Physical Chemistry III: Electrochemistry & Chemical Kinetics

Arrhenius theory of electrolytic dissociation, conductivity, equivalent and molar conductivity and their variation with dilution for weak and strong electrolytes, molar conductivity at infinite dilution, Kohlrausch law of independent migration of ions, Debye-Hückel-Onsager equation, Wien effect, Debye-Falkenhagen effect, Walden’s rule.

Ionic velocities, mobilities and their determinations, transference numbers and their relation to ionic mobilities, determination of transference numbers using Hittorf and moving boundary methods, applications of conductance measurement: degree of dissociation of week electrolytes, ionic product of water, solubility and solubility product of sparingly soluble salts, conductometric titrations, and hydrolysis constants of salts.

Quantitative aspects of Faraday’s laws of electrolysis, rules of oxidation/reduction of ions based on half-cell potentials, applications of electrolysis in metallurgy and industry.

Chemical cells, reversible and irreversible cells with examples, electromotive force of a cell and its measurement, Nernst equation, standard electrode (reduction) potential and its application to different kinds of half-cell, application of EMF measurements in determining free energy, enthalpy and entropy of a cell reaction, equilibrium constants, and pH values, using hydrogen, quinone-hydroquinone, glass and SbO/Sb₂O₃ electrodes.

Concentration cells with and without transference, liquid junction potential, determination of activity coefficients and transference numbers, qualitative discussion of potentiometric titrations (acid-base, redox, precipitation).

Order and molecularity of a reaction, rate laws in terms of the advancement of a reaction, differential and integrated form of rate expressions up to second order reactions, experimental methods of the determination of rate laws, kinetics of complex reactions (integrated rate expressions up to first order only): opposing reactions, parallel reactions and consecutive reactions and their differential rate equations (steady-state approximation in reaction mechanisms), chain reactions, temperature dependence of reaction rates, Arrhenius equation, activation energy, collision theory of reaction rates, Lindemann mechanism, qualitative treatment of the theory of absolute reaction rates.