KUVEMPU UNIVERSITY DEPARTMENT OF CHEMISTRY SAHYDRI SCIENCE COLLEGE (AUTONOMOUS) SHIMOGA-577 203 APPROVED SYLLABUS FOR INTEGRATED M.Sc. (Hons.) COURSE IN APPLIED CHEMISTRY V-SEMESTER PAPER-VII INORGANIC CHEMISTRY 20 hours 17 hrs Chapter 1 Co-ordination Chemistry: Double salts, complex salts, definition of terms-complex ion, ligand, co-ordination number, co-ordination sphere. Types of ligands with example-monodentate, bidentate, polydentate, Ambidentate and macro cyclic ligands(crown ethers, porphyrins). methods of detection of complex formation- conductivity, pH, colour. Nomenclature of complex compounds, Sidwick’s theory of concept of effective atomic number (EAN). Isomerism in complex compounds a. Structural isomerism-Ionization isomerism, hydrate isomerism, linkage isomerism and co-ordinate isomerism. b. Stereoisomerism in complex compounds with co-ordination number 4 and 6. Stability of complex compounds- stability constant, factors influencing the stability of complexes-Nature of metal ion, nature of ligands, chelation and macrocyclic effects. Application of complex formation in (a) Metallurgy (in the extraction of nickel and gold) (b) Qualitative and quantitative analysis. Valance Bond Theory (VBT) as applied to complexes- inner and outer orbital complexes. The structure and geometry of the following complexes to be discussed: 1. [Fe(CN)6]2- 2. [Fe(CN)6]33.[Fe(H2O)6]3+ 4. [CoF6]3- 5. [Ni(CN)4]222+ 6. [Ni(CO)4] 6. [Cu(NH3)4] Crystal Field Theory (CFT): Splitting of d-orbitals in octahedral and tetrahedral fields, tetragonal and square planar complexes with examples, effect of weak and strong field ligands, spectrochemical series of ligands, crystal field stabilization energy, calculation of CFSE for different systems, applications of CFT, experimental evidences for metal –ligand covalent bonding in complexes, comparison between CFT and VBT. Chapter 2 Organic reagents in inorganic qualitative analysis: Uses of the following organic reagents in inorganic quantitative analysis 1. EDTA 2. Oxine 3. DMG 4. 1,10-phenonthraline Advantages and structures to be discussed. 1 3 hrs ORGANIC CHEMISTRY 20 hours Chapter 1 12hrs Stereochemistry Concept of isomerism, structural isomerism, stereoisomerism and its types. Optical isomerism Elements of symmetry, molecular chirality, cause for optical activity – van’t Hoff – Lebel hypothesis, enantiomers, and diastereoisomers – Fischer projection formulae and properties. Configuration – D and L-configuration, erythro-threo configuration and R and S-configuration. Optical isomerism of lactic acid and tartaric acid. Racemisation, resolution (mechanical, biochemical and chemical), Walden inversion, asymmetric synthesis (Using optically active reagent, optically active substrate, optically active catalyst). Geometrical isomerism Conditions for the compound to exhibit geometrical isomerism, Cause for geometrical isomerism, Nomenclature – cis-trans nomenclature, E-Z nomenclature, syn-anti nomenclature in aldoximes and ketoximes. Determination of configuration of geometrical isomers – physical methods, chemical methods, Beckmann rearrangement. Conformational isomerism Cause for conformational isomerism, conformers, Newmann projection formulae. Conformational isomerism of ethane, 1,2-dichloroethane, cyclohexane. Chapter 2 5hrs Heterocyclic compounds Definition, nomenclature, classification, Synthesis - pyrrole, furan, thiophene, pyridine, Chemical properties of pyrrole and pyridine, Comparison of basicity and aromaticity (MOT) of pyrrole and pyridine, Synthesis and chemical properties of indole. Chapter 3 3hrs Retro synthetic analysis Planning of synthesis, synthones, synthetic equivalents, retro synthetic analysis of cinnamic acid, methyl orange, hydroxyl amine, 2,6-dihydroxynitrobenzene, 2-propyl pentanoicacid. PHYSICAL CHEMISTRY 20 hours Chapter 1 Thermodynamics I 5 hrs Definition of thermodynamic terms, intensive and extensive variables, isolated, open and systems, state functions, thermodynamic processes, isothermal, adiabatic and isochoric, isobaric, reversible and irreversible. Work, heat and internal energy. Brief resume of Zeroth law and first law of thermodynamics, enthalpy and molar heat capacities of gases, Cp and Cv and relation between them derived. Expression for maximum work done in reversible isothermal and adiabatic expansion of an ideal gas to be derived. Joul-Thomson effect, Joul-Thomson Coefficient, inversion temperature, variation of entholpy of reaction with temperature (Kirchoff’s equation to be derived and its applications). 2 Chapter 2 Thermodynamic - II Spontaneous processes, heat engine, Carnot’s cycle and its efficiency. Refrigeration and thermodynamic scale of temperature. Concept of entropy. Entropy as a state function. Limitations of First law and need for the second law. Statements of second law of thermodynamics. Entropy changes of an ideal gas with P, V and T. Calculation of entropy changes in different processes Molecular interpretation of entropy. Physical significance of entropy. Entropy changes in phases. Free energy - Helmholtz free energy (A). Gibb’s free energy (G) and their relationship. Free energy and useful work. Significance of free energy and useful work. Significance of free energy change - criteria for equilibrium and spontaneity. Variation of free energy with P.V. and T. Derivation of Gibbs – Helmholtz equation. Equilibrium constant and its variation with temperature - Vant Hoff’s isotherm, Vant Hoff’s equation , Clausius Clapeyron equation and its applications. 10 hrs Chapter 3 Physical properties and molecular structure: Additive properties, constitutive properties, additive - constitutive properties (Molar refraction, refractive index, molar volume - parachor). Polarisation: Induced polarization, orientation polarization, molar polarization, Classius Mosotti equation (No derivation) and its importance. Dipole moment: Explanation its importance in comparison of bond polarity taking hydro acids of halogens. Shape of the molecules: a) b) c) Tetratomic molecules ex. : PF3 , PCl3 Pentatomic molecules ex. : CCl4 , SiCl4 Differentiating between cis and trans isomers ex. : 1,2-dichloro ethane 5 hrs 3 KUVEMPU UNIVERSITY DEPARTMENT OF CHEMISTRY SAHYDRI SCIENCE COLLEGE (AUTONOMOUS) SHIMOGA-577 203 SYLLABUS FOR INTEGRATED M.Sc. (Hons.) COURSE IN APPLIED CHEMISTRY V-SEMESTER PAPER-VIII INORGANIC CHEMISTRY 20 hours Chapter 1 Pulp and paper Industry: 5 hrs Introduction, raw materials, pulp definition, methods of production chemical and semichemical, sulphate (Kraft), Pulp process (outline). Process description, bleaching of pulp by product utilization, pollution and waste disposal, paper products, definition, types of paper production, outline of production. Fertilizer Industry: 4 hrs Introduction, nitrogenase fertilizers, ammonia, urea, ammonium nitrate. Phosphorous fertilizers-calcium phosphate, nitro phosphate, super phosphate and ammonium phosphate. Principles of Gravimetric Analysis: 4 hrs 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, precipitation from homogeneous solution (PFHS), pH change, ion release reagents, change in oxidation state, use of mixed solvents and analytical applications. Separation technique: Chromatography-types, column, thin layer and paper chromatography, high performance liquid chromatography (HPLC), gas chromatography. 7 hrs ORGANIC CHEMISTRY Chapter 1 8hrs Carbohydrates Definition, Classification, Constitution of glucose and fructose (open chain and ring structure), Inter conversion – aldose to ketose and ketose to aldose, chain lengthening and chain shortening of aldoses. Epimerisation.(conversion of glucose to mannose). Mechanism of mutarotation. Disaccharides - Elucidation of structure of maltose and sucrose. Polysaccharides – Structure of starch and cellulose. Chapter 2 2hrs Vitamins Definition, Classification and biological importance; synthesis of vitamin C from D(+)-Glucose, synthesis of vitamin A 4 Chapter 3 2hrs Hormones Definition, Classification, Biological importance of hormones, synthesis of adrenaline and thyroxin. Chapter 4 3hrs Enzymes Definition, Classification, active site; factors affecting activity of enzymes with explanation, Specificity of enzymes, Mechanism of enzyme catalysis (Chymotrypsin as an example). Chapter 5 Nucleic acid Composition, Synthesis of nucleosides and nucleotides, Structure of DNA. 2hrs Chapter 6 3hrs Dyes Definition, classification with examples, Theory of colour and constitution chromophore-auxochrome theory, modern theory. Synthesis and uses of Congo red, malachite green, indigo. Structural elucidation, synthesis and uses of alizarin. PHYSICAL CHEMISTRY 20 hours Chapter 1 Electrochemistry II: Potentiometric titrations i) Acid –base titrations ii) Redox titrations 3 hrs Chapter 2 Fuel cells: 5 hrs Different types, their constructions and working, important of fuel cells, polarization, decomposition potential, over voltage. Chapter 3 Solar energy: 4 hrs Direct solar power, indirect solar power with examples, photovoltaic cells, construction and working of photovoltaic cell, advantages and disadvantages. Chapter 4 Crystallography: 8 hrs Different types of crystals, Laws of constancy of angles. Elements of symmetry - plane , axes and centre of symmetry. Elements of symmetry in cubic system. Crystal lattice - space lattice and unit cell crystal sytems. Bravis lattice, Miller indices, lattice planes in different cubic systems. Xray diffraction and Bragg’s law (to be derived). Determination of crystal structure of rock salt by Bragg’s method. Avogadro number. 5 V SEMESTER PRACTICALS 4 hrs per week Part A 01. Estimation of Barium in Barium chloride solution. 02. Estimation of Iron as Iron oxide in Mohr’s salt. 03. Estimation of Aluminium as aluminium oxide in potash alum solution. 04. Estimation of Nickel as Nickel dimethylglyoximate in Nickel ammonium sulphate solution. 05. Estimation of Copper as Cuprous thiocyanate in copper sulphate solution. 06. Estimation of Zinc as Zinc Oxinate in zinc sulphate solution. Part B 01. Preparation of double salt (nickel ammonium sulphate). 02. Preparation of complex compound (copper ammonium sulphate). 03. Preparation of complex compound (potassium trioxalato aluminate). 04. Preparation of organic compounds by a) Oxidation b) Acetylation c) Nitration d) Bromination 6 KUVEMPU UNIVERSITY DEPARTMENT OF CHEMISTRY SAHYDRI SCIENCE COLLEGE (AUTONOMOUS) SHIMOGA-577 203 SYLLABUS FOR INTEGRATED M.Sc. (Hons.) COURSE IN APPLIED CHEMISTRY VI-SEMESTER PAPER-IX INORGANIC CHEMISTRY 20 hours Chapter 1 Co-ordination Chemistry MOT of co-ordination complexes, σ- and л-bonding in octahedral complexes, σ- and л-bonding in tetrahedral complexes. л-acceptor ligands, metal carbonyls- bonding in metal carbonyls, IR spectra of metal complexes, determination of geometry of metal carbonyls. 10 hrs Chapter 2 Magnetic Properties Types and origin of magnetic behaviour, effect of temperature, Pascal’s constant, magnetic susceptibility, effect of temperature on magnetic moment (), calculation of , factors influencing of complexes-number of unpaired electrons, strength and symmetry of ligand field orbital contribution, spin-orbit coupling, quenching of orbital moments. Magnetic behaviour of polynuclear complexes determination of magnetic susceptibility-Gouy and Farady methods, application of magnetic data in the study of complexes. 5 hrs Chapter 3 Metallurgy Extraction, properties and uses of Titanium, Molybdenum, tungsten, Chromium. Separation of Zirconium and Hafnium, zone refining 5 hrs ORGANIC CHEMISTRY Chapter 1 20 hrs Spectroscopy 8hrs Electromagnetic radiation, interaction of electromagnetic radiation with organic molecules, Frequency, wavelength, energy of a wave. UV-Visible spectroscopy Range, frequency and energy of UV radiations, interaction of UV radiation with organic molecules, types of transitions, allowed and non-allowed transitions, Concept of chromophores and auxochromes, bathochromic shift and hypso chromic shift, hyper chromic effect and hypo chromic effect. Comparison of max organic compounds taking following examples giving reasons 1. CH3CHO and C6H5CHO 2. Ethylene and 1,3-butadiene 3. Cis and trans stilbene 4. Cis-trans cinnamic acid 7 IR spectroscopy Range, frequency and energy of IR radiations, interaction of IR radiation with organic molecules, molecular vibrations – stretching and bending vibrations, Hook’s law, finger print region, Stretching frequency of functional groups in benzaldehyde, acetophenone, ethyl acetate, aniline and methyl amine. Chapter 2 4hrs Polymers Definition, Types of polymers, Addition polymers - mechanism of polymerization (ionic and free radical). Synthesis and uses of PVC, Teflon. Condensation polymers – polyester (Dacron), polyamides (Nylon-6,6). Thermoplastics and thermosetting plastics – phenolic resins, epoxy resins. Chapter 3 4hrs Drugs Definition, Requisites of a drug, chemotherapy, sources of drugs. Sulpha drugs – examples, mode of action, Synthesis and uses of Sulphanilamide, Sulpha thiazole. Antimalarial drugs – Synthesis and uses of chloroquin. Antipyretics – Synthesis and uses of paracetamol, aspirin. Hypnotics and sedatives Chapter 4 4hrs Nanochemistry Introduction to nanoscale science and technology, fabrication-‘top-down’ vs ‘bottomup’ processes, fabrication of nanostructures for advanced device applications, nanoscale functional materials for bio-applicaions(in energy, informatics, medicine, food safty, agriculture etc.), characterization of nanoparticles-imaging, visualization and manipulation, nanotoxicology-safty issues with nanoscale powders and nanocomposites PHYSICAL CHEMISTRY 20 hours 4 hrs Chapter 1 Spectrophotometry Laws of absorption of light – (Lambert’s law, Beer’s law, Beer-Lambert’s law, Absorption spectra Absorption co-efficient , molar absorption co-efficient , molar extinction co-efficient, Instrumentation of spectrophotometer and determination of absorption band. Uses of Spectrophotometer. (Problems to be solved). Chapter 2 10 hrs Photochemistry Photo physical processes, photochemical processes, photoelectric effect with examples. Laws of photochemistry. (Grothus – Draper law, Einstein’s - Stark law of photochemical equivalence) , quantum yield or efficiency. Reasons for low and high quantum yield with examples. Primary and secondary processes. Mechanism of the following photochemical processes. 8 a) Decomposition of HI b) Combination of H2 and Br2 c) Combination of H2 and Cl2 Problems based on quantum yield. Chemiluminescence, bioluminescence, fluorescence, phosphorescence, photo inhibitors, photosensitization, photosynthesis, chemical actinometers (uranyl oxalate actinometer). Jablansky’s diagram. Photography: Photographic plate, exposure, developing, fixing and printing. Chapter 3 6 hrs Radiation chemistry Radiolysis, radiolysis of water vapour. Radiation dosimetry (units). Dosimeters (Fricks dosimeter and ceric sulphate dosimeter). Application to some simple organic and inorganic reactions. (C2H2 , CH4 , C6H6 , HCOOH, CH3COOH) . Lind’s cluster theory, Erying , Hircefelder and Taylor Theory (EHT theory). Difference between photochemistry and Radiation chemistry. 9 KUVEMPU UNIVERSITY DEPARTMENT OF CHEMISTRY SAHYDRI SCIENCE COLLEGE (AUTONOMOUS) SHIMOGA-577 203 SYLLABUS FOR INTEGRATED M.Sc. (Hons.) COURSE IN APPLIED CHEMISTRY VI-SEMESTER PAPER-X INORGANIC CHEMISTRY 20 hours Chapter 1 Organometallic Chemistry 8 hrs Ionic compounds, Organometallic compounds of group II, III, IV and V, compounds of transition metals with multi centered bonds with л- bonded ligands, bonding in лmeal complexes, bonding in л-metal alkenyl complexes( Zeis Salt), bonding in ferrocene (elementary account), aromatic character of ferrocene, reactions of phenyl rings(electrophilic substitution reactions), aromaticity of cyclic CnHn ligands, classification of ligands in Organometallic compounds, 18-elecctron rule (inert gas rule). Chapter 2 Bio-inorganic Chemistry 6 hrs Elements in biological systems- metal and nonmetals, bulk metal and trace metal, role of bulk metal and trace metals. Iron: Co-ordination environment in HEAME, functions of HEAME and GLOBIN, structure of haemoglobin. Zinc: Zinc containing metalloenzymes, role of carbonic anhydrase and carboxy peptidase. Magnesium: Co-ordination environment in chlorophyll, skeletal structure of chlorophyll, role of chlorophyll in photosynthesis. Cobalt: Vitamin B12. Molybdenum: Nitorgenase. Chapter 3 Environmental Chemistry 6 hrs Air pollution - air pollutants - oxides of carbon, nitrogen and sulphur. Global warming, acid rain. Photochemical smog, depletion of ozone layer-causes and its effect, control of air pollution. Water pollution –types of pollutants, domestic sewage, industrial effluents, dissolved metal ions and their effects, DO, BOD, COD. Soil pollution- pollutants-agricultural and animal manures. Uses of pesticides: radio active wastes, control of soil pollution. ORGANIC CHEMISTRY Chapter 1 4hrs Oils, fats and waxes Definition, chemical composition, Chemical properties - hydrogenation, hydrogenolysis, hydrolysis, drying oils, rancidity, Analysis of oils and fats saponification value, iodine and acid value, manufacture of soaps - hot process, 10 cleansing action. Synthetic detergents, comparison of soaps and detergents, types of detergents (cationic, anionic and nonionic) animal and plant waxes. Chapter 2 4hrs Amino acids and proteins Definition and classification of amino acids, methods of synthesis of α-amino acids (Gabriel’s phthalimide, Streckers synthesis). Zwitter ion and isoelectric point, Peptides: peptide bond, carbobenzoxy method of synthesis of peptides Protein: Classification based on composition, structure and function, primary and secondary structures of proteins. Denaturation of proteins, Ninhydrin and Biuret tests. Chapter 3 4hrs Alkaloids Definition, method of isolation; elucidation of structure of nicotine and its synthesis by spath process. Structure and uses of atropine and cocaine. Chapter 4 4hrs Terpenes Definition, Classification, Isolation; isoprene rule. Structural elucidation of menthol, Structural elucidation of citral and its synthesis from methyl heptenone Chapter 5 4 hrs Molecular rearrangements Types of rearrangements, Benzilic acid rearrangement, Hoffmann rearrangement, Curtius rearrangement, Lossen rearrangement, Benzidine rearrangement. PHYSICAL CHEMISTRY 20 hours Molecular spectroscopy Chapter 1 Microwave spectroscopy 10 hrs Spectrum of electromagnetic radiations, interaction of electro magnetic radiations with molecules, quantisatiation of different forms of energies in molecules. Condition for energy absorption by molecules (emissions and absorption spectrum). Spectroscopic terms, classification, types of molecules, (microwave active and microwave inactive), Linear molecules, spherical top molecules, symmetric top molecules, asymmetric top molecules. Diatomic molecule as a rigid rotator. Model, moment of intertia expression. Rotation energy expression, wave number of Rotational spectral spectral line expression (to be derived), Energy level diagram (selection rate and rotational transitions). Determination of moment of intertia and bond length of diatomic molelcules (CO, HCl molecules) isotopic effect on the Rotational spectra , Intensity of Rotational Spectral lines. Non rigid rotator model, limitations of rigid rotator model, frequency of rotational spectal line(to be derived), Applications of Microwave spectroscopy (Problems to be solved). 11 Chapter 2 Vibrational spectroscopy 5 hrs Vibration spectra of diatomic molecules - diatomic molecule as a simple harmonic oscillator (one – dimensional , Hook’s law and force constant). Vibration energy diagrams, zero point energy, selection rule. Chapter 3 Raman spectroscopy 5 hrs Raman spectra, Rayleigh’s line, stokes lines and antistokes lines in Raman spectra, pure rotational Raman spectrum of diatomic molecule, selection rules for rotational – vibrational Raman spectra of diatomic molecules, energy level diagram, experimental set up of Raman spectrophotometer, advantages of Raman spectroscopy over IR spectroscopy. VI SEMESTER PRACTICALS 4 hrs per week Paper -VII 01. Determination of percentage composition of a binary mixture of organic liquids by using Abbe’s Refractometer. 02. Determination of rate constant of inversion of cane sugar by Polarimeter. 03. Determination of cell constant (0.1N KCl solution to be prepared by students) and determine the equivalent conductance of the given electrolyte solution by using conductivity bridge. 04. Determination of cell constant (0.1N KCl solution to be prepared by students) and determine the equivalent conductance at infinite dilution for weak electrolyte of given solution. 05. Conductometric titrations a) Sodium hydroxide vs Hydrochloric acid b) Mixture of weak acid and strong acid vs Sodium hydroxide. 06. Determine the pH of mixture of acetic acid and sodium acetate at different concentrations and determination of dissociation constant of acid by using pH meter. 07. Potentiometric titrations a) Mohr’s salt solution vs Potassium dichromate/Potassium permanganate solution b) Hydrochloric acid vs Sodium hydroxide. 08. Estimation of Cu(II) in the given solution by colorimetric method. 09. Estimation of Fe(III) in the given solution by colorimetric method. VI SEMESTER PRACTICALS 4 hrs per week 1. 2. 3. 4. Paper -VIII Part A Preparation of p-Bromo aniline from aniline. Preparation of p-Nitroaniline from aniline. Preparation of Adipic acid from cyclohexanone. Cannizzaro’s reaction. Part B 1. Estimation of citric acid from lemon juice. 12 2. 3. 4. 5. Estimation of salicylic acid from aspirin tablets. paper chromatography. Estimation of proteins. Estimation of carbohydrates. 13