Unit 1:
Gaseous state [14 h]Kinetic theory of gases, ideal gas equation, Maxwell distribution of energy and velocities, collision parameters. Relation between mean free path and coefficient of viscosity. van der Waals equation, other state equations, law of corresponding states, liquefaction, Andrews curves, critical parameters, methods for liquefaction. Critical phenomena, critical constants and their determination.
Unit 2:
Thermodynamics I[13 h]Thermodynamic processes – reversible and irreversible, isothermal and adiabatic processes. State and path functions. Exact and inexact differentials, concept of heat and work. First law of thermodynamics. Relation between Cp and Cv. Calculation of w, q, dE and dH for expansion of ideal and real gases under isothermal and adiabatic conditions of reversible and irreversible processes. Thermochemistry – Enthalpy change of a reaction and different enthalpy changes – relation between enthalpy of reaction at constant volume and at constant pressure. Temperature dependence of heat of reaction – Kirchhoffs equation. Bond energy and its calculation from thermochemical data – integral and differential heats. Numerical problems.
Unit 3:
Thermodynamics-II[12 h]Second law of thermodynamics – different statements of the law, Carnots cycle and efficiency of heat engine, Carnots theorem. Thermodynamic scale of temperature – concept of entropy – definition and physical significance of entropy – entropy as a function of P, V and T. Entropy changes during phase changes, entropy of mixing. Entropy criterion for spontaneous and equilibrium processes in isolated system, Gibbs free energy (G) and Helmholtz free energy (A) – variation of A and G with P, V and T Gibbs – Helmholtz equation and its applications. Thermodynamic equation of state Maxwells relations. Numerical problems.
Unit 4:
Thermodynamics III[7h]Third law of thermodynamics – need for third law, calculation of absolute entropy, unattainability of absolute zero, thermodynamic systems of variable composition. Fugacity functions, partial molar quantities, thermodynamics of ideal solutions, real solutions and regular solutions, dilute solutions of nonelectrolytes, Henrys law, Raoults law, Gibbs-Duhem equations, Gibbs-Duhem-Margules equations, and activity and standard states of non-electrolytes. Numerical problems.
Unit 5:
Chemical Kinetics [14 h]Molecularity and order of a reaction, rate law expression and rate constant. First, second, third and zero order reactions, pseudo-first order reactions (pseudo-unimolecular reactions). Effect of temperature on reaction rates – Arrhenius equation and its derivation, activation energy, characteristics of activated complex. Theories of reaction rates collision theory derivation of rate constant of bimolecular gases reaction failure of collision theory Lindemanns theory of unimolecular reaction. Theory of absolute reaction rates derivation of rate for a bimolecular reaction. Eyring equation significance of entropy and free energy of activation. Equilibrium and steady state approximations, Kinetics of parallel, chain, opposing and consecutive reactions. – mechanism of these reactions.