Learning objectives
Students will learn (a) the basic thermodynamics tools and their use in the experimental and theoretical study of chemical systems and chemical processes; (b) the basic knowledge of the experimental and theoretical methods for the study of the kinetic aspects of chemical reactions.
Prerequisites
Basic notions of general chemistry, of general physics, and of calculus.
Course unit content
1. The zero law of thermodynamics and the gas properties. 2. The First law of Thermodynamics. 3. The second law of Thermodynamics. 4. The Gibbs energy and the chemical potentials. 5. Physical transformations of pure substances. 6. The solutions. 7. Phase diagrams. 8. Chemical equilibrium. 9. Chemical kinetics.
Full programme
1. The zero law of thermodynamics and the gas properties. Primitive concepts: system, environment. Thermodynamic state functions. The temperature and the zero Law of thermodynamics. The state equation of the ideal gas. Real gases. Van der Waals equation. The principle of corresponding states.
2. The First law of Thermodynamics. Work, heat and internal energy. The first law of thermodynamics. Expansion work. Heat capacity. The properties of the internal energy. The enthalpy and the transformations at constant pressure. Transformations of the ideal gas. Thermochemistry. Variations of enthalpy in chemical reactions and phases transformations. Standard state of elements and compounds. The standard enthalpies of formation and the reaction enthalpies. The Hess law. The temperature dependence of reaction enthalpies.
3. The second law of Thermodynamics. The Kelvin and Clausius formulations of the second law. The entropy. The Carnot cycle. The Clausius inequality and the irreversible transformations. Variations of entropy in elementary transformations. The third law of Thermodynamics. The molecular interpretation of the entropy. Criterion for spontaneity for isolated systems. The Helmoltz energy and the spontaneous transformations at constant volume and temperature . The Gibbs free energy and the spontaneous transformations at constant pressure and temperature.
4. The Gibbs energy and the chemical potentials. The fundamental equation of thermodynamics. The Maxwell relations. The effects of the pressure and temperature on the Gibbs energy. The chemical potential of pure substances. The chemical potential of real gases.
5. Physical transformations of pure substances. Phases diagrams. The stability of phases. Phases boundaries. The triple point and the critical point. The thermodynamic criterion of the phases equilibrium. The Clapeyron equation and the phase boundaries. The Ehrenfest classification of the phase transitions.
6. The solutions. Partial molar quantities. Chemical potentials. The Gibbs-Duhem equation. The thermodynamics of mixing. Chemical potentials in ideal solutions. The Raoult law. The Henry law. The properties of solutions. Excess functions. Colligative properties. The thermodynamic activities. The solvent activity. The solute activity. The regular solutions.
7. Phase diagrams. Phases, components and degrees of freedom. The Gibbs phases rule. Two components systems. Vapor-liquid phases diagrams. Liquid-liquid phases diagrams. Liquid-solid phases diagrams.
8. Chemical equilibrium. The Gibbs free energy of reaction and the spontaneity of chemical reactions. The standard free energy of reaction, the reaction quotient and the equilibrium constant. Reactions between ideal gases. Reactions in solution. The effect of temperature and pressure on the chemical equilibrium.
9. Chemical kinetics. The reaction rate: definition and measurements. The kinetic laws and the order of reaction. Integrated forms of the zero, first and second order kinetic laws. The effect of the temperature on the reaction rates. Catalysis.
Bibliography
Peter W. Atkins,Julio De Paula, Chimica Fisica, 5a Ed., Zanichelli, 2012.
Teaching methods
The teaching activities consist of Lectures, including tutoring seminars, and of Laboratory practice sessions. The slides used during the Lectures will be weekly uploaded on the Elly platform. The slides will be part of the teaching material along with the reference text book.
Assessment methods and criteria
The final verifications will consist of:
- a critical discussion on the written reports of the experiences performed during the laboratory practice, with evaluation scale 0-30 and weight 0.25
- a written examination (2h) with open answers, and with evaluation scale 0-30 and weight 0.25
- an oral examination, with evaluation scale 0-30 and weight 0.50.
Other information
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2030 agenda goals for sustainable development
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