CH3025 Physical Organic Chemistry
General introduction. Brief introduction to potential energy surfaces. Thermodynamic formulation of activated complex theory. Linear free energy relationships. Hammett equation. Separation of polar and resonance effects in aromatic systems. Application of Hammett equation in hydrolysis, elimination reactions, etc. Cross-conjugation; definition of s+, s-. Steric effects; Taft equation. Proton-transfer reactions. Iodination of acetone as example of reaction where there is specific and general acid-base catalysis. Bronsted equation. Hammond hypothesis. Kinetic isotope effects. Simple theory - assuming zero point energy only in reactants. Zero point energy contribution in activated complex. Dependence of kH/kD on transition state structure; quantum mechanical tunnelling. Brief introduction to secondary isotope effects. Solvent effects (some years only).
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