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10CH301 PHYSICAL CHEMISTRY – I Credits 4:0:0 Course Objectives: • To know about Chemical thermodynamics & statistical thermodynamics • To know about phase rule for one component, two component and three component systems • To know about surface chemistry Course Outcome • Students acquire a good understanding of the basic principles of chemical and statistical thermodynamics, application of phase rule to different chemical systems and surface chemistry principles Unit I Chemical Thermodynamics: First law of thermodynamics – Limitation of first law of thermodynamics - Second law of thermodynamics – Third law of thermodynamics – Entropy – Entropy change in phase transformations – Entropy changes of an ideal gas in different processes – Entropy at absolute zero – Determination of absolute entropies of solids, liquids and gases – Trouton’s rule - Partial molar properties – Chemical potential – Gibbs – Duhem equation – Variation of chemical potential with temperature and pressure – Activity – Activity coefficient – Ideal solution – Real solution – Fugacity – Determination of a fugacity of a gas. Unit II Surface Chemistry: Adsorption of gases by solids – Langmuir, Freundlich and B-E-T isotherms – applicability to heterogeneous catalysis – determination of surface area of adsorbents – Electrokinetic phenomena – Donnan membrane equilibrium – emulsions. Unit III Phase rule: Gibbs phase rule and phase equilibria – Degree of freedom – One component system – Water system – Sulphur system – Carbon-di-oxide system – Carbon system – Helium System – Two components system – Reduced phase rule – Lead – silver system – Pattinson’s process – Ferric chloride – water system – Potassium iodide–water system – Sodium chloride–water system – Sodium–potassium system – Zinc-magnesium alloy system – Copper-nickel alloy system – sodium-sulphate system – Ironcarbon alloy system – Three component system – Brief description about two salts and water system – Allotropy – Heat treatment. Unit IV Statistical Thermodynamics – I: Concepts of probability and Maxwell Boltzmann distribution – Basic derivation – prove that β = 1/KT – Relationship between entropy and thermodynamic probability systems with degeneracy – Definitions of partition function – applications – derivation of thermodynamic functions from partition function – entropy for monoatomic gases – Sackur – Tetrode equation – The Bose – Einstein’s system – Basic derivation – Fermi – Dirac system – Basic derivation – negative Kelvin temperature Unit V Statistical Thermodynamics – II: Heat capacity of solids – Debye and Einstein models – Thermodynamics functions of ideal gases, translational, vibrational and rotational contributions at different levels of approximation Irreversible thermodynamics – the steady – coupled flows – application – over potential – decomposition potential – electrical double layer – structure of electrical double layer – capacity – steaming potential – electro dialysis – the Dorn effect Text Books: 1. P.W. Atkins, “Physical Chemistry”, 8th edition, Oxford University Press, 2006 2. B.R., Puri, L.R. Sharma and Madan S. Pathania, “Principles of Physical Chemistry”, Shoban Lal Nagin Chand & Co., Jalandhar, 2000 3. Kundu and S.K. Jain, “Physical Chemistry” S. Chand & Company Ltd., New Delhi, 1984 4. Duncan Shaw, “Introduction to colloid and surface chemistry”, Elsevier, 1992 Reference Books: 1. J. C. Kuriacose and J.Rajaram, “Thermodynamics”, Shoban Lal Nagin Chand & Co., Jalandhur, 1996 2. G.W. Castellan, “Physical Chemistry”, Narosa publishing house, Chennai, 1989 3. H. Snehe, “Comprehensive Physical Chemistry”, Prgati Prakashan, Meerut, 1987 4. S. Glasstone and D.Lewis, “Elements of Physical Chemistry”, 2nd Ed.,1982 5. N.D. Smith, “Elementary Statistical Thermodynamics”, Plenum Press, New York, 1982 6. B.C. McClelland, “Statistical Thermodynamics”, Chapman and Hall, London, 1973 7. M. C. Gupta, “Statistical Thermodynamics”, Wiley Eastern Limited, 1993 8. L.K. Nash, “Elements of classical the statistical thermodynamics”, Addision-Wesley 1970 9. S Glasstone, “Thermodynamics for Chemists”, Affiliated Wast Wes Press, New Delhi, 1965 10. Gabor A. Somorjai, “Surface Chemistry and Catalysis”, Wiley, New York, 1994