Chemical Sciences

ALESSANDRO LATINI

The course aims to teach theoretical knowledge and laboratory skills related to the study of systems and processes from a thermodynamic point of view. Therefore, theoretical models for the study of equilibrium systems will be developed and the related demonstrations will be discussed. Furthermore, laboratory experiments related to some thermodynamic topics will be carried out, in order to consolidate the theoretical knowledge and acquire the ability to elaborate experimental data.
At the end of the course, as regards essential knowledge, the student must have acquired skills regarding the general principles of thermodynamics and the chemical-physical properties of gas, liquid, solid and solutions systems. In particular, it will have to know the thermodynamic quantities involved and their physical significance at the macroscopic level. The thermodynamic aspects of a process must be clearly understood. The student is expected to have the ability to: i) discern the thermodynamic aspects from the kinetic aspects among those that govern events; ii) select the equations and formulas most suitable for solving quantitative problems; iii) to understand how to measure a thermodynamic quantity (Dublin descriptors 1 and 2).
Laboratory experiences with related reports and classroom exercises are expected to be able to convey to the student the logical approach to the problems, the ability to synthesize and communicate the learned concepts with appropriate language (descriptors of Dublin 3 and 4) . Through the laboratory experiences and continuous references, made in the lectures, to phenomena that are daily manifested in human life, it will be provided solid scientific bases for the understanding of processes that take place in various areas and for their independent deepening by the student (Dublin descriptor 5).

Basic competence about the most important concepts of chemical thermodynamics, as state functions, internal energy, enthalpy, entropy, free energy as well as their applications in the calculation of chemical equilibria and in the prediction of the spontaneity of chemical reactions. Knowledge of basic concepts of chemical kinetics and its most important applications.

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.

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.

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

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

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.

- Illustrate the principles of thermodynamics.
- Given a set of thermodinamic quantities, calculate other quantities that can be obtained from the set.
- Derivation of Maxwell relations.