SYLLABUS

 PHYSICAL CHEMISTRY – II

UNIT – I: Phase Rule
Definitions of terms; derivation of phase rule; application to
one component systems – water and sulphur – super cooling,
sublimation; two component systems – solid liquid equilibria –
simple eutectic (lead – silver and bismuth – cadmium), freezing
mixtures (potassium iodide – water), compound formation with
– congruent melting points (magnesium – zinc and ferric
chloride – water system), peritectic change (sodium –
potassium), solid solution (gold-silver); copper sulphate – water
system.

UNIT – II: Chemical Equilibrium
Law of mass action – thermodynamic derivation – relationship
between Kp and Kc – application to the homogeneous equilibria
– dissociation of PCl5 gas, N2O4 gas – equilibrium constant
and degree of dissociation – formation of HI, NH3 and SO3 –
heterogeneous equilibrium – decomposition of solid calcium
carbonate – Lechatelier principle -Van’t Hoff reaction isotherm
– temperature dependence of equilibrium constant – Van’t Hoff
reaction isochore – Clayperon equation – Clasius Clayperon
equation and its applications.

UNIT – III: Binary Liquid Mixtures
Ideal liquid mixtures – non ideal solutions – azeotropic mixtures
– fractional distillation – partially miscible mixtures –
phenol-water, triethylamine-water, nicotine-water – effect of
impurities on critical solution temperature; immiscible liquids
– steam distillation; Nernst distribution law – applications.

UNIT – IV: Electrical Conductance and Transference
Arrhenius theory of electrolytic dissociation – Ostwald’s
dilution law, limitations of Arrhenius theory; behaviour of
strong electrolytes – interionic effects – debye Huckel theory –
Onsager equation (no derivation), significance of Onsagar
equation, Debye Falkenhagen effect, Wien effect. Ionic

mobility – Discharge of ions on electrolysis (Hiltorf’s
theoretical device), transport number – determination – Hittorf’s
method, moving boundary method – factors affecting transport
number – determination of ionic mobility; Kohlrausch’ law –
applications; molar ionic conductance and viscosity (Walden’s
rule); applications of conductance measurements –
determination of – degree of dissociation of weak electrolyte,
dissociation constant of weak acid and weak base, ionic product
of water, solubility and solubility product of sparingly soluble
salts – conductometric titrations – acid base titrations.

UNIT – V: Galvanic Cells and Applications
Galvanic cell, representation, reversible and irreversible cells,
EMF and its measurement – standard cell; relationship between
electrical energy and chemical energy; sign of EMF and
spontaneity of a reaction, thermodynamics and EMF –
calculation of Δ G, ΔH and ΔS from EMF data; reversible
electrodes, electrode potential, standard electrode potential,
primary and secondary reference electrodes, Nernst equation for
electrode potential and cell EMF; types of electrodes –
metal/metal ion, metal amalgam/metal ion, metal, insoluble
salt/anion, gas electrode, redox electrode; electrochemical series
– applications of electrochemical series. Chemical cells with and
without transport, concentration cells with and without transport;
Applications of EMF measurements applications of EMF
measurements – determination of activity coefficient of
electrolytes, transport number, valency of ions, solubility product,
pH using hydrogen gas electrode, quinhydrone electrode and glass
electrode, potentiometric titrations – acid base titrations, redox
titrations, precipitation titrations, ionic product of water and
degree of hydrolysis; redox indicators – use of diphenylamine
indicator in the titrations of ferrous iron against dichromate.

Industrial component
Galvanic cells – lead storage, Ni-Cd, Li and Zn-air, Al-air
batteries Fuel cells H2−O2 cell – efficiency of fuel cells.
Corrosion – mechanism, types and methods of prevention.