Kinetics and thermodynamics – chemical equilibrium – activation – transition state model – potential energy surface for substitution and elimination reactions – the rate limiting step – Hammond postulate – the principle of microscopic reversibility – the principle of least motion – isokinetic relationship – kinetic and thermodynamic control of products – isotope effects – primary, secondary and solvent isotope effects.
Correlation of structure with reactivity – linear free energy relationships Hammett equation – interpretation of substitutent and reaction constants – ?, ?+, ? -, polar and steric substitutent constants – the Taft model – deviation from Hammett equation – acidity functions – determination of solvent polarity and solvent polarity scales.
Determination of reaction mechanism, reactions and mechanistic classifications – kinetics as an aid – detection and trapping of reactive intermediates – stereochemical probe – isotope effects – solvent effect – salt effect – ion pairs in solvolysis raction – intra- and intermolecular reactions – anchimeric assistance – stereoelectronic effects on rates and course.
Catalysis – homogeneous – acids and bases and their strengths – specific and general acid base catalysis – Bronsted catalysis law – intepretation of Bronsted coefficient – nucleophilic and electrophilic catalysis – mechanisms of some acid- base catalysed reactions in carbonyl and olefin chemistry.
Reactive intermediats – carbenes – nitrenes – arynes – free radicals – carbonium ions and carbanions – their generation, detection, characterization, structure and reactivity.
Recent topics in mechanistic organic chemistry – electron transfer reactions – electron transfer catalysed reactions – substitution via free radicals – free radical cyclization – Baldwin;s rules – Lewis acid catalysis of some common organic reactions.