Physical Chemistry II: Chemical Thermodynamics & Its Applications

Intensive and extensive variables, state and path functions; isolated, closed and open systems, zeroth law of thermodynamics, first law: Concept of heat, q, work, w, internal energy, U, and statement of first law, enthalpy, relation between heat capacities, calculations of q, w, U and H for reversible, irreversible and free expansion of gases (ideal and van der Waals) under isothermal and adiabatic conditions, relation between Joule-Thomson coefficient and other thermodynamic parameters, inversion temperature.

Thermochemistry: Heats of reactions, standard states, enthalpy of formation of molecules and ions and enthalpy of combustion and its applications, calculation of bond energy, bond dissociation energy and resonance energy from thermochemical data, effect of temperature (Kirchhoff’s equations) and pressure on enthalpy of reactions, adiabatic flame temperature, explosion temperature.

Second Law: Concept of entropy, thermodynamic scale of temperature, statement of the second law of thermodynamics, molecular and statistical interpretation of entropy, calculation of entropy change for reversible and irreversible processes.

Third Law: Statement of third law, concept of residual entropy, calculation of absolute entropy of molecules.

Free Energy Functions: Gibbs and Helmholtz energy, variation of S, G and A with T, V and P, free energy change and spontaneity, Gibbs-Helmholtz equation, Maxwell relations, thermodynamic equation of state.

Partial molar quantities, dependence of thermodynamic parameters on composition, Gibbs Duhem equation, chemical potential of ideal mixtures, change in thermodynamic functions in mixing of ideal gases.

Criteria of thermodynamic equilibrium, degree of advancement of reaction, chemical equilibria in ideal gases, concept of fugacity, thermodynamic derivation of relation between Gibbs free energy of reaction and reaction quotient, coupling of exoergic and endoergic reactions, equilibrium constants and their quantitative dependence on temperature, pressure and concentration, free energy of mixing and spontaneity, thermodynamic derivation of relations between the various equilibrium constants K_p, K_c and K_x, Le Chatelier principle (quantitative treatment), equilibrium between ideal gases and a pure condensed phase.

Dilute solutions, lowering of vapour pressure, Raoult’s and Henry’s Laws and their applications, excess thermodynamic functions, thermodynamic derivation using chemical potential to derive relations between the four colligative properties and amount of solute, applications in calculating molar masses of normal, dissociated and associated solutes in solution.