4 credits 60 theoretical hours
OBJECTIVES:
Present the student with a quantitative or semi-quantitative approach to chemical interactions or reactions, based on mathematical models with predictive capacity.
SUMMARY:
1. Models for chemical bonds
2. Kinetics and Thermodynamics
3. Correlation of Structure with Reactivity
4. Solvent Effects
5. Equilibrium in Conformational Isomerization, cis-trans Isomerization and Ring Formation.
6. Acids and Bases, Electrophiles and Nucleophiles
7. Kinetic Isotope Effect
8. Homogeneous Catalysis
9. Organic Photochemistry
PROGRAM CONTENT:
Stereisomerism of cyclic systems
01. Models for Chemical Bonds
Covalency and molecular structure. Molecular orbital theory: valence bond, Hückel method and advanced methods. Properties of covalent bonds. Intermolecular forces.
02. Kinetics and Thermodynamics
Enthalpy. Entropy. Gibbs function. Factors that contribute to entropy. Chemical balance. Thermodynamic relationships. Application of thermodynamics to chemical reactions. Chemical kinetics. Transition state properties. The use of activation parameters. The location of the transition state.
03. Correlation of Structure with Reactivity
Electronic requirements. Hammett’s equation. Substituent constants. Theories of substituent effects. Interpretation for s values. Reaction constants r. Deviations from the Hammett equation. Correlations using dual parameters: inductive and resonance. Taft’s equation. Considerations using molecular orbitals.
04. Solvent Effects
The structure of liquids. Solutions. Solvation. Thermodynamic measurements of solvation. The effects of solvation on reaction rates and equilibrium. Empirical solvation indices. Correlations between empirical solvation scales. The use of solvation scales in mechanistic studies.
05. Equilibrium in Conformational Isomerization, in cis-trans Isomerization. and Ring Formation
Conformational equilibrium in acyclic compounds. Conformational equilibrium in cyclohexane and derivatives. Conformational equilibrium in other cyclic compounds. Calculation of relative conformational stabilities. Equilibrium in cis-trans isomerization. Formation of various types of rings. Comparison between cyclization reactions and analogous non-cyclization reactions.
06. Acids and Bases, Electrophiles and Nucleophiles
Acid-base dissociation. The strength of oxygenated and nitrogenous acids. Linear free energy relationships. Proton transfer speed. Structural effects on the dissociation of amines. Acidity of carbon acids. Factors influencing carbon acidity. Ionization rate of carbon acids. Acidity and basicity in the gas phase. Proton transfer theories. Highly acidic and highly basic solutions. Nucleophilicity and electrophilicity. Measurements of nucleophilicity and electrophilicity.
07. Kinetic Isotope Effect
Isotopic replacement. Isotopic effect theory. Transition state geometry. Secondary kinetic isotope effect. Isotopic effect of heavy atoms. The tunnel effect. Isotopic effect of the solvent.
08. Homogeneous Catalysis
Acid and basic catalysis. The mechanism of some acid-catalyzed reactions. Catalysis by non-covalent interactions.
09. Organic Photochemistry
Electronically excited states. Photochemistry of the carbon-carbon double bond. Photoreactions of carbonyl compounds. Photochemistry of aromatic compounds.
BIBLIOGRAPHY:
01. N.S. Isaacs – “Physical Organic Chemistry”, 2nd ed. Ed. Longman 1995.
02. J. Hine – “Structural Effects on Equilibria in Organic Chemistry”, John Wiley and Sons, Inc., 1975
03. N.J. Turro, “Modern Molecular Photochemistry”, Benjamin Cummings Publishing Co., Inc. California, 1978.
04. C. Reichardt, “Solvents and Solvent Effects in Organic Chemistry”, VCH Verlags gesellschft, Weinheim, 1990
05. R.P. Wayne, “Principles and Applications of Photochemistry”, Oxford University Press, London, 1988.
06. A. Gilbert and J. Baggott, “Essentials of Molecular Photochemistry”, Blackwell Scientific Publications, London, 1991
