Chemistry

Intermolecular forces: Classification of Forces and Pair Potentials - Covalent and Coulomb Interactions - Interactions Involving Polar Molecules - Van der Waals Forces - Hydrophobic and Hydrophilic Interactions Chemistry of interfaces. Stability of colloids: the interparticle forces, intermolecular forces based on the interparticle interactions, forces of van der Waals and Hamaker constant, influence of the solvent medium, electrostatic interactions: the electrical double layer, influence of adsorbed material on the particle surface, reversible adsorption, effect of polymers. Potential DLVO. Processes leading to destruction of colloids. Importance of colloids for nanotechnology. Applications. Translational diffusion and properties of colloids. Effects of interactions on the self-diffusion coefficient and the collective diffusion. Free diffusion coefficient: Stokes-Einstein equation and hydrodynamic radius. Methods for calculating the hydrodynamic radius from the structure of the particles. Nuclear Magnetic Resonance - basic principles. The relaxation times. Spin echo sequence and the Hahn's experiment. Spin-echo in pulsed magnetic field: main sequences. The coefficient of self-diffusion. Polydispersity: average value and distribution of diffusion coefficients. Applications. Circular dichroism. Optical activity. Physical origins of circular dichroism. Description of the instrumentation. Calculation of the circular dichroism of a dime (exciton splitting). The circular dichroism in proteins, nucleic acids and supramolecular aggregates. Semiempirical calculations for the simulation of spectra. Applications. Statistical thermodynamics – Ensembles, postulates on ensemble average, ergodic theory. The canonical partition function and relations with the molecular partition function (distinguishable and indistinguishable particles). Canonical partition function and thermodynamic functions. The partition function for the ideal gas ( mono and diatomic). Partition functions and equilibrium constants. The Theory of activated complex (Eyring theory). Perfect solids (Einstein model). Conformational equilibria in polymers: cooperative and non-cooperative transitions. Statistical mechanics of cooperative transitions according to the Ising model. Applications. Real gases. Polymers-ligand interactions in equilibrium conditions. Macroscopic and microscopic constants. Model of independent binding sites: Scatchard plot. Interacting binding sites: plot and binding constants according to the Hill's model. Cooperative and uncooperative binding. Applications. Propagation of electromagnetic radiation. Polarizability of matter (orientational, distortional and electronic). The inelastic and elastic scattering of electromagnetic radiation. Rayleigh and Thompson scattering. Interference of waves scattered from a discrete and continuous distributions of diffusers. Scattering from a dispersion of colloidal particles in the presence of solvent (case of X-rays and light). Static light and X-rays scattering. Scattering intensity from a dispersion of small particles with respect to the wavelength of the incident radiation. The structure factor and the radial distribution function. Compressibility. The virial coefficients. The Debye plot. Scattering intensity from a dispersion of large particles compared to the wavelength of the incident radiation. Form factor and radius of gyration. Zimm plot and Guinier plot. Polymers and the Kratky plot. Polydispersity and effects on the determination of the mass and radius of gyration. Reconstruction of the structure of colloidal particles in dilute solutions. Concentrated solutions and approximation of decoupling. Instrumentation for measurements of light and X-rays scattering at small angles.

For a better learning of the topics proposed in this course, basic skills of classical thermodynamics (first, second and third principles, chemical equilibrium, thermodynamics of solutions, first-order transitions), statistical thermodynamics (principles, Gibbs ensembles, microcanonical and canonical partition functions, perfect gas model), quantum mechanics (principles, Schrødinger equations of simple systems such as the harmonic oscillator, rigidly rotating molecules, particle in a box, and single-electron systems, Schrødinger equation of many-electron systems) and classical spectroscopies (vibrational, electronic, fluorescence, nuclear magnetic resonance). In addition, the student should be familiar with the basic knowledge of mathematics (derivatives and partial derivatives, differentials, integrals and differential equations, simple series) and physics (mechanics, electrostatics and electromagnetism).

There is not a reference text considering that the course belongs to the master degree Chemistry (second cycle). Suggested texts: 1. Colloid Science: Principles, Methods and Applications, 2nd Edition, Terence Cosgrove Editor, Wiley-Blackwell (collection of chapters written by various authors) 2. Principles of Physical Biochemistry – Kensal E. van Holde, W. Curtis Johnson, P. Shing Ho, Second Edition, Prentice Hall (available at the library G. Illuminati of Chemistry Department) 3. Slides shown during the lessons 4. Lessons in pdf files from bamboo paper program 5. Equilibrium Statistical Mechanics - F. C. Andrews, J. Wiley and Sons, INC (some chapters, book provided as pdf by Moodle) 6. Chimica Fisica - W. Moore, Piccin Editore (sjust a chapter on Eyring theory provided as pdf by Moodle)

The course is composed of seventy-six hours, sixty-four of which are devoted to the theoretical treatment of the topics proposed in the program (theoretical models, mathematical proofs, applications and limits of the obtained equations, techniques and methods for investigating disperse systems) while the remaining twelve will be used to discuss the investigation of significant systems (choice of methodology and techniques). In addition, applications of the investigated systems in the field of material science and nanotechnology will be proposed.

Lesson attendance is not mandatory but strongly recommended

The student will be evaluated by an oral exam in which the student should discuss the physico-chemical properties of colloid and polymer solutions, the related models, and the experimental methods and techniques used for their investigation (principles of techniques and applications). The capability of analysis, making judgment and communication will be also evaluated. Simple and exemplary systems will be discussed to evaluate the student skills to frame the chemical problem in the correct context and choose the most suitable methodologies of investigation. In addition, the student should be capable of discussing some applications of the investigated systems in the most advanced fields of material science.

To deep some topics: 1. Intermolecular and Surface Forces - Jacob N. Israelachvili, third edition, Elsevier (available at the library G. Illuminati of Chemistry Department) 2. Biophysical Chemistry, second volume: Techniques for the Study of Biological Structure and Function, third volume: Transitions in polymers: Ising model – Charles R. Cantor, Paul R. Schimmel – W. H. Freeman and Company (available at the library G. Illuminati of Chemistry Department) 6. Some articles published in international journals that will be discussed during the lessons

The course is composed of seventy-two hours devoted to the theoretical treatment of the topics proposed in the program (theoretical models, mathematical proofs, applications and limits of the obtained equations, techniques and methods for investigating disperse systems). Applications of the investigated systems in the field of material science and nanotechnology will be proposed.

Intermolecular forces: Classification of Forces and Pair Potentials - Covalent and Coulomb Interactions - Interactions Involving Polar Molecules - Van der Waals Forces - Hydrophobic and Hydrophilic Interactions Chemistry of interfaces. Stability of colloids: the interparticle forces, intermolecular forces based on the interparticle interactions, forces of van der Waals and Hamaker constant, influence of the solvent medium, electrostatic interactions: the electrical double layer, influence of adsorbed material on the particle surface, reversible adsorption, effect of polymers. Potential DLVO. Processes leading to destruction of colloids. Importance of colloids for nanotechnology. Applications. Translational diffusion and properties of colloids. Effects of interactions on the self-diffusion coefficient and the collective diffusion. Free diffusion coefficient: Stokes-Einstein equation and hydrodynamic radius. Methods for calculating the hydrodynamic radius from the structure of the particles. Nuclear Magnetic Resonance - basic principles. The relaxation times. Spin echo sequence and the Hahn's experiment. Spin-echo in pulsed magnetic field: main sequences. The coefficient of self-diffusion. Polydispersity: average value and distribution of diffusion coefficients. Applications. Circular dichroism. Optical activity. Physical origins of circular dichroism. Description of the instrumentation. Calculation of the circular dichroism of a dime (exciton splitting). The circular dichroism in proteins, nucleic acids and supramolecular aggregates. Semiempirical calculations for the simulation of spectra. Applications. Statistical thermodynamics – Ensembles, postulates on ensemble average, ergodic theory. The canonical partition function and relations with the molecular partition function (distinguishable and indistinguishable particles). Canonical partition function and thermodynamic functions. The partition function for the ideal gas ( mono and diatomic). Partition functions and equilibrium constants. The Theory of activated complex (Eyring theory). Perfect solids (Einstein model). Conformational equilibria in polymers: cooperative and non-cooperative transitions. Statistical mechanics of cooperative transitions according to the Ising model. Real gases. Conformational equilibria in polymers: cooperative and non-cooperative transitions. Statistical mechanics of cooperative transitions according to the Ising model. Applications. Polymers-ligand interactions in equilibrium conditions. Macroscopic and microscopic constants. Model of independent binding sites: Scatchard plot. Interacting binding sites: plot and binding constants according to the Hill's model. Cooperative and uncooperative binding. Applications. Propagation of electromagnetic radiation. Polarizability of matter (orientational, distortional and electronic). The inelastic and elastic scattering of electromagnetic radiation. Rayleigh and Thompson scattering. Interference of waves scattered from a discrete and continuous distributions of diffusers. Scattering from a dispersion of colloidal particles in the presence of solvent (case of X-rays and light). Static light and X-rays scattering. Scattering intensity from a dispersion of small particles with respect to the wavelength of the incident radiation. The structure factor and the radial distribution function. Compressibility. The virial coefficients. The Debye plot. Scattering intensity from a dispersion of large particles compared to the wavelength of the incident radiation. Form factor and radius of gyration. Zimm plot and Guinier plot. Polymers and the Kratky plot. Polydispersity and effects on the determination of the mass and radius of gyration. Reconstruction of the structure of colloidal particles in dilute solutions. Concentrated solutions and approximation of decoupling. Instrumentation for measurements of light and X-rays scattering at small angles. Dynamic light scattering. Time dependence of the scattering intensity. Autocorrelation functions of the electric field and the scattering intensity. Collective diffusion coefficient. Polydispersity: methods for the determination of the relaxation time distribution. Autocorrelation functions for dispersions of larger particles and rotational contribution. Applications.

For a better learning of the topics proposed in this course, basic skills of classical thermodynamics (first, second and third principles, chemical equilibrium, thermodynamics of solutions, first-order transitions), statistical thermodynamics (principles, Gibbs ensembles, microcanonical and canonical partition functions, perfect gas model), quantum mechanics (principles, Schrødinger equations of simple systems such as the harmonic oscillator, rigidly rotating molecules, particle in a box, and single-electron systems, Schrødinger equation of many-electron systems) and classical spectroscopies (vibrational, electronic, fluorescence, nuclear magnetic resonance). In addition, the student should be familiar with the basic knowledge of mathematics (derivatives and partial derivatives, differentials, integrals and differential equations, simple series) and physics (mechanics, electrostatics and electromagnetism).

There is not a reference text considering that the course belongs to the master degree Chemistry (second cycle). Suggested texts: 1. Colloid Science: Principles, Methods and Applications, 2nd Edition, Terence Cosgrove Editor, Wiley-Blackwell (collection of chapters written by various authors) 2. Principles of Physical Biochemistry – Kensal E. van Holde, W. Curtis Johnson, P. Shing Ho, Second Edition, Prentice Hall (available at the library G. Illuminati of Chemistry Department) 3. Slides shown during the lessons 4. Lessons in pdf files from bamboo paper program 5. Equilibrium Statistical Mechanics - F. C. Andrews, J. Wiley and Sons, INC (some chapters, book provided as pdf by Moodle) 6. Chimica Fisica - W. Moore, Piccin Editore (sjust a chapter on Eyring theory provided as pdf by Moodle) Bibliography To deep some topics: 1. Intermolecular and Surface Forces - Jacob N. Israelachvili, third edition, Elsevier (available at the library G. Illuminati of Chemistry Department) 2. Biophysical Chemistry, second volume: Techniques for the Study of Biological Structure and Function, third volume: Transitions in polymers: Ising model – Charles R. Cantor, Paul R. Schimmel – W. H. Freeman and Company (available at the library G. Illuminati of Chemistry Department) 6. Some articles published in international journals that will be discussed during the lessons

Lesson attendance is not mandatory but strongly recommended

The student will be evaluated by an oral exam in which the student should discuss the physico-chemical properties of colloid and polymer solutions, the related models, and the experimental methods and techniques used for their investigation (principles of techniques and applications). The capability of analysis, making judgment and communication will be also evaluated. Simple and exemplary systems will be discussed to evaluate the student skills to frame the chemical problem in the correct context and choose the most suitable methodologies of investigation. In addition, the student should be capable of discussing some applications of the investigated systems in the most advanced fields of material science.

The course is composed of seventy-two hours devoted to the theoretical treatment of the topics proposed in the program (theoretical models, mathematical proofs, applications and limits of the obtained equations, techniques and methods for investigating disperse systems). Applications of the investigated systems in the field of material science and nanotechnology will be proposed.