CHE513T
PHYSICAL CHEMISTRY – I (Thermodynamics and Kinetics):
UNIT : I Equilibrium Thermodynamics – I :
Brief review of the concepts of laws of thermodynamics: state and path functions, exact and inexact differentials, zeroth and first law, isothermal and adiabatic processes.
Second law: Thermodynamic view of the entropy, Carnot Cycle, Clausius inequality, Helmholtz and Gibbs free energies, Maxwell’s relations.
Third law: Nernst heat theorem, Residual entropies.
UNIT : II Equilibrium Thermodynamics – II :
Thermodynamics of ideal and real gases and gas mixtures, mixing of gases, fugacities of gases and their determination, chemical potentials of liquids and liquid mixtures.
Thermodynamics of ideal and non-ideal binary solutions, excess functions for non-ideal solutions, regular .solutions. Thermodynamic criteria for chemical equilibria, equilibrium constant of chemical reactions, dependence of equilibrium constant on temperature and pressure.
Phase equilibrium, derivation of the Gibbs phase rule. Partial molar properties, the Gibbs – Duhem equation, the chemical potential and its significance.
UNIT: III Non-Equilibrium Thermodynamics :
Thermodynamic functions for non-equilibrium states, entropy production and entropy flow, transformations of the generalized fluxes and forces, phenomenological equations, Microscopic reversibility and Onsager’s reciprocity relations, electrokinetics phenomena, diffusion, electric conduction, the stationary non-equilibrium states.
UNIT : IV Chemical Kinetics – I :
Arrhenius equation, statistical derivation of activated complex theory. Comparison of absolute reaction rates with those of collision theory. Thermodynamic formulation of reaction rates. Reactions in solution. Comparison of gas and liquid phase reactions. Primary and secondary salt effects (kinetic salt effect). Effects of solvent (concept only) and ionic strength on rate constants.
UNIT : V Chemical Kinetics – II :
Complex reactions, Mechanisms of chain, photochemical and oscillatory reactions, homogeneous catalysis, Kinetics of enzyme reactions, study of fast reactions by flow methods, relaxation methods, flash photolysis and the nuclear magnetic resonance method.
ESSENTIAL READING:
1. P. W. Atkins – Physical Chemistry, 7th Edn. Oxford (2000).
2. I. N. Levine, Physical Chemistry, 4th Edn., McGraw Hill, New Delhi, (1995).
3. G. K. Vemulapally, Physical Chemistry, Prentice Hall, India, 1997.
4. I. Prigogine – Introduction to Thermodynamics of Irreversible processes, Interscience Publ. (1961)
5. K. J. Laidler, Chemical Kinetics, Harper & Row.
6. RP Rastogi and Mishra, Chemical thermodynamics, PHI New Delhi
ADDITIONAL READING:
7. V. Fried, U. Blukis and H. F. Hameka – Physical Chemistry Macmillan (1975).
8. K. J. Laidler & J. H. Meiser, Physical Chemistry, Houghton Mifflin Company, Bonton, 1998.
9. I. N. Levine, Physical Chemistry, McGraw Hill, New York, 1988.
10. Y. A. Gersimov, Physical Chemistry, Mir Publishers, Moscow, 1985.
11. J. Rajaram & J. Kuriakose, Kinetics and Mechanism of Chemical Transformations, McMillan India, 1993.
- Teacher: Soumendra Nath Bandyopadhyay