Course

Unit I

Surface ChemistryDifferent types of interfaces, molecular and atomic surface structure, surface chemical reactions, surface tension of solutions, surface excess, thermodynamics of surfaces, Gibbs equation and its derivation, surface films, surface potential, adsorption by solids, Langmuir isotherm – its kinetic and statistical derivation, Freundlich equation, multilayer adsorption, BET isotherm – its kinetic derivation, measurement of surface area. Colloids – their preparation, purification, stability & electro kinetic phenomena, Donnan membrane equilibrium, micro and nano emulsions. Surface analysis using photoelectron spectroscopy, surface imaging techniques like SEM, TEM, AFM etc., sputter coating, ion beam principles, design of surfaces with novel properties.

Unit II

Electrochemistry IReview of Faradays laws, conductivity of electrolytes, ionic mobility, transference number, Kohlrausch law, pH of acids, bases and buffers, solubility product and salt hydrolysis and Ostwald dilution law. Deviations from the Ostwald law, activity and activity coefficients in electrolytic solution, modern theory of conductance of strong electrolytes and its tests and improvements, Debye-Huckel-Onsager equation theory of mean activity coefficients of strong electrolyte Debye-Huckel limiting law and its testing and improvement.

Unit III

Electrochemistry IIElectrochemical cells, standard electrode potentials, reversible cell, concentration cells with and without transference, standard electrode potentials, reversible cell, cell notation and calculation of emf variation of potential with concentration, pressure and temperature, Liquid Junction Potential its calculation and elimination – Thermodynamics of cell reactions and equilibrium constant – applications of e.m.f. measurements, potentiometric measurement of pH reference electrodes – glass and quinhydrone electrodes and their performance and limitations, ion selective electrodes biomembranes, Interfacial region electrical double layers and their structure Helmholtz-Perrin, Gouy-Chapman and Stern models – charge transfer across interfaces, mass transport diffusion and convection controlled transport irreversible electrode processes – activation, concentration and IR polarisation, decomposition potential, Butler-Vohmer equation – over potential (hydrogen, oxygen and metal decomposition over voltage), theories of over voltage, Tafel equation, and Tafel plots corrosion and its rate from Tafel equation.

Unit IV

Chemical Kinetics IReaction rates and order of reactions, determination of order of reactions, complex reactions, reversible, consecutive and concurrent reactions, reactions of variable order, steady state treatment, reaction mechanism and molecularity, theories of unimolecular reactions and termolecular reactions, Arrhenius equation, collision theory and transition state theory, comparative study of the theories of reaction rates, free energy of activation, effect of solvent on rate of reactions, ionic reactions and effect of ionic strength – salt effect, effect of pressure on velocity of gas reactions.

Unit V

Chemical Kinetics IIReaction dynamics, fast reactions, flash photolysis and relaxation methods, catalysis and inhibition, homogeneous catalysis, acid, base and enzyme catalysis, kinetics of enzyme catalysed reaction – the Michaelis- Menten equation. Photochemical kinetics, steady state treatment of photochemical reactions, Semenov- Hinshelwood theory of chain reactions and explosions, free radical reactions – the Rice-Herzfeld mechanism.

TEXTBOOKS1.Gilbert W. Castellan, Physical Chemistry, 3rd Edition, Narosa Publishing House, 2004.2.K. J. Laidler, Chemical-Kinetics, 3rd Edition, McGraw Hill, New York, 2004.3.An introduction to Electrochemistry, Samuel Glassstone (2007)REFERENCES1.W. J. Moore and R. G. Pearson, Kinetics and Mechanism, 2nd edition, Wiley, 1981.2.Physical Chemistry, Peter Atkins, Julio D Paula, OUP Oxford; 9 edition (19 November (2009)3.Textbook of Physical Chemistry, Samuel Glassstone, D. Van Nostrand company, inc; 2nd edition (1946)4.John O’M. Bockris, Amulya K.N .Reddy,Modern Electrochemistry 1: Ionics, 2nd Edition, Springer, 19985.John O’M. Bockris, Amulya K.N. Reddy, Maria E. Gamboa-Aldeco, Modern Electrochemistry 2A: Fundamentals of Electrodics 2nd Edition, Springer, 2001