Course

Unit I

Chemical Thermodynamics
First and second laws of thermodynamics, thermodynamic functions, heat capacity, thermochemistry, need for second law of thermodynamics, entropy and free energy functions, calculation of changes in thermodynamic function for ideal and non-ideal gases in isothermal and adiabatic process, relation between thermodynamic functions – Maxwell relations, Joule Thomson effect, coefficient of thermal expansion and compressibility factor, applications of free energy function to physical and chemical changes, equilibrium in chemical reactions, third law of thermodynamics – need for third law, calculation of absolute entropy, unattainability of absolute zero, thermodynamic systems of variable composition – fugacity functions, partial molar quantities, thermodynamics of ideal solutions, real solutions and regular solutions, dilute solutions of nonelectrolytes, Henrys law, Raoults law, Gibbs-Duhem equations, Gibbs-Duhem-Margules equations, activity and standard states of non-electrolytes.

Unit II

Irreversible Thermodynamics
Examples for irreversible process, entropy production, non-equilibrium, steady state and near equilibrium conditions, linear relation, phenomenological coefficients, Onsager reciprocal relations, one component systems with heat and matter transport, application of irreversible thermodynamics to thermal diffusion, thermal osmosis etc., electro kinetic effects, the Glansdorf-Pregogine equation.

Unit III

Statistical Thermodynamics
Statistical concept, probability and thermodynamic states, entropy and probability, canonical ensemble, Maxwell-Boltzmann, Fermi-Dirac and Bose-Einstein Statistics, electron gas concept, Bose-Einstein condensation, relation among MB, FD & BE Statistics, partition function, partition function for free linear motion, free motion in a shared space, linear harmonic vibration, translational, rotational and vibrational partition function, molecular partition functions, partition functions and thermodynamic properties, calculation of equilibrium constant, heat capacity of gases, mono atomic solids, Einsteins and Debys theory.

Unit IV

Equilibrium
Gibbs free energy, direction of spontaneous change of a reaction, chemical potential, chemical potential and equilibrium, ?G in terms of K, equilibrium constants real gases and real reactions, equilibrium respond to catalyst, temperature, pressure and PH, application of ?G and K extraction of metals from their oxides, Ellingham diagram, and thermodynamics of ATP & respiration, biological energy conversion.

Unit V

Phase Equilibrium
Gibbs Phase rule, one component system, two component systems, vapour pressure diagrams and their interpretation, lever rule, temperature-composition diagrams, liquid-liquid phase diagrams, distillation of partially miscible liquids, azeotropes, liquid-solid phase diagrams, phase diagram for the system Na/K/Na2K, phase diagram – steel, alloys, Fe-C system, zone refining, three component system, triangular coordinates, three component system partially miscible liquids – H2O/CHCl3/CH3COOH, phase diagram – NH4Cl/(NH4)2SO4/H2O

• CO01: Apply the laws of thermodynamics to elucidate thermodynamic properties of real/ideal gas behavior, fugacity, partial molar quantities and solution thermodynamics to explain physical and chemical equilibrium.
• CO02 Understand the basics of mathematical operations involved in statistical thermodynamics
• CO03 Apply entropy of mixing and partition functions to treat thermodynamics systems
• CO04 Achieve comprehensive knowledge on irreversible thermodynamics and apply this for different thermodynamic phenomena
• CO05: Explain non-equilibrium processes using concepts of entropy production, steady-state conditions, linear phenomenological laws, and Onsager reciprocal relations, and interpret transport phenomena such as thermal diffusion, thermal osmosis and electrokinetic effects.

Textbooks

1. Robert J. Silbey, Robert A. Alberty, Moungi G. Bawendi, Physical Chemistry 4^thEdition, Wiley, 2004
2. Samuel H. Maron, Carl F. Prutton, Principles of Physical Chemistry, The Macmillan Company; 4^thedition (1970)
3. Samuel Glasstone, ‘Thermodynamics for Chemists’, Lightning Source Incorporated, 2007.

References

1. Francis Weston Sears and Gerhard L. Salinger, ‘Thermodynamics, kinetic theory and statistical thermodynamics’ 3^rdedition,  Addison – Wesley Publications, 1975.
2. Prigogine, ‘Introduction to Thermodynamic Irreversible Processes’, Interscience Publishers, 3^rd edition, 1968.
3. R .P. Rastogi and R .R. Misra, ‘An Introduction to Chemical Thermodynamics’, 6^th Revised edition, Vikas Publishing House Pvt. Ltd., 2006.
4. W. Sears, ‘Introductions to Thermodynamics, Kinetic Theory of Gases and Statistical Mechanics’, Addison Wesley Pub., Cambridge, 1972