Physical Organic Chemistry


The aim of the discipline is to understand the intimate relationship between structure, properties and reactivity of organic compounds.

As far as competencies are concerned, in addition to the aims of formation in this scientific area, it is expected that Physical Organic Chemistry will enable the student to understand emerging knowledge areas such as Bioorganic  and Organometallic Chemistry, Supramolecular Chemistry, Material Sciences and Nanotechnologies.

General characterization





Responsible teacher

João Carlos dos Santos Silva e Pereira de Lima, Nuno Miguel Jesuíno Basílio


Weekly - 2

Total - 36

Teaching language



Available soon


E. V. Anslyn, D. A. Dougherty, Modern Physical Organic Chemistry, 1st Edition, University Science Books, 2006


F. A. Carroll, Perspectives on Structure and Mechanism in Organic Chemistry, 1st Edition, Pacific Grove, CA, 1997


H. Lowry, K. S. Richardson, Mechanism and Theory in Organic Chemistry, 3rd Edition , Harper & Row Publishers, 1987


P. A. Sykes, A Guidebook to Mechanism in Organic Chemistry, 7th Edition, Longman, 1980

Teaching method

Dicussion of theoretical fondamental concepts.
Illustration with simple examples.
Problem solving about every subject.
Permanent tutorial suppot.

Evaluation method

Continuous evaluation. Coordination with other disciplines of the curriculum.
Continuous evaluation by 2 or 3 Tests, during the semester.
Alternatively, final examination (written and/or, eventually, oral).

Subject matter

1. Molecular Structure and Chemical Thermodynamics

Review of basic bonding concepts

Modern Theory of Organic Bonding

Molecular orbital theory

Reactive intermediates

Strain and Stability

Structure/Energy Relationships

Binding forces


2. Reactivity, Kinetics and Mechanism

Potential Energy Surfaces

Reaction coordinate diagrams. Transition states. Reaction order and rate constants

3. Linear Free Energy Relationships

Hammett Plots

Sigma and Rho Values. Deciphering reaction mechanisms. Prevision of rate and equilibrium constants.

4. Frontier Molecular Orbital Theory

Frontier orbitals HOMO and LUMO

HSAB Principle

Charge vs. Orbital control

5. Pericyclic Reactions

 Cycloaddition, Electrocyclic, Sigmatropic and Cheletropic reactions

  Conservation of Orbital Symmetry


Programs where the course is taught: