Instrumental Analytical Chemistry Applications
A.Y. 2024/2025
Learning objectives
The course highlights the analytical application of powder diffraction and thermal analysis in material chemistry and furnishes the basic notions of Mass Spectrometry and Nuclear Magnetic Resonance spectroscopy for the structural elucidation of organic compounds.
Expected learning outcomes
At the end of the course the student will be able to:
-interpret thermal events in DSC and TGA analyses
-interpret powder diffraction patterns, use the crystallographic databases and perform simple quantitative and qualitative analyses on polycrystalline mixtures.
- interpret the result of a multivariate analysis
- interpret spectra and to identify the structure of simple organic compounds from 1H and 13C NMR and MS spectra.
-interpret thermal events in DSC and TGA analyses
-interpret powder diffraction patterns, use the crystallographic databases and perform simple quantitative and qualitative analyses on polycrystalline mixtures.
- interpret the result of a multivariate analysis
- interpret spectra and to identify the structure of simple organic compounds from 1H and 13C NMR and MS spectra.
Lesson period: First semester
Assessment methods: Esame
Assessment result: voto verbalizzato in trentesimi
Single course
This course can be attended as a single course.
Course syllabus and organization
Single session
Responsible
Lesson period
First semester
Course syllabus
Module on Diffraction and thermal analyses.
States of matter. Anisotropy and the meaning of order. Elementary crystallography requirements. Crystallographic planes and directions. Diffraction theory: history, nature and production of X-rays. Conventional X-ray sources and synchrotron radiation. X-ray diffraction: scattering by an electron, an atom (the atomic scattering factor), and a lattice (the structure factor). Diffusion from a crystal: the Bragg interpretation, the reciprocal lattice, the Ewald sphere. The diffraction pattern of a polycrystalline sample. Experimental techniques: diffraction geometries for polycrystalline samples. Sample preparation and data acquisition strategies. Practical aspects of powder X-ray diffraction (PXRD). Qualitative analysis of multiple crystalline. Quantitative analysis: the RIR and the Rietveld methods. Determination of the amorphous component and use of the internal standard. Use of crystallographic databases. The PDF database and its use for phase recognition; NIST standards for powder diffraction; the characterization of the microstructure and the problem of preferential orientation. The use of synchrotron radiation for PXRD quantitative analysis. Basics of X-ray fluorescence (XRF): principles. Qualitative and quantitative analysis with XRF.
Thermal analyses: principles. Thermogravimetry and differential scanning calorimetry. Instrumentation and practical aspects. Simultaneous thermal analyses (STA and DTA). Analysis of thermograms, determination of solvent content and final residue, determination of enantiomeric purity and identification of polymorphs. Thermal analyses in a controlled atmosphere. Combined thermal analyses: thermodiffractometry. Examples of qualitative/quantitative analysis with combined techniques. Examples of industrial applications of powder diffraction and thermal analysis in the pharmaceutical sector, in materials science and in the field of cultural heritage.
Module of NMR spectroscopy and MS.
The basics of NMR spectroscopy. NMR active nuclei. Pulsed spectroscopy. The relaxation times T1 and T2. The NMR observables: chemical shift, coupling constant and integral.
The NMR spectrum of the proton (1H): typical values of chemical shift and coupling constant.
The NMR spectrum of carbon (13C): typical values of chemical shift and coupling constant. The use of decoupling and simple sequences in the acquisition of 13C spectra. DEPT Spectra.
The observation of chemical exchange in the NMR spectrum.
Assignment of one-dimensional 1H and 13C spectra of molecules with known and unknown formulas.
Two-dimensional homonuclear (COSY) and heteronuclear (HSQC) NMR spectra
The basics of mass spectrometry (MS). Ionization and the main ion sources: electron impact (EI), chemical ionization (CI), fast atom bombardment (FAB), matrix-assisted laser ionization (MALDI), electrospray (ESI). How to read an MS spectrum and the fragmentation of the main functional groups in MS. Resolution and Accuracy. The analyzers: magnetic analyzer, dual focusing, quadrupole (and derivatives), ion trap, time of flight (TOF), Fourier transform ion cyclotron resonance (FT-ICR). The detectors. Combined chromatography-MS techniques: GC-MS and LC-MS and their applications.
Examples of interpretation of NMR and MS spectra for the identification of unknown organic molecules.
States of matter. Anisotropy and the meaning of order. Elementary crystallography requirements. Crystallographic planes and directions. Diffraction theory: history, nature and production of X-rays. Conventional X-ray sources and synchrotron radiation. X-ray diffraction: scattering by an electron, an atom (the atomic scattering factor), and a lattice (the structure factor). Diffusion from a crystal: the Bragg interpretation, the reciprocal lattice, the Ewald sphere. The diffraction pattern of a polycrystalline sample. Experimental techniques: diffraction geometries for polycrystalline samples. Sample preparation and data acquisition strategies. Practical aspects of powder X-ray diffraction (PXRD). Qualitative analysis of multiple crystalline. Quantitative analysis: the RIR and the Rietveld methods. Determination of the amorphous component and use of the internal standard. Use of crystallographic databases. The PDF database and its use for phase recognition; NIST standards for powder diffraction; the characterization of the microstructure and the problem of preferential orientation. The use of synchrotron radiation for PXRD quantitative analysis. Basics of X-ray fluorescence (XRF): principles. Qualitative and quantitative analysis with XRF.
Thermal analyses: principles. Thermogravimetry and differential scanning calorimetry. Instrumentation and practical aspects. Simultaneous thermal analyses (STA and DTA). Analysis of thermograms, determination of solvent content and final residue, determination of enantiomeric purity and identification of polymorphs. Thermal analyses in a controlled atmosphere. Combined thermal analyses: thermodiffractometry. Examples of qualitative/quantitative analysis with combined techniques. Examples of industrial applications of powder diffraction and thermal analysis in the pharmaceutical sector, in materials science and in the field of cultural heritage.
Module of NMR spectroscopy and MS.
The basics of NMR spectroscopy. NMR active nuclei. Pulsed spectroscopy. The relaxation times T1 and T2. The NMR observables: chemical shift, coupling constant and integral.
The NMR spectrum of the proton (1H): typical values of chemical shift and coupling constant.
The NMR spectrum of carbon (13C): typical values of chemical shift and coupling constant. The use of decoupling and simple sequences in the acquisition of 13C spectra. DEPT Spectra.
The observation of chemical exchange in the NMR spectrum.
Assignment of one-dimensional 1H and 13C spectra of molecules with known and unknown formulas.
Two-dimensional homonuclear (COSY) and heteronuclear (HSQC) NMR spectra
The basics of mass spectrometry (MS). Ionization and the main ion sources: electron impact (EI), chemical ionization (CI), fast atom bombardment (FAB), matrix-assisted laser ionization (MALDI), electrospray (ESI). How to read an MS spectrum and the fragmentation of the main functional groups in MS. Resolution and Accuracy. The analyzers: magnetic analyzer, dual focusing, quadrupole (and derivatives), ion trap, time of flight (TOF), Fourier transform ion cyclotron resonance (FT-ICR). The detectors. Combined chromatography-MS techniques: GC-MS and LC-MS and their applications.
Examples of interpretation of NMR and MS spectra for the identification of unknown organic molecules.
Prerequisites for admission
Knowledge of the basic concepts of organic chemistry and of molecular structure. Mathematics and numerical calculation (as per the first year program).
Moreover, for this course, the following curses are suggested as prerequisites:
-Organic chemistry I and II
-General and inorganic chemistry
-Mathematics I
Moreover, for this course, the following curses are suggested as prerequisites:
-Organic chemistry I and II
-General and inorganic chemistry
-Mathematics I
Teaching methods
The teaching approach involves a combination of methods to enhance learning and engagement. Frontal lessons with projected slides provide structured content delivery, supplemented by explanations on the blackboard for deeper understanding. Guided exercises, including case studies, enable practical application of concepts with teacher support.
Interactive engagement is fostered through the use of an app, allowing real-time interaction with the class. Easy questions are posed anonymously to assess understanding instantly. This facilitates active participation and enables quick feedback.
Hands-on sessions with computers will be exploited to offer practical experience, where students apply learned methods to real case studies.
Interactive engagement is fostered through the use of an app, allowing real-time interaction with the class. Easy questions are posed anonymously to assess understanding instantly. This facilitates active participation and enables quick feedback.
Hands-on sessions with computers will be exploited to offer practical experience, where students apply learned methods to real case studies.
Teaching Resources
- Analisi di Materiali Policristallini Mediante Tecniche di Diffrazione, Guagliardi & Masciocchi Ed.s, Insubria University Press, Varese 2007.
- Fundamentals of Powder Diffraction and Structural Characterization of Materials, Springer; 2nd ed. 2009 edition. Pecharsky, Vitalij, Zavalij, Peter.
- Introduction to Thermal Analysis: Techniques and Applications - Edited by Michael E. Brown. Springer; 2nd edition.
- Guida Pratica alla Interpretazione di Spettri NMR, Antonio Randazzo, Loghia, 2018
- The course includes handouts and additional notes provided by the teachers. These resources serve to supplement the lectures and provide students with comprehensive coverage of the topics discussed in class.
- Fundamentals of Powder Diffraction and Structural Characterization of Materials, Springer; 2nd ed. 2009 edition. Pecharsky, Vitalij, Zavalij, Peter.
- Introduction to Thermal Analysis: Techniques and Applications - Edited by Michael E. Brown. Springer; 2nd edition.
- Guida Pratica alla Interpretazione di Spettri NMR, Antonio Randazzo, Loghia, 2018
- The course includes handouts and additional notes provided by the teachers. These resources serve to supplement the lectures and provide students with comprehensive coverage of the topics discussed in class.
Assessment methods and Criteria
The learning verification will be conducted through a written exam with a maximum score of 30/30. The exam will be divided into two sections: one focusing on diffraction/thermal analyses and the other on Mass Spectrometry (MS) and Nuclear Magnetic Resonance (NMR). Each section will contain both theoretical questions and exercises, with a total score of 30 points available for each. The final grade will be calculated as the arithmetic average of the scores obtained in both sections.
CHIM/01 - ANALYTICAL CHEMISTRY - University credits: 6
Lessons: 48 hours
Professors:
Colombo Valentina, Vasile Francesca
Shifts:
Professor(s)