Physical Organic Chemistry

Mechanistic singnificance of entropy, enthalpy and Gibb’s free energy, Arrhenius equation, transition state theory, uses of activation parameters, Hammond’s postulate, Marcus theory of electron transfer, reactivity and selectivity principles, theory of isotope effects, primary and secondary kinetic isotop effects, heavy atom isotop effects, tunneling effect, solvent effects.

Linear free energy relationships (LFER), the Hammett equation, substituent, constants, theories of substituent effects, interpretation of σ values, reaction constant ρ, deviations from Hammett equation, dual-parameter corrections, inductive substituent constant, the Taft model σI - and σR – scales.

Various type of steric strain and their influence on reactivity, steric acceleration, molecular, measurements of steric, effects upon rates, steric LFER, conformational barrier to bond. Rotation-spectroscopic detection, of individual conformers , acyclic and monocyclic, systems, rotation around partial double bond, Winstein-Holness and Curtin-Hammett principle.

Acid-base dissociation, electronic and structural effects and basicity, acidity functions and their applications, hard and soft acids and bases, nucleophilicity, scalesl nucleofugacity, the α- effect , ambivalent nucleophiles, acid-base catalysis- specific and general catalysis, Bronsted catalysis, nucleophilic catalysis, catalysis by non-covalent-micellar catalysis.

Principle of molecular association and organization as exemplified in biological macromolecules like anzymes, nucleic acids, membranes and model systems like micelles and vesicles, molecular receptors and design principle, cryptands, cyclophanes, calixeranes, cyclodextrines, supramolecular reactivity and catalysis, molecular channels and transport processes, molecular devices and nanotechnology.