Learning objectives
Knowledge and understanding
Acquisition of the fundamental knowledge of chemical thermodynamics as tool for the study of chemical and physical transformations even in complex systems. Basic approach to chemical kinetics.
Applied knowledge and understanding
The student will be able to identify the chemical-physical quantities relevant in physical and chemical processes, to calculate their variation in order to verify the direction of the transformations and the energies involved.
Autonomy of judgment
The student will be able to define the appropriate approach to a specific physico-chemical problem and to find the necessary data in the literature to arrive at the solution
Communication skills
The language of thermodynamics is rigorous: once acquired, the student will be able to exchange information with colleagues, to write clear and precise reports and to communicate ideas and results without the possibility of error or misunderstanding.
Ability to learn
At the end of the course, the student will have acquired knowledge that will allow him to update and deepen autonomously in different directions, depending on the needs of the educational and scientific path that he will face.
Prerequisites
Basic knowledge of General Chemistry and Mathematical Analysis
Course unit content
Fundamentals of Classical Thermodynamics and Gas Laws
The First Principle. Enthalpy. Thermochemistry.
II Second and Third Principles. Entropy. The energies of Helmholtz and Gibbs.
Physical transformations of pure substances.
The mixtures. Phase diagrams of binary systems. Chemical equilibrium
Elements of chemical kinetics
Full programme
Fundamentals of Classical Thermodynamics and Gas Laws
Thermodynamic system, state functions, thermodynamic equilibrium, equation of state.
Equation of state of the Ideal Gas. Ideal gas mixtures: Dalton's law. Real gases: deviations from ideal behavior. Van der Waals equation. Andrews diagram and critical parameters.
The First Principle.
Exchanges of energy between system and environment: heat and work, conventions. Zero principle of thermodynamics. Thermal capacities and specific heats. The First Principle of thermodynamics: internal energy U and the equivalence between heat and work.
Enthalpy.
Relationship between Cp and Cv. Mayer equation. Joule-Thomson coefficient and partial molar volumes. Free expansion of a gas. Internal energy and enthalpy of an ideal gas. Real gases: Joule-Thompson coefficient. Intensive and extensive quantities. Partial molar volumes.
Thermochemistry.
Heat of reaction and thermochemical equations. Enthalpy variations in physical and chemical transformations. Calorimetry. Calculation of the enthalpy of the reaction, HR. Standard state. Standard enthalpies of formation. Hess's law. Kirchhoff's law.
The Second and Third Principles.
Entropy as a function of state. Spontaneous processes and entropy variation: Clausius inequality. Thermal machines and the Kelvin-Planck statement. The Third Law of Thermodynamics. Calculation of the standard entropies S of pure substances under standard conditions. Entropy variations in physical and chemical processes.
The energies of Helmholtz and Gibbs.
Principles of spontaneity and equilibrium. Gibbs energy of reaction. Combination of the first and second Principles. Maxwell relations. Fundamental equation of chemical thermodynamics. Variation of G with T and P.
Physical transformations of pure substances.
Stability of the phases. Phase transitions. Phase rule. Phase diagrams of pure substances. Clapeyron equation.
The mixtures.
Partial molar quantities. Chemical potential. Thermodynamics of mixing. Chemical potential of liquids. Liquid mixtures. Colligative properties. Activities.
Phase diagrams of binary systems
Liquid-vapor diagrams. Azeotropes. Liquid-liquid diagrams. Liquid-solid diagrams. Notes on ternary systems.
Chemical equilibrium
Equilibrium constant. Equilibrium response to T and P variations. Electrochemical cells and electrode potentials.
Chemical Kinetics
The reaction rate. Kinetic laws and their determination. Integrated kinetic laws. Arrhenius law. Reaction mechanisms.
Bibliography
Atkins – De Paula- Keeler
Chimica Fisica
Zanichelli
Teaching methods
Frontal teaching. Numerical exercises will be carried out on selected topics.
Assessment methods and criteria
Oral examination. Duration: about 35-40 minutes. Three topics of the course will generally be addressed. The possibility of having the student solve simple exercises of the type done in class is not excluded. To achieve sufficiency it will be necessary to demonstrate that you have acquired the minimum knowledge relating to the fundamental aspects addressed in the course. A fourth question may possibly be of help for deepening purposes, in order to verify the possibility of increasing the vote or assigning honors.
Other information
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