Chemical Sciences

First law of Thermodynamics Definitions, aims and limits of Thermodynamics. Thermodynamic systems. State variables and state functions. Thermodynamic state. Thermal, mechanical and chemical equilibrium. Reversible and irreversible processes. Mechanical work. First law of Thermodynamics. Heat, work and internal energy variations in thermodynamic transformations. Heat capacities. Internal energy and its dependence on temperature and volume. Ideal and real gases. Enthalpy and its variations in chemical reactions. Enthalpy changes determinations in chemical processes by calorimetric measurements. Second law of Thermodynamics Irreversibility of natural processes and the entropy function as a measure of the irreversibility of thermodynamic transformations; second law of Thermodynamics. Thermodynamic temperature and the Carnot cycle. Entropy changes in gases, liquids and solids physical transformations. Statistical interpretation of entropy, microstates and macrostates. Microstates number calculation. Boltzmann’s equation. Entropy and disorder. Entropy of mixing. Third law of Thermodynamics Nernst theorem and Planck’s statement. Brief introduction to experimental measurement of absolute entropies and to the calculation of the same. Thermodynamic equilibrium Thermodynamic potential. Gibbs free energy and Helmotz free energy. First order phase transitions and some very basic information about higher order transitions. Phase diagrams of one-component systems. Fugacities, activities and chemical potentials of pure gases, liquids and solids. Multi-component systems Partial molar quantities, Gibbs-Duhem law. Experimental methods for the determination of partial molar quantities. Ideal and regular solutions. Properties of solutions: colligative properties. Activity and activity coefficient. Phase rule for multi-component systems. Chemical equilibrium in homogeneous and heterogeneous systems Chemical equilibrium. Thermodynamic equilibrium constant and its variation with temperature. Electrochemical equilibrium. Electrochemical potential. Standard electrode potentials. Electromotive force: definition and measurement. Basics of electrochemical cells and electrodes. Ions and their activity in solution. Electrolytic solutions: basics of the Debye-Hückel theory. Basics of chemical kinetics Reaction mechanism. Molecularity. Reaction rate. Reaction order. Equilibrion constants and rate constants. Reaction rate and temperature. Photochemical reactions. Catalysts. Heterogeneous catalysis. Enzyme catalysis. Homogeneous catalysis.

In order to fully understand the topics presented in the course, it is advisable for the students to have already taken the curriculum's Maths courses and the first Physics course and passed the respective exams.

Daniele Gozzi, Termodinamica Chimica, IV Edizione, Edizioni Nuova Cultura Paolo Silvestroni, Fondamenti di Chimica, qualunque edizione. Daniele Gozzi, Problemi svolti di termodinamica chimica, Edizioni Nuova Cultura

Lectures attendance is not compulsory. The course is composed of classroom lectures and practical activities, i.e. numerical exercises and laboratory experiments. Weekly lectures take place and they are performed using the blackboard. Three midterms two hours each, are written. They take place in classrooms. This methodology aims at providing the students with the opportunity of verifying their knowledge and competencies. Furthermore, such method offers the opportunity of a more gradual evaluation of the preparation of the students.

not compulsory

The exam is aimed at verifying the knowledge and understanding level of the topics of the course, as well as the reasoning capabilities acquired by the student. The final grade is out of 30 (minimum 18/30, maximum 30/30 cum laude). The exam consists of an oral exam. The exam allows for the verification of the knowledge, skills and communication abilities of the students. The oral examination is aimed to check the degree of understanding of the course’s topics and the clarity of the presentation.

Classroom lessons, numerical problems solution, laboratory experiments with data analysis.

The first law of thermodynamics. Definition of a thermodynamic system. States and properties of the systems. State functions and thermodynamic state. Thermal, mechanical and chemical equilibrium. Reversible and irreversible processes. Reversible work. The first law of thermodynamics: the formulation, heat, work, internal energy and its changes in the thermodynamic processes. Heat capacity, enthalpy, its changes in the chemical reactions and dependence on the temperature. Thermochemistry. The second law of thermodynamics. Irreversibility of natural events and entropy as a measure of irreversibility of thermodynamic transformations. Clausius inequality. Thermodynamic temperature. Changes of entropy in different conditions. The statistical view of the entropy. Boltzmann equation. Entropy change in the phase transitions. Mixing entropy. Temperature and its measurement. The third law of thermodynamics. Nernst theorem and Planck statement. Absolute entropy and its evaluation. Thermodynamic equilibrium. Thermodynamic potentials; Gibbs and Helmholtz free energy. Phase transitions. Phase diagrams for pure materials. Fugacity and activity, and chemical potential of pure gases, liquids and solids. Multi-components systems. Chemical potential, partial molar quantities, Gibbs-Duhem equation: fugacity and activity, Solutions and their properties: osmotic pressure, freezing point lowering, boiling point raising. Ideal solutions and regular solutions. Experimental methods to determine the partial molar quantities. Phase rule. Chemical equilibrium. Chemical reactions. Chemical equilibrium, thermodynamic constant and its dependence on temperature. Equilibrium electrochemistry: electrochemical potential, ions, ion activity, electrodes, electrochemical cells, standard electrode potential, electromotive force. Work in chemical reactions. Thermodynamic functions from electromotive force measurements. Theories of ionic solutions: Debye-Hückel theory (outline). Chemical kinetics. The rate of chemical reactions. Order, molecularity and mechanism of a reaction. Kinetics of consecutive reactions, steady-state kinetics, kinetics of reversible and irreversible. The temperature dependence of the rate of chemical reactions. Experimental methods to measure the rate of a chemical reaction. Catalysis. Homogeneous catalysis. Enzymatic kinetics: kinetics of Michaelis-Menten. Heterogeneous catalysis (outline) Experimental activities 1. Measurement of the combustion heat of benzoic acid. 2. Measurement of heat capacity of metals. 3. Thermodynamic data of a chemical reaction by measurements of electromotive force as a function of temperature. 4. Determination of partial molar volumes by measurements of density of aqueous solutions.

For a better learning of the topics proposed in this course, basic skills of Chemistry (inorganic chemistry, the periodic table of the elements, the concept of mole, kinds of concentrations, balancing chemical equations, balancing redox reactions, law of mass action, colligative properties, pH, basic background of electrochemistry). In addition, the student should be familiar with the basic knowledge of mathematics (derivatives and partial derivatives, differentials, simple integrals and differential equations, study of functions).

There is no reference text. Some are suggested: 1. D. Gozzi Termodinamica Chimica, Edizioni Nuova Cultura 2. P. W. Atkins, J. de Paula - Chimica Fisica, Zanichelli 3. Notes on practical experiences written by Prof. Daniele Gozzi: https://www.chem.uniroma1.it/sites/default/files/allegati_insegnamento/dispense%20labChimFis.pdf 4. Notes on Chemical Kinetics written by Prof. Guido Gigli: https://www.chem.uniroma1.it/sites/default/files/allegati_insegnamento/cinetica_chimica.pdf

The course is composed of eighty hours, sixty-eight 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) and numerical exercises focused on thermodynamics and kinetics while the remaining twelve will be used to laboratory experiences where the student will carry practical experiences, the results of which have to be described and discussed in a report.

The student will be evaluated by a written and oral exam in which the student should discuss one of the laboratory experiences (theoretical principles, materials, methods, processing of experimental data and results), some thermodynamic and kinetic issues with the relative proofs, and solve some numerical exercises. The capability of analysis, making judgment and communication skills will be also evaluated. Simple 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.

To deepen some topics: 1. E. Fermi Termodinamica, Boringhieri (available at the library G. Illuminati of Chemistry Department) 2. G. N. Lewis, M. Randall Termodinamica, Leonardo Edizioni Scientifiche (per approfondimenti) (available at the library G. Illuminati of Chemistry Department)

The course is composed of eighty hours, sixty-eight 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) and numerical exercises focused on thermodynamics and kinetics while the remaining twelve will be used to laboratory experiences where the student will carry practical experiences, the results of which have to be described and discussed in a report.

Structure of Macromolecules (Chim02 for LM71) 1. Introduction: • Complexity of Structure in a Macromolecular (Polymer) Materials. Concept of the hierarchy. • Morphological Length Scales • Experimental Techniquies applied for Exploring Macromolecular Structure. 2. X-Ray Diffraction. • Diffraction and Interference, Huygens–Fresnel Principle. • Definition of the EM Wave, Young's Interference Experiment. • Diffraction Grating, calculation of the Fringes Positions • X-Ray, Wave properties. Lauer and Braggs Discoveries. • Discovery of X-Ray. Production of X-Ray. • Characteristic and Continuous X-Ray spectrum 3. X-ray Interactions with Matter • Absorption (Lambert Beer Low), Fluorescence, Elastic and Inelastic Difiussion. • Thomson Diffiusion at free electron. Compton Scattering • Atomic Form Factor • Diffraction from a Polyatomic System. Interference function. Debye equation. 4. Diffraction from Cristalline Materials (WAXS) • Definition of Crystalline Unit Cell, cell’s parameters, Operation of Symmetry, Bravais lattice, Space Groups, Miller Indexes • Bragg’s law. Diffractometers. Phase identification. 5. Structure of Crystalline/Semicrystalline Polymers. • WAXS for Polymers. Amorphous and Crystalline Polymers. • Crystalline polymers: Cell Identification, Thermal Expansion Coefficients. Macroscopic strain and Defects, Crystallinity; Crystallite size and Lattice Distortions. • Orientation in Polymers (fibers). In plane orientation. Axial of Fiber Orientation. 2 D Diffraction. 6. Small Angle Scattering (SAXS/SANS) • Instrumentation, sample preparation, Measurments, Data Reduction. • Concept of contrast. Babinet principe • Polymer conformation in the Bulk. Lamellae order. Scattering from the Phase separated Blends. • Case of the deluted /concentrated Polymer solutions. Definition of Form/Strcture Factors. Analitical models for the data analysis. Guinier approximation , Radius of Giration. Porod law, definition of the Form Factor. Kratky Plot.

comprensione dei concetti di fisica 2

Course slides, together with the materials indicated in the program

Mandatory to participate in laboratory experiences

The final evaluation will consist of an oral examination during which the contents of the course will be discussed, including the laboratory reports.

The course consists of 40 hours of lectures and 3 laboratory experiences. Laboratory experiences are mandatory