Semester IV (Major, NEP, 2020 2023-2024)

Real gas and Virial equation (07 L)

Deviation of gases from ideal behavior; compressibility factor; Boyle temperature; Andrew's and Amagat's plots; van der Waals equation and its features; its derivation and application in explaining real gas behavior, other equations of state ; 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).

Transport processes and Liquid State (09 L)

Viscosity General features of fluid flow (streamline flow and turbulent flow); Newton’s equation, viscosity coefficient; Poiseuille’s equation; principle of determination of viscosity coefficient of liquids by falling sphere method and using Ostwald's viscometer. Temperature variation of viscosity of liquids and comparison with that of gases. Relation between viscosity coefficient of a gas and mean free path.

Surface tension and energy

Surface tension, surface energy, excess pressure, capillary rise and surface tension; Work of cohesion and adhesion, spreading of liquid over other surface; Temperature dependence of surface tension

Solid State (12 L)

Bravais Lattice and Laws of Crystallography

Types of solid, Bragg’s law of diffraction; Laws of crystallography (Haϋy’s law and Steno’s law); Permissible symmetry axes in crystals; Lattice, space lattice, unit cell, crystal planes, Bravais lattice. Packing of uniform hard sphere, close packed arrangements (fcc and hcp); Tetrahedral and octahedral voids. Void space in cubic systems.

Crystal plane

Distance between consecutive planes [cubic and orthorhombic lattices]; Indexing of planes,Miller indices; calculation of dhkl; Relation between molar mass and unit cell dimension for cubic system; Bragg’s law (derivation). Determination of crystal structure: Powder method; Structure of NaCl and KCl crystals.

Chemical Equilibrium (08 L)

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.

Conductance (09 L)

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.

Reference Books:

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. 5. Levine, I. N. Physical Chemistry, Tata McGraw-Hill. 6. Rakshit, P.C., Physical Chemistry Sarat Book House. 7. Kapoor, K. L., A Text Book of Physical Chemistry, 6th Edn, McGraw-Hill.