SPECTROSCOPY AND STATISTICAL THERMODYNAMICS

Paper Code: 
CHY 613
Credits: 
3
Contact Hours: 
45.00
Max. Marks: 
100.00
Objective: 

Course Objective(s):

This course will enable the students to –

  • understand the basis of molecular spectroscopy and its applications.
  • acquaint the students with the fundamentals of statistical thermodynamics and its applications in calculating thermodynamic properties.

Course Outcomes (COs):

Course Outcomes

 

Teaching Learning Strategies

Assessment

Strategies

The students will be able to:

CO167: discuss qualitative and quantitative knowledge of the fundamental concepts of spectroscopy.

CO168: describe principle, selection rules and applications of rotational, vibrational, Raman and  electronic  spectroscopy.

CO169: analyse spectroscopic data for molecular characterization.

CO170:  select suitable statistics for a particular system.

CO171: formulate thermodynamic properties in terms of partition function and their exact values for an ideal gas.

  • Interactive lectures
  • Tutorials
  • Multimedia presentations

 

  • Oral and written examinations (scheduled and surprise tests)
  • Closed book and open book tests
  • Quiz
  • Assignments
  • Presentation

 

 

9.00
Unit I: 
Basic Elements of Spectroscopy

Pre requisite- interaction of electromagnetic radiation with matter, characterization of electromagnetic radiation, quantisation of energy, regions of the spectrum, representation of spectra, basic elements of practical spectroscopy, signal-to-noise ratio – resolving power, line width – natural line broadening, Doppler broadening, Heisenberg uncertainty principle, intensity of spectral lines –transition probability, population of states, path length of sample, Born-Oppenheimer approximation, rotational, vibrational and electronic energy levels in molecules, transition moment, selection rules, Fourier Transform methods (IR and NMR)

 

9.00
Unit II: 
Rotational and Vibrational Spectroscopy

Rotational spectroscopy- diatomic molecule, energy levels of a rigid rotor (semi-classical principles), selection rules, intensities of spectral lines, determination of bond lengths of diatomic and linear triatomic molecules, qualitative description of non-rigid rotor, isotopic effect.
Vibrational spectroscopy- classical equation of vibration, computation of force constant, amplitude of diatomic molecular vibrations, anharmonicity, Morse potential, dissociation energies, fundamental frequencies, overtones, hot bands, degrees of freedom for polyatomic molecules, modes of vibration, concept of group frequencies, rotational-vibrational spectrum.

 

9.00
Unit III: 
Raman and Electronic Spectroscopy

Raman spectroscopy- concept of polarizability, pure rotational Raman and pure vibrational Raman spectra of diatomic molecules, selection rules, effect of nuclear spin.
Electronic spectroscopy- concept of potential energy curves for bonding and antibonding molecular orbitals, qualitative description of s, p and n molecular orbitals, electronic transitions, selection rules, Franck-Condon principle, Jablonski diagram, singlet and triplet states, fluorescence and phosphorescence, dissociation and predissociation.

9.00
Unit IV: 
Introduction to Statistical Thermodynamics

Introduction, quantum mechanical aspects, common terms- canonical ensemble, occupation number, statistical weight factor, configuration, phase space, macroscopic state, microscopic, state, system, assembly and ensemble, statistical equilibrium, Boltzmann distribution law, type of statistics, Bose-Einstein statistics, Fermi-Dirac statistics.

 

9.00
Unit V: 
Statistical Approach to Thermodynamics Properties

Partition function- molecular partition function for an ideal gas, translational partition function, rotational partition function, vibrational partition function, electronic partition function, nuclear partition function.
Calculation of thermodynamics properties in terms of partition function- internal energy, enthalpy, entropy, Helmholtz function, pressure, Gibbs functions, residual entropy, chemical potential, heat capacity of monoatomic gases.

 

Essential Readings: 
  • Fundamentals of Molecular Spectroscopy, Fourth Edition; C.N. Banwell & E. M. McCash.; Tata McGraw-Hill, New Delhi, 2017.
  • Spectroscopy; H.Kaur; Pragati Prakashan, 2017.
  • Text book of Physical Chemistry, Second Edition; H. K. Moudgil, PHI Learning Private Limited,  2015.

 

References: 

SUGGESTED READINGS:

  • Modern Spectroscopy, Fourth Edition; J. M. Hollas; John Wiley & Sons Ltd., 2003.
  • Statistical thermodynamics, Revised Second Edition; M.C Gupta; New Age International Pvt Ltd., New Delhi, 2013.
  • An Introduction to Chemical Thermodynamics, Sixth Revised Edition; R. P. Rastogi, R. R. Mishra; Vikas Publishing House, Private Limited, 2018.
  • Thermodynamics, Statistical Thermodynamics and Kinetics; T. Engel and P. Reid; Pearson Education, 2008.
  • A Textbook of Physical Chemistry, Dynamics of Chemical Reactions, Statistical Thermodynamics, Macromolecules and Irreversible Processes Volume V, Fourth Edition; K. L. Kapoor; McGraw Hill Education Private Limited, 2020.

e-RESOURCES:

 

Academic Year: