Course Syllabus

(Total 22 Lectures & 4 Mock Tests )

Systems of Variable Composition:

Partial molar quantities, dependence of thermodynamic parameters on composition; Gibbs-Duhem equation, chemical potential of ideal mixtures, change in thermodynamic functions in mixing of ideal gases. Activities and activity coefficients. Fugacity and fugacity coefficient.

 Applications of Thermodynamics – I

Chemical Equilibrium:

Thermodynamic conditions for equilibrium, degree of advancement; van’t Hoff’s reaction isotherm (deduction from chemical potential); Variation of free energy with degree of advancement; Equilibrium constant and standard Gibbs free energy change; Van’t Hoff’s reaction isobar and isochore from different standard states; Le Chatelier’s principle and its derivation, variation of equilibrium constant under different conditions Nernst’s distribution law; Application- (eg. dimerization of benzene in benzoic acid). Solvent Extraction.

ELECTROCHEMISTRY:

 (i) Conductance and transport number

Ion conductance; Conductance and measurement of conductance, cell constant, specific conductance and molar conductance; Variation of specific and equivalent conductance with dilution for strong and weak electrolytes; Kohlrausch’s law of independent migration of ions; Equivalent and molar conductance at infinite dilution and their determination for strong and weak electrolytes; Debye –Huckel theory of Ion atmosphere (qualitative)-asymmetric effect, relaxation effect and electrophoretic effect; Debye-Huckel limiting law-brief qualitative description. Estimation of activity coefficient for electrolytes using Debye-Huckel limiting law. Ostwald’s dilution law; Ionic mobility; Application of conductance measurement (determination of solubility product and ionic product of water); Conductometric titrations.Transport number, Principles of Hittorf’s and Moving-boundary method; Wien effect, Debye-Falkenhagen effect, Walden’s rule

 (ii) Ionic equilibrium:

Strong, moderate and weak electrolytes, degree of ionization, factors affecting degree of ionization, ionization constant and ionic product of water. Ionization of weak acids and bases, pH scale, common ion effect; dissociation constants of mono-, di-and triprotic acids (exact treatment).

Salt hydrolysis- calculation of hydrolysis constant, degree of hydrolysis and pH for different salts (exact Treatment).Determination of hydrolysis constant conductometrically. Buffer solutions; derivation of Henderson equation and its applications; buffer capacity, buffer range, buffer action . Qualitative treatment of acid – base titration curves (calculation of pH at various stages). Theory of acid–base indicators; selection of indicators and their limitations. Multistage equilibrium in polyelectrolyte systems; hydrolysis and hydrolysis constants

 (iii) Electromotive Force: Rules of oxidation/reduction of ions based on half-cell potentials,; Chemical cells, reversible and irreversible cells with examples; Electromotive force of a cell and its measurement, Thermodynamic derivation of Nernst equation; Standard electrode (reduction) potential and its application to different kinds of half-cells. Application of EMF measurements in determining (i) free energy, enthalpy and entropy of a cell reaction, (ii) equilibrium constants, and (iii) pH values, using hydrogen, quinone-hydroquinone and glass electrodes Concentration cells with and without transference, liquid junction potential; determination of activity coefficients and transference numbers; Potentiometric titrations (acid-base, redox, precipitation)

Reference Books

1. Levine, I. N. Physical Chemistry, 6th Edition , McGraw-Hill India
2. Castellan, G. W. Physical Chemistry, Narosa
3. McQuarrie, D. A. & Simons, J. D. Physical Chemistry: A Molecular Approach, Viva Press 
4. Kapoor K.L, A Text Book Of Physical Chemistry , McGraw Hill India
5. Engel, T. & Reid, P. Physical Chemistry, 3rd Edition ,Pearson India
6. Atkins, P. W. & Paula, J. de Atkins’ Physical Chemistry, 10th Edition, Oxford University Press
7. Maron, S. & Prutton , Physical Chemistry
8. Ball, D. W. Physical Chemistry, Thomson Press
9. Mortimer, R. G. Physical Chemistry, 2nd Edition, Elsevier
10. Glasstone, S. & Lewis, G.N. Elements of Physical Chemistry
11. Rakshit, P.C., Physical Chemistry,Sarat Book House
12. Moore, W. J. Physical Chemistry, Orient Longman
13. Denbigh, K. The Principles of Chemical Equilibrium ,Cambridge
14. Zemansky, M. W. & Dittman, R.H. Heat and Thermodynamics, Tata-McGraw- Hil
15. Glasstone, S. An Introduction to Electrochemistry, East-West Press.
16. Klotz, I.M., Rosenberg, R. M.Chemical Thermodynamics:Basic Concepts and Methods , 7th Edition, Wiley