CHIMICA FISICA III
Academic Year 2021/2022 - 3° YearCredit Value: 7
Scientific field: CHIM/02 - Physical chemistry
Taught classes: 42 hours
Exercise: 12 hours
Term / Semester: 1°
Learning Objectives
Knowledge and understanding ability:
The objective is to enable the students, owing to the knowledge of phenomenology and theoretical model of surface thermodynamics and interatomic forces, to identify, recognize and analyse, qualitatively and quantitatively, the basic phenomena and processes occurring at surfaces and interfaces in condensed phase, as well as their dependence on the surfaciala and interfacial properties. A particular attention will be devoted to the phenomena and processes occurring at the fluid-fluid and solid-fluid interfaces.
Knowledge and applied understanding ability:
The objective is to enable the students to apply the theoretical knowledge of surface and ointerface physical chemistry to phenomena and processes relevant to environmental problems an innovative manufacturing, as for instance the nucleation and growth processes, relevant both in environmental phenomena and in agrifood industry, the colloidal systems, the emulsions and the micro-emulsions, the adhesion and adsorption processes of molecules and macromolecules, as well as the lubrication, friction wetting and corrosion, so relevant for the advanced micromechanics, microelectronics, macro (smart)- and micro(smart)-packaging and, last but not least, the structuring of charged interfaces for energy.
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.
Course Structure
Class Lectures.
Class numerical exercises.
Open discussion sessions at the end of specific and thematically homogeneous part of the course.
Detailed Course Content
| Argomenti | Riferimenti testi | |
| 1 | Intermolecular forces I - Forces and energies of intermolecular interaction - Interaction energy of molecules in spaces: couple potential model – Elementary form of the couple potential: rigid sphere model - Attractive and repulsive components - Interaction potentials in condensed phases: many body effects - Mean field potential and Sel-energy definition – Cohesive energy for a simple liquid - Genarization of cohesive energy concept. | |
| 2 | Intermolecular forces II - Boltzmann distribution of interaction energies and definition of chemical potential – Molecular distribution in equilibrium systems - Thermal energy (KbT) as reference scale for intermolecular interactions – Boltzmann distribution and orientational states. | |
| 3 | Intermolecular forces III - General classification of intermolecular forces - Functional form of relevant couple potentials - Electrostatic forces: Free energy of a coulombian bond - Definition of “self-energy” (or Born energy) of an ion - Nature of the “self-energy” – Partition processes of ions among phases with different dielectric constant – Ionic solubility in different solvents: continuus approximation – Ions of different dimension and dielectric constant. | |
| 4 | Intermolecular forces IV - Forces depending on dipoles: basic features of molecular dipoles – Vectorial character of dipoles - “Self-energy” of a dipole - Ion-Dipole and Dipole-Dipole interactions – Rotating dipoles and mean potential approximation – Orientation energy of Keesom - Molecular polarizability: an elementary model – Orientational polarizability – Debye-Langevin equation – Forces of London – Dipole-dipole and dipole-induced dipole interactions - Debye forces. | |
| 5 | Thermodynamics of surfaces and interfaces I - Intefaces: definition and propertie. Models of Gibbs and Guggenhaim – Correlation between the interface thickness and correlation length of specific properties - Definition of work of surface and surface tension – Basic characters of surface tension – Young-Laplace equation and properties of curved surfaces of liquids - Kelvin equation: curvature of a liquid surface and vapour tension – Capillary condensation. | |
| 6 | Thermodynamics of surfaces and interfaces II - Interface fre energy – Gibbs free energy and surface tension - Adsorption equation of Gibbs – Two component- systems : Surface tension and composition in miscible systems - Aqueous solutions – Surface tension of amphiphilic solutions - Gibbs monolayers and lateral pressure of films at surfaces – Wilhelmy method for surface tension measurement. | |
| 7 | Thermodynamics of surfaces and interfaces III - State equation for Gibbs monolayers - Molecular area/lateral pressure correlation: Bidimensional ideal vs real gas models – Adsoprtion of vapours on liquid surfaces – “Independent Surface Action” principle - Mlecular orientation and cohesive/adhesive work - Langmuir-Blodgett films: “Gas-like” and “liquid-like” states: state equations, phase transitions and Clausius-Clapeyron equation – Condensed state. | |
| 8 | Thermodynamics of surfaces and interfaces IV - Spreading of liquids onto liquids: quasi-immiscible liquids - Spreading process energetics – Transient behaviours – Spreading of a liquid on solid surfaces: wettability – Mechanisms and energetics of wetting by spreading: Young equation and spreading pressure – Fowkes model: polar vs apoolar contributions - “Wetting by spreading”, “Wetting by adhesion” and “Wetting by immersion” - | |
| 9 | Electrically charged interfaces I – Volta, Galvani and surface potentials – Work-function and electrochemical potential – Model of electrical double layer: continuum models – Poisson-Boltzmann equation – Concentration distribution of ions and charge density distribution vs. potential - Weak potentials and Poisson-Boltzmann linearized equation – Debye length. | |
| 10 | Electrically charged interfaces II – High potentials and “full one-dimensional” equation - Grahame equation – Discrete models and Stern double layer models – Gibbs free energy of an electrical double layer: Gouy-Chapman model – Electrokinetic potentials and zeta potential – Helmholtz/Smoluchowski equation - Application to colloidal systems. | |
| 11 |
Applications - Molecular basis of friction, lubrication and wear processes - Macroscopic laws of friction processes (Amonton, Coulomb) - Static and kinetic aspects of friction processes - Frictional modes - Techniques of measurement of friction - Hydrodynamical lubrication processes - Thin films for lubrication - Molecular features for lubrication - Wear processes of surfaces - Biointerfaces and biomaterials - Surface free energy and biocompatibility - Adhesion of biomolecules to surfaces - Principles of cell- and protein-surface interactions |
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Textbook Information
1 : Intermolecular and Surface Forces, di J.N. Israelachvili, Academic Press 1998 - cap.I-II
2 : Intermolecular and Surface Forces, di J.N. Israelachvili, Academic Press 1998 - cap.II-III
3 : Intermolecular and Surface Forces, di J.N. Israelachvili, Academic Press 1998 - cap.III-IV
4 : Intermolecular and Surface Forces, di J.N. Israelachvili, Academic Press 1998 - cap.IV-VI
5 - 7 : Physics and Chemistry of Interfaces, 3rd Edition Hans-Jürgen Butt, Karlheinz Graf, Michael Kappl; Wiley 2013 - Cap. I-III
8 : Physics and Chemistry of Interfaces, 3rd Edition Hans-Jürgen Butt, Karlheinz Graf, Michael Kappl; Wiley 2013 - Cap.VI
9 : Physics and Chemistry of Interfaces, 3rd Edition Hans-Jürgen Butt, Karlheinz Graf, Michael Kappl; Wiley 2013 - Cap.IV
10 : Physics and Chemistry of Interfaces, 3rd Edition Hans-Jürgen Butt, Karlheinz Graf, Michael Kappl; Wiley 2013 - Cap.IV
11 : Lecture notes from the teacher