In this course the student is challenged to combine all of his or her current knowledge of all fields of chemistry into the understanding, applications and evaluation of a selected set of models from physical chemistry. Through group discussions the students are activated to formulate their own opinions and ideas about the models and their application to (organic) systems which are considerably more complicated than those originally used to set up the model.
In Chapter 1 intuitive connections are made between the structure of molecules and their reactivity. Both internal (non-bonding and weak interactions, Chapter 5) and external effects (influence of the solvent, Chapter 4), that may influence the outcome or rate of a reaction, are considered. After a more general introduction on kinetics and thermodynamics, the influence of the molecular structure on the energy-reaction coordinate-diagram is discussed and the relationship between structure and reactivity is investigated using the Hammett and comparable formalisms. Then, two methods to ascertain the reaction mechanism are discussed: kinetic isotope effects and computational chemistry (Chapter 3). The influence of the solvent on kinetics and thermodynamics are investigated (Chapter 4), as is the influence of weak interactions on reactivity (Chapter 5). Finally, two topics from current physical organic chemistry are discussed: photochemistry and aromaticity. Using the E/Z isomerisation of C=C bonds as a practical example, photochemical processes are compared with their thermochemical counterparts and the structure of the excited state is considered (Chapter 6). Aromaticity, anti-aromaticity and non-aromaticity are discussed, after defining these concepts and acknowledgeing the difficulties associated with this, in the framework of the experimental and theoretical methods available to quantify them; finally, the validity and usefulness of these concepts is discussed (Chapter 7).