UPSC GE Chemistry Paper III Syllabus

There are two parts: Part A is Analytical Chemistry and Part B is Organic Chemistry.

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 interferences - spectroscopic 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 ¹H-¹H first order coupling: some simple ¹H-¹H splitting patterns: the magnitude of ¹H-¹H coupling constants, diamagnetic anisotropy.

Mass spectrometry: Basic Principles, the mass spectrometer, isotope abundances; the molecular ion, metastable ions. McLafferty rearrangement.