Unit I: Thermodynamics
Introduction, definition of thermodynamic terms, intensive and extensive properties, path and state functions, exact and inexact differentials, zeroth law of thermodynamics First law of thermodynamics, reversible and irreversible processes, internal energy and enthalpy, heat capacity, Cp and Cv relation in ideal gas systems, change in thermodynamic properties of an ideal gas during (i) isothermal/adiabatic, reversible/irreversible processes. Joule-Thomson experiment, JouleThomson coefficient, inversion temperature. Second law: Limitations of first law – statements of second law, Carnot’s cycle – efficiency of heat engines, Carnot theorem. Entropy – entropy change for various reversible/irreversible processes, 8 spontaneous and non spontaneous processes. Change in entropy of an ideal gas with pressure, volume and temperature. Third law of thermodynamics-statement and significance. Helmholtz energy and Gibbs energy – variation of Gibbs energy with T and P. Criteria for reversible and irreversible processes. Gibbs-Helmholtz equation. Clasius- Clapeyron equation, applications. Partial molar properties – chemical potential, Gibbs-Duhem equation, chemical potential in a system of ideal gases, concept of activity.
Unit II: Chemical Equilibrium and Phase Equilibria
Recognising a system at Chemical Equilibrium. Attributes of Chemical Equilibrium, Thermodynamic derivation of law of mass action, Equilibrium constant and free energy. Factors that affect the chemical equilibrium and Le Chatelier’s principle. Calculations involving equilibrium constant, Ionic equilibria in aqueous solutions, sparingly soluble salts, solubility product common ion effect, selective precipitation, applications in qualitative analysis. Ionisation of water, pH scale, weak acids and bases, hydrolysis, buffer solutions, acid Base indicators, acid base titrations and multi stage equilibria. Reaction isotherm and reaction isochore Statement and meaning of the terms – phase, component and degree of freedom, derivation of Gibbs phase rule, phase equilibria of one component system – water, CO2 and S systems. Phase equilibria of two component system – solid-liquid equilibria – simple eutectic –Pb-Ag.
Unit III: Solutions
Solutions of Gases in liquids. Henry’s law and its applications, solutions of solids in liquids. Distribution law, application of distribution law to association, dissociation and extraction. Dilute Solution: Colligative properties, Osmosis, Osmotic pressure, Vant Hoff Theory, Lowering of Vapour Pressure, Depression in Freezing point and Elevation in Boiling Point, Vant Hoff Factor. Solid solutions – compound formation with congruent melting point (Mg – Zn) and incongruent melting point (NaCl – H2O), (FeCl3 – H2O) and (CuSO4 – H2O) system. Freezing mixtures, acetone dry ice. Liquid – liquid mixtures: Ideal liquid mixtures, Raoult’s and Henry’s law. Non-ideal system – Azeotropes – HC – H2O and ethanol – water systems. Partially miscible liquids – Phenolwater, trimethylamine – water, nicotine – water systems. Immiscible liquids, steam distillation. Nernst distribution law – thermodynamic derivation, applications.
Unit IV: Electrochemistry
Migration of ions Kohlrausch law, Arrhenius theory of electrolyte dissociation and its limitations, weak and strong electrolytes, Ostwald’s dilution law, its uses and limitations. Debye-Huckel-Onsager’s equation for strong electrolytes (elementary treatment only). Transport number, definition and determination by Hittorf method and moving boundary method. Applications of conductivity measurements: Determination of degree of dissociation, determination of Ka of acids, determination of solubility product of a sparingly soluble salt, conductometric titrations. Electrode reactions, Nernst equation, derivation of cell E.M.F. and single electrode potential, standard hydrogen electrode-reference electrodes – standard electrode potential, sign conventions, electrochemical series and its significance. Electrolytic and Galvanic cells – reversible 9 and irreversible cells, conventional representation of electrochemical cells. EMF of a cell and its measurements. Computation of cell EMF, Calculation of thermodynamic quantities of cell reactions (G, H and K), Chemical cells with and without transport.
Unit V: Photochemistry
Laws of photochemistry – Grothus-Draper law, Stark-Einstein law, examples of photochemical reactions. Beer law and Beer-Lambert’s law. Jablonsky diagram, qualitative description of fluorescence, phosphorescence, non-radiative processes (internal conversion, intersystem crossing). Quantum yield, primary and secondary processes. Basic concepts of photosensitized reactions – photosynthesis, dissociation of hydrogen molecule, isomerization of 2-butene, and chemiluminescence.