Syllabus of Combined Geo-Scientist (Main) Examination

Stage-II (Descriptive Type)

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.