Syllabus for Chemist

Chemistry : Paper-I (Inorganic Chemistry)

1. Inorganic solids:

Defects, non-stoichiometric compounds and solid solutions, atom and ion diffusion, solid electrolytes. Synthesis of materials, monoxides of 3d-metals, higher oxides, complex oxides (corundrum, ReO3, spinel, pervoskites), framework structures (phosphates, aluminophosphates, silicates, zeolites), nitrides and fluorides, chalcogenides, intercalation chemistry, semiconductors, molecular materials.

2. Chemistry of coordination compounds:

Isomerism, reactivity and stability: Determination of configuration of cis- and trans- isomers by chemical methods. Labile and inert complexes, substitution reactions on square planar complexes, trans effect. Stability constants of coordination compounds and their importance in inorganic analysis. Structure and bonding: Elementary Crystal Field Theory: splitting of dn configurations in octahedral, square planar and tetrahedral fields, crystal field stabilization energy, pairing energy. Jahn-Teller distortion. Metal-ligand bonding, sigma and pi bonding in octahedral complexes and their effects on the oxidation states of transition metals. Orbital and spin magnetic moments, spin only moments and their correlation with effective magnetic moments, d-d transitions; LS coupling, spectroscopic ground states, selection rules for electronic spectral transitions; spectrochemical series of ligands, charge transfer spectra.

3. Acid base titrations:

Titration curves for strong acid-strong base, weak acid-strong base and weak base-strong acid titrations, polyprotic acids, poly-equivalent bases, determining the equivalence point: theory of acid-base indicators, pH change range of indicator, selection of proper indicator. Principles used in estimation of mixtures of NaHCO3 and Na2CO3 (by acidimetry).

4. Gravimetric Analysis:

General principles: Solubility, solubility product and common ion effect, effect of temperature on the solubility; Salt hydrolysis, hydrolysis constant, degree of hydrolysis. Stoichiometry, calculation of results from gravimetric data. Properties of precipitates. Nucleation and crystal growth, factors influencing completion of precipitation. Co-precipitation and postprecipitation, purification and washing of precipitates. Precipitation from homogeneous solution. A few common gravimetric estimations: chloride as silver chloride, sulphate as barium sulphate, aluminium as oxinate and nickel as dimethyl glyoximate.

5. Redox Titrations:

Standard redox potentials, Nernst equation. Influence of complex formation, precipitation and change of pH on redox potentials, Normal Hydrogen Electrode (NHE). Feasibility of a redox titration, redox potential at the equivalence point, redox indicators. Redox potentials and their applications. Principles behind Iodometry, permanganometry, dichrometry, difference between iodometry and iodimetry. Principles of estimation of iron, copper, manganese, chromium by redox titration.

6. Complexometric 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: indicators for EDTA titrations, titration methods employing EDTA: direct, back and displacement titrations, indirect determinations, titration of mixtures, selectivity, masking and demasking agents. Typical applications of EDTA titrations: hardness of water, magnesium and aluminium in antacids, magnesium, manganese and zinc in a mixture, titrations involving unidentate ligands: titration of chloride with Hg2+ and cyanide with Ag+.

7. Organometallic compounds:

18-electron rule and its applications to carbonyls and nature of bonding involved therein. Simple examples of metal-metal bonded compounds and metal clusters. Wilkinson’s catalyst.

8. Nuclear chemistry:

Radioactive decay- General characteristics, decay kinetics, parent-daughter decay growth relationships, determination of half-lives. Nuclear stability. Decay theories. Unit of radioactivity. Preparation of artificial radionuclides by bombardment, radiochemical separation techniques. Experimental techniques in the assay of radioisotopes, Geiger-Muller counters. Solid state detectors.

9. Chemistry of d- and f-block elements:

d-block elements: General comparison of 3d, 4d and 5d elements in terms of electronic configuration, elemental forms, metallic nature, atomization energy, oxidation states, redox properties, coordination chemistry, spectral and magnetic properties. f-block elements: Electronic configuration, ionization enthalpies, oxidation states, variation in atomic and ionic (3+) radii, magnetic and spectral properties of lanthanides, separation of lanthanides (by ion-exchange method).

Chemistry : Paper-II (Physical Chemistry)

1. Kinetic theory and the gaseous state:

Real gases, Deviation of gases from ideal behaviour; compressibility factor; van der Waals equation of state and its characteristic features. Existence of critical state. Critical constants in terms of van der Waals constants. Law of corresponding states and significance of second virial coefficient. Boyle temperature.

2. Solids:

Nature of solid state. Band theory of solids: Qualitative idea of band theory, conducting, semiconducting and insulating properties. Law of constancy of angles, concept of unit cell, different crystal systems, Bravais lattices, law of rational indices, Miller indices, symmetry elements in crystals. X-ray diffraction, Bragg's law.

3. Chemical thermodynamics and chemical equilibrium:

Chemical potential in terms of Gibbs energy and other thermodynamic state functions and its variation with temperature and pressure. Gibbs-Duhem equation; fugacity of gases and fugacity coefficient. Thermodynamic conditions for equilibrium, degree of advancement. vant Hoff's reaction isotherm. Equilibrium constant and standard Gibbs energy change. Definitions of KP, KC and Kx; vant Hoff's reaction isobar and isochore. Activity and activity coefficients of electrolytes / ions in solution. Debye-Hückel limiting law.

4. Chemical kinetics and catalysis:

Second order reactions. Determination of order of reactions. Parallel and consecutive reactions. Temperature dependence of reaction rate, energy of activation. Collision Theory and Transition State Theory of reaction rates. Enthalpy of activation, entropy of activation, effect of dielectric constant and ionic strength on reaction rate, kinetic isotope effect. Physisorption and chemisorption, adsorption isotherms, Freundlich and Langmuir adsorption isotherms, BET equation, surface area determination; colloids, electrical double layer and colloid stability, electrokinetic phenomenon. Elementary ideas about soaps and detergents, micelles, emulsions.

5. Electrochemistry:

Types of electrochemical cells, cell reactions, emf and Nernst equation, ᐃG, ᐃH and ᐃS of cell reactions. Cell diagrams and IUPAC conventions. Standard cells. Half-cells / electrodes, types of reversible electrodes. Standard electrode potential and principles of its determination. Concentration cells. Determination of ᐃGº, Kº, Ksp and pH. Basic principles of pH metric and potentiometric titrations, determination of equivalence point and pKa values.

6. Quantum chemistry:

Eigenfunctions and eigenvalues. Uncertainty relation, Expectation value. Hermitian operators. Schrödinger time-independent equation: nature of the equation, acceptability conditions imposed on the wave functions and probability interpretation of wave function. Schrödinger equation for particle in a one-dimensional box and its solution. Comparison with free particle eigenfunctions and eigenvalues. Particle in a 3-D box and concept of degeneracy.

7. Basic principles and applications of spectroscopy:

Electromagnetic radiation, interaction with atoms and molecules and quantization of different forms of energies. Units of frequency, wavelength and wavenumber. Condition of resonance and energy of absorption for various types of spectra; origin of atomic spectra, spectrum of hydrogen atom. Rotational spectroscopy of diatomic molecules: Rigid rotor model, selection rules, spectrum, characteristic features of spectral lines. Determination of bond length, effect of isotopic substitution. Vibrational spectroscopy of diatomic molecules: Simple Harmonic Oscillator model, selection rules and vibration spectra. Molecular vibrations, factors influencing vibrational frequencies. Overtones, anharmonicity, normal mode analysis of polyatomic molecules. Raman Effect: Characteristic features and conditions of Raman activity with suitable illustrations. Rotational and vibrational Raman spectra.

8. Photochemistry:

Franck-Condon principle and vibrational structure of electronic spectra. Bond dissociation and principle of determination of dissociation energy. Decay of excited states by radiative and non-radiative paths. Fluorescence and phosphorescence, Jablonski diagram. Laws of photochemistry: Grotthus-Draper law, Stark-Einstein law of photochemical equivalence; quantum yield and its measurement for a photochemical process, actinometry. Photostationary state. Photosensitized reactions. Kinetics of HI decomposition, H2-Br2 reaction, dimerisation of anthracene.

Chemistry : Paper-III (Analytical and Organic)

PART-A (Analytical Chemistry)

A1. Errors in quantitative analysis:

Accuracy and precision, sensitivity, specific standard deviation in analysis, classification of errors and their minimization, significant figures, criteria for rejection of data, Q-test, t-test, and F-test, control chart, sampling methods, sampling errors, standard reference materials, statistical data treatment.

A2. Separation Methods:

Chromatographic analysis: Basic principles of chromatography (partition, adsorption and ion exchange), column chromatography, plate concept, plate height (HETP), normal phase and reversed phase concept, thin layer chromatography, frontal analysis, principles of High Performance Liquid Chromatography (HPLC) and Gas Liquid Chromatography (GLC), and Ion-exchange chromatography. Solvent extraction: Classification, principle and efficiency of the technique, mechanism of extraction, extraction by solvation and chelation, qualitative and quantitative aspects of solvent extraction, extraction of metal ions from aqueous solutions.

A3. Spectroscopic methods of analysis:

Lambert-Beer's Law and its limitations. UV-Visible Spectroscopy: Basic principles of UV-Vis spectrophotometer, Instrumentation consisting of source, monochromator, grating and detector, spectrophotometric determinations (estimation of metal ions from aqueous solutions, determination of composition of metal complexes using Job’s method of continuous variation and mole ratio method). Infra-red Spectrometry: Basic principles of instrumentation (choice of source, monochromator and detector) for single and double beam instruments, sampling techniques. Flame atomic absorption and emission spectrometry: Basic principles of instrumentation (choice of source, monochromator, detector, choice of flame and burner design), techniques of atomization and sample introduction, method of background correction, sources of chemical interferences and methods of removal, techniques for the quantitative estimation of trace level metal ions. Basic principles and theory of AAS. Three different modes of AAS - Flame-AAS, VG-AAS, and GF-AAS. Single beam and double beam AAS. Function of Hollow Cathode Lamp (HCL) and Electrode Discharge Lamp (EDL). Different types of detectors used in AAS. Qualitative and quantitative analysis.

A4. Thermal methods of analysis:

Theory of thermogravimetry (TG), basic principle of instrumentation, techniques for quantitative analysis of Ca and Mg compounds.

A5. X-ray methods of Analysis:

Introduction, theory of X-ray generation, X-ray spectroscopy, X-ray diffraction and X-ray fluorescence methods, instrumentation and applications. Qualitative and quantitative measurements. Powder diffraction method.

A6. 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 types of interferencesspectroscopic and non-spectroscopic interferences, isobaric and molecular interferences, applications.

A7. Analysis of geological materials:

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 metals 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’. Introduction to petroleum: constituents and petroleum fractionation. Analysis of petroleum products: specific 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. Types of coal and coke, composition, preparation of sample for proximate and ultimate analysis, calorific value by bomb calorimetry.

PART B (Organic chemistry)

B1. Unstable, uncharged intermediates:

Structure and reactivity of carbenes and nitrenes and their rearrangements (Reimer-Tiemann, Hoffman, Curtius, Lossen, and Schimdt,).

B2. Addition reactions:

Addition to C-C multiple bonds: Mechanism of addition involving electrophiles, nucleophiles and free radicals (polymerization reactions of alkenes and substituted alkenes), Ziegler-Natta catalyst for polymerization, polyurethane, and conducting polymers; addition to conjugated systems (Diels-Alder reaction), orientation and reactivity (on simple cis- and trans- alkenes). Addition to carbon-heteroatom multiple bonds: Addition to C=O double bond, structure and reactivity, hydration, addition of ROH, RSH, CN-, bisulphite, amine derivatives, hydride ions.

B3: Reactions at the carbonyl group:

Cannizzaro, Aldol, Perkin, Claisen ester, benzoin, benzil-benzilic acid rearrangement, Mannich, Dieckmann, Michael, Strobe, Darzen, Wittig, Doebner, Knoevenagel, Reformatsky reactions.

B4. Oxidation and Reduction:

Reduction of C=C, Meerwein-Pondorf reaction, Wolff-Kishner and Birch reduction. Oxidation of C=C, hydration, hydroxylation, hydroboration, ozonolysis, epoxidation, Sharpless epoxidation.

B5. Electrocyclic Reactions:

Molecular orbital symmetry, frontier orbitals of ethylene, 1,3-butadiene, 1,3,5-hexatriene, allyl system, FMO approach, pericyclic reactions, Woodward-Hoffman correlation diagram method and perturbation molecular orbital (PMO) approach for the explanation of pericyclic reactions under thermal and photochemical conditions. Simple cases of Norrish type-I and type-II reactions. Conrotatory and disrotatory motions of (4n) and (4n+2) polyenes with emphasis on [2+2] and [4+2] cycloadditions, sigmatropic rearrangements- shift of H and carbon moieties, Claisen, Cope, Sommerlet-Hauser rearrangement.

B6. Spectroscopic methods of analysis:

Infrared spectroscopy: Characteristic frequencies of organic molecules and interpretation of spectra. Modes of molecular vibrations, characteristic stretching frequencies of O-H, N-H, C-H, C-D, C=C, C=N, C=O functions; factors affecting stretching frequencies. Ultraviolet spectroscopy: Chromophores, auxochromes. Electronic transitions (σ−σ*, n-σ*, π-π* and n-π*), relative positions of λmax considering conjugative effect, steric effect, solvent effect, red shift (bathochromic shift), blue shift (hypsochromic shift), hyperchromic effect, hypochromic effect (typical examples). Woodward rules. Applications of UV spectroscopy to conjugated dienes, trienes, unsaturated carbonyl compounds and aromatic compounds. Nuclear Magnetic Resonance Spectrometry: (Proton and Carbon-13 NMR) Nuclear spin, NMR active nuclei, principle of proton magnetic resonance, equivalent and non-equivalent protons. Measurement of spectra, the chemical shift, shielding / deshielding of protons, upfield and downfield shifts, intensity of NMR signals and integration factors affecting the chemical shifts: spin-spin coupling to 13C IHIH first order coupling: some simple IHIH splitting patterns: the magnitude of IHIH coupling constants, diamagnetic anisotropy. Mass spectrometry: Basic Principles, the mass spectrometer, isotope abundances; the molecular ion, metastable ions. McLafferty rearrangement.