Unit-I : Thermodynamics -I (A) Recapitulation of thermodynamic terms : System, surrounding types of system (closed, open & isolated), Thermodynamic, variables, intensive & extensive properties, thermodynamic processes (isothermal, adiabatic, isobaric, cyclic, reversible & irreversible) State function & path functions, properties of state functions (exact differential, cyclic rule), integrating factor, concept of heat & work. [3L] (B) Statements of first law of thermodynamics : Definition of internal energy & enthalpy, heat capacity at constant volume & at constant pressure, Joule-Thomson experiment, Joule Thomson coefficient & Inversion temperature, calculations of W,Q,ΔE & ΔH for expansion of gases for isothermal & adiabatic conditions for reversible process, carnot's cycle & its efficiency, thermodynamic scale of temperature. [5L] (C) Thermochemistry : Heat of reaction, standard states, relation between heat of reaction at constant volume & at constant pressure, Hess's law of constant heat of summation & its applications, bond dissociation energy & its calculations from thermochemical data, variation of heat of reaction with temperature (Kirchoff's equation). [4L] Unit-II : Thermodynamics-II (A) Second law of thermodynamics : Need for second law of thermodynamics, statements of second law of thermodynamics, concept of entropy, entropy as a state function of V & T, P&T, entropy change in phase change for ideal gas, entropy as criteria of spontaneity & equilibrium. [4L] (B) Free energy functions : Helmholtz free energy (A) & Gibb's free energy (G) & their properties, standard free energies, effect of temperature on free energy (Gibb's-Helmholtz equation) & its applications, A&G as criteria for thermodynamic equilibrium. [4L] (C) System of variable composition : Partial molar quantities, chemical potential, Van't-Hoff's reaction isotherm, relation between standard free energy change & equilibrium constant (thermodynamic derivation of law of mass action), effect of temperature on equilibrium constant (reaction isochore) [4L] Unit-III : Phase Equilibria (A) Phase rule : Statement of phase rule, definition of phase, component and degree of freedom, derivation of phase rule, Clapeyron equation & its application in deciding slopes of line for two phase equilibria, applications of phase rule to two phase equilibria of i) water system, ii) sulphur system & iii) Pb-Ag system. [6L] (B) Liquid-Liquid mixtures : Ideal liquid mixtures, Raoults law of ideal solutions, Henry's law, non-ideal systems, azeotropes: HCl -H2O & ethanol-water system. Partial miscible liquids : Phenol-water system, trimethylamine-water, nicotine-water system, lower & upper consolute temperature, effect of impurity. Immiscible liquids : Steam distillation, Nernst distribution law, Limitations, deviations & applications. [6L] Unit-IV : Solid State Laws of crystallography : (i) Law of constancy of interfacial angles, (ii) Law of rationality of indices, (iii) Law of symmetry, symmetry of elements in crystals. Unit cell, space lattice, orientation of lattice plane (Miller indices). Bravais lattices, crystal systems, X-ray diffraction by crystal, derivation of Braggs' equation.
