UPSC GE Chemistry Paper II Syllabus
Paper II contains Physical Chemistry. There are eight units: (1) Kinetic theory and the gaseous state (2) Solids (3) Chemical thermodynamics and chemical equilibrium (4) Chemical kinetics and catalysis (5) Electrochemistry (6) Quantum chemistry (7) Basic principles and applications of spectroscopy (8) Photochemistry.
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 nonradiative 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.