ELECTROCHEMISTRY AND 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-Huckel-Onsager equation, Wien effect, Debye-Falkenhagen effect, Walden’s rules, activity coefficient, ionic strength.
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: (i) degree of dissociation of weak electrolytes (ii) ionic product of water (iii) solubility and solubility product of sparingly soluble salts (iv) conductometric titration and (v) hydrolysis constants of salts.

Electrolytic and Galvanic cells- reversible and irreversible cells, free energy and EMF of a cell, Nernst equation, EMF of a cell and its measurements, calculation of thermodynamic quantities of cell reactions (∆G, ∆H & K), electrochemical series and its significance, representation of electrochemical cell, standard electrode potential, single electrode potential, standard hydrogen electrode- reference electrodes, types of reversible electrodes – gas-metal ion, metal-metal ion, metal-insoluble salt-anion and redox electrodes.

Concentration cell- electrode concentration cell and electrolyte concentration cell (with and without transport), liquid Junction potential, applications of concentration cell - valency of ions, solubility product, activity coefficient, potentiometric titrations. Determination of pH using hydrogen, quinhydrone and glass electrodes and by potentiometric method. Corrosion and protection from corrosion.

Introduction of reaction rate in terms of extent of reaction, rate constants, order and molecularity of reactions, Reactions of zero order, first order, second order, third order and fractional order, half life, mean life, Pseudo first order reactions, determination of order of a reaction by half-life and differential method, experimental methods of the determination of rate laws, temperature dependence of rate constant, Arrhenius equation, energy of activation, collision theory and activated-complex theory of reaction rates.
Equilibrium and steady-state approximation – explanation with suitable examples, kinetics of complex reactions (integrated rate expressions up to first order only)- opposing reactions, parallel reactions and consecutive reactions.

Types of catalyst, specificity and selectivity, mechanisms of catalyzed reactions at solid surfaces, effect of particle size and efficiency of nanoparticles as catalysts, enzyme catalysis, Michaelis-Menten mechanism, acid-base catalysis.