Applications of Thermodynamics

Gibbs and Helmholtz functions, Gibbs function (G) and Helmholtz function (A) as thermodynamic quantities, A & G as criteria for thermodynamic equilibrium and spontaneity, their advantages over entropy change, variation of G & A with P, V & T.

Equilibrium constant and free energy, thermodynamic derivation of law of mass action. Le Chatelier’s principle,reaction isotherm and reaction isochore- Clapeyron equation and Clausius -Clapeyron equation, applications.
 

Introduction to phase, component and degree of freedom, derivation of Gibbs phase rule; phase equilibria of one component system-water, CO₂ and sulphur system.
Phase equilibria of two component system-solid-liquid equilibria, simple eutectic – Bi-Cd, Pb-Ag systems, desilverisation of lead.
Solid solutions: compound formation with congruent melting point (Mg-Zn), (FeCl₃ – H₂O) and incongruent melting point (NaCl-H₂O)and (CuSO₄ – H₂O) system; freezing mixtures (acetone – dry ice).
 

Types of reversible electrodes – gas-metal ion, metal-metal ion, metal-insoluble salt-anion and redox electrodes; electrode reactions, Nernst equation, EMF of a cell and its measurements, computation of cell EMF, calculation of thermodynamic quantities of cell reactions (∆G, ∆H & K),derivation of cell E.M.F. and single electrode potential; standard hydrogen electrode- reference electrodes, standard electrode potential, sign conventions, electrochemical series and its significance.

Electrolytic and Galvanic cells: reversible and irreversible cells, conventional representation of electrochemical cells.
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 and glass electrodes and by potentiometric method.