### CHEM242 Physical Chemistry I

Course Description:

This course will explore the application of quantum mechanics to understanding chemical phenomena, with special emphasis on atomic structure and properties. The postulates of quantum mechanics will be introduced and applied to simple systems. Examination of the simple, yet practically useful, harmonic oscillator and rigid rotor systems will lead into discussion of hydrogenic atoms and hybridization.

Intended Outcomes for the course:

• Apply the postulates of quantum mechanics to simple systems of chemical interest, such as the particle-in-a-box, harmonic oscillator, rigid rotor, hydrogenic atoms, hybrid orbitals.

• Students shall be able to visualize atomic orbitals of hydrogenic atoms

• Shall have ability to solve introductory problems in quantum mechanics

• Shall have ability to identify various molecular symmetry elements and their operations and construct group multiplication table and character table.

Course Content:

Unit I: Blackbody radiation - photoelectric effect - Hydrogen emission and Rydberg formula - Louis de Broglie postulate - Bohr theory - Heisenberg Uncertainty

Unit II: Classical wave equation - oscillating string - superposition of normal modes - vibrating membrane - Schrodinger equation and particle in a box – - Eigen values - quantized energy values and quantum number - uncertainty principle - probabilistic interpretation of wave function - free particles – particle in rectangular well – tunnelling

Unit III: Postulates and General principles in quantum mechanics - properties of operators, Eigen functions, Eigen values, normalization, orthogonality, commuting and non-commuting operators

Unit IV: Solution to Harmonic Oscillator - solution to rigid rotor - solution to hydrogen atom - quantum numbers - atomic orbitals - Hybrid atomic orbitals - construction and visualization of hybrid atomic orbitals - sp, sp2, sp3, dsp2, dsp3, d2sp3 - shape and directional behaviour

Unit V: Symmetry elements and Operations, point groups, non-degenerate representations

Textbook:

Physical Chemistry, A molecular approach, Donald A McQuarrie and John D Simon, 1998, Viva Books Limited

For Unit 5: Molecular symmetry and Group Theory, A programmed introduction to chemical applications, Alan Vincent, 2ed, John Wiley, 2001

### CHEM546 Electroanalytical Techniques

Unit I (Kinetics of Electrode Reactions): Mass transfer by Diffusion and Migration – models of electrode reactions – current potential characteristics – general mass transfer equation , migration and diffusion

Unit II (Potential Step Methods): Types of techniques, step under diffusion control, Ilkovic equation – polarographic analysis – sampled current voltammetry: reversible, irreversible processes, multicomponent systems

Unit III (Chrono Methods): Chronoamperometry, chrono coulometry – pulse polarographic methods: Tast pulse, normal pulse, differential pulse

Unit IV (Potential Sweep Methods): Cyclic Voltammetry: Nernstian reversible, totally irreversible, quasi-reversible processes, multicomponent systems – convolute or semi-integral techniques

Unit V (Bulk Electrolysis Techniques): Classification of methods – Controlled Potential methods: current – time behaviour, electrogravimetry, electro-separation – Coulometric measurements: controlled current methods: characteristics, coulometric methods – Electrometric end point detection: classification, potentiometric, amperometry methods.

### CHEM444 Statistical Thermodynamics & Reaction Dynamics

*Unit I (Equilibrium Thermodynamics –Review)*Review of equilibrium thermodynamics. First law, second law, third law of thermodynamics, chemical equilibrium, equilibrium electrochemistry. Students are expected to work numerical problems and read themselves.

*Unit II (Statistical Thermodynamics – Partition function and implications)*Probability, Bose-Einstein, Fermi-Dirac, Boltzmann statistics and distribution and sterling’s approximation, Partition function and thermodynamic properties - Partition function- translational, rotational, vibrational, electronic,- entropy, energy and heat capacity – heat capacity of solids – equilibrium constant

*Unit III (Non-equilibrium Thermodynamics)*Entropy production, flux-force relationship, Onsager reciprocal relationship, electrochemical potential, steady state entropy

*Unit IV (Reaction Dynamics)*Potential energy surfaces-electronically excited molecules, bimolecular collisions, Molecular beam Scattering, statistical approach of reaction dynamics to transition state theory, unimolecular reaction dynamics, transition state theory of solution reactions, kramers’s theory,

*Unit V (Electrode Kinetics)*Electrical double layer, Aspects of electrochemical reactions, elucidation of mechanism of an electrode reaction