ANALYTICAL CHEMISTRY

At the end of the course the student should be able to face a given analytical problem, choising the suitable instrumental teechnique, discussing it and explainig the choice.

Lectures and numerical exercices

Introduction to instrumental analysis - Qualitative and quantitative analysis – Sampling - Sensitivity and detection limits - Dynamic range - Noise and signal to noise ratio - Relationship between instrumental measures and the concentration: calibration by means of standard, internal standard and standard additions methods. Short outline of error theory – Systematic and casual error – Precision and accuracy - Statistical distribution function – Error propagation theory - Dixon Test - T Student.

Solute extraction by solvent –influence of pH - Influence of complex formation - Countercurrent extraction - Theoretical distribution of a two solute extraction.

Chromatography – Generality - Chromatographic plate theory - Chromatographic velocity theory - Partition and adsorption chromatography: on paper, thin film, columns. High performance liquid chromatography - Ionic chromatography - Size exclusion chromatography - Instrumentation.

Gas chromatography; principles and comparison with liquid chromatography; instrumentation.

Atomic spectroscopy – Atoms electronic levels – Boltzmann distribution – Flame atomic spectroscopy; emission and absorption phenomena – Spectral line width; uncertainty principle, Doppler and collisional effects - Influence of gas composition on flame temperature – Spectral, chemical and physical interferences - Graphite furnace – Inductively coupled plasma (ICP) – Instrumentation.

Infrared Spectroscopy – Vibrational energy – Freedom degrees – Electrical dipole moment – Linear and nonlinear molecules - Vibrational spectrum – Harmonic and inharmonic oscillator, classical and quantum treatment – Stretching and bending vibrations – Group vibrations – Qualitative and quantitative analysis – Fourier transform infrared spectroscopy and its comparison with dispersive spectroscopy – Instrumentation – NIR spectroscopy.

UV-Vis spectroscopy - Generality - Absorption and emission phenomena – Chromophores and auxochromes - Classification of the electronic transitions – Singlet and triplet states - Franck and Condon principle and its effect on vibrational-electronic spectra –- Qualitative and quantitative analysis - Influence of electronic structure, pH and solvent on the ʎ. Red shift and blue shift. Beer law and its deviations (chemical and instrumental) - Photometric error – Applications: analysis of mixture and criteria of the ʎ choice, photometric titrations, Job method.

Fluorescence spectroscopy – Photo-physics and photo-chemical processes – Excitation and emission spectra – Quantum yield – Relationship between concentration and fluorescence intensity - Comparison with UV spectroscopy – Instrumentation.

Mass Spectrometry – Fundamentals – Ion sources: electron impact (EI), chemical ionization (CI), field ionization (FI), field desorption (FD), fast atom bombardment (FAB), matrix assisted laser ionization-desorption (MALDI), electrospray – Fragmentation pattern – Metastable ions - Mass analyzer: magnetic sector, electrostatic sector, quadrupole, ion trap, time of flight (ToF), orbitrap – Detectors - Approximate and exact masses – Resolution – Isotopic abundances of C, S, Cl, Br and their effects on mass spectrum – Nitrogen rule – Unsaturation degree – Recognition of simple organic compounds.

Nuclear Magnetic resonance – Fundamentals – Comparison between classical theory and quantum-mechanical theory – Origin of NMR spectrum - ¹H and ¹³C spectra – Chemical Shift – Coupling of ¹H signal in organic molecules – Rules for the interpretation of simple NMR spectra.

- Douglas A. Skoog, James Holler and Stanley R. Crouch - Principles of Instrumental Analysis, VI ed. - Thomson Brooks/Cole

- Daniel C. Harris - QuantitativeChemical Analysis, 9th edition, W.H. Freeman and Company, New York, 2016