Thermodynamics and Surface Chemistry

Thermodynamics of open system: Partial molar properties, determination of these quantities and their significance, chemical potential in a system of ideal gases, Gibbs- Duhem equation, fugacity and determination of fugacity.

Non-ideal systems: excess functions for non-ideal solutions, the concept of activity and activity coefficient.

Quantum mechanical aspects: Concept of distribution, thermodynamic probability and most probable distribution, common terms- occupation number, statistical weight factor, configuration, phase space, macroscopic state, microscopic state, system, assembly, canonical, grand canonical and microcanonical ensemble, ensemble averaging and its postulates.

Type of statistics- Maxwell-Boltzmann statistics, Bose-Einstein statistics and Fermi-Dirac statistics. Applications of statistics to helium, photon gas and metals.

Molecular partition function for an ideal gas, translational, rotational, vibrational, electronic and nuclear partition function.

Calculation of thermodynamic properties in terms of partition function-

translational energy, entropy, enthalpy, Helmholtz function, Gibb’s free energy of a monoatomic gas. Equilibrium constant, equipartition principle, heat capacity of mono and diatomic gases, mixture of o and p- hydrogen, heat capacity of solids. 

Entropy, probability, Boltzmann-planck equation, significance of thermodynamics probability, entropy of expansion of ideal gas, molecular basis of residual entropy, statistical calculation of entropy, vibrational entropy, nuclear spin entropy, virtual entropy, rotational entropy, comparison of third law and statistical entropies, random orientation in the solids, entropy of hydrogen and deuterium.

Thermodynamic criteria for non-equilibrium states, entropy production and entropy flow, entropy balance equations for different irreversible processes (heat flow, chemical reaction etc.), transformations of the generalized fluxes and forces, non-equilibrium stationary states, phenomenological equations, microscopic reversibility and Onsager’s reciprocity relations, electrokinetic phenomenon, diffusion and electric conduction. Irreversible thermodynamics for biological systems, coupled reactions.

Adsorption of gases by solids, BET adsorption isotherm, adsorption from solution, Gibbs adsorption isotherm. Surface films on liquids (electrokinetic phenomena), catalytic activity of surfaces.

Surface active agents, classification, hydrophobic interaction, micelle formation- mass action model and phase separation model, shape and structure of micelles, micellar aggregation numbers, critical micelle concentration (CMC), factors affecting CMC of surfactants, counter ion binding to micelles, thermodynamics of CMC, thermodynamics of micellization, micelle temperature range (MTR) or Kraft point, solubilization, micro emulsion and reverse micelles.