Physical Chemistry I with Lab

Conventional and reference states. Variables and equations of state. Behavior of ideal gases. Isothermal processes, isobars, isochors. Kinetic theory of gases and Maxwell-Boltzmann distribution. Real gases. Van der Waals and virial equations of state. Principle of corresponding states. Critical constants.
Heat, work, energy. State functions. Exact and inexact differentials. First law of thermodynamics. Joule's experiment. Thermal expansion. Reversible and irreversible processes. Calorimetry. Thermal capacities. Enthalpy. Thermochemistry: Hess law, Born-Haber cycles. Joule-Thomson effect. Adiabatic transformations. Kirchoff's law.
Second Law of Thermodynamics. Clausius inequality. Entropy. Third Law of Thermodynamics and Nernst's Theorem. Heating and cooling machines. Helmholtz and Gibbs free energies. Maxwell's state equations. Natural variables. Gibbs-Helmholtz equation. Gibbs-Duhem equation.
Chemical equilibrium in the gas phase and in the liquid phase. Degree of progress of a reaction. Endergonic and exergonic transformations. Thermodynamic definition of the equilibrium constant. Le Chatelier-Brown principle. Effects of temperature and pressure on equilibrium. van't Hoff equation.
Simple mixtures. Partial molar quantities. Henry's law. Raoult's law. Chemical potential of liquids: ideal and ideal-diluted solutions. Mixtures: excess functions. Colligative properties: boiling point elevation, freezing point depression, osmosis. Activity and fugacity. Real solutes.
States of aggregation of matter. Thermodynamic phases. Clapeyron and Clausius-Clapeyron equations. Gibbs phase rule. Phase diagrams of pure substances and binary systems. Leverage rule. Eutectic, peritectic, eutectoid and peritectoid mixtures. Azeotropic mixtures. Incongruent melting. Spinodal decomposition. Crystallization (outline). Azeotropic distillation (outline).
Supramolecular binding. General thermodynamics of binding phenomena. Cooperativity: allosterism, multivalency. Enthalpic-entropic compensation. Binding isotherms. Saturation. Hill equation. Experimental methods: UV/Vis, isothermal calorimetry (outline).

The module will be divided into 3 CFU of theory and 3 CFU of an experimental laboratory.
THEORY (3 CFU): ELECTROCHEMISTRY AND MOLECULAR INTERACTIONS. Electrochemical systems: batteries and electrolyzers. Electrode reactions: stoichiometry and global reaction. The Nernst equation and the thermodynamics of the galvanic cell: the Volta, surface and Galvani potentials. The electrochemical potential. The formation of the electric double layer; thermodynamics of the interphase: the electrocapillary curve. Debye Huckel's theory: limit law. Pourbaix diagrams. Electrical properties of molecules: electric dipole moment, polarizability, polarization. The interactions between the molecules: charge-dipole, dipole-dipole, dipole- induced dipole and induced dipole - induced dipole, hydrogen bond. Total interaction (repulsive and attractive sum), Lennard-Jones potential. Molecular interactions in liquids. Notes on the treatment and propagation of errors.
EXPERIMENTAL LABORATORY (3 CFU). During the experimental laboratory, chemical and physical quantities are determined (values of ΔU, ΔH, ΔG and the equilibrium constant, K) by the collection of experimental data (calorimetric, electrochemical, spectrophotometric, and vapour pressures) which are then plotted and processed through thermodynamic relationships. Specifically, the experiments will be: 1) Determination of the vapour pressure of different solvents and their enthalpy of vaporization, 2) Determination of the pKa of the bromocresol green by spectrophotometry, 3) Determination of the heat of combustion of an unknown substance by means of a calorimetric bomb; 4) Determination of the iodide-iodide equilibrium constant by spectrophotometric measurements; and 5) Determination of Delta-rG°, Delta-rS° and Delta-rH° of a reaction by open circuit cell potential measurements at different temperatures.