Physical Chemistry (2018/2019)

Course code
Adolfo Speghini
Academic sector
Language of instruction
Teaching is organised as follows:
Activity Credits Period Academic staff Timetable
teoria 5 II semestre Adolfo Speghini

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laboratorio [laboratorio 1° turno] 1 II semestre Adolfo Speghini

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laboratorio [laboratorio 2° turno] 1 II semestre Adolfo Speghini

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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 examples on various physical-chemical aspects will be considered in order to familiarise the student with the solution of real problems.

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



Recall to the concepts of heat and work. Heat capacity.
Internal energy, enthalpy and their variations with temperature.
Phase transition enthalpy. Standard enthalpy of reaction and its variations with temperature.
Entropy and its variations with temperature. Phase transition entropy. Overview on the statistical interpretation of entropy. Standard 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.

Molecular energy structure. Molecular spectroscopies.
Introduction to quantum theory. Particles in confined systems. Harmonic oscillator and molecular vibrational modes. 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. Decay of the excited states. Radiative and non-radiative transitions. Fluorescence and phosphorescence. Fluorescence quenching. Energy transfers among particles.
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 nanocrystalline systems. Hydrodynamic radius and Zeta potential for colloids and their measurement with Dynamic Light Scattering (DLS) technique.


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 exam focus on a written test including questions on the entire program of the Course, aimed at ascertaining the knowledge of the contents of the course. Particular attention will be devoted to the main concepts of Chemical-Physics and the knowledge of the methods, tools and techniques used in laboratory experiences..
For both attending and not attending students the exam will cover all the topics discussed both in the theoretical part and in that of the laboratory experiences.
For the part of the laboratory a written report is required about the methods and the results obtained during the laboratory experiences.

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 Peter Atkins, Julio de Paula Physical Chemistry for the Life Sciences (Edizione 2) Oxford University Press 2011 9780199564286
laboratorio Speghini Adolfo Dispense per esercitazioni di laboratorio di Chimica Fisica (Edizione 1) 2019