Himachal Pradesh Public Service Commission, known commonly as HPPSC, is a government agency and topmost constitutional body of Government of Himachal Pradesh. Here is a detailed syllabus for HPAS Main Exam Optional Paper CHEMISTRY.
Optional Paper – CHEMISTRY
PAPER-I
- Quantum mechanics: Plank's hypothesis of quantization of energy. Implications of Plank' hypothesis for black - body radiation, heat capacities of solids, photoelectric effect. wave - particle duality and Heisenberg uncertainty principle. The wave function, information in a wave function, normalization of wave function. Eign values and eign functions. Operators, postulates of quantum mechanics (principals and introduction). Schrodinger wave equation for free particle and particle in one dimension and three dimension box. Schrodinger wave equation for hydrogen atom, radial and probability wave function.
- Chemical bonding: Ionic bond, characteristics of ionic compounds, factors affecting stability of ionic compounds, lattice energy, Born-Haber cycle; covalent bond and its general characteristics, polarities of bonds in molecules and their dipole moments Valence bond theory, concept of resonance and resonance energy. Molecular orbital theory, (LCAO method); bonding in homonuclear molecules: H2+, H2 to Ne2, NO, CO, HF, CN, BeH2 and CO2. Comparison of valence bond and molecular orbital theories, bond order, bond strength and bond length.
- Molecular spectroscopy: Rotational spectrum of rigid diatomic molecule, vibrational spectrum of simple harmonic oscillator, effect of isotopic substitution. Raman spectroscopy, stokes' and anti - stokes'Raman lines, and Raman shifts. Introduction and principle of resonance spectroscopy (nuclear magnetic, electron spin resonance techniques).
- States of matter:
- Gaseous State: Maxwell's law of velocity distribution among gas molecules. Equi partition of energy. Equations of state for ideal and real gases. Vander Walls and Virial equations of state, critical phenomena, principle of corresponding state, equation of reduced state.
- Liquefaction of gases, collision between gas molecules and mean free path. Solid State:
- Types of solids, law of constancy of interfacial angles. Crystal and their classification.
- Crystal lattice and unit cells. Imperfection in crystals. Laws of rational indices. Bragg's law of X-ray diffraction by crystals. Properties of solids: electrical, magnetic and thermal (only qualitative interpretation).
- Thermodynamics and statistical thermodynamics:
- First law of thermodynamics: Thermodynamic systems, states and processes, work heat and internal energy. Different types of work done on a system in reversible and irreversible processes. Calorimetry and thermochemistry. Enthalpy dependence on temperature in physical and chemical processes. Joule - Thomson effect and inversion temperature. Heat capacities of gases. Second law of thermodynamics and its applications: Spontaneity of a process, entropy and entropy changes in various processes. Free energy functions and their significance. Relation between equilibrium constant and thermodynamic properties. Statistical Thermodynamics: Configuration and weights. Canonical and grand canonical ensemble The molecular partition function.
- Thermodynamic information in partition function.
- Phase equilibria and solutions:
- Equilibrium between liquids solids and vapours of a pure substance. Clausius-Clapeyron equation and its applications. Phase rule and its applications for simple one component (water and sulfur) and two components (lead - silver, salt hydrates) systems. Raoult's and Henry's laws, fractional steam distillation. Phase diagram for partially miscible liquids. Partial molar quantities and their determination. Distribution law its modifications, limitations and applications.
- Chemical kinetics: Rates of chemical reactions and their dependence on the concentration of the reactants.
- Photochemistry
- Colloids, surface phenomenon and catalysis
- Bio-Inorganic chemistry
- Coordination chemistry
- General chemistry of ‘f’ block elements
- Non-Aqueous Solvents
PAPER-II
- Delocalized covalent bonding:
Conjugation, Cross conjugation, Hyperconjugation, Bonding in fullerenes, Tautomerism, Aromaticity in benzenoid and non-bezenoid compounds, Anti-aromaticity, Homoaromaticity, PMO approach; Bonds weaker than covalent, Crown ethers complexes, Cryptands, Inclusion compounds, Cyclodextrins, Catanenes and Rotaxenes.
- Reaction mechanisms:
(a) Kinetic and thermodynamic requirements and control of organic reactions, potential energy diagrams, Hammet equation and linear free energy relationship, Taft equation, Methods (both kinetic and non-kinetic) of study of mechanism of organic reactions illustrated by examples–use of isotopes, cross-over experiment, intermediate trapping and stereochemistry.
(b) Reactive intermediates: Generation, geometry, stability and reactions of carbonium ions, carbanions, free radicals, carbenes, benzynes and nitrenes.
(c) Catalysis in Organic Chemistry: Mechanisms and applications of enzymatic catalysis, micellar catalysis and phase transfer catalysis.
(d) Substitution reactions: SN1, SN2, SNi, and SET mechanisms, Neighbouring group participation and anchimeric resistance, Classical and non-classical carbonium ions, Nucleophilic reactions at an allylic and vinyl carbon, Structure and reactivity relationship in substitution reactions, Ambident nucleophile, and Regioselectivity.
(e) Elimination reactions: E1, E2, E2C and E1CB mechanisms, Spectrum of mechanisms, Effect of substrate structure on reactivity, Orientation in E2 reactions–Saytzeff and Hoffmann; Mechanism and examples of syn elimination, Mechanism of pyrolytic elimination in vapour phase, Structure and reactivity relationship in elimination reactions.
(f) Addition reactions: Electrophilic and nucleophilic addition to C=C and CC, nucleophilic addition to C=O, C=N, Conjugated olefins and carbonyls, Structure and reactivity relationship, Hydrogenation of double and triple bonds, Asymmetric synthesis, Sharpless epoxidation.
(g) Rearrangements: Pinacol-pinacolone, Demjanov ring expansion, Hoffmann, Schmidt, Lossen, Beckmann, Baeyer–Villiger, Favorskii, Fries, Claisen, Cope, Stevens, Wolf and Wagner-Meerwein rearrangements.
- Pericyclic reactions:
Classification, Conservation of orbital symmetry, Woodward-Hoffmann rules— electrocyclic and cycloaddition reactions [2+2 and 4+2] and sigmatropic shifts [1, 3; 3, 3 and 1, 5], FMO and PMO approach.
- Chemistry and mechanism of following reactions: Aldol condensation (including directed aldol condensation), Claisen condensation, Dieckmann, Knoevenagel, Perkin, Witting, Clemmensen, Wolff-Kishner, Cannizzaro and Von Richter reactions; Stobbe, Benzoin and acyloin condensations; Fischer indole and Skraup synthesis, Bischler-Napieralski, Sandmeyer, Reimer-Tiemann and Reformatsky reactions.
- Polymers
- Synthetic uses of reagents
- Photochemistry
- Principles of spectroscopy and applications in structure elucidation:
- Modern Concept in Chemistry
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