KUVEMPU UNIVERSITY DEPARTMENT OF CHEMISTRY SAHYADRI SCIENCE COLLEGE SHIMOGA – 577 203 INTEGRATED M.Sc. (Hons.) COURSE IN APPLIED CHEMISTRY I – SEMESTER Hours: 75 Inorganic chemistry Chapter 1:Atomic Structure 11 hrs Wave nature of electron, de-Broglie equation, (derivation of problems), Heisenberg uncertainty principle, Schrodinger wave equation (no derivation), Significance of and 2- atomic orbitals, Eigen function and Eigen values, radial and angular wave function and probability distribution curve. Quantum numbers and their significance, Shapes of s, p, d - orbitals and their nodal planes. Assigning of quantum numbers to a given electrons in an atom (I and II period elements) in the periodic table. Pauli’s exclusion principle, energy level diagram, Aufbau principle, Hund’s multiplicity rule, exchange energy, promotional energy, electronic configuration of elements (up to 3d-series), (n + l) rule, effective nuclear charge, screening effect based on Slater’s rule. Chapter 2: Periodic Properties 8 hrs Atomic radii, covalent radii, vander Waal’s radii, ionic radii, variation of atomic radii in a group and period, iso-electronic ions. Ionization of energy: Explanation, factors influencing ionization energies, variation of ionization energy in a group and period, successive ionization energies, effect of ionic size and electronic configuration (III period). Electron affinity: Explanation, variation in a group and in a period. Explanation for the observed trend. Electronegativity: Explanation, factor affecting electronegativity, variation in a group and in a period, explanation for the observed trend, anomalies to be accounted. Pauling scale and Mullikan’s scale of electronegativity, Alfred and Rochow’s method. Chapter 3: s-Block elements 5 hrs Hydrogen: Atomic hydrogen-preparation and properties, ortho and para hydrogens, definition, differences in physical properties Alkaline earth metals: Comparative properties of alkaline earth metals, electronic configuration, melting point, boiling point, softness and density, hydration of ions, electropositive characters, flame coloration, comparative studies of properties of compounds like oxides, hydroxides, carbonates, sulphates, solubility thermal decomposition, amphoteric and basic nature. Anomalous properties of beryllium, diagonal relationship between Be and Al. 1 Organic chemistry Chapter 1: Introduction to analytical chemistry 11 hrs Introduction to analytical chemistry, history, application of analytical chemistry in clinical, pharmaceutical and chemical analysis. Statistical analytical chemistry. Errors, types of errors, accuracy and precession. Distribution of random errors-frequency distributions, statistical treatment of finet samples, mean, medium, range, average deviation, standard deviation and variance. Reliability of results rejection of results, confidence intervals. Test for significance, Q-test, F-test, Chi-isoqurane test, comparison of means of two samples, control charts, significant fugures, least square method of deriving calculation plots. Introduction to qualitative analysis of inorganic salts: Common ion effect, solubility products, principle. Application of common ion effect and solubility products, principle in qualitative analysis. Chapter 2: Purification of organic compounds 4 hrs Method of purification of solids, crystallization, fractional crystallization, sublimation. Method of purification of liquids, distillation, distillation under reduced pressure, steam distillation, fractional distillation. Criteria of purity, melting point and boiling point. Chapter 3:Composition of Organic Compounds 4 hrs Estimation of elements - C, H – Liebig’s method, N - Kjeldahl’s method, P, S, X – Carius method (with numerical problems), calculation of Empirical and Molecular formula. Chapter 4: Types of Reactions, Reagents and Reaction Intermediates 5 hrs Introduction to reaction, reaction mechanism, addition, elimination, substitution and rearrangement reactions, homolysis, heterolysis, electrophiles, nucleophiles, free radicals, carbocations, carbenes, carbanions (definition, formation, geometry, stability and reactivity). Chapter 5:Hybridisation 4 hrs Overlapping of atomic orbitals, types of overlapping s-s, s-p, p-p, sp3, sp2, sp hybridization taking example of methane, ethane, ethene and ethylene molecules. Bond length, bond angle and bond energy. Chapter 6:Electronic effects 4 hrs Inductive effect, electromeric effect, mesomeric effect, concept of resonance, resonance effect and hyper conjugation effect with examples. Chapter 7:Hydrocarbons 8 hrs Alkanes: Nomenclature, synthesis from alkyl halides, Wurtz reaction, chlorination of methane, free radical mechanism, pyrolysis of alkanes, pyrolysis of alkanes, knocking property. Alkenes: Nomenclature, types of alkenes, synthesis alkenes (dehydration and dehydrohalogenation), chemical properties: addition of Br2 to ethene (mechanism), mechanism of addition of HBr to symmetrical and unsymmetrical alkenes, 2 Markovnikov’s rule, peroxide effect- mechanism, oxidation reaction of alkeneshydroxylation, oxidative degradation, epoxidation, ozonolysis taking examples of propene, 1-butene, 2-butene, 2-methyl-2-butene. Physical chmeistry Chapter-1: Liquid Mixtures 7 hrs Classification of binary liquid mixtures into partially miscible, completely miscible and completely immiscible liquids. Completely miscible liquids- Raoult’s law- ideal liquid mixtures- -non-ideal liquid mixtures showing (a) very slight +ve deviation from ideal behaviour (type-I) from Raoult’s law benzene, toluene as example (b) very high +ve deviation Eg: ethanol-water (type-II) system (c) –ve deviation (type-III) from Raoult’s law- HCl-water as example. Vapour pressure – composition diagram and diagram and vapour pressure temperature diagrams for all the three types of liquid mixtures, principle of fractional distillation of type–I, type-II and type-III liquid mixtures and azeotropes. Partially miscible liquid mixtures, mutual solubility temperature–critical solution temperature (CST ) – mutual solubility temperature for phenol-water system trimethylamine-water, Nicotine-water system- effect of addition of impurity on CST with an example (electrolyte and an organic compound impurities on phenol-water system) – completely immiscible liquids-immiscible liquid pairs with examples, weight fraction of distillation-steam distillation and its application-problems on weight fraction of components. Chapter-2: Distribution law 3 hrs Statement of Nernst distribution law, conditions for validity of distribution law, limitations of distribution law, distribution coefficients –verification of Nernst distribution law taking I2 in water and CCl4 as example. Association and dissociation of the solute in one of the solvent, application of the distribution of law with respect to solvent extraction process- de-silverisation of lead, Henry’s law and its limitations. Chapter-3: Phase equilibrium 5 hrs Gibb’s phase rule-statement-definition of the terms-phase, component and degree of freedom with examples, applications- (a) phase equilibria of one component system, water and CO2 and sulphur system Phase equilibria of two component system-reduced phase and reduced system, solidliquid equilibria-simple eutectic system, silver-lead system and its application, desilverisation of lead – solid solutions-compound formation with incongruent melting point, ferric chloride- water system, KI-water system-principles of freezing point. 3 KUVEMPU UNIVERSITY DEPARTMENT OF CHEMISTRY SAHYADRI SCIENCE COLLEGE SHIMOGA – 577 203 INTEGRATED M.Sc. (Hons.) COURSE IN APPLIED CHEMISTRY II – SEMESTER Hours: 75 Inorganic chemistry Chapter 1: Chemical bonding 12 hrs Ionic bond: Definition, lattice energy, factor controlling lattice energy, variation of lattice energy with charges of ions and internuclear distance between oppositely charged ions and internuclear distance between oppositely charged ions. Ionic size and hydration energy, polarizing power, polarizability of ions, Fazan’s rule, covalent in ionic bonds (problems to be solved). Covalent bond VBT-formation of H2 molecule- (taking wave function of atomic orbital) and bonds with their characteristics. Polar and non-polar bonds, electronegativity differences variation of percentage ionic character of the bond (problems to be solved). Chapter 2: Hybridization 3 hrs 2 3 3 4 3 3 2 3 3 7 sp (BF ), sp (CH ), sp d(PCl5), sp d (SF6), sp d (IF ) VSEPR Theory: shape of SF4, ClF3, XeF2, ICl, SnCl2, BO33-. Chapter 3: Resonance 2 hrs Concept of resonance energy calculation of resonance energy, requirements of contributing resonance forms, resonance structures of CO2, NO, NO3-. Chapter 4: Molecular orbital theory (MOT) 5 hrs Linear combination of atomic orbital, in terms of wave functions, conditions for combinations of atomic orbitals, energy levels of molecular orbitals, rules for filling molecular orbitals, molecular orbital structure and bond order, O2, O2+, O22-, O2-. Hetero nuclear diatomic molecules: CO, NO, CN-, HF (prediction of magnetic properties of these species) Chapter 5: Theory of volumetric analysis Titrometric method of analysis-Introduction, equivalent weight, acidity, basicity. Primary and secondary standards. Requirement of a primary standard, units of standard solutions (normality molarity, molality, mole fraction, ppm, ppb). Acid base titration: Types, Ostwald’s theory of acid-base indicator, choice of acid-base indicator. Redox titration- theory of redox indicators with reference to diphenyl amine. Complexometric titrations-Definitions, types of EDTA titrations, estimation of Zn2+ using EDTA, metal indicators, principles and theory. Iodometric titrations-principles, applications (estimation of copper, available chlorine in bleaching powder). 8 hrs 4 Organic chemistry Chapter 1: Dienes 3 hrs Types, with examples, synthesis of 1,3-butadiene (two methods), localized and delocalized p-orbitals in 1,3-butadiene and 1,4-pentadiene, mechanism of addition of Br2 to 1,3-butadiene, Diels-Alder reaction. Chapter 2: Alkynes 3 hrs Nomenclature, preparation by dehydrohalogenation of dihalides and dehydrogenation of tertahalides, acidity of alkynes- formation of metal alkynides, addition of water and HCl to ethyne and propyne. Chapter 3: Arenes and Aromaticity 8 hrs Modern structure of benzene, resonance structures of benzene, resonance hybrid, resonance energy, aromaticity, Huckel rule, aromatic ions and their stability, aromatic, anti-aromatic non-aromatic and pseudo-aromatic. Substitution reaction– mechanism of electrophilic reaction in benzene (nitration, sulphonation, halogenation and Friedel-Craft’s alkylation mechanism of reaction (amination, hydroxylation), derivatives of benzene- different classes of derivatives of benzene, nomenclature, orienting influence of substituents in benzene – ortho and para directors, meta directors, activatry effect, deactivating effect of substituent. Chapter 4: Polynuclear Hydrocarbons 6 hrs Fused, linked and bridged polynuclear aromatic hydrocarbons, synthesis of naphthalene from benzene-Haworth’s method, addition, electrophilic, substitution reaction of naphthalene, Reduction and oxidation of naphthalene, resonance structure of naphthalene, constitution of naphthalene. Introduction to annulenes, heteroannulenes, Fullerenes – preparation, structure and properties. Chapter 5: Alkyl Halides 5 hrs Classification, nucleophilic substitution reaction, SN1 and SN2 with mechanism (taking example of t-butyl bromide and methyl bromide) Elimination reaction- E1 and E2 reaction (taking example of t-butyl bromide and butyl bromide), effect of solvent, alkyl halide and nucleophilic halogen of nucleophilic substitution reaction and elimination reactions (stereochemistry of SN1 and SN2), elimination reaction of secondary butyl bromide, Saytzeff rule and Hoffmann rule for alkyl halides. Chapter 6: Aryl Halides 2 hsr Reactivity of chlorine in chlorobenzene, benzyl chloride, vinyl chloride and alkyl chlorides, allyl chloride. 5 Chapter 1: Gases 6 hrs Molecular velocities-Maxwell-Boltzmann distribution of molecular velocities (no derivation)-types of molecular velocities-derivation of expression for RMS velocityderivation expression for average velocity and most probable velocity-relationship between the three and problems based on temperature dependence-explanation of effect of temperature on distribution of molecular velocities using distribution graph-MaxwellBoltzmann energy distribution as a function of temperature-degree of freedom-law of equipartition of energy and its calculation for mono, di and triatomic molecule Specific heat and molar heat of gases-the relation of molar heats of a gases with kinetic theory. Chapter 2: Critical Phenomena 4 hrs Real gases, PV-isotherm of CO2- critical constants, Tc, Pc, and Vc definitionsexperimental determination of Tc and Pc using Caignard –de-la Tours apparatus and Vc by Cailletets and Mathias method-vander Waal’s equation of state for real gasesrelationship of vander Waal’s constants (a and b) with critical constants Tc, Pc and Vc (to be derived using isotherm of CO2) numerical problems on Tc, Pc and Vc –law of corresponding states and reduced equation of state (to be derived). Chapter 3: Liquefaction of gases 3 hrs Intermolecular forces- hydrogen bonding-brief account of dipole-dipole, dipole-induced dipole and induced dipole- induced dipole interactions-vander Waal’s force of attraction in explaining the physical properties of liquids –principle understanding liquefaction of gases-Joule-Thomson effect, inversion temperature relation between it and vander Waal’s constants a and b and its calculations. Chapter 4: Colligative Properties 7 hrs Raoult’s law of dilute solutions, osmotic pressure, relationship between relative lowering of vapour pressure and molar mass of solute to be derived, determination of osmotic pressure by Berkeley-Hartley method, plasmolysis, haemolysis, turgid state, reverse osmosis, laws of osmotic pressure,. Elevation in boiling point, relation between elevation in boiling point to molar mass (to be derived), Ebullioscopic constant, experimental determination of molecular weight by Walker-Lumsden method. Depression in freezing point, relation between depression in freezing point to molar mass (to be derived), Cryoscopic constant, experimental determination of molecular weight by Beckmann’s method. Determination of molecular weight of solute by Rast’s method. Abnormal molecular masses-Van’t Hoff factor-degree of dissociation, (numerical problems to be worked out). I SEMESTER CHEMISTRY PRACTICALS 6 I Systematic semimicro qualitative analysis Systematic semimicro qualitative analysis of inorganic mixture two simple salts involving following anions and cations. Anions: CO3-2, HCO3-1, SO3-2, S-2, Cl-1, Br-1, I-1, NO3-1, SO4-2, BO3-3, PO4-3. Cations:Pb+2, Cd+2, Bi+3, Al+3, Fe+2, Fe+3, Zn+2, Mn+2, Ni+2, Ba+2, Ca+2, Sr+2, Mg+2, + + NH4 , K , Na + II Organic preparations Bromination: Acylation : Oxidation : Nitration : p-Bromo acetanilide from acetanilide Acetanilide from aniline Benzoic acid from benzyl alcohol m-Dinitro benzene from nitro benzene II SEMESTER CHEMISTRY PRACTICALS Volumetric analysis 1. Calibration of burette, pipette, standard flask. 2. Estimation of NaOH using approximately 0.1N HCl solution and anhydrous sodium carbonate 3. Estimation of HCl using approximately 0.1N NaOH solution and pot. biphtalate crystals. 4. Estimation of Mohr’s salt using approximately 0.1N KMnO4 solution and oxalic acid crystals. 5. Estimation of ferric chloride using approximately 0.1N K2Cr2O7 solutions and Mohr’s salt crystals (diphenyl amine indicator method) 6. Estimation of copper sulphate solution using approximately 0.1N sodium thiosulphate solution and K2Cr2O7 crystals. 7. Estimation of sodium chloride using approximately 0.1N AgNO3 solution using KCl crystal. 8. Estimation of available chlorine in bleaching powder. 7