CHIMICA FISICA III
Academic Year 2020/2021 - 3° YearCredit Value: 7
Scientific field: CHIM/02 - Physical chemistry
Taught classes: 42 hours
Exercise: 12 hours
Term / Semester: 1°
Learning Objectives
- Enable the understanding and use the concepts of matter aggregation states by means of the concepts of intermolecular forces.
- Provide to the students an exhaustive picture of the nature and classes of intermolecular forces.
- Highlight the relationship between intermolecular forces and phase chemical potential.
- Enable the student to use the concepts of interfacial energy functionals.
- Enable the student to evaluate phase surface or interface free energy, as well as its adhesive abd cohesive energy.
- Enable the student of use concepts and techniques related to electrically charged interfaces.
- Providing basic concepts of friction, lubrication and wear processes.
Course Structure
Class Lectures.
Numerical exercises.
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 |
|
|
|
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