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

Should teaching be carried out in mixed mode or remotely, it may be necessary to introduce changes with respect to previous statements, in line with the programme planned and outlined in the syllabus.

Learning assessment may also be carried out on line, should the conditions require it.

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