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.

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 titrations and (v) hydrolysis constants of salts.

Types of reversible electrodes – gas-metal ion, metal-metal ion, metal-insoluble salt-anion and redox electrodes; electrode reactions, Nernst equation, EMF of a cell and its measurements, computation of cell EMF, calculation of thermodynamic quantities of cell reactions (∆G, ∆H & K), 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 and irreversible cells, conventional representation of electrochemical cells. Concentration cell with and without transport, liquid Junction potential, applications of concentration cell - valency of ions, solubility product, activity coefficient, potentiometric titrations. Definition of pH and pKa, determination of pH using hydrogen, quinhydrone and glass electrodes and by potentiometric method.

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 (example using acid catalyzed hydrolysis of methyl acetate),Radioactive decay as first order reaction. 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 of reaction rates.

Kinetics of complex reactions (integrated rateexpressions up to first order only): Opposing reactions, parallel reactions and consecutive reactions. Rate-determining and steady-state approximation – explanation with suitable examples. 

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.