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ACH 2C 08 SEMESTER II PHYSICAL CHEMISTRY II (3 Credits)

UNIT I Statistical Thermodynamics I
Basic principle, Permutations. Probability distribution of particles in energy states.
Ensembles Micro states and macro states. Statistical weight. Most probable distribution.
Thermodynamic probability and entropy. Maxwell-Boltzmann distribution law of energy
for a system of distinguishable and indistinguishable particles. The partition function and
its relation to the thermodynamics functions.
Factorization of the partition function in to the translational, rotational, vibrational and
electronic parts. Evaluation of the thermodynamic functions and equilibrium constants
using partition functions. The perfect gas-ideal monatomic and diatomic gases. Sackur-
Tetrode equation. Heat capacity of gases. Classical and quantum theories. The
anomalous heat capacity of hydrogen. Ortho and para hydrogen.

UNIT II Statistical Thermodynamics II
(a) The atomic crystal – Einstein theory of atomic crystals, Debyes modification of
Einsteins model. (b) Imperfect gases, the virial expressions and the virial coefficients,
relation between the virial coefficients and the cluster integrals.
Need for Quantum statistics-The ideal Fermi Gas. Fermi-Dirac distribution law. Gas
Degeneracy. Application to electrons in metals. The ideal Bose gas. Bose-Einstein
distribution law. Gas Degeneracy. Bose-Einstein condensation. Application to liquid
helium. Comparison of the three statistics.

UNIT III Solid State Chemistry
Theories of solid-free electron, MO band and zone theories. Classification of solids in to
conductor, semiconductors and insulators. Preparation, properties and industrialimportance of Semi conductors, Imperfections of solids, Point, line and plane defects and
electrons and holes. New materials-zeolites, fullerines, conducting polymers.
Imperfection and Physical properties of solids (Brief survey). Electrical properties-
Electrical conductivity, Hall effect, dielectric properties, piezoelectricity, Ferro electricity
and conductivity. Super conductivity-Type I and Type II superconductors, High T
materials. Meisener effect, brief discussion of Cooper theory of superconductivity.
Optical properties-Photoconductivity, luminescence, colour centers, laser, refraction,
birefringence, Magnetic properties-diamagnetism, Para magnetism, ferromagnetism,
antiferromagnetism. Thermal properties-thermal conductivity and specific heat.
Mechanical properties: Strength of real crystals as compared with an ideal crystal,
different strengthening mechanisms.

UNIT IV Photochemistry
Physical photochemistry: laws of Photochemistry, quantum yield and its determination.
Effect of temperature, wavelength and intensity of radiation on photochemical reaction.
Different types of photochemical reactions. Kinetics of photochemical chain reactions.
H2-Br2 reaction H2Cl reaction, polymerization, photosensitization, photo stationary states.
Photolysis ammonia. Excimers and Exciplexes. Photosensitization by Hg. Photophysical
phenomena. Radiative and non-radiative transitions. Jablonski diagram.
Fluorescence: quantum efficiency of fluorescence, Stern-Volmer equation; delayed
fluorescence. E-type and P-type phosphorescence. Luminescence, chemiluminescences
and thermo luminescence. Chemistry of photography. Principle of utilization of solar
energy. Solar cells: Different types, working and applications (brief mention only)

UNIT V Spectroscopy
(i) General Theory of Spectra: Electromagnetic radiation and its different regions,
Interaction of matter with radiation and its effect on the energy of the molecule. Origin
of molecular spectra, Theory of the origin of rotational, vibrational and electronic spectra.
Intensity of spectral lines, Dependence of intensity on population, transition probabilities,
Transition moment integral, Selection rules. Line widths, Doppler broadening, Lifetime
broadening.
(ii)Microwave spectroscopy: Rotation spectra of diatomic and poly atomic molecules,
Rigid and non rigid rotator models, Asymmetric, symmetric and spherical tops. Isotope
effect on rotation spectra, Stark effect, Nuclear and electron spin interactions. Rotational
transitions and selection rules. Microwave spectrometer -Principles - Instrumentation
(brief mention only). Applications.
(iii)Vibrational spectroscopy: Vibrational spectra of diatomic and poly atomic
molecules, Harmonic oscillator model, Anharmonicity. Vibrational transitions and
selection rules. Morse potential, Fundamentals, Overtones, Hot bands, Combination
hands, Difference bands.
Vibrational spectra of diatomic and polyatomic molecules, P, Q, R branches. IR and
FTIR spectrophotometer - Principles - Instrumentation (brief mention only),
Applications.
(iv)Raman Spectroscopy: Pure rational, pure vibrational Raman spectra, Vibrationalrotational
Raman spectra, Selection rules, Mutual exclusion principle. Raman
spectrophotometer - Principles - Instrumentation (brief mention only) Laser Raman
spectroscopy, Applications.
(v) Electronic Spectroscopy: Basic principles, Beet-Lambert Law, Molar extinction
coefficient, intensity of electronic transitions. Types of electronic transitions. Franck-
Condon principle, Ground and excited electronic states of diatomic molecules.
Electronic spectra of polyatomic molecules,. Chromphores. The fate of electronically
excited state species - Vibrational relaxation, External conversion, Internal conversion,
Fluorescence, Phosphorescence, Jablonski diagram. Electronic spectra of conjugated
molecules - Dissociation and predissociation spectra.UV-Visible spectrophotometer - Principles - Instrumentation (brief mention only).
Applications.

UNIT VI Resonance Spectroscopy
(i) NMR Spectroscopy: Magnetic properties of nuclie, Theory and measurement techniques,
Solvents used, Chemical shift and factors influencing chemical shift, Shielding effects,
Spin-Spin interaction coupling constant, factors influencing coupling constant, Effects of
chemical exchange, Fluxional molecules, Hindered rotation on NMR spectrum, Karl's
relationships, NMR spectrometer - Principles and instrumentation (brief mention
only).Applications of NMR spectroscopy to structure elucidation of simple organic and
inorganic molecules .FTNMR.
(ii) ESR Spectroscopy: Theory and measurement techniques, hyperfine interactions,
Equivalent and nonequivalent protons, Kramer's theorem. ESR