PHYSICAL CHEMISTRY II (CHEMICAL THERMODYNAMICS AND ITS APPLICATIONS)

CHE123T

The course contains the basics of thermodynamics and its applications in chemistry. Classical thermodynamics will be taught in this course which includes the first, second and third laws of thermodynamics. Concepts of related topics, like mechanical work, internal energy, enthalpy, entropy, different types of free energies are also included in the syllabus and will be thoroughly discussed.

Systems of variable compositions, chemical equilibrium and colligative properties are also part of this course as the extension and application of thermodynamics in chemical systems.

The detailed discussions of the above mentioned topics will be done in the class along with necessary derivations and visual aids. This course will enable the students to learn more advanced topics in thermodynamics, kinetics, electrochemistry etc in future.

SYLLABUS

Chemical Thermodynamics: Intensive and extensive variables; state and path functions; isolated, closed and open systems. First law: Concept of heat, Q, work, W, internal energy, U, and statement of first law; enthalpy, H, relation between heat capacities, calculations of Q, W, ΔU and ΔH for reversible, irreversible and free expansion of gases (ideal and van der Waals) under isothermal and adiabatic conditions.

Thermochemistry: Heats of reactions: standard states; enthalpy of formation and enthalpy of combustion and its applications; effect of temperature (Kirchhoff’s equations) and pressure on enthalpy of reactions.

Second Law: Concept of entropy; thermodynamic scale of temperature, statement of the second law of thermodynamics. 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, A with T, V, P; Free energy change and spontaneity. Relation between Joule-Thomson coefficient and other thermodynamic parameters; inversion temperature; Gibbs-Helmholtz equation; Maxwell relations; thermodynamic equation of state. Systems of Variable Composition: 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.

Chemical Equilibrium: Criteria of thermodynamic equilibrium, degree of advancement of  reaction, chemical equilibria in ideal gases. Thermodynamic derivation of relation between Gibbs free energy of reaction and reaction quotient. Equilibrium constants and their quantitative dependence on temperature, pressure and concentration (Le Chatelier Principle, Quantitatively). Free energy of mixing and spontaneity. equilibrium between ideal gases and a pure condensed phase.

Solutions and Colligative Properties: Dilute solutions; lowering of vapour pressure, Raoult’s and Henry’s Laws and their applications. Thermodynamic derivation using chemical potential to derive relations between the four colligative properties [(i) relative lowering of vapour pressure, (ii) elevation of boiling point, (iii) Depression of freezing point, (iv) osmotic pressure] and amount of solute. Applications in calculating molar masses of normal, dissociated and associated solutes in solution.

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