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M.Sc. Physical Chemistry

Advanced Electrochemistry (4302)

Prerequisite: Good knowledge of Mathematics and Physical Chemistry upto B.Sc. (Chem. Hons.)


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 Readings


(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.) Milan Paunovic and Mordechay Schlesinger, Fundamentals of Electrochemical Deposition, 2nd Edition 2006.

(4.) V. S. Bagotsky, Fundamental of Electrochemistry, 2nd Ed.

(7.) C. H. Hamann, A. Hamnett & W. Vielstich, Electrochemistry 2nd Ed.




(II) Irreversible Thermodynamics and Nonequilibrium Statistical Mechanics:

Irreversible thermodynamics:

Prerequisite: Good knowledge of Mathematics and Physical Chemistry upto B.Sc. (Chem. Hons.)

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.


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.



 (III) Applications of Statistical Mechanics:

Prerequisite: Good knowledge of Mathematics and Physical Chemistry up to B.Sc. (Chem. Hons.)


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 Readings:

(1.) Paul J. Flory, Principles of Polymer Chemistry, (2.) Atkins’ Physical Chemistry,  (3) Fred W. Billmeyer, Textbook of Polymer Science.



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 Readings:

(1.) L.I. Antropov, Theoretical Electrochemistry, (2.) Bockris & Reddy, Modern Electrochemistry.



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 Readings:

(1.) K. J.  Laidler, Chemical Kinetics;  (2.) A. A. Frost & R. G. Pearson, Kinetics and Mechanism;  (3.) Atkins’ Physical Chemistry.




Ph.D. Course

Contemporary Electrochemistry




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