Electrochemistry and Chemical Kinetics

Paper Code: 
CHY 323
Credits: 
4
Contact Hours: 
60.00
Max. Marks: 
100.00
Objective: 

To understand the behaviour of ions in solution and structure of electrode surface. To learn rate laws from a proposed mechanism and analyze kinetics in gases and solutions.

8.00
Unit I: 
Ions in solution

Debye Huckel theory of strong electrolytes, Debye Huckel Onsager equation, activity coefficient, mean ionic activity coefficient, physical significance of activity coefficients, mean activity coefficient of an electrolyte and its determination, ionic strength, Debye Huckel theory of mean ionic activity coefficient, Debye-Huckel limiting law, qualitative and quantitative verification of Debye-Huckel limiting law, Debye length, ionic strength, Bjerrum model of ion-association.

12.00
Unit II: 
Electrochemistry: Electrical Double Layer
Introduction, evidences and structure of electrical double layer- Helmholtz-Perrin, Guoy-Chapman, Stern theory, measurement of zeta potential (electrokinetic phenomena), influence of ions on electrokinetic phenomena, electro capillary phenomenon: Electro capillary curves, Lipmann’s equation.
 
Graham Devanathan-Mottwatts, Tobin Bockris, Devanathan models. Quantum aspects of charge transfer at electrodes-solution interfaces, tunneling.
14.00
Unit III: 
Kinetics of Electrode Reactions
Electrodics of elementary electrode reactions: Determination of anode and cathode  potential, decomposition voltage of electrolyte, diffusion over potential, hydrogen and oxygen over voltage, influence of various factors on over voltage, theoretical investigation of kinetics of an electrode reaction: standard rate constant (k0) and transfer coefficient (α), exchange current. Butler-Volmer equation, Tafel equation.
 
Electrocatalysis: introduction and influence of various parameters.
 
Semiconductor solution interfaces, effect of light at semiconductor solution interface.
13.00
Unit IV: 
Statistical Theories of Kinetics

Collision theory of reaction rates, steric factor, activated complex theory, comparison between collision theory and activated-complex theory. Unimolecular gas reactions: Dynamics of unimolecular reactions (Lindemann, Hinshelwood, RRK and RRKM theories), primary and secondary salt effects: influence of ionic strength and dielectric constant on reactions involving (i) ions  (ii) dipoles (iii) ion and dipole.

13.00
Unit V: 
Complex Reactions

Equilibrium and steady state approximation and their application in reaction mechanisms, Rate expression for opposing, parallel and consecutive reactions, kinetic and thermodynamic control of the reactions, chain reactions: thermal and photochemical reactions, dynamic chain (mechanism of hydrogen-bromine and hydrogen-chlorine reactions), decomposition of ethane, pyrolysis of acetaldehyde, oscillatory reactions: Belousov-Zhabotinsky reaction.

Essential Readings: 
  1. Modern Electrochemistry Vol. I, II A & II B; Second Edition; J. O’m. Bockris and K.N. Reddy; Kluwer Academic/Plenum Press, New York, 2000.
  2. An Introduction to Electrochemistry; Seventh Edition; S. Glasstone, Affiliated East-West press Pvt. Ltd., New Delhi, 2016.
  3. Electrochemistry- Principles, Methods and Applications; C. M. A. Brett and A. M. O. Brett; Oxford University Press, Great Britain, 1994.
  4. Chemical Kinetics; Third Edition; K.J. Laidler; Pearson Education Pvt. Ltd., Singapore, 2013.
  5. Kinetics and Mechanisms of Chemical Transformations; First Edition; J. Rajaram and J.C. Kuriacose; Macmillan Publisher India Ltd., New Delhi, 2009.
  6.  Advanced Physical Chemistry; Sixteenth Edition; J. N. Gurtu and A. Gurtu,  Pragati Prakashan, Meerut 2014.

 

Academic Year: 
2018-2019
  • Printer-friendly version
  • PDF version