Thermodynamics

Importance and scope, definitions of system and surroundings; type of systems (isolated, closed and open). Extensive and intensive properties. Steady state and equilibrium state. Concept of thermal equilibrium and the zeroth-law of thermodynamics. Thermodynamic coordinates, state of a system, equation of state, state functions and path functions. Partial derivatives and cyclic rule. Concept of heat and work (IUPAC convention). Graphical explanation of work done during expansion and compression of an ideal gas. Reversible and irreversible processes and work done. First law of thermodynamics, internal energy (U) as a state function. Enthalpy as a state function. Heat changes at constant volume and constant pressure; relation between C_P and C_V using ideal gas and vander Waals equations. Joule's experiment and its consequence. Explanation of term (δU/δV)T. Isothermal and adiabatic processes. Joule-Thomson experiment and its consequences; inversion temperature. Joule-Thomson coefficient for a van der Waals gas, General heat capacity relations.

Thermochemistry: heat changes during physicochemical processes at constant pressure/volume. Hess's law of constant heat summation and applications, Kirchoff's relations. Bond dissociation energies. Changes of thermodynamic properties in different chemical changes.

Second law of thermodynamics – need for a Second law. Concept of heat reservoirs and heat engines. Kelvin – Planck and Clausius statements and equivalence of the two statements with entropic formulation. Carnot cycle and refrigerator. Carnot's theorem; thermodynamic scale of temperature.

Physical concept of entropy. Entropy as a measure of the microscopic but not macroscopic disorder. Entropy change of systems and surroundings for various processes and transformations. Entropy change during the isothermal mixing of ideal gases. Nernst Heat Theorem, Third law of thermodynamics (elementry idea) Entropy and unavailable work. Auxiliary state functions (G and A) and their variation with T, P and V. Criteria for spontaneity and equilibrium.

Thermodynamic relations: Maxwell's relations, thermodynamic equation of state, Gibbs- Helmholtz equation.

Open system, chemical potential and activity, partial molar quantities, chemical potential in terms of Gibb's free energy and other thermodynamic state functions and its variation with temperature and pressure. Gibbs-Duhem equation; fugacity of gases and fugacity coefficient.

Thermodynamic conditions for equilibrium, degree of advancement. Van't Hoff's reaction isotherm (deduction from chemical potential). Explanation of the free energy versus degree of advancement plot. Equilibrium constant and standard Gibbs free energy change. Definitions of K_P, K_C and K_x ; van't Hoff's reaction isobar and isochore from different standard states. Shifting of equilibrium due to change in external parameters e.g. temperature and pressure. Le Chatelier's principle and degree of advancement. Activity and activity coefficients of electrolyte / ion in solution. Debye-Huckel limiting law (statement and applications only). Solubility equilibrium and common ion effect