BANGALORE

UNIVERSITY

M. Sc. Chemistry Syllabus

(w.e.f. 2010-2011)

DEPARTMENT OF CHEMISTRY

SYLLABUS 2010-11
1. Name of the Course : 2. Duration of the Course : 3. Eligibility : M.Sc., Chemistry Two Years (FOUR SEMESTERS) A candidate must have secured 40% marks in the aggregate and studied Chemistry (cognate subject) securing 50% marks in this subject at the B Sc., level and studied Mathematics at 10 + 2 or Pre-university level. 60 + Supernumerary seats + Payment seats
As per University regulations

4. Intake 5. Admission

:
:

Scheme of Study and Examination M. Sc., CHEMISTRY First Semester

Theory/ Practical (HRS/ Week) Total No.of Hrs/ Semester Duration of Exam. Hours Continuous Evaluation Maximum Marks (Exam) Code No. Total Marks Title

C-101 C-102 C-103 C-104 C-105 C-106

Inorganic Chemistry I Organic Chemistry I

4 4 4 4 9 9

52 52 52 52 140 140

3 3 3 3 6 6

80 80 80 80 40 40

20 20 20 20 10 10

100 100 100 100 50 50 500

Physical Chemistry I Analytical Chemistry & Mathematics for Chemists Inorg/Org/Phy Inorg/Org/Phy

Second Semester
Maximum Marks (Exam) Total No.of Hrs/ Semester Duration of Exam. Hours Theory/ Practical (HRS/ Week) Continuous Evaluation Code No. Total Marks Title

C-201 C-202 C-203 C-204 C-205 C-206

Inorganic Chemistry-II Organic Chemistry-II Physical Chemistry-II Spectroscopy-I Inorg/Org/Phy Inorg/Org/Phy

4 4 4 4 9 9

52 52 52 52 140 140

3 3 3 3 6 6

80 80 80 80 40 40

20 20 20 20 10 10

100 100 100 100 50 50 500

Scheme for continuous evaluation Theory (each paper) Attendance : 5 marks Tests* : 15 marks Total : 20 Marks * Two tests will be conducted and the average marks of the two tests will be taken for Continuous assessment. Practicals: (each practicals) Attendance : 2 marks Records : 3 marks Tests : 5 marks Total : 10 marks

M. Sc., Chemistry III & IV SEMESTERS (After 2 semester study tour-cum-industrial visits are proposed in and around Bangalore/Karnataka for the students of 3rd/4th semester)
nd

Scheme of continuous evaluation for all specialisation Theory (each paper) Attendance : 5 marks Tests (2) : 15 marks Total : 20 Marks Practicals: (each practical) Attendance : 2 marks Records : 3 marks Tests : 5 marks Total : 10 marks
3

M. Sc. Chemistry (Analytical Chemistry Specialisation) III Semester

Teaching/conta ct hrs/week Examination Hrs. Max.Marks Continuous Evaluation Title of the Paper (Syllabus hours for each theory paper: 52) Total Marks Code

C-301-AC

Principles of Chemical Analysis. (Existing C-402) (approved) C-302-AC Reaction Mechanism Catalysis and Organometallic Chemistry C-303 Advanced Analytical Techniques C-304 Spectroscopy-II C-305-AC Analytical Chemistry Practicals-I C-306-AC Analytical Chemistry Practicals-II Total marks for the semester

80

20

100

4 4 4 9 9

3 3 3 6 6

80 80 80 40 40

20 20 20 10 10

100 100 100 50 50 500

IV Semester
Teaching/conta ct hrs/week Examination Hrs. Max.Marks Continuous Evaluation Title of the Paper (Syllabus hours for each theory paper: 52) Total Marks Code

C 401-AC Instrumental Methods of Analysis C 402-AC Environmental & Biochemical Analysis. C 403 Chemistry of Materials C 404 Spectroscopy III C 405-AC Analytical practical III C 4 06-AC Analytical practical IV Total marks for the semester

4 4 4 4 9 9

3 3 3 3 6 6

80 80 80 80 40* 40#

20 20 20 20 10 10

100 100 100 100 50 50 500

* 30 marks (for practicals) + 10 marks (Viva-voce) # 20 makrs (for practicals) + 20 marks (project work based on Experiments in particular specialization.

M. Sc. Chemistry (Inorganic Specialisation) III Semester

Teaching/conta ct hrs/week Examination Hrs. Max.Marks Continuous Evaluation Title of the Paper (Syllabus hours for each theory paper: 52) Total Marks Code

C-301-IC C-302-IC

Solid State Chemistry Inorganic Reaction Mechanisms Bioinorganic Chemistry C-303 Nuclear Chemistry OR Advanced Analytical Techniques C-304 Spectroscopy - II C-305-IC Inorganic Chemistry Practicals-I C-306-IC Inorganic Chemistry Practicals-II Total Marks for the semester

4 & 4 4 4 9 9

3 3 3 3 6 6

80 80 80 80 40 40

20 20 20 20 10 10

100 100 100 100 50 50 500

IV Semester
Teaching/conta ct hrs/week Examination Hrs. Max.Marks Continuous Evaluation Title of the Paper (Syllabus hours for each theory paper: 52) Total Marks Code

C-401-IC C-402-IC

Organometallic Chemistry Homogeneous and Heterogeneous Catalysis C-403 Photoinorganic Chemistry OR Chemistry of Materials C-404 Spectroscopy-III C-405-IC Inorganic Chemistry Practicals-III C-406-IC Inorganic Chemistry Practicals-IV Total Marks for the semester

4 4 4 4 9 9

3 3 3 3 6 6

80 80 80 80 40* 40#

20 20 20 20 10 10

100 100 100 100 50 50 500

* 30 marks (for practicals) + 10 marks (Viva-voce) # 20 marks (for practicals) + 20 marks (project work based on Experiments in particular specialization.

M. Sc. Chemistry (Organic Specialisation) III Semester

Teaching/conta ct hrs/week Examination Hrs. Max.Marks Continuous Evaluation Title of the Paper (Syllabus hours for each theory paper: 52) Total Marks Code

C-301-OC Organic Reaction Mechanisms C-302-OC Organic Synthesis-I C-303-OC Chemistry of Natural Products C-304 Spectroscopy-II C-305-OC Organic Chemistry Practical -I C-306-OC Organic Chemistry Practical -II Total Marks for the semester

4 4 4 4 9 9

3 3 3 3 6 6

80 80 80 80 40 40

20 20 20 20 10 10

100 100 100 100 50 50 500

IV Semester
Teaching/conta ct hrs/week Examination Hrs. Max.Marks Continuous Evaluation Title of the Paper (Syllabus hours for each theory paper: 52) Total Marks Code

C-401-OC

Organometallic and Heterocyclic Chemistry C-402-OC Stereochemistry & Retrosynthetic Analysis C-403-OC Organic Synthesis-II C-404-OC Medicinal Organic Chemistry C-405-OC Organic Chemistry Practical-III C-406-OC Organic Chemistry Practical-IV Total Marks for the semester

80

20

100

4 4 4 9 9

3 3 3 6 6

80 80 80 40* 40#

20 20 20 10 10

100 100 100 50 50 500

* 30 marks (for practical) + 10 marks (Viva-voce) # 20 marks (for practical) + 20 marks (project work based on Experiments)

M.Sc. Chemistry (Physical Specialisation) III Semester

Teaching/conta ct hrs/week Examination Hrs. Max.Marks Continuous Evaluation Title of the Paper (Syllabus hours for each theory paper: 52) Total Marks Code

C-301-PC

Chemistry of Solids & Diffraction Techniques C-302-PC Photochemistry C-303-PC Quantum Chemistry & Surface chemistry OR Physical Organic Chemistry C-304 Spectroscopy-II C-305-PC Physical Chemistry Practicals-I C-306-PC Physical Chemistry Practicals-II Total Marks for the semester

4 4 4

3 3 3

80 80 80

20 20 20

100 100 100

4 9 9

3 6 6

80 40 40

20 10 10

100 50 50 500

IV Semester
Teaching/conta ct hrs/week Examination Hrs. Max.Marks Continuous Evaluation Title of the Paper (Syllabus hours for each theory paper: 52) Total Marks Code

C-401-PC C-402-PC

C-403-PC

Applied Electrochemistry Physical Chemistry of Macromolecules OR Nanomaterials Kinetics and Reaction Mechanism

4 4

3 3

80 80

20 20

100 100

4 C-404 Spectroscopy-III C-405-PC Physical Chemistry Practicals-III C-406-PC Physical Chemistry Practicals-IV Total Marks for the semester 4 9 9

3 3 6 6

80 80 40* 40#

20 20 10 10

100 100 50 50 500

* 30 marks (for practical) + 10 marks (Viva-voce) # 20 marks (for practical) + 20 marks (project work based on Experiments)

FIRST SEMESTER
C-101 INORGANIC CHEMISTRY I
52 Hours I. Chemical Bonding A. Review of periodic properties of elements, oxidation numbers, octet rule, concepts of resonance and hybridization. VSEPR model, shapes of molecules; bent rules and energetics of hybridization. Electronegativity and partial ionic character; Bonds: covalent, coordinate, multicentre quadruple and Synergic. Hydrogen bonds- types and detection, agostic bond, Intermolecular forces, metallic bond. 9h B. Lattice energy, Born-Lande equation, Fajans rules, Slaters rules, radius-ratio rules, structures of simple solids and Zintl isoelectric relationships in solids. MO Theory: , and molecular orbital, MOs of diatomic molecules and walsh diagrams of BeH2 and H2O. 8h II. Chemistry of the Main Group Elements A. Polymorphism of carbon, phosphorous and sulphur, properties, structure and bonding in boranes, carboranes metallo carboranes, , borazines, phosphazenes, sulphur- nitrogen compounds, oxyacids of nitrogen, phosphorous, sulphur and halogens; noble gas compounds. 10hs B. Silicates-classification and structures, isomorphous replacement, pyroxenes, layered and vitreous silicates, zeolites and molecular sieves, condensed phosphates, polyhalides. 11h C. Solvent systems; Review of Bronsted and Lewis acids and bases, pH and pKa, HSAB concept, acid-base concept in non-aqueous media, leveling effect, super acids, reactions 6h in BrF3, N2O4. III. Isopoly and heteropoly acids of W, Mo and V Preparation properties structure and applicatons. 4h

IV. Nuclear Chemistry Sub atomic particles and their properties, Nuclear stability, structural models; Liquid drop model and Shell model of the nucleus. 4h SUGGESTED BOOKS
1. 2. 3. 4. 5. 6. 7. 8. Basic Inorganic Chemistry, F. A. Cotton, G. Wilkinson and P. L. Gaus, John Wiley & sons (1995). Advanced Inorganic Chemistry 3rd, 5th and 6th Editions. F. A. Cotton, G. Wilkinson. Inorganic Chemistry,4th Edition, J. E. Huheey, E. A. Keiter and R. L. Keiter, Addison-Wesley (1993) Inorganic Chemistry, 2nd Edition, D. F. Shriver, P. W. Atkines and C. H.Langford, ELBS (Oxford Uni. Press) (1994). Chemistry of the Elementals, N. N. Greenwood and A. E. Earnshaw, Butterworth Heinemann (1997). Essential Trends in Inorganic Chemistry, D. M. P. Mingos, Oxford Univ.Press (1998). Concise Inorganic Chemistry; 5th Edition; J. D. Lee (1996). Essentials of Nuclear Chemistry, Fourth Edition, H. J. Arnikar, NAIL Pub (1995).

C-102 ORGANIC CHEMISTRY I

52 Hours I. Nature of Bonding in Organic Molecules 5h Delocalized chemical bonding: Conjugation, cross conjugation, resonance. Aromaticity. Huckels rule of aromaticity. Aromatic systems with electron numbers other than six (including azulene, tropone, tropolone and annulenes). Antiaromaticity. Aromaticity in benzenoids, meso-ionic compounds. Homo-aromaticity. Alternant and nonalternant hydrocarbons, Energy levels in odd and even-alternant hydrocarbons, energy levels for the benzyl cation, benzyl free-radical and benzyl carbanion. Hyperconjugation. Tautomerism. . II. Reaction Mechanisms: Structure and Reactivity 12h Generation, structure, stability and reactivity of carbocations, carbanions, carbon free radicals, carbenes and nitrenes. Classification of reactions and mechanisms. Thermodynamic and kinetic requirements, kinetic and thermodynamic control, Hammond postulate, Curtin-Hammett principle. Potential energy diagrams, transition states and intermediates. Methods of determining mechanisms: Based on the structure of products, determination of the presence of intermediates, isotopic labeling, isotope effects, from stereochemical evidence. Acids and bases: Hard and soft acids and bases. Effect of structure on the strengths of acids and bases. Effect of structure on reactivity:- Resonance and field effects; steric effects. The Hammett equation and linear free energy relationship, substituent and reaction constants. Taft equation. Nucleophilic substitution reaction at a saturated carbon: SN1, SN2, and SET mechanisms. Effect of substrate structure, attacking nucleophile, leaving group. Ambident nucleophiles and substrates. III. Stereochemistry 10h Fischer, Newman, Sawhorse and flying wedge projections and their interconversions. Optical isomerism: Elements of symmetry and chirality. D-L conventions. CIP rules, R-S and M-P conventions. Chirality in compounds with a stereogenic centre, and in allenes, alkylidene cycloalkanes and spiranes (with a stereogenic axis). Crams and Prelogs rules. Conformational analysis: Conformational analysis of cycloalkanes: cyclobutane, cyclopentane, cychexanes (monosubstituted e.g., methyl, iso-propyl, tert-butyl and disubstituted cyclohexanes e.g., dialkyl, dihalo, diols), and cycloheptane. Nomenclature and conformations of fused rings and bridged ring systems. Prochirality: Enantiotopic and diastereotopic atoms, groups and faces. IV. Amino acids and Peptides Synthesis of amino acids. 11h

Classification and nomenclature of peptides. Sanger and Edman methods of sequencing. Cleavage of peptide bond by chemical and enzymatic methods. Peptide synthesis- Protection of amino group (Boc-, Z- and Fmoc-) and carboxyl group as alkyl and aryl esters. Use of DCC, EEDQ, HOBt and active esters, acid halides, anhydrides in peptide bond formation reactions. Deprotection and racemization in peptide synthesis. Solution and solid phase techniques. Synthesis of oxytocin, gramicidin, enkephalins, LH-RH. Introduction to peptidomimetics. V. Carbohydrates 7h Introduction. Kiliani-Fischer synthesis, Determination of configuration of the monosaccharides, conformational analysis of monosaccharides. Synthesis of aldonic, uronic, aldaric acids and alditols. Structure elucidation of sucrose and maltose. Structures of trehalose, cellobiose, lactose, gentiobiose, meliobiose, and chitin. Photosynthesis of carbohydrates. VI. Heterocyclic compounds 7h Nomenclature of heterocyclic compounds. Structure, reactivity, synthesis and reactions of pyrazole, imidazole, oxazole, isoxazole, thiazole, isothiazole, pyrimidine and puine. Preparation and reactions of coumarins, chromones, flavones and isoflavones. SUGGESTED BOOKS
1. 2. 3. 4. 5. 6. 7. Advanced Organic Chemistry Reactions, Mechanism and Structure, Jerry March, John Wiley (2008). Advanced Organic Chemistry, F A Carey and R J Sundberg Plenum, (1990). A Guide Book to Mechanism in Organic Chemistry, Peter Sykes, Longman, (2000). Structure and mechanism of Organic Chemistry, C K Ingold, Cornell University Press (1999). Organic Chemistry, R T Morrison and R N Boyd, Prentice-Hall, (1998). Modern Organic Reactions, H O House, Benjamin, (1972). Principles of Organic Synthesis, R O C Norman and J M Coxon, Blackie Academic and Professional, (1996). 8. Stereochemistry of Organic Compounds, D Nasipuri, New-Age International, (1999). 9. Stereochemistry of Carbon Compounds, E L Eliel, S H Wilen and L N Mander, John Wiley, (1994). 10. Stereochemistry, Potapov, MIR, Moscow, 1984. 11. Organic Chemistry, Volumes I and II, I L Finar, Longman, (1999). 12. Peptides Chemistry : A practical text book, M. Bodansky, Springer-Verlag NY, 1988. 13. Solid-phase peptide synthesis: A practical approach-E. Artherton & R.C. Sheppard, I R L, Oxford Univ. Press, 1989. 14. Peptides: Chemistry and Biology, N Selwad and H.-D. Jakubke, Wiley-VCH, 2002.

10

C-103 Physical Chemistry I

52 hours

I. Quantum Mechanics
A. Equations of wave motion: Progressive and stationary waves, wave equation for a stationary wave (stretched string). Formulation of quantum mechanics: Wave particle duality of material particles, deBroglie relation, Heisenberg uncertainty principle. Schrdinger wave equation. Time-independent and time-dependent Schrdinger equations and the relations between their solutions. Eigen function and eigen value. Physical interpretation of wave function. Concept of operators. Laplacian, Hamiltonian, linear and Hermitian operators. Angular momentum operators and their properties. Commutation of operators. Normalisation, orthogonality and orthonormality of wave functions. Average (Expectation) values. Postulates of quantum mechanics. Solutions of Schrdinger equation for a free particle, particle on a ring and particle in a threedimensional box. Quantum mechanical degeneracy,tunneling (no derivation). 10h B. Application of Schrdinger equation to harmonic oscillator and rigid rotator. Eigen functions and eigen values of angular momentum. Ladder operator method for angular momentum. Schrdinger equation to hydrogen atom in spherical polar coordinates. Solution of , equations and statement of solution of R equation. Total wave function of hydrogen atom. Quantum numbers and their characteristics. List of wave functions for few initial states of hydrogen-like atoms. Diagrams of radial and angular wave functions. Radial and angular distribution functions and their significance. Electron spin (Stern-Gerlach experiment), spin orbital, antisymmetry and Pauli exclusion principle, Slater determinants. Coupling of angular momenta. Russell-Saunders and JJ-coupling, Term symbols. Spin-orbit interaction and explanation of term multiplicities (Na-D doublet). Zeeman Effect. 11h C. Approximate methods: Need for approximate methods. Perturbation method. Rayleigh Schrdinger Perturbation theory for time-independent non-degenerate system. Application to electron in a box under the influence of an electric field. Application to He atom. Variation theorem-Statement and proof. Application of variation method to particle in a one dimensional box, linear oscillator and He atom. Slater type orbitals, expresiions for Slater orbitals for 1s, 2s,3s, 2p and 3d electrons (no derivation). Slaters rules for calculation of effective nuclear charge. STOs, for He, C and N. SCF method for many electron atoms. HMO theory for conjugated systems. Application to ethylene, ally radical, butadiene and benzene 8h II. CHEMICAL DYNAMICS A. Macroscopic and microscopic kinetics, Factors affecting the order of reactions, Methods of determination of order of a reaction, Review of theories of reaction rate-Collision theory, Transition state theory, Comparison of collision theory and transition state theory, Arrhenious equation, Significance of energy of activation, Temperature coefficient, Thermodynamical
11

formulation of reaction rates (Wyne-Jones and Eyring treatment), Reaction between ions in solutions- Influence of ionic strength on reaction rates (primary and secondary salt effects). 5h B. Steady state kinetics, Chain reactions- Chain length and chain inhibition, Comparison of photochemical and thermal reactions, Mechanisms of thermal and photochemical reactions between hydrogen-bromine and hydrogen-chlorine. Comparative study of thermal and photochemical hydrogen-halogen reactions. Pyrolysis of acetaldehyde, Decomposition of ethane. 4h C. Kinetics of homogeneous catalysis-Kinetics of auto catalytic reactions, Kinetics of acidbase catalysed reactions, Comparison of enzyme catalysed and chemical catalysed reactions, Mechanism (lock and key theory), Kinetics of enzyme catalysed reactions- Henri-MichaelisMenten mechanism, Significance of Michaelis-Menten constant, Lineweaver-Burk plot. Effects of concentration, pH, temperature, activators and inhibitors on enzyme activity. 5 h D. Kinetics of fast reactions-Study of fast reactions by relaxation method (Temperature and pressure jump), flow method (Plug flow method and stopped flow method), flash photolysis and shock tube method. 3h E. Theories of unimolecular reactions: Perrin theory, Lindemann theory and Hinshelwood theory. 2h F. Surface chemistry-Types of adsorption isotherms, Effect of temperature on adsorption, Mechanical adsorption, Estimation of surface area using BET equation, Gibbs adsorption isotherm, Surface tension and surface energy, Pressure difference across curved surface (Laplace equation), Vapour pressure of droplets (Kelvin equation), Surface film on liquids (electro-kinetic phenomena), Catalytic activity of surfaces. 4h SUGGESTED BOOKS
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. Physical Chemistry, P.W.Atkins, Julio de Paula, ELBS, 7th edition, (2002). Physical Chemistry: A Molecular Approach, McQuarie and Simon, Viva, New Delhi (2001). Introduction to Quantum Chemistry, A.K.Chandra, Tata McGraw Hill, (1988) Quantum Chemistry, Ira N.Levine, Prentice Hall, New Jersey, (1991) Coulsons valence, R.Mc Weeny, ELBS, (1982). Quantum Chemistry, 2nd edition, R. K. Prasad, New Age International,(2000). Quantum Chemistrry Through Problems and Solutions, R. K. Prasad, New Age International (1997). Chemical Kinetics-K.J.Laidler, McGraw hill. Inc. New York (1988). Principles of Chemical Kinetics-House J.E. Wm C Brown Publisher, Boston, (1997). Kinetics and Mechanism- A.A. Frost and R.G.Pearson , John-Wiley, New York, (1961). Chemical kinetics Methods-C.Kalidas, New Age International Publisher, New Delhi (1995) Kinetics of Chemical Reactions-S.K.Jain Vishal Publications, Delhi (1982). Kinetics and Mechanism of Chemical Transformation-J.Rajaraman and J.Kuriakose, Mc Millan. (1986). 14. Physical Chemistry of Surfaces-A.W.Adamson, Interscience Publisher Inc., New York (1967). 15. Surface Chemistry: Theory and Applications, J.J.Bikerman, Academic Press, New York (1972). 12

C-104 ANALYTICAL CHEMISTRY AND MATHEMATICS FOR CHEMISTS.

52 hours

Part A - ANALYTICAL CHEMISTRY

[28 h]

I. Errors in Chemical Analysis 5h Classification of errors, Determinate, indeterminate, methodic, human and instrumental errors. Accuracy and precision. Distribution of random errors frequency distribution, the normal error curve, absolute error, relative error. Measure of central tendency-,mean, median, range average deviation, relative average deviation, standard deviation and variance. Criteria for rejection of observation, Q test. F test, confidence intervals, confidence limits. II. Separation Techniques 9h Solvent Extraction-Types-batch, continous, efficiency, selectivity, Distribution coefficient, Nernst distribution law, derivation, applications and numerical problems. Chromatography- Types, Terminology, Principles of paper, Thinlayer, Column, Gas chromatography, Medium Performance liquid Chromatography,High performance liquid chromatography, Reversed phase liquid chromatography, Super critical liquid chromatography, 2D-thinlayer chromatography, Electrophoresis. III. Optical Methods of Chemical Analysis 9h Interaction of electromagnetic radiation with matter, Beer-Lamberts law, derivation, verification, deviations, molar extinction coefficient, choice of solvent, Sandell sensitivity, Ringboms plot, photometric titrations, Single beam & double beam UV-VIS spectrophotometer, Application of quantitative and qualitative analysis, Principle, Instrumentation and applications of Fluorimetry, Turbidimetry and Nephelometry. Numerical problems on all these techniques IV. Radioanalytical Methods 5h Radioactivity, Ionisation, Working principles of GM counter, -ray counter, neutron activation analysis, Isotopic dilution analysis, Radiotracer technique, Applications of all these techniques, Use of radioactive isotopes in solving analytical and Physico chemical problems. SUGGESTED BOOKS
1. Analytical Chemistry. Gary D Christian, 5th Edition, John Wiley and Sons Inc., (1994) 2. Instrumental Methods of Analysis.H. H. Willard, L. L. Merritt , J. A. Dean and F. A. Set, CBS Publishers (1996). 3. Instrumental methods of Chemical Analysis, G. W. Ewing, 5th edition, McGraw-Hill, New York, 1988. 4. Vogels text book of Quantitative Chemical analysis 5th edition, Ed., Jeffery et. al ELBS/Longman, 1989 5. Fundamentals of Analytical Chemistry, 8th Edition, Skoog, West, Holler and Crouch; Thomson Asia Pvt. Ltd(2004) 6. Fundamentals of Instrumental Analysis, Skoog, West, Holler and Crouch; Thomson Asia Pvt. Ltd (2004).

13

Part B - MATHEMATICS FOR CHEMISTS

[24 h]
Vectors: vectors, dot and cross products; scalar and vector triple products and their applications. Tensors and their applications. 3h Matrix Algebra: Review of different types of matrices (including Hermitian and skewHermetian); matrix addition and multiplication; determinant of a square matrix, transpose, adjoint and inversre of a square matrix. Solution to system of linear equations (a) by matrix method & (b) by Cramers Rule. Characteristic equation of a square matrix, eigen values and eigen vectors. 4h n Calculus: Rule for differentiation; Chain Rule (for f(x)= U , sin u, log u etc.) implicit differentiation and parametric differentiation and successive differentiation of order 2. (for explicit functions only). 2h Applications of differentiation- derivative as a slope of the tangent, derivative as a rate measure velocity and acceleration, increasing and decreasing functions- maxima and minima- second derivative test- point of inflections- problems restricted to polynomials 2h Integration : Basic rules- simple substitution- Method of partial fractions- Integration by parts. Definite integral and application to areas of plane curves. 2h Functions of several variables; partial derivatives; co-ordinate transformation from cartesian co-ordinates to spherical and cylindrical co-ordinates and vice- versa. 3h

Elementary Differential Equation: Variable seperable, exact first order equations, linear and homogeneous equation. 2h Second order homogeneous differential equation with constant coeffecients; f(D)y=0. Solution of differential equations by power series method. 2h Fourier series: Simple problems. 2h

Probability: Review of permutations and combinations. Probability and addition theorem for mutually exclusive events and multiplication theorem for independent events. Curve Fitting- method of least squares. 2h

14

SUGGESTED BOOKS
1. 2. 3. 4. 5. 6. 7. Calculus and analytical Geometry, Thomas, Finney. Narosa Publishing House. Short Course in differential equations, Rainville and Bedient, IBH Publishers. Theory and Problems in Mathematics, Vol II, S.S. Bosco, Algebra- hall and Knight. Mathenmatics for Chemistry, Doggett and Sucliffe, Longmann Publishers. mathematical preparation for Physical Chemistry, F. Daniels, McGraw Hill. Chemical mathematics, D.M. Hirst, Longman publishers. Basic mathematics for Chemists, Tebbutt, Wiley publishers.

8.

C105 AND C106: PRACTICALS (4 days a week 4 hours a day) C105 Inorganic chemistry practical I
A. Semi-micro qualitative analysis of mixtures containing two each of common cations and anions and one of the following less familiar elements: W, Se, Mo, Ce, Th, Zr, V, U and Li. B. Preparation and quantitative analysis of inorganic complexes: 1. Ferrous oxalate. 2. Potassium trioxalatofetrrate (III) trihydrate. 3. Hexammine cobalt (III) chloride. 4. Cis and trans-potassium dioxalatodiaquochromium(III)

C106. Inorganic Chemistry Practical-II

1. Gravimetric determination of Fe in an iron ore as Fe2O3 1. Volumetric/redox and gravimetric determination of the following mixtures:(a)Copper and nickel (b) Copper and iron (c) Copper and zinc(d)Nickel and zinc 2. Analysis of alloys: (a) German silver (b) Steel (c) Solder. 3. Colorimetric determination of nickel SUGGESTED BOOKS
1. 2. 3. 4. Vogels Text book of Qualitative Chemical Analysis, J.Bassett, G.H. Jeffery and J.Mendham, ELBS (1986). Vogels Text book of Quantitative Chemical Analysis, 5th Edition,J.Bassett, G.H. Jeffery and J.Mendham,and R.C.Denny, Longman Scientific and Technical (1999). Inorganic Semimicro Qualitativwe Analysis, V.V. Ramanujam, The National Pub.Co.(1974). Practical Inorganic Chemistry, G.Marr and B.W. Rockett, Von Nostrand Reinhold (1972).

15

C- 105 Organic Chemistry Practical-I

(4 days a week, 4 hours a day) Preparation (one stage) 1. Cannizarro reaction: Benzaldehyde. 2. Fries rearrangement: Phenyl acetate. 3. Friedel-Crafts reaction: Benzene and Acetyl chloride. 4. Claisen-Schmidt reaction: Acetophenone and Benzaldehyde / benzaldehyde. 5. Sandmeyer reaction: 4-Chlorotoluene from 4-toluidine. 6. Pechmann reaction: Resorcinol and ethylacetoacetate. 7. Oxidation of Cyclohexanol. 8. Preparation of S- Benzylisothiuronium chloride. 9. Synthesis of p-iodonitrobenzene 10. Synthesis of N-Phenyl-2,4-dinitroaniline 11. Synthesis of 2,4,6-tribromoaniline 12. Synthesis of 2,4-dichlorophenoxyacetic acid II Qualitative analysis Systematic analysis and identification of organic compounds. I

acetone and

C-106 Organic Chemistry Practical II

I (4 days a week, 4 hours a day) Preparation (Two and three stages) Preparation of the following compounds: 1. 4-Nitroaniline from aniline. 2. 3-Nitrobenzoic acid from methyl benzoate. 3. 2,4-Dinitrophenylhydrazine from chloronitrobenzene. 4. Anthranilic acid from phthalic acid. 5. Benzanilide from benzophenone. 6. Benzilic acid from benzoin. 7. Synthesis of Acridone. 8. Synthesis of Hydantoin. II Quantitative analysis 1. Determination of equivalent weight of carboxylic acids. 2. Saponification value of oil. 3. Estimation of glucose. 4. Estimation of keto group. 5. Estimation of amines/phenols. 6. Iodine value of oil (chloramine-T method). SUGGESTED BOOKS
1. 2. Laboratory manual of Organic Chemistry- B. B. Dey, M V Sitaraman and T R Govindachari, Allied Publishers, New Delhi, (1996). Practical Organic Chemistry Mann and Saunders, (1980). 16

Text Book of Practical Organic Chemistry- A. I. Vogel, (1996). Test Book of Quantitative Organic Analysis- A. I. Vogel, (1996). A Handbook of Organic Analysis Clarke and Hayes, (1964). Comprehensive practical organic chemistry : Preparation and quantitative Analysis, V. K. Ahluwalia, R. Aggarwal, Universities Press (India), 2000. 7. Comprehensive practical organic chemistry: Qualitative analysis, V. K. Ahluwalia, S. Dhingra, Universities Press (India), 2000. 8. An advanced course in practical chemistry, A. Ghoshal, B. Mahapatra and A. Kr. Nad, New central book agency, Calcutta, 2000. 9. Advanced practical organic chemistry, J. Mohan, Vol. I and II, Himalaya Publishing House, 1992. 10. Practical organic chemistry (Quantitative analysis), B. B. Dey, M. V. Sitaraman and T. R. Govindachari, Allied Publishers, New Delhi, 1992.

3. 4. 5. 6.

C 105 Physical Chemistry Practical I

(4 days a week, 4 hours a day) Chemical Kinetics 1. Determination of the velocity constant, catalytic coefficient, temperature coefficient, t and energy of activation for the acid hydrolysis of methyl acetate. 2. Evaluation of Arrhenius parameter for the reaction between potassium persulphate and potassium iodide (Ist order). 3. Velocity constant for the saponification of ethyl acetate. 4. Determination of the order of reaction between hydrogen peroxide and potassium iodide (clock reaction). Colorimetry 5. Test for the validity of Fe and Cu ions by Beer Lambert Law and estimation of unknown concentrations in solutions. Calculation of molar extinction coefficient. 6. Titration of ferrous ammonium sulfate with potassium permanganate colorimetrically. 7. Simultaneous estimation of Mn and Cr in a solution of KMnO4 and K2Cr2O7 colorimetrically. 8. Kinetics of reaction between K2S2O8 KI colorimetrically. 9. Determination of concentration of Fe using EDTA by spectrophotometric titration. Cryoscopy 10. Determination of molecular weight of a solute by cryoscopic method. Partial Molal Volume 11. Determination of partial molal volume of ethanol by reciprocal density method/ intercept method. 12. Determination of partial molal volume of NaCl-H2O system by apparent molar volume method. Phase diagram 13. Construction of Phase diagram of a two-component system and determination of eutectic temperature and eutectic composition. Adsorption 14. Adsorption of oxalic acid on charcoal. Verification of Langmuir adsorption isotherm.
17

C 106 Physical Chemistry Practical II

(4 days a week, 4 hours a day) Conductometry 1. Determination of the solubility of sparingly soluble salt. 2. Titration of mixture of strong and weak acids against strong base. 3. Titration of mixture of strong acid, weak acid and salt (copper sulfate) against strong base. 4. Titration of weak acid against weak base. 5. Precipitation titration: lithium sulfate against barium chloride. 6. Dissociation constant of weak electrolyte (weak base NH4OH; weak acid CH3COOH). 7. Verification of Onsagers equation - determination of 0 of an electrolyte. Potentiometry 8. Determination of single electrode potential of Cu2+ / Cu and Zn2+ / Zn and testing the validity of Nernst equation. 9. Determination of pH of buffers by using quinhydrone electrode and comparison of the pH values obtained with glass electrode. 10. Potentiometric titration of ferrous ammonium sulfate against potassium dichromateCalculation of formal redox potential of Fe3+ / Fe2+. 11. Potentiometric titration of potassium iodide against potassium permanganate. 12. Titration of silver nitrate against potassium chloride. 13. Determination of EMF of a concentration cell and calculation of solubility product of AgCl. 14. Titration of weak acid against a strong base using quinhydrone electrode and calculation of pKa value of the weak acid. 15. Titration of a mixture of HCl and CH3COOH potentiometrically and determination of the composition of the mixture. SUGGESTED BOOKS
1. 2. 3. 4. 5. 6. 7. 8. Findlays Practical Physical Chemistry revised by Levitt, Longmans London (1966). Experiments in Physical Chemistry by Shoemaker and Garland, McGraw Hill International edn.(1996). Advanced Practical Chemistry by J.B. Yadav, Goel Publication house, Meerut(1989). Experimental Physical Chemistry by Daniel etal., McGraw Hill (1962). Experimental Physical Chemistry by Wilson, Newcombe and others, Pergamon Press, New York (1962). Practical Physical Chemistry by A,M. James and D.E. Pritchard, Longman Group Ltd. (1968). Experimental Physical Chemistry by V. D. Athawale and Parul mathur, New Age International, New Delhi (2001). Experiments in Physical Chemistry by J. G. Ghosh , Bharathi Bhavan, (1974). Practicals in Physical Chemistry, A Mordren Approach by P.S. Sindhu, Mac-millan

9.

Publishers, Delhi, (2006).

18

II SEMESTER C-201 INORGANIC CHEMISTRY II

52 hours I. Metal-Ligand Equilibria in solution Step-wise and overall formation constant and their relationship, trends in step-wise constant, kinetic and thermodynamic stability of metal complexes, factors affecting the stability of metal complexes with reference to the nature of the metal ion and ligand, chelate and macrocyclic effect and their thermodynamic origin, determination of binary formation constant by pH-metry, spectrophotometry, polarography and by ion exchange methods. 10h II. Metal-Ligand bonding Crystal field theory limitation, stereochemistry, coordination Nos,3 to 8, Evidences for metal-ligand orbital overlap, MO theory (including - bonding), Jahn-Teller distortion in metal complexes and metal chelates, Spectrochemical series, Nephelauxetic series, angular overlap model. 9h III. Structure and bonding Hydride, dihydrogen, dioxygen, isocyanide, carbonyl, nitrosyl, dinitrogen and tertiary phosphine complexes, stereochemical non-rigidity, self-assembly in supramolecular chemistry, Stereoisomerism-chirality, optical activity, CD,ORD, Cotton effect and magnetic circular dichroism, absolute configurations. 14h IV. Electronic Spectra of transition Metal Complexes. Spectroscopic ground states, selection rules, term symbols for dn ions, Racah parameters, Orgel correlation and Tanabe-Sugano diagrams, Spectra of 3d metal aqua complexes of trivalent V,Cr divalent Mn, Co and Ni; [CoCl4]2-, calculation of Dq, B and parameters, charge transfer spectra. Spectral properties of Lanthanides and actinides. 12h V. Magnetic Properties of Metal Complexes Magnetic susceptibility, types of magnetic behavior, diamagnetic correction, orbital contribution, spin-orbit coupling, Ferro and antiferromagnetic coupling, spin crossover, Magnetic properties of lanthanides and Actinides. 7h SUGGESTED BOOKS
1. 2. 3. 4. 5. 6. 7. 8. Basic Inorganic Chemistry, F.A.Cotton , G.Wilkinson and P.L.Gaus, John Wiley & sons. Inc, 6th Edition (1999). Inorganic Chemistry, 4th Edition, J.E. Huheey, E.A.Keiter and R.L.Keiter, Addition-Wesley (1993). Inorganic Chemsitry, 2nd Edition, D.F.Shriver, P.W. Atkins and C.H.Langford, ELBS (Oxford Uni. Press) (1994). Chemistry of Elements, N.N.Greenwood and A.E.Earnshaw, Butterworth Heinemann (1997). Inorganic Electronic spectroscopy, A.B.P.Lever, Elsevier. (1968) Essential Trends in Inorganic Chemistry, D.M.P.Mingos, Oxford Univ. Press (1998). Magnetochemistry, R.L. Carlin, Springer Verlag. Electronic Absorption Spectroscopy and Related Techniques, D.N.Sathyanarayana, Universities Press (2001).

19

C-202 ORGANIC CHEMISTRY-II

52 Hours I. Aromatic Substitution Reactions 12h Electrophilic Substitution Reactions: The arenium ion mechanism. Orientation and reactivity. Energy profile diagrams. The ortho/para ratio, ipso attack, orientation in other ring systems. Quantitative treatment of reactivity in substrates and electrophiles. Effect of leaving group. Amination, sulfonylation reactions; Diazonium coupling, Vilsmeier-Haack reaction, Gatterman reaction, Gatterman-Koch reaction and Hoesch reaction. Nucleophilic substitution reactions: The SNAr, SN1, benzyne and SRN1 mechanisms. Reactivity: effect of substrate structure, leaving group and attacking nucleophile. Goldberg reaction, Bucherer reaction and Schiemann reaction. von Richter, Sommelet-Hauser and Smiles rearrangements. II. Addition Reactions 12h Addition to carbon-carbon multiple bonds: mechanistic and stereochemical aspects of addition reactions involving electrophiles, nucleophiles and free radicals. Regio, stereo- and chemoselectivities. Orientation and reactivity. Addition to cyclopropane ring. Hydrogenation of double and triple bonds, hydrogenation of aromatic rings. Addition of alkenes and/or alkynes to alkenes and/or alkynes. Ene synthesis. Michael reaction. Addition to carbon-heteroatom multiple bonds: Mechanism of metal hydride reduction (NaH, LiH, LiAlH4, NaBH4) of saturated and unsaturated carbonyl compounds, acids, esters and nitriles. Addition of Grignard reagents and organolithium reagents to carbonyl compounds and unsaturated carbonyl compounds. Conversion of aldehydes to nitriles. Hydrolysis of nitriles and addition of amines to isocyanates. Formation of xanthates. Wittig, Mannich and Stobbe reactions. III. Elimination Reactions 4h The E2, E1 and E1cB mechanisms and their spectrum. E2C and E2H mechanisms. Orientation of the double bond. Reactivity-effects of substrate structure, attacking base, the leaving group and the medium. Mechanism and orientation in pyrolytic elimination reactions (including Chugaev reaction). IV. Rearrangements 12h Wagner-Meerwein, Pinacol-Pinacolone, Fries, Wolff, Beckmann, Hofmann, Curtius, Lossen and Schmidt rearrangements. Benzil-benzilic acid rearrangement, Arndt-Eistert reaction, Tiffeneau-Demjanov reaction, Firtsch-Buttenberg-Wiechell rearrangement. Stevens, Wittig and Favorskii rearrangements, Dienone-phenol rearrangement. Baeyer-Villiger oxidation. Neber rearrangement. Benzidine rearrangement, V Vitamins Biological importance and synthesis of Vitamins A, Vitamin B1 (thiamine), Vitamin B6 7h

20

(pyridoxine), folic acid, pantothenic acid, riboflavin, Vitamin C, Vitamin E (-tocopherol), Vitamin H (biotin), Vitamins K1 and K2. VI. Synthetic Molecular receptors 5h Definition and significance. Structure and function of receptors with molecular clefts, molecular tweezers. Receptors with multiple hydrogen bonding sites. Cyclophanes, calixarenes and cyclodextrins. SUGGESTED BOOKS
1. 2. 3. 4. 5. 6. 7. Advanced Organic Chemistry Reactions, Mechanism and Structure, Jerry March, John Wiley (2008). Advanced Organic Chemistry, F. A. Carey and R. J. Sundberg, Plenum (1990). A Guide Book to Mechanism of Organic Chemistry, Peter Sykes, Longman (2000). Structure and Mechanism of Organic Chemistry, C. K. Ingold, Cornell University Press. Organic Chemistry, R. T. Morrison and R. N. Boyd, Prentice-Hall (1998). Modern Organic Reactions, H. O. House, Benjamin (1972). Principles of Organic Synthesis, ROC Norman and J. M. Coxon, Blackie Academic and Professional (1996). 8. Stereochemistry of Organic Compounds, D. Nasipuri, New-Age International (1999). 9. Stereochemistry of Carbon Compounds, E. L. Eliel, S. H. Wilen and L. N. Mander, John Wiley (1994). 10. Organic Chemistry, Volumes I and II, I L Finar, Longman. (1999). 11. Medicinal Chemistry, A Kar, Wiley (2000).

C-203 PHYSICAL CHEMISTRY-II

52 hours 26h Classical Thermodynamics : Brief resume of concepts of laws of thermodynamics- free energy, chemical potential and entropies. Partial molar properties- partial molar free energy, partial molar volume, partial molar heat content and their significance. Determination of these quantities. Concept of fugacity and its determination by graphical method and compressibility factor method. Non ideal systems - Excess functions for non-ideal solutions. Activity and activity coefficient. Relationship between mole fraction, molality and molarity activity coefficients. Determination of activity coefficient by EMF and solubility methods. Phase rule - Derivation of phase rule from the concept of chemical potential, application of phase rule to three component systems 9h Statistical Thermodynamics: Concepts of distribution, thermodynamic probability and most probable distribution. Ensemble averaging- postulates of ensemble averaging. Canonical, grand canonical and micro canonical ensembles with corresponding distribution laws (using Lagranges method of undetermined multipliers). Partition functions - translational, rotational, vibrational and electronic partition functions. Calculation of thermodynamic properties in terms of partition functions. Applications of partition functions. Chemical equilibrium and equilibrium constant in terms of partition functions. Fermi-Dirac statistics - distribution law and applications to metal. Bose-Einstein statistics-distribution law and application to helium. Heat capacity behaviour of solids. 10h
21

I. Thermodynamics

Heat Capacity of Solids Theories of heat capacity of Solids-Einsteins and Debyes equation, Characteristic temperature, Determination of heat capacity at low temperature.

4h

Non Equilibrium Thermodynamics: Thermodynamic criteria for non-equilibrium states, entropy production and entropy flow. Entropy balance equation for different irreversible processes (e.g., heat flow, chemical reaction etc.) .Transformations of the generalized fluxes and forces, non equilibrium stationary states, phenomenological equations, microscopic reversibility and Onsagers reciprocity relations. 3h II.ELECTROCHEMISTRY 26h Electrochemistry of solutions: Debye-Huckel-Onsager treatment and its extension ion solvent interactions. Debye-Huckel-BJerum mode. Thermodynamics of electrified interface equations. Derivation of electro-capillarity, Lippmann equations (surface excess), methods of determination. Structure of electrified interfaces. Helmholtz, Guoy-Chapman, Stern and Devanathan models. Over potentials: Concentration and activation over potential, exchange current density, derivation of Butler-Volmer equation, Tafel plot. Quantum aspects of charge transfer at electrodes-solution interfaces, quantization of charge transfer, tunneling. Semiconductor interfaces theory of double layer at semiconductor, electrolyte solution interfaces, structure of double layer interfaces. Effect of light at semiconductor-solution interfaces. Electrocatalysis influence of various parameters. Hydrogen electrode. Polarography theory, Ilkovic equations; half wave potential and its significance. Introduction to corrosion, homogeneous theory, forms of corrosion, corrosion monitoring and prevention methods. SUGGESTED BOOKS
Kinetics and mechanism of chemical transformation, J. Rajaraman and J. Kuriacose, Mc Millan, (1986) 2. Molecular thermodynamics, Donald A.Mc Quarrrie, John D.Simon University Science Books, California, (1999). 3. Thermodynamics for Chemists by S. Glasstone, Affiliated East-West Press, New Delhi, (1960). 4. Thermodynamics, Rajaraman and Kuriacose, East West, 1986. 5. Statistical Thermodynamics, M. C. Gupta (Wiley eastern Ltd.) 1993. 6. Elementary Statistical Thermodynamics , N.D. Smith, Plenum Press, N.Y. (1982). 7. Elements of Classical and Statistical Thermodynamics, L. K. Nash, AddisonWiley (1970). 1. Modern Electrochemistry- Vol. I and II, J.O.M.Bockris and A.K.N.Raddy, Plenum, New York (1978). 2. An Introduction to Electrochemistry- Samuel Glastone, East-West edition, New Delhi (1942). 3. Text Book of Physical Chemistry- Samuel Glastone, 2nd edition, Mac Millan India Ltd. (1991). 12. Electrochemistry, Principles and Applications, Edmund, C. Potter, Cleaver Hume Press, London (1961) 13. Principles and Applications of Electrochemistry - D.R.Crow, 3rd ed., (Chapmanhall, London) 1988. 22 1.

C-204 SPECTROSCOPY-I
52 hours I. Symmetry and Group Theory in Chemistry 12h Definition of groups, subgroups, cyclic groups, conjugate relationships, classes, simple theorems in group theory. Symmetry elements and symmetry operations, point groups, Schenflies notations, representations of groups by matrices, reducible and irreducible representations, characters of representations, Great Orthogonality Theorem (without proof) and its applications, character tables and their uses (representations for the Cn, Cnv, Cnh, Dnh etc groups to be worked out explicitly) Mulliken symbols for irreducible representations Direct products, Applications of group theory to quantum mechanics- identifying non-zero matrix elements, derivation of the orthonormalization conditions II. Unifying principles 3h Interaction of electromagnetic radiation with matter- time-dependent perturbation theory, transition moment integral, selection rules- symmetry and spin forbidden transitions III. Microwave Spectroscopy 6h Rotations of molecules, rigid diatomic molecule- rotational energy expression, energy level diagram, rotational wave functions and their symmetry, selection rules, expression for the energies of spectral lines, computation of intensities, effect of isotopic substitution, centrifugal distortion and the spectrum of a non-rigid rotor. Rotational spectra of polyatomic molecules- linear, symmetric top and asymmetric top molecules Stark effect, techniques and instrumentation IV. Infrared Spectroscopy 12h Vibrations of molecules, harmonic and anharmonic oscillators- vibrational energy expression, energy level diagram, vibrational wave functions and their symmetry, selection rules, expression for the energies of spectral lines, computation of intensities, hot bands, effect of isotopic substitution Diatomic vibrating rotor, Born-Oppenheimer approximation, vibrational-rotational spectra of diatomic molecules, P, Q and R branches, breakdown of the Born-Oppenheimer approximation Vibrations of polyatomic molecules: Normal coordinates, translations, vibrations and rotations, vibrational energy levels and wave functions, fundamentals, overtones and combinations Vibration-rotation spectra of polyatomic molecules- parallel and perpendicular vibrations of linear and symmetric top molecules Techniques and instrumentation, FTIR

23

V. Raman Spectroscopy 7h Classical theory of the Raman effect, polarizability as a tensor, polarizability ellipsoids, quantum theory of the Raman effect, Pure rotational Raman spectra of linear and aymmetric top molecules, vibrational Raman spectra, Raman activity of vibrations, rule of mutual exclusion, rotational fine structure- O and S branches, Polarization of Raman scattered photons Structure determination from Raman and IR spectroscopy-AB2 and AB3 molecules Techniques and instrumentation VI. Electronic Spectroscopy 12h Born-Oppenheimer approximation, vibrational coarse structure, intensities by FranckCondon principle, Dissociation energy, rotational fine structure, Fortrat diagram, predissociation Electronic structure of diatomic molecules- basic results of MO theory, classification of states by electronic angular momentum-,,, and molecular orbitals, selection rules, spectrum of singlet and triplet molecular hydrogen Electronic spectra of polyatomic molecules- localized MOs, spectrum of HCHO, change of shape on excitation Decay of excited states- radiative (fluorescence and phosphorescence) and non-radiative decay, internal conversion SUGGESTED BOOKS
1. 2. 3. 4. 5. 6. Chemical Applications of Group Theory, F. A. Cotton, Wiley Eastern (1976). Molecular Symmetry, D. S. Schonland, Van Nostrand (1965). Introduction to Molecular Spectroscopy, C. N. Banwell, TMH Edition (1994). Introduction to Molecular Spectroscopy, G. M. Barrow, McGraw Hill (Int. Students Edition) (1988). Molecular Spectroscopy, J. D. Graybeal, McGraw Hill (Int. Students Edition) (1990). Spectroscopy, Vols. 1-3, B. P. Straughan and W. Walker, Chapman Hall (1976). Modern Spectroscopy, J. M. Hollas, John Wiley.

C 205 and 206 Practicals (4.5 hrs per day, 4 days per week) Inorganic Chemistry practicals I & II Organic Chemistry Practicals I & II Physical Chemistry Practicals - I & II Experiments are as in first semester. Every student will carry out experiments in each of the three branches of chemistry on a rotation basis from 1st to 3rd Semester

24

THIRD SEMESTER
ANALYTICAL CHEMSITRY SPECIALISATION C - 301 AC PRINCIPLES OF CHEMICAL ANALYSIS
52 hours

I. Acid Base Titrations: 5h Basic principles, Titration curves for mono functional acids and bases, pH calculations, theory of indicators, fractions of phosphoric acid species as a function of pH. Titration curves for polyfunctional acids [H3PO4], polyamines and amino acid systems. II. Redox Titrations: 6h Nernst equation, Standard & formal potentials. Titration curves, end point signals, Indicators, criteria for the selection of indicators. Feasibility of redox titration. Titration of multicomponent system. Adjustment of analytes oxidation state. Applications: Oxidants such as Permanganate, dichromate, Ce (IV), bromate, Iodates. III. Precipitation titrations: 5h Solubility product. Theoretical principles: Titration curves, end point signals, Mohr, Volhard and adsorption indicators. Applications: Estimation of F-, K+, CO32-, C2O42-, acetylenes and mixture of halides IV. Complexometric titrations: 6h Complexometric titrations with particular reference to EDTA titrations, suitability of polydentate ligands as titrants, expressions for the different forms of EDTA in solution as a function of pH, conditional stability constants, derivation of titration curve, effect of pH and second complexing agent on the conditional stability constant and titration curve. Selectivity by pH control, masking and demasking, metal ion indicators, types of EDTA titrations, titrations involving monodentate V. Karl-Fischer titrations: 5h Stoichiometry of the reaction, preparation of the reagent, titration method, standardization of the reagent using water-in-methanol, determination of water in samples, interference and their elimination, application to quantitative analysis of some organic compounds- alcohols, carboxylic acids, acid anhydrides and carbonyl compounds. VI. Non-Aqueous titrations: 5h Acid base titrations in non-aqueous solvents- classification of solvents, leveling and differentiating solvents, acidic and basic titrants, methods of titration. Titrations in glacial acetic acid and ethylene diamine, applications of non-aqueous titrations. VII. Gravimetric analysis: 5h Formation and treatment of precipitates, co-precipitation, homogeneous precipitation, important precipitating agents and their significance in inorganic analysis.
25

VIII. Kinetic methods of analysis: 5h Rate laws, psuedo first order kinetics, types of kinetic methods, fixed time methods. Applications of catalytic and non-catalytic kinetic methods. IX.Electroanalytical techniques 10h Membrane indicator electrodes- Classification of membranes, properties of ion-selective membranes, the glass electrode for PH measurements, glass electrodes for other cations, crystalline membrane electrodes,liquid membrane electrodes. Ion-selective field-defect transistors (ISFETs): Mechanisam of ISFET ion-selective behavior, application of ISFETs. Molecular selective electrode systems: Gas-sensing probes, biocatalytic membrane electrodes, disposable multiplayer p-ion systems. SUGGESTED BOOKS
1. 2. 3. 4. 5. 6. 7. 8. Fundamentals Of Analytical Chemistry-Skoog, West And Holler 7th Edition Saunders College Publishing Int.Ltd. (1996) Modern methods of Chemical analysis-Pecsok, Shields, Cairns and McWilliams (2nd edition), John Wiley and Sons (1976). Vogels Textbook of Quantitative Inorganic Analysis, Bassett, Denney, Jeffery and Mendham, (4th edition) ELBS (1989). Analytical Chemistry-G.D.Christian (5th edition) John Wiley & sons (19946). Treatise on analytical Chemistry-Kolthoff, Elving and Krivan (2nd edition) John Wiley & Sons (1986). Commercial methods of analysis-Snell and Biffen, McGraw Hill, (1944) Hand Book Of Instrumental Techniques For Analytical Chemistry, Frank Settle, Prentice Hall PTR (1997) Fundamentals of Analytical Chemistry, Eigth Edition, Skooj, West,Holler and Crouch; Thomson Asia Pvt. Ltd(2004).

C-302 AC REACTION MECHANISM, CATALYSIS AND ORGANOMETALLIC CHEMISTRY

52 hours A. Kinetics and mechanism Labile, inert, stable and unstable complexes; Classification of mechanisms-energy profile of reactions having different mechanisms. 3h Substitution in square planar complexes: Trans effect, trans influence, theories of trans effect, application of trans effect in the synthesis of new complexes. 3h Mechanism of ligand substitution in octahedral complexes-kinetics, leaving groups, chelate and metal effects, Acid and Base catalysis: acid catalyzed equation and anation reactions, base hydrolysis, conjugate base hydrolysis, Stereochemistry of octahedral substitution, Application of ligand substitution reactions for the synthesis of new octahedral complexes. 6h Electron transfer reactions: complementary and non-complementary, outer-sphere electron transfer, Marcus equation. Inner-sphere electron transfer-one and two electron transfer. Use of electron transfer reactions for the synthesis of new complexes. 5h Oxidative addition , reductive elimination, Isomerisation, migratory insertion reactions. 3h

26

B Catalysis 16h Introduction basic principles, industrial requirements, thermodynamic and kinetic aspects, classification of catalytic systems. Catalysis involving metal complexes and organometallics: hydrogenation, asymmetric hydrogenation, hydroformylation (oxo process), Wacker processacetaldehyde from ethylene; Reppe Monsanto process-acetic acid from methanol, Reppe carbonylation-acrylic ester from acetylene; ethylene glycol from synthesis gas, water gas shift(WGS)reaction, Ziegler-Natta catalysis, Fischer Tropsch process C Organometallic chemistry 16h Organometallic complexes, stability and decomposition pathways, classification of ligands, Nomenclature of organometallic complexes, 16- and 18-electron rules, Electron counting covalent and ionic models. Synthesis, structure , bonding and decomplexation reactions of organotransition metal complexes having - and -M-C bonds -Bonded systems involving carbonyls, carbenes and carbynes -bonded systems involving dihapto to octohapto ligands like acetylene, olefins, allyl moieties, butadiene, cyclobutadiene, cyclopentadiene, arenes, cyclohexa and cycloheptadienyl moieties, cyclohepta and cyclooctatrienes, cyclooctatetraene moities, Fluxional behaviour in organometallic compounds, Isoelectronic and isolobal concepts SUGGESTED BOOKS
1.Inorganic and Organometallic reaction mechanisms, J.D.Atwood, Brooks/cole publishing co. (1985). 2.Reaction mechanisms of Inorganic and Organometallic systems, J.B. Jordon, Oxford University press, 2nd edition (1998). 3. Inorganic Chemistry, G.L Miessler and D.A. Tarr, 4. Organometallic Chemistry, R.C. Mehrotra and A. Singh, Wiley Eastern (1991). 5. Principles and applications of Organo-transition metal chemistry, J.P. Colman and L.S. Hegedus, University Science Book (1980). 6. The Organometallic Chemistry of the transition elements, R.H. Crabtree, John Wiley & Sons. (1998). 7. Catalytic Chemistry, B.C. Gates , John Wiley & Sons (1992). 8. Homogeneous catalysis by metal complexes, M.M. Taqui Khan and E.A. Martell, Academic Press (1974). 9. Principles and application of the organotrnsition metal chemistry, J. P. Collman, L. S. Hegedus, University Science books, 1980. 10. Organometallics, Vol. 1 & 2, M. Bochmann, Oxford Chemistry primers, Oxford University Press, 1994 11. Organotransition metal chemistry, S. G. Davies, Pergamon Press, Oxford, 1982. 12. Applied organometallic chemistry and catalysis R. Whyman oxford University press,2001

27

C - 303 ADVANCED ANALYTICAL TECHNIQUES

(Common to Inorganic and Analytical Chemistry) 52 hours 1 Optical spectroscopy methods 15h Atomic spectroscopy, absorption, emission, fluorscence techniques, principles and differences, Flame AAS, Instrumentation, different types of nebulizers, Nonflame techniques, GAAS, electrothermal vapourisers, cold vapour AAS, radiation sources, HCL, EDL, TGL etc. detectors, photoemmissive cells, PMT, photodiodes, Interferences, spectral, chemical, matrix, background absorption, correction methods, deuterium arc, zeeman effect, SmithHieftje methos, single beam and double beam instruments, evaluation procedures, applications of AAS, AES and AFS. Inductively coupled plasma optical emission spectrometry, theory, ICP characteristics, sample introduction methods, tourch configuration and view modes, analytical performance. Microwave induced plasma systems in atomic spectrometry, principal processes, mass spectrometry in the analysis of inorganic compounds 8h II Electroanalytical techniques 12h Electrode Potentials, Currents in Electrochemical cells, Potentiometric titrations. Electrogravimetry, Coulometry, and Coulometric titrations. Voltammetry, HydrodynamicVoltammetry, Cyclic voltammetry, Anodic stripping voltammetry, Polarography, Pulse polarography and Amperometry. III Thermal methods of analysis Principle, methodology and applications: thermogravimetric and differential thermal analysis, differential scanning calorimetry; Thermo-mechanical and dynamic mechanical analysis ; thermometric titrations. IV Analysis of Biomolecules 9h Introduction, single biomolecule detection and characterization, Fluorescence based biosensors, mass spectrometry in structural biology, NMR of biomolecules, Raman spectroscopy in analysis of biomolecules, Voltammetry in Vivo for chemical analysis of nervous system SUGGESTED BOOKS
1. Analytical Chemistry. Gary D Christian, 5th Edition, John Wiley and Sons Inc., (1994) 2. Fundamentals of Analytical Chemistry.D. A. Skoog, D. M. West and F. J. Holler, 7th Edition, Saunders College Publishing (1996). 3. Instrumental methods of Analysis.H. H. Willard, L. L. Merrit , J. A. Dean and F. A. Set, CBS Publishers (1996). 4. Instrumental methods of Chemical Analysis, G. W. Ewing, 5th edition, McGraw-Hill, New York, 1988. 5. Electrochemical methods: A.J. Bard & l. R. Faulkner, 2nd edition, Wiley, New York, 2000. 6. Vogels text book of Quantitative Chemical analysis 5th edition, Ed., Jeffery et. al ELBS/Longman, 1989 7. Encyclopedia of Analytical Chemistry: Ed. By R.A. Meyers Vol. 1 15, John Wiley, 2000. 8. Fundamentals of Instrumental Analysis, Skoog, D. M. West and F. J. Holler, 8th Edition, Saunders College Publishing (2004).

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C-304 SPECTROSCOPY II
(Common to Analytical, Inorganic, Organic and Physical Chemistry Students) 52 hours I. Ultraviolet and visible spectroscopy 3h Classification of elecgronic transitions, Terminology, Substituent and solvent effects, UV spectral study of alkenes, polyenes, enones and aromatic compounds. Empirical rules for calculating maxII. Vibrational Spectroscopy: spectroscopy 9h Sampling techniques, Group frequencies, factors affecting group frequencies,Bond order, Mass effect, Conjugation, Inductive, resonance, Steric effects. Intramolecular interactions. Applicaton of IR in the stuy of H-bonding, stereoisomerism and tautomerisam. Complimentarity of IR and Raman. Identification of the following organic compounds by IR: Alkanes, Alkenes, Alkynes, Aromatic compounds, Aldehydes, Ketones, Alcohols, Acids, Acid chlorides, Amides, Amines, Esters, Halides, Nitro compounds, etc., problems using UV and IR. III. Nuclear magnetic resonance spectroscopy 15h Introduction, Magnetic properties of nuclei- Resonance condition. Nuclear spin, population of nuclear spin levels and NMR isotopes, Relaxation methods. Insturmetnation and sample handling, FT-NMR. Chemical shift- Mechanism of shielding and deshielding in Alkanes, Alkyl halides, Alkenes, Aromatic compounds, Carbonyl compounds and Annulenes. Pascals triangle-low and high resolution, spectrum of ehnaol. Karplus Curve, Diamagnetic and paramagnetic effects and magnetic anisotropy. Equivalence of protons-chemical and magnetic equivalence. Spinsystems: First order and second order coupling of AB systems, Simplifications of complex spectras. Problems. Spin-spin interactions- AX,AX2, AX3, AMX,AB types. Vicinal, geminal and long range coupling-Spin decoupling. Chemical shift reagents and deuterium exchange. Stereochemistry and hindered rotations. Termperature effects. CIDNP, Nuclear Overhauser effect (NOE)., Factors influencing coupling constants and Relative intensities. Protons attached to elements other than carbon. C NMR and Correlation Spectroscopy: 10h C NMR Spectroscopy- Types of CMR spectra-undecoupled, proton decoupled, Offresonance decouled (SFORD): Selectivity decoupled and gated decoupled spectra. 13C chemicals shifts of Alkanes, Alkyl halides, Alkenes, Alcohols, Ethers, Carbonyl compounds and aromatic compounds, Factors affecting the chemical shifts. Applications of 13C NMR Spectroscopy in confirmation of structure and stereochemistry of organic molecules and in determinng the reaction mechanism and dynamic processes of organic reactions- examples.
13 13

29

Introduction to 2D-NMR Pulse sequences. FT-Methods. Classification of 2D Experiments. 2D-J-resolved spectroscopy. HOMO and HETERO-2D-J-Resolved spectra. Correlation Spectroscopy (COSY). Homonuclear (13C-13CJ), and heteronuclear (13C-1H, 13C-2HJ) couplings, DEPT. Explanation of the principle, applications to structure elucidation and stereochemistry of simple organic molecules. IV.Mass spectrometry and Composite Prooblems: 8h Basic principles-instrumentation ion production-ion analysis-magnetic sector instrumentsQuadrapole mass spectrometers. Time of flight mass spectrometers-ion cyclotron resonance spectrometers- Mass spectrum-molecular ion-types of ions in mass spectra and effects of isotopes on mass spectra. Methods of ionization, EI, FAB mass and MALDI methods. Fragmentation of: Alkanes, Alkenes, alkyl halides, alcohols, aldehydes, ketones, acids, esters, ethers, amines, nitro and halo compounds peptides, Nitrogen rule, Factors affecting cleavage patterns. MeLafferty and MeLafferty +1 rearrangment. Determination of molecular formula. Composite problems. Use of HRMS to determine exact molecular formulae of compounds. Application of NMR and MS methods and chemical reactions in structureelucidation of organic compounds. 7h SUGGESTED BOOKS
1. Applications of absorption spectroscopy to organic compounds, J. R. Dyer, Prentice-Hall, New Delhi, 1969. 2. Organic spectroscopy, P. Laszlo and P. Stang, Harper & Row, New York, 1971. 3. Organic spectroscopy, W. Kemp, ELBS London, 2000. 4. Spectrometric identification of organic compounds, R. M. Silverstien, and W. P. Weber, 2005. 5. Introduction to spectroscopy, 3rd Edn., D. L. Pavia, G. M. Laupman and G. S. Kriz, Harcourt College Publishers, 2001. 6. Organic mass spectroscopy, K. R. Dass & E. P. James, IBH New Delhi, 1976. 7. Interpretation of organic mass spectra, F. W. McLafferty, W. A. Benjamin, London, 1973. 8. Practical Organic Mass Spectroscopy, 2nd Edn. J R Chapman, John Wiley, NY, 1993. 9. The IR Spectra of complex molecules, Vols. I and II, L J Bellamy, Chapman and Hall, London, 1975. 10. Spectroscopic techniques for Organic Chemists, J W Cooper, John Wiley, NY, 1980. 11. Biomolecular NMR Spectroscopy, J N S Evans, Oxford Univ. 1995. 12. Mass spectrometry a foundation course, K Downard, RSC, Cambridge, 2004. 13. Mass spectrometry of organic compounds, H. Budzkiewicz, Djerassi C. and D. H. Williams, Holden-Day, New York, 1975. 14. Modern NMR techniques and their Applications, Ed. A I Popov, Marcel Deckker, 1991. 15. Modern structural theory of organic compounds, L. N. Ferguson, Prentice-Hall, New Delhi, 1973. 16. Instrumental methods of analysis, H. H. Willard, L. L. Merrit, J. A. Dean and F.A. Settle, CBS Publishers and Distributors, 1986. 17. Fundamentals of molecular spectroscopy, 4th edn., C. N. Banwell and E. M. McCash,Tata McGraw-Hill, New Delhi, 1999.

30

C- 305 Analytical Chemistry Practical I (Organic Chemistry)

I Preparation of one stage compounds 12. Cannizarro reaction: Benzaldehyde. 13. Friedel-Crafts reaction: Benzene and Acetyl chloride. 14. Claisen-Schmidt reaction: Acetophenone and Benzaldehyde / acetone and benzaldehyde. 15. Sandmeyer reaction: p-Chlorotoluene from p-toluidine.. 16. Preparation of S- benzylisothiuronium chloride.

II Preparation of two and three stage compounds 9. p-Nitroaniline from aniline. 10. p-Bromoaniline from acetanilide. 11. Anthranilic acid from phthalic acid. 12. 2,4-Dinitrophenylhydrazine from chloronitrobenzene. 13. m-Nitrobenzoic acid from methyl benzoate. III Quantitative analysis 7. Saponification value of oil. 8. Estimation of glucose. 9. Estimation of Keto group 10. Estimation of amines/phenols by acylation method. 11. Iodine value of oil. SUGGESTED BOOKS
11. Laboratory manual of Organic Chemistry- B. B. Dey, M V Sitaraman and T R Govindachari, Allied Publishers, New Delhi, (1996). 12. Practical Organic Chemistry Mann and Saunders, (1980). 13. Text Book of Practical Organic Chemistry- A. I. Vogel, (1996). 14. Test Book of Quantitative Organic Analysis- A. I. Vogel, (1996). 15. A Handbook of Organic Analysis Clarke and Hayes, (1964). 16. Comprehensive practical organic chemistry : Preparation and quantitative Analysis, V.K. Ahluwalia, R. Aggarwal, Universities Press (India), 2000. 17. Comprehensive practical organic chemistry: Qualitative analysis, V.K. Ahluwalia, S. Dhingra, Universities Press (India), 2000. 18. An advanced course in practical chemistry, A. Ghoshal, B. Mahapatra and A.Kr. Nad, New central book agency, Calcutta, 2000. 19. Advanced practical organic chemistry, J. Mohan, Vol. I and II, Himalaya Publishing House, 1992. 20. Practical organic chemistry (Quantitative analysis), B. B. Dey, M V Sitaraman and T R Govindachari, Allied Publishers, New Delhi, 1992. 11. Laboratory Techniques in Organic Chemistry, V K Ahluwalia, Pooja Bhagat and Renu Aggarwal, I K international Publishing House, New Delhi, 2005. 12. Intermediates for Organic Synthesis, V K Ahluwalia, Pooja Bhagat, Ramesh Chandra and Renu Aggarwal, I K International Publishing House, New Delhi, 2005.

31

C- 306 Analytical Chemistry Practical II

I Ore Analysis: Analysis of haematite: Estimation of silica by gravimetry and iron by volumetry. Analysis of Portland cement: Estimation of insoluble residue by gravimetry and CaO by volumetry Analysis of bauxite :Estimation of silica by gravimetry and aluminium by gravimetry Analysis of dolomite: Estimation of CaO and MgO by volumetry Analysis of pyrolusite:Estimation of metallic hydroxides by gravimetry and manganese by volumetry II Alloy Analysis: Analysis of brass: Estimation of copper by gravimetry and zinc by EDTA titration Analysis of bronze: Estimation of copper by volumetry and tin by gravimetry Analysis of type metal: Analysis of lead by volumetry and tin by gravimetry Analysis of chrome steel: Estimation of iron by volumetry and Cr by colorimetry Analysis of mint alloy: Estimation of copper by volumetry and nickel by gravimetry Analysis of hindalium: Estimation of aluminium Analysis of woods alloy III Soil Analysis: 13. Analysis of N, P, K and micro nutrients like Cu, Zn etc in the soil samples.

SUGGESTED BOOKS
1. Quantitative Inorganic Analysis by A.I.Vogel.2nd edition .ELBS London. 2. A Text Book of Soil Chemical Analysis, P.R. Hesse CBS, new Delhi, 2002. 3. Practical Inorganic Chemistry, G. Marr and B.W. Rockett, Van Nostrand Reinhold Co. London 1972. 4. Quantitative Inorganic Analysis, Day and Underwood

32

THIRD SEMESTER
INORGANIC CHEMISTRY SPECIALISATION C-301 IC SOLID STATE CHEMISTRY 52 hours
1 `Electronic structure of solids 7h Bonding in solids: Ionic, covalent, metallic and molecular solids Free electron theory, Fermi sphere, Fermi-Dirac statistics, Ohms law, limitations of the free electron theory Electrons in a weak periodic potential (Independent electron model), energy levels in extended, repeat and reduced zone schemes II Electrical and Magnetic Properties of Solids 9h Metals: calculation of density of states, origin of resistivity, weak paramagnetism. Semiconductors: Intrinsic and extrinsic- p and n-types, Hall effect, Junctions and their applications- metal-metal, metal-semiconductor, semiconductorsemiconductor types and transistors Insulators- dielectric properties, piezo and inverse piezoelectric effects, ferroelectricity, ferroelectric transitions in BaTiO3, ionic conductivity applications of band theory to TiO and NiO: Limitations of the Independent electron model, modeling electron correlation Organic conductors- polyacetylene, polyparaphenylene, polypyrrole and related materials III Dynamics of Atoms in a Solid 4h Dispersion curves of an elastic structureless medium, Longitudinal and Transverse modes, Optical and Acoustic modes of a crystal, total vibrational energy of a crystal. Case study of calcite. IV. Defects in Solids Point defects, Line defects and Plane defects, Stacking faults and grain boundaries 2h

V Superconductivity 4h Superconductivity, Meisner effect, Type I and type II superconductors, Features of superconductors, Frolich diagram, Cooper pairs, Theory of low temperature superconductivity, Junctions using superconductors VI Phase Transition in Solids 2h Definitions, Classification of phase transitions, First and second order phase transitions: Martensitic transition, order-disorder transitions and spinodal decomposition VII. Geometric Crystallography Symmetry elements, Bravais lattices, Screw axes and glide planes, point groups, space groups and nomenclature. Law of Interfacial angle (Eulers construction).
33

5h and

VIII. Diffraction theory and Single crystal X-ray diffraction 9h X-rays, Braggs law, assignment of lines, diffraction pattern of a primitive cubic lattice, space group extinctions, Scaterring factor and structure factor, intensities from atomic positions for BCC and FCC lattices; Ewalds sphere of reflection, Reciprocal Lattice concept, Electron density function, Fourier synthesis, Fourier transform of the structure factor, Phase problem and Patterson synthesis. IX. Experimental Methods: 3h Rotation, Oscillation, Weissenberg and Precession methods,. Debye-Scherrer method (Powder method), Determination of lattice parameters from these methods. X. Electron diffraction: Experimental technique, Wierl equation, Radial-Distribution method. XI. Neutron diffraction: Principle and Theory, advantages and uses. SUGGESTED BOOKS
Introduction to Solids, L. V. Azaroff, McGraw Hill Book Co., New York, 1960. Solid State Physics, N. W. Ashcroft and N. D. Mermin, Holt Saunders International Ltd., New York (1976). Physical Chemistry, G. M. Barrow, McGraw Hill (2nd ISE) (1966). An Introduction to X-ray Crystallography, M. M. Woolfson, Cambridge University Press-Vikas Publishing House, New Delhi (1980). 5. Principles of the Solid State, H. V. Kheer, Wiley Eastern Ltd., New Delhi (1993). 6. Dynamics of Atoms in Crystals, W. Cochran, Edward Arnold, London, 1973. (pages 24-37) 7. Vibrational Spectroscopy of Solids, P.M.A. Sherwood, University Press, Cambridge, 1972. (pages: 1-45) 8. Phase Transitions, C.N.R. Rao and K.J. Rao, Cambridge University Press 9. X-ray Structure determination: A practical guide, George H Stout and Lyle H Jenson, Macmillan Publishing Co.Inc and Collier Macmillan Publishers 10. Crystal Structure analysis for chemists and biologists, J.P.Glusker, M. Lewis and M. Ross,Wiley-VCH (1994). 1. 2. 3. 4.

2h

2h

C-302 IC INORGANIC RACTION MECHANISMS & BIOINORGANIC CHEMISRTY

52 Hrs 1. Kinetics and mechanism Labile, inert, stable and unstable complexes; Classification of mechanisms-energy profile of reactions having different mechanisms. 3h Substitution in square planar complexes: Trans effect, trans influence, theories of trans effect, application of trans effect in the synthesis of new complexes. 3h Mechanism of ligand substitution in octahedral complexes-kinetics, leaving groups, chelate and metal effects, Acid and Base catalysis: acid catalyzed equation and anation reactions,

34

base hydrolysis, conjugate base hydrolysis, Stereochemistry of octahedral substitution, Application of ligand substitution reactions for the synthesis of new octahedral complexes. 6h Electron transfer reactions: complementary and non-complementary, outer-sphere electron transfer, Marcus equation. Inner-sphere electron transfer-one and two electron transfer. Use of electron transfer reactions for the synthesis of new complexes. 5h Oxidative addition , reductive elimination, Isomerisation, migratory insertion reactions. 3h II Introduction to Bioinorganic chemistry Essentials and trace elements in biological processes, elements in biological cell, biomolecules associated with metal ions and their roles. Molecular mechanism of ion transport across cell membranes, ionophores, crown ethers, Na+/K+ ion pump. Metal ion storage and transfer-ferritin, transferrin and siderophores. Metal ligand interactions with DNA. Importance of Ca2+ in muscle contractions and in blood clotting process. Metal ion deficiency, toxicity, detoxification, chelation therapy, metal complexes used as anticancer and antiarthritic drugs. 13h Metalloproteins: Transport and storage of dioxygen: Heme proteins and oxygen uptake, structure and functions of haemoglobin and myoglobin, dioxygen binding, model complexes; Nonporphyrin systems-hemerythrin and hemocyanin. Structure and functions of metalloproteins in electron transfer process-cytochromes-, ferridoxines and rubredoxines. Mitochondrial flow of electrons from NADH to oxygen. Cytochrome c, Cytochrome c oxidase 7h Metalloenzymes: Zinc enzymes-carboxypeptidase, carbonic anhydrase and alcohol dehydrogenase. Copper enzyme-superoxide dismutase. Molybdenum enzymes-oxotransferase enzyme, xanthineoxidase. Iron enzymes-catalase, peroxidase and cytochrome P-450. Coenzymes containing cobalt, vitamin B12, Co-C bond cleavage,mutase activity of coenzyme B12, alkylation reaction of methyl cobalamin. 8h Photosynthesis and nitrogen fixation: Nitrogen fixation; nitrogenase-bacterial nitrogenase systems and synthetic studies. Photosynthesis: Structure of chlorophyll, PS I & PS II in cleavage of water. 4h SUGGGESTED BOOKS
1. 2. 3. Inorganic and organometallic reaction mechanism, J.D.Atwood, Brooks/cole publication co. (1985). Reaction mechanism of inorganic and organometallic systems, J.B.Jordon, Oxford University press, 2nd edition (1998). Inorganic Chemistry, G.L. Miessler and D.A. Tarr, Pearson education 3rd edition (2007). 35

4. 5. 6. 7. 8. 9.

10.

Inorganic Chemistry , K.F.Purcell and J.C.Kotz, Saunders company, (1977) Principle and Application of Organotransition metal chemistry, J.P.Collmann, L.S.Hegedus, J.R.M.Norton and R.G.Finke, University Science Books, (1987). Inorganic Chemistry, G.Wulfsberg, Viva Books private Ltd. (2002). Bioinorganic chemistry, N.Hussain Reddy. New Age international publications (2003) Bio-inorganic chemistry, I.Bertini, H.B.Gray, S.J.Lippard & J.S.Valentine, Viva Books Pvt.Ltd. (1998) Principles of Bioinorganic Chemistry, S.J.Lippard and J.M.Berg, Panima Pub. Corpotation (1997). Bioinorganic Chemistry, Asim K das, Books and allied (p) Ltd. (2007).

C-303 IC NUCLEAR CHEMISTRY

52 hours I Nuclear properties and models 8h Mechanical effects due to orbiting and spinning of nucleons, magnetic properties of nucleons, electrical quadrupole moment of nucleides, nuclear parity, nuclear statistics, nuclear forces and interactions.Nuclear models: :Liquid drop, shall Fermi gas model, collective model and optical model. II Nuclear reactions 7h Fundamentals, Types, Conservation and Threshold, Reaction cross section, Fission and Fusion, Compound nucleus theory III Radioactivity 9h Radioactive decay kinetics, Parent-daughter decay-growth relationships- Secular and transient equilibria, Theories of -, -, + and - decay, Internal conversion, Auger effect IV Applications of radioactivity 9h Synthesis of various useful isotopes, Use of isotopes in elucidation of reaction mechanism, structure determination, kinetics of exchange reactions, measurement of physical constants including diffusion constants, radioanalysis- isotope dilution techniques, NAA, PGNAA, neutron absorptiometry and age determination, Radioisotopes in the field of medicine. V Radiation chemistry 9h Interaction of matter with radiation, radiation dosimetry-units and measurement using chemical dosimeters, radiolysis of water, the hydrated electron- preparation and properties, free radical generation, radiation damage to solids- effects of radiation on metals, alloys, semiconductors, insulators and catalysts. VI Nuclear reactors 5h Fission energy, Criticality, Fermis four factor formula, Classification of reactors based on fuel, neutron energy, moderator and coolant types. Fuel-moderator-coolant combinations to achieve criticality, CANDU reactors: Safety implications (Elective)

36

VII Particle accelerators 5h Van deGraff generator, CW voltage multiplier, LINACS, Cyclotron, Synchrocyclotron, Betatron SUGGESTED BOOKS
1. 2. Essentials of Nuclear Chemistry, H. J. Arnikar, 4th Edition NAIL Pub, 1995. Nuclear and Radiochemistry, J. Friedlander, J. W. Kennedy and J. M. Miller, Wiley-Interscience, New York (1981). 3. Nuclear Physics, I. Kaplan, India Book House, Bombay (1978). 4. Source Book on Atomic Energy, S. Glasstone, East West Press, Delhi (1977) 5. Nuclear Chemistry;U.N. Dash;Sulthan Chand and Sons(1991).

C - 303 ADVANCED ANALYTICAL TECHNIQUES

(Common to Inorganic and Analytical Chemistry) 52 hours 1 Optical spectroscopy methods 15h Atomic spectroscopy, absorption, emission, fluorscence techniques, principles and differences, Flame AAS, Instrumentation, different types of nebulizers, Nonflame techniques, GAAS, electrothermal vapourisers, cold vapour AAS, radiation sources, HCL, EDL, TGL etc. detectors, photoemmissive cells, PMT, photodiodes, Interferences, spectral, chemical, matrix, background absorption, correction methods, deuterium arc, zeeman effect, Smith-Hieftje methos, single beam and double beam instruments, evaluation procedures, applications of AAS, AES and AFS. Inductively coupled plasma optical emission spectrometry, theory, ICP characteristics, sample introduction methods, tourch configuration and view modes, analytical performance. Microwave induced plasma systems in atomic spectrometry, principal processes, mass spectrometry in the analysis of inorganic compounds 8h II Electroanalytical techniques 12h Electrode Potentials, Currents in Electrochemical cells, Potentiometric titrations. Electrogravimetry, Coulometry, and Coulometric titrations. Voltammetry, Hydrodynamic Voltammetry, Cyclic voltammetry, Anodic stripping voltammetry, Polarography, Pulse polarography and Amperometry. III Thermal methods of analysis 8h Principle, methodology and applications: thermogravimetric and differential thermal analysis, differential scanning calorimetry; Thermo-mechanical and dynamic mechanical analysis ; thermometric titrations. IV Analysis of Biomolecules 9h Introduction, single biomolecule detection and characterization, Fluorescence based biosensors, mass spectrometry in structural biology, NMR of biomolecules, Raman spectroscopy in analysis of biomolecules, Voltammetry in Vivo for chemical analysis of nervous system
37

SUGGESTED BOOKS
1. Analytical Chemistry. G. D. Christian, V Edition, John Wiley and Sons Inc., (1994) 2. Instrumental methods of Analysis.H. H. Willard, L. L. Merrit , J. A. Dean and F. A. Set, CBS Publishers (1996). 3. Instrumental methods of Chemical Analysis, G. W. Ewing, 5th edition, McGraw-Hill, New York, 1988. 4. Electrochemical methods: A.J. Bard & l. R. Faulkner, 2nd edition, Wiley, New York, 2000. 5. Vogels text book of Quantitative Chemical analysis 5th edition, Ed., Jeffery et. al ELBS/Longman, 1989 6. Encyclopedia of Analytical Chemistry: Ed. By R.A. Meyers Vol. 1 15, John Wiley, 2000. 7. Fundamentals of Analytical Chemistry, Eigth Edition, Skooj,West,Holler and Crouch; Thomson Asia Pvt. Ltd(2004).

C-304 SPECTROSCOPY II
(Common to Analytical, Inorganic, Organic and Physical Chemistry Students) 52 hours I. Ultraviolet and visible spectroscopy 3h Classification of elecgronic transitions, Terminology, Substituent and solvent effects, UV spectral study of alkenes, polyenes, enones and aromatic compounds. Empirical rules for calculating maxII. Vibrational Spectroscopy: spectroscopy 9h Sampling techniques, Group frequencies, factors affecting group frequencies,Bond order, Mass effect, Conjugation, Inductive, resonance, Steric effects. Intramolecular interactions. Applicaton of IR in the stuy of H-bonding, stereoisomerism and tautomerisam. Complimentarity of IR and Raman. Identification of the following organic compounds by IR: Alkanes, Alkenes, Alkynes, Aromatic compounds, Aldehydes, Ketones, Alcohols, Acids, Acid chlorides, Amides, Amines, Esters, Halides, Nitro compounds, etc., problems using UV and IR. III. Nuclear magnetic resonance spectroscopy 15h Introduction, Magnetic properties of nuclei- Resonance condition. Nuclear spin, population of nuclear spin levels and NMR isotopes, Relaxation methods. Insturmetnation and sample handling, FT-NMR. Chemical shift- Mechanism of shielding and deshielding in Alkanes, Alkyl halides, Alkenes, Aromatic compounds, Carbonyl compounds and Annulenes. Pascals triangle-low and high resolution, spectrum of ehnaol. Karplus Curve, Diamagnetic and paramagnetic effects and magnetic anisotropy. Equivalence of protons-chemical and magnetic equivalence. Spinsystems: First order and second order coupling of AB systems, Simplifications of complex spectras. Problems. Spin-spin interactions- AX,AX2, AX3, AMX,AB types. Vicinal, geminal and long range coupling-Spin decoupling. Chemical shift reagents and deuterium exchange. Stereochemistry and hindered rotations. Termperature effects.

38

CIDNP, Nuclear Overhauser effect (NOE)., Factors influencing coupling constants and Relative intensities. Protons attached to elements other than carbon.
13

C NMR and Correlation Spectroscopy: 10h C NMR Spectroscopy- Types of CMR spectra-undecoupled, proton decoupled, Offresonance decouled (SFORD): Selectivity decoupled and gated decoupled spectra. 13C chemicals shifts of Alkanes, Alkyl halides, Alkenes, Alcohols, Ethers, Carbonyl compounds and aromatic compounds, Factors affecting the chemical shifts. Applications of 13C NMR Spectroscopy in confirmation of structure and stereochemistry of organic molecules and in determinng the reaction mechanism and dynamic processes of organic reactions- examples. Introduction to 2D-NMR Pulse sequences. FT-Methods. Classification of 2D Experiments. 2D-J-resolved spectroscopy. HOMO and HETERO-2D-J-Resolved spectra. Correlation Spectroscopy (COSY). Homonuclear (13C-13CJ), and heteronuclear (13C-1H, 13C-2HJ) couplings, DEPT. Explanation of the principle, applications to structure elucidation and stereochemistry of simple organic molecules. IV. Mass spectrometry and Composite Prooblems: 8h Basic principles-instrumentation ion production-ion analysis-magnetic sector instrumentsQuadrapole mass spectrometers. Time of flight mass spectrometers-ion cyclotron resonance spectrometers- Mass spectrum-molecular ion-types of ions in mass spectra and effects of isotopes on mass spectra. Methods of ionization, EI, FAB mass and MALDI methods. Fragmentation of: Alkanes, Alkenes, alkyl halides, alcohols, aldehydes, ketones, acids, esters, ethers, amines, nitro and halo compounds peptides, Nitrogen rule, Factors affecting cleavage patterns.MeLafferty and MeLafferty +1 rearrangment. Determination of molecular formula. Composite problems. Use of HRMS to determine exact molecular formulae of compounds. Application of NMR and MS methods and chemical reactions in structureelucidation of organic compounds. 7h SUGGESTED BOOKS
1. Applications of absorption spectroscopy to organic compounds, J. R. Dyer, Prentice-Hall, New Delhi, 1969. 2. Organic spectroscopy, P. Laszlo and P. Stang, Harper & Row, New York, 1971. 3. Organic spectroscopy, W. Kemp, ELBS London, 2000. 4. Spectrometric identification of organic compounds, R. M. Silverstien, and W. P. Weber, 2005. 5. Introduction to spectroscopy, 3rd Edn., D. L. Pavia, G. M. Laupman and G. S. Kriz, Harcourt College Publishers, 2001. 6. Organic mass spectroscopy, K. R. Dass & E. P. James, IBH New Delhi, 1976. 7. Interpretation of organic mass spectra, F. W. McLafferty, W. A. Benjamin, London, 1973. 8. Practical Organic Mass Spectroscopy, 2nd Edn. J R Chapman, John Wiley, NY, 1993. 9. The IR Spectra of complex molecules, Vols. I and II, L J Bellamy, Chapman and Hall, London, 1975. 10. Spectroscopic techniques for Organic Chemists, J W Cooper, John Wiley, NY, 1980. 11. Biomolecular NMR Spectroscopy, J N S Evans, Oxford Univ. 1995. 12. Mass spectrometry a foundation course, K Downard, RSC, Cambridge, 2004. 13. Mass spectrometry of organic compounds, H. Budzkiewicz, Djerassi C. and D. H. Williams, Holden-Day, New York, 1975. 39

13

14. Modern NMR techniques and their Applications, Ed. A I Popov, Marcel Deckker, 1991. 18. Modern structural theory of organic compounds, L. N. Ferguson, Prentice-Hall, New Delhi, 1973. 19. Instrumental methods of analysis, H. H. Willard, L. L. Merrit, J. A. Dean and F.A. Settle, CBS Publishers and Distributors, 1986. 20. Fundamentals of molecular spectroscopy, 4th edn., C. N. Banwell and E. M. McCash,Tata McGraw-Hill, New Delhi, 1999.

THIRD SEMESTER
ORGANIC CHEMISTRY SPECIALISATION

C-301 OC

ORGANIC REACTION MECHANISMS

52 Hours 10h

I. Aliphatic nucleophilic and electrophilic substitution reactions

Nucleophilic substitution reactions: Substitution at allylic carbon (allylic rearrangement), at a trigonal carbon (hydrolysis of esters and amides, use of DCC in the formation of anhydrides), substitution at a vinylic carbon. Neighboring group participation and SNi reactions. Electrophilic substitution reactions: SE2, SE1 and SEi mechanisms. Hydrogen exchange, migration of double bonds, halogenation of aldehydes, ketones and acids. Aliphatic diazonium coupling, nitrosation at carbon bearing active hydrogens, diazo transfer reaction, carbene and nitrene insertion, decarboxylation of aliphatic acids, haloform reaction, Haller-Bauer reaction. II. Free-radical chemistry 10h Generation of free-radicals: Thermal homolysis of peroxides, peresters and azo compounds, photochemical methods. Free radical reactions: Free-radical mechanisms in general. Free-radical substitution mechanisms. Mechanisms at an aromatic substrate. Neighboring group assistance in freeradical reactions. Reactivity for aliphatic substrates, reactivity at a bridgehead, reactivity in aromatic substrates, reactivity in the attacking radical. Halogenation at an alkyl carbon and an allylic carbon, hydroxylation at an aliphatic carbon, hydroxylation at an aromatic carbon, oxidation of aldehydes to carboxylic acids, formation of hydroperoxides and peroxides, Orton reaction, Gomberg-Bachmann reaction, Meerwein arylation, Sandmeyer reaction, Kolbe reaction and Hunsdiecker reaction. III. Photochemistry Physical and Chemical processes, Jablonski diagram. Photosensitization, quantum efficiency, quantum and chemical yields. Photochemistry of functional groups:
40

11h

i) Olefins: Cis-trans isomerism, [2 + 2]-cycloaddition, rearrangements. Reaction of conjugated olefins; di--methane rearrangements (including oxa- and aza- di--methane rearrangements). ii) Ketones: Excited state of C=O. Norrish type-I and type-II cleavages. Paterno-Buchi reaction. ,-unsaturated ketones. [2+2] addition. Rearrangement of cyclohexadienones (application in the synthesis of some important natural products). iii) Aromatic compounds: Photorearrangement of benzene and its derivatives, cycloaddition of benzene. iv) Photochemical oxidations and reductions: Cycloaddition of singlet molecular oxygen {[2+2], [4+2]-additions}. Oxidative coupling of aromatic compounds, photoreduction by hydrogen abstraction. IV. Pericyclic reactions 11h Molecular orbital symmetry, Woodward-Hoffmann correlation diagrams. FMO and PMO approaches. Frontier orbitals of ethylene, 1,3-butadiene, 1,3,5-hexatriene and allyl system. Electrocyclic reactions: conrotatory and disrotatory motions, 4n, 4n+2 and allyl systems. Cycloadditions: antarafacial and suprafacial additions, [ms + na] and [ms + ns]cycloadditions. [2a + 2s] and [4s + 2s]-cheletropic reactions. Regio, enantio and Endo selectivities in Diels-Alder reactions. Hetero Diels-Alder reaction. Sigmatropic rearrangements: suprafacial and antarafacial shifts of H, sigmatropic shifts involving carbon moieties. [i, j]- sigmatropic rearrangements (including Walk, Claisen, Cope, oxy and aza-Cope rearrangements). V. Biochemical mechanisms 10h Introduction. The mechanistic role of the following in living systems. i). Thiamine pyrophosphate (TPP) in decarboxylation of -ketoacids and in the formation of -ketols. ii). Pyridoxal phosphate (PLP) in transamination, decarboxylation, dealdolisation and elimination reactions of amino acids. iii). Lipoic acid in the transfer of acyl group reactions. iv). Coenzyme A (CoASH) in the transfer of acyl group. v). Biotin and vi). Vitamin KH2 coenzyme in carboxylation reactions. vii). Tetrahydrofolic acid (H4F) in one-carbon transfer reactions. viii). Vitamin B12 coenzymes in molecular rearrangement reactions and in the synthesis of methionine and methane. ix). Nicotinamide and x). Flavin coenzymes in biological redox reactions SUGGESTED BOOKS
1. Advanced Organic Chemistry Reactions, Mechanism and Structure, Jerry March, John Wiley (2008). 41

2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17.

Understanding organic reaction mechanisms, A. Jacob, Cambridge Univ. Press, 1997. Introduction to organic chemistry A. Streitweiser, Jr and C. H. Heathcock, Macmillan, 1985. Physical and mechanistic organic chemistry, R.A.Y. Jones, 1st Edn. Cambridge Univ. Press, 1979. Mechanisms of molecular migrations, Vols I and II, B. S. Thiagarajan, 1st Edn. Pergamon Press, Oxford, 1979. P. J. Garratt in Comprehensive organic chemistry, D. Barton and W. D. Ollis, 1st Edn. Pergamon Press, Oxford, 1979. Radicals in organic synthesis, B. Giese, Pergamon Press, 1986. Stereoelectronic effects in organic chemistry, P. Deslongchamps, 1st Edn. Pergamon Press, 1983. Frontier orbitals and organic chemical reactions, Ian Fleming, John Wiley, 1980. Molecular orbital theory for organic chemistry, A. Streitweiser, 1st Ed. Wiley & Sons, NY, 1969. Organic photochemistry, J. M. Coxon and B. Halton, 1st Edn, Cambridge Univ. Press, London, 1974. Orbital symmetry, R. E. Lehr and A. P. Marchand, Academic Press, 1972. Molecular reactions and photochemistry, C. H. Deputy and D. S. Chapman, 1st Edn. Prentice-hall India, New Delhi, 1972. Stereochemistry of Organic Compounds: Principles and Applications, D Nasipuri, New-Age International, (1999). Biochemistry, G. Zubey, Macmillan, NY, 1998. Biochemistry, D. Voet and J. G. Voet, John Wiley & Sons, 1998. Principles of Biochemistry, A. L. Lehninger, D. L. Nelson & M. M. Cox, 2nd Edn. Worth Publishers, NY, 2005.

C-302 OC ORGANIC SYNTHESIS

52 Hours I. C-C and C-N bond forming reactions 13h Darzen's reaction, Use of acetylides in C-C bond formation reactions. Acid-catalyzed self condensation of olefins, Prins reaction, Shapiro reaction, Dieckmann cyclization, Robinson annulation, Hofmann-Loeffler-Freytag reaction. Hofmann-Martius reaction. Acyloin condensation. Houben-Hoesch reaction. Stork-enamine synthesis. Meyer synthesis. Use of nucleophilic nitrogen and electrophilic carbon (NH3, amines and nitrite as nucleophiles in substitution, NH3 and amines in addition to ketones and aldehydes) and electrophilic nitrogen and nucleophilic carbon (nitration, nitrosation) for the bond formation reactions (including Chichibabin reaction, Skraup synthesis, Mitsunobu reaction, N-Nitroaromatic amine rearrangement, Fisher-Hepp reaction. Japp- Klingemann reaction). II. Reagents in organic synthesis Use of the following in organic synthesis and functional group tansformations.
42

10h

Lithium iso-propoxide, NBS, LDA, DCC, DDQ, trimethylsufoxoniun iodide, Raney-Nickel, diazomethane, TMS-chloride, 1,3-Dithiane (reactivity and umpolung), Bakers yeast, Fentons reagent. Woodward and Prevost hydroxylation. III. Oxidations 10h Cr (VI) oxidants, Mn (VII) oxidants, OsO4, SeO2, Pb (OAc)4, HIO4, Ag2O, DMSO, ozone, peroxides (H2O2, t-BuOOH, dibenzoylperoxide) and peracids (Preparation, properties and applications of CF3COOOH, m-CPBA, momoperphthalic acid) as oxidizing agents. DessMartin oxidation. IV. Reductions 10h Complex metal hydrides, dissolving metal reductions (including Birch, Benkeser, Clemmensen reductions), diimide reduction, catalytic hydrogenation (homogeneous and heterogeneous), organoboranes as reducing agents. Wolf-Kishner reduction, McMurry reaction. Pummer, Willgerdot, Corey-Bakshi-Shibata and Tishchenko reactions. V. Name Reactions in organic synthesis 9h Studies on the mechanistic aspects and use of the following in organic synthesis: PasseriniUgi reactions. Hantsch and Biginelli reactions. Deobner-Miller, Ritter and Jacobson reactions, Betti and Robinson-Schopf reactions, Barbier, Baylis-Hillmann, Ivanov, BischlerNapiaralski reactions and Suzuki coupling reaction. SUGGESTED BOOKS
Advanced organic chemistry, J. March, 4th Edn. John Wiley, 2008. Organic synthesis, R.E.Ireland, Prentice-hall India, New Delhi, 1975. 2. Understanding organic reaction mechanisms, A. Jacob, Cambridge Univ Press, 1997. 3. Introduction to organic chemistry, A. Streitweiser, Jr and C. H. Heathcock, Macmillan, 1985. 4. Physical and mechanistic organic chemistry, R. A.Y. Jones, 1st Edn. Cambridge Univ Press, 1979. 5. Modern synthetic reactions, H. O. House, W. A. Benjamin, California, 2nd Edn. 1972. 6. Some modern methods of organic synthesis, W. Carruthurs, Cambridge Univ. Press, London, 2nd Edn. 1978. 7. Mechanisms of molecular migration, Vols I & II, B.S. Thyagarajan, Pergamon Press, Oxford, 1979. 8. Comprehensive organic chemistry, D. Barton and W. D. Wallis, Pergamon Press, Oxford, 1983. 9. Organic chemistry Vol. II, I. L. Finar 6th Edn. Longman, 1992. 10. Organic reaction Mechanisms, 3rd Edn., V. K. Ahluwalia and R. K. Prashar, Narosa, New Delhi, 2005. 1.

C-303 OC

CHEMISTRY OF NATURAL PRODUCTS

52 Hours 12h

I. Terpenoids and Carotenoids Classification, nomenclature, occurrence and isolation. Isoprene rules. Stereochemistry of citral, farnesol, limonene, 1,8-cineole, menthols and borneols. Correlation of configurations of terpenoids.
43

Structure elucidation of camphene, -pinene, -caryophyllene, -santonin and gibberrillic acid. Synthesis and biosynthesis of the following: Linalool, -terpineol, fenchone, eudesmol, abietic acid. Commercial synthesis of camphor. Biosynthesis of squalene and cyclisation of squalene into -lanosterol and friedelene. Carotenoids: Methods of isolation. Structural relationship of -, - and -carotenes. Structure elucidation and synthesis of -carotene. II. Alkaloids 10h Definition, nomenclature, occurrence, isolation, classification, General methods of structure elucidation. Synthesis and biosynthesis of the following alkaloids: Ephedrine, hygrine, coniine, cocaine, cinchonine and morphine. Structure elucidation and synthesis of papaverine, reserpine and ergotamine. Photochemical synthesis of Nuciferine, coradyline and tylophorine. 8h III. Porphyrins and vitamin B12 Structure elucidation and synthesis of haemin, chlorophyll-a and vitamin-B12 (synthesis of Vitamin-B12 from cobyric acid). IV. Nucleic acids 9h Introduction, components of nucleic acids, nucleosides, nucleotides and oligonucleotides. Structure elucidation and synthesis of nucleosides and nucleotides. Chemical synthesis of oligonucleotides: Protecting groups for hydroxy group in sugar, amino group in the base and phosphate functions. Methods of formation of internucleotide bonds: DCC, phosphodiester approach, phosphotriester approach, phosphite triester and phosphoramidite methods. Solid phase synthesis of oligonucleotides. V. Prostaglandins 7h Introduction, nomenclature, classification and biological role of prostaglandins. Structure elucidation and stereochemistry of PGE1, PGE2 and PGE3. Synthesis of PGE1 and PGE2 by Coreys and Storks approaches. Synthesis of PGE3 by Upjohns approach. Synthesis of prostacyclin I2 and thromboxane B2. Biosynthesis of prostaglandins. VI. Insect pheromones Introduction, classification. Pheromones in pest control. Syntheses of (one synthesis should be stereoselective synthesis) i) Grandisol (component of boll weevil pheromone) ii) Farenal (trail pheromone of pharaohs ants) iii) Brevicomin (pheromone from Dendroitis brevicomis) iv) (+)- Disparlure (gypsy moth sex pheromone). v) 3,11-Dimethy1-2-nonacosanone (pheromone of German cockroaches).
44

6h

vi) Bombykol (sex pheromone of silkworm moth). vii) Multistriatin (Elm bark beetle sex pheromone). SUGGESTED BOOKS 1. Natural products: Their chemistry and biological significance-J. Mann, R. S. Davidson, J. B. Hobbs, D.
V. Banthorpe & J. B. Harborne, Longman, UK, 1994. 2. Terpenes, J. Verghese, Tata McGraw-Hill, New Delhi, 1982. 3. Chemistry of terpenes and terpenoids, A. Newman, Academic Press, London, 1975. 4. Handbook of naturally occurring compounds Vol. II: Terpenes, T. K. Davon, A. I. Scott, Academic Press, NY, 1972. 5. Natural products chemistry Vol. I & II, K. Nakanishi, T. Goso, S. Ito, S. Natori & S. Nozoe, Academic Press, NY, 1974. 6. Total synthesis of natural products Vol. I & VI, Apsimon, John Wiley, NY, 1973-1981. 7. Organic chemistry Vol.II, I. L. Finar, 6th Edn. Longman, 1992. 8. Chemistry of natural products Vol. I & II, O. P. Aggarwal, Goel Publishing House, 6th Edn. 1982. 9. Total synthesis of natural products: The chiral approach Vol.III, S. Hanessian Pergamon Press, 1983. 10. Total synthesis of steroids, Akhaun & Titov, Jerusalem, 1969. 11. Medicinal natural products: A biosynthetic approach, P. M. Dewick. John Wiley, Chichester, 1997. 12. The colours of life: An introduction to the chemistry of porphyrins and related compounds, L. R. Milgrom, Wiley Chichester, 1995. 13. Interpretation of the UV spectra of natural products, A.I. Scott, Pergamon Press, Oxford, 1964. 14. Spectral data of natural products Vol. I- K.Yamaguchi, Elsevier Publishing Co, London, 1970. 15. Chemistry of natural products: A unified approach, N. R. Krishnaswamy, University Press, India, 1999.

C-304 SPECTROSCOPY II
(Common to Analytical, Inorganic, Organic and Physical Chemistry Students) 52 hours I. Ultraviolet and visible spectroscopy 3h Classification of elecgronic transitions, Terminology, Substituent and solvent effects, UV spectral study of alkenes, polyenes, enones and aromatic compounds. Empirical rules for calculating maxII. Vibrational Spectroscopy: spectroscopy 9h Sampling techniques, Group frequencies, factors affecting group frequencies,Bond order, Mass effect, Conjugation, Inductive, resonance, Steric effects. Intramolecular interactions. Applicaton of IR in the stuy of H-bonding, stereoisomerism and tautomerisam. Complimentarity of IR and Raman. Identification of the following organic compounds by IR: Alkanes, Alkenes, Alkynes, Aromatic compounds, Aldehydes, Ketones, Alcohols, Acids, Acid chlorides, Amides, Amines, Esters, Halides, Nitro compounds, etc., problems using UV and IR.

45

III. Nuclear magnetic resonance spectroscopy 15 h Introduction, Magnetic properties of nuclei- Resonance condition. Nuclear spin, population of nuclear spin levels and NMR isotopes, Relaxation methods. Insturmetnation and sample handling, FT-NMR. Chemical shift- Mechanism of shielding and deshielding in Alkanes, Alkyl halides, Alkenes, Aromatic compounds, Carbonyl compounds and Annulenes. Pascals triangle-low and high resolution, spectrum of ehnaol. Karplus Curve, Diamagnetic and paramagnetic effects and magnetic anisotropy. Equivalence of protons-chemical and magnetic equivalence. Spinsystems: First order and second order coupling of AB systems, Simplifications of complex spectras. Problems. Spin-spin interactions- AX,AX2, AX3, AMX,AB types. Vicinal, geminal and long range coupling-Spin decoupling. Chemical shift reagents and deuterium exchange. Stereochemistry and hindered rotations. Termperature effects. CIDNP, Nuclear Overhauser effect (NOE)., Factors influencing coupling constants and Relative intensities. Protons attached to elements other than carbon.
13

C NMR and Correlation Spectroscopy: 10 h C NMR Spectroscopy- Types of CMR spectra-undecoupled, proton decoupled, Offresonance decouled (SFORD): Selectivity decoupled and gated decoupled spectra. 13C chemicals shifts of Alkanes, Alkyl halides, Alkenes, Alcohols, Ethers, Carbonyl compounds and aromatic compounds, Factors affecting the chemical shifts. Applications of 13C NMR Spectroscopy in confirmation of structure and stereochemistry of organic molecules and in determinng the reaction mechanism and dynamic processes of organic reactions- examples. Introduction to 2D-NMR Pulse sequences. FT-Methods. Classification of 2D Experiments. 2D-J-resolved spectroscopy. HOMO and HETERO-2D-J-Resolved spectra. Correlation Spectroscopy (COSY). Homonuclear (13C-13CJ), and heteronuclear (13C-1H, 13C-2HJ) couplings, DEPT. Explanation of the principle, applications to structure elucidation and stereochemistry of simple organic molecules. IV. Mass spectrometry and Composite Prooblems: 8h Basic principles-instrumentation ion production-ion analysis-magnetic sector instrumentsQuadrapole mass spectrometers. Time of flight mass spectrometers-ion cyclotron resonance spectrometers- Mass spectrum-molecular ion-types of ions in mass spectra and effects of isotopes on mass spectra. Methods of ionization, EI, FAB mass and MALDI methods. Fragmentation of: Alkanes, Alkenes, alkyl halides, alcohols, aldehydes, ketones, acids, esters, ethers, amines, nitro and halo compounds peptides, Nitrogen rule, Factors affecting cleavage patterns.MeLafferty and MeLafferty +1 rearrangment. Determination of molecular formula. Composite problems. Use of HRMS to determine exact molecular formulae of compounds. Application of NMR and MS methods and chemical reactions in structureelucidation of organic compounds. 7h
46

13

SUGGESTED BOOKS
1. Applications of absorption spectroscopy to organic compounds, J. R. Dyer, Prentice-Hall, New Delhi, 1969. 2. Organic spectroscopy, P. Laszlo and P. Stang, Harper & Row, New York, 1971. 3. Organic spectroscopy, W. Kemp, ELBS London, 2000. 4. Spectrometric identification of organic compounds, R. M. Silverstien, and W. P. Weber, 2005. 5. Introduction to spectroscopy, 3rd Edn., D. L. Pavia, G. M. Laupman and G. S. Kriz, Harcourt College Publishers, 2001. 6. Organic mass spectroscopy, K. R. Dass & E. P. James, IBH New Delhi, 1976. 7. Interpretation of organic mass spectra, F. W. McLafferty, W. A. Benjamin, London, 1973. 8. Practical Organic Mass Spectroscopy, 2nd Edn. J R Chapman, John Wiley, NY, 1993. 9. The IR Spectra of complex molecules, Vols. I and II, L J Bellamy, Chapman and Hall, London, 1975. 10. Spectroscopic techniques for Organic Chemists, J W Cooper, John Wiley, NY, 1980. 11. Biomolecular NMR Spectroscopy, J N S Evans, Oxford Univ. 1995. 12. Mass spectrometry a foundation course, K Downard, RSC, Cambridge, 2004. 13. Mass spectrometry of organic compounds, H. Budzkiewicz, Djerassi C. and D. H. Williams, Holden-Day, New York, 1975. 14. Modern NMR techniques and their Applications, Ed. A I Popov, Marcel Deckker, 1991. 15. Modern structural theory of organic compounds, L. N. Ferguson, Prentice-Hall, New Delhi, 1973. 16. Instrumental methods of analysis, H. H. Willard, L. L. Merrit, J. A. Dean and F.A. Settle, CBS Publishers and Distributors, 1986. 17. Fundamentals of molecular spectroscopy, 4th edn., C. N. Banwell and E. M. McCash,Tata McGraw-Hill, New Delhi, 1999.

THIRD SEMESTER PHYSICAL CHEMISTRY SPECIALISATION

C-301 PC CHEMISTRY OF SOLIDS AND DIFFRACTION METHODS 52 hours

1 Electronic structure of solids: 7h Free electron theory, Zone theory, band theory, Fermi sphere, Fermi-Dirac statistics, Ohms law, limitations of the free electron theory, Electrons in a weak periodic potential, energy levels in extended, repeat and reduced zone schemes II Electrical and Magnetic Properties of Solids: 8h Metals: calculation of density of states, origin of resistivity, weak paramagnetism Semiconductors: Intrinsic and extrinsic- p and n-types, Hall effect, Junctions and their applications- metal-metal, metal-semiconductor, semiconductor-Semiconductor types and transistors Insulators- dielectric properties, piezo and inverse piezoelectric effects, Ferroelectricity, ferroelectric transitions in BaTiO3, ionic conductivity. Magnetic properties: classification of materials, cooperative phenomena, Magnetic domains, hysteresis
47

Optical properties: optical reflectance, photoconduction and photoelectric effects III Crystal Defects and Non-Stoichiometry : Point defects, Line defects and Plane defects, Stacking faults and grain boundaries 2h

IV Superconductivity : 4h Superconductivity, Meisner effect, Type I and type II superconductors, Features of superconductors, Frolich diagram, Cooper pairs, Theory of low temperature superconductivity, Junctions using superconductors V Solid State Reactions: 4h General principles, experimental procedures, co-precipitation as a precursor to solid state reactions, kinetics of solid state reactions. VI Phase transition in Solids: 4h Definitions, Classification of phase transitions, First and second order phase transitions: Martensitic transition, order-disorder transitions and spinodal decomposition VII. Geometric Crystallography : 5h Symmetry elements, Bravais lattices, Screw axes and glide planes, point groups, and space groups and nomenclature. Law of Interfacial angle (Eulers construction). VIII . X-ray Diffraction : 12h X-rays, Braggs law, Miller indices, laue method, Bragg method, Debye-Scherrer method of X-ray structural analysis, Indexing of reflection identifiycation of unit cells from systematic absences , Scaterring factor and structure factor and its relation to intensities and electron density, phase problem, absolute configation of molecules, Ramachandran diagram. Reciprocal Lattice concept, Electron density function, Fourier synthesis, Fourier transform of the structure factor, Rotation, Oscillation, Weissenberg and Precession methods,. DebyeScherrer method (Powder method), Determination of lattice parameters from these methods. IX. Electron diffraction: 3h Scattering intensity and scattering angle, Experimental technique, Wierl equation (no derivation), Radial-Distribution, elucidation of structure of simple gas phase molecules. X .Neutron diffraction: 3h Scattering of Neutrrons by solids, magnetic scattering measurements technique, Advantages of Neutron diffraction. SUGGESTED BOOKS:
1. 2. Introduction to Solids, L. V. Azaroff, McGraw Hill Book Co., New York, 1960. Solid State Physics, N. W. Ashcroft and N. D. Mermin, Holt Saunders International Ltd., New York (1976). 48

3. 4. 5. 6. 7. 8. 9. 10. 11.

An Introduction to X-ray Crystallography, M. M. Woolfson, Cambridge University Press-Vikas Publishing House, New Delhi (1980). Principles of the Solid State, H. V. Kheer, Wiley Eastern Ltd., New Delhi (1993). Introduction to Solid State Physics, C. Kittel, Wiley Eastern Ltd., New Delhi (1987) Phase Transitions, C.N.R. Rao and K.J. Rao, Cambridge University Press X-ray Structure determination: A practical guide, George H Stout and Lyle H Jenson, Macmillan Publishing Co.Inc and Collier Macmillan Publishers Solid State Chemistry and its applications. A. R West, John Wiley & Sons 2990 Solid State Chemistry, N. B. Hannay. Solid State Physics, Al:Omar, 1994. Crystal Structure analysis for chemists and biologists, J.P.Glusker, M. Lewis and M. Ross,Wiley-VCH (1994).

C-302 PC PHOTOCHEMISTRY

52hours

I. Introduction to Photochemistry: 10h Importance of photochemistry, Laws of photochemistry, Photochemistry and spectroscopy, units and dimensions. Quantum yields, Interaction between light and matter, wavelength of radiation, Particle nature of radiation, Dual nature of radiation, electronic energy states of atom, The selection rules, Diatomic and polyatomic molecules, Spectroscopic terms for electronic state, Orbital symmetry and molecular symmetry, Notation for excited states of organic molecules and Energy levels for inorganic complexes. Types of chemical reactions: Photodissociation, predissociation, Induced pre dissociation II. Mechanism of absorption and emission of radiation of photochemical interest: 12h Electric dipole transition, Einsteins treatment of absorption and emission phenomenon, Fates of excited species, light sources, Measurment of light intensity, Experimental techniques of detection of intermediates, time resolved experiments . Transition moment integrals and correlation with experimental quantities. Intensity of electronic transition: Theoretical absorption intensity, Strength of an electronic transition, Rules governing transition between two energy levels: Basis of selection rules, Selection rules for molecular transitions, modification of selection rules, Directional nature of light absorption, life times of excited electronic states of atom and molecules, Types of electronic transition of organic molecules, two photon absorption spectroscopy. III. Physical properties of the electronically excited molecules: 10h Nature of changes on electronic excitation, potential energy diagram, shapes of absorption bands and Franck Condon principle, Non crossing rule of Teller Emission spectra, Environmental effect on absorption and emission spectra, Excited state dipole moment, Excited state acidity constants pk* values, Excited state redox potential, Wigners spin correlation rule

49

IV. Photo physical process: 10h Jablonski diagram, Quenching and collision deactivation, Stern-Volmer plot,Types of photo physical pathways, radiation less transition-internal conversion and intersystem crossing, fluorescence emission, triplet states and phosphorescence emission, emission property and the electronic configuration state diagram, Lasers excimers and exciplexes. V. Organic and Inorganic photochemistry: 10h Reaction in compounds containing carbonyl groups photo reduction and related reaction, photocyclo addition reactions, Woodward-Hoffmanns rule of electro cyclic reaction, chemiluminescences, Notation for excited states of organic molecules, unsaturated molecules with conjugated system of double bond, energy levels for inorganic complexes, Transition metal complexes. Some current topics: Photoelectrochemistry, solar energy conversion and storage, photocatalysis.

REFERENCES:
1 2 3 4 6 7 8 9 Fundamentals of photochemistry, K.K.Rohatgi Mukhergee, Wiley Eastern Limited (1986) Photochemistry, Carol E Wayne and Richard P Wayne, Oxford University Press (1996) Introduction to Semiconductor Materials and devices M S Tyagi, John Wiley and Sons (1991) Organic Photochemistry, J M Cozen and B Halton, Cambridge University Press (Ist Edition) (1974) Molecular Reactions and photochemistry, C H Deputy and D S Chapman, Prentice -Hall India, New Delhi (1st Edition), 1972. Concepts of Inorganic Photochemistry, A.W Adamson and P D Fleischaves Wiley. Elements of Inorganic Photochemistry G J Ferranti, Wiley Physical Chemistry, P W Atkins, Julio de Paula ELBS 7th Edition (2002)

C-303 PC QUANTUM CHEMISTRY & SURFACE CHEMISTRY (Elective)

52 hours

I. QUANTUM CHEMISTRY
Theories of Valence A. Introductory aspects: Linear and non-linear variation functions. The Rayleigh-Ritz method, secular equations, coulombic, exchange, normalization and overlap integrals, secular determinants. 2h B. Molecular orbital (MO) theory, LCAO-MO approximation, application to hydrogen molecule ion (H2+), energy levels of H2+, bonding and anti-bonding molecular orbitals, electron distribution, potential energy diagrams, comparison of theoretical and experimental values of energy. 3h C. Valence bond theory of H2 molecule, the Heitler-London method, energy levels, electron distribution. Various modifications of the Heitler-London wave function. 3h D. Comparison of V.B. and M.O. theories, ionic terms, fractional ionic character and its importance. Equivalence of simple MO and VB methods, ion-covalent resonance and
50

configuration interaction. LCAO treatment of diatomic molecules, LCAO forms of simple wave function and molecular orbitals, notation of molecular orbitals, full notation, Mulliken notation. Molecular orbital configuration of homo- and hetero-nuclear diatomic molecules. Molecular electronic terms. Bond order, stability and magnetic behaviour of molecules from M.O. diagrams, isoelectronic systems. Correlation diagrams, noncrossing rule. The HF-SCF-LCAO method. 8h E. Directed valence, hybridization, Expressions for hybrid orbitals in terms of wave functions of s and p orbitals and explanation of directed valences of sp, sp2 and sp3 hybrid orbitals. Few examples of hybridization involving d-orbitals Localised and non-localised molecular orbitals in polyatomic molecules (H2O). 4h F. Huckel molecular orbital theory: Outline of the method including assumptions. Application to ethylene, allyl radical, cyclopropenyl radical, butadiene, cyclobutadiene, bicyclobutadiene and benzene. Calculation of delocalization energy, charge density, mobile bond order and free valence. Introduction to extended Huckel method. Brief description of CNDO, INDO and NDDO methods. 5h II. SURFACE CHEMISTRY A. Introductory: Review of adsorption curves, Adsorption-desorption, Adsorption forces, Heat of adsorption- Types, Measurements of heat of adsorption (Calorimetric and ClausiusClapeyron method), Measurement of adsorption isotherms (Volumetric and Gravimetric methods), Determination of entropy of adsorption, Electrostatic adsorption, adsorption indicators. 5h B. Adsorption theories: Polanyis potential theory, Polarization theory, Hysteries of adsorption. 2h C. Surface structure: Surface mobility, Surface heterogeneity, Surface area and its determination by point-B method, Harkins-Jura method, Radio active tracer method and Benton and White method, Importance of surface area, Examination of surfaces by Interferometer method, Scanning electron microscopy (SEM), Low energy electron diffraction method (LEED method), Field Emission microscopy, Auger electron spectroscopy (AES), STM and TEM. 10h D. Kinetics of adsorption: Kinetics of chemisorption (Hertz-Knudsen equation), Chemisorptive bond, Competitive adsorption, Mechanism of some catalyzed surface reactions, Kinetic effects of surface heterogeneity, Kinetic effects of interactions, Potential energy curves for adsorption, Transition state theory of surface reactions, Rates of desorption, Kinetics of bimolecular surface reactions, Langmuir-Hinshelwood Mechansim, Langmuir-Rideal mechanism, Rideal-Eley mechanism and their comparison, Applications of adsorption. 10h

51

SUGGESTED BOOKS
1. 2. 3. 4. 5. 6. 7. 8. 9. 10 Quantum Chemistry by Eyring, Walter and Kimball, John Wiley, New York (1944). Valence by C. A. Coulson, ELBS, London (1961). Introductory Quantum Chemistry by A. K. Chandra, Tata McGraw Hill (1994). Quantum Chemistry by R. K. Prasad, 2nd edn., New Age International (2000). Quantum Chemistry by Ira N. Levine, Prentice Hall, New Jersey (1991). Molecular Quantam Mechanics, P.W.Atkins and R.S.Friedman, Oxford University Press(1997) Physical Chemistry of Surfaces by A. W. Adamson, Interscience Publishers Inc., New York (1967). Surface Chemistry : Theory and Applications by J. J. Bikerman, Academic Press, New York (1972). Chemical Kinetics by K. J. Laidler, 3rd edn., Harper International edn.,(1987). Text book of Physical Chemistry by S. Glasstone, McMillan India Ltd., 2nd edn.,(1986).

C-303 PC PHYSICAL ORGANIC CHEMISTRY

(Elective)
1

52 hours

CONCEPTS IN MOLECULAR ORBITAL (MO) AND VALENCE BOND (VB)THEORY

Introduction to Huckel molecular orbital (MO) method as a means to explain modern theoretical methods. Advanced techniques in PMO and FMO theory Molecualr mechanics, semi empirical methods and ab into and density functional methods. Scope and limitations of several computational programmes. Quantitiative MO theory Huckel molecular orbital (HMO)method as applied to ethane, allyl and butadiene. Qualitative MO theory ionization potential. Electron affinities. MO energy levels. Orbital symmetry. Orbital interaction diagrams. MO of simple organic systems such as ethane, allyl, butadiene, methane and methyl group. Conjugation and hyperconjugation, Aromaticity. Valence bond (VB) configuration mixing diagrams. Relationship between VB configuration mixing and resonance theory. Reaction profiles. Potential energy diagrams. Curve-crossing model-nature of activation barrier in chemical reactions. 15h
II PRINCIPLES OF REACTIVITY

A. Mechanistic significance of entropy, enthalpy and Gibbs free energy. Arrhenius equation. Transition state theory. Uses of activation parameters. Hammonds postulate. Bell-Evans-Polanyi principle. Potential energy surface model. Marcus theory of electron transfer Reactivity and selectivity principels.
B. KINETIC ISOTOPE EFFECT:

Theory of isotope effects. Primary and secondary kinetic isotope effects. Heavy atom isotope effects. Tunneling effect. Solvent effects.

52

C. STRUCTURAL EFFECTS ON REACTIVITY

Linear free energy relationships (LFER). The Hammett equation, substituent constants, theories of substituent effects. Interpretation of o-values. Reaction constant p. Deviations from Hammett equation. Dual-parameter correlations, inductive substituent constant. The Taff model, O1 and OR-Scales.
D. SOLVATION AND SOLVENT EFFECTS

Qualitative understanding of solvent-solute effects on reactivity. Thermodynamic measure of salvation. Effects of salvation on reaction rates and equilibria. Various empirical indexes of salvation based on physical properties. Solvent-sensitive reaction rates, spectroscopic properties and scales for specific salvation. Use of salvation scales in mechanistic studies. Solvent effects from the curve-crossing model. 14h
ACIDS, BASES, ELECTROPHILES, NUCLEOPHILES AND CASTALYSIS: Acid-base dissociation. Electronic and structural effects, acidity and basicity.Acidity functions and their applications. Hard and soft acids and bases. Nucleophilicity scales. Nucleofugacity. The -effect. Ambivalent nucleophiles. Acid-base catalysis- specific and general catalysis. Bronsted catalysis. Nucleophilic and electrophilic catalysis. Catalysis by non-covalent binding-micellar catalysis. III VII STERIC AND CONFORMATIONAL PROPERTIES

Various type of steric strain and their influence on reactivity. Steric acceleration. Molecualr measurements of steric effects upon rates. Steric LEER. Confromational barrier to bond rotation-spectroscopic detection of individual conformers. Acyclic and monocyclic systems. Rotation around partial double bonds. Winstein-Holness and Curtin-Hammett Principle.
VIII NUCLEOPHILIC AND ELECTROPHILLIC REACTIVITY

Structrual and electronic effects on Sn1 and Sn2 reactivity. Solvent effects. Kinetic isotope effects. Intramolecular assistance. Electron transfer nature of SN2 reaction. Nucleophilicity and Sn2 reactivity based on curve- crossing model. Relationship between plar and electron transfer reactions. SRN1 mechanism. Electrophilic reactivity, general mechanism Kinetic of SE2-Ar reaction. Structural effects on rates and selectivity. Curve-crossing approach to electrophilic reactivity.
IX RADICAL AND PERICYCLIC REACTIVITY

Radical stability, polar influences, solvent and steric effects. A curve crossing approach to radical addition, factors effecting barrier heights in additions, regioselectivity in radical reactions, Reactivity, specificity and periselectivity in pericyclic reactions. 14h
X SUPRAMOLECULAR CHEMISTRY

Properties of covalent bonds bond length, inter-bond angles, force constant, bond and molecular dipole moments. Molecualr and bond polarizability, bond dissociation enthalpy, entropy. Intermolecular forces, hydrophobic effects. Electrostatic, induction, dispersion and

53

resonance energy magnetic interactions, magnitude of interaction energy, forces between macroscopic bodies, medium effects. Hydrogen bond. Principles of molecular association and organization as exemplified in biological macromolecules like enzymes, nucleic acids, membranes and model systems like micelles and vesicles. Molecular receptors and design principles , Cryptands, Cyclophanes, Calixeranes, cyclodextrines, Supramolecular reactivity and catalysis. Molecualr channels and transport processes, Molecualr devices and nanotechnology. 9h SUGGESTED BOOKS
1 2 3 4 5 6 7 Molecular Mechnics.U.Burker and N.L.Allinger, ACS Monograph 177, 1882. Oranic ChemistsBook of Orbitats. L.Salem and W.L.Jorgensen, Academic Press. Mechanism and Theory in Organic Chemistry, T.H.Lowry and K.C.Richardson, Harper and Row Introduction to Theoretical Organic Chemistry and Molecular Modeling, W.B Smith, VCH, Weinheim. Physical Organic Chemisty, N.S.Isaacs, ELBS/Longman. Supramolecular Chemistry: Concepts and Perspectives, J M Lehn, VCH The Physical Basis of Organic Chemistry, H.Maskill,Oxford University Press.

C-304 SPECTROSCOPY II
(Common to Analytical, Inorganic, Organic and Physical Chemistry Students) 52 hours 1. Ultraviolet and visible spectroscopy 3h Classification of elecgronic transitions, Terminology, Substituent and solven effects, UV spectral study of alkenes, polyenes, enones and aromatic compounds.Empirical rules for calculating max2. Vibrational Spectroscopy: spectroscopy 9h Sampling techniques, Group frequencies, factors affecting group frequencies, BVOnd order, Mass effect, Conjugation, Inductive, resonance, Steric effects. Intramolecular interactions. Applicaton of IR in the stuy of H-bonding, stereoisomerism and tautomerisam. Complimentarity of IR and Raman. Identification fo the following organic compounds by IR: Alkanes, Alkenes, Alkynes, Aromatic compounds, Aldehydes, KEtones, Alcohols, Acids, Acid chlorides, Amides, Amines, Esters, Halides, Nitro compounds, etc., problems using UB and IR.

3. Nuclear magnetic resonance spectroscopy 15h Introduction, Magnetic properties of nuclei-Resonance condition. Nuclear spin, population of nuclear spin levels and NMR isotopes, Relazation methods. Insturmetnation and sample handling, FTNMR.
54

Chemical shift- Mechanism of shielding and deshielding in ALkanes, Alkyl halides, Alkenes, Aromatic compounds, Carbonyl compounds and Annulenes. Pascals triangle-low and high resolution, spectrum of ehnaol. Karplus Curve, Diamagnetic and paramagnetic effects and magnetic anisotropy. Equivalence of protons-chemical and magnetic equivalence. Spinsystems: First order and second order coupling of AB systems, Simplifications of complex spectras. Problems. Spin-spin interactions- AX,AX2, AX3, AMX,AB types. Vicinal, geminal and long range coupling-Spin decoupling. Chemical shift reagents and deuterium exchange. Stereochemistry and hindred rotations. Termperature effects. CIDNP, Nuclear OVerhauser effect (NOE)., Factors influencing coupling constants and Relative intensities. Protons attached to elements other than carbon.
13

C NMR and Correlation Spectroscopy: 10h C NMR Spectroscopy- Types of CMR spectra-undecoupled, proton decoupled, Offresonance decouled (SFORD): Selectivity decoupled and gated decoupled spectra. 13C chemicals shifts of ALkanes, Alkyl halides, Alkenes, Alcohols, Ethers, Carbonyl compounds and aromatic compounds, Factors affecting the chemical shifts. Applications of 13C NMR Spectroscopy in confirmation of structure and stereochemistry of organic molecules and in determinng the reaction mechanism and dynamic processes of organic reactions- examples. Introduction to 2D-NMR Pulse sequences. FT-Methods. Classification of 2D Experiments. 2D-J-resolved spectroscopy. HOMO and HETERO-2D-J-Resolved spectra. Correlation Spectroscopy (COSY). Homonuclear (13C-13CJ), and heteronuclear (13C-1H,13C-2HJ) couplings, DEPT. Explanation of the principle, applications to structure elucidation and stereochemistry of simple organic molecules. 4. Mass spectrometry and Composite Prooblems: 8h Basic principles-instrumentation ion production-ion analysis-magnetic sector instrumentsQuadrapole mass spectrometers. Time of flight mass spectrometers-ion cyclotron resonance spectrometers- Mass spectrum-molecular ion-types of ions in mass spectra and effects of isotopes on mass spectra. Methods of ionization, EI,FAB mass and MALDI methods. Fragmentation of: ALkanes, Alkenes, alkyl halides, alcohols, aldehydes, ketones, acids, esters, ethers, amines, nitro and halo compounds peptides, Nitrogen rule, Factors affecting cleavage patterns. MeLafferty and MeLafferty +1 rearrangment. Determination of molecular formula. Composite problems. Use of HRMS to determine exact molecular formulae of compounds. Application of NMR and MS methods and chemical reactions in structure elucidation of organic compounds. 7h

13

SUGGESTED BOOKS
1. Applications of absorption spectroscopy to organic compounds, J. R. Dyer, Prentice-Hall, New Delhi, 1969. 2. Organic spectroscopy, P. Laszlo and P. Stang, Harper & Row, New York, 1971. 3. Organic spectroscopy, W. Kemp, ELBS London, 2000. 55

4. Spectrometric identification of organic compounds, R. M. Silverstien, and W. P. Weber, 2005. 5. Introduction to spectroscopy, 3rd Edn., D. L. Pavia, G. M. Laupman and G. S. Kriz, Harcourt College Publishers, 2001. 6. Organic mass spectroscopy, K. R. Dass & E. P. James, IBH New Delhi, 1976. 7. Interpretation of organic mass spectra, F. W. McLafferty, W. A. Benjamin, London, 1973. 8. Practical Organic Mass Spectroscopy, 2nd Edn. J R Chapman, John Wiley, NY, 1993. 9. The IR Spectra of complex molecules, Vols. I and II, L J Bellamy, Chapman and Hall, London, 1975. 10. Spectroscopic techniques for Organic Chemists, J W Cooper, John Wiley, NY, 1980. 11. Biomolecular NMR Spectroscopy, J N S Evans, Oxford Univ. 1995. 12. Mass spectrometry a foundation course, K Downard, RSC, Cambridge, 2004. 13. Mass spectrometry of organic compounds, H. Budzkiewicz, Djerassi C. and D. H. Williams, Holden-Day, New York, 1975. 14. Modern NMR techniques and their Applications, Ed. A I Popov, Marcel Deckker, 1991. 15. Modern structural theory of organic compounds, L. N. Ferguson, Prentice-Hall, New Delhi, 1973. 16. Instrumental methods of analysis, H. H. Willard, L. L. Merrit, J. A. Dean and F.A. Settle, CBS Publishers and Distributors, 1986. 17. Fundamentals of molecular spectroscopy, 4th edn., C. N. Banwell and E. M. McCash,Tata McGraw-Hill, New Delhi, 1999.

C 305 and 306 Practicals

Inorganic, Organic, Physical and Analytical chemistry practicals (4 days a week, 4 1/2 hours a day) Analytical Chemistry Practicals C 305 Physical Chemistry Practical I
1. 2. 3. 4. Experimental Physixcal Chemistry by Wilson, Newcombe, Denaro and Rickett, Pergamon Press, (1962) Practical Physical Chemistry by Palit and De, Science Book Agency, Calcutta ( 1974) Advanced Physical Chemistry by J B Yadav, Goel Pub. House, (1981) Methods of Soil Analysis Part I & II, C.A. Black et al (Ed) American Society of Agronomy, Inc

56

FOURTH SEMESTER
(Analytical Chemistry Specialisation)

C-401 AC INSTRUMENTAL METHODS OF ANALYSIS 52 h

I. Diffraction theory & Practice 15h Diffraction: X-ray, Braggs law, assignment of lines, diffraction pattern of a primitive cubic lattice, space group extinctions, scattering factor and structure factor, intensities from atomic position. Rotation, Oscillation, Weissenberg and Precession methods,. Debye-Scherrer method (powder method), Determination of lattice parameters. Using these methods, Electron diffraction, experimental technique, Wierl equation Radial-Distribution method. II. Advanced Radioanalytical methods: 6h Part A: Nuclear properties and models Subatomic particles: protons, neutrons, quarks, spin and magnetic properties of nucleons, electrical quadrupole moment of nuclides, nuclear parity, nuclear statistics, nuclear forces and interactions. Nuclear models: liquid drop, shell model, Fermi gas model, collective model and optical model. Part B: Applications of Radioactivity 9h Synthesis of various useful isotopes, use of isotopes in the elucidation of reaction mechanism, structure determination, kinetics of exchange reactions, measurement of physical constants including the diffusion constants, radio analysis-isotope dilution techniques, NAA, PGNAA, neutron absoptiometry and age determination, radio isotopes in field of medicine. Part C: Radiation Chemistry 7h Interaction of matter with radiation, radiation dosimetry-units and measurements using chemical dosimeters, radiolysis of water, the hydrated electron-precipitation and properties, free radical generation, radiation damage to solids-effects of radiation on metals, alloys, semiconductors, insulators and catalysts . III. Advanced Separation Techniques 15 h High Performance Liquid Chromatography: Principle-instrumentation-sample injection detectors (absorbance detector, reflective index detector, electrochemical detector)-mobile phase selection, ion pair chromatography-HPLC- MS-chromatography with chiral phases, applications. Ion exchange chromatography:Principle-types of stationary phases-applications Size exclusion and affinity chromatography:Principle and size effects, applications. Super critical fluid chromatography and extraction:Principle, instrumentation, merits and applications.. Electrophoresis and electro chromatography: Principle and instrumentation iso electrophoresis-capillary zone electrophoresis.

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SUGGESTED BOOKS
1. 2. 3. 4. 5. 6. 7. 8. Introduction to Solids, L.V.Azaroff, McGraw Hill Book Co., New York, 1960. Solid State physics, N.W.Ashcroft and N.D.Mermin, Holt Saunders International Limited.,New York(1976). An Introduction to X-ray Crystallography, M.M.Woolfson, Cambridge University Press-Vikas Publishing House,New Delhi(1980) X-ray Structure determination: A Practical Guide, George H Stout and Lyle H Jenson,Macmillan Publishing Co.Inc and Macmillan Publishers Essentials of Nuclear Chemistry, H.J. Arnikar Wiley Eastern Ltd. New Delhi Instrumental method of analysis.H.H.Willard, L.L.Merrit, J.A.Den and F.A.Settle, CBS publishers and distributors, 1986. Principles of Instrumental Analysis, D.A Skoog, F.J. Holler and T.A. Nieman, Thomson 5th Edn. 2004 Instrumental methods of Chemical Analysis, G.W. Ewing McGraw Hill 2004

C-402 AC ENVIRONMENTAL AND BIOCHEMICAL ANALYSIS

52 Hours I Air Pollution 6h Types and sources of air pollutants; Natural background concentrations of air pollutants; Principles and methods of sampling; A survey of reactions and methods involved in the determination of carbon monoxide, sulphur oxides, nitrogen oxides, hydrocarbons and particulates; Consequences of air pollution. II Water Pollution Origin of waste water; Types of water pollutants and their effects; Sources of water pollution: domestic, industrial and agricultural soil as sources of pollution; Objectives of analysis; Parameters of analysis: colour, turbidity, total solids, conductivity, acidity, alkalinity, hardness, chloride, sulphate, fluoride, silica, phosphates and different forms of nitrogen; Heavy metal pollution: public health significance of cadmium, chromium, copper, lead, zinc, manganese, mercury and arsenic, general survey of instrumental techniques for the analysis of heavy metals in aqueous systems; Pesticides as water pollutants and their analysis; Water pollution laws and standards. III. Soil Analysis 5h Physical properties of soils-soil texture and soil structure. Chemical properties of soil-types of soil colloids, types of clays and their swelling and adsorption properties, cation exchange capacity and its determination, acid soils-types of soil acidity, liming, measurement of pH and conductivity of soil- saline and alkaline soils, analysis of major constituents of soilorganic matter, nitrogen, sulphur, sodium, potassium and calcium. IV. Radioactive Pollution 3h Sources of pollutants; Effects on vegetation and health; Detection and monitoring of radioactive pollutants; Methods of safe disposal of radioactive wastes.

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V. Fuel Analysis 3h Solid, liquid and gas fuels; Ultimate and proximate analysis, heating values, grading of coal; Liquid fuels: flash point, aniline point, octane number and cetane number, carbon residue; Gaseous fuels: producer gas and water gas, calorific values. VI. Food Analysis 7h Estimation of moisture, ash, crude protein, fat, crude fibre, carbohydrate, calcium, potassium, sodium and phosphate in foods; Analysis of common adulterants in foods: Milk and milk products- alcohol test, fermentation test, dye reduction tests( methylene blue and resazurin ) , tests to distinguish butter and margarine, phosphatase test for pasteurisation, estimation of added water; Beverages- caffeine and chicory in coffee, methanol in alcoholic drinks; Estimation of saccharin, coal tar dyes, aflatoxins in foods; Pesticide analysis in food products- extraction and purification of sample, gas chromatography for organophosphates, thin-layer chromatography for chlorinated pesticides. VII. Analysis of Drugs and Poisons 8h Classification of drugs; Characterisation of common drugs: Analgesics-aspirin, paracetamol, Expectorants- Benadryl, Vitamins- A and C, Sedatives- diazepam, barbiturates, Antibioticspenicillin, chloramphenicol, ampicillin,Cardiovascular- sorbitrate, methyldopa. Drugs of abuse: Analysis of narcotics (nicotine, morphine, heroin) and other dangerous drugs; screening by gas and thin-layer chromatography and spectrophotometric measurement, Estimation of drug residues in biological samples. General discussion of poisons with special reference to mode of action of snake venom, war gases, cyanide, carbon monoxide and opium. Estimation of cyanide, carbon monoxide and barbiturates. VIII. Clinical Chemistry 7h Composition of blood; Collection and preservation of samples; Clinical analysis: serum electrolytes, blood glucose, blood urea nitrogen, uric acid, albumin, globulins, and blood gas analysis. Immunoassay: ELISA and RIA and their applications. Enzyme analysis: Assay of acid and alkaline phosphatases, isoenzymes of lactate dehydrogenase, aldolase,. Metal deficiency and disease; Estimation of calcium, iron, and copper. IX. Lipid Analysis 6h General composition of edible oils; Qualitative tests for purity; Estimation of rancidity, Tests for groundnut oil, castor oil, cottonseed oil and mustard oil; Tests for common adulterants like argemone oil and mineral oils. SUGGESTED BOOKS
1. 2. 3. 4. 5. 6. Environmental Pollution Analysis, S.M. Khopkar, Wiley Eastern. Experiments in Environmental Chemistry, P.D. Vowels and D.W. Connel, Pergamon Measurement of Air Pollutants, M. Katz. WHO (1969) Handbook on Air Pollution, Stern, APHA (1980) Fundamentals of Analytical Chemistry, Skoog, West, Holler and Saunders Principles of Instrumental Analysis, D.A . Skoog and W. B. Saunders 59 (1980)

7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21.

Quantitative Analysis, R.A. Day and A.L. Underwood, Prentice Hall Food Analysis, A. G. Woodman, McGraw Hill (1971) Foods: Facts and Principles, Shadaksharaswamy and Manay, Wiley Eastern, (1987) Milk and Milk Products, C.H. Eckles, W.B. Combs and H.Macy, Tata McGraw Hill (1976) Wilson and Gisvold's Textbook of Organic Medicinal and Pharmaceutical Chemistry, Ed. R.F. Dorge The Essentials of Forensic medicine and Toxicology, K.S. Narayan Reddy [Suguna Devi, Hyderabad] (2002) Hawk's Physiological Chemistry, Ed. B.I. Oser, Tata McGraw Hill (1976) Practical Clinical Biochemistry, H. Varley, Arnold Heinmann Lynch's medical Laboratory Technology, S.S. Rapher, Itaku-Shoin / Saunders (1983) A Biologist's Guide to Principles and Techniques of Practical Biochemistry, Wilson and Goulding ( 1981 ) Analytical Biochemistry, Holmes and Peck, Longmans (1983) Separation Techniques in Chemistry and biochemistry, Roy Keller, M. Dekker Inc. (1967) Chemistry: Principles and Applications, Miller, Wadsworth Publishing Co. ( 1976 ) Methods of Soil Analysis Part I & II, C.A. Black et al (Ed) American Society of Agronomy, Inc. (1965) A text book of Soil Chemical Analysis P.R. Hesse, CBS Publishers, (1994).

C 403 - CHEMISTRY OF MATERIALS

(ELECTIVE) (Common to Inorganic and Analytical Chemistry) 52 hours I Preparative techniques 8h Principles of solid state synthesis - ceramic methods , solid solution and compound precursors (nitrates ,carbonates, hydroxides ,cyanides and organometallics), sol-gel, spray pyrolysis, combustion, hydrothermal, electrosynthetic II. A New Materials 8h Fullerenes and fullerides structure, synthesis, functionalisation approaches conducting properties of fullerides. NASICON and alumina structure and conducting properties. High-Tc Oxides - structure, perovskite A & B, structure and synthesis of La,Sr and Ba cuprates, applications. Conducting polymers - PA, PPP, PPS, PPY mechanism of conduction and applications II B Nanomaterials 12h Classification types of carbon nano tubes synthesis, functionalization charecterization and applications. Principles of self-assembly: surfactant solutions, importance of non-covalent forces, the hydrophobic effect, co-operativity, statistical mechanics of one-dimensional self-assembly. Preparation of nanoscale materials: Precipitation, mechanical milling, colloidal routes, selfassembly: chemical vapour depostition, sputtering, evaporation. Synthesis, characterization and applications of nanoparticles, nano wires and nanotubes. Elemental nanoparticles: Pure, Gold, Silicon, Silver ,Cobalt, Oxide nanoparticles: Silica, Zinc oxide, Iron oxide, Alumina.
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III Intercalation compounds 6h Intercalation reactions - layered structure-graphite interlayer compounds(GILC), staging of graphite, TaS2, Microporous materials zeolites and zeolitic materials, AlPO4- GaPO4. . IV Fibres and Composites 8h Synthetic inorganic polymers- zirconia and other fibre Classification, microscopic composites, dispersion strengthned, particle reinforced,Fibre-glass reinforced composites, metal-matrix, plastic-matrix composites, hybrid composites. V Amorphous Materials 6h Crystalline versus amorphous solids, glass formation, Prepararion techniques- meltspinning, sputtering, ion implantation, Structural models of amorphous materials, Properties of metglasses - mechanical, electronic and magnetic properties. VI Liquid crystals 4h Mesomorphic behaviour, classification - thermotropic and lyotropic liquid crystals Calamitic, mesophase, nematic phase, smectic phase, chiral nematic phase and optical Properties of liquid crystals SUGGESTED BOOKS
1. 2. 3. 4 5 6 7. Encyclopedia of Nanomaterials and Nanoteachnology Hari Singh Nalva Nanostructured Materials: Processing, Properites and Applications, ed. By C.C.Koch, Willaim Andrew Publishing, New York, 2002. Nanomaterials: Synthesis, properties and applications, Ed. By A.S.Edelstein and R.C. Cammarata, Inst. of Physics, UK 1966. Science of Engineering Materials, C.M. Srivastava and C. Srinivasan, Wiley-Eastern Ltd. (1991) Solid State Chemistry and its applications , A.R. West, John Wiley & Sons.(1989). Material Science and Engineering. W.D. Callister , John Wiley and Sons Inc. (1985). Nanotubes and Nano wires CNR Rao, & A Govindaraj, RSC, London 2005.

C-404

SPECTROSCOPY III
52 h

(Common to Inorganic ,Physical Chemistry and Analytical)

I Vibrational spectroscopy 9h Vibrational spectra of diatomic, linear and bent triatomic, AB3, AB4, AB5 and AB6 molecules, spectra of metal complexes: Ammine, amido, Nitro, Nitrito, lattice water, aquo and hydroxo, carbonato, nitrato, sulphato and other acido complexes, cyano and nitrile complexes, cyanato and thiocyanato complexes, mono and multinuclear carbonyl complexes, nitrosyls, phosphines and arsines, ambidentate ligands, ethylenediamine and diketonato complexes
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II Raman spectroscopy 4h Resonance Raman Spectroscopy, Nonlinear Raman effects-Stimulated, hyper and inverse types, Lasers and their use in Raman spectroscopy III Photoacoustic spectroscopy Basic description and applications 2h

IV Photoelectron spectroscopy 8h Basic principles- photoelectric effect, Koopmans theorem, XPS and UPS, spin-orbit coupling in core level spectra, applications of core level spectra-ESCA, chemical shift, Valence level spectra- n, and bands, Auger electron spectroscopy and applications, Electron energy loss spectroscopy- basic principles and applications Applications to the study of solids V NMR spectroscopy of inorganic molecules 8h Proton NMR spectra of metal hydride complexes NMR spectra of nuclei other than hydrogen: 19F, 31P, 11B NMR spectra of simple compounds, Proton/hydride interactions with 103Rh, 183W, 195Pt and 207Pb in metal complexes/organometallic compounds, Solid State NMR. VI Electron spin resonance spectroscopy 10h Basic principles, the position of ESR absorption, significance of g factor, determination of gfactor. Electron-nucleus coupling (Hyperfine splitting). ESR spectrometer, electronelectron coupling, double resonance in ESR, ENDOR, ELDOR. Interpretation of ESR spectra and structure elucidation of organic radicals using ESR spectroscopy. Spin density and Mc Connell relationship. Spin polarization for atoms and transition metal ions, spin-orbit coupling and significance of g-tensors, zero/non-zero field splitting, Kramers degeneracy, application to transition metal complexes (having one to five unpaired electrons) including biological molecules and inorganic free radicals such as PH4, F2 and BH3. VII Mossbauer spectroscopy 5h Basic principles, isomer shift, quadrupole splitting and magnetic hyperfine interactions, application to the study of bonding and structures of Fe2+ and Fe3+ compounds, Sn2+ and Sn4+ compounds VIII NQR spectroscopy 4h NQR isotopes, electric field gradients, Nuclear Quadrupole coupling constants, Experimental techniques and applications XI X-ray absorption spectroscopy Near edge measurements and EXAFS 2h

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SUGGESTED BOOKS
1. 2. 3. 4. Physical methods in Inorganic Chemistry, R.S. Drago, Affiliated East West Press Pvt. Ltd., New Delhi (1965). Infrared spectra of Inorganic and Coordination Compounds, K. Nakamoto, Wiley-Interscience, New York (1970). Vibrational Spectroscopy: Theory and Applications, D.N. Sathyanarayana, New Age International Publishers, New Delhi (2000). Electronic Absorption Spectroscopy and Related Techniques, D.N. Sathyanarayana, Universities Press, Bangalore (2001).

C- 405 Analytical Chemistry Practicals III

1. Estimation of nitrite using chloramines T 2. Estimation of copper using salicylaldoxime 3. Estimation of sulphate as benzidine sulphate 4. Estimation of metal acetates using perchloric acid in glacial acetic acid medium 5. Separation of metal ions by paper chromatography/TLC 6. Separation of zinc and cadmium by ion exchange chromatography 7. Estimation of Iron III by solvent Extraction 8. AAS Estimation of Cu, Fe, Mg and Ca 9. Flame photometric estimation of K, Na 10. Analysis of calcium and magnesium in milk 11. Preparation and characterization of a metal complex by IR spectroscopy 12. Synthesis of zeolites and measurement of surface acidity 13. Synthesis of spinels/pervoskites and their characterization by XRD studies 14. Differential potentiometric titration of acetic acid vs. sodium hydroxide 15. Determination of pka of amino acids by potentiometric titrations 16. Determination of dissociation constant of phosphoric acid by potentiometric titration 17. Determination of stability constant of copper-ethylenediamine complex by potentiometry 18. Complexometric titration of copper/nickel using DMG by potentiometry 19. Conductometric titration of HCl vs. NaOH in methanol medium 20. Flame spectrophotometric estimation of potassium sodium and potassium 21. Spectrophotometric determination of metal-ligand ratio in Iron-iron complex using Jobs method 22. Spectrophotometric determination of pK1 value of an indicator 23. Spectrophotometric determination of uranyl ion by solvent extraction 24. Estimation of copper by electrogravimetric method 25. Polarographic analysis-identification and estimation of metal ions 26. Amperometric titration-estimation of lead using potassium dichromate 27. Cyclic voltammetric behaviour of a metal complex

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SUGGESTED BOOKS
1. 2. 3. 4. 5. 6. Text book of Quantitative Inorganic Analysis by A.I. Vogel,ELBS(1978) Advanced Physicochemical Experiments by Rose, Isaac Pitman(1964) Polarographic methods of analysis by Meites, L. Intersciences Publishers, Inc. NeYork,(1955) Findlays Practical Physical Chemistry by Levitt, Longmanns(1966) Experimental Physical chemistry by J B Yadav, Goel Pub. House,(1981) Methods of Soil analysis Part I & II, C.A. Black et al(Ed) American Society of Agronomy, Inc. (1965).

C - 406 Analytical Chemistry Practicals - IV

1. Estimation of Nitrogen, Nitro and Methoxy groups 2. Separation of essential oils by column chromatography 3. Separation of lipids by thin layer Chromatography 4. Separation of amino acids by thin layer chromatography 5. separation of alcohols by gas chromatography 6. Separation of proteins by gel electrophoresis 7. Separation of fatty acids using gas chromatography 8. Estimation of fat in milk 9. Estimation of rancidity in a sample of butter 10. Estimation of sulphur oxide and nitrogen oxides in air samples 11. Estimation of nicotine in tobacco 12. Estimation of morphine in a drug sample 13. Estimation of a common drug(paraacetamol) 14. Estimation of BOD and COD of a water sample 15. Estimation of lead in water samples 16. Estimation of pesticide in soil samples 17. Extraction of caffeine from tea leaves, characterization by IR, NMR, MS 18. Estimation of glucose in serum 19. Estimation of Cholesterol in serum 20. Estimation of blood urea nitrogen 21. Estimation of nucleic acids 22. Estimation of protein in food samples 23. Estimation of Vitamin A in food samples 24. Determination of carbon residue in petrol 25. Assay of alanine and aspartate aminotransferases 26. Estimation of alkaline phosphatase SUGGESTED BOOKS
1. 2. 3. 4. 5. 6. Experiments in Environmental chemistry, P.D.Vowels and D.W.Connel, Pergamon(1980). Vogels Practical Organic Chemistry, Ed.A.J.Hannaford, ELBS London (1978). Practical Clinical Biochemistry , H.Varley and Anold Heinmann(1978) An introduction to practical Biochemistry, David Plummer,Tata McGraw Hill(1979) Laboratory Manual in Biochemistry, J. Jayaraman,Wiley Eastern(1981) Chromatography, C. G. Sharma 64

FOURTH SEMESTER
INORGANIOC CHEMISTRY SPECIALISATION C- 401 IC ORGANOMETALLIC CHEMISTRY
52 Hours I. Organometallic complexes. 4h Stability and decomposition paths, classification of ligands, Nomenclature of Organometallic complexes, 16- and 18- electron rules, Electron counting-covalent and ionic models. II. Organometallic compounds of main group elements. Group trends-Synthesis, structure and bonding in Li, Be, Mg and Al alkyls. 6h

III. Synthesis, structure, bonding, reactivity and decomplexation reactions of organotransition metal complexes having -and -M-C bonds. 12h -Bonded systems involving carbonyls, isocyanides, carbenes and carbynes -bonded systems involving dihapto to octohapto ligands like acetylene, olefins, allyl moieties, butadiene, cyclobutadiene, cyclopentadiene, arenes, cyclohexa and cycloheptadienyl moieties, cyclohepta and cyclooctatrienes, cyclooctatetraene moieties and ring slippage reactions. IV. Isoelectronic and isolobal concepts . 6h Introduction to M-M bonds and metal atom carbonyl clusters LNCCS HNCS. Structure and bonding in carbonyl clusters-the isoelectronic and isolobal analogy. Wade-Mingos-Lauher rules. Cluster valence electron count. V. Fluxional behavior in organometallic compounds. 5h Introduction, Rates of rearrangement and techniques of study, classification, Fluxionality and dynamic equilibria in compounds such as CO, 2-olefin, 3-allyl and dienyl complexes. VI. Activation of small molecules. CO, CO2, CF and alkane activation (cyclometallation reaction). 4h

VII. Organometallic compounds in organic synthesis. 9h General introduction , Green rules, uses of iron and chromium carbonyls in the synthesis of aromatic compounds. Heck reaction , use of zinc dialkyls, Grignard reagent; lithium alkyls, Gilman reagent (lithium dialkyl cuprate), organoaluminium and organomercurials in organic synthesis. VIII. Photochemical reactions of organotransition metal complexes. 3h Introduction, photochemical substitution at metal carbonyls. Photochemical reactions with cleavage of Metal-Metal bonds, Metal-hydrogen bonds and metal-carbon bonds.

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IX. Reactions of organometallic complexes 3h Substitution reaction in carbonyl complexes, oxidation-addition and reduction elimination, insertion and elimination reactions. Nucleophilic and electrophilic attack of coordinated ligands. Carbonylate anions as nucleophiles. SUGGESTED BOOKS
1. 2. 3. 4. 5. 6. 7. 8. Organometallic chemistry, R.C.Mehrotra and A.Singh, New age international, 2nd edition, 2000. The organometallic chemistry of transition metals, R.H. Crabtee, John Wiley 3rd edition 2001. Principles and application of organotransition metal chemistry, J.P.Collman, L.S.Hegdus, J.R.Norton, and R.G. Finke ,University Science book, 1987. An introduction to organometallic chemistry A.W. Parkins and R.C. Poller, Macmillan, 1986. Organometallics, Vol. 1 and 2, M. Bochmann, Oxford Chemistry primers, OxfordUniversity Press, 1994. Organotransition metal chemistry, S.G. Davies, Pargamon Press, oxford, 1982. Organometallic chemistry, ch. Elschewbroich and A.Slazer, VCH, 2nd edition 1992. Organometallic reagents in synthesis, P.R. Jenkins, Oxford Chemistry primers, 1992.

C-402 IC HOMOGENEOUS AND HETEROGENEOUS CATALYSIS

52 Hours 1. Introduction 4h Basic principles, industrial requirements, thermodynamic and kinetic aspects, classification of catalysis systems. II. Homogeneous catalysis 19 h Principle, experimental techniques, acid-base catalysis, catalysis involving transition metal salts, metal complexes and organometallic complexes- hydrogenation, transferhydrogenation, asymmetric hydrogenation , hydrosilation, hydrocyanation-Nylon intermediates: buta-1,3-diene hydrocynation, hydrogenation hydroformylation involving cobalt and rhodium catalysts (oxo process). Wacker process-acetaldehyde from ethylene, Reppe Monsanto process-acetic acid from methanol, Reppe carbonylation- acrylic ester from acetylene: ethylene glycol from synthesis gas, alkene isomerisation. Olefin metathesis, water- gas shift reaction, oligomerisation -Shell high olefin process, Tennessee Eastman process- Acetic anhydride from methyl acetate. III. Heterogeneous catalysis 10 h General aspects, gas-solid interface, physisorption and chemisorption; Adsorption isotherms-Langmuir and BET isotherms, surface area and pore structure of catalysts and their determination, Experimental methods and laboratory reactors. 10 h Fischer-Tropsch process, Zeigler-Natta polymerization syndiotactic and Isotactic polymersLiving polymerization, Ammonia synthesis, Acrylonitrile synthesis using mixed metaloxides, alcohol dehydration on -alumina, reactions of olefins on zinc oxide, clays as catalysts, Pillared clays- advantages, Decomposition of iso-propanol using oxide catalysts, Catalytic converters 9h Anchored catalysis- merits, polymer and metal oxides as supports, Zeolites-shape selectivity, phase transfer catalysis- catalyst preparation, displacement reactions, advantages.
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Biological catalysts- Michaelis-Menten kinetics, organic catalysis Ribonuclease and lysozyme, metalloenzymes- carbonic anhydrase, free radical reaction catalysed by vitamin B12. SUGGESTED BOOKS
Organometallic Chemistry, R.C.Mehrotra and A.Singh, New Age international (P) Ltd., 2nd edition, 2000. 2. Principles and applications of organo-transition metal chemistry, J.P.Colman and L.S.Hegedus, University Science Book (1980). 3. The organometallic Chemistry of the transition elements, R.H.Crabtee, John Wiley & Sons. 1998. 4. Catalytic Chemistry, B.C.Gates, JohnWiley & sons (1992). 5. Catalysis-Science and Technology, J.R.Anderson and M.Boudart, Springer-Verlag (1984). 6. Adsorption and catalysis by solids, D.K.Chakarborty, Wiley Eastern Ltd. (1991). 7. Homogeneous catalysis by metal coplexes, M.M.Taqui Khan and E.A.Martell, Academic press (1974). 8. Principles and practice of heterogeneous catalysis, J.M.Thamas and W.J.Thamas; VCH (1996). 9. Heterogeneous catalysis D.K. Chakarborty & B.Viswanathan, New Age international (P) Ltd., 2000. 10. Applied organometallic Chemistry and Catalysis Robin Whyman, Oxford University primers, (2001). 1.

C-403 IC PHOTOINORGANIC CHEMISTRY (ELECTIVE)

(Common to Inorganic and Analytical Chemistry) 52 Hours I Basics of photochemistry 9h Absorption, excitation, photochemical laws, quantum yield, electronically excited states-life time measurements. Flash photolysis, stopped flow techniques. Energy dissipation by radiative and non-radiative processes, absorption spectra, Franck-Condon principle, photochemical stages- primary and secondary processes II Properties of excited states 9h Structure, dipole moment, acid-base strengths and reactivity. Photochemical kineticscalculation of rates of radiative processes. Bimolecular deactivation- quenching III Excited states of metal complexes 8h Excited states of metal complexes: comparison with organic compounds, electronically excited states of metal complexes, charge transfer spectra, charge transfer excitations, methods of obtaining charge transfer spectra IV Ligand field photochemistry 8h Photosubstitution, photooxidation and photoreduction, lability and selectivity, zero vibrational levels of ground state and excited state, energy content of the excited state, zerozero spectroscopic energy, development of the equations for redox potentials of the excited states V Redox reactions by excited metal complexes 13 h Energy transfer under conditions of weak interaction and strong interaction- exciplex formation, conditions for the excited states to be useful as redox reactants, excited electron transfer, metal complexes as attractive candidates (2,2-bipyridine and 1,10-phenanthroline
67

complexes), illustration of reducing and oxidizing character of Ru2+ bipyridal complex, comparison with Fe(bipy)3, role of spin-orbit coupling- life time of these complexes. Application of redox processes of electronically excited states for catalytic purposes, transformation of low energy reactants into high energy products, chemical energy into light VI Metal complex sensitizers 5h Metal complex sensitizers, electron relay, metal colloid systems, semiconductor supported metal or oxide systems, water photolysis, nitrogen fixation and carbon dioxide reduction SUGGESTED BOOKS
1. 2. 3. 4. 5. 6. Concepts of Inorganic Photochemistry, A.W. Adamson and P.D. Fleischauer, Wiley. Inorganic Photochemistry, J. Chem. Ed., 60 (No. 10), 1983. Progress in Inorganic Chemistry, Ed. S.J. Lippard, Vol. 30. Photochemistry of Coordination Compounds, V. Balzari and V. Carassiti, Academic Press. Coordination Chemistry Reviews., 39 (1981) 121, 131; 15 (1975) 321; 97 (1990) 313. Elements of Inorganic Photochemistry, G.J. Ferraudi, Wiley.

C -403- CHEMISTRY OF MATERIALS

(ELECTIVE) (Common to Inorganic and Analytical Chemistry) 52 h I Preparative techniques 8h Principles of solid state synthesis - ceramic methods , solid solution and compound precursors (nitrates ,carbonates, hydroxides ,cyanides and organometallics), sol-gel, spray pyrolysis, combustion, hydrothermal, electrosynthetic II. A New Materials 8h Fullerenes and fullerides structure, synthesis, functionalisation approaches conducting properties of fullerides. NASICON and alumina structure and conducting properties. High-Tc Oxides - structure, perovskite A & B, structure and synthesis of La,Sr and Ba cuprates, applications. Conducting polymers - PA, PPP, PPS, PPY mechanism of conduction and applications II B Nanomaterials 12h Classification types of carbon nano tubes synthesis, functionalization charecterization and applications. Principles of self-assembly: surfactant solutions, importance of non-covalent forces, the hydrophobic effect, co-operativity, statistical mechanics of one-dimensional self-assembly. Preparation of nanoscale materials: Precipitation, mechanical milling, colloidal routes, selfassembly: chemical vapour depostition, sputtering, evaporation.

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Synthesis, characterization and applications of nanoparticles, nano wires and nanotubes. Elemental nanoparticles: Pure, Gold, Silicon, Silver ,Cobalt, Oxide nanoparticles: Silica, Zinc oxide, Iron oxide, Alumina. III Intercalation compounds 6h Intercalation reactions - layered structure-graphite interlayer compounds(GILC), staging of graphite, TaS2, Microporous materials zeolites and zeolitic materials, AlPO4- GaPO4. . IV Fibres and Composites 8h Synthetic inorganic polymers- zirconia and other fibre Classification, microscopic composites, dispersion strengthned, particle reinforced,Fibre-glass reinforced composites, metal-matrix, plastic-matrix composites, hybrid composites. V Amorphous Materials 6h Crystalline versus amorphous solids, glass formation, Prepararion techniques- meltspinning, sputtering, ion implantation, Structural models of amorphous materials, Properties of metglasses - mechanical, electronic and magnetic properties. VI Liquid crystals 4h Mesomorphic behaviour, classification - thermotropic and lyotropic liquid crystals Calamitic, mesophase, nematic phase, smectic phase, chiral nematic phase and optical Properties of liquid crystals SUGGESTED BOOKS
1. 2. 3. 4 5 6 7. Encyclopedia of Nanomaterials and Nanoteachnology Hari Singh Nalva Nanostructured Materials: Processing, Properites and Applications, ed. By C.C.Koch, Willaim Andrew Publishing, New York, 2002. Nanomaterials: Synthesis, properties and applications, Ed. By A.S.Edelstein and R.C. Cammarata, Inst. of Physics, UK 1966. Science of Engineering Materials, C.M. Srivastava and C. Srinivasan, Wiley-Eastern Ltd. (1991) Solid State Chemistry and its applications , A.R. West, John Wiley & Sons.(1989). Material Science and Engineering. W.D. Callister , John Wiley and Sons Inc. (1985). Nanotubes and Nano wires CNR Rao, & A Govindaraj, RSC, London 2005.

C404 SPECTROSCOPY III

(Common to Inorganic and Physical Chemistry) 52Hours I Vibrational spectroscopy 9h Vibrational spectra of diatomic, linear and bent triatomic, AB3, AB4, AB5 and AB6 molecules, spectra of metal complexes: Ammine, amido, Nitro, Nitrito, lattice water, aquo and hydroxo, carbonato, nitrato, sulphato and other acido complexes, cyano and nitrile complexes, cyanato and thiocyanato complexes, mono and multinuclear carbonyl complexes,

69

nitrosyls, phosphines and arsines, ambidentate ligands, ethylenediamine and diketonato complexes II Raman spectroscopy 4h Resonance Raman Spectroscopy, Nonlinear Raman effects-Stimulated, hyper and inverse types, Lasers and their use in Raman spectroscopy III Photoacoustic spectroscopy Basic description and applications 2h

IV Photoelectron spectroscopy 8h Basic principles- photoelectric effect, Koopmans theorem, XPS and UPS, spin-orbit coupling in core level spectra, applications of core level spectra-ESCA, chemical shift, Valence level spectra- n, and bands, Auger electron spectroscopy and applications, Electron energy loss spectroscopy- basic principles and applications Applications to the study of solids V NMR spectroscopy of inorganic molecules 8h Proton NMR spectra of metal hydride complexes NMR spectra of nuclei other than hydrogen: 19F, 31P, 11B NMR spectra of simple compounds, Proton/hydride interactions with 103Rh, 183W, 195Pt and 207Pb in metal complexes/organometallic compounds, Solid State NMR. VI Electron spin resonance spectroscopy 10h Basic principles, the position of ESR absorption, significance of g factor, determination of gfactor. Electron-nucleus coupling (Hyperfine splitting). ESR spectrometer, electronelectron coupling, double resonance in ESR, ENDOR, ELDOR. Interpretation of ESR spectra and structure elucidation of organic radicals using ESR spectroscopy. Spin density and Mc Connell relationship. Spin polarization for atoms and transition metal ions, spin-orbit coupling and significance of g-tensors, zero/non-zero field splitting, Kramers degeneracy, application to transition metal complexes (having one to five unpaired electrons) including biological molecules and inorganic free radicals such as PH4, F2 and BH3. VII Mossbauer spectroscopy 5h Basic principles, isomer shift, quadrupole splitting and magnetic hyperfine interactions, application to the study of bonding and structures of Fe2+ and Fe3+ compounds, Sn2+ and Sn4+ compounds VIII NQR spectroscopy 4h NQR isotopes, electric field gradients, Nuclear Quadrupole coupling constants, Experimental techniques and applications

70

XI X-ray absorption spectroscopy Near edge measurements and EXAFS SUGGESTED BOOKS
1. 2. 3. 4.

2h

Physical methods in Inorganic Chemistry, R.S. Drago, Affiliated East West Press Pvt. Ltd., New Delhi (1965). Infrared spectra of Inorganic and Coordination Compounds, K. Nakamoto, Wiley-Interscience, New York (1970). Vibrational Spectroscopy: Theory and Applications, D.N. Sathyanarayana, New Age International Publishers, New Delhi (2000). Electronic Absorption Spectroscopy and Related Techniques, D.N. Sathyanarayana, Universities Press, Bangalore (2001).

C405 INORGANIC CHEMISTRY PRACTICALS- III

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. (4 days a week 4 hours a day) Determination of the percentage purity of nitrite Estimation of sulphate by the EDTA method Estimation of sulphate using benzidinehydrochloride Microvolumetric estimation of chloride. Analysis of Woods alloy. Preparation and analysis of Potassium ris(oxalato)ferrate(III)trihydrate Preparation of Potassium tris(oxalato)aluminate(III)trihydrate Preparation and analysis of Hexamminecobalt(III) chloride Preparation of Pentamminechlorocobalt(III) chloride Preparation and magnetic susceptibility studies of Mercury cobalt(II)thiocyanate Magnetic susceptibility studies of copper sulphate pentahydrate and ammonium ferrous sulphate Preparation and analysis of lead tetraacetate (non-aqueous reaction) Preparation and IR spectral studies of Pentamminenitrocobalt(III) chloride and the corresponding nitrito complex Redox chemistry of WO3 Paper chromatographic separation of Co2+, Ni2+ and Cu2+ ions Preparation and analysis of cis and trans- potassium dioxalatodiaquochromium (III) complex

C406 INORGANIC CHEMISTRY PRACTICALS-IV

1. 2. 3. (Instrumental Techniques) Preparation and spectrophotometric analysis of Hexamminenickel(II) chloride. Synthesis and spectral study of copper(II) complexes Synthesis and electrogravimatric analysis of Copper(II) aspirinate
71

4 5. 6. 7. 8. 9. 10. 11. 12. 13. 14.

Flame photometric determination of Na, K, Li and Ca. Determination of the stability constant of silverammine complex by potentiometry Determination of the stability constant of the ferricsalicylate complex spectrophotometrically Equilibrium constant of the Monothiocyanatoiron(II) ion Colorimetric estimation of Ni, Fe (orthophenanthroline method), Al, Ti and Mn in steel. Visible absorption spectrum of KMnO4, K2Cr2O7 and other complexes prepared in C205 Determination of the conductivity of 1:3, 1:2 and 1:1 complexes Electrogravimetric analysis of Copper, Nickel,Cobalt and Lead. Determination of Copper and Cobalt Spectrophotometrically. Non-aqueous titrations. Interpretation of IR, UV-visible and HINMR spectra of selected complexes.

SUGGESTED BOOKS
1. 2. 3. 4. 5. 6. 7. A text book of quantitative analysis, A. I. Vogel, ELBS (1962). Practical inorganic chemistry, G. Marr and B. W. Rockett, Von Nostrand Reinhold Co., London (1972). Experimental inorganic chemistry, G. Plamer, Cambridge University Press (1954). Hand book of preparative inorganic chemistry, Vols I and II, G. Brauer, Academic Press(1963). Non aqueous titrations, W. Huber, Academic Press (1967). Experimental Methods in inorganic chemistry, T. Tanaka and S. L. Suib, Prentice Hall (1999). Experiments in Chemistry ;D.V.Jahagirdar;Himalaya Pub House(2003).

FOURTH SEMESTER ORGANIC CHEMISTRY SPECIALISATION C-401 OC ORGANOMETALLIC AND HETEROCYCLIC CHEMISTRY
52 Hours I. Organometallic Compounds In Organic Synthesis Chemistry of Organotransition metal complexes: General introduction. 18- and 16-Electron rules. General rules. Complexation and De-complexation Reactions: s-Bonded systems including h1 ligands. pBonded systems involving dihapto to octahapto ligands such as- olefins, acetylenes, allyl moieties, butadiene, cyclobutadiene, arenes, cyclopenta, cyclohexa and cycloheptadienyl moieties; cyclohepta, cyclooctatrienes, and cyclooctatetraene moieties. 5h Use of organotransition metal complexes as protecting and stabilizing groups: Protection of olefins, acetylenes and dienes. Stabilization of cyclobutadines and norbornadienones. Organometallics as electrophiles and nucleophiles: Nucleophilic addition to h2, h5 and h6 complexes. Electrophilic addition to h4, h6 and carbene complexes. 3h

72

Organometallics in coupling and cyclization reactions: Coupling and cyclization of organic nucleophiles with olefins (including Heck reaction), and coupling of olefins with acetylenes (including Felkins reaction). 2h Organometallics in isomerization, oxidation and reduction reactions: Isomerization of olefins, allylic alcohols and allylic ethers. Oxidation of olefins (including Wackers process and epoxidation) and reduction of olefins and ,-unsaturated compounds (including Wilkinsons reaction). 3h Carbonylation reactions: Use of zirconium complexes in the synthesis of esters, acids, aldehydes or acyl halides from alkyl halides and in the hydroformylation of olefins and dienes. Use of iron complexes for the insertion of CO group into organic molecules such as dienes, alkyl halides, and vinyl epoxides. Use of cobalt complexes in the synthesis of ketones from epoxides, lactones from allylic alcohols and in the hydroformylation of olefins. Use of palladium complexes for the carbonylation of alkyl halides, dienes and allenes. 4h Application of the following organometallics in Organic Synthesis: Organozincs: Preparation, reaction with compounds containing acidic protons, reaction with C-C multiple bonds, trans-metallation, addition reactions of zinc reagents with carbonyl compounds. Simmons Smith, and Reformatsky reaction. Organolithiums: Preparation. Deprotonation reactions, nucleophilic addition reactions, reactions with imines, nitriles and isonitriles. Organocopper reagents: (Gilman reagents-lithium dialkyl cuprates): Preparation, reactions with alkyl, allyl, vinyl, benzyl and aryl halides, aldehydes, ketones (including a,b-unsaturated carbonyl compounds) and epoxides. 4h Organoseleniums: preparation. Use of organoseleniums in the synthesis of alkenes fromalkyl halides, , -unsaturated carbonyl compounds from carbonyl compounds. Organotelluriums: Debromination of vic-dibromides, deoxygenation of epoxides, oxidation of hydroquinone and synthesis of biaryls. Organoaluminiums: Preparation, hydroalumination and carboalumination of alkenes. Nucleophillic addition reactions with carbonyl compounds and Hydrocyanation. Preparation of alkenyldialkylalanes and their reactions. 4h Organosilicons: Introduction, preparation and general reactions of trialkylsilyl halides. Peterson olefination. Organotins: Preparation and reactions of tri-n-butyltin hydride, Barton decarboxylation and Barton- McCombie reaction. Organocerates: Preparation and reactions of organocerates. Organomercurials: Preparation. Electrophilic substitution reactions. Solvomercuration-demercuration and cyclopropanation of alkenes. 5h
73

II. Heterocyclic Chemistry Small ring heterocycles: Properties and reactions of 3- and 4- membered heterocycles:oxiranes, thiranes, aziridines, azetidines, oxetanes and thietanes. Benzo-fused heterocycles: Synthesis and reactions of benzofurans, benzothiophenes, benzoxazoles, benzothiazoles and benzimidazoles.

2h

3h

Six-membered heterocycles with two or more heteroatoms: Synthesis of Diazines, triazines, tetrazines and thiazines. 2h Seven and large membered heterocycles: Synthesis and reactions of azepanes, oxepines, thiepines, diazepines, thiazepines, azocines, diazocines, dioxocines and dithiocines. 6h Heterocycles containing P, As, Sb and B: Synthesis of 5- and 6- membered heterocycles with P, As, Sb and B. Mesoionic compounds: General classification, chemistry of some important meso-ionic heterocycles of type-A and type-B and their applications. Rotaxanes: Preparation of any two important rotaxanes and their applications. Cryptands: Preparation of [2]-cryptands and spherocrptands and their applications. Calixarenes: Preparation of [4[-, [6]- and [8]-calixarenes and their application. SUGGESTED BOOKS
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. Organometallic Chemistry, R. C. Mehrotra and A. Singh, Wiley Eastern, 1991. The Organometallic Chemistry of the transition metals, R. H. Crabtree, 1988. Principles and application of the organotrnsition metal chemistry, J. P. Collman, L. S. Hegedus, University Science books, 1980. An introduction to Organometallic Chemistry, A. W. Parkins and R. C. Poller, Macmillan, 1986. Modern Synthetic Reactions, H. O. House, W.A. Benjamin, California, 2nd Edn. 1972. Organometallics, Vol. 1 & 2, M. Bochmann, Oxford Chemistry primers, Oxford University Press, 1994. Advanced Organic Chemistry, J. March, 4th Edn. John Wiley, 2008. Organotransition metal chemistry, S. G. Davies, Pergamon Press, Oxford, 1982. Heterocyclic Chemistry, Vols. 1-3, R. R. Gupta, M. Kumar and V. Gupta, Springe rVerlag. The Chemistry of Heterocycles, T. Eicher and S Hauptimann, Thieme. Heterocyclic Chemistry, J. A. Joule, K. Mills and G. F. Smith, Chapman and Hill. Heterocyclic Chemistry, T. L. Gilchrist, Longman Scientific Tech. Contemporary Heterocyclic Chemistry, G. R. Newkome, and W. W. Paudler, Wiley-Inter Science. An introduction to Heterocyclic Compounds, R. M. Acheson, John Wiley. Comprehensive Heterocyclic Chemistry, A. R. Katritzky and C. W. Rees, Eds. Pergamon Press. Stereochemistry of Organic Compounds, D Nasipuri, New-Age International, (1999).

3h

6h

74

C-402 OC STEREOCHEMISTRY AND RETROSYNTHETIC ANALYSIS

52Hours

STEREOCHEMISTRY
I. Optical activity in the absence of chiral atoms 5h Chirality in biphenyls, adamentanes, ansa compounds, cyclophanes, trans-cyclooctene, catenanes, rotaxanes and helicenes. Assignment of R, S- configuration to these classes of compounds. II. Optical activity due to the presence hetero atoms 4h Chirality of organic compounds due to the presence of silicon, nitrogen, phosphorous, arsenic and sulphur atoms. Determination of R,S-configuration of these compounds using CIP rules.

III. Determining absolute and relative configuration 10h i). Chemical correlation of configuration: Methods without involving the chiral centre. Chemical transformation involving the chiral centre. Chemical correlation involving diastereomers. ii). Methods based on comparison of optical rotation: Distance rule, Rule of shift, Rule of optical superposition, Mills rule, Method based on molecular rotation difference iii) The method of quasi-racemate. iv). Use optical rotatory dispersion curves: -axial haloketone rule and its applications, octant rule (application of these rules in the determination of absolute configuration of substituted cyclohexanones, decalones and cholestanones). v). Method based on anomalous X- ray scattering. IV. Transannular reactions 3h Conformational analysis of medium rings. Trasnannular reactions: Hydrolysis of medium ring epoxides and bromination of C8C10 cyclic dienes.

RETROSYNTHETIC ANALYSIS
I. Disconnection approach 6h Introduction to synthons, and synthetic equivalents, disconnection approach. Basic principles and terminologies used in disconnection approach. One group C-X and two group C-X disconnections. Chemoselectivity, reversal of polarity, cyclisation reactions. II. Protecting groups Principle of protection of alcohols, amines, acids and carbonyl groups 3h

75

III. C-C one group and C-C two group disconnections 8h Synthesis of alcohols, carbonyl compounds and alkenes. Use of acetylides and aliphatic nitro compounds in organic syntesis. Diels-Alder reaction, 1,3-difunctionalised compounds, ,unsaturated compounds, carbonyl compounds condensations, 1,5- difunctionalised compounds. Micheal addition and Robinson annelation. IV. Ring Synthesis Synthesis of saturated heterocycles, and 3-, 4-, 5- and 6-membered rings. 3h

V. Synthesis of some complex molecules 10h Application of the above in the synthesis of following compounds: Aromadendrene, longifloene, cortisone, reserpine, vitamin-D, juvabione, aphidicolin and fredericamycin-A and Lycorane. SUGGESTED BOOKS
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. Stereochemistry of carbon compounds, E. L. Eliel, S. H. Wilen and L. N. Mander, John Wiley & Sons, 1994. Stereochemistry, Potapov, MIR, Moscow, 1984. Stereochemistry, Nasipuri, D, New Age, 1999. Advanced organic chemistry, J. March, 4th Edn. John Wiley, 2008. Organic Chemistry, R. E. Ireland Prentice-Hall India, New Delhi, 1975. Some modern methods of Organic Synthesis, W. Caruthers, Cambridge Uni. Press London, 2nd Edn., 1998. Stereochemistry of organic compounds- Principle and applications, D. Nasipuri, 2nd Edn., New Age International Publishers, 2001. Organic synthesis: The synthon approach, S. Warren, John Wiley & Sons, New York, 1st. Edn. 1983. Designing organic synthesis: A disconnection approach, S. Warren, John Wiley & Sons, New York, 2nd Edn. 1987. Organic synthesis, C. Willis and M. Wills, Oxford University Press, 1995. Organic synthesis: Concepts, methods and starting materials, J. Furhfop and G. Penzillin, Verlag VCH. Principles of organic synthesis, R. Norman and J. M. Coxon, Blackie Academic & Professional. Advanced organic chemistry Part B, F. A. Carrey and J. Sundberg, Plenum Press, 1999. Organic chemistry Vol. 2, 6th Edn., I. L. Finar, Longman, 1992.

C-403 OC Organic Synthesis-II

52 Hours I. Asymmetric Synthesis ee and methods of determination of ee. Stereoselectivity: classification, terminology and principle. Asymmetric synthesis and asymmetric induction. Double diastereoselection and double asymmetric induction.

4h

76

Acyclic stereoselection: Addition of nucleophiles to carbonyl compounds (1,2- 1,3- and 1,4asymmetric induction). Asymmetric aldol condensation. Addition of allylmetal and llylboranes to carbonyl group. 3h Diastereoselection in cyclic systems: Nucleophilic addition to cyclic ketones (formation of axial and equatorial alcohols, catalytic hydrogenation, alkylation, diastereoselective oxidations and stereoselective cyclization of poylenes). 3h Enantioselective synthesis: Reduction with chiral hydride donors [(S)-PBMgCl, (-)i BOAlCl2, alpine-borane, (S)-BINAL-H, (R,R)-DIOP, and (S,S)-CHIRAPHOS).

4h

Enantioselective alkylation of ketones via hydrazones. Enantioselective alkylation with chiral PTC. Enantioselective Michael addition. Enantioselective intramolecular aldol condensation. Use of (+)- and ()- DET in asymmetric epoxidation. Polymer-bound chiral catalysts in asymmetric induction. Asymmetric amplification. 6h II. Use of ultrasound and Microwaves in Organic Synthesis 6h Use of ultrasound: Introduction, instrumentation, the phenomenon of cavitation. Sonochemical esterification, substitution, addition, alkylation, oxidation, reduction and coupling reactions. Use of Microwaves: Introduction, concept, reaction vessel/medium, specific effects, atom efficiency (% atom utilization), advantages and limitations. N-alkylation and alkylation of active methylene compounds, condensation of active methylene compounds with aldehydes and amines. Diels-Alder reaction. Deprotection of esters and silyl ethers. Oxidation of alcohols and sulfides. III. Ionic-liquids: Introduction, structure, synthesis and applications of some important ionic liquids in organic synthesis. . 2h IV. Polymer supported reagents in organic synthesis 6h Introduction- properties of polymer support, advantages of polymer supported reagents and choice of polymers. Applications: Substrate covalently bound to the support: Synthesis of oligosachcharides, Dieckmann cyclisation, solid-state Edman degradation. Preparation of polymer bound aldehyde and application in aldol and Wittig reactions. Synthesis of polystyryl boronic acid and use in diol protection reaction. Reagent linked to a polymeric material: Preparation of sulfonazide polymer and application in diazotransfer reaction. Preparation polymeric n-butyl- triphenylphosphonium bromide and its use in Wittig reaction. Synthesis of polymer bound per acid and its applications. Polymer supported catalytic reactions: Preparation of polymer supported AlCl3 and application in etherification and acetal formation reactions.
77

V. Phase transfer catalysis and Crown ethers 6h Phase transfer catalysis: Introduction, definition, mechanism of phase transfer catalysis. Types of phase transfer catalysts and reactions and their Advantages. Preparation of catalysts and their application in substitution, elimination, addition, alkylation, oxidation and reduction reactions. Crown ethers: Introduction, nomenclature, features, nature of donor site. General synthesis of Crown ethers. Synthetic applications: Alkylation, generation of carbenes, aromatic substitution and displacement reactions. Generation and application of superoxide anions. Cation deactivation reactions. VI. Nonbenzenoid and polycyclic aromatic Compounds 6h Nonbenzenoid aromatic compounds: Introduction, synthesis of cyclopropenyl cations, cyclobutadienyl dications, cyclopentadienyl anions, cycloheptatrienium cation, cyclooctatetraenyl dication, [10]-, [14], and [18]-annulenes, azulene and their reactions. Polycic aromatic compounds: Introduction, nomenclature, preparation of anthracene, phenenthrene, naphthacene, chrysene, 20-methylcholanthrene, pyrene, perylene, coronene and lapachol. Reactions of anthracene and phenanthrene. VII. Pesticides and insecticides 6h Introduction, classification. Synthetic insecticides: Introduction, classification, mode of action and synthesis of chlorinated insecticides (DDT, chlordane, heptachlor and hexachlorocyclohexane). Organop[hosphorous insecticides: Malathion, parathion, DDVP, diazenon. Carbamate insecticides: Sevin, carbofluron, aldicab, beygon. Naturally occurring insecticides: Rotenones, pyrethrins, precocenes. Introduction to the use of the following in the control of pests and insects: Fumigants, nematicides, acaricides, hormones (juvenile hormone), insect repellents, molluscicides and rodenticides. SUGGESTED BOOKS
1. 2. 3. 4. 5. 6. 7. 8. 9. Stereochemistry of carbon compounds, E. L. Eliel, S. H. Wilen and L. N. Mander, John Wiley & Sons, 1994. Stereochemistry, Potapov, MIR, Moscow, 1984. Stereochemistry, Nasipuri, D, New Age, 1999. Advanced organic chemistry, J. March, 4th Edn. John Wiley, 2008. Organic Chemistry, R. E. Ireland Prentice-Hall India, New Delhi, 1975. Some modern methods of Organic Synthesis, W. Caruthers, Cambridge Uni. Press London, 2nd Edn. 1998. Stereochemistry of organic compounds- Principle and applications, D. Nasipuri, 2nd Edn., New Age International Publishers, 2001. Principles and applications of asymmetric synthesis, G D Lin, Y M Li and A S C Chan, Wiley Interscience, 2001. A textbook of organic chemistry, V. K. Ahluwalia and M. Goyal, Narosa Publishing House, New Delhi, 2000. 78

10. Organic synthesis: Special techniques, V. K. Ahluwalia and R. Aggarwal, Narosa, New Delhi, 2003. 11. Green Chemistry, environment friendly alternatives, R. Sanghi and M MSrivastava, Narosa, New Delhi, 2003. 12. Green Chemistry-an introduction text, Royal Society of Chemistry, UK, 2002. 13. Organic chemistry Vol. 2, 6th Edn., I. L. Finar, Longman, 1992. 14. Crownethers & cryptands, G. W. Gokel, Monograph, The Royal Society of Chemistry, 1991. 15. Macrocyclic Polyether Chemistry, G. W. Gokel, S. M. Korzeniowski, Vol 1 to 3, Wiley, NY, 1978, 1981, 1987. 16. Phase Transfer Catalysis in Organic Synthesis, W. B. Weber, G. W. Gokel, Springer, Berlin, 1977. 17. Phase Transfer Catalysis, E. V. Dehmlov, S. S. Dehmlov, 2nd Edn., Verlagchemie, Wienheim, 1983. 18. Polymers as aids in Organic synthesis, N. K. Mathur, C. K. Narang and R. E. Williams, Academic Press, NY, 1980.

C-404 OC MEDICINAL ORGANIC CHEMISTRY

52 hours I. Pharmacokinetics, Pharmacodynamics, Theories of drug activity& Drug design Classification and nomenclature of drugs. Pharmacokinetics, pharmacodynamics, prodrugs and active pharmacodynamic agents, hard and soft drugs, generics and analogs, metabolites and antimetabolites, agonists and antagonists. Concept of drug receptors. Elementary treatment of drug-receptor interactions. Theories of drug activity: Occupancy theory, rate theory, induced-fit theory. Factors governing drug design. Physicochemical parameters: lipophilicity, partition coefficient. Rational approach to drug design. Quantitative structureactivity relationships (QSAR). Hansch equation. Computer-aided drug design and molecular modeling. Factors governing the enhancement of biological activity of drugs. Iso-sterism and bioisosterism. Generics and analogues. General principles of drugdelivery: principles of dosage form design and drug administration. Drug toxicity testing: LD50, ED50, ID50, IC50 (mathematical derivations excluded). 10h II. Steroids Occurrence. Nomenclature, basic skeleton, Diels hydrocarbon and stereochemistry. Isolation, structure and structural elucidation of sterols and bile acids (determination of ring size, nature of side chain, position of angular methyl and stereochemistry of ring junctions). Sex hormones and corticosteroids. Synthesis of cholesterol, estrone, progesterone, androsterone, testosterone. Photo products of ergosterol- vitamins D. Barton reaction for the synthesis of aldosterone. Marker degradation. Brief discussion of homosteroids, norsteroids and oral contraceptives. Synthesis of (dl)-norgestrel and ethinyl oestradiol. 12h III. Antibiotics Chemistry (structure elucidation, stereochemistry, reactions and synthesis) of streptomycin, penicillins, cephalosporin-C and tetracyclins (terramycin and aureo-mycin Interconversion of penicillins to cephalosporins; and aureomycin to tetracycline. 8h
79

IV. Mechanism of drug action and synthesis of the following classes of drugs, with recent developments: Antipyretics, analgesics and non steroidal anti-inflammatory drugs: Aspirin, paracetamol, phenacetin, novalgin, phenylbutazone and ibuprofen. Antidiabetics: Sequence of A- & B- chains of insulin, glibenclamide, metformin, ciglitazone. Antihistamines: Methapyrilene, chlorpheniramine. Antivirals : Acyclovir, amantidine, rimantidine and zidovudine. Antineoplastic agents: Introduction, cancer chemotherapy, special problems, role of alkylating agents and antimetabolites in treatment of cancer. Mention of carcinolytic antibiotics and mitotic inhibitors. Synthesis of mechlorethamine, cyclophosphamide, melaphan, uracil mustards and 6-mercaptopurine. Recent development in cancer chemotherapy. Hormone and natural products. Cardiovascular drugs: Introduction, cardiovascular diseases, drug inhibitors of peripheral sympathetic function, central intervention of cardiovascular output. Direct acting arteriolar dilators. Synthesis of amyl nitrite, sorbitrate, diltiazem, quinidine, verapamil, methyldopa, atenolol, oxrprenol. 12h Local anti-infective agents: Introduction and general mode of action. Synthesis of sulphonamides, furazolidone, nalidixic acid, ciprofloxacin, dapsone, aminosalicyclic acid, isoniazide, ethionamide, ethambutal, fluconazole, econozole, griseofulvin, chloroquin and primaquin. Psychoactive drugs- chemotherapy of the mind: Introduction, neurotransmitters, CNS depressants, general anaesthetics, mode of action of hypnotics, sedatives, anti-anxiety drugs, benzodiazepines, buspirone, neurochemistry of mental diseases. Antipsychotic drugs- the neuroleptics, antidepressants, butyrophenones, serendipity and drug development, stereochemical aspects of psychotropic drugs. Synthesis of diazepam, oxazepam, chlorazepam, alprazolam, phenytoin, ethosuximide, trimethadione, barbiturates, thiopental sodium, glutethimide. 10h SUGGESTED BOOKS
1. Burger's Medicinal Chemistry and Drug Discovery, Vols. 1-6 Ed. D.J. Abraham, John Wiley, 2003 2. Foyes Principles of Medicinal Chemistry, 6th Edn., T L Lemke and D A WilliamsEds., Lippincott, Williams and Wilkins, 2007 3. An Introduction to Medicinal Chemistry, P Graham, III Ed., Oxford, 2006 4. Medicinal Chemistry, N Weaver, Oxford, 2006 5. Goodman and Gilman's Pharmacological Basis of Therapeutics, 11th Edn., TataMcGraw-Hill, 2005. 6. The Organic Chemistry of Drug Design and Drug Action, R B Silverman,II Edn, Academic Press, Amsterdam, 2004. 7. Wilson and Gisvold's Text Book of Organic Medicinal and Pharmaceutical chemistry, J H Block and J M Beale, Jr., Eds., Lippincott, Williams and Wilkins, 2003. 8. Medicinal Chemistry G R Chatwal, Himalaya, New Delhi, 2002 9. Instant Notes Medicinal Chemistry, P Graham, Viva, New Delhi, 2002 10. Medicinal Chemistry, A Kar, Wiley, 2000. 80

11. An Introduction to Drug Design, S.S. Pandey and J.R. Dimmock, New Age International, 1999. 12. Strategies for Organic Drug Synthesis and Design, D. Lednicer, John Wiley,1998. 13. Synthetic drugs, G. R. Chatwal, Himalaya, New Delhi, 1995. 14. Natural Products Chemistry Vol 1 and 2, G R Chatwal, Himalaya, New Delhi, 1990 15. Comprehensive Organic Chemistry, Vol. 5 (Antibiotics), D. H. R. Barton, W. D. Ollis, Pergamon Press, NY, 1979. 16. Organic chemistry Vol.II, I. L. Finar, 6th Edn. Longman, 1992. 17. Total synthesis of natural products: The chiral approach Vol.III, S. Hanessian Pergamon Press, 1983. 18. Total synthesis of steroids, Akhaun & Titov, Jerusalem, 1969. 19. Medicinal natural products: A biosynthetic approach, P. M. Dewick. John Wiley, Chichester, 1997. 20. Natural products: Their chemistry and biological significance-J. Mann, R. S. Davidson, J. B. Hobbs, D. V. Banthorpe & J. B. Harborne, Longman, UK, 1994. 21. Natural products chemistry Vol. I & II, K. Nakanishi, T. Goso, S. Ito, S. Natori & S. Nozoe, Academic Press, NY, 1974. 22. Chemistry of natural products Vol. I & II, O. P. Aggarwal, Goel Publishing House, 6th Edn. 1982. 23. Total synthesis of natural products: The chiral approach Vol.III, S. Hanessian Pergamon Press, 1983. 24. Interpretation of the UV spectra of natural products, A.I. Scott, Pergamon Press, Oxford, 1964. 25. Spectral data of natural products Vol. I- K.Yamaguchi, Elsevier Publishing Co, London, 1970. PRACTICALS

(4 days a week, 4 hours a day)

C405 ORGANIC CHEMISTRY PRACTICALS - III

I PREPARATIONS 1. Preparation of NBS from succinic acid and its application in allylic bromination reactions. 2. Preparation of benzpinacolone from benzophenone. 3. Generation of benzyne and its trapping with tetracyclone. 4. Preparation of 2-phenylindole from phenylhydrazine 5. Anthrone from Anthracene. 6. Synthesis of stilbene. 7. Synthesis of benzocaine from 4-nitrobenzoic acid. 8. Preparation of tetraphenyldihydrophthalic anhydride from N-phenylglycine. 9. Preparation of 2,4,5-triphenyloxazole from benzoin 10. Biosynthesis of ethanol from sucrose. 11. Synthesis of Methyl Red 12. Synthesis of 1-bromo-2-naphthol from 2-naphthol 13. Synthesis of Hippuric acid 14. 1,2,3,4- Tetrahydrocarbazole 15. Diels-Alder reaction of anthracene with maleic anhydride 16. Synthesis of 2,3-diphenylquinoxaline

81

II-INSTRUMENTAL METHODS IN ORGANIC ANALYSIS 1. Recording/predicting/downloading from web sites the UV, IR, NMR and GC-MS/mass spectra of the compounds prepared in C-105/205/305 (Organic Practical I), C106/206/306 (Organic Practical II), C-405 (Organic Practical III) and C- 406 (Organic Practical IV). 2. Structural elucidation of organic compounds with the help of spectra provided by the instructors/examiners. III QUANTITATIVE ANALYSIS Estimations: 1. Estimation of Nitro group by reduction using SnCl2. 2. Estimation of Nitrogen by Kjeldahls method. 3. Estimation of an acid in presence of an amide. 4. Estimation of an ester in the presence of an acid.

C406 ORGANIC CHEMISTRY PRACTICALS

I - QUALITATIVE ANALYSIS Separation of a binary mixture of organic compounds and identification of the separated components by systematic qualitative organic analysis. II- EXTRACTIONS AND SEPARATIONS (Preliminary Chromatographic Techniques) Extractions 1. Extraction of piperine from pepper. 2. Extraction of caffeine from tea leaves. 3. Extraction of (+)-limonene from citrus rinds. 4. Extraction of azelaic acid from caster oil. Separations 1. Separation of p-rosaniline and methyl red by column chromatography. 2. Separation of amino acids by paper chromatography. 3. Separation of carbohydrates by thin layer chromatography.

SUGGESTED BOOKS
1. 2. 3. 4. 5. Semi-micro qualitative organic analysis, Cheronis, Entrikin & Hoanett. Preparation of organic intermediates, D. A. Hirley, John Wiley. Text book of practical organic chemistry, A. I. Vogel, Pearson, 5th Edition, Delhi, 2004. A laboratory manual of qualitative organic analysis, H.T. Openshaw, Univ. Press, 1999. Organic Synthesis collective Vols. I to X, 1956-1999. 82

6. 7. 8. 9. 10. 11. 12. 13. 14. 15.

Natural products, Laboratory manual, Ikan, 2000. Organic experiments, L. F. Fieser, 2nd Edn. D. C. Heath & Co. USA, 1974-2000. Practical organic chemistry F.G. Mann and B. C. Saunders 4th Edn. Longman, 2002. Comprehensive practical organic chemistry : Preparation and quantitative Analysis, V. K. Ahluwalia, R. Aggarwal, Universities Press (India), 2000. Comprehensive practical organic chemistry: Qualitative analysis, V. K. Ahluwalia, S. Dhingra, Universities Press (India), 2000. An advanced course in practical chemistry, A. Ghoshal, B. Mahapatra and A. K. Nad, New central book agency, Calcutta, 2000. Advanced practical organic chemistry, J. Mohan, Vol. I and II, Himalaya Publishing House, 1992. Practical organic chemistry (Quantitative analysis), B. B. Dey, M V Sitaraman and T. R. Govindachari, Allied Publishers, New Delhi, 1992. Laboratory Techniques in Organic Chemistry, V K Ahluwalia, Pooja Bhagat and Renu Aggarwal, I K international Publishing House, New Delhi, 2005. Intermediates for Organic Synthesis, V K Ahluwalia, Pooja Bhagat, Ramesh Chandra and Renu Aggarwal, I K international Publishing House, New Delhi, 2005.

FOURTH SEMESTER PHYSICAL CHEMISTRY SPECIALISATION

C-401 PC APPLIED ELECTROCHEMISRY
52 Hours I. Metal finishing Electroplating: Technological importance theories and mechanism of electroplatingeffect of plating variables on the properties of electrodeposits comparative account of complexing and non-complexing baths (general treatment) additives in the plating bath significance. Metallic Coatings: Surface preparation electropolishing electroplating of Cu,Ni,Cr Zn plating electroplating for electronics (Ag & Au) . Solar- selective coatings characteristics, methods of preparation and applications. Techniques of electroplating: Galvanostatic and potentiostatic techniques elementary account of electroless plating, galvanizing, anodizing, phosphating, chromating, organic finishes and industrial effluent treatment. Testing of electrodeposits: Principles of the measurement of coating thickness, adhesion, porosity, corrosion resistance, reflectance and hardness surface analysis of coatings by XPS and AES. 8 hrs II. Corrosion and its prevention About corrosion: Theories and mechanism of corrosion thermodynamic and kinetic approaches to the study of corrosion methods of determination of corrosion rates Tafel extrapolation, linear polarization and impedance techniques. Methods of corrosion prevention: Cathodic and anodic protection corrosion inhibitors.

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Passivity: Characteristics Flade potential theories and mechanism of passivation transpassivity use of ellipsometric technique in the study of passivating films. 10 h III. Electroanalytical methods Voltammetry at a dropping mercury electrode(DME): Review of the principles of normal dc polarography types of currents obtained at a DME Ilkovic equation and its application current-potential relation for a cathodic process half-wave potential tests for the reversibility of a process irreversible processes at a DME factors that set the sensitivity and selectivity limits in normal dc polarography. Modified polarographic techniques: Tast polarography normal pulse polarography differential pulse polarography ac polarography. Stripping analysis: Hanging drop mercury electrode (HDME) principle and applications of cathodic and anodic stripping voltammetry. Cyclic voltammetry: Principle experimental set up quantitative analysis determination of diffusion coefficients diagnostic criteria for reversible, quasi-reversible and irreversible processes study of coupled chemical reactions like ErCr, CrEr and ErCiEr. Chronomethods: Basic concepts, methodology and applications of chronoamperometry, chronocoulometry and chronopotentiometry. Spectroelectrochemical techniques: Principle and application of transmission IR spectroelectrochemical technique. Hydrodynamic electrodes: Construction and use of rotating disc and rotating ring disc electrodes in the study of electrochemical processes. 15 h IV. Electrochemical energy conversion and storage Efficiency: Efficiency of electrochemical energy conversion vis--vis thermal conversion (Carnot limitation). Batteries: Classification characteristics voltage, current, capacity, electricity storage density, energy density, power density, energy efficiency, cycle life, shelf life. Primary batteries: Construction, reactions and uses of Leclanche dry cell and metal-air batteries. Secondary batteries: Construction, reactions during charge-discharge and applications of Pb-acid, Ni-Cd, silver oxide-Zn batteries. Lithium batteries: Primary and secondary lithium battery lithium based conducting polymer batteries. Fuel cells: Classification alkaline fuel cells, solid polymer electrolyte fuel cells, phosphoric acid fuel cells, molten carbonate fuel cells and solid oxide fuel cells brief description, reactions and applications of each type of fuel cell. Electrochemical supercapacitors: Brief description, advantages and applications. 10 h

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V. Electroorganic synthesis Description: Special features of electroorganic synthesis as compared to conventional synthesis reaction variables (electrode material, electrode potential, solvent, supporting electrolyte, temperature, agitation ) in electroorganic synthesis. Classification: Syntheses involving cathodic, anodic, paired, phase-transfer catalysed and electropolymerisation reactions. One or two typical examples of each type of reaction. Two examples of electroinorganic synthesis. 6h VI. Bioelectrochemistry The electrochemical interface between biomolecules, cellular membrane, transmembrane potential, bilayer lipid membranes, electroporation. The nerve impulse. Enzyme electrodes, bioelectrocatalysis, bioelectroanalysis. 3h SUGGESTED BOOKS
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. Modern Electrochemistry Vol 1,2A&2B by Bockris & Reddy, Plenum, N.Y (2000). Electrochemistry by Potter, Cleven Hume, London (1961). Industrial Electrochemistry by D. Pletcher and F. C. Walsh, Chapman & Hall, Cambridge (1990). An introduction to Metallic Corrosion and its Prevention by Rajanarayan, Oxford & IBH Publishing Co.,New Delhi(1983). Polarography and Allied Techniques by V. Suryanarayana Rao, Universities Press (India) Pvt. Ltd., Hyderabad (2002). Chemical and Electrochemical Energy Systems by Narayan & Viswanathan, Hyderabad, Universities Press (India) Ltd.,(1998). Electrochemistry by S. Glasstone, East-West Press, New Delhi (1985). Techniques and Mechanisms in Electrochemistry by P. A. Christensen and A. Hammett, Chapman & Hall, London (1984). Electrochemistry Principles, Methods and Applications by Christopher M. A. Brett, Ana Maria and Oliveria Brett, Oxford University Press, Oxford & New York (1993). Synthetic Organic Electrochemistry by A. M. Fry, 2nd Edition, Wiley (1989). Basics of Electroorganic synthesis byDemetrior K. Kyriacon, John Wiley & Sons (1981). Fundamental Principles in Modern Electrochemistry by Lowenheim, John Wiley & Sons (1968). Corrosion Engioneering by Mars Fontanna, 3rd ed., McGraw Hill, New York (1987). Fuel Cells by Bockris & Srinivasan, John Wley & Sons (1972). Electroanalytical Chemistry by B. H. Vassos and G. W. Ewing, John Wiley & Sons, New York (1983). Principles of Electroanalytical Methods by T. Riley and C. Tomlinson (Analytical Chemistry by open learning), John Wiley & Sons (1987). Lithium battery technology by H. V. Venkatasetty, John Wiley & Sons Inc.,(1984). Electrochemical Methods Fundamentals and Applications, 2nd ed. By A, J. Bard and L. R . Faulkner, John Wiley & Sons Inc., New York (2001).

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C-402 PC PHYSICAL CHEMISTRY OF MACROMOLECULES

(ELECTIVE) 52 Hours I. Polymerization process: 9h Chain polymerization: Free radical polymerization: initiation, propagation and termination, chain transfer, inhibitors. Ionic polymerization, coordination polymerization, Ziegler-Natta catalyst. Step polymerization: polycondensation, polyaddition, ring opening polymerization and miscellaous polymerization. Electrochemical polymerizarion: Matathetical polymerization, group transfer polymerization II. Synthetic High Polymers: 14h

i) Chemical and Geometrical Structure of Polymer molecules:Polymer micro structure; organic and inorganic polymers, homo chain and hetero chain polymers, homopolymers and copolymers. Microstructures based on geometrical structures: linear, branched and cross linked polymers, random, alternating, block and graft copolymers. Stereo regular polymers: Optical isomerism and geometric isomerism. ii) Glass Transition temperature: States of aggregation, states of phase, transitions and associated properties, factors influencing the Tg, Tg and molecular weight, Tg and plasticizers, Tg and melting point. Importance of Tg. i) Tg, Tm and Tf : Characteristics and evaluation of Tg, Tm and Tf in accordance with crystalline and amorphous polymers. Effect of temperature, crystallanity and molecular weight on mechanical behavior of polymers. III. Thermodynamics of polymer solution: 4h Partial molar and partial specific quantities, Chemical potential of macromolecular solution. Gibbs Duhem equation, concepts of second viral coefficient and excluded volume. Expressions for models postulated for the shapes of macromolecules in solution: spheres, ellipsoid, long rod and flexible random coil. IV. Molecular weight determinations: 10h Determinatiopn of molecular weight average by (i) Osmotic pressure. Donnan membrane equilibrium. (ii) light scattering, (iii) Sedimentation velocity (iv) sedimentation equilibrium. (v) density gradient sedimentation (vi) viscosity (vii) electrophorises. Derivation of relevant exopression in each case. Use of these methods in evaluation of shapes and confirmations of macromoleuclaes.

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II. Spectroscopic studies of Macromolucules: 5h Determination of structure of macromolecules by UV-Visible, Infrared, NMR, ORD and CD techniques. III. Mechanical properties: 5h Structure property relation ship of polymers: Strength, plastic deformation (Rheology), physical state of polymers, chemical resistance, crystallanity, Mechanism of Deformation, Methods of testing: Static testing- Poissons ratio, stress-strain curves. Transient testing and Impact testing. IV. Degradation, Stability and Environmental issues: 5h Thermal degradation, oxidative and UV-stability, chemical and hydrolytical stability, radiation effects. Mechanical degradation, photodegradation, degradation by ultra sonic waves. Management of plastics in the environment. Recycling, Incineration and bio degradation. SUGGESTED BOOKS
1. 2. 3. 4. 5. 6. 7. 8. Text book of polymer science: F.W.Billmeyer (John.Wiley), London, 1994. Polymer science: V.R.Gowariker, N.V.Viswanathan & T.Sreedhar (Wiley Eastern) New Delhi, 1990. Introduction to Physical polymer science, L.H.Sperling, Wiley-Interscience, New York (1986). Fundamentals of Polymer science and Engineering. Anil Kumar and S.K. Gupta, Tata Mc-Graw hill-LCUE Series, New Delhi (1978). Principles of polymer chemistry-P.J.Flory, Cornell Univeristy, Press Ithaca (1953). Principles of polymerization, G.Odian, 3rd edition, Wiley Interscience, New York 1992. A Laboratory Manual of Polymers, S.M. Ashraf, Sharif Ahmad and Ufana Riaz. I.K. International Publishing House Pvt.Ltd. New Delhi, 2009. Polymer Science and Technology, J.R.Fried (Prentice hall) New Delhi 1999.

C -402 PC NANOMATERIALS (Elective)

52hours I. Introduction: Introduction and definition of nanoparticles nanotechnology, Challenges of nanotechnology: and nanomaterials, Emergency 2h of

II. Properties of individual nanoparticles: 20h Metal nanoclusters, Magic numbers , Theoretical modeling of nanoparticles, Geometric structures, Electronic structures, Reactivity, Fluctuation, Magnetic clusters, Bulk to nano transition, Semiconducting nanoparticles: Optical properties, Photo fragmentations, Coulombic explosion, Rare gas and molecular clusters: Inert-gas cluster, Super fluid cluster, molecular cluster. Methods of synthesis: RF plasma, Chemical methods, thermolayers, pulsed laser methods, conclusions.
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III. Special nanometerials: 20h Carbon molecules, nature of the carbon bond,, New carbon structures, carbon clusters-small carbon clusters, discovery of C60, Strucure of C60 and its crystal, Alkali doped C60, Larger and smaller Fullerenes, other bucky balls, Carbon nanotubes, and nanowires structures, electrical properties, Vibrational properties, Mechanical properties, Micro and mesoporous materials: Ordered and random mesoporous structures, crystalline micro porous materialsZeolites, Core shell structure, metal oxide, metal polymer and oxide polymer structure, Organic and inorganic hybrids: Class I and Class II Hybrids, intercalation compoundsNanocomposites and nanograined materials. IV. Quantum wells, wires and dots: 10h Introduction, preparation of quantum nanostructures, size and dimensionality effects, size effects, Conduction electron and dimensionality Fermi gas and density of states, potentials wells partial confinement, properties dependent on density of states, Excitations, single electron tunneling, Application: Infrared detectors, Quantum dot lasers, Conductivity. SUGGESTED BOOKS
1. 2. 3. 4. 5. Charles P. Poole Jr, Frank J. Owens, Introduction to Nanotechnology (2nd Edition), Wiley-India Edition, Delhi, 2008. Mick Wilson, Kamali Kannangara Geoff Smith, Michelle Simmons, Burkhard Raguse, Nanotechnology, Overseas Press, Inida, 2005. Guozhong Cao, Nanostrutures and nanomaterials, Imperial College press, University of Washington, USA, 2004. S. V. Bhat, Biometerials (2nd Edition), Narosa Publishing House, New Delhi, 2005. Manasi Karkare, Nanotechnology Fundamentals and Applications, I.K. International, Publishing House Pvt. Ltd., Bangalore, 2008.

C-403 PC REACTION KINETICS AND MECHANISMS

52 Hours I. Reactions in solution Cage effect, Reaction between gas phase and solution phase. Influence of solvent on reaction rates (double sphere model), Primary and secondary isotope effects on reaction rates, Linear Free Energy relationships (LFER): Thermodynamic implications of LFER, Inductive and electromeric effects on reaction rates, Effect of substitutents on activation energies, Hammett and Taft equations, Swain-Scott and Edward equations, Winstein Grunwald relationship, Isokinetic relationship-Evaluation of isokinetic temperature and its significance, Diffusion and activation controlled reactions. 10h II. Reaction mechanisms Importance and general approaches of reaction mechanism, Volume of activation- entropy of activation, significance of volume of activation, Kinetics and mechanisms of- Decomposition of N2O5, Halogenation of acetone, Dehydrogenation of ethane, Hypohalite-iodide reaction,
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Pyrolysis of butane and, Nucleophilic and electrophilic substitution reactions, Mechanisms of N-haloamines, Microscopic reversibility. 10h III. Chain and complex reactions Introduction, Production and identification of free radicals, Kinetics of Branched chain reactions, H2-O2 reaction explosion limits, Oscillatory reactions- Introduction, Oxidation of malic acid by bromate ion catalysed by Ce(III), Kinetics and mechanisms of polymerization reactions-Addition (Free radical, Anionic and Cationic) and Condensation polymerization 7h IV. Kinetics of catalyzed reactions Heterogeneous catalysis- Intermediate compound formation theory and adsorption theory, Role of surfaces in heterogeneous catalysis, Acidity functions- Relationship between the rate constant and acidity function, Ru(III) chloride catalyzed oxidation reactions of alcohols and aminoacids by chloramine-T in acid and alkaline media, Deduction of reaction mechanisms, rate laws, catalytic coefficients and decomposition constants, Industrial catalysts- catalyst carrier, catalyst promoter, catalyst inhibitor and catalyst poison. Role of surfaces in heterogeneous catalysis. 9h V. Pharmacokinetics Basic considerations, Objectives, Kinetic orders of reactions, Plasma drug concentration time profile, Pharmacokinetic and Pharmacodynamic parameters, Protein binding of drugs, Factors affecting protein-drug binding, Kinetics of protein-drug binding, Drug dissolution rate. Bioavailability- Objectives and enhancement of bioavailability, Physico-chemical factors affecting bio-availability. Compartment modeling: Introduction, one compartment open model, calculation of elimination rate constants. 8h VI. Molecular reaction dynamics Reactions in molecular beams, potential energy surface for H+H2, Theoretical calculation of activation energies of potential energy surfaces, Transmission co-efficient, Quantum mechanical tunneling, Reaction co-ordinate, Symmetry numbers and statistical factors, Mean free path, Reaction rates and cross sections. 8h SUGGESTED BOOKS
1. 2. 3. 4. Chemical Kinetics, K.J. Laidler 3rd Edition (Mc-Graw Hill Inc.) New York, 2007. Kinetics and Mechanism, Frost and R.G.Pearson (John-Wiley) New York, 1962. Physical Chemistry, 7th Edition, P. W. Atkins (Oxford) 2004. Introduction to Molecular Dynamics and Chemical Kinetics, G.D.Billing and Milkelson (Wiley Interscience), 1996. 5. Organic Reaction Mechanism, R.K.Bansal (Mc-Graw Hill) New Delhi, 1978. 6. Kinetics of Chemical Reactions, S.K.Jain (Vishal Publications) 1982. 7. Reaction Mechanism in Organic Chemistry, S.M.Mukheji, S.P.Singh and R.P.Kapoor (Mc.Millan India Ltd., Bangalore) 1978. 8. Catalysis, J.C.Kuriacose (McMillan India Ltd.,) 1991. 9. Text Book of Polymer Science,F.W.Billmeyer (Jhon Wiley) 1984. 10. Introductory Polymer Chemistry, G.S.Misra (Wiley Eastern Ltd.,) New Delhi, 1993. 89

11. Polymer Science,Gowrikar et al (Wiley Eastern Ltd.,) New Delhi, 1990. 12. Introduction to Physical Organic Chemistry,R.D.Gilliom (Additions Wesley) USA, 1970. 13. Physical Organic Chemistry, Reaction Rates Equilibrium and Mechanisms, 2nd Edition, L.P.Hammett (Mc-Graw Hill Book Co.) 1970. 14. Biophysical Chemistry-Principles and Techniques, A Upadyayay, K-Upadyayay, N. Nath (Himalaya Publishing House), Mumbai, 1998. 15. Foundation of Chemical Kinetics, S.W. Benson (Mc-Graw Hill), New York, 1960. 16. Comprehensive Chemical Kinetics, Vol-I, Banford and Tipper (Elsevier Publishing Co.,) New York, 1969. 17. Statistical Thermodynamics,M.C.Gupta (Wiley Eastern Ltd.,) New Delhi, 1990. 18. Physical Chemistry, 5th Edition ,G.M.Barrow, (Tata-Mc-Graw Hill), 1992. 19. Elementary reaction Kinetics, 3rd Edition, (Butterworths) ,London, 1977. 20. Principles of Chemical Kinetics, J.E. House (Wm C Brown publisher), Boston, 1997. 21. Modern Physical Organic Chemistry-V.A. Eric and A.D. Dennis, University Science Books, USA (2006).

C-404

SPECTROSCOPY III

(Common to Inorganic and Physical Chemistry) 52Hours I. Vibrational spectroscopy 9h Vibrational spectra of diatomic, linear and bent triatomic, AB3, AB4, AB5 and AB6 molecules, spectra of metal complexes: Ammine, amido, Nitro, Nitrito, lattice water, aquo and hydroxo, carbonato, nitrato, sulphato and other acido complexes, cyano and nitrile complexes, cyanato and thiocyanato complexes, mono and multinuclear carbonyl complexes, nitrosyls, phosphines and arsines, ambidentate ligands, ethylenediamine and diketonato complexes II. Raman spectroscopy 4h Resonance Raman Spectroscopy, Nonlinear Raman effects-Stimulated, hyper and inverse types, Lasers and their use in Raman spectroscopy III. Photoacoustic spectroscopy Basic description and applications 2h

IV. Photoelectron spectroscopy 8h Basic principles- photoelectric effect, Koopmans theorem, XPS and UPS, spin-orbit coupling in core level spectra, applications of core level spectra-ESCA, chemical shift, Valence level spectra- n, and bands, Auger electron spectroscopy and applications, Electron energy loss spectroscopy- basic principles and applications Applications to the study of solids V. NMR spectroscopy of inorganic molecules Proton NMR spectra of metal hydride complexes
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8h

NMR spectra of nuclei other than hydrogen: 19F, 31P, 11B NMR spectra of simple compounds, Proton/hydride interactions with 103Rh, 183W, 195Pt and 207Pb in metal complexes/organometallic compounds, Solid State NMR. VI. Electron spin resonance spectroscopy 10h Basic principles, the position of ESR absorption, significance of g factor, determination of gfactor. Electron-nucleus coupling (Hyperfine splitting). ESR spectrometer, electronelectron coupling, double resonance in ESR, ENDOR, ELDOR. Interpretation of ESR spectra and structure elucidation of organic radicals using ESR spectroscopy. Spin density and Mc Connell relationship. Spin polarization for atoms and transition metal ions, spin-orbit coupling and significance of g-tensors, zero/non-zero field splitting, Kramers degeneracy, application to transition metal complexes (having one to five unpaired electrons) including biological molecules and inorganic free radicals such as PH4, F2 and BH3. VII. Mossbauer spectroscopy 5h Basic principles, isomer shift, quadrupole splitting and magnetic hyperfine interactions, application to the study of bonding and structures of Fe2+ and Fe3+ compounds, Sn2+ and Sn4+ compounds VIII. NQR spectroscopy 4h NQR isotopes, electric field gradients, Nuclear Quadrupole coupling constants, Experimental techniques and applications XI. X-ray absorption spectroscopy Near edge measurements and EXAFS SUGGESTED BOOKS
1. Physical methods in Inorganic Chemistry, R.S. Drago, Affiliated East West Press Pvt. Ltd., New Delhi (1965). 2. Infrared spectra of Inorganic and Coordination Compounds, K. Nakamoto, WileyInterscience, New York (1970). 3. Vibrational Spectroscopy: Theory and Applications, D.N. Sathyanarayana, New Age International Publishers, New Delhi (2000). 4. Electronic Absorption Spectroscopy and Related Techniques, D.N. Sathyanarayana, Universities Press, Bangalore (2001).

2h

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C-405 PHYSICAL CHEMISTRY PRACTICALS - III (At least fifteen experiments are to be carried out)
CHEMICAL KINETICS 1. Determination of order of the reaction for hydrolysis of methyl acetate and evalutaion of activation parameters. 2 Determination of Ea for hydrolysis of t-butyl chloride by conductivity method. 3 Kinetics of oxidation of glycine by chloramine-T, determination of order with respect to glycine. 4 Study of the kinetics of hydrolysis of t-butylchloride by conductivity method determination of rate constant, energy of activation and thermodynamic parameters. 5 Degree of hydrolysis of urea-hydrochloride from the study of acid hydrolysis of methylacetate. 6 Study of acetone-iodine reaction - determination of order with respect to each reactant by ratio variation method. 7 Kinetics of decomposition of H2O2-effect of catalyst and promoter. 8 Study of decomposition of diacetone alcohol using dilatometer - Evaluation of catalytic coefficient of OH- ions, Ea and thermodynamic parameters. 9 Kinetics of oxidation of indigo carmine by chloramine-T-Spectrophotometrically. Determination of Ea and Thermodynamic parameters. 10 Determination of catalytic efficiency of RuCl3 for the reaction between a primary amine and CAT. 11 Study of the effect of dielectric constant using methanol on the kinetics of the reaction between a primary amine and CAT. 12 Study the effect of salt (ionic strength) on the kinetics of the reaction between potassium persulphate and potassium iodide. 13 Kinetics of autocatalytic reaction between potassium permanganate and oxalic acid.

SPECTROSCOPY
14 15 Absorption spectrum of a conjugated dye and verification of quantum mechanics of particle in a one dimensional box. Spectral Interpretation for structure elucidation of simple organic compounds (-COOH, -OH, -NH2 and-Cl) by FT-IR.

X-RAY DIFFRACTION STUDIES:

16 17 Powder diffraction pattern of simple salts and determination of lattice type and the parameters. Evaluation of cell parameters from rotation photograph.

PHOTOCHEMISTRY 18 Demonstration of Fluorescence of solution of Anthracene in benzene with the respective UV visible absorption spectra.
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PHASE RULE: 19 To construct the phase diagram of a three component systems. (CHCl3 acetic acid water).

C 406 PHYSICAL CHEMISTRY PRACTICALS IV

(At least fifteen experiments are to be carried out) POTENTIOMETRY and pH METRY 1. Study of the complex formation and determination of the stability constant of silverammonia complex. 2. Determination of the free energy change of a cell reaction. 3. Determination of mean-ion activity coefficient of HCl and the study of the effect of ionic strength on the activity coefficient of Ag+ ions. 4. Determination of the solubility of silver halides in a mixture. 5. Determination of acid and base dissociation constants of an amino acid and hence its isoelectric point by pH metry. 6. Determination of pKa values of a polybasic acid potentiometrically using quinhydrone electrode. 7. Determination of pKa values of a polybasic acid pH metrically. 8. Titration of ferrous ammonium sulphate against potassium dichromate using a bimetallic electrode. 9. Differential potentiometric titrations: i) Weak acid against strong base ii) Mixture of strong and weak acids against strong base CONDUCTOMETRY 10. Conductometric titrations: (i) Thorium nitrate with potassium tartrate. (ii) Potassium iodide with mercuric perchlorate. (iii) Acetic acid, monochloro acetic acid and trichloro acetic acid with strong alkali 11. Determination of hydrolysis constant of aniline hydrochloride conductometrically. 12. Determination of equivalent conductance of a weak electrolyte (acetic acid) at infinite dilution following Kohlarauch law. SPECTROPHOTOMETRY 13. Spectrophotometric determination of indicator constant (Bromophenol blue). 14. Determination of stability constant of a complex formed between salicylic ferric ion by variation of pH. CORROSION 15. Determination of corrosion rate of: (i) Zn in NaOH by weight loss method. method.
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acid and

Mild steel in HCl by polarization

POLAROGRAPHY 16. a) Identification of metal ions in a mixture. b) Quantitative determination of electroreducible species. CYCLIC VOLTAMMETRY 17. Study of the redox behaviour of K4Fe(CN)6 / K3Fe(CN)6. POLYMER CHEMISTRY 18. Determination of molecular weight of a polymer by viscosity method.

SUGGESTED BOOKS
Findlays Practical Physical Chemistry revised by P. B. Levitt, Longmans London (1966). Experiments in Physical Chemistry by Shoemaker and Garland, McGraw Hill International Edn.(1966). Advanced Practical Physical Chemistry by J. B. Yadav, Goel Publication, Meerut (1988). Senior Practical Physical Chemistry by B. C. Kosla, Simla Printers, New Delhi (1987). Experimental Physical Chemistry by Daniel et. al., McGraw Hill, New York (1962). Practical Physical Chemistry by A. M. James and P. E. Pritchard, Longmans Group Ltd., (1968). Experimental Physical Chemistry by Wilson, Newcombe & others, Pergamon Press, New York (1962). Experimental Physical Chemistry by R. C. Behra and B. Behra, Tata McGraw Hill, New Delhi (1983). Experimental Physical Chemistry by V. D. Atavale and Parul Mathur, New Age International, New Delhi (2001). 10. Physical Chemistry Laboratory Principles and Experiments by H. W. Salzberg, J. I. Morrow, S. R. Cohen and M. E. Green, Macmillan Publishing Co.,New York. 11. Practicals in Physical Chemistry, A Mordren Approach by P.S. Sindhu, Mac- millan Publishers, Delhi, (2006). 1. 2. 3. 4. 5. 6. 7. 8. 9.

4885-BUP-200-Jan. 2010

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