Part-A, Analytical Chemistry: 100 Marks
Theoretical basis of Quantitative inorganic analysis:
Law of mass action, chemical and ionic equilibrium, solubility, Solubility product and common ion effect, effect of temperature upon the solubility of precipitates, the ionic product of water, pH, effect of temperature on pH, Salt hydrolysis, hydrolysis constant, degree of hydrolysis, buffer solutions, different types of buffers and Henderson's equation.
General principles, stoichiometry, calculation of results from gravimetric data. Properties of precipitates. Nucleation and crystal growth, factors influencing completion of precipitation. Co-precipitation and post-precipitation, purification and washing of precipitates. Precipitation from homogeneous solution, a few common gravimetric determinations-chloride as silver chloride, sulphate as barium sulphate, aluminum as the oxinate and nickel as dimethyl glyoximate.
Sampling and treatment of samples for chemical analysis:
Techniques of collection of Solids, liquids and gaseous samples, dissolution of solid samples, attack with water, acids, and alkalis, fusion with Na2CO3, NaOH, Na2O2, K2S2O7; Microwave assisted digestion techniques (only elementary idea).
Equivalent weights, different types of solutions, Normal solutions, Molar solutions, and molal solutions and their inter relations. Primary and secondary standard substances. principles of different type of titrations-i) acid-base titration, ii) redox titration, iii) complexometric titrations. Types of indicators - i) acid-base, ii) redox iii) metal-ion indicators. Principles in estimation of mixtures of NaHCO3 and Na2CO3 (by acidimetry); Principles of estimation of iron, copper, manganese, chromium (by redox titration);
Acid base titrations:
Principles of titrimetric analysis, titration curves for strong acidstrong base, weak acid-strong base and weak base-strong acid titrations, poly protic acids, poly equivalent bases, determining the equivalence point-theory of acid base indicators, colour change range of indicator, selection of proper indicator.
Principles behind the Iodometry, permaganometry, dichrometry, difference between iodometry and iodimetry.
Fundamentals of potentiometry. indicator and ion-selective electrodes. Membrane electrodes. Glass electrode for pH measurement, glass electrodes for cations other than protons. Liquid membrane electrodes, solid state ion selective detectors and biochemical electrodes. Applications of potentiometry. Direct potentiometric measurements-determination of pH and fluoride. Redox and potentiometer titrations- Balancing redox reactions, calculation of the equilibrium constant of the reaction, titration curves, visual end point detection. Redox indicators-theory, working and choice. Potentiometric end point detection. Applications of redox titrations.
Complex formation reactions, stability of complexes, stepwise formation constants, chelating agents, EDTA-acidic properties, complexes with metal ions, equilibrium calculations involving EDTA, conditional formation constants, derivation of EDTA titration curves, effect of other complexing agents, factors affecting the shape of titration curves-completeness of reaction, indicators for EDTA titrations-theory of common indicators, titration methods employing EDTA-direct, back and displacement titrations, indirect determinations, titration of mixtures, selectivity, masking and de-masking agents, typical applications of EDTA titrations-hardness of water, magnesium and aluminium in antacids, magnesium, manganese and zinc in a mixture, titrations involving uni-dentate ligands-titration of chloride with Hg2+ and cyanide with Ag+.
Chromatographic methods of analysis:
Basic principles and classification of chromatography. Importance of column chromatography and thin layer chromatography; Theory and principles of High Performance Liquid Chromatography (HPLC) and Gas Liquid Chromatography (GLC). Ion-exchange chromatography.
Basic Principles of UV-Vis spectrophotometer. Lambert -Beer's Law and its limitations. Instrumentation consisting of source, monochromator, grating and detector. Spectrophotometric determination.
Flame photometry and Atomic absorption spectrometry:
Emission spectra Vs absorption spectra. Basic Principles and theory of flame photometry. Applications of Flame photometers. Basic Principles and theory of AAS. Three different modes of AAS - Flame-AAS, VGAAS, and GFAAS. Single beam and double beam AAS. Function of Halo Cathode Lamp (HCL) and Electrode Discharge Lamp (EDL). Different types of detectors used in AAS. Different types of interferencesMatrix interferences, chemical interferences, Spectral interferences and background correction in AAS. Use of organic solvents. Quantitative techniques-calibration curve procedure and the standard addition technique. Typical commercial instruments for FP and AAS. Applications. Qualitative and qualitative analysis. Relative detection abilities of atomic absorption and flame emission spectrometry.
X-ray methods of Analysis:
Introduction , theory of X-ray generation, , X-ray spectroscopy, , X-ray diffraction and X-ray fluorescence methods, Braggs law, instrumentation , dispersion by crystals, applications. Preparation of pallets, glass beads, quantitative and qualitative measurement.
Inductively coupled plasma spectroscopy:
Theory and Principles, plasma generation, utility of peristaltic pump, sampler - skimmer systems, ion lens, quadrupole mass analyzer, dynode /solid state Detector, different type of interferences- spectroscopic and non-spectroscopic interferences, isobaric and molecular interferences, applications.
Analysis of Minerals, Ores and Alloys:
Analysis of Minerals and Ores- estimation of (i) CaCO3 , MgCO3 in dolomite (ii) Fe2O3, Al2O3, and TiO2 in Bauxite. (iii) MnO and MnO2 in Pyrolusite. Analysis of Metal and Alloys: (i) Cu and Zn in Brass (ii) Cu, Zn, Fe, Mn, Al and Ni in Bronze (iii) Cr, Mn, Ni, and P in Steel (iv) Pb, Sb, Sn in type metal.
Analysis of petroleum and petroleum products:
Introduction, constituents and petroleum fractionation. Analysis of petroleum productsspecific gravity, viscosity, Doctor test, aniline point, colour determination, cloud point, pour point. Determination of water, neutralization value (acid and base numbers), ash content, Determination of lead in petroleum.
Analysis of coal and coke:
Types, composition, preparation of sample, proximate and ultimate anlaysis calorific value by bomb Calorimetry.
PART-B (Organic Chemistry): 100 Marks
Basic organic chemistry:
Inductive effect, resonance and resonance energy. Homolytic and heterolytic bond breaking, electrophiles and nucleophiles; carbocations, carbanions and radicals (stability and reactivity). Alkanes, alkenes and alkynes: Synthesis and chemical reactivity of alkanes, mechanism of free-radical halogenation of alkanes. General methods of synthesis, electrophilic addition reactions and polymerization reaction (definition and examples only) of alkenes. General methods of synthesis, acidity, hydration and substitution reactions of alkynes.
Grignard reagents - preparations and reactions, application of Grignard reagents in organic synthesis. Organic compounds containing nitrogen: aromatic nitro compounds - reduction under different conditions. Methods of synthesis of aliphatic amines, Heinsberg's method of amine separation, Hofmann degradation, Gabriel's phthalimide synthesis, distinction of primary, secondary and tertiary amines; methods of synthesis of aromatic amines, basicity of aliphatic and aromatic amines. Sandmeyer reactions; synthetic applications of benzene diazonium salts.
Bonding and physical properties:
Valence bond theory: concept of hybridisation, resonance (including hyperconjugation), orbital pictures of bonding sp3, sp2, sp: C-C, C-N & C-O system). Inductive effect, bond polarization and bond polarizability, steric effect, steric inhibition of resonance. MO theory: sketch and energy levels of MOs of i) acyclic p orbital system ii) cyclic p orbital system, iii) neutral system. Frost diagram, Huckel's rules for aromaticity & antiaromaticity; homoaromaticity. Physical properties: bond distance, bond angles, mp/bp & dipole moment in terms of structure and bonding. Heat of hydrogenation and heat of combustion.
Aldol and related reactions:
Keto-enol tautomerism, mechanism and synthetic applications of aldol condensations, Claisen reaction, Schmidt reaction, Perkin reaction, Knovenogal, benzoin, Cannizaro reaction, Michael addition. Aromatic substitution reactions - electrophilic, nucleophilic and through benzynes - radical substitution of arenes - orientation of nucleophilic substitution at a saturatéd, carbon, SN1, SN2, SNi reactions -effect of structure, nucleophile, leaving group, solvent. Additions involving electrophiles, nucleophiles and free radicals.
Mechanism of some name reactions:
Aldol, Perkin, Benzoin, Cannizaro, Wittig, Grignard, Reformatsky, Hoffmann, Claisen and Favorsky rearrangements. Openauer oxidation, clemmensen reduction, Meerwein - Pondorf and Verley and Birch reductions. Stork enamine reactions, Michael addition, Mannich Reaction, Diels - Alder reaction.
Molecular orbital symmetry, frontier orbitals of ethylene, 1,3 Butadiene, 1,3,5-Hexatriene, allyl system, classfication of pericyclic reactions FMO approach, Woodwrd- Hoffman correlation diagram method and perturbation of molecular (PMO) approach for the explanation of pericyclic reactions under thermal and photochemical conditions. Conrotatory and disotatory motions (4n) and (4n+2).
Organic Reaction Mechanisms:
Addition Elimination Mechanisms: (a) Addition to carbon multiple bonds- hydrogenation of double and triple bonds, hydroboration, birch reduction, Michael reaction, addition of oxygen and N, (b) Addition to carbon-hetero atom multiple bonds: Mannich reaction, Reductions of Carbonyl compounds, acids, esters, nitrites, addtion of Grignard reagents, Reformatsky reaction, Tollen's reaction, Wittig reaction: (c) Elimination reactions: Stereochemistry of eliminations in acyclic and cyclic systems, orientation in eliminations - Saytzeff and Hoffman elimination.
Infrared spectroscopy: Units of frequency wave length and wave number, molecular vibrations, factors influencing vibrational frequencies, the IR spectrometer, characteristic frequencies of organic molecules and interpretation of spectra.
Ultraviolet spectroscopy: Introduction, absorption laws, measurement of the spectrum, chromophores, definitions, applications of UV spectroscopy to Conjugated dines, trienes, unsaturated carbonyl compounds and aromatic compounds.
Nuclear Magnetic Resonance Spectroscopy: (Proton and Carbon -13 NMR) The measurement of spectra, the chemical shift: the intensity of NMR signals and integration factors affecting the chemical shifts: spin-spin coupling to 13C IH-IH first order coupling: some simple IH-IH splitting patterns: the magnitude of IH-IH coupling constants.
Mass spectroscopy: Basic Principles: instrumentation: the mass spectrometer, isotope abundances; the molecular ion, meta stable ions.