ELECTROCHEMISTRY AND SOLUTIONS

Electrical transport, conductance in metals and electrolytes, specific conductance and equivalent conductance, measurement of equivalent conductance, variation of equivalent and specific conductance with dilution.
Arrhenius theory of electrolytic dissociation and its limitations, weak and strong electrolytes, Ostwald’s dilution law, its uses and limitations, Debye-Hückel-Onsager’s equation for strong electrolytes (elementary treatment only), migration of ions and Kohlrausch’slaw, transport number – definition and determination by Hittorf and moving boundary method.
Applications of conductivity measurements- determination of degree of dissociation, acid dissociation constant, solubility product of a sparingly soluble salt, conductometric titrations.

Electrolytic and Galvanic cells- reversible and irreversible cells, free energy and EMF of a cell, Nernst equation, EMF of a cell and its measurements, calculation of thermodynamic quantities of cell reactions (∆G, ∆H & K), electrochemical series and its significance, representation of electrochemical cell, standard electrode potential, single electrode potential, standard hydrogen electrode- reference electrodes, types of reversible electrodes – gas-metal ion, metal-metal ion, metal-insoluble salt-anion and redox electrodes.

Concentration cell- electrode concentration cell and electrolyte concentration cell (with and without transport), liquid junction potential, applications of concentration cell- valency of ions, solubility product, activity coefficient, potentiometric titrations.
Definition of pH and pKa, determination of pH using hydrogen, quinhydrone, glass electrodes and by potentiometric method.

Solutions- Ideal and non-ideal solutions, distillation of solutions, lever rule, methods of expressing concentrations of solutions, activity and activity coefficient.
Henry’s law, deviation from Henry’s law, Nernst distribution law and its applications.
Non ideal system- azeotropes, ethanol-water systems.
Partially miscible liquids- phenol-water, trimethylamine-water, nicotine-water systems, effect of impurity on consolute temperature, immiscible liquids, principle of steam distillation.

Introduction, colligative properties, Raoult’s law, relative lowering of vapour pressure and its measurement, osmotic pressure and its measurement by Barkeley –Hartley’s method, elevation of boiling point and its measurement by Landsberger’s method, depression of freezing point and its measurement by Rast method, use of colligative properties in molecular weight determination, non-ideal behaviour and van’t Hoff’s factor ‘i’.