M Sc Chemistry‐ Part‐I Course structure with credits Compulsory Theory courses, Semester‐I & II CHAC‐401 Spectroscopic Methods in Chemistry 4 Credits 100 marks 60 hrs CHIC‐401 General Inorganic Chemistry 4 Credits 100 marks 60 hrs CHOC‐401 Concepts in Organic Chemistry 4 Credits 100 marks 60 hrs CHPC‐401 General Physical Chemistry 4 Credits 100 marks 60 hrs Compulsory Practical Courses, Semester‐I & II CHAC‐402 Laboratory Course in Analytical 2 Credits 100 marks 60 hrs Chemistry CHIC‐402 Laboratory Course in Inorganic Chemistry 2 Credits 100 marks 60 hrs 100 marks 60 hrs CHOC‐402 Laboratory Course in Organic Chemistry 2 Credits CHPC‐402 Laboratory Course in Physical Chemistry 2 Credits 100 marks 60 hrs Optional Theory courses, Semester I & II CHAO‐401 Analytical techniques‐I 2 Credits 100 marks 30 hrs CHAO‐402 Analytical techniques‐II 2 Credits 100 marks 30 hrs CHIO‐401 Selected topics in Inorganic Chemistry 2 Credits 100 marks 30 hrs CHIO‐402 Environmental Chemistry 2 Credits 100 marks 30 hrs CHOO‐401 Concepts in Organic Chemistry ‐ II 2 Credits 100 marks 30 hrs CHOO‐402 Concepts in Organic Chemistry ‐ III 2 Credits 100 marks 30 hrs Selected topics in Physical Chemistry 2 Credits 100 marks 30 hrs CHPO‐401 CHPO‐402 Mathematical Preparations for 2 Credits 100 marks 30 hrs Chemistry and Introduction to Computers CHPO‐403 Diffraction methods 2 Credits 100 marks 30 hrs Note: 1 Nomenclature: CH‐ Chemistry; A/I/O/P (third letter)‐ branch of chemistry (Analytical/ Inorganic/ Organic /Physical); C or O (fourth letter) Core or Optional; 4 (course for 1st or 2nd Semester)‐first digit; second and third digit ( course number). 2 The Department Council shall declare which of the two (viz. Inorganic/ Organic OR Physical /Analytical etc) subjects are floated together in a given semester before the beginning of the first semester of any academic year depending upon availability of required facilities. 3 In order to get a specialization in a particular branch (viz. Inorganic/Organic/physical) the student shall have opted for all Core theory and practical courses from that branch at both part‐I & II level. 4 The weightage of marks for internal and external assessments in both theory and practical course shall be 50:50 5
6
The number shown against respective topics in the syllabus of individual courses indicate percentage weightage in terms of marks and /or time. All other criteria for passing and evaluation etc shall be as per the relevant Ordinance/ Guidelines framed by the Goa University from time to time. CHAC‐401: Spectroscopic Methods in Chemistry (4 credit, 60 hrs) SECTION‐I (50) 1. General Introduction 1.1 Characterization of Electromagnetic radiation;1.2 Quantization of Energy; 1.3 Regions of Spectrum;1.4 Atomic and Molecular Spectra.;1.5 Representation of Spectra;1.6 Basic Elements of Practical Spectroscopy;1.7 Radiation sources, monochromators;1.8 Signal‐to‐noise: Resolving Power.;1.9 Width and Intensity of Spectral Transitions;1.10 Fourier Transform Spectroscopy (Banwell & McCash ‐ Chapter 1) 2. Spectroscopic Methods in Chemistry 2.1 Interaction of Electromagnetic Radiation with Matter.;2.2 Electronic Spectra and Molecular Structure.; 2.3 Infrared Absorption and Molecular Structure; 2.4 Near‐ Infrared Spectrometry.; 2.5 Solvents for Spectrometry; 2.6 Quantitative Calculations; 2.7 Spectrometric Instrumentation.; 2.8 Spectrometric Errors in Measurements; 2.9 Deviation from Beer’s Law; 2.10 Fluorometry; 2.11 Flame Emission Spectrometry; 2.12 Distribution between Ground and Excited States‐Most Atoms Are in the Ground State;2.13 Atomic Absorption Spectrophotometry;2.14 Internal Standard and Standard Addition Calibration; Basic Principles and Introduction to Microwave, Raman and Magnetic Resonance Specroscopy (G D. Christian Chapter 14 &15; Banwell & McCash ‐ Chapter 2, 4 &7) 3. Diffraction Techniques 4.1 Crystal Structure‐ Lattices and unit cells, identification of lattice planes 4.2 X‐ ray diffraction‐ The Bragg Law, The powder method, Single‐ crystal X‐ray diffraction 4.3 Information from X‐ray analysis 4.4. Theory of XRF (P.W. Atkins Chapter 21) SECTION‐ II (50) 1. Ultraviolet and visible Spectroscopy 1.1 Theory of Electronic Spectroscopy 1.2 Chromophore and auxochrome,1.3 1.3 Instrumentation and Sampling (Demonstration of the instrument) 1.4 Applications of Electronic Spectroscopy‐ Conjugated Dienes, Trienes, polyenes, α, ß‐ unsaturated carbonyl compounds, aromatic hydrocarbons. 1.5 Stereochemical factors in Electronic Spectroscopy (Kemp ‐ Chapter 4) 2. Proton NMR Spectroscopy 2.1 Theory of NMR 2.2 Chemical shift, factors influencing chemical shift 2.3 Solvents used in NMR 2.4 Theory of spin‐ spin splitting and simple spin systems, AB, A2B3, A2B2;2.5 Factors influencing coupling constant (Kemp ‐ Chapter 3) 3. Mass Spectrometry 3.1 Basic Principles 3.2 Instrumentation 3.3 Isotope Abundances 3.4 Molecular Ion 3.5 Metastable Ions 3.6 Fragmentation Processes 3.7 Fragmentations associated with simple components like alcohols, amines, alkenes, simple aromatic and aliphatic hydrocarbons, aldehydes and ketones, halogen compounds (Kemp ‐ Chapter 5) 4. Infrared Spectroscopy 4.1 Molecular vibrations, factors influencing vibrational frequencies 4.2 Instrument‐ation and sampling techniques 4.3 Characteristic vibrational frequencies of various functional groups and frequency shifts associated with structural changes. (Kemp ‐ Chapter 2) 5. Conjoint IR‐UV/ VIS‐NMR‐Mass Spectrometry Problems Text Books 1 Fundamentals of Molecular Spectroscopy, C.N. Banwell and E. M. McCash, Tata McGraw‐Hill, New Delhi 4th Edition. 2 Organic Spectroscopy, William Kemp, Palgrave 3rd Edition Reference Books 1. Analytical Chemistry, G. D. Christian, John Wiley 5th Ed. 2. Physical Chemistry, P W. Atkins, W.H. Freeman 5th Edition 3. Spectrometric Identification of Organic Compounds, R M Silverstein, and F.X. Webster Wiley‐ India 6th Edition 4. Vogel’s Textbook of Quantitative Inorganic Analysis, J. Mendham, R.C. Denney, J.D. Barnes and M. Thomas, 6th Edition, Pearson Education Asia 2000 5. Instrumental Methods of Chemical Analysis, by G W Ewing, McGraw‐Hill (Singapore) 5th Edition 6. Analytical Chemistry:Principles, J.H. Kennedy, Saunders College Publishing, 2nd Ed 7. Instrumental Methods of Analysis, by H.H. Willard, L.L. Merritt, J.A. Dean, F.A. Settle CBS Publishing New Delhi 7th Edition 8. Spectroscopy of Organic Compounds P.S. Kalsi, New Age International 2nd Ed. 9. Organic Chemistry, R.T. Morrison and R.N. Boyd, Prentice Hall India 4rd Ed Note: The students are encouraged to refer to older or newer editions of any of the above books, if available in the library. CHIC‐401 GENERAL INORGANIC CHEMISTRY (4 credit, 60 hrs) 1. Atomic Structure, Molecular structure and bonding (25) 1.1 Atomic Structure: classification of elements: patterns and periodicity, the modern periodic table, Structure of hydrogenic atoms, atomic orbitals: many electron atoms, Atomic states and term symbols: Russell‐Saunders coupling or L‐S coupling; Atomic parameters:Atomic and ionic radii, ionisation energy, electron affinity, electronegativity (Pauling, Allred‐Rochow definition, Mulliken definition); 1.2 Molecular structure and bonding: Lewis structures, Structure and bond properties, The VSEPR Model: Walsh diagrams (tri and penta‐atomic molecules), Valence bond theory: hydrogen molecule, homonuclear diatomic molecules, polyatomic molecules, hybridisation. Molecular orbital theory: approximations of the theory (LCAO‐MO), bonding and antibonding orbitals, homonuclear and heteronuclear diatomic molecules. 2. Solid state chemistry (20) 2.1 Packing of spheres: Unit cell and description of crystal structure close packing of spheres, holes in closed‐packed structures. 2.2 Structure of Metals: polytypism, structures that are not closed packed, polymorphism of metals, atomic radii of metals, alloys 2.3 Ionic solids: Characteristic structures of ionic solids, the rationalization of structures, the energetics of ionic bonding, consequences of lattice enthalpy. 3. Molecular Symmetry (10) 3.1 Symmetry elements and symmetry operations, 3.2 equivalent symmetry elements and equivalent atoms, 3.3 symmetry point groups with examples, 3.4 point groups of very high symmetry; 3.5 systematic procedure for symmetry classification of molecules and illustrative examples, 3.6 dipole moment, optical activity and point groups 4. Coordination, organometallic and bio‐inorganic chemistry (35) 4.1 Coordination chemistry: Werner’s work, nomenclature of coordination compounds, shapes of coordination compounds, bonding in coordination compounds: valence bond theory and crystal field theory, magnetism in coordination compounds, colour of coordination compounds, reaction mechanisms in transition metal complexes in brief 4.2 Organometallic chemistry: Definitions, classification of organo‐transition metal complexes, the EAN, 18‐electron and 16‐electron rules. Synthesis, structure, bonding and important reactions of metal carbonyls, metal nitrosyls, dinitrogen and dioxygen complexes, 4.3 Bioinorganic chemistry: Metal ions in biological systems, deficiency of trace metal ions (Fe, Zn, Cu and Mn), Proteins and their functions: Heme proteins, synthetic oxygen carriers, electron transfer proteins‐cytochromes, metalloproteins as enzymes‐carboxypeptidase and Vit B12 coenzyme, chlorophyll and its use in photosynthesis. 5 Selected Inorganic compounds (10) 5.1 Compounds of boron: boranes, carboranes, borazine and its derivatives, 5.2 Compounds of phosphorus: phosphazenes, 5.3 metal‐metal clusters. Text Books: 1. Inorganic Chemistry, D. F. Shriver and P.W. Atkins, Oxford University press (1999) 2. Principles of Solid state Chemistry, H. V. Keer, New age Intl. Ltd, New Delhi (1995) 3. Basic Inorganic Chemistry, F. A. Cotton and G. Wilkinson, 3rd ed, John Wiley & sons, Singapore (1995) 4. Inorganic Chemistry: Principles of Structure and Reactivity. J. E. Huheey, E. A. Kiter, R. L. Keiter, 4th Ed, Addison‐Wesley publishing house(1993) 5. Advanced Inorganic Chemistry, F. A. Cotton and G. Wilkinson, 3rd Ed, Wiley Eatern, New Delhi (1984) 6. Concise Inorganic Chemistry, J. D. Lee, 5th Ed, Chapman and Hall (1996) Reference books 1. Theoretical Inorganic chemistry, 2nd Ed. M. C. Day and J. Selbin, Van Nostrand‐Reinhold, New York (1969) 2. Nature of chemical bond. L. Pauling, 3rd Ed, Cornell University Press (1960) 3. Solid State Chemistry and Its Applications by A. R. West, John Wiley & sons, Singapore (1987) 4. Solid state chemistry, 2nd Ed by D. K. Chakrabarty, New Age Publishers (1996) 5. Ionic crystals, lattice defects and non‐stoichiometry, N.N. Greenwood, (1968) 6. Chemical applications of group theory, F. A. Cotton, 3rd Ed,Wiley Eastern, New Delhi (1976) 7. Molecular structure and spectroscopy, G. Aruldhas, Prentice‐Hall of India, New Delhi 8. Coordination Chemistry, D. Banerjea, Tata McGraw‐Hill, New Delhi (1994) 9. Introduction to coordination chemistry, solid state and descriptive inorganic chemistry, G. Rodgers, McGraw‐Hill, Inc. (1994) 10. Elements of magnetochemistry, R. L. Datta and A. Syamal, 2nd Ed, Affiliated East‐West Press, New Delhi (1993) 11. Chemistry of the Elements, N.N. Greenwood and A. Earnshaw, Pergamon press, Exetr, Great Britain (1984) 12. Advanced Inorganic Chemistry, F. A. Cotton, G. Wilkinson, Hurillo and Bochmann, 6th Ed. Wiley Interscience (1999) CHOC‐401 Concepts in Organic Chemistry – I 4 Credits, 60 hrs 1. Molecular orbitals and delocalized chemical bonding (12) Qualitative description of Molecular orbitals of simple acyclic and monocyclic Systems, Frontier orbitals, Importance of FMOs in Organic Reactions. Conjugation, cross conjugation, resonance, hyperconjugation and tautomerism, Alternant and non‐alternant hydrocarbons, Aromaticity in benzenoid and non‐benzenoid compounds, Huckel's rule, annulenes., aromatic, non‐aromatic and antiaromatic compounds. 2. Structure & Reactivity (12) Acidity & basicity‐ different Concepts, HSAB concept & Factors affecting it, Effect of structure & medium on acid and base strength, Concept of superacids and superbases, Electrophilicity & Nucleophilicity, ambident nucleophiles & electrophiles, concepts & examples Tautomerism: Concept, Tautomeric equilibrium, Relation with isomerism; Types of tautomerism including Ring chain tautomerism and valence tautomerism, prototropic shift in different systems. 3. Stereochemistry (30) Configurational Nomenclature: R & S; D &L;E &Z; cis & trans and syn & anti nomenclature. Chirality in molecules with two and more chiral centres. Conformational analysis of open chain compounds. Erythro and threo nomenclature. Structure conformation and stereochemistry of monocyclic cycloalkanes (cyclopropane., cyclobutane, cyclopentane, cyclohexane, cycloheptane and cyclooctane) with simple 1, and 1,3 substituent. Topicity and Prostereoisomerism: Topicity of ligands and faces:, homotopic, enantiotopic and diastereotopic ligands and faces. Chemoselective., regioselective and stereoselective reactions. Stereochemistry of cis‐ and trans‐decalins, Conformation and reactivity of cyclohexane and substituted cyclohexanes. Introduction to stereochemistry of compounds containing N, S and P. 4. Reaction Mechanism: (26) Generation, structure, stability and reactivity of carbocations, carbanions, free radicals, carbenes and nitrenes; Types of mechanisms, types of reactions, thermodynamic and kinetic requirements. kinetic and thermodynamic control. The Hammond postulate and principle of microscopic reversibility, Methods of determining reaction mechanisms like 1) Identification of products, 2) Determination of the presence of intermediates (isolation, detection, trapping and addition of suspected intermediate, 3) Isotopic labeling, 4) Stereochemical evidence,, 5) Kinetic evidence and 6) Isotope effect (sufficient reactions to exemplify each method be studied) 5. Addition to Carbon‐Carbon Multiple bonds (10) Mechanism and stereochemistry of addition reactions involving electrophiles, nucleophiles and free radicals. Addition of HX (HCI, HBr, HI, HOH, R‐OH, HCI, NH3, H2SO4 etc.) and halogens like Br2 to carbon‐carbon double and triple bonds in open chain and cyclic compounds. Addition of H2 (Hydrogenation) to C‐C multiple bonds. Hydroboration‐oxidation and oxymercuration/de‐
mercuration. 6. Elimination reactions (10) The E2, E1 and E1lcB mechanisms. Orientation of the double bond, Saytzeff and Hofmann rule. Effects of changes in the substrate, base, leaving group and medium on 1) overall reactivity,2) E1l vs. E2 vs. E1cB and 3) elimination vs substitution, Mechanism and orientation in pyrolytic syn elimination (various examples involving cyclic and acyclic substrates to be studied). TEXT BOOKS : 1 . D.. Nassipuri, Stereochemistry of Organic compounds ‐ Principles and Application 2nd ed. 1994, Wiley Eastern Limited 2. E.L. Eliel, Stereochemistry of carbon compounds, Tata MacGraw Hill 3. Jerry March, Advanced Organic Chemistry Reaction, Mechanism and Structure, 4th Ed, Wiley 4. R. J. Fessenden and J. S. Fessenden, Organic Laboratory Techniques, Brookes/Cole Publishing Co. REFERENCE BOOKS: 1. I.L. Finar Stereochemistry and Chemistry of Natural products, ELBS, Longmans 2. V.M. Potapov, Stereochemistry MIR Publishers, Moscow. 3. E.S. Gould et al., Mechanism and structure in Organic Chemistry 4. F. A. Carey, Organic Chemistry 5. S.H. Pine, Organic Chemistry, 5h edno McGraw‐Hill International Edn. 6. F.A. Carey and R.J. Sundberg, Advanced Organic Chemistry By Vol.I & II. Plenum Press. 7 . Milton Hamis Carl C. Wamser, Fundamentals of Organic Reaction Mechanisms, John Wiley & Sons. Inc. 8. F.M. Menger, D.J. Goldsmith and L. Mendell, Organic Chemistry, A concise approach CHPC‐401 1.
1.1 1.2 1.3 1.4 1.5 2.
2.1 2.2 2.3 3.
3.1 3.2 3.3 4.
4.1 4.2 4.3 4.4 4.5 General Physical Chemistry (4 Credits, 60 Hrs) Thermodynamics: (26) Thermodynamic properties: Gas laws, Real gasses, Boyle temperature, State and path properties. Intensive and extensive properties. Exact and inexact differentials. Intrinsic energy, enthalpy, entropy, free energy and their relations and significances. Maxwll relations. Thermodynamic equations of state. Joule‐Thomson effect. Joule‐Thomson coefficient for van der Waals’ gas. Joule‐Thomson effect and production of low temperature, adiabatic demagnetization, Joule‐Thompson coefficient, inversion temperature. The third law of thermodynamics. Need for the third law. Nernst heat theorem. Apparent exceptions to third law. Application of third law. Use of thermodynamic functions E, H, S and G in predicting direction of chemical change, entropy and third law of thermodynamics Phase equilibria: Phase rule, Discussion of two component systems forming solid solutions with and without maximum or minimum in freezing point curve. Systems with partially miscible solid phases. Three component systems: Graphical representation. Three component liquid systems with one pair of partially miscible liquids. Influence of temperature. Systems with two pairs and three pairs of partially miscible liquids. The role of added salts. Electrochemistry: (17) EMF series, decomposition potential and overvoltage, electronegativity, basic principles, completeness of deposition, Separation with controlled potentials, constant current electrolysis, composition of electrolyte, potential buffers, physical characteristics of metal deposits. Electroplating and electroless plating, electrosynthesis. Concepts of acid‐base aqueous and non‐aqueous solvents, hard and soft acid‐base concept and applications. Chemical Kinetics: (20) General introduction to various types of order of reaction including fractional order, Comparative study of transition state and collision state theory (derivation not required). Free radical reactions, Complex reactions such as acetaldehyde decomposition and reaction between H2 and Br2, Homogeneous reactions and acid‐base catalysis Elementary enzyme reactions. Quantum Chemistry (37) Historical development of quantum theory, Principal of quantum mechanics, wave particle duality, uncertainty principles Operators, Functions, Eigen value equations Schrodinger equation, application to simple system viz. free particle, particle in one dimensional, two dimensional and three dimensional box (quantization, separation of variables, degenerate wave functions) Hydrogen like atoms, Schrodinger equation and its solutions, atomic orbital wave function and interpretation. Hückel MO theory, Secular equations, Secular determinant, delocalization energy, charge density, pi‐bond order, free valence, applications to C2H4, C3H5(radical), C4H6, C4H4, C6H6, C6H8 Reference Books: 1.
2.
3.
4.
5.
Physical Chemistry, P.W. Atkins Physical Chemistry, J.M. Castellan. Modern Electrochemistry, J.O’M. Bockris and A.K. Reddy, Plenum Publishers.. Chemical Kinetics, K.J. Laidler, Tata McGraw Hill Quantum Chemistry, Ira N. Levine. CHAC‐402 Laboratory Course in Analytical Chemistry (2 Credit, 60 hrs) 1. Calibration of apparatus and preparation of standard solutions and standardisation COLORIMETRY 2. Estimation of Iron from Pharmaceutical sample (capsule) by thiocyanate method 3. Estimation of lead/nitrate in water sample UV‐VISIBLE SPECTROPHOTOMETRY 4. Estimation of KNO3 5. Estimation of K2CrO4 6. Verification of law of additivity of absorbances (K2Cr2O7 and KMnO4) 7. Estimation of phosphoric acid in cola drinks by molybdenum blue method FLAME SPECTROPHOTOMETRY 8. Estimation of Na 9. Estimation of K or Ca THERMAL STUDIES 10. TG‐DTA and Isothermal weight loss studies of various hydrated solids like CuSO4.5H2O 11. CaC2O4.H2O 12. Fe2C2O4.2H2O VOLUMETRY 13. Estimation of Ca in pharmaceutical tablet. 14. Estimation of Al and Mg in antacid tablet ION EXCHANGE CHROMATOGRAPHY 15. Separation and Estimation of Zn and Mg 16. Separation and Estimation of chloride and bromide SOLVENT EXTRACTION 17. Extraction of Cu as copper dithiocarbamate (DTC) using solvent extraction and estimation by spectrophotometry X‐RAY POWDER DIFFRACTOMETRY 18. Calculation of lattice parameters from X‐ray powder pattern of cubic system such as NiFe2O4, NiMn2O4, CoFe2O4 etc. References 1. Analytical chemistry, G. D. Christian, 5th Ed, John Willey and Sons, 1994 2. Vogel’s Text book of Quantitative Inorganic Analysis, 6th Ed, Pearson Education, Asia, 2000. 3. Collection of interesting chemistry experiments, A. J. Elias, University press, 2002. 4. Solid State Chemistry and its Applications, A R West, john Wiley & Sons, 1987. 5. Quantitative Analysis, 6th Ed., Day & Underwood, prentice Hall, 2001. 6. Analytical Chemistry for technicians, 3rd Ed., Kenkel, Lewis publishers, 2002. CHIC‐402 LABORATORY COURSE ININORGANIC CHEMISTRY (2 credit, 60 hrs) Preparation of following Complexes 1
[Ni(NH3)6]Cl2 2
[Co(NH3)3(NO2)3]Cl3 3
[Co(NH3)6]Cl3 4
K3[Al(C2O4)3].H2O 5
K3[Cr(SCN)6].4H2O 6
K3[Cr (C2O4)3] 7
Potash alum from scrap aluminium Quantitative Estimations 8
Estimation of Ni in [Ni(NH3)6]Cl2 volumetrically/ gravimetrically 9
Estimation of Co in [Co(NH3)6]Cl3 volumetrically/ gravimetrically 10 Estimation of oxalate in K3[Al(C2O4)3].H2O 11 Estimation of oxalate in K3[Cr(C2O4)3].H2O 12 Colorimetric determination of Cr and Ni 13 Estimation of Nitrite by volumetry 14 Estimation of Calcium in Calcite ore 15 Estimation of Copper in Gun Metal alloy or Devarda’s alloy iodometrically Reference Books 1. Vogel’s Text book of quantitative chemical analysis (3rd and 4th Ed.) 2. G. Brauer, “Handbook of preparative Inorganic Chemistry”, Vol 1 and 2 CHOC‐402 Laboratory Course in Organic Chemistry 2 Credits, (60 hrs) N.B: Students should be given suitable pre‐ & post‐lab assignments & explanation covering the theoretical aspects of laboratory experiments prior to the conduct of each experiments by the concerned teacher. Each of the below mentioned experiments should be done individually by the students. 1. Laboratory Techniques a) Simple distillation : Ethanol‐water mixture using water condenser, Nitrobenzene and aniline using air condenser. b) Steam distillation : Naphthalene from its suspension in water or Clove oil from cloves or separation of o‐and p‐ nitrophenols. c) Crystallisation : Concept of induction of crystallization i) Crystallisation of phthalic acid from hot water using fluted filter paper and stemless funnel.ii) Acetanilide from boiling water iii) Naphthalene from ethanol (any one). ii) Decolorisation and crystallization of brown sugar (sucrose) with animal charcoal using gravity filtration. d) Sublimation : Simple and vacuum of camphor and succinic acid 2. Organic Synthesis (any 9 / 10 experiments). a) Aliphatic electrophilic substitution : Preparation of iodoform from ethanol & acetone. b) Aromatic electrophilic substitution : Preparation of p‐bromoacetanilide c) Oxidation : i) Benzoic acid from toluene ii) Cyclohexanone from cyclohexanol iii) Borneol to camphor using Jones reagent (any one). d) Reduction : p‐nitrophenyl methylcarbinol from p‐nitro acetophenone by NaBH4 and purification of the product through distillation under reduced pressure. e) Bromination of an alcohol using CBr4 / triphenylphosphine. f) Grignard reaction : Triphenylmethanol from benzoic acid ester or benzophenone. g) Aldol condensation : Dibenzal acetone from Benzaldehyde h) Acetoacetic ester condensation : Preparation of ethyl‐n‐butylacetoacetate or ethylacetoacetate. i) Cannizzaro reaction using 4‐chlorobenzaldehyde as substrate. j) Friedel Crafts reaction : using toluene and succinic anhydride. k) Solvent‐free preparation of coumarin by the Knoevenagel condensation under MW irradiation. Text Book: 1.
Vogel’s Textbook of Practical Organic Chemistry, A. R. Tatchell, John Wiley. Reference books 1.
Experiments and Techniques in Organic Chemiatry, D. Pasto, C. Johnson and M. Miller, Prentice Hall. 2.
Organic Experiments, K.L.Williamson, D. C. Heath. 3.
Experimental Organic Chemistry, Vol I & II, P.R.Singh, D.S.Gupta and K.S.Bajpai, Tata McGraw Hill. 4.
Laboratory Manual in Organic Chemistry, R.K.Bansal, Wiley Eastern. 5.
Green Chemistry, Samuel Delvin, IVY Publishing House, Delhi. 6.
Organic Chemistry Laboratory, O.R.Rodig, C.E.Bell Jr. and A.K.Clark, Saunders College Publishing, N.York. 7.
Organic Analytical Chemistry, Jag Mohan, Narosa Publishing House, N.Delhi. CHPC‐402: Laboratory Course in Physical Chemistry (2 Credits, 60 Hrs) 1. To study the kinetics of hydrolysis of ethyl acetate and to determine a) Energy of activation b) Entropy of activation and c) Free energy change. 2. To study the kinetics of the reaction between Potassium persulphate (K2S2O8), and Potassium iodide (KI), and to determine a) Energy of activation b) Entropy of activation and c) Free energy change. 3. To determine the order of reaction between potassium persulphate and potassium iodide by graphical, fractional change and differential methods. 4. To determine the degree of hydrolysis of salt of weak base and strong acid using conductometer. 5. To determine the composition of a mixture of acetic acid, dichloroacetic acid and hydrochloric acid by condoctometric titration. 6. To determine the dissociation constants of a dibasic acid and obtain derivative plot to get equivalence point. 7. To determine the dissociation constants of a tribasic acid (Phosporic acid) obtain derivative plot to get equivalence point. 8. To determine formal redox potential of Fe2+/Fe3+ and Ce3+/Ce4+ system obtain derivative plot to get equivalence point. 9. To study the three component system such as C6H5CH3; C2H5OH; and H2O. 10. To study the three component system such as CH3COOH; CHCl3; and H2O and obtain tie line. 11. To determine the molecular weight of high polymer (polyvinyl alcohol) by viscosity measurement. 12. To determine the molecular weight of high polymer (Polystyrene) by viscosity measurement. Reference Books: 1.
2.
3.
4.
A.Finlay and J.Akitchener, “Practical Physical Chemistry”, Longman F.Daniels and J.H.Mathews, “Experimental Physical Chemistry”, Longman. A.M.James, “Practical Physical Chemistry”, J.A.Churchil. D.P.Shoemaker and C.W.Garland, “Experimental Physical Chemistry”, McGraw‐Hill. CHAO‐401 ANALYTICAL TECHNIQUES – I (2 Credit, 30 hrs) 1. Data handling and statistical methods (35) 1.1 Accuracy and precision, 1.2 determinate and indeterminate errors, 1.3 significant figures, 1.4 rounding off, 1.5 standard deviation, 1.6 confidence limits, 1.7 tests of significance, 1.8 rejection of results, 1.9 least squares, 1.10 correlation coefficient. 2. Electroanalytical techniques (40) 1.1 Introduction to electroanalytical techniques, 1.2 electrochemical cells, electrode potentials, 1.3 potentiometric titrations, 1.4 voltametry and polarography, 1.5 cyclic voltametry, 1.6 coulometry, controlled potential coulometry and coulometric titrations, 1.7 Stripping voltammetry, 1.8 amperometric titrations, 1,9 ion‐selective electrodes and sensors. 3. Thermal techniques (25) Theory, instrumentation and applications of a) differential thermal analysis, b) thermogravimetric analysis, and c) differential scaning calorimetry Text books / References 1. Analytical chemistry, G. D. Christian, 5th Ed, John Wiley, New York (1994) 2. Fundamentals of analytical chemistry, D. A. Skoog, D. M. West and F. J. Holler, 7th Ed., Sounders College publishing (1996) 3. Principles of Instrumental analysis, F. J. Holler, D. A. Skoog, S. R. Crouch, 6th Ed. Thomson Books/Cole 4. Analytical Chemistry:Principles, J.H. Kennedy, 2nd Ed. Saunders College Publishing 5. Vogel’s Textbook of Quantitative Inorganic Analysis, J. Mendham, R.C. Denney, J.D. Barnes and M. Thomas, 6th Edition, Pearson Education Asia 2000 6. Instrumental Methods of Analysis, by H.H. Willard, L.L. Merritt, J.A. Dean, F.A. Settle CBS Publishing New Delhi 7th Edition 7. Instrumental Methods of Chemical Analysis, by G W Ewing, 5th Ed. McGraw‐Hill (Singapore) 8. Principles and Practise of Analytical Chemistry, Fifield and Kealy, 5th Ed, Blackweel Science Ltd. ,2000. CHAO‐402 ANALYTICAL TECHNIQUES – II (2 Credit, 30 hrs) 1. Chromatographic techniques (50) 1.1 Introduction to chromatographic techniques, 1.2 Ion‐exchange chromatography: theory, classification of ion exchange resins, and their properties, basic requirements of useful resin, ion exchange equilibrium and applications, 1.3 Thin layer chromatography, basic principles and applications, 1.4 electrophoresis, 1.5 Gas chromatography: theory, instrumentation, applications, problems, GC‐MS analysis. 1.6 HPLC: Theory, principles, instrumentation, applications. 2. Solvent extraction (15) 2.1 Basic principles, 2.2 efficiency of extraction classification, 2.3 extraction equilibrium, 2.4 liquid – liquid extraction, 2.5 solid liquid extraction, 2.6 applications of solvent extraction. (15) 3. Radioanalytical techniques Theory and principles of radioanalytical technique, detection of nuclear radiation, radiation detectors, pulse height analysis, counting errors, analytical applications of radioisotopes, neutron activation analysis and isotope dilution analysis 4. Analysis of food, body fluid and drugs (20) 4.1 Food adulteration‐ common adulterants in food, contamination of food stuff. 4.2 Body fluid: composition blood‐ collection and preservation of blood samples, clinical analysis, serum electrolytes, blood glucose, blood urea nitrogen, uric acid, albumin, globulins, acid and alkaline phosphatases 4.3 Drugs: narcotics and dangerous drugs, classification of drugs Text books / References 1. Analytical chemistry, G. D. Christian, 5th Ed, John Wiley, New York (1994) 2. Fundamentals of analytical chemistry, D. A. Skoog, D. M. West and F. J. Holler, 7th Ed., Sounders College publishing (1996) 3. Principles of Instrumental analysis, F. J. Holler, D. A. Skoog, S. R. Crouch, 6th Ed. Thomson Books/Cole 4. Analytical Chemistry:Principles, J.H. Kennedy, 2nd Ed. Saunders College Publishing 5. Vogel’s Textbook of Quantitative Inorganic Analysis, J. Mendham, R.C. Denney, J.D. Barnes and M. Thomas, 6th Edition, Pearson Education Asia 200 6. Instrumental Methods of Analysis, by H.H. Willard, L.L. Merritt, J.A. Dean, F.A. Settle CBS Publishing New Delhi 7th Edition 7. Instrumental Methods of Chemical Analysis, by G W Ewing, 5th Ed. McGraw‐Hill (Singapore) 8. Analytical Chemistry: Principles and Techniques, Hargis, L.G, Prentice Hall, New Jersey (1988) 9. Basic concepts of analytical chemistry, S.M. Khopkar, Willey Eastern 10. Handbook of instrumental techniques for analytical chemistry, F. Settle, Prentice hall 11. Quantitative analysis, R. A. Day, Jr. and A. L. Underwood, 6th Ed, Prentice hall, 2001. CHIO‐401 SELECTED TOPICS IN INORGANIC CHEMISTRY (2 credit, 30 hrs) 1. Chemistry of transition and inner transition elements (35) 1.1 Transition elements: metallic character, oxidation states, atomic and ionic size, colour, melting and boiling points, ionisation energy, density, magnetic properties, catalytic properties, important compounds and complexes, biological importance, difference between first row and subsequent row elements 1.2 Inner‐transition elements: Lanthanides and actinides: occurrence, properties, oxidation states, electronic structure, colour and spectra, magnetic properties, lanthanide contraction, compounds of lanthanides and actinides, separation techniques. 2. Main group elements and their compounds (35) 1.1 Carbon group: Allotropes of Carbon, C60 and compounds (fullerenes), Intercalation compounds of Graphite, Carbon nanotubes, carbides. 1.2 Compounds of silicon: silanes, silicates and silicones, Zeolites 1.3 Nitrogen group: Nitrogen activation, oxidation states of nitrogen & their interconversion PN & SN compounds 1.4 Oxygen group: metal selenides & tellurides, oxyacids & oxoanions of S & N. 1.5 Ring, Cage and Cluster compounds of P‐ block elements, 1.5 Halogen group: Interhalogens, Pseudohalogen, synthesis, properties & applications, structure, oxyacids & oxoanions of halogens, 1.6 compounds of noble gases. 3. Chemistry of selected Anions (15) 3.1 Oxide, hydroxide, alkoxide ions, polynuclear oxo anions, halogen containing anions, sulphide and hydrosulfide anions. (15) 4. Acids and Bases 4.1 Bronsted Acidity, periodic trends in Bronsted Acidity, 4.2 Lewis acidity, Systamatics of Lewis acids and bases, 4.3 heterogenous acid‐base reactions. Text books / Reference books 1. Inorganic Chemistry, D. F. Shriver and P.W. Atkins, Oxford University press (1999) 2. Inorganic Chemistry: Principles of Structure and Reactivity. J. E. Huheey, E. A. Kiter, R. L. Keiter, 4th ed, Addison‐Wesley publishing house(1993) 3. Advanced Inorganic Chemistry, F. A. Cotton and G. Wilkinson, 3rd ed, Wiley Eatern, New Delhi (1984) 4. Concise Inorganic Chemistry, J. D. Lee, 5th Ed, Chapman and Hall (1996) 5. Basic Inorganic Chemistry, F. A. Cotton and G. Wilkinson, 3rd Ed, John Wiley & sons, Singapore (1995) 6. Chemistry of the Elements, N.N. Greenwood and A. Earnshaw, Pergamon press, Exetr, Great Britain (1984) 7. Advanced Inorganic Chemistry, F. A. Cotton, G. Wilkinson, Hurillo and Bochmann, 6th Ed. Wiley Interscience (1999) CHIO‐402 ENVIRONMENTAL CHEMISTRY (2 Credit, 30 hrs) 1. Atmosphere: Structure and properties of the atmosphere, composition of atmosphere and vertical temperature behavior, lapse rate and temperature inversion. Biogeochemical cycles of C, N, S and P (in brief). (15) 2. Air Pollution : Classification of air pollutants and photochemical reactions in the atmosphere. Common air pollutants (e.g. CO, NOx, SO2, hydrocarbons and particulates) (a) sources (b) physiological and environmental effect (c) monitoring / analysis, (d) various remedial and technological measures to curb pollution. Air Quality standards. (35) 3. Water pollution : Importance of buffer and buffer index in waste water treatments. Chemical, physical and biological characteristics of water pollution, specific and non‐specific characterization of water. DO, BOD, COD, and chlorine demand, typical water treatment and waste water treatment (Municipal) (25) 4. Treatment of Industrial wastes: Electroplating industry, fertilizer industry, cement, sugar, paper & pulps and pharmaceuticals industries. Water conditioning. (15) (10) 5. Chemistry of soils: Trace and toxic elements in soil, organic pollutants in soil. Recommended Books: 1. G.W. Vanloon and S.J. Duffy, “Environmental Chemistry”, Oxford University Press (2003) 2. P. O’Neil, “Environmental Chemistry”, Blackie Academic & Professionals (2007) 3. S.E. Manahan, “Environmental Chemistry” Lewis Publisher (1994) 4. A. K. De, “Environmental Chemistry”, Wiley eastern Ltd., (1995) 5. A. C. Stern, R.W. Boubel, “Fundamentals of air pollution”, D. Bruce turner and D.L.Fox, Academic press, (1984) 6. R.A. Horne, “Chemistry of our environment”, John Wiley, N.Y. (1978). 7. C.N. Sawyer & P.J. Macarty, “Chemistry for environmental engineering, Mc. Graw Hill, (1978). 8. J. E. Zajic, “Water pollution disposal & resuse”, (Vol. 1 & 2), Marcel Dekker (1972). 9. L.L. Ciaccio, “Water and water pollution hand book”, Marcel Dekker, (1973). 10. J.C. Lamb, “Water quality and its control”, John Wiley & sons, N.Y., (1985). 11. E.D. Schroede, “Water & waste water treatment”, Mc. Graw Hill, (1977). CHOO‐401 Concepts in Organic Chemistry – II 2 Credits, 60 hrs 1. Aliphatic Nucleophilic Substitution (40) The SN2, SN1, mixed SN1 and SN2 and SET mechanisms. The neighboring group mechanism, neighboring participation by π and σ bonds, anchimeric assistance. Classical and nonclassical carbocations, phenonium ions, norbornyl system, common carbocation rearrangements. The SN1 mechanism. Nucleophilic susbstitution at an allylic, aliphatic and a vinylic carbon. Reactivity effects of substrate structure, attacking nucleophiles, leaving group and reaction medium, 2. Aliphatic Electrophilic Substitution (10 ) Bimolecular mechanisms‐ SE2 and SEi. The SE1 mechanism, electrophilic substitution accompanied by double bond shifts. Effects of substrates, leaving group and the solvent polarity on the reactivity. 3. Aromatic electrophilic & nucleophilic substitution (40) Introduction to General mechanisms involved, reactivity of arenes, product distribution. Ipso attack and orientation in benzene with more than one substituent, Friedel‐Crafts and related reactions‐ alkylation, acylation, formylationr (Vilsmeier reaction, Gattermann‐Koch reaction), Fries rearrangement and Prins reaction. Diazotization, nitrosation, nitration, sulphonation, mercuration. Introduction to SNAr, SN1, Benzyne and SRN1 mechanisms for aromatic nucleophilic substitution Ullmann reaction, Schiemann reaction, von Richter reaction, Sommelet‐Hauser rearrangement, Smiles rearrangement 4. Addition to Carbon‐Hetero Multiple Bonds (10) Mechanism of condensation reactions involving enolates‐ Aldol, Knoevenegel Claisen, Darzen , Stobbe , Perkin and Benzoin reactions. Hydrolysis of esters and amides, amminolysis of esters. TEXT BOOKS: 1. Jerry March, Advanced Organic Chemistry Reaction, Mechanism and Structure, 4th Ed, Wiley 2. P Sykes, A guidebook to mechanisms in organic chemistry, 6th Ed, Pearson Edu. 3. Clayden, Greeves, Warren and Wothers, Organic Chemistry, Oxford University Press, 2001. REFERENCE BOOKS: 1 E.S. Gould et al., Mechanism and structure in Organic Chemistry 2 F. A. Carey, Organic Chemistry 3 S.H. Pine, Organic Chemistry, 5th Ed McGraw‐Hill International Edn. 4 F.A. Carey and R.J. Sundberg, Advanced Organic Chemistry By Vol.I & II. Plenum Press. CHOO‐402 Concepts in Organic Chemistry ‐ III 2 Credits (30 hrs) Mechanism, Stereochemical aspects & applications of :‐ Oxidation reactions : (40) Oppenauer oxidation, aromatization & dehydrogenation, oxidation of hydroxyl group with Triphenylbismuth carbonate, O2/Pt catalyst, silver carbonate /celite, sodium bromate/CAN & NaOCl/CH3COOH. Chromium & Manganese compounds: oxidation of alcohols, aldehydes, C‐C double bonds & C‐H bonds in hydrocarbons. Peracids and other peroxides : Types of peracids & preparation, oxidation of C‐C double bonds in acyclic & cyclic systems, carbonyl compounds, amines & sulfides, allylic C‐H bonds & oxidation with molecular oxygen. Other methods of oxidation involving Periodic acid, Na/K metaperiodate, Lead tetraacetate, Mercuric acetate, Selenium dioxide, Ruthenium tetroxide, Osmium tetroxide, DMSO, Thallium nitrate, DDQ, Prevost’s reagent & Woodward conditions, Ozonolysis, Catalytic oxidation over Pt, Photosensitised & Palladium‐catalysed oxidation of alkenes. Reduction reactions : (32) Catalytic hydrogenation : Different Catalysts used, solvents & equipment, functional group reductions & homogeneous catalytic hydrogenation. Reductions by hydride‐transfer reagents and related reactions : MPV reduction, NaBH4, NaB(CN)H3, Trialkyl borohydrides, LAH & lithium hydridoalkoxyaluminates, mixed LAH‐AlCl3 reagents, DIBAL & Reductions with borane and dialkylboranes. Enzymatic reduction involving liver alcohol dehydrogenase/NADH & Bakers’ yeast. Other methods of reduction : Wolff‐Kishner, Raney Ni desulphurisation, di‐imide, low‐valent titanium species, trialkyltin hydrides & trialkyl silanes. Halogenation : (14) Reactions with C‐C double bonds, alcohols, carbonyl compounds, benzylic & allylic C‐H bonds & saturated compounds. Green Chemistry Concepts : (14) The need for green chemistry, Green chemistry – Innovations for a cleaner world, introduction, inception and evolution of green chemistry Text / Reference Books 1. Modern Synthetic Reactions (2nd Ed.,), Herbert O. House, W. A. Benjamin, INC. 2. Some Modern Methods of Organic Synthesis, W. Carruthers, Cambridge University Press, Cambridge. 3. Advanced Organic Chemistry, Reaction, Mechanism and Structure, Jerry March, Mc Graw Hill Int. Books Co. 4. Advanced Organic Chemistry‐ vol I & II, F. A. Carey and R. J. Sundberg, Plenum Press. 5. Green Chemistry – Environment Friendly Alternatives, Rashmi Sanghi and M. M. Srivastava (Ed.,), Narosa Publishing House, New Delhi. 6. Green Chemistry – Frontiers in Benign Chemical Synthesis and Processes, Paul T. Anastas and Tracy C. Williamson (Ed.,), Oxford University Press, Oxford. CHPO‐401: Selected Topics in Physical Chemistry (2 Credits, 30 hrs) 1. Magnetic Properties: (33) 1.1 Types of magnetism (dia, para, ferro, antiferro and ferrimagnetism), Langevin and Van Vleck theory, Magnetic susceptibility and its determination. 1.2 Magnetization curves and hysteresis, magnetic anisotropy, magnetic exchange interactions, Neel temperature, magnetic transition. 1.3 Ceramic magnetic materials. 2. Photochemistry (33) 2.1 Absorption and emission of radiation of photochemical interest (derivation of Einstein’s equation is not expected). 2.2 Jablonskii’s diagram illustrating fluorescence and phosphorescence. 2.3 Flash photolysis and lasers. 2.4 Photosensitised reactions and photosynthesis 2.5 Mechanism of chemiluminescence. 3. Polymers (17) 3.1 Types of polymers, molecular weight distributions and determination of chain length and conformation, thermodynamics of polymers 3.2 Degree of polymerization from kinetic data, mechanism of free radical and condensation polymerization 3.3 Electrically conducting polymers, applications of polymers. 4. Nanomaterials 4.1 Introduction, Chemical synthesis and methods of structural characterisation. 4.2 Areas of application, Societal health and environmental impact. (17) Reference Books: 1.
2.
3.
4.
Magnetic susceptibility, L.N. Muley, Interscience Publishers, New York 1963. Fundamentals of Photochemistry, K.K. Rohatgi‐Mukherjee, Wiely Eastern Ltd. New Delhi 1988. Polymer science, V.R. Gowarikar, V.N. Viswanathan, Wiley Eastern Ltd., New Delhi, 1993. Nanochemistry: A chemical approach to Nanomaterials, G.A. Ozin and A.C. Arsenault, RSC Publishing, Cambridge, 2005. CHPO‐402: Mathematical Preparations for Chemistry and Introduction to Computers (2 Credits, 30 Hrs) Mathematical Preparations (53) 1.1 Introduction to various functions and function plotting (exponential, logarithmic, trigonometric etc.), functions of many variables. 1.2 Basic rules of differentiation and integration, Partial differentiation, critical points of a function. 1.3 Regression methods, curve fitting. 1.4 Introduction to series, convergence and divergence, power series, Fourier series, Fourier transformations. 1.5 Complex numbers and complex functions. 1.6 Linear equations, vectors, matrices and determinants. 1.7 Numerical methods 1.7 Probability (permutations and combinations). 2. Introduction to computers 2.1 Need of computers for chemistry, brief introduction and history of computers. 2.2 Number representation and Computer arithmetic. 2.3 Programming languages (low level & high level) 2.4 Problem solving with computers, Algorithm, Flow chart and Program. (14) 3. Practical hands on experience (33) Following computational experiments may be carried out. Programming language may be chosen from BASIC/FORTRAN/C depending on availability of compiler. 3.1 To generate a mark sheet to learn various features of spreadsheets. 3.2 To generate a plot for a given function (functions such as linear, exponential, parabolic, trigonometric, exponential etc.) 3.3 To generate a derivative plot for pH‐metry and potentiometric experiments. 3.4 To write a computer program to find molar mass of a given molecular formula. 3.5 To write a computer program to obtain a slope and intercept for linear data using least square fit. 3.5 To write a computer program to obtain center of mass of given molecule and distances of atoms from center of mass. 3.6 To write a computer program to generate a table to plot data for a given function. Reference Books: 1.
2.
3.
4.
Mathematics for Science and Engineering, P.L. Alger, McGraw‐Hill, New York (1963). Principles of Mathematics, C.B. Allendoerfer and C.O. Oakley, McGraw‐Hill, New York (1963). Advance Engineering Mathematics, E. Kreyszic, Wiley‐Eastern, New Delhi (1987). Computers in chemistry, K.V. Raman, Tata McGraw‐Hill (1993). CHPO‐403: Diffraction methods (2 Credits, 30 hrs) 1. X‐Diffraction methods: (53) 1.1 Cubic and hexagonal close packing, radius ratio rule, interdependace of ionic radii and coordination, crystal geometry, lattice energy. 1.2 Types of unit cells and their characteristics. 1.3 Principles, instrumentations, scope and limitations of the methods, X‐ray scattering factors, calculations of unit cell dimensions from powder diffraction patterns of cubic, tetragonal and orthorhombic systems, reciprocal lattice concept. 1.4 X‐ray intensity calculations to decide the ionic configurations. 1.5 Fourier synthesis. 1.6 Comparison of X‐ray and neutron diffraction and applications. 1.7 Electron diffraction: Principle and practice. 2. Problem solving on X‐ray diffraction (47) 2.1 Introduction to spreadsheet based software viz. Microsoft Excel. 2.2 Development of spreadsheets for some simple test cases viz. Gaussian Curve (study of effect of standard deviation and center of Gaussian). 2.3 Development of spreadsheets for plotting trigonometric functions such as sin, cos and their linear combinations (Fourier synthesis). 2.4 Crystal structure determination I: Cubic structure. 2.5 Crystal structure determination II: Hexagonal structure. 2.6 Precise lattice parameter measurements. Reference Books: 1. Solid state Chemistry and its applications, A.R. West, John‐Wiley and Sons, Chinchester 1984. 2. X‐ray diffraction: A practical Approach, C. Suryanarayana and M. Grant, Norton Plenum Press, New York, 1998.