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M.Sc. Physical Chemistry
Advanced Electrochemistry (4302)
Prerequisite: Good
knowledge of Mathematics and
Adsorption and Electric Double Layer
Thermodynamics of the double layer, Electrocapillary
phenomena; Adsorption- Ionic and organic molecules, Adsorption isotherms-
Langmuir, Frumkin, Temkin;
Experimental evaluation of surface excesses and Electrical parameters,
Structure of electrified Interfaces - Derivation of Gouy-Chapman
and Stern model, Qualitative aspects of Graham-Devanathan-Mottwatts, Tobin, Bockris, Devanathan models.
Kinetics of Electrochemical Reactions
Electrode Kinetics: Overpotentials,
Exchange current density, Derivation of Butler-Volmer
equation and its implications, Tafel plot, Multistep
electrode reactions, Determination of multistep electrode reactions, Mass
transfer by diffusion.
Quantum Aspects: Marcus theory of charge transfer at electrode-solution interfaces,
Quantization of charge transfer, Tunneling.
Semiconductor Interfaces: Structure of double layer at semiconductor-solution interface, Effect
of light at semiconductor-solution interface.
Relaxation Methods-Theory and Techniques
Equivalent circuit based analysis, Diffusion equation and electrode boundary
conditions
Controlled potential techniques: Single potential step methods for reversible,
quasi-reversible charge transfer with and without uncompensated solution resistance;
Single potential step method with coupled homogeneous chemical reaction; Double
potential steps method for reversible charge transfer; Cottrell equation, Anson
equation
Pulse Voltammeteries for reversible charge transfer,
Randles-Sevcik equation
Impedance Methods: Derivation of Warburg, Gerischer,
Randles- Ershler Impedance
equations in presence of DC component and uncompensated solution resistance
Controlled current techniques: Galvanostatic and
power law current method for the reversible charge transfer, Sand equation
Hydrodynamic techniques, Scanning probe techniques.
Electrocrystallization, Bioelectrochemistry, Applied
Electrochemistry
Electrogrowth of metals on
electrode - Nucleation, Growth, Surface diffusion, Underpotential
deposition, Varity of shapes formed in Electrodeposition
Membrane potentials, Nernst-Planck equation, Hodgkin-Huxley equations,
Core Conductor model, Electrocardiography
Corrosion: Introduction to corrosion,
Forms of corrosion, Corrosion monitoring and prevention methods.
Conversion and Storage of Electrochemical Energy: Fuel cells and batteries.
Electrocatalysis: Influence of
various parameters, Hydrogen electrode.
Suggested
(1.) Bard &. Faulkner, Electrochemical Methods:
Fundamentals and Applications, Second Edition
(2.) Brett & Brett, Electrochemistry: Principles,
Methods and Applications, 1993
(3.) L.I. Antropov,
Theoretical Electrochemistry,
(4.) Bockris & Reddy,
Modern Electrochemistry. Vol. I, 2A, 2B
(4.)
(4.) V. S. Bagotsky,
Fundamental of Electrochemistry, 2nd Ed.
(7.) C. H. Hamann, A. Hamnett & W. Vielstich,
Electrochemistry 2nd Ed.
Assignments
(II)
Irreversible Thermodynamics and Nonequilibrium Statistical
Mechanics:
Irreversible thermodynamics:
Prerequisite: Good knowledge of Mathematics and
Meaning and scope of irreversible
thermodynamics, Thermodynamic criteria for non-equilibrium states,
Phenomenological laws- Linear laws, Gibbs equation, Onsager’s reciprocal
relations, Entropy production- specific examples of entropy production,
Non-equilibrium stationary states, Prigogine’s principle of maximum entropy
production, Coupled phenomena. Some important applications.
Assignments
Transport phenomena:
Diffusion coefficients, Fick’s first and
second laws, relation between flux and viscosity, Relation between diffusion
coefficient and mean free path, Relation between thermal conductivity/viscosity
and mean free path of a perfect gas, Einstein relation, Nernst-Einstein
equation, Stokes-Einstein equation, Einstein-Smoluchowski
equation.
Assignments
(III) Applications of Statistical Mechanics:
Prerequisite:
Good knowledge of Mathematics and
Theories
of Polymers Size and Molecular Weight Distributions:
Configuration of Polymer Chains: Statistical Distribution of End-to
End Dimensions - Freely Jointed Chain in One Dimension, Freely Jointed Chain in
Three Dimensions, The Distribution at High Extensions, Influence of Bond
Angle Restrictions, Average end-to-end distance, Radius of gyrations and its
relation to end-to-end distance.
Conformational Entropy in Random Coil Model, Dilute Polymer Solutions - Theta state of polymers.
Concepts on number average
and mass average molecular
weights. Methods of determining
molecular weights
- Osmometry, Viscometry, Sedimentation
equilibrium methods.
Suggested
(1.) Paul J. Flory, Principles of Polymer Chemistry,
(2.) Atkins’
Assignments
Theories
of Electrolyte Solutions:
Ionic activity and activity
coefficients, Physical significance of activity coefficients, mean
activity coefficient of an electrolyte and its determination.
Distribution of ions in solution according to Arrhenius and Ghosh Model, The Debye-Hückel
model of electrolytic solutions, Calculation of the energy of ionic interaction
and activity coefficients, further development of the Debye-Hückel
theory i.e. finite ionic size correction. Excess functions.
Suggested
(1.) L.I. Antropov,
Theoretical Electrochemistry, (2.) Bockris &
Reddy, Modern Electrochemistry.
Assignments
Theories
of Homogeneous Chemical Reaction Rates:
Reactions in Gaseous State: The Kinetic Theory
of Collisions. Potential energy surfaces (basic idea).
Transition state theory (both thermodynamic and statistical mechanics formulations).
Theory of unimolecular reactions, Lindemann mechanism, Hinshelwood treatment.
Reactions in Solution: Factors affecting reaction rates in solution.
Effect of solvent and ionic strength (primary salt effect) on the rate constant. Secondary salt effects.
Suggested
(1.) K. J.
Laidler, Chemical Kinetics; (2.) A. A. Frost & R. G. Pearson,
Kinetics and Mechanism; (3.) Atkins’
Physical Chemistry.
Assignments
Ph.D. Course
Contemporary
Electrochemistry
"Knowledge
is Eternal"