M. Sc.
Hydrochemistry syllabus
20-304-0204 – Thermodynamics and Statistical Mechanics
Unit I - Laws of Thermodynamics
Concept of entropy. Reversible and irreversible process. Clausius inequality, free energies and
maxwell’s relations. Gibbs-Helmholtz equations. Third law of thermodynamics and calculation
of entropy. Criteria of spontaneity. Free energy and entropy of mixing. Fundamental equations
in open systems. Gibbs Duhem equation. Partial molar quantities. Chemical potential: fugacity,
activity and activity coefficients
Unit II – Thermodynamics of Solutions
Duhem Marghules equation. Clausius-Clapeyron equation and its applications. Equilibrium
constants: Temperature dependence of equilibrium constants. Van-Hoff equation. van’t Hoff’s
reaction isochore and isotherm. Relation between KP , KC and KX. Fundamentals and advances
in the study of Phase Equilibria. Phase diagram of two and three-component systems.
Unit III – Statistical Mechanics
Thermodynamic probability, Stirling’s approximation, Ensemble, Boltzmann distribution and
molecular partition function, Translational, rotational and vibrational partition functions,
Relationship between partition functions and thermodynamic properties, Sackur-Tetrode
equation. Statistical formulation of the third law of thermodynamics, Residual entropy,
Quantum Statistics: Fermi-Dirac and Bose-Einstein and Maxwell Boltzmann statistics, Heat
capacity of solids-the vibrational properties of solids, Einstein’s theory, Debye theory,
Limitations of these theories.
Unit IV - Thermodynamics of Irreversible Processes
Postulates of irreversible processes. Non-equilibrium stationary states. Entropy production:
rate of entropy production. Entropy production via heat transfer and chemical reactions.
Phenomenological relations. Onsager reciprocal relations. Onsager relations in
thermodynamics and chemical kinetics point of view. Thermal osmosis. Thermoelectric
phenomena: Seebeck, Peltier, Thomson effect and their comparison.
Unit V - Bioenergetics
Coupled reactions. ATP and its role in bioenergetics. High energy bond. Free energy and
entropy change in ATP hydrolysis. Thermodynamics aspects of metabolism, and respiration
and glycolysis. Biological redox reactions.
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M. Sc. Hydrochemistry syllabus
Learning Outcomes
After completion of the course, the students will be able to:
1. Explain fundamental thermodynamic properties, energy and entropy concept of the
systems, and solve the problems behind it.
2. Understand the role of Clausius-Clapeyron equations, and Van-Hoff equations, and the
Gibbs phase rule in the equilibrium media and solutions.
3. Describe fundamental idea on the way of the distribution of particles, the relation
between thermodynamic properties and partition function and statistical interpretation
of various thermodynamic properties.
4. Become familiar with postulates, entropy production, thermal osmosis, thermoelectric
phenomena and Onsager relations of irreversible thermodynamic processes.
5. Investigate the role of thermodynamic process in various metabolic pathways of living
cells and find the queries and answers behind it.
References
1. I. Dincer, Thermodynamics: A Smart Approach, Wiley-Blackwell, 2020
2. R. H. Swendsen, An Introduction to Statistical Mechanics and Thermodynamics,
Oxford University Press, 2020
3. R.P. Rastogi and R.R. Misra, An Introduction to Chemical Thermodynamics, Vikas
Publishing House Pvt Ltd, 6th ed., 2018
4. P. Nag, Basic & Applied Thermodynamics, McGraw Hill Education, 2nd ed., 2017
5. T. L. Hill, An Introduction to Statistical Thermodynamics, Doverr, 2012
6. K. Stowe, An Introduction to Thermodynamics and Statistical Mechanics, Cambridge,
2016
7. B. G. Kyle, Chemical and Process Thermodynamics, Pearson Education India, 3rd ed.,
2015
8. S. I. Sandler, Chemical, Biochemical, and Engineering Thermodynamics, Wiley, 5 th
ed., 2017
9. I. Teraoka, Statistical Thermodynamics: Basics and Applications to Chemical Systems,
Wiley, 2019
10. M. Zemansky, R. Dittman, Heat and Thermodynamics, McGraw Hill Education,8th ed.,
2017
11. S. R. De Groot, P. Mazur, Non-equilibrium Thermodynamics, Dover Publications Inc.,
2003
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M. Sc. Hydrochemistry syllabus
12. J. C. Kuriacose, J. Rajaram, Chemical Thermodynamics: Classical, Statistical and
Irreversible, Pearson Education India, 1st ed., 2013
13. Y. L. Yao, Irreversible thermodynamics. Science Press, 1981
14. Y. Demirel, V. Gerbaud, Non-equilibrium Thermodynamics: Transport and Rate
Processes in Physical, Chemical and Biological Systems, Elsevier, 4th ed., 2018
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