spectra.  Degeneracy’s.  Solution of secular equations.  The self‑consistent field method.  Electron correlation in the helium atom.  Angular moment. The spin of electron. The configurations of 1s, 2s and 1s, 2p of helium atom.  Spin‑orbit interaction.  Vector model of the atom. The self‑consistent field method.  SCF and Variation method. Slater’s treatment of complex molecules:  Wave function for the system of three hydrogen atoms.  Generalized valence bond method. The generalized Hellmann‑Feynmann theorem and its significance.

    Note :  At least 100 problems to be worked out from all the units put together. 30% of the questions for Examination shall contain numerical problems

 

Semester - IV

CHE 541  Analytical And Environmental Chemistry                        

Unit I  Analytical principles-I

      Accuracy and precision.  The mean and median.  Standard deviation, variance and coefficient of variation. Student “t” test. Confidence limits. Estimation of detection limits. Classification of errors.  Distribution of random errors.  Propagation of errors.  Minimization of errors.  Significant figures and computation rules. Approximation. Scatter diagram. Correlation coefficient, r.  Calculation of r by the method of least squares.  Correlation tables.  Linear regression.  Standard error of estimate.  Nonlinear regression. Regression and ratio of variation.     

Unit II  Analytical principles-II

      Classification of reactions in volumetry (titrimetry). Acid‑base equilibria in water. Ionization constant ‑ role of solvent. Classification of solvents. Leveling and differentiating solvents. Acid‑base equilibria in nonaqueous solvents. Buffers. Titration curves. Titrations in nonaqueous solvents. Theories of indicators of different types. Solubility products. Supersaturation and precipitate formation.  Mechanism of precipitate formation. Aging of precipitates. Precipitation from homogeneous solutions.  Purity of precipitate. Coprecipitation and postprecipitation. Contamination of precipitates. Washing of precipitate. Ignition of precipitate. Fractional precipitate. Organic reagents used in gravimetry ‑ oxine, dimethylglyoxime and cupferron.    

Unit III  Environmental Chemistry-I

      Scope of environmental chemistry. Environmental segments. Atmospheric composition. Atmospheric structure Heat balance of the earth. Chemical processes. Human activities and meteorology. Air pollutants Sulfur oxides Nitrogen oxides. Carbon monoxide. Cancer in our life style. Hydrocarbons as pollutants. Photochemical smog. Main components in photochemical smog. Green house effect. Consequences of Green house effect. Control and remedial measures of green house effect. Air pollution incidents. Acid rain. Control measures for air pollutants. Stratospheric chemistry-ozone. Antarctic and Arctic ‘ozone hole’ formation Abatement of ozone depletion. The Montreal Protocol.

 Unit IV Environmental Chemistry-II

      Water in the environment. Unique characteristics of water Pollution and environmental problems Waste disposal. Water pollutants. Organic matter in water. Oxygen demanding wastes. Soaps and detergents. Eutrophication. Oil pollution. Role of microorganism in oil cleanup operation. Heavy metals. Water treatment. Abatement procedures for water pollution.

      Composition of lithosphere. Soil properties, pollutants in soil, nuclear waste disposal, radioactive pollutants, nuclear catastrophes, pollutants from industries and agriculture, future strategy for pesticide use, polymers and plastics, chemical toxicology, biochemical effects of pesticides and heavy metals, environmental management.

 

CHE 542  Dissertation     

      Each student must carry out an original research in a topic in accordance with the electives chosen during Semesters III and IV and under the guidance and supervision of a faculty member of the Department as the course advisor.

 

CHE 504  Advanced Inorganic Chemistry-II  

Unit I   Inorganic Synthesis

      Inorganic synthesis: Special techniques such as chemical vacuum line, plasmas, photochemical apparatus and electrolysis. Synthesis of the following non‑metal compounds:  BCl₃, AlF₃, SiF₄, NF₃, OF₂, S₂C_l2, ClF₃, BrF₃, SbF₃, SbF₅, SF₄ and N₂F₄.  Synthesis of transition metal complexes involving the following methods:  Electron transfer reaction, substitution reaction, reactions of coordinated ligands, aldol condensation, imine bromination hydrolysis, substituent exchange reaction, template effect and macrocyclic ligands. Complexes with interlocking ring ligands.  Formation of supramolecular species.

Unit III   Bioinorganic Chemistry-I

       Metals in biological systems: Trace metals and ultratrace metals. The role of metal ions in biological systems. Biochemistry of iron: Iron storage and transport. Ferritin, hemosiderin and transferrin. Bacterial iron transport. Siderophores. Hemoglobin and myoglobin. Nature of heme-dioxygen binding. Cooperativity in hemoglobin. Synthetic Blood. Cytochromes. Peroxydases and catalysases. Other natural oxygen carriers. Hemerythrins.  Iron‑sulphur proteins.

Unit IV   Bioinorganic Chemistry-II

      Biochemistry of metals other than iron: Carboxypeptidase A, carbonic anhydrase and metallothioneins. Blue copper proteins Hemocyanins and oxydases Biomethylation of mercury.  Nitrogenases. Molybdo‑enzymes. Vanadium storage and transport. Alkali metals and regulation of membrane potentials. Ionophores. Ion pumps. Ca²⁺ in blood clotting. Mg²⁺ in phosphate transfer.  Ru complexes. Nucleic acid structural probes. The application of therapeutic chelating agents and preformed coordination compounds.                                                     

 Unit V   Inorganic Photochemistry

      Inorganic photochemistry: Photochemical laws and kinetics. Photophysical processes. Photo substitution, redox, dissociation and isomerization reactions. Photoreactions and solar energy conversions.  Chlorophyll and photosynthesis.  Photochemistry of photographic systems.

 

CHE 505  Advanced Organic Chemistry-II            

Unit  I  Physical Organic Chemistry

      Linear free energy relationships: electronic and steric effects. Hammett and Taft equations The Hammond  postulate. Curtin-Hammett principle. Isotope effects. Effect of solvents on reactivity. Solvent polarity and its scales. Primary and secondary effects. Salt effects and special salt effects in S_N reactions. Phase transfer Catalysis.

Unit II Techniques in Organic Synthesis

      Synthetic planning, disconnections, synthons and retrosynthetic analysis. Functional group interconversions FGI and protection-deprotection of amino, hydroxy, carbonyl and carboxyl groups. Enzymes in organic synthesis. Baldwin’s rules for cyclisations. Synthesis of pyrazole, imidazole, thiazole, oxazole and pyrimidine ring systems. Synthesis of small and large carbo and heterocyclic rings. Introduction to solid phase organic synthesis. Principles of combinatorial synthesis.

Unit III  Reagents and Reactions in Synthesis

      Oxidations using chloranil, DDQ and Cr(VI) reagents. Swern oxidation, Moffatt oxidation, allylic and benzylic oxidations. Sharpless assymetric epoxidation. Elbs reaction. Oxidative coupling of phenols. Epoxidation of C=C using peracids. Reduction using Boranes. Hindered boranes and bulky metal hydrides in selective reductions. Diimide reduction. Alkali metal  reductions. Reductions using DIBAL, Li trialkylborohydrides, tri-n-butyl tin hydride, McFadeyan-Stevens reaction. Mitsonobu reaction. Story synthesis of carbocycles. Barton synthesis of hindered olefins by extrusion reactions. Conversion of epoxide to alkenes. Prevost and Woodward procedures for diols. Olefin metathesis.

Unit IV  Organometallics  in Organic Synthesis

      Reactions of organolithium reagents – Li exchange reaction and its use in the preparation of RLi compounds, addition to C=O, COOH and CONR₂. Li dialkylcuprates – preparation, reaction with alkyl halides, with acyl halides and with enones. Alkynyl Cu(I) reagents. Organometallic reagents of Al, Cd,  Zn, Ti and Fe. Alkylation, oxirane addition, carbon dioxide addition, carbonyl addition, enone 1,2- and 1,4- additions, reduction and enolisation reaction. Dialkyl Cd compounds: preparation and reaction with acyl halides. Na tetracarbonylferrate and its use in ketone synthesis. Benzenetricarbonyl chromium: Preparation and reaction with carbanions.

 

CHE 506 Advanced Physical Chemistry-II         

Unit I Surface Phenomena

      External and internal surfaces of solids. Microporous solids. Clean surfaces. Gas-solid interface.  Solid-liquid interface. The techniques of surface science. Adsorption phenomena. Integral and differential heats of adsorption. General purpose of adsorption isotherms. Classes of adsorption isotherms. Comparison of T₁ a_S and f-plots. Selectivity coefficients. Hysterisis. Sticking probabilities.  Selectivity coefficient.                      

Unit II Rate Processes

      Monitoring of concentration of reacting species. True rate of reaction. Order from time-dependent concentration. Steady state approximation. Chain reactions. Explosion reactions. Quantum efficiency of photochemical reactions. Photochemical processes in the atmosphere. Trimolecular reactions. Free radical polymerization. Relaxation methods for fast reaction monitoring.

      Theories of reaction rate. Absolute reaction rate theory. Thermodynamic functions of reaction rates. Reactions in liquid solutions. Ionic reactions. Encounters, collisions and cage effects. Diffusion controlled reactions. Factors influencing reaction rates. Salt effects. Hammett and Taft equations.

     

Unit III Liquids and Liquid Crystals

      X-ray diffraction study of simple liquids and their structures. Theories of liquid state. Oscillator.  Free space and van der Waals theories. Lennard-Jones theory of melting. Specific heats of liquids.  Liquid crystals. Mesomorphic state. Types, examples and applications of liquid crystals. Theories of liquid crystals.

Unit IV Spectra of Polyatomic Molecules                                                                      

      Molecular vibrations:  Normal coordinates.  Normal vibrations.  Classification of normal vibrations.  Vibrational spectra and vibrational‑rotational spectra of linear polyatomic, symmetric top, spherical top and asymmetric top molecules. Vibrational‑rotational Raman spectrum.  Complementarity and mutual exclusion principles.  Calculation of bond length and force constant.  Elementary idea of normal coordinate analysis. NMR spectrum:  Internuclear spin‑spin coupling.  Shielding and deshielding.  Anisotropic effects.  Chemical  shifts.  Second order effects.  Spin‑lattice and spin‑spin relaxation, dipole‑dipole relaxation, electric quadrupole relaxation, relaxation time and spectral line width.  Elementary idea of 2D and 3D NMR spectra.   

 

CHE 507  Instrumental Methods      

Unit I  Spectral methods

      Principles, instrumentation and applications of UV-visible spectrophotometer, IR spectrophotometer, spectrofluorometer and atomic absorption spectrometer. Analysis of samples using the above instruments.

Unit II  Chromatographic methods

      Principles, instrumentation and applications of column chromatography, paper chromatography, thin layer chromatography, ion-exchange chromatography, gas chromatography and liquid chromatography.  Analysis of samples using the above techniques.

Unit III Electroanalytical methods

      Principles, instrumentation and applications of electrogravimetry, coulometry, polarogarphy, amperometry, cyclic voltametry, potentiometry and conductometry.  Analysis of samples using the above instruments.

Unit IV  Thermal analysis methods

      Principles, instrumentation and applications of thermogravimetry (TG), derivative thermogravimetry (DTG), differential thermal analysis (DTA) and differential scanning calorimetry (DSC).  Analysis of samples using the above instruments.

 

CHE 508  Computational Chemistry-Theory and Lab    

Unit I  Computer Applications

      Introduction to structure drawing, spread sheet and chemistry related softwares.  Web resources in chemistry learning. Accessing databases on molecular structures, spectra and crystal data.

Unit II  Introduction to Computational Chemistry

      Brief description of computational methods: ab initio, semi empiricalmolecular mechanics and molecular dynamics approaches.  General applications: introduction to model building, energy minimization, conformation searching, transition state modeling, reaction pathway modeling, visualization of results and molecular property calculations.

Unit III   Molecular Mechanics and Dynamics Based Applications

      Introduction to molecular modeling. Potential energy surfaces, optimization methods, molecular mechanics, force fields, geometry optimization, transition states searching., reaction path following: gradient, stationary points, saddle point. Molecular dynamics: Calculation of bulk properties such as free energy and viscosity. Hand-on use of software packages: free as well as priced softwares in computer lab.

Unit IV QM Based Applications     

      Introduction to electronic structure methods: ab initio and semi-empirical. Introduction to HF-SCF. Introductory DFT. Basis set, STO and GTO. Gaussian.  Coordinate specifications.  Z-matrix. Hands-on use of software packages such as GAMESS, MOLCHEM, MOLDEN, CHEMCRAFT and other free and priced softwares in lab.

 

CHE 51A  Bioorganic and Natural Products Chemistry    

Unit I  Bioorganic Chemistry

      Molecular Recognition [MR] and noncovalent interactions. MR and biomacromolecules  Supramolecular chemistry. Molecular receptors and hosts. Self assembly of supramolecular structures. Introduction to MR based chemo and biosensors and organic nanochemistry.

Unit II Natural Products

      Classes: Typical examples of secondary metabolites. Structure: Chemical and spectral methods. Isolation: chemical, chromatographic and supercritical solvent extraction of phytochemicals.  Significance: medicinal and nutraceutical chemistry. Demonstration and hands-on lab.

 

CHE 51B  Analytical and Environmental Chemistry      

Unit I  Analytical principles-I

      Accuracy and precision.  The mean and median.  Standard deviation, variance and coefficient of variation. Classification of errors. Minimization of errors. Significant figures and computations.  Statistical methods in analysis.   

Unit II  Analytical principles-II      Classification of reactions in volumetry (titrimetry).  Acid‑base equilibria in water.    Buffers.  Titration curves.  Theories of indicators.  Solubility product. Common ion effect.  Supersaturation and precipitate formation. Precipitation from homogeneous solutions. The purity of precipitate. Coprecipitation and postprecipitation. Contamination of precipitates. Washing of precipitate. Ignition of precipitate.  Organic reagents used in gravimetry.     

Unit III  Environmental Chemistry-I

      Components of Environment. Environment and development. Atmospheric composition and behavior. Chemical processes. Air pollutants. Photochemical smog. Green house effect. Impact of green house effect on global climate. Air pollution incidents. Acid rain. Adverse effect of acid rain. Control measures for air pollutants. Creation of ozone layer. Depletion of ozone layer. Protection of ozone umbrella.

Unit IV  Environmental Chemistry-II

      Water in the environment. Physical and chemical properties of water. Pollution and environmental problems. Waste disposal. Water pollutants,. Soaps and detergents. Eutrophication. Oil pollution. Heavy metals. Water treatment. Pollutants in soil. Radioactive pollutants. Pollutants from industries and agriculture. Chemical toxicology. Biochemical effects of pesticides and heavy metals.