Thermodynamics and Electrochemistry

An overview of thermodynamic terms, intensive and extensive properties, state and path functions and their differentials; thermodynamic processes; concept of heat and work.

First law of thermodynamics: statement, definition of internal energy and enthalpy, heat capacity, heat capacities at constant volume and pressure and their relationship; Joule-Thomson coefficient

Standard state, standard enthalpy of formation; Hess’s law of heat summation and its applications; heat of reactions at constant pressure and at constant volume; enthalpy of neutralization; bond dissociation energy and its calculation from thermo-chemical data; Kirchoff’s equation.

Second law of thermodynamics: need for the law, different statements of the law, Carnot cycle and its efficiency, Carnot theorem, thermodynamic scale of temperature.

Concept of entropy: entropy as a state function, entropy as a function of V & T, entropy as a function of P & T, entropy change in physical processes, third law of thermodynamics: Nernst heat theorem, statement and concept of residual entropy, evaluation of absolute entropy from heat capacity data

Electrical transport, conductance in metals and electrolytes, specific conductance and equivalent conductance, measurement of equivalent conductance, variation of equivalent and specific conductance with dilution.

Applications of conductivity measurements: determination of degree of dissociation, acid dissociation constant Ka, solubility product of a sparingly soluble salt; conductometric titrations

Arrhenius theory of electrolytic dissociation and its limitations, weak and strong electrolytes; Ostwald’s dilution law, its uses and limitations; Debye-Huckel-Onsager’s equation for strong electrolytes (elementary treatment only); migration of ions and Kohlraush law; transport number – definition and determination by Hittorf and moving boundary method.