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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-H�ckel
model of electrolytic solutions, Calculation of the energy of ionic interaction
and activity coefficients, further development of the Debye-H�ckel
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"