Syllabus (CHEMISTRY)

Course Type: MAJ-6

Semester: 5

Course Code: BCEMMAJ06C

Course Title: Physical Chemistry – II

(L-P-Tu): 4-2-0

Credit: 6

Practical/Theory: Combined

Course Objective: Course Objective of Major-6: The syllabus of Major-6 is divided into four modules: (1) Kinetic theory of gases; (2) Applications of Thermodynamics-II; (3) Applications of Thermodynamics-II; and (4) Transport Process-I. The first module deals with the theo

Learning Outcome: Course Outcomes of Major - 6: CO - 6.1: Kinetic Theory of Gases, Behaviour of Real Gases, and Related Theories CO - 6.2: Thermodynamic rationale of the behaviour of solutions and mixtures, the thermodynamics of different phases of matter, and phase trans

THEORY:

KINETIC THEORY OF GASES: (20 L)

1. Kinetic Theory of gases: Concept of pressure and temperature; Collision of gas molecules; Collision diameter; Collision number and mean free path; Frequency of binary collisions (similar and different molecules); Wall collision and rate of effusion.

2. Maxwell’s distribution of speed and energy (without derivation): Nature of distribution of velocities, Maxwell's distribution of speeds in one, two and three dimensions; Kinetic energy distribution in one, two and three dimensions, calculations of average, root mean square and most probable values in each case; Calculation of number of molecules having energy ≥ε.

3. Real gas and virial equation: Deviation of gases from ideal behavior; compressibility factor; Boyle temperature; Andrew's and Amagat's plots; vander Waals equation and its features; its derivation and application in explaining real gas behaviour, other equations of state (Berthelot, Dietrici); Existence of critical state, Critical constants in terms of van der Waals constants; Law of corresponding states; virial equation of state; van der Waals equation expressed in virial form and significance of second virial coefficient; Intermolecular forces (Debye, Keesom and London interactions; Lennard-Jones potential - elementary idea). Equipartition principles.

APPLICATION OF THERMODYNAMICS-II: (20 L)

1. Binary mixture: Chemical potential of individual components. Thermodynamic parameters of mixing ideal solution; Colligative properties: Vapour pressure of solution; Ideal solutions, ideally diluted solutions and colligative properties; Raoult's law; Thermodynamic derivation using chemical potential to derive relations between the four colligative properties [(i) relative lowering of vapour pressure, (ii) elevation of boiling point, (iii) Depression of freezing point, (iv) Osmotic pressure] and amount of solute. Applications in calculating molar masses of normal, dissociated and associated solutes in solution; Abnormal colligative properties.

2. Phase rule: Definitions of phase, component and degrees of freedom; Phase rule and its derivations; Definition of phase diagram; Phase diagram for water, CO2, Sulphur.

3. First order phase transition and Clapeyron equation; Clausius-Clapeyron equation - derivation and use; Liquid vapour equilibrium for two component systems; Phenol-water system.

4. Binary solutions: Ideal solution; Positive and negative deviations from ideal behaviour; Principle of fractional distillation; Duhem-Margules equation; Henry's law; Konowaloff's rule; Azeotropic solution; Liquid-liquid phase diagram using phenol- water system; Solid-liquid phase diagram; Eutectic mixture.

APPLICATION OF THERMODYNAMICS-III: (12 L)

1. Electromotive Force: Quantitative aspects of Faraday’s laws of electrolysis, rules of oxidation /reduction of ions based on half-cell potentials, applications of electrolysis in metallurgy and industry; Chemical cells, reversible and irreversible cells with examples; Electromotive force of a cell and its measurement, 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, quinine-hydroquinone, glass and SbO/Sb2O3 electrodes.

2. Concentration cells with and without transference, liquid junction potential; determination of activity coefficients and transference numbers; Qualitative discussion of potentiometric titrations (acid-base, redox, precipitation).

TRANSPORT PROCESS-I: (8 L)

1. Diffusion; Fick’s law: Flux, force, phenomenological coefficients & their interrelationship(general form), different examples of transport properties.

2. Viscosity: General features of fluid flow (streamline flow and turbulentflow);Newton’s equation, viscosity coefficient; Poiseuille’s equation;principle ofdetermination of viscosity coefficient of liquids by falling sphere method, Viscosity of gasesand effect of temperature and pressure on coefficient of viscosity (qualitative treatment only),Temperature variation of viscosity of liquids and comparison with that of gases.

READING REFERENCES:

1. Castellan, G. W. Physical Chemistry, Narosa.
2. Atkins, P. W. & Paula, J. de Atkins’ Physical Chemistry, Oxford University Press
3. McQuarrie, D. A. & Simons, J. D. Physical Chemistry: A Molecular Approach, Viva Press
4. Levine, I. N. Physical Chemistry, Tata McGraw-Hill
5. Moore, W. J. Physical Chemistry, Orient Longman
6. Glasstone, S. & Lewis, G.N. Elements of Physical Chemistry
7. Rakshit, P.C., Physical Chemistry Sarat Book House
8. Bera, N. K., Ghosh, S., Ghosh, P., Vol-(I, II & III), Physical Chemistry Concepts & Models, Techno World, Kolkata.
9. Mortimer, R. G. Physical Chemistry, Elsevier
10. Denbigh, K. The Principles of Chemical Equilibrium Cambridge University Press
11. Engel, T. & Reid, P. Physical Chemistry, Pearson
12. Rastogi, R. P. & Misra, R.R. An Introduction to Chemical Thermodynamics, Vikas
13. Ashish Kumar Nag, Physical Chemistry (Vol-I & II), McGraw Hill Education (India) Pvt. Ltd.
14. K. L. Kapoor, A Textbook of Physical Chemistry, Vol-I to Vol-V, Macmillan Publishers India Ltd. 2004.
15. Ghoshal, A. Numerical Problems on Physical Chemistry, Books & Allied Pvt. Ltd. Kolkata
16. Klotz, I.M., Rosenberg, R. M. Chemical Thermodynamics:Basic Concepts and Methods Wiley
17. Glasstone, S. An Introduction to Electrochemistry, East-West Press.
18. Reddy, A. K., Bockris, John O'M.; Modern Electrochemistry: An Introduction to an Interdisciplinary Area, Springer, 1995.

PRACTICALS:

1. Determination of Keq for KI + I2 = KI3, using partition coefficient betweenwater and CHCl3.

2. Study of viscosity of unknown liquid (glycerol, sugar) with respect to water.

3. Potentiometric titration: (a) weak acid vs. base, (b) Redox, determination of E⁰.

4. Determination of strength of unknown HCl by NaOH pH-metrically.

REFERENCES FOR PRACTICALS:

1. University Hand Book of Undergraduate Chemistry Experiments, edited by Mukherjee, G N., University of Calcutta.
2. Levitt, B. P. edited Findlay’s Practical Physical Chemistry Longman Group Ltd.
3. Gurtu, J. N., Kapoor, R., Advanced Experimental Chemistry S. Chand & Co. Ltd.
4. Saharay, S. K. &Basu, A. S. A Guide to Practical Physical Chemistry, University of Burdwan.
5. Viswanathan, B., Raghavan, P.S. Practical Physical Chemistry Viva Books (2009)
6. Mendham, J., A. I. Vogel’s Quantitative Chemical Analysis 6th Ed., Pearson

7. Harris, D. C. Quantitative Chemical Analysis. 6th Ed., Freeman (2007).