SEMESTER 3
AN3C09 STRUCTURAL INORGANIC CHEMISTRY
Credits: 4 Contact Lecture Hours: 72
Unit 1: Solid State Chemistry (18 Hrs)
Structure of solids: Imperfections in solids-point defects, line defects and plane defects. Structure of compounds of AX (Zinc blende, Wurtzite), AX2 (Rutile, fluorite, antifluorite), AmX2 (Nickel Arsenide), ABX3 (Perosvskite, Ilmenite). Spinels. Inverse spinel structures.
Solid state reactions-diffusion coefficient, mechanisms, vacancy diffusion, thermal decomposition of solid-Type I reactions, Type II reactions.
Phase transition in solids: classification of phase transitions-first and second order phase transitions, Martensitic transformations, order-disorder transitions and spinodal decomposition. Kinetics of phase transitions, sintering. Growing single crystals-crystal growth from solution, growth from melt and vapor deposition technique.
Unit 2: Electrical, Magnetic and Optical Properties (18 Hrs)
Kronig-Penney model, Free electron theory, Zone theory and MO theory of solids. Energy bands-conductors and non-conductors, intrinsic and extrinsic semiconductors. Electrons and holes. Mobility of charge carriers. Hall Effect. Pyroelectricity, piezo electricity and ferro electricity. Conductivity of pure metals.
Magnetic properties of transition metal oxides, garnets, spinels, ilmenites and perovskites, magnetoplumbites.
Optical properties-photoconductivity, photovoltaic effects, luminescence. Applications of optical properties
Super conductivity-Type I and Type II superconductors, Frolich diagram, Cooper pairs, theory of low temperature super conductors, junctions using superconductors, BCS theory of superconductivity (derivation not required). Super conducting cuprates – YbaCu oxide system, Meisner effect, conventional superconductors, organic superconductors, fullerenes, carbon nanotubes, high temperature superconductors.
Unit 3: Inorganic Chains and Rings (18 Hrs)
Chains – catenation, heterocatenation. Silicate minerals. Structure of silicates-common silicates, silicates containing discrete anions, silicates containing infinite chains, silicates containing sheets, framework silicates. Silicones. Zeolites-synthesis, structure and applications. Isopoly acids of vanadium, molybdenum and
tungsten. Heteropoly acids of Mo and W. Condensed phosphates-preparation, structure and applications. Phosphate esters in biological systems. Polythiazil-one dimensional conductors.
Rings-topological approach to boron hydrides, Styx numbers. Structure and bonding in borazines, ring silicates and silicones, phosphorous-nitrogen compounds, phosphazenes. Heterocyclic inorganic ring systems-structure and bonding in phosphorous-sulphur and sulphur-nitrogen compounds. Homocyclic inorganic ring systems-structure and bonding in sulphur, selenium and phosphorous compounds.
Unit 4: Inorganic Cages and Metal Clusters (9 Hrs)
Cages: synthesis, structure and bonding of cage like structures of phosphorous. Boron cage compounds-Wade Mingos Lauher rules, MNO rule, boranes, carboranes, metallacarboranes.
Metal clusters: dinuclear compounds of Re, Cu and Cr, metal-metal multiple bonding in (Re2X8)2-, trinuclear clusters, tetranuclear clusters, hexanuclear clusters. Polyatomic zintl anion and cations. Infinite metal chains.
Unit 5: Chemistry of Materials (9 Hrs)
Glasses, ceramics, composites, nanomaterials-preparative procedures. Sol-gel synthesis, glassy state-glass formers and glass modifiers, ceramic structures-mechanical properties, clay products, refractories- characterizations, properties and applications.
References
L.V. Azaroff, Introduction to Solids, Mc Graw Hill, 1984.
A.R. West, Solid State Chemistry and its Applications, Wiley-India, 2007.
D.K. Chakrabarty, Solid State Chemistry, New Age Pub., 2010.
D.M. Adams, Inorganic solids: An Introduction to Concepts in Solid State Structural Chemistry, Wiley, 1974.
C.N.R. Rao, K.J. Rao, Phase Transitions in Solids, McGraw Hill, 2010.
B.E. Douglas, D.H. McDaniel, J.J. Alexander, Concepts and Models of Inorganic Chemistry, 3rd Edn., John Wiley & sons, 2006.
A. Earnshaw, Introduction to Magnetochemistry, Academic Press, 1968.
J.E. Huheey, E.A. Keiter, R.L. Keiter, Inorganic Chemistry Principles of Structure and Reactivity, 4th Edn., Harper Collins College Pub.,1993.
F.A. Cotton, G. Wilkinson, C.A. Murillo, M. Bochmann, Advanced Inorganic Chemistry, 6th Edn., Wiley-Interscience,1999.
K.F. Purcell, J.C. Kotz, Inorganic Chemistry, Holt-Saunders, 1977.
P.C. Jain, M. Jain, Engineering Chemistry, 12th Edn., Dhanpat Rai Pub., 2006.
C.V. Agarwal, Chemistry of Engineering Materials, 9th Edn., B.S. Pub., 2006.
AN3C10 ORGANIC SYNTHESES
Credit : 4 Contact Lecture Hours: 72
Unit 1: Organic Synthesis via Oxidation and Reduction (18 Hrs)
Survey of organic reagents and reactions in organic chemistry with special reference to oxidation and reduction. Metal based and non-metal based oxidations of (a) alcohols to carbonyls (Chromium, Manganese, aluminium and DMSO based reagents) (b) alkenes to epoxides (peroxides/per acids based)-Sharpless asymmetric epoxidation, Jacobsen epoxidation, Shi epoxidation (c) alkenes to diols (Manganese and Osmium based)-Prevost reaction and Woodward modification (d) alkenes to carbonyls with bond cleavage (Manganese and lead based, ozonolysis) (e) alkenes to alcohols/carbonyls without bond cleavage-hydroboration-oxidation, Wacker oxidation, selenium/chromium based allylic oxidation (f) ketones to ester/lactones- Baeyer-Villiger oxidation.
(a) Catalytic hydrogenation (Heterogeneous: Palladium/Platinum/Rhodium and Nickel. Homogeneous: Wilkinson). (b) Metal based reductions- Birch reduction, pinacol formation, acyloin formation (c) Hydride transfer reagents from Group III and Group IV in reductions – LiAlH4, DIBAL-H, Red-Al, NaBH4 and NaCNBH3, selectrides, trialkylsilanes and trialkylstannane. Meerwein-Pondorff-Verley reduction. Baker’s yeast.
Unit 2: Modern Synthetic Methods and Reagents (18 Hrs)
Baylis-Hillman reaction, Henry reaction, Nef reaction, Kulinkovich reaction, Ritter reaction, Sakurai reaction, Tishchenko reaction, Ugi reaction, Noyori reaction. Brook rearrangement. Tebbe olefination. Metal mediated C-C and C-X coupling reactions: Heck, Stille, Suzuki, Suzuki-Miyaura, Negishi-Sonogashira, Nozaki-Hiyama, Buchwald-Hartwig, Ullmann and Glaser coupling reactions. Wohl-Ziegler reaction. Reagents such as NBS, DDQ and DCC. Gilmann reagent.
Introduction to multicomponent reactions-Click reactions.
Unit 3: Construction of Carbocyclic and Heterocyclic Ring Systems (9 Hrs)
Different approaches towards the synthesis of three, four, five and six-membered rings. Photochemical approaches for the synthesis of four membered rings-oxetanes and cyclobutanes, ketene cycloaddition (inter and intra molecular), Pauson-Khand reaction, Volhardt reaction, Bergman cyclization, Nazarov cyclization, Mitsunobu reaction, cation-olefin cyclization and radical-olefin cyclization.
Inter-conversion of ring systems (contraction and expansion)-Demjenov reaction, Reformatsky reaction. Construction of macrocyclic rings-ring closing metathesis.
Formation of heterocyclic rings: 5-membered ring heterocyclic compounds with one or more than one hetero atom like N, S or O – pyrrole, furan, thiophene, imidazole, thiazole and oxazole.
Unit 4: Protecting Group Chemistry (9 Hrs)
Protection and deprotection of hydroxy, carboxyl, carbonyl, and amino groups. Chemo and regio selective protection and deprotection. Illustration of protection and deprotection in synthesis.
Protection and deprotection in peptide synthesis: common protecting groups used in peptide synthesis, protecting groups used in solution phase and solid phase peptide synthesis (SPPS).
Functional equivalence and reactivity Umpolung. Role of trimethyl silyl group in organic synthesis.
Unit 5: Reterosynthetic Analysis (9 Hrs)
Basic principles and terminology of reterosynthesis: synthesis of aromatic compounds, one group and two group C-X disconnections, one group C-C and two group C-C disconnections.
Amine and alkene synthesis: important strategies of retrosynthesis, functional group transposition, important functional group interconversions. Enantioselective synthesis of Corey lactone, longifolene and luciferin. Umpolung equivalent – Peterson olefination, enolate formation, Ireland method.
Unit 6: Biosynthesis and Biomimetic Synthesis (9 Hrs)
Basic principles of the biosynthesis of terpenes, steroids, alkaloids, carbohydrates, proteins and nucleic acids. Biosynthesis of cholesterol, α- terpineol, morphine, glucose and phenyl alanine. Biogenesis of isoprenoids and alkaloids. Biomimetic synthesis of progesterone and spatreine.
References
M.B. Smith, Organic Synthesis, 3rd Edn., Wavefunction Inc., 2010.
F.A. Carey, R. I. Sundberg, Advanced Organic Chemistry, Part A and B, 5th Edn., Springer, 2007.
S. Warren, P. Wyatt, Organic Synthesis: The disconnection Approach, 2nd Edn., Wiley, 2008.
V.K. Ahluwalia, Oxidation in Organic Synthesis, CRC Press, 2012.
I. Ojima, Catalytic Asymmetric Synthesis, 3rd Edn., John Wiley & Sons, 2010.
W. Carruthers, I. Coldham, Modern Methods of Organic Synthesis, 4th Edn., Cambridge University Press, 2004.
J. Clayden, N. Greeves, S. Warren,P. Wothers, Organic Chemistry, Oxford University Press, 2001.
R. Noyori, Asymmetric Catalysis in Organic Synthesis, John Wiley & Sons, 1994.
L. Kuerti, B. Czako, Strategic Applications of Named Reactions in Organic Synthesis, Elsevier Academic Press, 2005.
R.O.C. Norman, J.M. Coxon, Principles of Organic Synthesis, 3rd Edn., Chapmann and Hall, 1993.
V.K. Ahluwalia, L.S. Kumar, S. Kumar, Chemistry of Natural Products, CRS Press, 2007.
AN3C11 SELECTED TOPICS IN PHYSICAL CHEMISTRY
Credit: 4 Contact Lecture Hours: 72
Unit 1: Chemical Kinetics and Catalysis (27 Hrs)
Theories of reaction rates: collision theory-steric factor, potential energy surfaces. Conventional transition state theory-Eyring equation. Comparison of the two theories. Thermodynamic formulation of the two theories. Thermodynamic formulation of the reaction rates. Significance of ΔG≠, ΔH≠ and ΔS≠. Volume of activation. Effect of pressure and volume on velocity of gas reactions.
Lindemann-Hinshelwood mechanism, qualitative idea of RRKM theory, chain reactions: free radical and chain reactions, steady state treatment, kinetics of H2-Cl2 and H2-Br2 reactions, Rice-Herzfeld mechanism, branching chains H2-O2, Semonov-Hinshelwood mechanism of explosive reactions, mechanisms of step-growth, ionic and addition polymerization, kinetics of anionic and cationic polymerization.
Fast reactions: relaxation, flow and shock methods, flash photolysis, NMR and ESR methods of studying fast reactions.
Reactions in solution: factors determining reaction rates in solutions, effect of dielectric constant and ionic strength, cage effect, Bronsted-Bjerrum equation, primary and secondary kinetic salt effect, influence of solvent on reaction rates, significance of volume of activation, linear free energy relationship, kinetic isotope effect.
Acid-base catalysis: specific and general catalysis, Skrabal diagram, Bronsted catalysis law, prototropic and protolytic mechanism with examples, acidity function.
Enzyme catalysis and its mechanism, Michelis-Menten equation, effect of pH and temperature on enzyme catalysis.
Mechanisms of heterogeneous catalysis: unimolecular and bimolecular surface reactions, mechanisms of catalyzed reactions like ammonia synthesis, Fischer-Tropsch reactions, hydrogenation of ethylene and catalytic cracking of hydrocarbons and related reactions.
Unit 2: Electrochemistry and Electromotive Force (9Hrs)
Theories of ions in solution, Drude and Nernst’s electrostriction model and Born’s model, Debye-Huckel theory, Derivation of Debye-Huckel-Onsager equation, validity of DHO equation for aqueous and non aqueous solutions, Debye-Falkenhagen effect, conductance with high potential gradients, activity and activity coefficients in electrolytic solutions, ionic strength, Debye-Huckel limiting law and its various forms, qualitative and quantitative tests of Debye-Huckel limiting equation, deviations from the DHLL.
Polarization – electrolytic polarization, dissolution and decomposition potential, concentration polarization, overvoltage, hydrogen and oxygen overvoltage, mechanism of anodic and cathodic processes (theories of overvoltage), Butler-Volmer equation for simple electron transfer reactions, transfer coefficient, exchange current density, rate constants, Tafel equation and its significance.
Unit 3: Crystallography (9 Hrs)
Methods of characterizing crystal structure, rotating crystal method, powder X-ray diffraction method, determination of structure of sodium chloride by powder method, comparison of the structures of NaCl and KCl, brief outline of single crystal X-ray diffraction and crystal growth techniques.
Structure factor: atomic scattering factor, coordinate expression for structure factor, structure by Fourier synthesis.
Liquid crystals: mesomorphic state, types, examples and applications of liquid crystals. Theories of liquid crystals. Photoconductivity of liquid crystals.
Unit 4: Surface Chemistry (9Hrs)
Different types of surfaces, thermodynamics of surfaces, Gibbs adsorption equation and its verification, surfactants and micelles, general properties of emulsions, foam structure, aerosols, surface films, surface pressure and surface potential and their measurements and interpretation. Application of low energy electron diffraction and photoelectron spectroscopy, ESCA and Auger electron spectroscopy, scanning probe microscopy, ion scattering, SEM and TEM in the study of surfaces.
Adsorption: Langmuir theory, kinetic and statistical derivation, multilayer adsorption-BET theory, Use of Langmuir and BET isotherms for surface area determination. Application of Langmuir adsorption isotherm in surface catalysed reactions, the Eley-Rideal mechanism and the Langmuir-Hinshelwood mechanism, flash desorption.
Colloids: Zeta potential, electrokinetic phenomena, sedimentation potential and streaming potential, Donnan membrane equilibrium.
Unit 5: Photochemistry (18 Hrs)
Quantum yield, chemical actinometry, excimers and exciplexes, photosensitization, chemiluminescence, bioluminescence, thermoluminescence, pulse radiolysis, hydrated electrons, photostationary state, dimerization of anthracene, ozone layer in the atmosphere.
Principle of utilization of solar energy, solar cells and their working.
Quenching of fluorescence and its kinetics, Stern-Volmer equation, concentration quenching, fluorescence and structure, delayed fluorescence, E-type and P-type,
effect of temperature on emissions, photochemistry of environment, green house effect, two photon absorption spectroscopy, lasers in photochemical kinetics.
References
J. Rajaram, J.C. Kuriakose, Kinetics and Mechanisms of Chemical Transformations, Macmillan India, 2000.
K.J. Laidler, Chemical kinetics, 3rd Edn., Harper&Row, 1987.
C. Kalidas , Chemical Kinetic Methods: Principles of Fast Reaction Techniques and Applications, New Age International, 2005.
J.W. Moore, R. G. Pearson, Kinetics and Mechanisms, John Wiley & Sons, 1981.
P.W. Atkins, Physical Chemistry, ELBS, 1994.
D.A. McQuarrie, J.D. Simon, Physiacl chemistry: A Molecular Approach, University Science Books,1997
S. Glasstone, Introduction to Electrochemistry, Biblio Bazar, 2011.
D. R. Crow, Principles and Applications of Electrochemistry, 4th Edn., S. Thornes, 1994.
B.K. Sharma, Electrochemistry, Krisna Prakashan, 1985.
L.V. Azaroff, Introduction to Solids, Mc Graw Hill, 1984.
D.K. Chakrabarty, Solid State Chemistry, New Age Pub., 2010.
A.R. West, Basic Solid State Chemistry, John Wiley & Sons, 1999.
A.W. Adamson, A.P. Gast, Physical Chemistry of Surfaces, 6th Edn., John Wiley & sons, 1997.
K.K. Rohatgi-Mukherjee, Fundamentals of photochemistry, 2nd Edn., New Age International,1986.
G. Aruldhas, Molecular structure and Spectroscopy, PHI Learning, 2007.
AN3C12 SPECTROSCOPIC METHODS IN CHEMISTRY
Credit : 3 Contact Lecture Hours: 54
Unit 1: Ultraviolet-Visible and Chirooptical Spectroscopy (9 Hrs)
Energy levels and selection rules, Woodward-Fieser and Fieser-Kuhn rules.
Influence of substituent, ring size and strain on spectral characteristics. Solvent effect, Stereochemical effect, non-conjugated interactions. Chirooptical properties-ORD, CD, octant rule, axial haloketone rule, Cotton effect.
Problems based on the above topics.
Unit 2: Infrared Spectroscopy (9 Hrs)
Fundamental vibrations, characteristic regions of the spectrum (fingerprint and functional group regions), influence of substituents, ring size, hydrogen bonding, vibrational coupling and field effect on frequency, determination of stereochemistry by IR technique.
IR spectra of C=C bonds (olefins and arenes) and C=O bonds.
Problems on spectral interpretation with examples.
Unit 3: Nuclear Magnetic Resonance Spectroscopy (18 Hrs)
Magnetic nuclei with special reference to 1H and 13C nuclei. Chemical shift and shielding/deshielding, factors affecting chemical shift, relaxation processes, chemical and magnetic non-equivalence, local diamagnetic shielding and magnetic anisotropy. 1H and 13C NMR scales.
Spin-spin splitting: AX, AX2, AX3, A2X3, AB, ABC, AMX type coupling, first order and non-first order spectra, Pascal’s triangle, coupling constant, mechanism of coupling, Karplus curve, quadrupole broadening and decoupling, diastereomeric protons, virtual coupling, long range coupling-epi, peri and bay effects. NOE. NOE and cross polarization.
Simplification non-first order spectra to first order spectra: shift reagents, spin decoupling and double resonance, off resonance decoupling. Chemical shifts and homonuclear/heteronuclear couplings. Basis of heteronuclear decoupling.
2D NMR and COSY, HOMOCOSY and HETEROCOSY
Polarization transfer. Selective Population Inversion. DEPT, INEPT and RINEPT. Sensitivity enhancement and spectral editing, MRI.
Problems on spectral interpretation with examples.
Unit 4: Mass Spectrometry (9 Hrs)
Molecular ion: ion production methods (EI). Soft ionization methods: SIMS, FAB, CA, MALDI, PD, Field Desorption Electrospray Ionization. Fragmentation patterns-nitrogen and ring rules. McLafferty rearrangement and its applications. HRMS, MS-MS, LC-MS, GC-MS.
Problems on spectral interpretation with examples.
Unit 5: Structural Elucidation Using Spectroscopic Techniques (9 Hrs)
Identification of structures of unknown organic compounds based on the data from UV-Vis, IR, 1H NMR and 13C NMR spectroscopy (HRMS data or Molar mass or molecular formula may be given).
Interpretation of the given UV-Vis, IR and NMR spectra.
References
D.L. Pavia, G.M. Lampman, G.S. Kriz, Introduction to Spectroscopy, 3rd Edn., Brooks Cole, 2000.
A.U. Rahman, M.I. Choudhary, Solving Problems with NMR Specroscopy, Academic Press, 1996.
L.D. Field, S. Sternhell, J.R. Kalman, Organic Structures from Spectra, 4th Edn., John Wiley & sons, 2007.
C.N. Banwell, E.M. McCash, Fundamentals of molecular spectroscopy, 4th Edn., Tata McGraw Hill, 1994.
D.F. Taber, Organic Spectroscopic Structure Determination: A Problem Based Learning Approach, Oxford University Press, 2007.
H. Gunther, NMR Spectroscopy, 2nd Edn., Wiley, 1995.
R.M. Silverstein, G.C. Bassler, T.C. Morril, Spectroscopic Identification of Organic Compounds, 5th Edn., Wiley, 1991.
D.H. Williams, I. Fleming, Spectroscopic Methods in Organic Chemistry, 6th Edn., McGraw-Hill, 2008.
W. Kemp, Organic Spectroscopy, 2nd Edn., Macmillan, 1987.
F. Bernath, Spectra of Atoms and Molecules, 2nd Edn., Oxford University Press, 2005.
E.B. Wilson Jr., J.C. Decius, P.C. Cross, Molecular Vibrations: The Theory of Infrared and Raman Vibrational Spectra, Dover Pub., 1980.
Online spectral databases including RIO-DB.
