Uttar Pradesh Combined State / Upper Subordinate Services (UPPCS) Mains Optional Subject Exam Syllabus "Chemistry"

:: PAPER - I ::

Atomic Structure: de Broglie equation, Heisenberg's uncertainty principle, quantum mechanical operators and the Schrodinger wave equation, physical significance of wave function and its characteristics (normalized orthogonal), radial distribution and shapes of s.p. & d orbitals, particle in one-dimensional box, quantization of electronic energies (qualitative treatment of hydrogen atom), Pauli's Exclusion principle. Hund's rule of maximum multiplicity. Aufbau principle, electronic configuration of atoms, Long form of periodic table including translawrencium elements. Periodicity in properties of the elements such as atomic and ionic ionization potential, electron affinity, eletronegativity and hydration energy.

Nuclear and Radiation Chemistry: nuclear forces, nuclear stability, N/P ratio, nuclear binding energy, Artificial transmutation of elements and nuclear reactions, nuclear fission & fusion, Kinetics of radioactive decay, radioactive isotopes and their applications. Radio carbon dating. Elementary ideas of radiation chemistry.

Chemical Bonding: Valence bond theory (Heitler-London and Pauling- Slater theories), hybridization, VSEPR theory and molecular orbital energy level diagrams for homo and hetero nuclear diatomic molecules, bond order, bond length and bond strength, sigma and pi bonds, hydrogen bond, characteristics of ionic compounds, Lattice energy, born-haber cycle, Characteristics of covalent bond.

Chemistry of s- and p-Block Elements: General properties of s-and p- Block elements, chemical reactivity of elements and group trends. Chemical behaviour with respect of their hydrides, halides and oxides.

Chemistry of Transition Elements: General Characteristics, variable oxidation states, complex formation, colour, magnetic and catalytic properties, Comparative study of 4d and 5d transition elements with 3d analogues with respect to their ionic radii, oxidation states and magnetic properties.

Chemistry of Lanthanides andActinides: Lanthanides contraction, oxidation states, Principles of separation of lanthanides and actinides. Magnetic and spectral properties of their compounds.

Coordination Chemistry: Werner's Theory of coordination compounds. IUPAC system of nomenclature, effective atomic number (EAN), Isomerism in coordination compounds. Valence bond theory and its limitations. Crystal field theory. Crystal field splitting of dorbitals in octahedral, tetrahedral and square planar complexes. Δ Value and factors affecting its magnitude, calculation of Crystal field stabilization energies (CFSE) for d1 to d9 weak and strong field. Octahedral complexes, spectrochemical series electronic spectra of d transition metal complexes, types of electronic transitions, selection rules for electronic transitions.

Bio-Inorganic Chemistry: Essential and trace elements in biological processes, Metalloporphyrins with special reference to haemoglobin and myoglobin, Biological role of alkali and alkaline earth metal ions with special reference to calcium ion.

Preparation, Properties and Uses of the following Inorganic Compounds: Heavy Water, Boric acid, diborance, hydrazine, hydroxylamine, potassium dichromate, potassium permanganate, Ce (IV) sulphate and titanium (III) sulphate.

Polymers: Molecular weight of polymers by sedimentation, light scattering viscosity and osmotic pressure methods, Number average and weight average molecular weights, elasticity and crystallinity of polymers, Borazines: Silicons and phosphonitrillic halide polymers.

Chemical Thermodynamics: Thermodynamic functions, first and second Laws of thermodynamics, heats of formation neutralization and combustion, Hess's Law of heat summation, variation of entropy with change of temperature, pressure and volume, GibbsHelmholtz equation, criteria of equlibirium and spontaneity, application of thermodynamics to various physico- chemical processes, concept of chemical potential Gibbs-Duhem

equation. Classius-Clapeyron equation. Thermodynamic treatment of colligative properties of dilute solutions.

Chemical Kinetics: Order and molecularity of reaction, Rate constant and specific rate constant, zero-order, first order and second order reactions, half life period. Methods for determining the order of a reaction, temperature coefficient,Arrhenius equation, Energy of activation, Collision theory of reaction rate. Steady state approximations. Transition state theory of reaction rates, kinetics of side, reversible and consecutive reactions.

Phase Equilibria: Phase, Components, degrees of freedom, phase diagram of one component (water and sulphur) and two component (Pb-Ag) systems, Nernst's distribution law,Applications of distribution law:

Electrochemistry: Theory of strong electrolytes, Debye-Huckel theory of activity coefficient laws of electrolytic conduction, transport number and its determination by Hittorf's method and moving boundary method. Electrodes and Electrode potential, Hydrogen electrode, Calomel electrode. E-M-F of galvanic cells, concentration cells with and without transference, liquid junction potential and fuel cell.

Solid State Chemistry: Elements of symmetry in crystals, space lattice and unit cell. The close packing of sphares, hexagonal close packing, cubic close packing and body centered cubic packing, co-ordination number and redus ratio effect. Bragg's law of X-ray diffraction, powder pattern method of crystalline structure of NaCl, KCl and ZnS.

Surface Chemistry: Coagulation, Hardy-Schulze Rule, Stability of colloids and origin of charge on colloids, Electrokinetic potential, adsorption, Various types of adsorption isotherms, catalysis, enzyme catalysis (Michelis-Menten equation).

Spectra: Raman Spectra: Raman effect, stokes and antistokes lines and their intensity difference. Rule of mutual exclusion. Electronic Spectra, Electronic transitions, Frank condom Principle, Phosphorescene and fluorescence.

Equilibrium: Equilbrium in physical and chemical process, dynamic nature of equilibrium, law of chemical equilibrium, equilibrium constant, factors affecting equilibrium, Lechatelier's principle, strong and weak electrolytes, common ion effect, ionization of polybasic acids, acid strength, concept of pH and hydrolysis of salts, buffer solutions, Henderson's equation, solubility and solubility product of sparingly soluble salts.

:: PAPER - II ::

1. General Organic Chemistry

Hyperconjugation, Delocalisation and their applications, Electrophiles, Nucleophiles, Hydrogen Bonding, andAromaticity andAntiaromaticity.

2. Reaction Mechanism:

(i) General methods of study of mechanism of organic reactions: Kinetic Isotope effect, Crossover Experiment, Intermediate trapping, and Thermodynamic vs Kinetic control of reactions.

(ii) Reactive Intermediates: Generation, geometry, nature, (electrophilic or nucleophilic character), reactions and stability of carbocations, carbanions, free radicals, carbenes and benzynes.

(iii)Addition Reactions: Electrophilic addition to carbon- Carbon double bond with bromine and carbenes, hydroboration-Oxidation, oxymercuration- demercuration, addition of peracids (formation of oxiranes) and iodolactonisation.

1,2 and 1,4 addition of conjugated diene with bromine, free radical addition of HBr. Nucleophilic addition to carbonyl group with carbon, oxygen, sulphur and nitrogen nucleophiles.

(iv) Elimination Reactions: E1, E2 and E1 cb reaction mechanism, orientation in E2 reaction (Saytzeff and Hofmann), Cope elimination.

(v) Substitution Reactions:

(a) SN1, SN2 mechanism

(b) Electrophilic aromatic substitution reactions: orientation and reactivity in monosubstituted benzenes.

3. Reactions and Rearrangements:

(i) Reactions: Aldol condensation, Claisen condensation, Knoevenagel reaction, Witting reaction, Michael addition, Mannich reaction, Perkin reaction, Riemer- tiemann reaction, Cannizzaro reaction and Benzoin condensation.

(ii) Rearrangements: Pinacol-Pinacolone, Hoffman, Beckmann, Curtius rearrangements and Rearrangement given by carbocations.

4. Stereochemistry:

Optical activity due to chiral centre, R-S nomenclature of compounds having chiral centre (one or two chiral centres). Properties of enantiomers and diastereomers, Separation of racemic mixture using chemical method.

Geometrical isomerism: E-Z nomenclature, Conformation of open-chain compounds (n-butane, 2-fluoroethanol, 1,2-ethanediol, 1,2- difluoroethane) Cyclohexane and monosubstituted and disubstituted cyclohexanes.

5. Spectroscopy

(IUV Spectroscopy: Types of electronic transitions, chromophore, auxochrome, bathochromic and hypsochromic shift, Woodward-Fieser rule for the calculation of max ʎ conjugated polyenes and carbonyl compounds.

(ii)Infra-red Specroscopy: Factors affecting vibrational frequencies.

(iii) 1HNMR Spectroscopy: Basic principles, chemical shift, spin-spin interaction and coupling constant.

Problems based on UV, IR and 1HNMR Spectroscopy of simple organic compounds.

6. Organic Polymers:

Mechanism of polymerization, Polymers of industrial importance (Polyamides, Polyesters, Orlon, PVC, Teflon, SBR, NBR).

7. Carbohydrates

Chemistry of Monosaccharides (Glucose and Fructose), Ring structure of glucose and fructose, Mutarotation, Epimerisation, Amadori rearrangement, Disaccharides (Maltose and Sucrose).

8. Pericyclic Reactions

Classification and examples, Woodward-Hoffmann Rule, Electrocyclic Reactions and Cycloaddition reactions ([2+2] and [4+2] cycloaddition reaction)

9. Heterocyclic Compounds :

Preparations,Aromaticity and Reactions of Pyrrole, Furan and Thiophene.

10. Environmental Chemistry

Air pollutants and their toxic effects, Depletion of Ozone layer, Oxides of nitrogen, Fluorocarbons and their effect on ozone layer, Greenhouse effect, Acid rain.