Physical Chemistry (2019/2020)



Course code
4S00097
Credits
6
Coordinator
Adolfo Speghini
Academic sector
CHIM/02 - PHYSICAL CHEMISTRY
Language of instruction
Italian
Teaching is organised as follows:
Activity Credits Period Academic staff Timetable
teoria 5 II semestre Adolfo Speghini

Go to lesson schedule

laboratorio [1° turno] 1 II semestre Chiara Nardon

Go to lesson schedule

laboratorio [2° turno] 1 II semestre Chiara Nardon

Go to lesson schedule

Learning outcomes

The Course aim to provide the students with the basic tools for understanding and interpreting chemico-physical phenomena concerning systems of biological and biotechnological interest, also through the use of theoretical models. The student will acquire the ability to apply chemical-physical concepts to real processes in order to quantify observables, of thermodynamic, transport, kinetic and spectroscopic type.

Some numerical exercises on various physical-chemical aspects will be considered and solved in order to familiarize the student with the solution of real problems, in particular on the thermodynamic part.

The course also includes some laboratory experiences to provide manual skills and critical skills in dealing with real chemico-physical problems, as well as providing knowledge on modern methods and equipment for the measurement of thermodynamic variables, kinetic constants, colloidal properties as well as for studying electronic and vibrational properties of molecules.

Syllabus

THEORY

Thermodynamics.
Perfect and real gases. Concepts of heat and work. Heat capacity.
Internal energy, enthalpy and their variations with temperature.
Enthalpy of phase transition. Enthalpy of reaction and its variation with temperature.
Entropy and its variation with temperature. Entropy of phase transition. Overview on the statistical interpretation of entropy. Entropy of reaction.
Gibbs free energy and its variation with pressure and temperature. Stability condition and phase diagrams. Definition of chemical potential. Chemical potential of components of gas mixtures and ideal solutions.
Free energy of reaction and correlation with the reaction conditions. Conditions of equilibrium. Variation of the equilibrium constant with the temperature. Free energy of mixing for ideal fluids.
Measurement of thermodynamic observables for processes of biological interest.
Statistical thermodynamics: overview of the Boltzmann distribution, partition functions and their correlation with thermodynamic properties.

Chemical kinetics.
Recall to the rate laws, kinetic constants and Arrhenius equation. Transition states and activation energies.
Reaction schemes: approach to equilibrium and relaxation methods. Consecutive reactions. Calculation of rate laws from reaction mechanism. Rate Determining Step. Steady state approximation. Pre-equilibrium. Chemical reactions controlled by diffusion or activation. Kinetic control of a chemical reaction.
Determination of the kinetic law. Isolation and initial velocities methods.

Atomic and molecular energy structure. Molecular spectroscopies.
Introduction to quantum theory. Particles in confined systems. Harmonic oscillator and molecular vibrational modes. Atomic structure. Hydrogen-like atoms. Spin functions. Pauli exclusion principle.
Valence bond and molecular orbital theories. Energy levels and molecular orbitals for diatomic molecules. LCAO approximation. Overview of the energy levels for polyatomic molecules.
Spectroscopic transitions in the ultraviolet, visible and infrared spectral regions. Circular dichroism. Decay of the excited states. Radiative and non-radiative transitions. Fluorescence and phosphorescence. Fluorescence quenching.
Principle of Nuclear Magnetic Resonance spectroscopy (NMR).
Applications of spectroscopy to the analysis of the energy structure for molecules of biological interest.

Colloidal systems.
Colloidal dispersions and their stability. Examples of colloids of biological importance. Overview of nanostructured systems.
Hydrodynamic diameter and Zeta potential for colloids and their measurements with Dynamic Light Scattering (DLS) technique.


LABORATORY EXPERIENCES

Experiences on:
- evaluation of the thermal capacity of a calorimeter and neutralization reaction enthalpy through calorimetric measurements;
- determination of the kinetic parameters for the reaction of hydrogen peroxide with iodine ion in acidic solution.
- study of spectroscopic transitions of fluorescine in the visible region through measurement and analysis of absorption and fluorescence spectra; fluorescence quenching of fluorescein with iodide ion; investigation on the quenching mechanism;
- study of the vibrational properties of simple organic molecules using Raman spectroscopy; measurement and interpretation of NMR spectra of simple organic molecules; measurement of hydrodynamic radius and Zeta potential for macromolecules and for nanoparticles; study of the dichroic properties of macromolecules.

Assessment methods and criteria

The oral examination will include all the topics of the Course about the theoretical part as well as the examples, exercises and laboratory experiences. Particular attention will be devoted on the Physical Chemistry concepts and the knowledge of the methods, tools and techniques used in laboratory experiences.
For both attending and not attending students the oral examination will cover all the topics discussed in the theoretical part, in the examples and exercises as well as in the laboratory experiences.
Written reports about the the laboratory experiences are required, describing the principles, the used experimental methods and the results obtained during the lab experiences. The reports have to be loaded to the Moodle platform as soon as the lab experiences will be completed.

Reference books
Activity Author Title Publisher Year ISBN Note
teoria Peter Atkins, Julio de Paula Elementi di Chimica Fisica (Edizione 4) Zanichelli 2018 9788808220684
teoria Thomas Engel Philip Reid Physical Chemistry: Quantum Chemistry and Spectroscopy (Edizione 4) Pearson 2019 9780134804590 e-book: https://www.pearson.com/store/p/physical-chemistry-quantum-chemistry-and-spectroscopy/P100002581245/9780134813981 ($29.99)
teoria Thomas Engel, Philip Reid Physical Chemistry: Thermodynamics, Statistical Thermodynamics, and Kinetics (Edizione 4) Pearson 2019 9780134804583 e-book : https://www.pearson.com/store/p/physical-chemistry-thermodynamics-statistical-thermodynamics-and-kinetics/P100000921807/9780134814643 ($ 29.99)
laboratorio Speghini Adolfo Dispense per esercitazioni di laboratorio di Chimica Generale e Inorganica 2019