Syllabus (CHEMISTRY)

Course Type: MAJ-9

Semester: 6

Course Code: BCEMMAJ09C

Course Title: Physical Chemistry – III

(L-P-Tu): 4-2-0

Credit: 6

Practical/Theory: Combined

Course Objective: Course Objective and Learning Outcome of Major 9: The syllabus of Major 9 has been designed to make the students learn the most modern aspects of Physical Chemistry, such as Quantum Mechanics, Molecular Spectroscopy, Photochemistry, Symmetry and Group The

Learning Outcome: Course Outcomes of Major-9: CO - 9.1: This module will be helpful in understanding the Fundamentals of Quantum Mechanics, which include the Postulates of Quantum Mechanics, the Concept of Wave Function, the Probabilistic Nature of Quantum Particles, and e

THEORY:

FOUNDATION OF QUANTUM MECHANICS: (16 L)

Beginning of Quantum Mechanics: Wave-particle duality, light as particles: photoelectric and Compton effects; electrons as waves and the de Broglie hypothesis; Uncertainty relations (without proof).

1. Wave function: Schrodinger time-independent equation; nature of the equation, acceptability conditions imposed on the wave functions and probability interpretations of wave function.

2. Concept of Operators: Elementary concepts of operators, eigenfunctions and eigenvalues; Linear operators; Commutation of operators, commutator and uncertainty relation; Expectation value; Hermitian operator; Postulates of Quantum Mechanics.

3. Particle in a box: Setting up of Schrodinger equation for one-dimensional box and its solution; Comparison with free particle eigenfunctions and eigenvalues. Properties of PB wave functions (normalisation, orthogonality, probability distribution); Expectation values of x, x2, px and px2 and their significance in relation to the uncertainty principle; Extension of the problem to two and three dimensions and the concept of degenerate energy levels.

4. Simple Harmonic Oscillator: setting up of the Schrodinger stationary equation, energy expression (without derivation), expression of wave function for n = 0 and n = 1 (without derivation) and their characteristic features.

5. Hydrogen atom problem, Schrodinger Equation, Concept of Quantum Numbers, Radial Distribution Function, Shape of orbitals, Concept of Angular Momentum and Spin Angular Momentum, Ground State Term Symbols.

MOLECULAR SPECTROSCOPY: (15 L)

1. Interaction of electromagnetic radiation with molecules and various types of spectra; Born-Oppenheimer approximation.

2. Rotation spectroscopy: Selection rules, intensities of spectral lines, determination of bond lengths of diatomic and linear triatomic molecules, isotopic substitution.

3. 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; Diatomic vibrating rotator, P, Q, R branches.

4. Raman spectroscopy: Qualitative treatment of Rotational Raman effect; Effect of nuclear spin, Vibrational Raman spectra, Stokes and anti-Stokes lines; their intensity difference, rule of mutual exclusion.

PHOTOCHEMISTRY: (10 L)

1. Lambert-Beer’s law: Characteristics of electromagnetic radiation, Lambert-Beer’s law and its limitations, physical significance of absorption coefficients; Laws of photochemistry, Stark-Einstein law of photochemical equivalence quantum yield, actinometry, examples of low and high quantum yields.

2. Photochemical Processes: Potential energy curves (diatomic molecules), Frank- Condon principle and vibrational structure of electronic spectra; Bond dissociation and principle of determination of dissociation energy (ground state); Decay of excited states by radiative and non-radiative paths; Predissociation; Fluorescence and phosphorescence, Jablonskii diagram.

3. Rate of Photochemical processes: Photochemical equilibrium and the differential rate of photochemical reactions, Photostationary state; HI decomposition, H2-Br2 reaction, dimerisation of anthracene; photosensitized reactions, quenching; Role of photochemical reactions in biochemical processes, photostationary states, chemiluminescence.

Symmetry and group theory- I: (10 L):

Point symmetry operations, groups and group multiplication tables, similarity transformation and conjugate classes, identification of point groups and stereographic projection, representation of symmetry operators and groups; characters of symmetry operators in a representation, invariance of character under similarity transformation, symmetry elements and symmetry operations of the Platonic solids.

Chemical Kinetics-II: (9 L)

Role of T and theories of reaction rate: Temperature dependence of rate constant; Arrhenius equation, energy of activation; Rate-determining step and steady-state approximation – explanation with suitable examples; Collision theory; Lindemann theory of unimolecular reaction; outline of Transition State theory (classical treatment).

READING REFERENCES:

1. Atkins, P. W. & Paula, J. de Atkins’ Physical Chemistry, Oxford University Press
2. Castellan, G. W. Physical Chemistry, Narosa
3. McQuarrie, D. A. & Simons, J. D. Physical Chemistry: A Molecular Approach, Viva Press
4. Levine, I. N. Physical Chemistry, Tata McGraw-Hill
5. Laidler, K. J. Chemical Kinetics, Pearson
6. Levine, I. N. Quantum Chemistry, PHI
7. Atkins, P. W. Molecular Quantum Mechanics, Oxford
8. Banwell, C. N. and McCash, E.M. Fundamentals of Molecular Spectroscopy, Edn. 4th, Tata McGraw-Hill, New Delhi.
9. Atomic and Molecular Spectroscopy: Basic Concepts and Applications, Rita Kakkar Cambridge University Press, 2015.
10. Moore, W. J. Physical Chemistry, Orient Longman.
11. Glasstone, S. & Lewis, G.N. Elements of Physical Chemistry
12. Bera, N. K., Ghosh, S., Ghosh, P., Vol-II, Physical Chemistry Concepts & Models, Techno World, Kolkata.
13. Rakshit, P.C., Physical Chemistry Sarat Book House.
14. Mortimer, R. G. Physical Chemistry, Elsevier.
15. Engel, T. & Reid, P. Physical Chemistry, Pearson.
16. Rastogi, R. P. & Misra, R.R. An Introduction to Chemical Thermodynamics, Vikas.
17. Ashish Kumar Nag, Physical Chemistry (Vol-I & II), McGraw Hill Education (India) Pvt. Ltd.
18. K. L. Kapoor, A Textbook of Physical Chemistry, Vol-I to Vol-V, Macmillan Publishers India Ltd. 2004.
19. Ghoshal, A. Numerical Problems on Physical Chemistry, Books & Allied Pvt. Ltd. Kolkata.
20. Klotz, I.M., Rosenberg, R. M. Chemical Thermodynamics:Basic Concepts and Methods Wiley.
21. F. A. Cotton, Chemical Applications of Group Theory, 3rd Edn Reprint, John Wiley and Sons.
22. L. Pauling and E. B. Wilson, Introduction to Quantum Mechanics, McGraw-Hill, 1939.
23. H. Eyring, J. Walter and G. F. Kimball, Quantum Chemistry, Wiley, New York, 1944.

PRACTICALS:

1. Verification of Beer and Lambert’s Law for KMnO₄.

2. Verification of Beer and Lambert’s Law for K₂Cr₂O₇.

3. Study of kinetics of K₂S₂O₈ + KI reaction, spectrophotometrically.

REFERENCES FOR PRACTICALS:

1. University Hand Book of Undergraduate Chemistry Experiments, edited by Mukherjee, G. N., University of Calcutta.
2. Levitt, B. P. edited Findlay’s Practical Physical Chemistry Longman Group Ltd.
3. Gurtu, J. N., Kapoor, R., Advanced Experimental Chemistry S. Chand & Co. Ltd.
4. Saharay, S. K. &Basu, A. S. A Guide to Practical Physical Chemistry, University of Burdwan.
5. Viswanathan, B., Raghavan, P.S. Practical Physical Chemistry Viva Books (2009).
6. Mendham, J., A. I. Vogel’s Quantitative Chemical Analysis 6th Ed., Pearson

7. Harris, D. C. Quantitative Chemical Analysis. 6th Ed., Freeman (2007).