KUVEMPU UNIVERSITY DEPARTMENT OF CHEMISTRY SAHYDRI SCIENCE COLLEGE(Autonomous) SHIMOGA - 577 203 SYLLABUS FOR INTEGRATED M.Sc.(Hons.) COURSE IN CHEMISTRY VII – SEMESTER ANALYTICAL CHEMISTRY UNIT–I 16 hours ANALYTICAL AND SEPARATION TECHNIQUES Roll of analytical chemistry, classification of analytical methods: Types of instrumental analysis, analytical methods on the basis of simple size. Errors, types of errors, determinate and indeterminate errors, accuracy and precision. Distribution of random errors, frequency distributions normal error curves. Statistical treatment of finet samples, measure central tendency -mean, medium, range, average deviation, relative average deviation, standard deviation and variance. Students’ confidence interval of the mean. Testing for significance comparison of two means and two standard deviations. Criteria for rejection of an observation-Q test. Control chart. Propagation of errors, significant figures. Least square methods of deriving calibration of plots. Principles of sampling the sampling step. Methods for sampling solid, liquid and gaseous samples. Effect of sampling uncertainties. Sampling hazards, need for quality assurance: ISO 9000 series of quality of system. Significance and importance of six sigma () concept in maintaining the quality. UNIT–II 16 hours TITRIMETRIC AND GRAVIMETRIC METHODS ANALYSIS Titrimetry: Introduction, theory of indicators-Ostwald’s theory, Brownsted concept, Indicator action, mixed indicators, theoretical basis for titrimetric analysis, classification of titrimetric analysis, acid-base titration- neutralization curves for different type of reaction, choice of indicators in neutralization reactions , theory of complexation titrations-stability complexes, factors influencing the stability of complexes, stability complexes of EDTA complexes, titration curves, types of EDTA titrations, titration of mixtures, masking and demasking agents, metal ion indicators, theory of redox titrationstitrations curves, formal potentials, detection of end point in redox titrations, theory of precipitation titration- titration curves, detection of end point in precipitation titration by formation coloured precipitate, coloured compounds, use of adsorption indicators and turbidity method, titrations in non-aqueous media. Gravimetry: General principles, conditions for precipitation, choice of precipitation, advantages of using organic precipitation, factors influencing the solubility of the precipitate, theories of precipitation, post precipitation, co-precipitation, effect of digestion, PFHS, pH Change, ion release reagents, change in oxidation state, use of mixed solvents and analytical applications. 1 UNIT–III 16 hours CHROMATOGRAPHY General description of chromatography, classification, chromatograms, migration rates of solute, retention time, capacity factors, selectivity factors, band broadening and column efficiency, plate theory and rate theory, theory of band bordering, Van-Deemeters equation, column resolution, factor influencing resolution. Planar Chromatography Paper and thin layer chromatography, stationary and mobile phase, various techniques of developments, visualization and evaluation of chromatograms, applications. Ion exchange Chromatography Introduction, principle, ion exchangers, classification of ion exchangers, ion exchange capacity, ion exchange techniques, applications, separation of lanthanides, actinides, amino acids and in metallurgy. UNIT–IV 16 hours GAS CHROMATOGRAPHY AND HIGH PERFORMANCE LIQUIDS CHROMATOGRAPHY Gas Chromatography : Introduction and over view of GSC and GLC. Instrumentation, sample injection systems, columns, detectors-TCD, FID,-ray ionization detector, temperature and pressure programming, applications – qualitative and quantitative analysis: GC-MS. High performance liquids chromatography. Introduction, instrumentation, column packing, pumping systems, detector systems and application. Derivative chromatography, pyrolysis gas chromatography. High performance liquids chromatography : Introduction, instrumentation, column packing, pumping systems, detector systems and application. Derivative chromatography, pyrolysis gas chromatography. REFERENCES 01. 02. 03. 04. 05. 06. 07. Principle of Quantitative Chemical Analysis – Robert de levie, International edition (1997) McGraw Hill Co. Quantitative Analysis- Day and Underwood, Prinitce Hall Indian, Pvt Ltd 6thedition (1993). Vogel’s Textbook of quantitative chemical analysis- Revised by G.H.jaffery, J. Bassett, J. Mendhm and R.C. Denney ELBS 5thedition (1998). Quantitative Chemical Analysis: D.C Harris W.M. Freeman and Co, NY, USA, Ed, (1995). Introduction to Instrumental Analysis – R.D Brun, McGraw Hill Book company (1982). Physical Methods in Inorganic Chemistry- R. Drago, Affiliated to East west Pvt, (1968). Introduction to chromatography- theory and practice-V.K. Srivastava and K.K.Srivastava, S. chand Company Ltd., IV Ed (1991). 2 08. 09. 10. 11. Basic Concepts of analytical Chemistry- S.M Khopkar, New Age Intentional Publishers, IIEd.,(1998). Analytical chromatography- G.R Chatwal, Himalaya Publishing House, VII Ed., (1998). Principle Instrumental Analysis- Skoog, Hollar and Nieman, , Harcourt, Asia pvt Ltd., Indian New Delhi, VEd, (1998). Fundamentals of Analytical Chemistry- Skoog, West and Hollar, Harcourt, Asia pvt Ltd., Indian New Delhi, VEd, (1998). 3 ORGANIC CHEMISTRY UNIT–I 16 hours REACTION MECHANISM Inductive effect, electromeric effect, mesomeric effect, concept of resonance, resonance effect and hyper conjugation effect with examples. Steric effect and hydrogen bonding, classification of organic reagents and reactions, carbocations, carboanions, free radicals, carbenes, nitrenes, arynes ( formation, geometry, stebility, stereo chemistry and their fate ). Methods of determining reaction mechanism 1) Kinetic and non kinetic. 2) Identification of products. 3) Detection of intermediates. 4) Study of catalysts. 5) Isotopic labeling 6) Stereo chemical evidence. UNIT–II 16 hours ADDITION REACTIONS AND ORGANIC ACIDS AND BASES Addition reactions : Types of addition – electrophilic, nucleophilic, free radical and cyclic additions with mechanism. Addition to carbon-carbon and carbon-hetero atom multiple bonds – mechanism of addition of halogen, hydrogen halides, carboxylic acids, alcohols and amines, orientation and stereo chemistry of addition. Addition to conjugated systems. Organic acids and bases : Brief idea of concept of acids and bases, acidity and basicity explanation, effect of substituents. UNIT–III 16 hours ELIMINATION REACTIONS AND SUBSTITUTION REACTIONS Elimination reactions : Mechanism of elimination - E1, E2, E2C and E1cB mechanism, orientation during elimination reactions, Saytzeff and Hofmann rule, pyrolytic elimination - Chugave and Cope eliminations, Hofmann degradation and dehalogenation of vicinal dihalides. Substitution reactions : Nucleophilic substitution at saturated carbon atom : SN1, SN2 and SNi reaction, effect of solvent, substrate and leaving group, neighboring group participation, substitution at allylic carbon. Aromatic electrophilic and nucleophilic substitution reactions: general mechanism of nitration, halogenation, sulphonation, Friedel craft’s alkalatoin and acylation, SNAr, SN1 reactions. UNIT–IV 16 hours STEREOCHEMISTRY Concept of chirality in compounds containing hetero atoms, absolute configuration-D and L, R and S nomenclature, enantiomers, anomers, epimres, diastereomers, racemic mixture, conformational analysis of allenes, spiranes, biphenyl compound, effect of conformational on reactivity in cylic and acyclic compounds, new methods of 4 asymmetric synthesis - using optically active reagent, optically active substrate, optically active catalyst and enzymes. Stereospecificity and stereoselectivity, Stereoselectivity – enantioselectivity, diastereoselectivity, substrate selectivity, product selectivity, regioselectivity. REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. J. March, Advanced Organic Chemistry, Willey Interscience, 1994. F. A. Carey and Sundberg, Advanced Organic Chemistry – Part A & B, 3rd edition, Plenum Press, New York, 1990. Comprehensive Organic Chemistry, Pergamon Press, New York, Vol 1, 1996, H. Pine, Hendrickson, Cram and Hammond, Organic Chemistry, Mac Grow Hill, New York, 1987. I. I. Finar, Organic Chemistry, ELBS Longmann, Vol. I & II, 1984 Principles of organic synthesis, Richard Norman and J. M. Coxon Stereochemistry by Eliel Steochemistry by Nasipuri 5 INORGANIC CHEMISTRY UNIT-I 16 hours CO-ORDINATION CHEMISTRY Crystal field effect on ionic radii, lattice energy, heat of ligation (hydration), geometry. Structure of spinels John-Teller distortion, template and macro cyclic effects, chelates, chelate effects, co-ordination for chelation, factor effecting stability of chelates, importance of chelates in medicine. Electronic Spectra of Complexes Spectra of transition metal ions, spectral terms, R-S states, multiplet term, symbols of dn ions, micro states, splitting of terms in weak crystal field ( octahedral and tetrahedral fields ) ligand field spectra, d-d transitions, spin and Laporte’s selection rule and their relaxation, symmetry, spin-orbit coupling and vibranic coupling effects, spectral band width. Orgel diagrams for d1, d2, d8and d9 ions in octahedral and tetrahedral fields. Racah parameters, Tanabe-Sugano diagrams for d1, d2 and d6 systems in octahedral and tetrahedral fields. Calculation from T-S diagram. UNIT-II 16 hours ORGANOMETALLIC COMPOUNDS Nomenclature, classification of ligands based on heptcity, 18 electron rule, prediction of stability and structure on the basis of 18 electron rule and 16 electron ruleorganometallics of Li, Mg, Al and Zn- preparation, properties and applications. Synthesis, properties, reactions structure and bonding in ferrocene, comparison with molybdecene, chromocene, toluacenes, heterocyclic sandwitch compounds- azaferrocene-arene complexes, complexes of chromium, uranium cyclooctatriene, sandwitch compounds, mixed complexes- metal carbenes- Fisher and Schrock carbenes. Nirtosyls, nitrogen and dinitrogen complexes, preparation structure and bonding. Metal clusters, types factor favouring cluster formation. UNIT-III 16 hours SOLID STATE CHEMISTRY Defects in solids, Types of defects, stochiometric defect, Schottky and Frenkel defect. Non stochiometric defects colour centers. Bond theory of Solids Metals, insulators and semiconductors, intrinsic and photo excited and impurity and defect semiconductors, Mixed oxides-spinels and penvoskites, p-n junctions-high temperature super conductors. Organic solids, conjugated systems, doped poly acetylenes. Solid State Reactions Common reactions. Ceramic (high temperature). Procedures, precursor methods. Combustion synthesis. Solgel synthesis. High pressure synthesis. Interculation methods. 6 UNIT-IV 16 hours MODERN CONCEPT OF ACIDS AND BASES Solvent system, concept-relative strength of acids and bases-leveling effect of solvents, Lux-Flood and Usanovich concepts-HSAB concept-basis of HSAB concept, acid-base strength, hardness and softness-symbiosis applications of HSAB concepts, reactions in non aqueous solvents. Types of solvents-physical properties of solvents, acid-base concept in non aqueous solvents-types of solvents-physical properties of solvents, acid-base concept in nonaqueous solvent-reaction in anhydrous H2SO4 and liquid SO2, metal-ammonia solution REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. Advanced Inorganic Chemistry , 5th ed., F.A. Cotton and G.Wilkinson; John Willey and sons, 1988. Inorganic Chemistry; Principles of structure and reactivity, 3rd ed., James E Huheey, Ellen E. Keither and Richard L Keither, Harper Collins college Pub., 1933. Inorganic Chemistry 3rd ed., Shriver and Atkins, Oxford University Press, 1999. Organometallic Chemistry, A Unified approach R.C.Mehrotra and A. Singh. Willey Eastern, New Delhi. Concepts and Models in Inorganic Chemistry II ed., Douglas , Mc Danial and Alexander A concise Inorganic Chemistry, J.D.Lee, ELBS Ed., 1991 Modern aspects of Inorganic Chemistry, H.J.Emeleus and A.G.Sharpe, ELBS. Chemistry of the elements, Green wood and Earnshaw, Pergaman Press, Oxford, 1986 Solid state Chemistry and its application, A.R. West, John Willey and sons Theoretical Principles of Inorganic Chemistry, IV ed., G.S.Manku, Tata, Mc Graw Hill, 1990 7 PHYSICAL CHEMISTRY UNIT–I 16 hours QUANTUM CHEMISTRY-I A brief resume of black body radiation, comparative studies between classical and quantum theory (classical and Plank quantum theories, atomic spectra model and its limitations, term symbols). Photoelectric and Compton effects. Derivation of Bohr’s principle of quantization of angular momentum of electron from de-Broglie’s relationship, consequences of de-Broglie equation, de-Broglie concept (To be derived). Uncertainty principle, mathematical expression for uncertainty principle. Postulates of quantum mechanics, operators, algebra of operators, properties. Hamiltonian properties of operators, Hamiltonian operators form of Schrödinger’s equation (with respect to space, with respect to time and with respect to steady state form). Physical significance of ψ and Characteristics of wave function, eigen function and eigen values, probability distribution function, normalization of ψ and orthogonality of ψ, well behaved ψ. Application of Schrödinger wave equation to one and three dimension boxed (quantization of energy). UNIT-II 16 hours THERMODYNAMICS Review of basic principles of thermodynamics (brief resume of laws of thermodynamics, concept of free energy and entropy, combined form of first and second laws of thermodynamics. Criteria for equilibrium and spontaneity, variation of free energy with temperature and pressure). Maxwell’s relation (to be derived). Thermodynamic equations of equipartition energy, physical equilibrium involving phase transitions, ClassiusClapeyron equation and its application (to be derived). Entropy of vaporization, Tranton’s rule and its limitations. vant-Hoff’s equation, integrated form of vant-Hoff’s equation. Nernst heat theorem, consequences of Nernst heat theorem. Comparison of Nernst’s heat theorem with third law. Third law of thermodynamics, consequences of third law, determination of absolute entropies, concept of residual entropy of CO, NO2, H2, conclusion. Experimental verification of the third law. Entropies of real gases, entropy changes in chemical reactions. The Boltzmann entropy equation. Entropy of reaction, thermodynamics of systems of variable compositions, variation of entropy change with temperature and pressure (problems to be solved). UNIT–III 16 hours ELECTROCHEMISTRY Electrolytic solutions, strong electrolytes, ionic atmosphere, relaxation and electrophoretic effects, quantitative treatment of Debey-Huckel theory and its extension by Onsogar activity co-efficient, mean ionic strength (Debey-Huckel limiting law), Debey-Huckel equation for appreciable sensors-ion selective electrodes, electro chemical biosensors. Thermodynamics of electrolytic cells, polarization and over voltage. Decomposition potential, electro chemical energy systems- introduction, fundamentals of batteries, classification of batteries, size of batteries, battery characteristics, primary batteries, dry cell, alkaline MnO2 batteries and other batteries, secondary batteries-lead acid, alkaline storage batteries-battery charging theory and practical. Energy economics, fuel cells-types, electrochemistry of fuel cells. 8 UNIT–IV 16 hours NUCLEAR AND RADIO CHEMISTRY Radio active series-nuclear models, radio active decay- artificial radio activity-nuclear reactions, application of radio activity, mossback spectroscopy, positron ammihilation. Nuclear fission and fusion. Power breader reactors. Methods of accelerating nuclear particles for bombardment. Detection and measurement of activity production and uses of radio active isotopes and labeled compounds. Tracer chemistry, experimental techniques in the assay of isotopes. Electroscope, counters, chamber and semiconductor radiation detectors, statistics of counting. Photo physical process, a review of laws of photochemistry, experiments in photochemistry, actinomers, quantum yield, photo properties, fluorescence, phosphorescence, chemiluminescence, stem-volmer equation, lasers in photochemical studies, photo electrochemistry, solar energy conversion and storage. Interaction of radiation with matter, method of losing energy and common units. Dossimetry (term and units, chemical Dossimetry-Fricke and seric sulphate dosimeter, calcium of absorbed dose. Radiation chemistry of gases, water, aqueous solution and solids. Biological effects of radiation. REFFERENCES 1. Physical chemistry-Atkins,ELRS,1982. 2. Physical chemistry –Moore,Orient Longman,1972. 3. An introduction to Chemical Thermodynamics–R.P.Rastogi and S.S.Misra,Vikash,Delhi,1978. 4. Thermodynamics –Rajaram and Kunakose,East West, Nagin Cx,Dehli,1986. 5. Chemical kinetics –Laidler,Harper and Row ,1987. 6. Kinetics of Chemical reactions -S,K,Jain Vishal Publications,19821. 7. Kinetics and mechanism- Moore and pearson,Willey,1980. 8. The foundations of Chemical kinetics –Bensen,Mc Graw. 9. Chemical kinetics – Laidler,Harper and Row .1987. 10. An introduction to Electrochemistry –Glastone,East west Ltd. 11. Electrochemistry principles and applications –Porter 12. Industrial Electrochemistry –D.Pletcher and F.C.Walsh,Chapman and Hall ,II Edition,1984 13. Introductory Quantum Mechanics – Atkins ,Claredon,Oxford 14. Quantum chemistry-Kauzman,Academic Press,1957. 15. Quantum chemistry-R.K.Prasad ,II.Ed,New Age Int-2000 9 VII SEMESTER CHEMISTRY PRACTICALS ORGANIC CHEMISTRY 01. Synthesis of benzanilide 02. Synthesis of 2,4,6 tribromo benzene from aniline 03. Synthesis of p-nitro aniline from aniline 04. Synthesis of sulphanyl amide 05. Estimation of protein by biuret method 06. Zak’s method 07. Synthesis of indigo Estimation of total hardness of water 08. Estimation of amide 09. Estimation of ester INORGANIC CHEMISTRY 01. Estimation of total hardness of water 02. Estimation of Ca2+ and Mg2+ ions 03. Estimation of Cu2+ ions by complexometrically 04. Estimation of Ni2+ ions 05. Estimation of Ca2+ and Mg2+ ions 06. Estimation of iron by K2Cr2O7 solution 07. Estimation of cerric ammonium sulphate 08. Estimation of iron by ammonium metavenadate solution 09. Estimation of lead ion complexometrically using solution PHYSICAL CHEMISTRY 01. Estimation of KMnO4 using hypo solution 02. Spectrophotometric estimation by Job’s method. 03. Hydrolysis of ethyl acetate 04. Hydrolysis of acetone 05. Verification of Beer’s law using KMnO4 solution 06. Verification of Beer’s law using K2Cr2O7 solution 07. Hydrolysis of methyl acetate 08. Verification of Beer’s law using Cuprous ammonium sulphate 10