Syllabus for M.Sc. (Chemistry) Entrance Test
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1 Syllabus for M.Sc. (Chemistry) Entrance Test INORGANIC CHEMISTRY: Atomic Structure de Broglie matter waves, Heisenberg uncertainty principle, atomic orbitals, Schrödinger wave equation, quantum numbers, radial and angular wave functions and probability distribution curves, shapes of s, p, d orbitals, Aufbau and Pauli exclusion principles, Hund s multiplicity rule. Periodic Properties Atomic and ionic radii, ionization energy, electron affinity and electronegativity definition and evaluation, trends in periodic table and applications in predicting and explaining the chemical behaviour. Chemical Bonding Valence bond theory and its limitations, characteristics of covalent bond, hybridization and shapes of simple inorganic molecules and ions. VSEPR theory, MO theory, homonuclear and heteronuclear (CO and NO) diatomic molecules, bond strength and bond energy. Ionic structures, radius ratio effect and coordination number, lattice defects, lattice energy and Born-Haber cycle, solvation energy and solubility of ionic solids, Fajan's rule. Weak Interactions-Hydrogen bonding, van der Waals forces. Chemistry of Group Elements Chemistry, physical and chemical properties of S - Block Elements, Groups {III (13), IV (14), V (15), VI (16) and VII (17)} and Zero Group Elements with special reference to their elemental derivatives. Functional reactions and applications. Chemistry of Transition Elements Characteristic properties of d -block elements. Properties of the elements of the all transition series, their binary compounds and complexes illustrating relative stability of their oxidation states, coordination number and geometry. Magnetic behaviour, spectral properties and stereochemistry of Transition Metal complexes. Valence bond theory of transition metal complexes, Crystal field theory, crystal field splitting in octahedral, tetrahedral and square planar complexes. Jahn-Teller effect. Coordination Compounds Werner's coordination theory, effective atomic number concept, chelates, nomenclature of coordination compounds, isomerism in coordination compounds. Chemistry of Lanthanide Elements Electronic structure, oxidation states and ionic radii and lanthanide contraction, magnetic properties, complex formation, occurrence and isolation, lanthanide compounds. Chemistry of Actinides Electronic structure, oxidation states and ionic radii, complex formation, chemistry of separation of Np, Pu and Am form U, similarities between later actinides and the later lanthanides. Bio - inorganic Chemistry Essential and trace elements in biological processes, metalloporphyrins with special reference to hemoglobin and myoglobin. Biological role of alkali and alkaline earth metal ions with special reference to Ca 2+. 1
2 ORGANIC CHEMISTRY: Fundamentals of Organic Chemistry IUPAC Nomenclature, Hybridization, Localised and delocalized bonds, Inductive and field effects, Electromeric effect, Mesomeric effect, resonance, hyperconjugation, hydrogen bonding and Aromaticity. Hemolytic and heterolytic bond cleavage, Electrophiles & nucleophiles, Reactive intermediates, Mechanism of addition, substitution and elimination reactions. Stereochemistry of Organic Compounds Concept of isomerism, types of isomerism, molecular chirality, enantiomers, diastereomers, meso compounds, resolution of enantiomers, inversion, retention and racemization. Relation absolute configuration, sequence rules, D &L, R & S nomenclature. Geometrical isomerism - E & Z nomenclature. Conformational isomerism- conformational analysis of ethane and n-butane, conformation of cyclohexane, axial & equatorial bonds, conformation of monosubstituted cyclohexane derivatives. Newman projection & saw horse formulae, Fischer & flying wedge formula. Aliphatic and Aromatic Hydrocarbons: Nomenclature, Synthesis, Mechanism and Chemical reactions of alkanes, alkenes, alkynes, dienes, cycloalkenes and arenes. Saytzeff rule, Hofmann elimination, Markownikoff s rule, hydroborationoxidation, oxymercuration-reduction, Epoxidation, Ozonolysis, hydration, hydroxylation, Diels-Alder reaction, hydroboration oxidation, metal-ammonia reductions, and polymerization. Aromatic electrophilic substitution - general pattern of the mechanism, role of and complexes. Mechanism of nitration, halogenation, sulphonation, mercuration and Friedal Craft reaction of benzene. Side chain reaction of benzene derivatives. Birch reduction. Alkyl and Aryl Halides Synthesis, properties and Chemical reactions of alkyl and aryl halides. Polyhalogen compounds: Chloroform, carbon tetrachloride. Relative reactivities of alkyl halides vs allyl, vinyl and aryl halides. Synthesis and uses of DDT and BHC. Grignard reagent, preparation, properties and applications. Alcohols and Phenols Classification, nomenclature, synthesis and chemical reactions of mono-, di- and polyhydric alcohols. Pinacol-pinacolone rearrangement. Synthesis, structure, acidic character and physical properties of Phenol. Reactions of phenol-electrophilic aromatic substitution, acylation and carboxylntion, mechanism of Fries rearrangement, claisen rearrangement, Gatterman synthesis, Hauben-Hoesch reiction, Reimer Tiemann reaction. Ethers and Epoxides Nomenclature of ethers and methods of their formation, physical properties. Chemical reactions- Cleavage and autoxidation, Ziesel s method. Synthesis of epoxides. Acid and base catalysed ring opening of epoxides, orientation of epoxide ring opening, reaction of Grignards and organolithium reagents with epoxides. Aldehydes and Ketones Synthesis of aldehydes from acid chlorides, synthesis of aldehydes and ketones using 1,3-dithiones. Synthesis of ketones from nitriles and from carboxylic acids. Physical properties, Mechanism of nucleophilic addition to carbonyl group with spectral emphasis on Benzoin, Aldol, Perkin and Knoevenagel condensations. Condensation with ammonia and its derivatives. Wittig reaction, Mannich reaction. Oxidation of aldehydes, Baeyer-Villiger oxidation of ketones, Cannizaro reaction, Clemmensen, 2
3 Wolff Kishner, LiAlH 4 and NaBH 4 reduction. Halogenation of enolizable ketones. An introduction of, unsaturated aldehydes and ketones. Carboxylic Acids and its derivatives Nomenclature, structure and bonding, physical properties, acidity of carboxylic acids, effects of substituents on acid strength. Preparation and reactions of carboxylic acids. Hell-Volhard-Zelinsky reaction. Synthesis of acid chlorides, esters and amides. Reduction of carboxylic acids. Mechanism of decarboxylation. Preparation and reactions of halocarboxylic acids, Malic, Tartaric and Citric acids. Physical properties, interconversion of acid derivatives by nucleophilic acyl substitution. Compounds of active methylene group-synthesis of malonic ester and acetoacetic ester. Properties and application of malonic ester and acetoacetic ester. Nitrogen containing Organic Compounds Preparation of nitroalkanes and nitroarenes. Chemical reactions of nitro alkanes. Mechanism of nucleophilic substitution in nitro arenes and their reduction in acidic, neutral and alkaline media. Picric acid. Stereochemistry of amines, separation of a mixture of primary, secondary and tertiary amines structural features effecting basicity of amines, preparation of alkyl and aryl amines by reduction of nitro compounds and nitriles, reductive amination of aldehydes and ketones compounds, Gabriel phthalamide reaction, Hofmann bromamide reaction. Reactions of amines, electrophilic aromatic substitution in aryl amines. Reactions of amines with nitrous acid, synthetic transformations of aryl diazonium salts, azo coupling. Carbohydrates Classification and nomenclature. Monosaccharides, mechanism of osazones formation, interconversion of glucose and fructose, chain lengthening and chain shortening of aldoses. Configuration of monosaccharides. Erythro and threo diastereomers. Conversion of glucose into mannose. Formation of glycosides, ethyl and esters. Determination of ring size of monosaccharides. Cyclic structure of D(+) glucose. Mechanism of mutarotation. Structures of ribose and deoxyribose. An introduction to disaccharides (maltose, sucrose and lactose) and polysaccharides (starch and cellulose) without involving structure determination. Amino acids, Peptides, Proteins and Nucleic acids Classification, structure and stereochemistry of amino acids. Acid-base behaviour, isoelectric point and electrophoresis. Preparation and reaction of amino acids. Structure and nomenclature of peptides and proteins. Classification of proteins. Peptide structure determination, end group analysis, selective hydrolysis of peptides. Classical peptide synthesis. Structures of peptides and proteins. Nucleic acids: introduction, constituents of nucleic acids. Ribonucleoside and ribonucleotides. Synthetic polymers Addition or chain growth polymerization. Free radical polymerization, ionic vinyl polymerization, Zigler Natta Polymerization and vinyl polymers. Condensation or step growth polymerization. Polysters, polyamides, phenol formaldehyde resins, urea formaldehyde resins, epoxy resins and polyurethanes. Heterocyclic Compounds lntroduction and aromatic characteristics of pyrrole, furan, thiophene and pyridine. Methods of synthesis and chemical reactions with particular emphasis on the mechanism of electrophilic substitution reactions in pyridine derivatives. Comparison of basicity of pyridine, Piperdine and pyrrole. 3
4 PHYSICAL CHEMISTRY: States of Matter: Gas laws, Ideal gas equation, Postulates of kinetic theory of gases, Kinetic gas equation. Molecular velocities, Maxwell's distribution of molecular velocities, Collision properties. Liquefaction of gases. Critical Phenomena: PV isotherms of real gases, Continuity of states, van der Walls equation, Law of corresponding states, Reduced equation of state. Intermolecular forces, structure of liquids, Liquid crystals: Classification, structure of nematic and cholestric phases. Crystalline and Amorphous solid, Symmetry of crystal systems, Space lattice and Unit cell, Summary of crystal systems, Applications of crystallographic studies; Law of rational of indices, Inter-planer spacing. X-ray diffraction, Bragg's equation. Powder method, Determination of Grain size using X-ray line broadening studies (Scherrer s formula), The Rotating crystal method. Determination of crystal structure of NaCl using powder method. Colloidal State Definition and classification of colloids, kinetic, optical and electrical properties of Sols, stability of colloids, protective action, Hardy-Schulze law, gold number. Emulsions, and gels. Dilute solutions and Colligative Properties Methods of expressing concentrations of solutions, activity and activity coefficient. Dilute solution, colligative properties, Raoult's law, relative lowering of vapour pressure, molecular weight determination. Osmosis, Law of osmotic pressure and its measurement, determination of molecular weight from osmotic pressure. Elevation of boiling point and depression of freezing point. Experimental methods for determining various colligative properties. Abnormal molar mass. Chemical Equilibria Reversible and irreversible reactions, Characteristics of chemical equilibrium, Formulation of equilibrium law, equilibrium law for ideal gases, relation between Kp and Kc and Kx. Reaction quotient, factors affecting the equilibrium constant. Equilibrium between gases and solids, equilibrium constant for a system of real gases, equilibrium constant of reactions in solution. Thermodynamic treatment of equilibrium constant. Variation of equilibrium constant with temperature, pressure and concentration, effect of inert gas on reaction equilibrium, Le Chatelier s principle. Ionic Equilibria Strong, moderate and weak electrolytes, degree of ionization, factors affecting degree of ionization. Acid-base concept. Dissociation constants of weak acids and weak bases. Ionization constant and Ionic product of water. The ph scale, Buffer solutions, Calculations of ph values of buffer mixtures, Derivation of Henderson equation and its applications, buffer capacity and buffer action. Salt hydrolysis, Determination of hydrolysis constant, degree of hydrolysis and ph for different salts. Relation between K h, K a and K b. Solubility and solubility product of sparingly soluble salts Applications of solubility product principle and Common ion effect. Phase Equilibrium Concept of phases, components and degrees of freedom, derivation of Gibbs Phase Rule for nonreactive and reactive systems; phase diagram for one component systems, with application. Phase diagram for systems of solid-liquid equilibria involving eutectic, congruent and incongruent melting points. Chemical Kinetics and Catalysis Rate of a reaction, factors influencing the rate of a reaction, mathematical characteristics of simple chemical reactions - zero order, first order, second order, pseudo order, half life and mean life. 4
5 Determination of the order of reaction, Theories of chemical kinetics, effect of temperature on the rate of reaction, Arrhenius equation, concept of activation energy. Theories of reaction rates - Simple collision theory and theory of absolute reaction rates, Expression for the rate constant based on equilibrium constant and thermodynamic aspects. Lindemann theory of unimolecular reactions. Catalysis, characteristics of catalytic reactions, classification of catalysis, miscellaneous examples. Thermodynamics Thermochemistry: standard state, standard enthalpy of formation, Hess law of heat summation and its applications. Heat of reaction at constant pressure and at constant volume. Enthalpy of neutralization, Bond dissociation energy and its calculation from thermo-chemical data, temperature dependence of enthalpy, Kirchoff s equation. First Law of Thermodynamics: Statement, definition of internal energy and enthalpy. Heat capacity, heat capacities at constant volume and pressure and their relationship. Joule's law, Joule-Thomson coefficient and inversion temperature. Calculation of w, q, U & H for the expansion of ideal gases under isothermal and adiabatic conditions for reversible process. Carnot cycle and its efficiency. Carnot theorem. Second law of thermodynamics, Concept of entropy, entropy as a function of P & T, entropy in physical change. entropy as a criterion of spontaneity and equilibrium. Entropy change in ideal gases and mixing of gases. Gibbs and Helmholtz function: Gibbs function (G) and Helmholtz function (A) as thermodynamic quantities, A & G as criteria for thermodynamic equilibrium and spontaneity, their advantage over entropy change. Variation of G and A with P, V and T. Third law of thermodynamics: Nernst heat theorem, concept of residual entropy, evaluation of absolute entropy. Electrochemistry Chemical cells, reversible and irreversible cells with examples. Electromotive force of a cell and its measurement, Nernst equation; Standard electrode (reduction) potential and its application to different kinds of half-cells. Application of EMF measurements in determining (i) free energy, enthalpy and entropy of a cell reaction, (ii) equilibrium constants, and (iii) p H values, using hydrogen, quinonehydroquinone, glass electrodes. Difference between chemical cells and concentration cells, liquid junction potential, its derivation, Electrode concentration cells, electrolyte concentration cells, concentration cells. Conductivity, equivalent and molar conductivity and their variation with dilution for weak and strong electrolytes. Molar conductivity at infinite dilution. Kohlrausch law. Elementary Quantum Mechanics Postulates of quantum mechanics, Black-body radiation, Planck s radiation law, photoelectric effect, Bohr s model of hydrogen atom. De Broglie hypothesis, the Heisenberg s uncertainty principle, Sinusoidal wave equation, Hamiltonian operator and Schrödinger wave equation. Molecular orbital theory, calculation of energy levels from wave functions, physical picture of bonding and anti bonding wave functions, concept of, *,, * orbitals and their characteristics. Spectroscopy Introduction: Electromagnetic radiation, regions of the spectrum, basic features of different spectrometers. Basic principles and applications of Rotational Spectroscopy, Vibrational Spectroscopy (IR and Raman), Electronic Spectroscopy and Nuclear Magnetic Resonance Spectroscopy. Interpretation of NMR spectra of simple organic molecules. Problems pertaining to the structure elucidation of simple organic compounds using UV, IR and NMR spectroscopic techniques. Photochemistry Interaction of radiation with matter, difference between thermal and photochemical processes. Laws of photochemistry, Jablonski diagram, qualitative description of fluorescence, phosphorescence, quantum yield, photosensitized reactions and energy transfer processes (simple examples). 5
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