Syllabus (CHEMISTRY)

Course Type: MAJ-13

Semester: 7

Course Code: BCEMMAJ13C

Course Title: Physical Chemistry – IV

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

Credit: 6

Practical/Theory: Combined

Course Objective: Course Objectives of Major-13: The syllabus of Major-13 covers a vast area of details of Crystal Structure, Statistical Thermodynamics, 3rd Law of Thermodynamics and Surface Chemistry.

Learning Outcome: Course Outcome of Major-13 The objectives of the present major course are manyfold. There are six modules in this course, and the objectives of the modules can be stated as below: CO - 13.1 This module is designed to provide students with molecular- or at

THEORY:

Crystal Structure: (8L)

1. Bravais Lattice and Laws of Crystallography: Concept of lattice, basis, primitive cell. Types of solid, Bragg’s law ofdiffraction; Laws of crystallography (Haϋy’s law and Steno’s law); Permissible symmetry axes in crystals; Lattice, space lattice, Cubical systems (SC, BCC, FCC).

2. Crystal planes: Distance between consecutive planes [cubic, tetragonal and orthorhombic lattices]; Indexing of planes, Miller indices; calculation of d_hkl; Relation between molar mass and unit cell dimension for cubic system;

3. Diffraction of X-ray by crystals, Braggequation, determination of crystal structure: Powder method; Structure of NaCland KCl crystals, elementary idea of structure factor.

STATISTICAL THERMODYNAMICS: (10 L)

1. Configuration: Macrostates, microstates and configuration; calculation with harmonic oscillator; variation of W with E; equilibrium configuration.

2. Boltzmann distribution: Thermodynamic probability, entropy and probability, Boltzmann distribution formula (with derivation); Applications to barometric distribution.

3. Partition function: molecular partition function and thermodynamic properties, Maxwell’s speed distribution; Gibbs’ paradox. Nature of particles and concept of other distribution formula (FD, BE).

3^rd LAW OF THERMODYNAMICS: (12 L)

Specific heat of solid: Coefficient of thermal expansion, thermal compressibility of solids; Dulong –Petit’s law; Equipartition theorem and heat capacities; Perfect Crystal model, Einstein’s theory – derivation from partition function, limitations; Debye’s T3 law – analysis at the two extremes. 1. 3rd law: Absolute entropy, Plank’s law, Calculation of entropy, Nernst heat Theorem.

2. Adiabatic demagnetization: Approach to zero Kelvin.

APPLICATION OF THERMODYNAMICS-IV: (10 L)

Ionic equilibria: Chemical potential of an ion in solution; Activity and activity coefficients of ions in solution; Debye-Huckel limiting law-brief qualitative description of the postulates involved, qualitative idea of the model, the equation (without derivation) for ion-ion atmosphere interaction potential. Estimation of activity coefficient for electrolytes using Debye-Huckel limiting law; Mean ionic activity coefficient; Applications of the Debye-Huckel equation and its limitations.

TRANSPORT PROCESS-II: (8 L)

1. 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 forstrong 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; Ionic mobility; Application of conductance measurement(determination of solubility product and ionic product of water);Conductometric titrations.

4. Transport number, Principles of Hittorf’s and Moving-boundary method; Wieneffect, Debye-Falkenhagen effect, Walden’s rule.

SURFACE CHEMISTRY & COLLOIDS: (12 L)

1. Surface tension and energy: Surface tension, surface energy, excess pressure, capillary rise and surface tension; Work of cohesion and adhesion, spreading ofliquid over other surface; Vapour pressure over curved surface; Temperature dependence of surface tension.

2. Adsorption: Physical and chemical adsorption; Freundlich and Langmuir

adsorption isotherms; multilayer adsorption and BET isotherm (no derivation required); Gibbs adsorption isotherm and surface excess; Heterogenous catalysis (single reactant); Zero order and fractional order reactions.

3. Colloids: Lyophobic and Lyophilic sols, Origin of charge and stability of Lyophobic colloids, Coagulation and Schultz-Hardy rule, Zeta potential and Stern double layer (qualitative idea), Tyndall effect; Electrokinetic phenomena(qualitative idea only); Determination of Avogadro number by Perrin’s method; Stability of colloids and zeta potential; Micelle formation.

READING REFERENCES:

1. Atkins, P. W. & Paula, J. de Atkins’ Physical Chemistry, Oxford University Press
2. Castellan, G. W. Physical Chemistry, Narosa
3. McQuarrie, D. A. & Simons, J. D. Physical Chemistry: A Molecular Approach, Viva Press
4. Levine, I. N. Physical Chemistry, Tata McGraw-Hill
5. Laidler, K. J. Chemical Kinetics, Pearson
6. Levine, I. N. Quantum Chemistry, PHI
7. Atkins, P. W. Molecular Quantum Mechanics, Oxford
8. McQuarrie, D. A. Statistical Mechanics, Viva Books Pvt. Ltd. 2003, New Delhi
9. Banwell, C. N. and McCash, E.M. Fundamentals of Molecular Spectroscopy, Edn. 4th, Tata McGraw-Hill, New Delhi.
10. Nash, L. K. Elements of Statistical Thermodynamics, Dover
11. Atomic and Molecular Spectroscopy: Basic Concepts and Applications, Rita Kakkar Cambridge University Press, 2015.
12. Moore, W. J. Physical Chemistry, Orient Longman
13. Glasstone, S. & Lewis, G.N. Elements of Physical Chemistry
14. Bera, N. K., Ghosh, S., Ghosh, P., Vol-(I, II and III), Physical Chemistry Concepts & Models, Techno World, Kolkata.
15. Rakshit, P.C., Physical Chemistry Sarat Book House
16. Mortimer, R. G. Physical Chemistry, Elsevier
17. Engel, T. & Reid, P. Physical Chemistry, Pearson
18. Rastogi, R. P. & Misra, R.R. An Introduction to Chemical Thermodynamics, Vikas
19. Ashish Kumar Nag, Physical Chemistry (Vol-I & II), McGraw Hill Education (India) Pvt. Ltd.
20. K. L. Kapoor, A Textbook of Physical Chemistry, Vol-I to Vol-V, Macmillan Publishers India Ltd. 2004
21. Ghoshal, A. Numerical Problems on Physical Chemistry, Books & Allied Pvt. Ltd. Kolkata

Klotz, I.M., Rosenberg, R. M. Chemical Thermodynamics:Basic Concepts and Methods Wiley.

PRACTICALS:

1. Determination of surface tension of a liquid using Stalagmometer.

2. Determination of solubility of sparingly soluble salt in water, in electrolyte with common ions and in neutral electrolyte (using common indicator).

3. Conductometric titration of a strong / weak acid by strong base.

4. Conductometric titration of a dibasic acid by strong base.

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)