• Thermodynamics and kinetics: Rate laws - Reactions of I, II and III order - Equilibrium and consecutive reactions - Approximation of the rate determining step - Steady-state approximation - Arrhenius equation - Eyring equation - Potential energy surfaces and diagrams of reaction - More O'Ferrall-Jencks Graphs - Hammond Postulate - Principle of microscopic reversibility - Principle of reactivity-selectivity - Principle of Curtin-Hammett • Linear free energy correlations (LFER): Hammett equation: substituent and reaction constants – Variations to Hammett scale - Non-linear Hammett correlations - Multiparameter LFER: the equation of Yukawa-Tsuno - Taft-Ingold equation for aliphatic systems - Biological activity correlations: QSAR • Isotope effect: kinetic and equilibrium isotope effect - Primary, secondary and solvent isotopic effects - Tunnel effect • Solvent effect: properties of solvents - Non-covalent interactions –Non-conventional solvents: ionic liquids and supercritical fluids - Solvation and electrostriction - Dielectric constant and Hildebrand constant- Grunwald-Winstein Y scale - Solvatocromism: Kosower Z and Dimroth and Reichardt ET(30) - Gutmann Scale - Abraham-Kamlet-Taft scale - Preferential solvation - Hydrophobic interaction and "iceberg" theory • Acids and bases: Hammett acidity function – Excess acidity and basicity functions - Nucleophiles and electrophiles: hard-soft principle • Acid-base catalysis: Specific and general acid-base catalysis - Electrophilic and nucleophilic catalysis - Brønsted equation - Theory of Marcus - Rate-pH profiles.
• Basic Principles of nuclear magnetic resonance: Magnetic properties of the nuclei, excitation and relaxation - Acquisition methods. Base sequences -FID and Fourier transform - Continuous wave and pulsed instruments (Pulse-FT-NMR) • Monodimensional NMR spectroscopy: proton spectroscopy (1H-NMR) chemical shift, spin coupling, spin systems of first order and higher order - Chemical and magnetic equivalence - Exchangeable protons - Selective spin decoupling. Chirality in 1H-NMR spectroscopy - Nuclear Overhauser effect (NOE): difference spectra, estimation of internuclear distances • Spectroscopy of carbon-13 (13C-NMR): 1H-13C coupling. Decoupled spectra. DEPT sequence - Chemical shift - Other important nuclei (31P, 15N-NMR) • Two-dimensional NMR spectroscopy: 1H-1H COSY and TOCSY correlation, 1H-1H NOESY correlation, 1H-13C HETCOR and HMQC correlation, 13C-13C INADEQUATE correlation • Mass spectrometry:
Physical principle - Instrumentation: sample introduction, ionization sources, analyzers, detectors - Types of ions generated. Patterns of fragmentation and rearrangements - Information obtained from a mass spectrum • IR spectrophotometry: theory and identification of the main functional groups • Application of mono- and two-dimensional NMR, mass spectrometry and IR spectroscopy spectrometric techniques in determining the structure of organic compounds.