Thermodynamics and Surface Chemistry

Paper Code: 
CHY 223
Credits: 
4
Contact Hours: 
60.00
Max. Marks: 
100.00
Objective: 

Course Objectives :

The course aims to acquaint the students with the fundamentals of statistical thermodynamics and its applications in calculating thermodynamic properties. To make the students aware of thermodynamics of irreversible system, advanced aspects of colloidal and surface phenomena.

Course Outcomes (COs):

COURSE

Learning outcomes (at course level)

Learning and teaching strategies

Assessment Strategies

Paper Code

Paper Title

CHY 223

Thermodynamics and Surface Chemistry

 The students will be able to-

 

CO57-determine partial molar properties and can explain the concept of excess functions for non-ideal solutions.

CO58- recognize suitable statistics for a particular system.

CO59-describe the concept of partition functions and calculate thermodynamic properties in terms of partition function.

CO60- explain the statistical approach to entropy.

CO61- explain the concept and theory of thermodynamics for non-equilibrium systems.

CO62-analyze and quantitatively determine interfacial phenomena and behavior of colloidal systems

Interactive lectures

 

Discussion

 

Tutorials

 

Multimedia presentations

 

Assignments

Individual/Group presentation

 

Google quiz

 

Tutorials

 

Assignment

 

Semester end examination
 

 

10.00
Unit I: 
Classical Thermodynamics

Thermodynamics of open system: Partial molar properties, determination of these quantities and their significance, chemical potential in a system of ideal gases, Gibbs- Duhem equation, fugacity and determination of fugacity.

Non-ideal systems: Excess functions for non-ideal solutions, the concept of activity and activity coefficient.

 

15.00
Unit II: 
Introduction to Statistical Thermodynamics

Quantum mechanical aspects: Concept of distribution, thermodynamic probability and most probable distribution, common terms- occupation number, statistical weight factor, configuration, phase space, macroscopic state, microscopic state, system, assembly, canonical, grand canonical and microcanonical ensemble, ensemble averaging and its postulates.

Type of statistics- Maxwell-Boltzmann statistics, Bose-Einstein statistics and Fermi-Dirac statistics. Applications of statistics to helium, photon gas and metals.

Molecular partition function for an ideal gas, translational, rotational, vibrational, electronic and nuclear partition function.

 

15.00
Unit III: 
Statistical Approach to Thermodynamic Properties and Entropy

Calculation of thermodynamic properties in terms of partition function-

Translational energy, entropy, enthalpy, Helmholtz function, Gibb’s free energy of a monoatomic gas. Equilibrium constant, equipartition principle, heat capacity of mono and diatomic gases, mixture of o and p- hydrogen, heat capacity of solids. 

Entropy, probability, Boltzmann-planck equation, significance of thermodynamics probability, entropy of expansion of ideal gas, molecular basis of residual entropy, statistical calculation of entropy, vibrational entropy, nuclear spin entropy, virtual entropy, rotational entropy, comparison of third law and statistical entropies, random orientation in the solids, entropy of hydrogen and deuterium.

 

 

9.00
Unit IV: 
Non-Equilibrium Thermodynamics

Thermodynamic criteria for non-equilibrium states, entropy production and entropy flow, entropy balance equations for different irreversible processes (heat flow, chemical reaction etc.), transformations of the generalized fluxes and forces, non-equilibrium stationary states, phenomenological equations, microscopic reversibility and Onsager’s reciprocity relations, electrokinetic phenomenon, diffusion and electric conduction. Irreversible thermodynamics for biological systems, coupled reactions.

 

11.00
Unit V: 
Surface and Colloidal Phenomena

Adsorption of gases by solids, BET adsorption isotherm, adsorption from solution, Gibbs adsorption isotherm. Surface films on liquids (electrokinetic phenomena), catalytic activity of surfaces.

Surface active agents, classification, hydrophobic interaction, micelle formation: Mass action model and phase separation model, shape and structure of micelles, micellar aggregation numbers, critical micelle concentration (CMC), factors affecting CMC of surfactants, counter ion binding to micelles, thermodynamics of CMC, thermodynamics of micellization, micelle temperature range (MTR) or Kraft point, solubilization, micro emulsion and reverse micelles.

 

 

References: 
  • An Introduction to Chemical Thermodynamics; Sixth Edition; R.P Rastogi and R.R Misra; Vikas Publishing House, 2018.
  • Thermodynamics for students of Chemistry; Third Edition; K. Rajaram and J.C Kuriacose; Shoban Lal & Company, Jalandhar.
  • Chemical Thermodynamics; Seventh Edition; I.M Klotz and R.M Rosenberg; Wiley-Interscience, California, 2010.
  • Statistical Thermodynamics; Revised Second Edition; M.C Gupta; New Age International Pvt Ltd., New Delhi, 2013.
  • Physical Chemistry, A Molecular Approach; Viva Student Edition; D.A. McQuarrie and J.D Simon; Viva Books Private Limited, New Delhi, 2019.
  • Thermodynamics for Chemists; Third Edition; S. Glasstone; Affiliated East -West Press Pvt. Ltd., New Delhi, 2015.
  • Micelles: Theoretical and Applied Aspects, Y. Moroi, Springer International Edition, 2013.
  • Advanced Physical Chemistry; Eighteenth Edition;  J. N. Gurtu and A. Gurtu; Pragati Prakashan, Meerut, 2015.
Academic Year: 
2020-2021
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