UNIVERSITY OF MADRAS
B.Sc. DEGREE COURSE IN CHEMISTRY
SEMESTER SYSTEM WITH CREDITS
(Effective from the Academic Year 2003-2004)

Semester VI - Paper XI - Physical Chemistry-II

Duration: 3 hrs
Maximum Marks: 100
Credits: 4

Unit - I

1.1 Photochemistry laws -- Fluorescence and phosphorescence primary and secondary reactions kinetics of hydrogen -- bromine reaction - photosentisation - chemilurninescence.

1.2 Group theory - Symmetry operations - products of symmeti operations - classes and subgroups - group multiplicaiton table - properties of a group - point groups - C2v, C3v, C2h, D4h, D6h, D2h, D3h, Td, Oh (any one example for each).

Unit - II Electrochemistry - Conductance.

2.1 Metallic and electrolytic conductors - specific, equivalent and molar conductance - mesurernent of conducatance - variation of cQnductance with dilution for strong and weak electrolytes (qualitative explanation) - Transport number and its determination by Hittorffs and moving boundary method -effect of temperature and concentration - ionic mobility and ionic conductance - Kohlausch's law and its applications - salt hydrolysis and pH of a salt solution, buffer action and explanation.

2.2 Theory of strong electrolytes - Debye - Huckel - Onsager theory - verification of Onsager equation -- Wein effect and Debye - Falkenhangen effect - ionic strength - activity and activity coefficients of strong electrolytes.

2.3 Applications of conductivity measurements degree of hydrolysis, solubility product and conductometric titrations.

Unit - III Electrochemistry

3.1 Galvanic cells - reversible and irreversible electrodes and cells - standard cell-emf and its measurement - types of electrodes - electrode reactions electrode potentials - reference electrodes -- standard electrode potentials.

3.2 Derivation of Nest equation for electrode potential and cell emf sign coventions - electrochemical series and its applications - formation of cells - electrode and cell reactions - cell emf - chemical cells and concentration cells with and without transference - examples and derivation of expressions for their emfs - liquid junction potential.

3.3 Applications of emf measurements - calculation of G.H, S and equilibrium constants - determination of pH using quinhydrone and glass electrodes - potentiometric titrations.

3.4 Applications of concentration cells - determination of valency of ions - transport number - equilibrium constant - solubility product - activity coefficients of electrolytes.

3.5 Polarisation - decomposition potential - overvoltage - storage cells - lead acid battery - mechanism of discharging and recharging - fuel cells.