CHIMICA FISICA SUPERIORE

Conoscenza e capacità di comprensione:

The aim of the course imvolves the development of solid basic knowledge of statistical thermodynamics and theory and simple models of phase transitions in "soft matter", neede to recognize and interpreting, in a semiquantitative way, the phenomena and processes related to the laminar and turbulent fluxes for simple and complex fluids, the connection between soft matter viscoelastic behavior and relaxation times, glass transition processes, phase separation in molecular systems, as well as the nucleation-and-growth mechanisms in nanoscopic phases, the basics of probability calculus for random discrete and continuous variables, and their applications to the description of the state functionals in statistical thermodynamics.

Knowledge and applied understanding ability:

It will be shown to the students how to apply the basic knowledge in order to rationally manipulate complex chemical systems, relevant to the fields of advanced functional materials, health, environment and energy. In fact, systems with an expected high social impact are the nanometric or “small cluster” systems, the materials with advanced optical, electrical and optoelectronic properties, the stimuli-responsive systems, the programmable multiphase systems, with tunable functional properties, the polymer gels, etc…The students will learn the basic notions to be able to operate these systems.

Authonomy in evaluation:

In order to promote the ability to autonomous evaluation of the suitability of the different methods of analysis to the above mentioned systems in view of their application to the innovative manufacturing, environmental technologies, renewable energetic and health fields, learning to critically consider the pertinence and the impact of the available technological option with respect to their efficiency and safety.

Communication skills:

The learning of communication skills will be achieved both by performing sessions of presentation of tutorial topics, as well as presentations of small seminars, based on the construction of synthetic analysis of complex topics.

Learning ability

The learning capability will be specifically addressed by showing the way diverse theoretical aspects and the related phenomenological phenomena are connected and showing to the students the way of critically evaluate the generality and specific pertinence of the statements related to coherence and knowledge cogency.

Classes on theory and applications (ppt and blackboard presentations).

Numerical exercises sessions.

1. Basics of Physical Chemistry of condensed phase complex systems – Intermolecular forces, energy, spatial dimension ad time in condensed phase – Transport processes: fluxes and viscosity in complex fluids – Viscosity and viscoelasticity in complex fluids – Laminar and turbulent fluxes - Newtonian vs. non-newtonia fluids – Viscous pseudoplastic fluids – Fluids with dilatational modes – Empirical equations for flux motions – Viscoplastic fluids and Bingham fluids – Maxwell relationship and related applications – Viscoelastic behavior and relaxation times – Entropy and relaxation modes: glass transitions – Arrhenius and non-Arrhenius relaxation regimes – Relaxation times deriving from vibrational modes and relaxation times deriving from configurational entropy – Kinetics phase transitions and related relaxation models – Free volume models: Fox-Flory and William-Landel-Ferry – Cooperative models: Gibbs-Di Marzio, Adam-Gibbs - Domains of cooperative reorganization, energy barriers and configurational entropy.

2. Phase transition in condensed molecular system – Basics about phase transitions in “soft matter” – Liquid-liquid unmixing transitions: Free energy of mixing, curvature of the mixing free energy function and phase separation – Stable and metastable systems – Flory parameter – Interfaces between phases and interface tension – Mechanisms of phase separation: spinodal decomposition – Homogenous and heterogeneous processes of nucleation – Liquid-solid phase transitions: Undercooling and solidification – Homogeneous nucleation processes in liquid-solid transitions: kinetics, energy barrier and critical nucleation radius – Heterogeneous nucleation processes: kinetics, energy barrier and critical nucleation radius – Stability of growing solidification fronts – Simple models of entanglement in polymers – Simple models of chain reptation.

3. Basics of Statistical Thermodynamics – Random events, probability and random variables – Poisson and Gauss distributions – Probability and “expectation values” – Maxwell distribution – Boltzmann distribution – Gibbs distribution and partition function of a system – Ensembles: Microcanonical, Canonical and Grand Canonical ensembles – Ensemble averages and “most probable distribution method” - Partition function, Lagrange multiplier method and value of b parameter – Partition function and thermodynamical functions for different ensembles – Fluctuations.

4. “Smart systems” – Basic of “smart systems” – Adaptive systems with variable response: “stimuli-responsive systems” – Stimuli factors and response times for different systems – Case studies: polymer gels, amorphous phases and glasses, “cellular” materials – Non-linear response in nanostructured systems.

Parts 1 e 2: chapters from “Soft Condensed Matter, R.A.L.Jones, Oxford University Press, UK, 2011

Parte 3: T.L.Hill - An Introduction to Statistical Thermodynamics", Dover Publications1, USA, 1986