Physical Chemistry (2017/2018)

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

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laboratorio [1° turno] 1 II sem. Adolfo Speghini

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laboratorio [2° turno] 1 II sem. 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 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.



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 spectroscopy.
Introduction to quantum theory. Particles in confined systems. Harmonic oscillator and vibrational modes. Energy levels and molecular orbitals for diatomic molecules. LCAO approximation. Overview of energy levels for polyatomic molecules.
Absorption spectroscopy in the UV and visible regions. Circular dichroism. Fluorescence and phosphorescence spectroscopy. Radiative and non-radiative transitions. Decay of excited states. Fluorescence quenching. Energy transfer among molecules and FRET.
Vibrational spectroscopy (infrared and Raman).
Nuclear Magnetic and Electron Spin Resonance spectroscopy (NMR and ESR).
Applications of the various spectroscopic techniques to organic 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.


Exercises about the thermodynamic part.


Experiences on:
- evaluation of the thermal capacity of a calorimeter and neutralization reaction enthalpy through calorimetric measurements;
- determination of the rate law with the isolation method for oxidation of iodine ion with hydrogen peroxide;
- 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 on the vibrational properties of simple organic molecules by analysis of infrared and Raman spectra; interpretation of NMR spectra for simple organic molecules; measurements of hydrodynamic radius and Zeta potential for nanocrystalline systems.

Assessment methods and criteria

The exam consists of a written test, including exercises on the thermodynamic part and questions on the entire program of the Course, aimed at ascertaining the student's knowledge about the contents of the course. Particular attention will be paid to the main concepts of Chemical-Physics, the correct resolution of numerical exercises 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 numerical exercises and 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 978-88-08-22068-4
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 2018