M.Sc. (FINAL)
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Paper-I: |
CH-501(a) Applications of Spectroscopy |
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CH-501(b) Photochemistry |
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CH-501(c) Solid State Chemistry |
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Paper-II: |
CH-502(a) Bioinorganic Chemistry |
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CH-502(b) Bioorganic Chemistry |
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CH-502(c) Biophysical Chemistry |
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Paper-III |
CH-503 Environmental Chemistry |
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Elective Paper-1 |
CH-504,Group-I Organotransition Metal Chemistry |
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Elective Paper-2 |
CH-505,Group-I Bioinorganic and Supramolecular Chemistry |
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Elective Paper-3 |
CH-506,Group-II Photoinorganic Chemistry |
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Elective Paper-4 |
CH-507,Group-I Polymers |
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Elective Paper-5 |
CH-504,Group-II Organic Synthesis I |
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Elective Paper-6 |
CH-505,Group-II Organic Synthesis-II |
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Elective Paper-7 |
CH-506,Group-II Heterocyclic Chemistry |
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Elective Paper-8 |
CH-507,Group-II Chemistry of Natural Products |
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Elective Paper-9 |
CH-504,Group-III Analytical Chemistry |
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Elective Paper-10 |
CH-505,Group-III Physical Organic Chemistry |
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Elective Paper-11 |
CH-506,Group-III Chemical Dynamics |
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Elective Paper-12 |
CH-507,Group-III Electrochemistry |
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M.Sc.(Final) Chemistry Practical |
| Duration : 3 Hrs. |
Max. Marks : 100 |
Inorganic Chemistry
Unit-I
Vibrational Spectroscopy
Symmetry and shapes of AB2, AB3, AB4, AB5 and AB6, mode of bonding of ambidentate ligands, ethylenediamine and diketonato complexes, application of resonance Raman spectroscopy particularly for the study of active sites of metalloproteins.
Electron Spin Resonance Spectroscopy
Hyperfine coupling, spin polarization for atoms and transition metal ions, spin-orbit coupling and significance of g-tensors, application to transition metal complexes (having one unpaired electron) including biological systems and to inorganic free radicals such as PH4, F2 and (BH3).
Nuclear Magnetic Resonance of Paramagnetic Substances in Solution
The contact and Pseudo contact shifts, factors affecting nuclear relaxation, some applications including biochemical systems, an overview of NMR of metal nuclide with emphasis on 195Pt and 119 SN NMR.
Mossbauer Spectroscopy
Basic principles, spectral parameters and spectrum display. Application of the technique to the studies of (1) bonding and structures of Fe+2 and Fe+3 compounds including those of intermediate spin, (2) Sn+2 SN=4 compounds nature of M-L bond, coordination number, structure and (3) detection of oxidation state and inequivalent MB atoms.
Unit-II
Organic Chemistry
Ultraviolet and Visible spectroscopy
Various electronic transitions (185-800 nm) Beer-Lambert law, effect of solvent on electronic transitions, ultraviolet bands for carbonyl compounds, unsaturated carbonyl compounds, dienes, conjugated polyenes, Fieser Woodward rules for conjugated dienes and carbonyl compounds, ultraviolet spectra of aromatic compounds. Steric effect in biphenyls.
Infrared Spectroscopy
Instrumentation and Sample handling
Characteristic vibrational frequencies of alkanes, alkenes, alkynes, aromatic compounds, alcohols, ether's, phenols and amines. Detailed study of vibrational frequencies of carbonyl compounds (ketone's, aldehyde's, esters, amides, acids, anhydride's, lactones, lactams and conjugated carbonyl compounds). Effect of hydrogen bonding and solvent effect on vibrational frequencies, overtones, combination bands and fermi resonance.
Optical Rotatory Dispersion (ORD) and Circular Dichromium (CD)
Definition, deduction of absolute configuration, octant rule for ketones.
Unit-III
Nuclear Magnetic Resonance Spectroscopy
General introduction and definition, chemical shift, spin-spin interaction, shielding mechanism, mechanism of measurement, chemical shift values and correlation for protons bonded to carbon (aliphatic, olefinic, aldehydic and aromatic) and other nuclei (alcohols, phenols, enols, carboxylic acids, amines, amides & mercapto), chemical exchange, effect of deuteration, complex spinspin interaction between two, three, four and five nuclei (first order spectra), Stereochemistry, hindered rotation, Karplus curve-variation of coupling constant with disordered angle. Simplification of complex spectranuclear magnetic double resonance, NMR shift reagents, solvent effects. Fourier transform technique, nuclear overhauser effect (NOE).
Carbon-13 NMR Spectroscopy 5 Hrs.
General considerations, chemical shift (aliphatic olefinic , alkyne, aromatic, heteroaromatic and carboynl carbon), coupling constants. Two dimension NMR spectroscopy-COSY, NOESY, DEPT, IONEPT, APT and INADEQUATE techniques.
Mass Spectrometry
Introduction ion production E1, C1 FD and FAB, factors affecting fragmentation, ion analysis, ion abundance Mass spectral fragmentation of organic compounds, common functional groups, molecular ion peak, metastable peak. Me Lafferty rearrangement. Nitrogen rule. High resolution mass spectrometry. Example of mass spectral fragmentation of organic compounds with respect to their structure determination.
Book Suggested
- Physical Methods for Chemistry, R.S. Drago, Saunders Compnay.
- Structural Methods in Inorganic Chemistry, E.A.V. Ebsworth, D.W.H. Rankin and S. Cradock, ELBS.
- Infrared and Raman Spectral : Inorganic and Coordination Compounds K. Nakamoto, Wiley.
- Progress in Inorganic Chemistry vol., 8, ed., F.A. Cotton, vol., 15 ed. S.J. Lippard, Wiley.
- Transition Metal Chemistry ed. R.L. Carlin vol. 3 dekker.
- Inorganic Electronic Spectroscopy, A.P.B. Lever, Elsevier.
- NMR, NQR, EPR and Mossbauer Spectroscopy in Inorganic Chemistry, .V. Parish, Ellis Haywood.
- Practical NMR Spectroscopy, M.L. Martin. J.J. Deepish and G.J. Martin, Heyden.
- Spectrometric Identification of Organic Compounds, R.M. Silverstein, G.C. Bassler adn T.C. Morrill, John Wiley.
- Introduction to NMR spectroscopy, R.J. Abraham, J. Fisher and P. Loftus, Wiley.
- Application of Spectroscopy of Organic Compounds, J.R. Dyer Prentice Hall.
- Spectroscopic Methods in Organic Chemistry D.H. Williams, I. Fleming, Tata McGraw-Hill.
Unit-I
Photochemical Reactions
Interaction of electromagnetic radiation with matter, types of excitations, fate of excited molecule, quantum yield, transfer of excitation energy, actinometry.
Determination of Reaction Mechanism
Classification, rate constants and life times of reactive energy state determination of rate constants of reactions. Effect of light intensity on the rate of photochemical reactions. Types of photochemical reactions-photo dissociation, gas-phase photolysis.
Photochemistry of Alkene
Intramolecular reactions of the olefinic bond-geometrical isomerism, cyclisation reactions, rearrangement of 1,4- and 1,5-dienes.
Unit-V
Photochemistry of Carbonyl Compounds
Intramolecular reactions of carbonyl compounds-saturated, cyclic and acyclic, b,g unsaturated and a, b unsaturated compounds, cyclohexadienones.
Intermolecular cyloaddition reactions-dimerisations and oxetane formation.
Photochemistry of Aromatic Compounds
Isomerisations, additions and substitutions.
Miscellaneous Photochemical Reactions.
Photo-Fries reactions of annelid's, Photo-Fries rearrangement.
Barton reaction. Singlet molecular Oxygen reaction. Photochemical formation of smog. Photodegration of polymers. Photochemistry of vision.
Books Suggested
- Fundamentals of photochemistry, K.K. Rothagi-Mukheriji, Wiley-Eastern.
- Essentials of Molecular Photochemistry, A Gilbert and J. Baggott, Blackwell Scientific Publication.
- Molecular Photochemistry, N.J. Turro, W.A. Benjamin.
- Introductory Photochemistry, A. Cox and t. Camp, McGraw Hill.
- Photochemistry, R.P. Kundall and A. Gilbert. Thomson Nelson.
- Organic Photochemistry, J. Coxon and B.halton, Cambridge University Press.
Unit-VI
Solid State Reactions
General principles, experimental procedure, co-precipitation as a precursory to solid state reactions, kinetics of solid state reactions.
Crystal Defects and Non-Stoichiometry
Perfect and imperfect crystals, intrinsic and extrinsic defects-point defects, line and plane defects, vacancies-Schottky detects and Frenkel defects. Thermodynamics of Schottky and Frenkel defect formation, colour centres, non-stoichiometry and defects.
Electronic Properties and Band Theory
Metal,s insulators and semiconductors, electronic structure of solidsband theory band structure of metals, insulators and semiconductors, Intrinsic and extrinsic semiconductors, doping semiconductors, p-n junctions, super conductors.
Optical properties-Application of optical and electron microscopy. Magnetic Properties-Classification of materials : Effect of temperature calculation of magnetic moment, mechanism of ferro and anti ferromagnetic ordering super exchange.
Organic Solids
Electrically conducting solids. organic charge transfer complex, organic metals, new superconductors.
Books Suggested
- Solid state chemistry and its applications, A.R. West. Peenum.
- Principles of the Solid State, H.V. Keer, Wiley Eastern.
- Solid State Chemistry, N.B. Hannay.
- Solid State Chemistry, D.K. Chakrabarty, New Wiley Eastern.
| Duration : 3 Hrs. |
4 hrs or 6 period/week |
Max. Marks : 75 |
Unit-I
Metal Ions in Biological Systems
Bulk and trace metals with special reference to Na, K, Mg, Ca, Fe, Cu, Zn, Co, and K+/Na+ pump.
Bioenergetics and ATP Cycle.
DNA polymerisation, glucose storage, metal complexes in transmission of energy; chlorophyll's, photosystem I and photosystem II in cleavage of water.
Unit-II
Transport and Storage of Dioxygen
Heam proteins and oxygen uptake structure and function of haemoglobin's, mygolobin, haemocyanms and hemerythrin, model synthetic complexes of iron, cobalt and copper.
Electron Transfer in Biology
Structure and function of metal of proteins in electron transport processes cytochrome's and ion-sulphure proteins, synthetic models.
Nitrogen fixation
Biological nitrogen fixation, and its mechanism, nitrogenase, Chemical nitrogen fixation.
Book Suggested
- Principles of Bioinogranic Chemistry, S.J. Lippard and J.M. Berg, University Science Books.
- Bioinorganic Chemistry, 1. Bertini, H.B. Gray, S.J. Lippard and J.S. Valentine, University Science Books.
- Inorganic biochemistry vol. I and II ed. G.L. Eichhorn, Elsever.
- Progress in Inorganic Chemistry, Vol 18 and 38 ed J.J. Lippard, Wiley.
Unit-III
Introduction
Basic considerations, Proximity effects and molecular adaption.
Enzymes
Introduction and historical perspective, chemical and biological catalysis, remarkable properties of enzymes like catalytic power, specificity and regulation. Nomenclature and classification, extraction and purification. Fischer's lock and key and Koshalnd's induced fit hypothesis, concept and identification of active site by the use of inhibitors, affinity labeling and enzyme modification by site-directed mutagenesis. Enzyme kinetics, Michael's-Menten and Lineweaver Burk plots, reversible and irreversible inhibition.
Mechanism of Enzyme Action
Transition-state theory, orientation and Steric effect, acid-base catalysis, covalent catalysis, strain or distortion. Examples of some typical enzyme mechanisms for chemotrypsin, ribonuclease, lysozyme and carboxypeptidase.
Kinds of Reactions Catalysed by Enzymes
Nucleophilic displacement on a phosphorus atom, multiple displacement reactions and the coupling of ATP cleavage to endergonic processes. Transfer of sulphate, addition and elimination reactions, enolic intermediates in Isomerisations reactions, b-Cleavage and condensation, some isomerization and rearrangement reactions. Enzyme catalyzed carboxylation and decarboxylation.
Unit-IV
Co-Enzyme Chemistry
Cofactors as derived from vitamines, coenzymes, prosthetic groups, apoenzymes. Structure and biological functions of coenzyme A, thiamine pyrophosphate, pyridoxal phosphate, NAD+, NADP+, FMN, FAD, lipoic acid, vitamin B12. Mechanisms of reactions catalyzed by the above cofactors.
Enzyme Models
Host-guest chemistry, chiral recognition and catalysis, molecular recognition, molecular asymmetry and prochirality Biometric chemistry, crown ether, cryptates. Cyclodextrins, cyclodextrion-based enzyme models, clixarenes, ionospheres, micelles synthetic enzymes or synzymes.
Biotechnological Applications of Enzymes
large-scale prodcution and purification of enzymes, techniques and methods of immobilization of enzymes, effect of immobilization on enzyme activity, application of immobilized enzymes, use of enzymes in food and drink industry-brewing and cheese-making, syrups from cron starch, enzymes as targets for drug design. Clinical uses of enzymes, enzyme therapy, enzymes and recombinant DNA Technology.
Book Suggested
- Bioorganic Chemistry : A chemical Approach to Enzyme Action, Hermann Dugas and C. Penny, Springer Verlag.
- Understanding Enzymes, Trevor Palmer, Prentice Hall.
- Enzyme Chemistry : Impact and applications, Ed. Collin J suckling, chemistry.
- Enzyme Mechanisms Ed. M.I. Page and A Williams, Royal Society of Chemistry.
- Fundamentals of Enzymology, N.C. Price and L. Stevens. Oxford University Press.
- Immobilized Enzymes : An Introduction and Applications in Biotechnology, Michael ID. Trevan, Hohn Wiley.
- Enzymatic Reaction Mechanisms. C. Walsh. W.H. Freeman.
- Enzyme Structure and Mechanism, A Fersht, W.H. Freeman.
- Biochemistry : The Chemical Reactions of Living Cells, D.E. Metzler, Academic Press.
Unit-V
Biological Cell and its Constituents
Biological cell, structure and functions of proteins, enzymes, DNA and RNA in living systems. Helix coils transition.
Bioenergetics
Standard free energy change in biochemical reactions, exergonic, endergonic. Hydrolysis of ATP, synthesis of ATP from ADP.
Statistical Mechanics in Biopolymers
Chain configuration of macromolecules, statistical distribution end to end dimensions, calculation of average dimensions for various chain structures. Polypeptide and protein structures, introduction to protein folding problem.
Biopolymer Interactions
Forces involved in biopolymer interactions. Electrostatic charges and molecular expansion, hydrophobic forces, dispersion force interactions. Multiple equilibrium and various types of bidning processes in biological systems. Hydrogen ion titration curves.
Unit-VI
Thermodynamics of Biopolymers Solutions
thermodynamics of Biopolymer Solutions
Thermodynamics of biopolymer solutions, osmotic pressure, membrane equilibrium, muscular contraction and energy generation in mechanochemical system.
Cell Membrane and Transport of Ions
Structure and functions of cell membrane, ion transport through cell membrane, irreversible thermodynamic treatment of membrane transport. Nerve conduction.
Biopolymers and their molecular Weights
Evaluation of size, shape, molecular weight and extent of hydration of biopolymer by various experimental techniques. Sedimentation equilibrium, hydrodynamic methods, diffusion, sedimentation velocity, viscosity, elecrophoresis and rotational motions.
Diffraction Methods
Light scattering, low angle X-ray scattering, X-ray diffraction and photo correlation spectroscopy ORD.
| Duration : 3 Hrs. |
2 Hrs. or 3 Period/week |
Max. Marks : 50 |
Unit-I
Atmosphere
Atmospheric layers, Vertical temperature profile, heat/radiation budget of the earth atmosphere systems. Properties of troposphere, thermodynamic derivation of lapse rate. Temperature inversion. Calculation of Global mean temperature of the atmosphere. Pressure variation in atmosphere and scale height. Biogeochemical cycles of carbon, nitrogen, sulphure, phosphorus oxygen. Residence times.
Unit-II
Atmospheric Chemistry
Sources of trace atmospheric constituents : nitrogen oxides, sulphure dioxide and other sulphure compounds, carbon oxides, chlorofluorocarbons and other halogen compounds, methane and other hydrocarbons.
Tropospheric Photochemistry
Mechanism of Photochemical decomposition of NO2 and formation of ozone. Formation of oxygen atoms, hydroxyl, hydroperoxy and organic radicals and hydrogen peroxide. Reactions of hydroxyl radicals with methane and other organic compounds. Reaction of OH radicals with SO2 and NO2. Formation of Nitrate radical and its reactions. Photochemical smog meteorological conditions and chemistry of its formation.
Unit-III
Air Pollution
Air pollutants and their classifications. Aerosols-sources, size distribution and effect on visibility, climate and health.
Acid Rain
Definition, Acid rain precursors and their aqueous and gas phase atmospheric Oxidation reactions. Damaging effects on aquatic life, plants, buildings and health. Monitoring of SO2 and NOx. Acid rain control strategies.
Stratospheric Ozone Depletion
Mechanism of Ozone formation, Mechanism of catalytic Ozone depletion, Discovery of Antarctic Ozone hole and Role of chemistry and meteorology. Control Strategies.
Green House Effect
Terrestrial and solar radiation Spectra, Major green house gases and their sources and Global warming potentials. Climate change and consequences.
Urban Air Pollution
Exhaust emissions, damaging effects of carbon monoxide. Monitoring of CO. Control strategies.
Unit-IV
Aquatic Chemistry and Water Pollution
Redox chemistry in natural waters. Dissolved oxygen, biological oxygen demand, chemical oxygen demand, determination of DO, BOD and COD.
Aerobic and anaerobic reactions of organic sulphure and nitrogen compounds in water acid-base chemistry of fresh water and sea water. Aluminum, nitrate and fluoride in water. Petrification. Sources of water pollution. Treatment of waste and sewage.
Purification of drinking water, techniques of purification and disinfection.
Unit-V
Environmental Toxicology
Toxic heavy metals : Mercury, lead, arsenic and cadmium. Causes of toxicity. Bioaccumulation, sources of heavy metals. Chemical speciation of Hg, Pb, As, and Cd. Biochemical and damaging effects.
Toxic Organic Compound : Pesticides, classification, properties and uses of organochlorine and ionospheres pesticides detection and damaging effects.
Polychlorinated biphenyls : Properties, use and environmental continuation and effects.
Polynuclear Aromatic Hydrocarbons : Source, structures and as pollutants.
Unit-VI
Soil and Environmental Disasters
Soil composition, micro and macronutrients, soil pollution by fertilizers, plastic an metals. Methods of re-mediation of soil.
Bhopal gas tragedy, Chernobyl, three mile island, Minimtata Disease, Sevoso (Italy), London smog.
Books
- Environmental Chemistry, Colin Baird, W.H. Freeman Co. New York, 1998.
- Chemistry of Atmospheres, R.P. Wayne, Oxford.
- Environment Chemistry, A.K. De, Wiley Eastern, 2004.
- Environmental Chemistry, S.E. Manahan, Lewis Publishers.
- Introduction to atmospheric Chemistry, P.V. Hobbs, Cambridge.
Group-I
- Organotransition Metal Chemistry.
- Bioinorganic and Supramolecular Chemistry.
- Photoinorganic Chemistry.
- Polymers.
Group II
- Organic synthesis-I
- Organic Synthesis-II
- Heterocyclic Chemistry
- Chemistry of Natural Products
Group-III
- Analytical Chemistry
- Physical Organic Chemistry
- Chemical Dynamics
- Electro Chemistry
(CH-504, Group-I)
| Duration : 3 Hrs. |
2 Hrs. or 3 Period/week |
Max. Marks : 50 |
Organotransition Metal Chemistry
Unit-I
Alkyls and Aryls of Transition Metals
Types, routes of synthesis, stability and decomposition pathways organocopper in organic synthesis.
Unit-II
Compounds of Transition Metal-Carbon Multiple Bonds
alkylidenes, alkylidynes, low valent carbenes and carbynes-synthesis, nature of bond, structural characteristics, nucleophilic and electrophilic reactions on the ligands, role in organic synthesis.
Unit-III
Transition Metal p-Complexes
Transition metal p-Complexes with unsaturated organic molecules, alkenes, alkynes, allyl, diene, dienyl, arene and trienyl complexes, preparation, properties, nature of bonding and structural features. Important reactions relating to nucleophilic and electrophilic attack on ligands and to organic synthesis.
Unit-IV
Transition metal compounds with bonds to hydrogen
Transition metal compounds with bonds to hydrogen.
Unit-V
Homogeneous Catalysis
Stoichiometric reactions for catalysis, homogeneous catalytic hydrogenation, Zeigler-Natta polymerization of olefins, catalytic reactions involving carbon monoxide such as hydrocarbonylation of olefins (oxoreaction), explanation reactions, activation of C-H bond.
Unit-VI
Fluxional Organometallic Compounds
Flexionality and dynamic equilibrium in compounds such as n-2 olefine, n3-allyl and dienyl complexes.
Books Suggested
- Principles and Application of Organotransition Metal Chemistry, J.P. Collman, L.S. Hegsdus, J.R. Norton and R.G. Finke, University Science Books.
- The Organometallic Chemistry of the Transition Metals, R.H. Crabtree. John Wiley.
- Metallo-organic Chemistry, A.J. Pearson, Wiley.
- Organometallic Chemistry, R.C. Mehrotra and A. Singh New Age International.
(CH-505, Group-I)
| Duration : 3 Hrs. |
2 Hrs. or 3 Period/week |
Max. Marks : 50 |
Bioinorganic and Supramolecular Chemistry
Unit-I
Metal Storage and Transport
Ferritin transferrin, and siderophores.
Unit-II
Calcium in Biology
Calcium in living cells, transport and regulation, molecular, aspects of intramolecular processes, extracellular binding proteins.
Unit-III
Metalloenzymes
Zinc enzymes-carboxypeptidase and carbonic anhydrase. Iron enzymes-catalase, peroxidase and cytochrome P-450. metallo enzyme-II Copper enzymes-superoxide dismutase. Molybdenum oxatransferase enzymes-xanthine oxidase. Coenzyme vitamin B12.
Unit-IV
Metal-Nucleic Acid Complexes
Metal ions and metal complex interactions. Metal complex nucleic acids.
Unit-V
Metals in Medicine
Metal deficiency and disease, toxic effects of metals, metals used for diagnosis and chemotherapy with particular reference the anticancer drugs.
Unit-VI
Supramolecular Chemistry-I
(A) Molecular recognition : Molecular receptors for different types of molecules including arisonic substrates, design and synthesis of co receptor molecules and multiple recognition.
(B) Supramolecular reactivity and catalysis.
Supramolecular Chemistry-II
transport processes and carrier design.
Supramolecular devices. Supramolecular photochemistry supramolecular electronic, ionic and switching devices.
Books Suggested
- Principals of Bioinogranic Chemistry. S.J. Lppard and J.M. Berg University Science Books.
- Bioinorganic Chemistry, I Bertini, H.B. Gray. S.J. Lippard and Jon Valentine, University Science Books.
- Inorganic Biochemistry Vols I and II Ed.
- Progress in Inorganic Chemistry Vols. 1i 18 Ed J.J. Lippard Wiley.
- Supramolecular Chemistry, J.M Lehn, New
(CH-506, Group-II)
| Duration : 3 Hrs. |
2 Hrs. or 3 Period/week |
Max. Marks : 50 |
Photoinorganic Chemistry
Unit-I
Basic of Photochemistry
Absorption, excitation, photochemical laws, quantum yield, electronically excited states-life times-measurements of the times. Flash photolysis, Energy dissipation by radiative an non-radiative processes, absorption spectra, Frank-Condon principle, photochemical stages-primary and secondary processes.
Unit-II
Properties of Excited States
Structure, dipole moment, acid-base strengths, reactivity. Photochemical kinetics-calculation of rates of radiative processes. Bimolecular deactivation-quenching.
Unit-III
Excited States of Metal Complexes
Excited states of metal complexes : Comparison with organic compounds, electronically excited states of metal complexes, charge transfer spectra, charge transfer excitations.
Unit-IV
Ligand Field Photochemistry
Photosubstitution, photooxidation and photoreduction, lability and selectivity, zero vibrational levels of ground state and excited state, energy content of excited state, zero-zero spectroscopic energy, development of the equations for redox potentials of the excited states.
Unit-V
Redox Reactions by Excited Metal Complexes
Energy transfer under conditions of weak interaction and strong interaction-examples formation; condition of the excited states to be useful as redox reactants, excited electron transfer, metal complexes as attractive condidates, (2,2-bipyridine and 1,10-phenanthroline complexes), illustration of reducing and oxidising character of Ruthenium+2 (bipyridal complex, comparsion with Fe (bipy); role of spin-orbit coupling-life time of these complexes. Application of redox processes of electronically excited states for catalytic purposes, transformation of low energy reactants into high energy products, chemical energy into light.
Unit-VI
Metal Complex Sensitizers
Metal complex sensitizer, electron relay, metal colloid systems, semiconductor supported metal or oxide systems, water photolysis, nitrogen fixation and carbon dioxide reduction.
Book Suggested
- Concepts of Inorganic Photochemistry, A.W. Adamson and P.D. Fleischauer, Wiley.
- Inorganic Photochemistry, J.Chem. Educ. vol. 60 No. 10, 1983.
- Progress in Inorganic Chemistry, Vol. 30ed. S.J. Lippard. Wiley.
- Coordination Chem. Revs. 1981, vol. 39, 121, 1231, 1975, 14, 321,; 1990 97, 313.
- Photochemistry of Coordination Compounds, V. Balzari and V. Carassiti, Academic Press.
- Elements in Inorganic Photochemistry, G.J. Ferraudi, Wiley.
(CH-507, Group-I)
| Duration : 3 Hrs. |
2 Hrs. or 3 Period/week |
Max. Marks : 50 |
Unit-I
Basics
Importance of polymers. Basic concepts : Monomers, repeat units, degree of polymerization Linear, branched and network polymers. Classification of polymers. Polymerization : condensation, addition/radical chain-ionic and co-ordination and copolymerization. Polymerization conditions and polymer reactins. Polymerization in homogeneous and heterogeneous systems.
Unit-II
Polymer Characterization
Polydispersion-average molecular weight concept. Number, weight and viscosity average molecular weights. Polydispersity an molecular weight distribution. The practical significance of molecular weight. Measurement of molecular-weights. End-group, viscosity, light scattering, osmotic and ultracentrifugation methods. Analysis and testing of polymers-chemical analysis of polymers, spectroscopic methods, X-ray diffraction study. Microscopy. Thermal analysis and physical testing-tensile strength. Fatigue, impact. Tear resistance, Hardness and abrasion resistance.
Unit-III
Inorganic Polymers
A general survey and scope of Inorganic Polymers special characteristics, classification, homo and hetero atomic polymers.
Unit-IV
Structure, Properties and Applications of
- Polymers based on boron-borazines, boranes and carboranes.
- Polymers based on Silicon, silicone's polymetalloxanes and polymetallosiloxanes, silazanes.
Unit-V
Structure, Properties and Application of
- Polymers based on Phosphorous-Phosphazenes, Polyphosphates
- Polymers based on Sulphure-Tetrasulphur tetranitride and related compounds.
Unit-VI
Structure, Properties and Applications of
- Metal clusters.
- Co-ordination and metal chelate polymers.
References :
- Inorganic Chemistry, J.E. Huheey, Harper Row.
- Developments in Inorganic polymer Chemistry, M.F. Lappert and G.J. Leigh.
- Inorganic polymers- N.H> Ray.
- Inorganic polymers, Graham and Stone.
- Inorganic Rings and Cages : D.A. Armitage.
- Textbook of Polymers Science, F.W. Billmeyer Jr. Wiley.
- Contemporary Polymer Chemistry, H.R. Al cock and F.W. Lambe, Prentice Hall.
(CH-505, Group-II)
| Duration : 3 Hrs. |
2 Hrs. or 3 Period/week |
Max. Marks : 50 |
Organic Synthesis I
Unit-I
Organometallic Reagents
Principle, preparations, properties and applications of the following in organic synthesis with mechanistic details.
Group I and II metal organic compounds
Li, Mg, Hg, Cd, Zn and Ce Compounds.
Unit-II
Transition metals.
Cu, Pd, Ni, Fe, Co, Rh, Cr, and Ti compounds.
Other elements
S, Si, B and I compounds.
Unit-III
Oxidation
Introduction, Different oxidative processes.
Hydrocarbons-alkenes, aromatic rings, saturated C-H groups (activated and unactivated)
Alcohols, diols, aldehyde's, ketones, ketals and carboxylic acids.
Amines, hydrazines, and sulphides.
Oxidations with ruthenium tetraoxide, iodobenzene diacetate and thallium. (III) Nitrate.
Unit-IV
Reduction
Introduction, Different reductive processes. Alkanes, alkenes, alkynes, and aromatic rings. Carbonyl compounds-aldehydes, ketones, acids and their derivatives. Epoxides. Nitro, nitroso, azo and oxime groups. Expoxide, Nitro, Nitroso, azo and oxime groups. Hydrogenolysis.
Unit-V
Rearrangements
General mechanistic considerations-nature of migration, migratory aptitude, memotry effects.
A detailed study of the following rearrangements. Pinacol-pinacolone, Wagner-Meerwein, Demjanov, Benzil-Benzillic acid. Favorskii, Arndt-Eister synthesis, Neber, Beckmann, Hotmann Curtius, Schmidt, Baeyer-Villiger, Shapiro reaction. Schmidt, Baeyer-Villiger. Shapiro reaction.
Unit-VI
Metallocenes, Nonbenzenoid Aromatics and Polycyclic Aromatic Compounds
General consideration. Synthesis and reactions of some representative compounds. (Tropone, tropolone, azulene, ferrocene, phenanthrene, fluorine and undone).
Books Suggested
- Modern Synthetic Reactions. H.O. House, W.A. Benjamin.
- Some Modern Methods of Organic Synthesis, w. Carruthers, Cambridge Univ. Press.
- Advanced Organic Chemistry, Reactions Mechanisms and Structure, J. March. John Wiley.
- Principles of Organic synthesis, R.O.C. Norman and J.M. Coxon, Blackie Academic & Professional.
- Advanced Organic Chemistry Part B.F.A. Carey and R.J. Sundberg Plenum Press.
- Rodd's Chemistry of Carbon Compounds. Ed. S. Coffey, Elsevier.
(CH-505, Group-I)
| Duration : 3 Hrs. |
2 Hrs. or 3 Period/week |
Max. Marks : 50 |
Organic Synthesis II
Unit-I
Disconnection Approach
An introduction to synthons and synthetic equivalents. Disconnection approach, functional group inter-conversions, the importance of the order of events in organic synthesis, one group C-X and two group C-X disconnections, chemoselectivity, reversal of polarity, cyclisation reaction, amine synthesis.
Unit-II
Protecting Groups
Principle of protection of alcohol, amine, carbonyl and carboxyl groups.
Unit-III
One Group C-C Disconnections
Alcohols and carbonyl compounds, regioselectivity, alkene synthesis, use of acetylenes and aliphatic Nitro compounds in organic synthesis.
Unit-IV
Two Group C-C Disconnections
Diels-Alder Reaction, 1,3-difunctionalised compounds, a-b- unsaturated carbonyl compounds, control in carbonyl condensations, 1,5-difunctionalised compounds. Micheal addition and Robinson annelation.
Unit-V
Ring Synthesis
Saturated heterocycles, synthesis of 3,4,5 and 6 membered rings. aromatic hetereocycles in organic synthesis.
Unit-VI
Synthesis of Some Complex Molecules
application of the above in the synthesis of following compounds : Camphor, Longifoline, Cortsone, Reserpine, Vitamin D, Juvabione, Aphidicolin and Fredericamycin A.
Books Suggested
- Designing Organic Synthesis, S. Warren. Wiley.
- Organic Synthesis-Concept, Methods and Starting Materials, J. Fuhrhop.
- Some Modern Methods of Organic Synthesis. W. carruthers, Cambridge Univ. Press.
- Modern Synthetic Reactions H.O. House, W.A Benjamin.
- Advanced Organic Chemistry : Reactions, Mechanisms and Structure, J. March. Wiley.
- Principles, of Organic Chemistry Part B. F.a. Carey and R.J. Sundberg, Plenum Press.
(CH-505, Group-II)
| Duration : 3 Hrs. |
2 Hrs. or 3 Period/week |
Max. Marks : 50 |
Heterocyclic Chemistry
Unit-I
Nomenclature of Heterocycles
Replacement and systematic nomenclature (Hantzsch-Widman system) for monocyclic fused and bridged heterocycles.
Aromatic Heterocycles
General chemical behaviour of aromatic heterocycles, classification (structural type), criteria of aromaticity (bond lengths, ring current and chemical shifts in 1H NMR-spectra. Empirical resonance energy, delocalization energy and Dewar resonance energy, diamagnetic susceptibility exaltations).
Heteroaromatic reactivity and tautomerism in aromatic heterocycles.
Unit-II
Non-aromatic Heterocycles
Strain-bond angle and torsional strains and their consequences in small ring heterocycles.
Conformatino of six-membered heterocycles with reference to molecular geometry, barrier to ring inversion, pyramidal inversino and 1,3-diaxial interactino.
Atereo-electronic effects anomeric and related effects, Attractive interactions-hydrogen bonding and intermolecular nucleophilic lectrophilic interactions.
Heterocyclic Synthesis
Princples of heterocyclic synthesis involing cyclization reactions and cycloaddition reactions.
Unit-III
Small Ring Heterocycles
Three-membered and four-membered heterocycles-synthesis and reactions of azirodines, oxiranes, thiranes, azetidines, oxetanes and thietanes.
Benzo-Fused Five-Membered Heterocycles
Synthesis and reactions including medicinal applications of benzopyrroles, bezofurans and benzothiophenes.
Unit-IV
Meso-ionic Heterocycles
General classification, chemistry of some important meso-ionic heterocycles of type-A and B and their applications.
Six-Membered Heterocycles with one Heteroatom
Synthesis and reactions of pyrylium salts and pyrones and their comparison with pyridinium & thiopyrylium salts and phridones.
Synthesis and reactions of quionlizinium and benzopyrylium salts, coumarins and chromones.
Unit-IV
Six Membered Heterocycles with Two or More Heteroatoms
Synthesis and reactions of diazones, triazines, tetrazines and thiazines.
Seven-and Large-Membered Heterocycles
Synthesis and reactions of azepines, oxepines, thiepines, diazepines thiazepines, azocines, diazocines, dioxocines and dithiocines.
Unit-VI
Heterocyclic Systems Containing P, As, Sb and B
Heterocyclic rings containing phosphorus : Introduction, nomenclature, synthesis and characteristics of 5- and 6-membered ring systemsphosphorinaes, phosphorines, phospholanes and phospholes.
Heterocyclic rings containing As and Sb : Introduction, synthesis and characteristics of 5- and 6-membered ring system.
Heterocyclic rings containing B : Introduction, synthesis reactivity and spectral characteristics of 3- 5- and 6- membered ring system.
Books Suggested :
- Heterocyclic Chemistry Vol. 1-3, R.R. Gupta, M. Kumar and V.Gupta, Springer Verlag.
- The Chemistry of Heterocycles, T. Eicher and S. Hauptmann, Thieme.
- Heterocyclic chemistry J.A. Joule, K. Mills and g.F. Smith, Chapman and Hall.
- Heterocyclic Chemistry, T.L. Gilchrist, Longman Scietific Techinal.
- Contemporary Hetrocyclic Chemistry, G,.R. Newkome and W.W. Paudler, Wiley-Inter Science.
- An Introductiion to the Heterocyclic Compounds, R.M. Acheson, Johnwiely.
- Comprehensive Heterocyclic Chemistry, A.R. Katrizky and C.W. Rees, eds. Pergamon Press.
(CH-505, Group-II)
| Duration : 3 Hrs. |
2 Hrs. or 3 Period/week |
Max. Marks : 50 |
Chemistry of Natural Products
Unit-I
Terpenoids and Carotenoids
Callsification, nomenclature, occurrence, isolation, general methods of structure determination, isoprene rule.
Structure determination, stereochemistry, biosynthesis and synthesis of the following representative molecules : Citral, Gerniol a-Terpeneol, Mentohl, Farnesol, Zingiberence, Santonin, Phytol, Abietic acid and b-Carotene.
Unit-II
Alkaloids
Definition, nomenclature and physiological action, occurrence, isolation, general methods of structure elucidation, degradation, classification based on nitrogen heteroctclic ring, role of alkaloids in plants.
Structure, stereochemistry, synthesis and biosynthesis of the following :
Ephedrine , (+)- Coniine, Nicotine, Atropine, Quinine and Morphine.
Unit-III
Steroids
Occurrence, nomenclature, basic skeleton, Diel's hydrocarbon and stereochemistry, Isolatin, Structure determination and synthesis of Cholesterol, Bile acids, Androsterone, Testosterone, Estrone, Progestrone, Aldosterone, Biosynthesis of Steroids.
Unit-IV
Plant Pigments
Occurrence, nomenclature and general methods of structure determination. Isolation and synthesis of Apigenin, Luteolin Quercetin, Myrcetin, Quercetin 3-glucoside, Vitexin, Diadzein, Buttein, Aureusin, Cyanidin-7arabinoside, Cyanidin, Hirsutidin, Biosynthesis of flavonoids: Acetate pathway and Shikimic acid pathway.
Unit-V
Prophyrins
Structure and synthesis of Haemoglobin and Chlorphyll.
Unit-VI
Prostaglandis
Occurrence, nomenclature, classification, biogenesis and physiological effects. Synthesis of PGE2 and PGF2a.
Pyrethroids and Rotennones
Synthesis and reactions of Pyrethroids and Rotenones.
(For structure educidation, emphasis is to be placed on the use of spectral parameters wherever possible).
Books Suggested
- Natural Products : Chemistry and Biological Significance, J. Mann, R.S. Davidson, J.B. Hobbs, D.V. Banthrope adn J.B. Harbome, Longman, Esses.
- Organic Chemistry : Vol. 2 1L. Finar, ELBS
- Stereoselective Synthesis : A Practical Approach, M. Norgradi, VCH.
- Rodd's Chemistry of Carbon Compounds, Ed. S. Coffey, Elsevier.
- Chemistry, Biological and Pharmacological Properties of Medicinal Plants from the Americas, Ed. Kurt Hostettmann, M.P. Gupta and A. Marston. harwood Academic Publishers.
- Introduction to Flavonoids, B.A. Bohm. Harwood Academic Publishers.
- New Trends in Natural Product chemistry, Ata-ur-Rahman and M.L. Choudhary, Harwood Academic Publishers.
- Insecteides of Natural Origin, Sukh Dev, Harwood Academic Publishers.
(CH-505, Group-III)
| Duration : 3 Hrs. |
2 Hrs. or 3 Period/week |
Max. Marks : 50 |
Analytical Chemistry
Unit-I
Introduction
Role of analytical chemistry Classification of analytical methods classical and instrumental. Types of instrumental analysis. Selecting an analytical method. Neatness and cleanliness. laboratory operations and practices. Analytical balance. Techniques of weighing, errors. Volumetric glassware cleaning and calibration of glassware. Sample Volumetric glassware cleaning and Calibratiion of glassware. Sample preparation-dissolution and decompositions. Gravimetric techniques. Selecting and handling or reagents. Laboratory notebooks. Safety in the analytical laboratory.
Unit-II
Errors and Evaluation
Definition of terms in mean and median. Precision-standard deviation, relative standard deviation. Accuracy-absolute error, relative error. Types of error in experimental data deterninate (systematic), indeterminate (or random) and gross. Sources of error and the effects upon the analytical results. Methods for reporting analytical data. Statistical evaluation of data-indeterminate errors. The uses of statistics.
Unit-III
Food analysis
Moisture, ash, crude protein, fat crude fibre, carbohydrates, calcium, potassium, sodium and phosphate. Food adulteration-common adulteratnts in food, contamination of foods stuffs. Microscopic examination of foods for adulterants. Pesticide analysis in food prodcuts. Extraction and purification of sample. HPLC. Gas chromatogrphay for organophosphates. Thin-layer chromatography for identification of chlorinated pesticides in food products.
Unit-IV
Analysis of Water Pollution
Origin of Waste water, types, water pollutants and their effects. Sources of water pollution-domestic, industrial, agriculatural soil and radioactive wastes as sources of pollution. Objectives of analysis-parameter for analysis-colour, turbidity, total solids, conductivity, acidity, alakalinity, hardness, chloride, sulphate, fluoride, silica, phosphates adn different forms of nitrogen, Heavy metal pollution-public health significance of cadmium, chromium, copper, lead, zinc, managanese, mercurry and arsenic. General survey of instrumental technique for the analysis of heavy metals in aqueous systems. Measurements of DO, BOD, and COD. Pesticides as water pollutants and analysis. Water pollution laws and standards.
Unit-V
Analysis of soil, Fuel, Body Fluids and Drugs
(a) Analysis of Soil, moisture pH total nitrogen, phosphorus, silica, lime, manesia, manganese, sulphur and alkali salts.
Fuel analysis : liquid and gas. Ultimate and proximate analysis-heating values-grading of coal. Liquid fuelss-flash point, aniline point, octane number and carbon residue. Gaseous fuels-produced gas and water gas-calcorific value.
Unit-VI
(a) Clinical Chemistry : Compositino of blood-collection and preservation of samples. Clinical analysis. Serum electrolytes, blood glucose, blood urea nirogen, uric acid, albumin, globulins, barbiturates, acid and alkaline phosphates. Immunoassy : principles of radio immunoassay (RIA) and applications. The blood gas analysis trace elements n the body.
(b) Drug analysis : Narcotics and dangerous drug. Classification of drugs. Screeing by gas and hing-layer chromatography and spectrophotometric measurements.
Book Suggested
- Analytical Chemistry, G.D. Christian, J.Wicy.
- Fundamentals o analytical Chemistry. D.A. Skoog. D.M. West and F.J. Hooler, W.B. Saunders.
- Analytical Chemistry-Principles. J.H. Kennedy. W.B. Saunders.
- Analytical Chemistry-Principles and Techniques. LG. Hargis. Prentice Hall.
- Principles of Instrumental analysis D.A. Skoog and J.L. Loary, W.B. Saunders.
- Principles of Instrumental Analysis D.A. Skoog W.B. Saunders.
- Quantitative Analysis, R.A. Day, Jr. and A.L. Underwood, Prentice Hall.
- Environmental Solution, S.M. Khopkar, Wiley Eastern.
- Basic Concepts of Analysis Chemistry, S.M. Khopkar, Wiley Eastern.
- Handbook of Instrumental Techniques for Analytical Chemistry, F. Settle, Prentice Hall.
(CH-505, Group-III)
| Duration : 3 Hrs. |
2 Hrs. or 3 Period/week |
Max. Marks : 50 |
Physical Organic Chemistry
Unit-I
concepts in Molecular Orbital (MO) and Valence Bond (VB) Theory
Introduction to Huckel molecular orbital (MO) method as a mean to explain mdoern theoretical methods. Advanced techniques in PMO and FMO theory. Molecular mechanics, semi empirical methods and abinito and density functional methods. Scope and limitations off several computational programmes.
Quanitative MO theory : Hyuckel molecular orbital (HMO - method as applied to ethene, allyl and butadiene. Qualitative MO theory ionisation potential. Electron affinities. MO energy levels. Orbital symmetry. Orbital interaction diagrams. MO of simple organic systems such as ethene, allyl, butadiene, methane and methyo group. Conjugation and hypeconjugation. Aromaticity.
Valence bodn (B) configuration mixing diagrams. Relationship between VB configuration mixing and resonance theory. Reaction profiles. Potential energy diagrams. Curve-crossing model-nature of activation barrier in chemical reactions.
Unit-II
Principles of Reactivity
Mechanistic significance of entropy, enthalphy and Gibb's free energy. Arrrhenius equation. Transition state theory. Uses of activation parameters, Hammond's postulate, Bell-Evans-Polanyi Principle. Potential energy surface model. Marcus theory of electron transfer. Reactivity and selectivity principles.
Kinetic Isotope Effect
Theory of isotope effects. Primary and secondary kinetic isotope effects. Heavy atom isotope effects. Tunneling effect. Solvent effects.
Unit-III
Structural Effects on Reactivity
Lienar free energy relationships (LFER). The Hammett equation, substitutent constants, theories sof substitutent effects. Interpretation of s-values. Reaction constantp. Deviations from Hammett equation. Dualparameter correlatins, inductive substituent constant. The Taft model, s1 and sR scales.
Solvation and Solvent Effects
Qualitative understanding of solvent-solut eeffects on reactivity. Thermodynamic measure of solvation. Effects of solvation on reaction rates and equilibria. Various empirical indexes of solvation based on physical properties, solvent-sensitive reaction rates, spectroscopic properties and scales for specific solvation. Use of solvation scales in mechanistic studies. Solvent effects from the curve-crossing model.
Unit-IV
Acids, Bases, Electrophiles, Nucleophiles and Catalysis
Acid-base dissociation, Electronic and structural effects, acidity and basicity. Acidity functions and their applicatins. hard and soft acids and bases. Nucleophilicity scales. Nucleofugacity. The a-effect. Ambivalent nucleophiles. Acid-base catalysis-specifica and general catalysis. Bronsted catalysis, Nuceophilic and electrophilic catalysis. Catalysis by noncovalent binding-micellar catalysis.
Steric and Conformation Properties
Various type of steric strain and their influence on reactivity. Steric acceleration. Molecular measurements of steric effects upon rates. Steric LFET, Conformational barrier to bond rotation-spectroscopic detection of individual conformers. Acyclic and monocyclic systems. Rotation around partial double bonds. Winstein-Holness and Curtin-Hammett principle.
Unit-V
Nucleophilic and Electrophilic Reactivity
Structural and electronic effects on SN1 and SN2 reactivity. Solvent effect Kinetic isotope effects. Intromolecular assisance. Electron transfer nature of SN2 reaction. Nucleophilicity and SN2 reactivity based on curvedcrossing mode. Relationshiop between polar and electron transfer reactions SRN1 mechanism. Electrophilic reactivity, general mechanism. Kinetic of SE2 Ar reaction. Structural effects on rates and selectivity. Curve-crossing approach to electrophilic reactivity.
Radical and Pericyclic Reactivity
Radical stability, polar influences, solvent and steric effects. A curve crossign approach to radical addition, factors effecting barrier heights in addition, regioselectivity in radical reactions.
Reactivity, specificity and periselectivity in pericyclic reactions.
Unit-VI
Supramolecular Chemistry
Properties of covalent bonds-bond length, inter-bond angles, force constant, bond and molecular dipole moments. Molecular and bond polarizability, bond dissociation enthalpy, entropy. ntermolecular forces, hydrophobic effects. Electrostatic, induction, dispersion and resonance energy, magnetic interactins, magnitude of interactioin enegy, forces between macroscopic bodies, medium effects. Hydrogen bond.
Princples of molecular association and organization as exemplified in biological macromolecules like enzymes, nucleic acids, membranes and model system like micelles and vesicles. Molecular receptors and design principles. Cryptands, cyclophanes, calixeranes, cyclodextrines. Supramolecular reactivity and catalysis. Molecular channels and trnasport processes, Molecular devices and nanotechnology.
Book Suggested :
- Molecular Mechanics, U. Burket and N.L. Allinger, ACS Monograph 177, 1982.
- Orgaic Chemists, Book of Orbitals : L. Salem and W.L. Jorgensen, Academic Press.
- Mechanism and Theory in Organic chemistry, T.H. Lowry and K.C. Richadson, Harper and Row.
- Introduction to Theoretical Organic Chemistry and Molecular Modeling.
- Physical Organic Chemistry : N.S. Isaacs, ELBS/Longman.
- Supramolecular Chemistry : Concepts and Perspective, J.M. Lehn, VCH.
- The Physical Basis of Organic Chemistry : H. Maskill, Oxford University Press.
(CH-506, Group-III)
| Duration : 3 Hrs. |
2 Hrs. or 3 Period/week |
Max. Marks : 50 |
Chemical Dynamics
Unit-I
Atmospheric Reactions
Physical structure of the atmosphere, chemical composition of the atmosphere, Kinetic and mechanism of NOx, CIOx cycles and H2+O2 reaction. Mechanism of general methane oxidation. Kinetics and mechanism of low temperature oxidation of methane. Concept of global warming.
Unit-II
(a) Oscillatory Reactions
Autocatlysis and oscilatory reactions, Kinetics and mechanism of Belousov-Zhabotinski (B-z) reactins.
(b) Enzymes and Inhibitions
Kinetics of one enzymes-Two substrate systems and their experimental characteristics.
Enzyme inhibitiors and their experimetnal characteristics.
Kinetics of enzyme inhibited reactions.
(c) Micelles catalysis and inhibition
Kinetics and mechanism of micelle catalyzed reactions (Ist order and second order) Various type of micelle cataeyzed reactions. Micelle inhibited reactions.
Unit-III
Dynamics of Gas-surface Reactions
Adsorption/desorption kinetics and transitin state theory. Dissociative adsorption and precursor state. Mechanism of Langimur's adsorption of the oxidation of carbon monoxide to carbon dioxide. True and apparent activation energies. Industrial imporance of heterogeneous catalysis.
Unit-IV
Radiation Chemistry
Radiation chemistry and photochemistry. Radiation chemistry of water and aqueous solutions. Hydrogen atom and hydroxyl radical-oxidizing and reducing conditions. Kinetics and mechanism of photochemical and photosensitized reactions (One example in each case). Stern-Volmer equation and its application. Hole-concept in the presence of semiconductor type photocatalysts. Kinetics and mechanism of electron transfer reaction in the presence of visible light. Kinetics of exchange reactions (Mathematical analysis)
Transition State
A brief aspect of statistical mechanics and transition state theory. Application in calculation of the second order rare constantfor reactions with collision for (1) and + (2) atom + molecular (3) + molecule reactions. Static solvent effects and thermodynamics formulatins. Adiabatic electron transfer reactions, energy surfaces.
Unit-V
Substitution Reactions
Substitution reactions. Classification of ligand substitution mechanism.Anation and base catalyzed kinetics of anation reactions. Aquation and acid catalyzed kinetics of aquation reactions (octahedral complexes).
Inner-sphere electron transfer reactinos and mechanism. Variaous types of inner sphere bridges, adjustment and remote attack. Linkage isomerism. Chemical and resonace mechanism. Marcus-Cross relatino in outtersphere reactions (no mathematical derivation). Its application in reactions :
Ce(IV) + Mo(CN)54- —>Ce(III) + Mo (CN)
Fe(CN) + Fe(CN) Fe(CN) + Fe(CN)
Bridged outer-sphere electron transfer mechanism.
Kinetics of reactions in the presence of cyclodextrines. Considering one full case study, Nucleophilic and electrophilci catalyst and their mode of action.
Unit-VI
Metal ion catalysis and induced Phenomena
Metal ion catalyzed reactins, their kinetics and reactino mechanism in solutions. Induced reactions, their characteristics. Mechanism of (i) Fe (II) induced oxidatin of iodine by Cr(VI).
(ii) As (III) induced oxidation of MN(II) byh chromate in acid solutions. Kinetics and mechanism of induced reactions in metal complexes (octahedral complexes of Cobalt (III) only). Kinetics of hydroformylation reaction.
Recommended Books
- Progress in Inorganic Chemistry, Vol. 30 1967.
- R. Lumry and R.W. Raymond, Electron Transer Reactions, Interscience.
- N.L. Bender, Mechanism of Homogeneous Catalysis from protein to protein, Wiley.
- A.G. Sykes, Kinetics of Inorganic reactins, Pergamon.
- S.W. Benson, Mechanism of Inorganic Reactions, Academic Press.
- Physical Chemistry Vol. 2, Ed. Prof Ya Grasimov, Mir publisher.
- Basolo and pearson, Inorganic Reactino Mechaims, Wiley.
- H. Taube, Electron Transfer Reactions, Oxford Press.
(CH-506, Group-III)
| Duration : 3 Hrs. |
2 Hrs. or 3 Period/week |
Max. Marks : 50 |
Electrochemistry
Unit-I
1. Conversion and Storage of Electrochemical Energy
Present status of energy consumption : Pollution problem. History of fuel cells, Direct energy conversion by electrochemical means. Maximum intrinsic efficiency of an electrochemical converter. Physical interpretation of the Carnot efficiency factor in electrochemical energy converters. Power outputs.
electrochemical Generators (Fuel Cells) : Hydrogen oxygen cells, Hydrogen Air cell, Hydrocarbon air cell, Alkaine fuel cell, Phosphoric and fuel cell, direct NaOH fuel cells, applications of fuel cells.
Unit-II
Electrochemical Energy Storage :
Properties of Electrochemical energy storers : Measure of battery performance, Charging and discharging of a battery, Storage Density, Energy Density.
Classical Batteries : (i) Lead Acid (ii) Nickel-Cadmium, (iii) Zinc manganese dioxide.
Modern Batteries : (i) Zinc-Air (ii) Nickel-Metal Hydride, (iii) Lithium Battery, Future Electricity storers : Storage in (i) Hydrogen, (ii) Alkali Metals, (iii) Non aqueous solutions.
Unit-III
Corrosion and Stability of Metals :
Civilization and Surface mechanism of the corrosion of the metals; Thermodynamics and the stability of metals, Potential -pH (or Pourbaix) Diaphragmsl; uses and abuses, Corrosion current and corrosion potential -Evans diagrams.
Measurement of corrosion rate : (i0 Weight Loss method, (ii) Electrochemical Method.
Inhibiting Corrosion : Cathodic and Anodic Protection. (i) Inhibition by addition of substrates to the electrolyte environment, (ii) by charging the corroding method from external source, anodic Protection, Organic inhibitors, The fuller Story Green inhibitors.
Passivation :
Structure of Passivation films, Mechanism of Passivation, Spontaneous Passivation Nature's method for stabilizing surfaces.
Unit-IV
Bioelectrochemistry :
bioelectrodics, Membrane Potentials, Simplistic theory, Modern theory, Electrical conductance in biological organism: Electronic, Protonic electrochemical mechanism of nervous systems, enzymes as electrodes.
Unit-V
Kinetic of Electrode Process :
Essentials of Electrode reaction. Current Density, Overpotential, Tafel Equation, Butler Volmer equation. Standard rate constant (K0) and Transfer coefficient (a), Exchange Current.
Irreversible Electrode processes : Criteria of irreversibility, informatino from irreversible wave.
Methods of determining kinetic parameters for quasi-rversible and irreversible waves : Koutecky's methods, Meits Israel Method, Gellings method.
Electrocatalysis :
Chemical catalysts and Electrochemical catalysts with special reference to purostates, porphyrin oxides of rare earths. Electrocatalysis in simple redox reactions, in reaction involving adsorbed species. Influence of various parameters.
Unit-VI
Potential Sweep Method :
Linear sweep Voltammetry, Cyclic Voltammetry, theory and applications. Diagnostic criteria of cycli voltammetry.
Controlled current microelectrode techniques : comparison with controlled potentials methods, chronopotentiometry, theory ad applications.
Bulk Electrolysis Methods :
Controlled potential coulometry, Controlled Coulometry, Electroorganic synthesis and its important applications. Stripping analysis : anodic and Cathodic modes, Pre electrolysis and Stripping steps, applications of Stripping Analysis.
Reference :
- Modern Electrochemistry Vol. I, IIa, Vol. IIB J'OM Bockris and A.K.N. Reddy, Plenum Publication, New York.
- Polarographic Techniques by L. Meites, Interscience.
- "Fuel Cells : Thjeir electrochemistry". McGraw Hill Book Company, New York.
- Modern Polarographic Methods by A.M. Bond, Marcell Dekker.
- Polarography and allied techniques by K. Zutshi, New age International publicatin. New Delhi.
- "Electroaalytical Chemistry by Basil H. Vessor & Galen W. ; Wiley Interscience.
- Electroanalytical Chemistry by Basil H. Vessor & alen w. ; Wiley Interscience.
- Topics in pure and Applied Chemistry, Ed. S. K. Rangrajan, SAEST Publication, Karaikudi (India)
| Duration : 18 Hrs. in three days |
Max. Marks : 200 |
Inorganic Chemistry
Preparation
Preparation of selected inorganic compounds and their study by IR, electronic spectra, Mossbauer. ESR and magnetic susceptibility measurements. Handiling of air and moisture sensitive compounds involving vacuum lines.
Selection can be made from the following :
- Sodium amide. Inorg. Synth., 1946, 2, 128.
- Synthesis and thermal analysis of group II metal oxalate hydrate. J. Chem. Ed., 1988, 65, 1024.
- Atomic absorption analysis of Mg and Ca.
- Trialkoxyboanes-IR and NMR spectra.
- PhBd2 Dichlorophenylborane - Synthesis in vacuum line.
- Preparation of Tin (IV) iodide, Tin (IV) chloride and Tin (II) iodide, Inorge, Synth., 1953, 4.119.
- Relative stability of Tin (IV) and Pb (IV). Preparation of ammonium hexachlorostannate (NH4)2 SnCl6 ammonium hexachlorophlumbate (NH4)2PbCl6.
- Hexa-bis (4,nitrophenoxy) cyclotriphosphazene.
- Synthesis of trichlorodiphenylantimony (V) hydrate. Inorg. Synths., 1985, 23, 194
- Sodium tetrathionate Na2S4O6.
- Metal complexes of dimethyl sulfoxide (IR) : CuCl2.2DMSO, PdCl2. 2DMSO, RuCl2. 4DMSO. J.Chem. Educ., 1982, 59, 57.
- Synthesis of metal acethylacetonate : Magnetic moment, IR, NMR, Inorg. Synths, 1957, 5, 130, 1963, 1, 183.
- Bromination of Cr (acac)3. J. Chem. Edu., 1986, 63, 90.
- Magnetic moment of Cu (acac)2H2O.
- Cis and Trns [Co(en)2CI2]+.
- Separation of optical isomer of cis-[Co(en)2CI2]CI.J. Chem. Soc., 1960. 4369.
- Ion exchange separation of oxidation state of vanadium. J. Chem. Educ., 1980, 57, 316; 1978, 55, 55.
- Determination of Cr (III) complexes. [Cr(H2O)6]NO3.3HO, [Cr(H2O)4Cl2]Cl.2H2O, [Cr(en)3]Cl3, Cr(acac)3. Inorg. synths., 1972, 13, 184.
- Preparation of N, N bis (salicycladehyde) ethylenedimine, salen H2. Co(Salen) J. Chem. Educ., 1977, 54, 443; 1973, 50, 670.
- Preparation of Fe(II) chloride (use it as Friedel-Craft chlorination source) J. Org. Chem., 1978, 43, 2423; J. Chem. Edu., 1984, 61, 645; 1986, 63, 361.
- Reaction of Cr(III) with a multidentate ligand; a kinetics experiment (visible spectra Cr-EDTA complex) J.A.C.S., 1953, 75, 6570.
- Preparation and use of Ferrocene. J. Chem. Edu. 1966, 43, 73; 1976, 53, 730.
- Preparation of copper glycine complex-cis and trans bis (glycinato Copper (II). J. Chem. soc. Dalton, 1979, 1901, J. Chem. Edu., 1982, 59, 1052.
- Preparation of phosphine Ph3P and its transition metal complexes.
- Any other experimetn such as conversion of p-xylene to terephtalic acid catalyzed by CoBr2 (homogeneous catalysis).
- Preparation of [Co(phenathroline-5,6 quinone)].
Spectrophotometric Determinations
- Manganese/Chromium/Vanadium in steel sample.
- Nickel/molybdenum/tungston/vanadium/uranium by extractive spectrophotometric method.
- Fluoride/nitrite/phosphate.
- Zirconium-alizarin Red-S complex : Mole-ratio method.
- Copper-Ethylene diamine complex : Slope-ratio method.
- Iron-phenanthroline complex : Job's method of continuous variations.
Flame Photometric Determinations
- Sodium and potassium when present together.
- Lithium/calsium/barium/strontium.
- Cadmium and magnesium in tap water.
Quantitative determinations of a three component mixture :
One Volumetrically and two gravimetrically
- Cu+2, Ni+2, Zn+2
- Cu+2, Ni+2, Ng+2
Chromatographic Separations
- Cadium and zinc
- Zinc and magnesium.
- Thin-layer chromatography-separation of nickel, manganeses, cobalt and zinc. Determination of Rf values.
- Separation and identification of the sugars present in the given mixture of glucose, fructorse and sucrose by paper chromatography and determination of Rf values.
Organic Chemistry
Qualitative Analysis
Separation, purification and identification of the components of a mixture of three organic compounds (three solids or two liquids and one solid or two solids and one liquid), using tc for checking the purity of the separated compounds, chemical analysis, IR, PMR and mass spectral data.
Multi-step Synthesis of Organic Compounds
The exercise should illustrate the use of organic reagents and may involve purification of the products by chromatographic techniques.
Photochemical reaction
Benzophenone -> Benzpinacol _> Benzpinacolone
Beckmann rearrangement : Benzanilide from benzene
Benzene -> Benzophenone -> Benzphenone oxime -> Benzanilide
Benzilic acid rearrangement : Benzilic acid from benzoin
Benzoin -> Benzil -> Benzilic acid
Synthesis of heterocyclic compounds
Skraup synthesis : Preparation of quinoline from aniline Fisher
Indole synthesis : Preparation of 2-phenylindole from phenylhydrazine.
Enzymatic synthesis
Enzymatic synthesis
Enzymatic reduction : reduction of ethyl acetoacetate using Baker's yeast to yield enantiomeric excess of S (+) ehtyl-3-hydroxybutanoate and determine its optical purity.
Biosynthesis of ethanol from sucrose.
Synthesis using microwave
Alkylation of diethyl malonate with benzyl chloride.
Synthesis using phase transfer catalyst.
Alkylation of diethyl malonate or ethyl acetoacetate with an alkylhalide.
Extraction of Organic Compounds from Natural Sources
- Isolation of caffeine from tea leaves.
- Isolation of casein from milk (the students are required to try some typical colour reactions of proteins).
- Isolation of lactose from milk (purity of sugar should be checked by LC and PC and Rf values reported).
- Isolation of nicotine dipicrate from tobacco.
- Isolation of cinchonine from cinchona bark.
- Isolation of piperine from black pepper.
- Isolation of lycopene from tomatoes.
- Isolation of b-carotene from carrots.
- Isolation of oleic acid from olive oil (involving the preparation of complex with urea and separation of linoleic acid).
- Isolation of eugenol from clove.
- Isolation of (+) limonine from citrus rind.
Paper Chromatography
Separation of identification of the sugars present in the given mixture of glucose, fructose and surcrose by paper chromatography and determination of Rf values.
Spectroscopy
Identification of organic compounds by the analysis of their spectral data (UV, IR, PMR, CMR & MS)
Spectrophotometric (UV/VIS) Estimations
- Amino acids
- Proteins
- Carbohydrates
- Cholesterol
- Ascorbic acid
- Aspirin
- Caffeine
Physical Chemistry
Number of hours for each experiment : 3-4 hours.
a list of experiments under different headings are given below. Typical experiments are to be selected from teach type.
Physical chemistry
Number of Hours to each experiment : 3 Hours.
A list of experiments under different headings are given below. Typical experiments are to be selected from each type.
(A) Thermodynamics
- Determination of partial molar volume of solute (e.g. KCl) and solvent in a binary mixture.
- Determination of the temperature dependence of the solubility of a compound in two solvents having similar intromolecular in tetractions (benzoic acid in water and in DMSO water mixture and calculate the partial molar heat of solution.
(B) Spectroscopy
- Determination of kPa of an indicator (e.g. methyl red) in (a) aqueous and (b) micellar media.
- Determination of stoichiometry and stability constant of Ferricisothicoyanation complex ion in solution.
- Determination of rate constant of alkaline bleaching of Malachite green and effect of ionic strength on the rate of reaction.
(C) Polarography
- Identification and estimation of metal ions such as Cd+2, Pb+2, Zn+2, and i+2 etc. polarographically.
- Study of a metal ligand complex polarographically (using Lingane's Method).
(D) Chemical Kinetics
- Determination of rate constant and formation constant of an intermediate complex in the reaction of Ce(IV) and Hypophosphorous acid at ambient temperature.
- Determination of energy and enthalpy of activation in the reaction of KMnO4 and benzyl alcohol in acid medium.
- Determination of energy of activation of and entropy of activation from a single kinetic run.
- Kinetics of an enzyme catalyzed reaction.
(E) Electronics
This lab course will have theory as well as practicals and the lectures shall be delivered during lab hours.
Basic Electronics
Notations used in the electronic circuit, study of electronic compounds and colour codes. Conversion of chemical quantities into electronic quantitles. transducer, illustration with electrodes, thermocouples and thermistors.
Passive components : Resistors, capacitors and inductors with some emphasis on solid state properties of materials. Net works of resistors. Thevenin's theorem, superposition theorem, loop analysis, RC circuits, LR Circuits, LCR circuits. Illustration of the use of circuits in NQR spectroscopy, Mossbauer spectroscopy cyclic voltammetry and in power supplied as filter circuits.
Active components
Introduction to ordinary diodes and Zener diode with some emphasis on p-n junction as a solid state property. Use of diode as rectifiers, clipping and clamping circuits. Power supplies. Transistors : An extension of p-n-p and n-p-n transistors. Characteristics of transistors, hybrid parameters; transistor circuits as amplifiers, high impedance (preamplifier) circuits. Darlinction pairs, differential amplifiers.
Operational Amplifiers
Ideal characteristics; inverter, summer, integrator, differentiator, voltage follower, illustrative use of operational amplifiers.
Introduction to Fourier transformation in instrumentation.
List of Experiments in electronics
(Do at least five experiments from this section)
- (a) To plot the diode characteristics and find its dynamic resistance and cut in voltage.
(b) To plot the characteristics of transistor used as a diode and compare the results with those of (a)
- To implement a diode dipper circuit for the given transffer characteristics and verify the
- (a) To plot the diode characteristics and find its dynamic resistance and cut in voltage.(b) To plot the characteristics of transistor used as a diode and compare the results with those of (a)
wave form.
- To implement a diode damper circuit which damps the positive peak of the input voltage to (a) Zero voltage adn (b) a given voltage. Verify the performance.
- (a) To plot the characgteristics of an NPN transistor in CE configuration.
(b) To find the h-paprameter of the transistor from the characteristics.
- (a) To plot the characteristics of an NPN transistor in CB configuration.
(b) To find the h-parameter of the transistor from the characterstics and compare it with the results of experiment No. 6.
- (a) To plot the drain and transfer chracteristics of a JEET in CS configuration.
(b) To find out the pinch off voltage, maximum drain to source saturation current and the transconductance.
- To obtain the frequency response of an RC coupled amplifier and estimate the bandwidth.
- (a) To plot the characteristics of Zener diode and find its dynamic resistance under reverse biased condition.
To use zener diode for a voltage regulation.
(i) Plot the line regulation curve.
(ii) Plot the load Regulation curve.
- (a) To vire a Half wave Rectifier circuit using diode and measure the rms voltage, de voltage and to find Riple factor
(b) To study the performance of half way and full wave doubler circuits.
- To plot the characteristics of UJT and find the peak voltage, peak current and valley voltage and use as a relaxation oscillator.
Note : A sheet containing 20 questiions/diagrams/circuits will be provided to the students to reply. These questiosn based on basic electronics will cover both theory and practicals as provided in the syllabi. They will b e of objective type for duration of 20 minutes with maximum scoring of 10 marks.
Books Suggested
- Inorganic Experimens, J. Derek Woolings, VCH.
- Microscale Inorganic Chemistry, Z. Szafran, R.M, Pike and M.M. Singh, Wiley.
- Practical Inorganic Chemistry, G. Marr and B. W. Rockett, Van Nostrad.
- The systematic Identification of Organic Compounds, R.L. Shriner and D.Y. curlin.