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SCHOOL OF CHEMICAL SCIENCES Swami Ramanand Teerth Marathwada University, Nanded-431606 Syllabus of M. Sc. First Year Chemistry (Credit System) Revised in academic year 2013-14 and to be implemented from academic year 2014-15 1 CONTENT 1. Credit System Ordinance for M. Sc. Courses in School of Chemical Sciences 2. M. Sc. First Year Chemistry Common Syllabus for following specializations running in the school i) Analytical Chemistry ii) Industrial Chemistry iii) Organic Chemistry iv) Medicinal Chemistry v) Physical Chemistry vi) Polymer Chemistry 3. Pattern for Question Papers 4. Internal Marks 2 Credit System Ordinance SCHOOL OF CHEMICAL SCIENCES SWAMI RAMANAND TEERTH MARATHWADA UNIVERSITY, NANDED (Credit–grade based performance and assessment (CGPA) System) Features of the credit system With effect from academic year 2014-2015 3 FEATURES OF THE CREDIT SYSTEM 1. Master’s degree would be of 100 credits each. 2. One credit course of theory will be of one clock hour per week running for 12 weeks. 3. Two credit course of theory will be of two clock hours per week running for 12 weeks. 4. Four credit course of theory will be of four clock hours per week running for 12 weeks 5. One credit course of practicals will consist of 4 hour of laboratory exercise for 6 weeks. 6. Two credit course of practicals will consist of 4 hour of laboratory exercise for 12 weeks. 7. Four credit course of practicals will consist of 8 hour of laboratory exercise for 12 weeks 4 Each Semester shall have 4 Theory courses, 2 Practical courses and 1 Seminar. 4 Theory Courses x 4 credits = 16 credits 2 Practical courses x 4 credits = 08 credits 1 Seminar x 1 credit 01 credit = _______________________________________________ Total = 25 credits Two Semesters X 25 Credits = 50 Credits Two Credits, One Each in Two Semesters have been allocated for seminar per paper. There shall be at least one seminar per paper. Marks out of 25 will be allotted per semester for this. One Credit = 25 Marks; Two Credits = 50 Marks. FOUR CREDITS (THEORY) = 100 Marks ______________________________________ Internal Exam External Exam (50 Marks) (50 Marks) Break up of Internal Theory Exam. (50 marks) is as follows: Test -1 Test-2 Home Assignment Total 15 15 20 50 5 Two credits (theory) = 50 marks (External Exam) Four Credits (PRACTICAL) = 100 MARKS ________________________________________ Internal Exam (50 Marks) External Exam (50 Marks) Break up of internal Practical exam.(50 marks) is as follows, Question 1 20 Question 2 Viva-voce 20 Record book 5 Total 5 50 Break up of External Practical exam.(50 marks) is as follows, Question 1 20 Question 2 Viva-voce 20 Record book Total 5 50 5 Two credits (SEMINAR) = 50 marks. Break up of Seminars (50 marks) is as follows, Semester 1 Semester 2 25 25 6 Total 50 Academic calendar showing dates of commencement and end of teaching, internal assessment test and term end examination shall be duly notified before commencement of each semester every year by the school. Credits system offers more options to the student. Credits system offer more flexibility to the student. Student can get requisite credits from the concerned school where he is mutually permitted on terms mutually agreed to complete the same and be eligible to appear for term end examination. The term end examinations however, shall be conducted by & at the school. Paper setting and assessment for a particular course would be the responsibility of the course in-charge. These activities, including preparation of the result–sheets for the students, would be coordinated by the School Examination committee comprising course In-charges and HOD under supervision of the (Director). 7 Marks obtained for each course would be converted to grade points as shown in table 1 Table 1: Conversion of marks to grades in credits system Marks obtained 100-90 89-80 79-70 69-60 59-55 54-45 44-40 39 and less 39 and less internal Grade A+ A B+ B C+ C D FC FR Grade points 10 09 08 07 06 05 04 0-FAIL BUT CONTINUE 0- FAILED ( CLEAR COURSE) A student who passes the internal tests but failed in semester Examination (External) of course shall be given FC grade. Student with FC grade in a course would be granted credits for that course but not the grade for that course. He/she shall have to clear the concerned course within 1.5 year from appearing for the first time in concerned paper, provided the number of courses with FC and FR grades together is 25% or less of the courses of that semester. Failing which he/she shall be disqualified for credits and will have to opt for other credits. Student who has failed in the internal tests of a course shall be given FR grade and shall have to (clear) the concerned course. 8 Grade points earned in each paper shall be calculated as grade points obtained (vide table 1 above) X credits for the paper. The Student Performance Index (SPI) gives weighted performance index of a semester with reference to the credits of a course. The SPI shall be calculated as follows: SPI = Total earned grade points for the semester _____________________________ Total credits for the semester. Final results: For the final results of a student Cumulative Performance Index (CPI) based on total earned credits vis a vis total earned grade points shall be calculated. The CPI shall be calculated as follows, CPI = Total earned grade points total credits i.e.100 Student will have to complete 75 compulsory credits for the concerned course, 15 elective credits in the subject concerned and 10 optional credits incorporated in the syllabus structure of respective master (PG) course. 9 Some of the elective credits and optional credits shall be chosen from elective and optional courses offered by the school of Chemical Sciences or other campus schools of the University. The school in consultation with the Dean, Faculty of Science can make changes in syallbi. CPI 9.0 8.0 7.0 6.0 5.5 4.5 4.0 0.0 - 10 8.9 7.9 6.9 5.9 5.4 4.4 3.9 FINAL GRADE A+ A B+ B C+ C D F Final mark list will only show the grade and grade points and not the marks. 10 M. Sc. First Year Chemistry Syllabus Swami Ramanand Teerth Marathwada University Nanded-431606 SCHOOL OF CHEMICAL SCIENCES M. Sc. First Year Chemistry (credit system with effect from 2014-15) Semester –I Credits CH-101 Physical Chemistry (60 lectures) 4 CH-102 Inorganic Chemistry (60 lectures) 4 CH-103 Organic Chemistry (60 lectures) 4 CH-104 Basic principles of spectroscopy (60 lectures) 4 CH-105 Laboratory Course 1 (Physical Chemistry) (60 Hrs) 4 CH-106 Laboratory Course 2 (Inorganic Chemistry) (60 Hrs) 4 CH-107 Seminar 1 Total Credits 25 Semester-II Credits CH-201 Physical Chemistry (60 lectures) 4 CH-202 Inorganic Chemistry (60 lectures) 4 CH-203 Organic Chemistry (60 lectures) 4 CH-204 Computer Applications in Chemistry (60 lectures) CH-205 Laboratory Course 3 (Organic Chemistry) (60 Hrs) 4 CH-206 Laboratory Course 4 (Analytical Chemistry) (60 Hrs) 4 CH-207 Seminar 1 Total Credits 25 11 4 SEMESTER–I CH-101: Physical Chemistry 1. (60 Lectures) Credits 4 Quantum Chemistry: (A) Introduction and applications of Schrödinger equation: Postulates of quantum mechanics, uncertainty principle, solutions of Schrödinger equation to model systems viz. particle in one dimensional box, harmonic oscillator and rigid rotor, numerical on 1D box. Home assignment: Application of Schrödinger equation to hydrogen atom. (B) Approximate Methods: The variation method, variation theorem, linear variation principle. Perturbation theory (first order and non degenerate) Home assignment: Applications of variation method and perturbation theory to the Helium atom. (C) Angular Momentum: Angular momentum, orbital and angular momentum operators, commutation relations, Eigen values and Eigen functions for angular momentum, spin antisymmetry and Pauli’s exclusion principle. Home assignment for students: Operator using ladder operators, addition of angular momentum. (D) Electronic Structure of Atoms: Electronic configuration, Russell-Saunders terms and coupling schemes, atomic states and term symbols, term separation energies of the pn configuration and dn configurations, spin-orbit coupling and Zeeman Splitting. Home assignment: Introduction to the methods of self consistent field, the virial theorem. 2. Thermodynamics (A) Classical Thermodynamics: Laws of thermodynamics, partial molar properties, partial molar free energy, chemical potential, partial molar volume, partial molar heat content, their significances, determinations of partial molar quantities, concept of 12 fugacity and determination of fugacity by graphical method, numericals. Non-ideal systems: Activity, activity coefficient, Debye-Huckel theory for activity coefficient of electrolytic solutions, determination of activity and activity coefficients, ionic strength, numerical on ionic strength and Debye-Huckel limiting law. Home assignment: Application of phase rule to three component systems, Phase Transformations. (B) Statistical Thermodynamics: Concept of distribution, thermodynamic probability and most probable distribution. Ensemble: canonical, grand canonical and micro-canonical ensembles, Partition functions: Translational, rotational, vibrational and electronic partition functions, Numerical on Partition functions. Home assignment: (a) Corresponding distribution laws, (Maxwell-Boltzmann distribution law) (b) Heat capacity behaviour of solids – chemical equilibria constant in terms of partition functions. (C) Non-equilibrium Thermodynamics: Thermodynamic criteria for non- equilibrium states, entropy production and entropy flow for different irreversible processes such as heat flow, chemical reaction. Transformation properties of fluxes and forces, principle of microscopic reversibility and Onsager’s reciprocity relations Home assignment: Irreversible thermodynamics for biological systems, coupled reactions. 3. Surface Chemistry-I Adsorption: Surface tension, capillary action, Freundlich adsorption isotherm, Langmuir adsorption isotherm, Gibbs adsorption isotherm, estimation of surface area (BET equation), surface films on liquids (Electro-kinetic phenomenon) and catalytic activity at surfaces. Home assignment: Modern techniques for investigating surfaces, Kelvin equation for vapour pressure of droplets. Books: 1) Physical Chemistry-P.W. Atkins, ELBS. 13 2) Introduction to Quantum Chemistry-A. K. Chandra, Tata McGraw Hill. 3) Quantum Chemistry-Ira N. Levine, Prentice Hall. 4) Coulson’s Valence-R. Mc Weeny ELBS. 5) Principles of Physical Chemistry-Puri, Sharma, Pathania, Vishal Publishing Co. 6) Molecular quantum mechanics, Vol. I & II, P. W. Atkins, Oxford university presss. 7) Physical Chemistry by Alberty and Silby, Jolly Wiley. 8) Statistical thermodynamics by T. L. Hill, Addison Wesley. 9) Chemical thermodynamics by F. T. Wall, W. H. Freeman & Co. CH-102: Inorganic Chemistry 1. (60 Lectures) Credits 4 Stereochemistry and Bonding in Main Group Compounds i) VSEPR Theory, Postulates, examples with its stereochemistry ii) Walsh diagrams (discussion related to BeH2, H2O, BeF2) iii) dπ- pπ bond, examples iv) Bent rule and energetics of hybridisation. v) Simple reaction of covalently bonded molecules (Atomic inversion, Berry pseudorotation, Nucleophilic displacement and free radical mechanism). 2. Reaction Mechanism of Transition Metal Complexes a) Introduction: i) Labile and Inert Complexes, ii) Kinetic aspects of valence bond and crystal field theories. b) Kinetics of octahedral substitution: i) Acid hydrolysis, factors affecting acid hydrolysis, base hydrolysis, ii) Base hydrolysis by conjugate mechanism (SN1CB), evidences in favour of conjugate base mechanism. c) Substitution reaction in square planar complexes: i) Trans effect, Theories of Trans effect (Grinberg’s polarization theory and Pi bonding theory), ii) Applications of Trans effect. ii) Mechanism of substitution reaction in square planar complexes. 14 d) Redox reactions: i)The classification of redox reactions, ii) Inner sphere mechanism and outer sphere mechanism 3. Metal – Ligand Bonding i) Limitations of Crystal field theory, Nephelauxatic effect ii) Linear Combination of atomic orbitals (LCAO), iii) Molecular orbital diagrams for homonuclear (from hydrogen to neon molecule) & heteronuclear diatomic molecules heteronuclear diatomic molecules iv) Molecular orbital theory for coordination complexes v) Ligand group orbital (LGO) with respect to octahedral (with diagrams), tetrahedral & square planar complexes (without diagrams). vi) Pi bonding in metal complexes, Explaination of pi-bonding in metal complexes by MOT (octahedral, tetrahedral and square planar complexes), vii) Evidences for Pi bond formation in metal complexes. 4. Home assignment: i)Role of metal ions in biological system (sodium, potassium, Magnesium, Calcium, Iron, Cobalt, Copper and Zinc). ii) Chemistry of hemoglobin, myglobin, vitamin B12, Chlorophyll, ferredoxins. iii) Model synthetic complexes of metals in inorganic chemistry Books: 1) Inorganic Chemistry (Principles of structure and Reactivity), 4th edition, James Huheey, Eller A. Keiter, Richard L. Keiter. Harper Collins College Publishers. 2) Selected Topics in Inorganic Chemistry. W. U. Malik, G.D. Tuli, R. D. Madan. S. Chand Publications. 3) Advanced Inorganic Chemistry Vol I. Gurdeep Raj. Goel Publishing House. 4) Principles of Inorganic Chemistry. B. R. Puri, L. R. Sharma and K. C. Kalia. Milestone Publishers & Distributors. 5) Advanced Inorganic Chemistry. Satish Kumar Agarwal & Keemti Lal. Pragati Prakashan 15 6) Advanced Inorganic Chemistry, (A comprehensive text). F.A. Cotton and G. Wilkinson, Interscience Publishers, John Wiley & Sons. 7) Inorganic Chemistry, 5th edition. Shriver and Atkins. W. H. Freeman and Company, New York. 8) Comprehensive Coordination Chemistry. Eds. G. Wilkinson, R. D. Gillars and J. A. McCleverty, Pergamon. 9) Essentials of Bio-inorganic Chemistry, Neerja Gupta and Monal Singh, Pragati Prakashan. CH-103: Organic Chemistry 1. (60 Lectures) Credits 4 Nature of Bonding in Organic Molecules a) Chemical bonding and reactivity- Chemical bond, delocalization, Conjugation, resonance, hyperconjugation, tautomerism, inductive effects, sterric effect. b) Bonding other than covalent bonding: Ionic, hydrogen bond, inclusion compounds, rotaxanes, catenanes, cyclodextrins, cryptands, fullerenes, crown ethers. c) The relation between structure and acidity and basicity d) Aromaticity: Benzenoid and non-benzenoid compounds, Huckels rule, antiaromaticity, homoaromaticity. Application to carbocyclic and heterocyclic systems, annulenes, azulenes. 2. Reaction Mechanism: structure and activity a) Elementry and simple reaction, Hamonds postulate, Molecularity, Energy profile diagram. b) Thermodynamics of the reaction, kinetic of the reaction, thermodynamic verses kinetic control of reactions, Hammett and Taft effect. c) Kinetic isotopic effects, method of determining reaction mechanism d) Structure and stability of reactive intermediates, carbenes, nitrenes, carbocations, carbanions, benzynes, ylides, enamines and free radicals. 3. Stereochemistry: a) Concept of chirality and molecular dissymmetry. 16 b) Symmetry elements and chiral centres, Prochiral relationship, homotopic, enantiotopic and disteriotopic groups and faces. c) Recemic modifications and their resolution, R and S nomenclature. Geometrical isomerism E and Z. nomenclature. d) Steriospeciffic and sterioselective reactions. e) Asymmetric synthesis, optical activity in absence of chiralcarbaon, biphenyl, allenes and spiranes, Chirality due to helical shape. f) Conformational analysis: Cyclohexane (mono and disubstituted i.e. halo, hydroxyl and methyl) and decallins, stability and reactivity. 4. Substitution Reactions: A. Aliphatic Nucleophilic: a) Types of Aliphatic nucleophilic substitution Reactions-SN1, SN2, SET mechanism, b) NGP by pi and sigma bonds, classical and non-classical carbocations, phenonium ions, norbornyl system, carbocation rearrangement in NGP, SNi mechanism, c) effect of structure, nucleophile, leaving group, solvent on rate of SN1 and SN2 reactions, ambident nucleophile, Phase transfer catalysis and regioselectivity. B. Aliphatic Electrophilic: a) Types of Aliphatic electrophilic substitution reaction: SE1, SE2, SEi. b) Electrophilic substitution accompanied by double bond shift. c) Effect of substrate, leaving group and solvent polarity on the reactivity. 5. Free Radical Reaction: a) Generation, charectrization and stability of free radicals. b) Free radical mechanism, NGP in free radical reactions. c) Reactivity for aliphatic and aromatic substrate at bridge head. d) Hundsdiecker reaction. 6. Home assignment: Anomeric effect, angle strain and its effect on reactivity, effect of conjugation on reactivity, stereochemistry of compounds containing N, P and S, confirmation of acyclic 17 molecules, isotopes in labelling experiments, Reed reaction, Diazo transfer reaction, esterification and ester hydrolysis. Hard and soft acid bases concept. Beckman reaarengment, rearrengment fragmentation of free radical reaction. Books: 1) Advanced organic chemistry-Reaction mechanism and structure, Jerry March, Jhon Wiley. 2) Structure and mechanism in organic chemistry, C. K. Ingold, Cornell University Press. 3) Advanced organic chemistry, F. A. Carey and R. J. Sundberg, Plenum. 4) A guide book to mechanism in organic chemistry, Peter Sykes, Longman. 5) Stereochemistry of organic compounds, D. Nasipuri, New Age International. 6) Reaction mechanism in organic chemistry, S. M. Mukherji and S. P. Singh, Macmilan. 7) Modern organic reactions , R. O. C. Norman and J. M. Coxon, Blackie Academic and Professional. 8) Organic chemistry, R. T. Morison Boyd, Prentice-Hall. 9) Stereochemistry of organic compounds, P. S. Kalsi, New Age Intrenational. 10) Modern organic reactions, H. O. House, Benjamin. CH-104: Basic Principals of Spectroscopy 1. (60 Lectures) Credits 4 Unifying Principles: Characterization of electromagnetic radiation, quantitation of energy, regions of the spectrum, interaction of radiation with molecular systems, typyes of molecular energies, factors affecting width and intensity of spectral lines, selection rule, general discussion on various molecular excitation processes. 2. Microwave spectroscopy: Classification of molecules according to their moment of inertia, rigid rotor model, effect of isotopic substitution on the transition frequencies, stark effect, non-rigid rotor, selection rules, mechanism of interaction, spectra of symmetric and asymmetric top molecules, applications of microwave spectroscopy. 3. Infrared spectroscopy: Review of linear harmonic ascillator, vibrational energies of diatomic molecules, zero point energy, force constant and band strengths, anharmonicity, morse potential energy diagram, vibration rotation spectroscopy, PQR branches, Breakdown of oppenheimer approximation, vibrations of polyatomic 18 molecules, selection rules, normal modes of vibrations, overtones, hot bands, fingerprint region, functional group identification. 4. Raman spectroscopy: Classical and quantum theory, Raman effect, Stokes and antistokes liner, Pure rotational, vibrational and rotation-vibration Raman spectra, selection rules, mutual exclusion principles. 5. Electronic spectroscopy: Beer-Lambert law, molar extinction coefficient, oscillator strength and intensity of electronic transition, Frank-Candan Principles, ground and first excited electronic states of diatomic molecule, radiative and non-radiative decay, internal conversion, intersystem crossing, fluorescence and phosphorescence, chromophore and qunochrome, types of electronic transitions in organic molecules. 6. Photoelectron spectroscopy: Basic principles, photoelectric effect, ionization process, koopman’s theory, photoelectron spectra of simple molecules, ESCA, chemical information from ESCA. 7. Electron spin resonance spectroscopy: Basic principles, zero field splitting, Kramer’s degeneracy, factors affecting ‘g’ value, hyperfine coupling phenomenon, representation of ESR spectra, Applications of ESR in chemical analysis. 8. Mossbauer Spectroscopy: The mossbauer effect, Principle, Mossbauer nuclei, spectral line width, chemical isomer shift, quadrupole splitting, magnetic hyperfine interaction, measurement techniques, elucidation of electronic structure of 119 Sn and 151 57 Fe, Eu complexes using mossbauer data, Doppler shift and recoilless fraction. 9. Home assignment: Books: 1. C. N. Banwell, Fundamentals of molecular spectroscopy. CH-105: Laboratory Course–1 (Physical Chemistry); (60 Hrs) Credit 4 Section-A: Instrumentation (any eight) 1. To determine velocity constant and energy of activation for saponification of ethyl acetate by NaOH conductometrically. 19 2. To determine the relative strength of chloroacetic acid and acetic acid by conductometrically. 3. To determine equivalent conductivity of strong electrolyte at several concentrations and to verify Onsager’s equation. 4. To determine the solubility and solubility product of sparingly soluble salt, [BaSO4/PbSO4] at different temperatures by conductometry. 5. To determine potentiometrically pK1 and pK2 values of H3PO4. 6. To determine Hammette constant of given substituted benzoic acid using pH-meter. 7. To determine pH values of various mixtures of sodium acetate and acetic acid in aqueous solution and hence find out dissociation constant of acid. 8. To determine concentration of Cu (II) ion in given solution titrating with EDTA solution by calorimetry. 9. To determine the relative strength of two acids by polarometry. 10. To study the variation of refractive index with composition of mixtures of CCl4 and ethyl acetate. Section-B: Non Instrumental (any eight) 1. To determine partial molar volume of ethanol and water mixture at given composition. 2. To determine molecular weight of high polymer by viscosity measurements. 3. To study the effect of surfactant on surface tension of water by using stalagmometer. 4. To determine the viscosity of mixtures by Ostwald’s viscometer. 5. To determine the solubility of benzoic acid at different temperature and hence to determine its heat of solution. 6. To construct the phase diagram of three component system. [CHCl3, CH3COOH and H2O] 7. Investigate the autocatalytic reaction between KMnO4 and oxalic acid. 8. To determine the rate constant of hydrolysis of ester [catalyzed by NaOH/HCl] 9. To investigate the adsorption of (oxalic acid/acetic acid) by activated charcoal and to test the validity of Freundlich and Langmuir isotherm. 10. To study the surface tension concentration relationship for the solution. 20 CH-106: Laboratory Course-2 (Inorganic Chemistry) (60 Hrs) Credits 4 Minimum 16 experiments should be completed 1-4. Basic Principles underlying Inorganic Chemistry Practicals, Laboratory safety & Chemical Hazards: 1) Basic concepts regarding preparation of normal, molar, and percentage solutions. 2) Theoretical principles underlying qualitative analysis of inorganic mixtures. 3) Preparations of reagents & solutions required for semimicro qualitative analysis. 4) Information about Laboratory safety and chemical hazards 5-10. Qualitative analysis of inorganic mixtures (Detection of three acidic radicals and three basic radicals) (6 mixtures) 11-16. Preparation of complexes (any six) (Relevant information about spectral, magnetic properties & applications should be collected & provided to the students at least wherever possible) (i) Vanadium acetylacetonate VO(acac)3 (ii) Manganese acetylacetonate Mn(acac)3 (iii) Potassium trioxalato ferrate(III) K3[Fe(C2O4)3] (iv) Hexammine nickel(II) chloride [Ni(NH3)6Cl2] (v) Hexammine Cobalt(III) Chloride [Co(NH3)6Cl3 ] (vi) Tetrammine Copper(II) sulphate [Cu(NH3)4SO4] (vii) Cis-Potassium dioxalatodiaquochromate Cis-K[Cr(C2O4)2(H2O)2] (viii) Chloropentammine cobalt(III) chloride [Co((NH3)5Cl)Cl2] (ix) Mercury(II) tetrathiocyanatocobaltate(II) [HgCo(SCN)4] IMPORTANT NOTES: 1. Each theory course is of 60 lectures out of which 15 lectures should be given for internal tests, seminars, home assignments / tutorials and discussion for answer books of internal tests. 2. Practical should be carried out on micro scale. 3. Each practical course should be given eight hours of laboratory work per week. 21 SEMESTER – II CH-201: Physical Chemistry 1. (60 Lectures) Credits 4 Surface Chemistry-II Micelles: Surface active agents, classification of surface active agents, micellisation, hydrophobic interaction, critical miceller concentration (CMC), factors affecting CMC of surfactants. Home assignment: Solubilisation, micro emulsion reverse micelles, thermodynamics of micellisation-phase separation and mass action models. Macromolecules: Polymers, classification of polymers, electrically conducting, fire resistant polymers, kinetics of polymerization, mechanism of polymerization, molecular mass, number and mass average molecular mass, molecular mass determination by osmometry, viscometry and light scattering methods, numericals. Home assignment: Sedimentation, chain configuration of macromolecules, calculation of average dimensions of various chain structures, proteins and nucleic acids. 2. Electrochemistry Electrochemistry of solutions: Debye-Huckel-Onsager treatment, ion solvent interactions, thermodynamics of electrified interface, Lippmann equation, over potential, exchange current density, derivation of Butler-Volmer equation, Tafel plot, quantum aspects of charge transfer at electrodes-solution interfaces, tunnelling. Semiconductor/electrolyte interface: Theory of double layer at semiconductor/electrolyte interface, structure of double layer interface, flatband potential, effect of light at semiconductor solution interface. Polarography: Principle and theory of polarography, Ilkovic equation, diffusion current and half wave potential and their significance. Numericals on Ilkovic equation and half wave potential. Corrosion: Introduction to corrosion, corrosion monitoring and prevention methods. Home assignment: a) Structure of electrolyte interfaces: Guoy-Chapman, Stern, Graham-Devanathan-Mottwatts, Tobin, Bockris, Devanathan models. b) Electrocatalysis–influences of various parameters, hydrogen electrode. c) Bioelectrochemistry, threshold membrane phenomena, Nernst-Planck equation. 22 d) Intrinsic and extrinsic semiconductors, p-type, n-type semiconductors. 3. Chemical Kinetics Order and molecularity of reaction, theories of reaction rates: collision theory of reaction rates, steric factor, activated complex theory, Arrhenius equation, reactions in solution: diffusion controlled reactions, ionic reactions and kinetic salt effect, steady state approximation, kinetics of complex reactions: dynamics of chain reactions (hydrogenbromine reaction, pyrolysis of acetaldehyde), photochemical (hydrogen-bromine and hydrogen-chlorine reactions). Kinetic and thermodynamic control of reactions, Homogeneous catalysis: acid base and enzyme kinetics, Michaelis-Menten equation, Fast reactions: study of fast reaction by flow methods, flash photolysis and nuclear magnetic resonance method. Dynamics of unimolecular reactions: Lindemann theory of unimolecular reactions. Numericals on rate constant, order of reaction and Arrhenius equation. Home assignment: (a) Steady state kinetics, treatment of unimolecular reactions. (b) Dynamics and molecular motions, probing the transition reactions, kinetic salt effects. Potential energy surfaces, dynamic chain (hydrogen-bromine reaction, pyrolysis state, and dynamics of barrierless chemical reactions in solution. (c) Dynamics of unimolecular reactions (Lindemann-Hinshelwood theory, Rice-Ramsperger-Kassel-Marcus [RRKM] theory of unimolecular reactions). Books: 1) Physical Chemistry-P. W. Atkins, ELBS. 2) Introduction to Quantum Chemistry-A. K. Chandra, Tata McGraw Hill. 3) Quantum Chemistry-Ira N. Levine, Prentice Hall. 4) Coulson’s Valence-R. Mc Weeny ELBS. 5) Chemical Kinetics-K. J. Laidler, McGraw Hill. 6) Kinetics and Mechanism of Chemical Transformations-J. Rajaraman and J. Kuriacose, Macmillan. 7) Principles of Physical Chemistry-Puri, Sharma, Pathania, Vishal Publishing Co. 8) Micelles, Theoretical and Applied Aspects-V. Moroi, Plenum. 23 9) Modern Electrochemistry Vol. I & II, J. O. M. Bockris & A. K. N. Reddy, Plenum. 10) Introduction to Polymer Science-V. R. Gowarikar, N, V. Vishwanathan & J. Sridhar, Wiley Eastern. 11) Physical chemistry of macromolecules, S. F. Sun, John-Wiley and Sons, INC. CH-202: Inorganic Chemistry 1. (60 Lectures) Credits 4 Electronic Spectra and Magnetic Properties of Transition Metal Complexes: a)Introduction, Coupling of orbital angular momentum, coupling spin angular momentum, Spin-orbit Coupling, Coupling Schemes (Russel Saunders and j-j Coupling). b) Term Symbol, Hund’s Rules for determination of ground state term symbol, Microstates, Prediction of ground state term symbol for different configurations of transition metals, Hole formulation, Racah Parameters. c) Effect of Weak Octahedral and tetrahedral crystal field potential on terms, Orgel diagrams (d1-d9 configuration) and Tanabe-sugano diagrams (d2 & d6 configuration). d) Selection rules, Charge Transfer Spectra, Applications of Orgel diagrams to electronic spectra of transition metal aqua complexes. e) Calculations of Dq , B and β parameters (Graphical method and Konig’s Numerical method). f) Prediction of Magnetic moment values of certain transition ions (d1- d9 with various oxidation states and various ligands), Anomalous magnetic moments, spin crossover. 2. Metal π – Complexes: a) Carbonyl complexes: i) Introduction, Classification of carbonyl complexes ii) Preparation, properties & structures of mono, di, & trinuclear carbonyl complexes [V(CO)6, Cr(CO)6, Ni(CO)4, Fe(CO)5, Mn2(CO)10, Co2(CO)8, Fe2(CO)9, Fe3(CO)12] iii) EAN rule and 18 electron rule for metal carbonyls, Numericals. iv) Bonding in metal carbonyls 24 b) Nitrosyl Complexes: i) Introduction, ii) Linear v/s Bent nitrosyl, iii) Preparation, properties, structure & applications of Sodium nitroprusside, iv) Brown ring compound c) Dioxygen and Dinitrogen complexes 3. Boranes, Carboranes and Metal Clusters: (a) Boranes & Carboranes i) Introduction, Classification & nomenclature of boranes. ii) Preparation, Properties and Structure of B2H6, B4H10 and B5H11 iii) Introduction & Classification of Carboranes. iv) Chemistry of C2B10H12 (Di-carbacloso-dodecacarborane) v) Wade’s rules for prediction of structure type in boranes & carboranes vi) styx code (determination of styx code for B2H6, B4H10, B5H11, B10H14, B6H10 by drawing their structures) (b) Metal clusters: i) Introduction, Classification of metal clusters ii) Structures of Carbonyl Clusters (LNCC and HNCC) iii) Structural aspects of Halide type Clusters (Di, tri, tetra & hexanuclear clusters) iv) Cheverel phases and Zintl ions v) Total electron count in HNCC, Numericals. 4. Home assignment: i) Metal deficiency and diseases ii) Gold complexes with anti-arthritic, antitumor and anti-HIV activity iii) Vanadium compounds in diabetes 25 Books: 1) Selected Topics in Inorganic Chemistry. W. U. Malik, G.D. Tuli, R. D. Madan. S. Chand Publications. 2) Inorganic Chemistry (Principles of structure and Reactivity). James Huheey, Eller A. Keiter, Richard L. Keiter. Harper Collins College Publishers. 3) Chemistry of the elements, 2nd edition. N. N. Greenwood and A. Earnshaw. Pergamon. 4) Inorganic Electronic Spectroscopy, A.B.P. Lever, Elsevier. 5) Magnetochemistry, R.L. Carlin, Springer Verlag. 6) Principles of Inorganic Chemistry. B. R. Puri, L. R. Sharma and K. C. Kalia. Milestone Publishers & Distributors. 7) Advanced Inorganic Chemistry. Satish Kumar Agarwal & Keemti Lal. Pragati Prakashan 8) Advanced Inorganic Chemistry, (A comprehensive text). F.A. Cotton and G. Wilkinson, Interscience Publishers, John Wiley & Sons. 9) Inorganic Chemistry, 5th edition. Shriver and Atkins. W. H. Freeman and Company, New York. 10) Advanced Inorganic Chemistry Vol II. Gurdeep Raj. Goel Publishing House. 11) Use of inorganic Chemistry in Medicine, Edited by Nicholas P. Farrell, Royal Society of Chemistry Publications. CH-203 : Organic Chemistry 1. (60 Lectures) Credits 4 Aromatic Substitution Reaction: A. Aromatic Electrophilic Substitution: Introduction, the arenium ion mechanism, orientation and reactivity. Energy Profile diagram, steric effect and the ortho/para rati, ipso attack, introduction of a third group into benzene ring, Electropihilic substitution in polycyclic and heterocyclic ring system. Some important name reactions: Diazonium coupling, Vilsmeieier-Haack reaction, Bischler Nepieralski reaction, Gatterman-koch reaction. A. Aromatic Nucleophilic Substitution: SN1, SN2 SNAr and SRN1 mechanism. Aromatic nucleophilic substitution via benzyne intermediate. Factor affecting reactivity in aromatic nucleophilic substitution reaction. 26 Some important name reactions: ChiChibabin reaction, Somlet Houser and Smiles rearrangement. 2. Addition to Carbon-Carbon Multiple Bonds. 1. Electrophilic addition to C-C double bond. 2. Mechanism and stereochemical aspects of addition reaction involving electrophile, nucleophile and free radicals. 3. Regio and chemo selectivity, orientation and reactivity, conjugate addition. 4. Addition to cyclopropane, hydroboration, Micheal reaction, Sharpless asymmetric epoxidation, hydroxylation of alkene-diol formation 3. Addition to Carbon-Heteroatom Multiple Bonds: 1. Some general and steriochemical aspect of addition to carbonyl compounds 2. Mechanism and stereochemistry of metal hydride reduction. 3. Addition of organo metallic compounds to carbon-heteromultiple bond (organo zinc, organo copper, organo lithium, reagents to carbonyl and unsaturated carbonyl compounds). 4. Some important name reactions: Wittig reaction, Knoevenagel, Claisen, Mannich, Perkin and stobbe condensation. 4. Elimination Reactions: 1. The E1, E2 and E1cB mechanisms. Orientation in Elimination reactions. 2. Hofman versus Saytzeff elimination, Pyrolytic syn-elimination. 3. Competition between substitution and elimination reactions. 4. Reactivity: effects of substrate structures, attacking base, the leaving group, the nature of medium on elimination reactions. Pyrolytic elimination reactions. 5. Pericyclic Reactions: 1. Molecular orbital symmetry, Frontier orbitals of ethelene, 1,3-butadien, 1,3,5hexatiene and allyl system. 2. Classification of pericyclic reactions 27 3. Woodward-Hoffmann correlation diagram, FMO and PMO approaches. 4. Electrocyclic reaction: conrotatory and disrotatary motion, 4n, 4n+2 and allyl system. 5. Cycloadditions: Superafacial and antrafacial addition, 4n and 4n+2 system, 2+2 addition of ketenes, 1,3 dipolar cycloaddition and chelotropic reaction. 6. Sigmatropic reaarengments: Superafacial and antrafacial shifts of H, sigmatropic shifts involving carbon moieties, 3,3 and 5,5 sigmatroic rearrengments. 7. Some important pericyclic reactions: Claisen, Cope and aza-cope rearrengments. 6. Home Assignment: 1. Electrophilic metallation, Hoesch reaction, Arenechromium carbonyl complexes, VonRichter rearrangement. 2. Birch reduction, hydrogenation of double and triple bond, addition of carbine (methylene), catalytic hydrogenation. 3. Amine catalysed condensation reaction, silanes, Reformatsky reaction, Dieckmann condensation. 4. Problems on pyrolytic syn elimination Ei elimination. 5. Problems on sigmatrophic reactions, chelotropic reactions, The Ene reactions, FMO approach and PMO approach. Books: 1. Advanced organic chemistry-Reaction mechanism and structure, Jerry March, Jhon Wiley. 2. Structure and mechanism in organic chemistry, C. K. Ingold, Cornell University Press. 3. Advanced organic chemistry, F. A. Carey and R. J. Sundberg, Plenum. 4. A guide book to mechanism in organic chemistry, Peter Sykes, Longman. 5. Stereochemistry of organic compounds, D. Nasipuri, New Age International. 6. Modern organic reactions, R. O. C. Norman and J. M. Coxon, Blackie Academic and Professional. 7. Organic chemistry, R. T. Morison Boyd, Prentice-Hall. 8. Organic reactions and their mechanism, P. S. Kalsi, New Age Intrenational. 9. Modern organic reactions, H. O. House, Benjamin. 10. Pericyclic reactions, S. M. Mukherji, Macmilan, India. 28 CH-204: Computer Applications in Chemistry A. (60 Lectures) Credits 4 MS-Office Introduction to MS-word: 1. Starting word, Title bar, Tool bars, The Ruler, Scroll bars, The menu bar, the status bar, wizards and templates. 2. Basic text editing, adding text, deleting text, undo and redo, selecting text and perform options, moving and copying text. 3. Formatting : Character formatting, adding bold, italic or underlining with the toolbar, font dialog box, select case, paragraph formatting adding borders and shading setting page margins, numbering pages. 4. Searching and proofreading tools: Find and replace, searching for special character, choosing custom dictionary, checking grammer, thesaurus. 5. Word file management: What is file management, creating folders, deleting files and folders printing . 6. Working with tables and columns: Creating table, using table tools, changing column widths with qutofit, merging cells, Formatting, changing the border and line styles, sorting tables, copying tables, deleting tables. 7. Introduction to MS-Excel: Spreadsheet overview, starting excel creating spreadsheet, excel menus, working with text and numbers: spreadsheets and numbers, spreadsheets and text, finding numbers and text, working with formulas and functions introduction, using basic formulas; using basic and advance functions, Formatting: Types of formatting, using borders, colors and patterns, conditional format using styles, printing spreadsheets and workbooks, Creating and formatting charts: Introduction to charts, creating charts, formatting charts, exploring charts, Introduction to MS-Power point: Applications of powerpoint, study of various power-point presentations, applying various designs to slides, creating presentations including image. B. Introduction to Programming in C 1. Introduction: History of C language Variables and constants Key words I/O statements in C. 29 Data types and operator, 2. Control structures: while, for) 3. string goto statement. Introduction to Array one dimensional and multi-dimensional string manipulation functions (strlen, strcpy, strcmp). standard (Library) function 4. Functions: 5. Structure and union: structure switch, l Looping statements (while, do – break and continue statements Array and strings : array if, if –else, nested if user defined functions Introduction to structure Array of structure structure within introduction to union. Books 1. Let Us C: Yeshwant Kanitkar CH-205: Laboratory Course – 3 (Organic Chemistry) (60 Hrs) Credits 4 Preparation Estimations A) Qualitative analysis (Separation of binary mixture) (any 8) 1. Separation, purification and identification of compounds from binary mixture solid-solid, solid-liquid and liquid-liquid mixtures are to be given for separation. Chemical methods (no ether), ether separation as well as physical methods are used for separation of mixtures. 2. Not more than one gram of each solid and 3 ml of each liquid should be used for preparing mixtures. Following list of mixtures is given for guidance or any other combination of mixture may be given. Separation by chemical methods (no ether) 1. Benzoic acid + Acetanilide 2. β-Naphthol + Aniline 3. α-Naphthyl amine + Urea 4. Salicyolic acid + p-Taluidine Ether separation 5. Salicyclic acid + Phthalic acid 6. Sulphonilic acid + Cinnamic acid 30 7. Oxalic acid + p-Nitroaniline 8. Oxalic acid + m-Dithiobenzene Low boiling liquids 9. Acetone + Nitrobenzene 10. Ethylacetate + p-Cresol High boiling liquids 11. O-Cresol + Nitrobenzene 12. m-cresol + p-Dichlorobenzene 3. Purity of recrystalized compounds should be checked by TLC. 4. Quality and quantity of the compounds and purity should be shown to the teacher / examiner. B. Organic synthesis (any 8 should be carried out on microscale using 10 mmol of starting material) 1. Synthesis of 4-chloro toluene from p-toluidine (Sandmayer reaction) 2. Synthesis of triphenyl methanol from benzoic acid. 3. Synthesis of Dibenzylacetone from benzaldehyde (Aldol-condensation) 4. Preparation of p-nitro/p-bromo-aniline from acetanilide. 5. Synthesis of 7-hydroxy coumarin from resorcinol. 6. Synthesis of 2,4-dihydroxy benzaldehyde from salicyaldehyde. 7. Synthesis of 2,4-dihydroxy acetophenone from recercinol. 8. Preparation of 1,2,4-tri-acetoxy benzene from hydroquinone 9. Synthesis of p-methoxy acetophenone from anisole. 10. Fries rearrangement of phenyl acetate to o/p-hydroxy acetophenone. 11. Synthesis of C. Quantitative analysis (any four) 1. Determination of iodine and saponification values of an oil sample. 2. Estimation of nitro group by reduction. 3. Estimation of glucose by iodination. 4. Estimation of –COOH group. -benzoil propionic acid from succinic anhydride. 31 5. Estimation of CONH2 group 6. Estimation of –COOR group CH-206: Laboratory Course-4 (Analytical Chemistry) (60 Hrs) Credits 4 Minimum 16 experiments should be completed Error analysis and statistical analysis: (1) (a) Determination of relative error and percentage relative error for the experimental data (b) Calculation of mean derivation and standard derivation for the experimental data (c) Application of‘t’ test for experimental data. (2) (a) Application of rejection criteria (‘Q’ test) for experimental data. (b) Treatment of analytical data with least square method applied to Beer’s law for KMnO4 solutions. Chromatography: (3) Separation of cations and anions by paper chromatography and determination of their Rf values (4) Determination of ion-exchange capacity of an cation exchanger and anion exchanger. Conductometry: (5) Determination of the strength of strong acid and weak acid from mixture solution conductometrically. (6) Analysis of aspirin by conductometric method. pH metry: (7) Acid-base titration in non-aqueous media by pH-metry (benzoic acid in ethanol/NaOH). (8) Determination pKa of weak acid by pH metry. (9) Determination of degree of dissociation of weak electrolyte and to study the deviation from ideal behaviour that occurs with a strong electrolyte. Colorimetry: (10) Verification of Beer’s law of (a) KMnO4 and Cu+2 ammonia complex solution. (11) Determination of empirical formula for the formation of ferric salicylate complex by Job’s method. (12) Determination of stability constant for the formation of complex between Fe+3 ions and 5-sulphosalicylic acid. Polarimetry: (13) Determination of rate constant for inversion of cane sugar by Polarimetry. (14) Study of inversion of cane sugar by enzyme kinetics. 32 Potentiometry: (15) Determination of the strength of halides in the given mixture using potentiometry. Kinetics: (16) To study the kinetics of iodination of acetone. Flame photometry: (17) Estimation of Na+/K+ by flame photometry (18) Determination of hardness of water by complexometric titration. IMPORTANT NOTES: 1. Each theory course is of 60 lectures out of which 15 lectures should be given for internal tests, seminars, home assignments / tutorials and discussion for answer books of internal tests. 2. Practical should be carried out on micro scale. 3. Each practical course should be given eight hours of laboratory work per week. 33 Pattern for Question Papers QUESTION PAPER PATTERN FOR 50 MARKS THEORY PAPER IMPORTANT NOTES: 1) Attempt any five questions out of seven. 2) All questions carry equal marks i.e. ten marks each. Q.1: Explain the following (3 + 3 + 4 = 10 marks). Q.2: Attempt the following questions (3 + 3 + 4 = 10 marks). Q.3: Attempt the following questions (3 + 3 + 4 = 10 marks). Q.4: Attempt the following questions (3 + 3 + 4 = 10 marks). Q.5: Answer the following questions (5 + 5 = 10 marks). Q.6: Answer the following questions (5 + 5 = 10 marks). Q.7: Write short notes on the following: 34 (10 marks). QUESTION PAPER PATTERN FOR 50 MARKS PRACTICAL PAPER Swami Ramanand Teerth Marathwada University, Nanded SCHOOL OF CHEMICAL SCIENCES M. Sc. Practical Examination (April-May/October-November 2014) M. Sc. First Year (Semester-I / II) Subject: Chemistry Lab. Course: Total Marks: 50 Time: 08 Hr Date: Q 1. 20 marks Q 2. 20 marks Q 3. Viva-Voce 05 marks Q 4. Record Book 05 marks 35 Internal Marks Home assignment should be completed for each theory course before 15th of the last month in the teaching semester. Mark list of internal tests, Seminars & Home Assignments should be submitted to the Director within eight days after completion of concern examination. Answer books of all Internal Examinations should be shown to the students. Maximum marks for each Internal Theory paper will be 50. Two test each of 15 marks (total 30 marks) + 20 mark for Home Assignment = 50 marks for internal assessment of each Theory course paper. Maximum marks for each Internal Practical paper will be 50. Two questions of 20 marks each + 5 marks for Viva- voce + 5 marks for Record Book = 50 marks for each internal Practical paper. Maximum marks for each External Theory Paper will be 50. Maximum marks for each External Practical paper will be 50. Two questions of 20 marks each + 5 marks for Viva- voce + 5 marks for Record Book = 50 marks for each External Practical paper. 36