PHYSICAL CHEMISTRY I WITH EXERCISES
Academic year and teacher
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- Versione italiana
- Academic year
- 2021/2022
- Teacher
- JUSEF HASSOUN
- Credits
- 8
- Didactic period
- Secondo Semestre
- SSD
- CHIM/02
Training objectives
- Knowledge and understanding
The aim of Physical Chemistry I with Exercises course is to provide a full understanding of the principles controlling the physical processes and chemical transformations, and the knowledge of the main chemical and physical models employed for their description. The course provides a deep understanding of the principles and applications of physical chemistry, and the basic concepts of chemical thermodynamics. The course illustrates the application of the chemical thermodynamic models to the study of phase transitions, properties of mixtures and to the chemical equilibrium conditions.
Knowledge and Understanding application
The graduate student is expected to apply in a critical way the chemical-physical knowledge allowing the theoretical interpretation of the observed processes, and the practical use of the related experimental techniques. The graduate should learn and apply the thermodynamics of chemical and physical processes; the graduate should know the phase transitions, the properties of mixtures and chemical equilibrium conditions as well as their implications in chemical systems; the graduate should be able to apply the knowledge for description of real systems; the graduate should be able apply the above knowledge for the characterization of chemical, physical systems and materials science. Prerequisites
- Mathematics, general chemistry, general physics.
Course programme
- Thermodynamic systems: isolated, closed and open systems. Thermodynamic equilibrium. Thermodynamic properties: extensive and intensive properties. Temperature: the zeroth law of Thermodynamics. Mercury thermometer and ideal gas thermometer. The equation of state for ideal gases. Approximate equation of state for liquids and solids. Thermal expansivity and isothermal compressibility. The first law of Thermodynamics: work, heat, internal energy. Internal energy for an ideal gas: the kinetic theory of gases. Exact differentials. Reversible and irreversible transformations: isothermal and adiabatic transformations for an ideal gas. Enthalpy: heat capacity at constant volume (Cv) and at constant pressure (Cp); evaluation of Cp-Cv. Joule's experiment and Joule-Thomson's experiment. Thermochemistry: thermodynamic functions of reactions; standard states; standard reaction enthalpy; Hess' law; Kirchhoff's law. The second law of Thermodynamics: entropy (S); dS is an exact differential. Probabilistic interpretation of entropy: Boltzmann's equation. Conversion of heat into work. Thermal machines. Carnot's cycle. Kelvin's thermodynamic scale of temperatures. The third law of Thermodynamics: Nernst's formulation; unachievability of absolute zero. Residual entropy. Thermodynamic functions: free energy of Helmholtz (A) and of Gibbs (G). Minimization of the free energies and attainment of equilibrium. Free energies and work supplied by a system. Thermodynamic relations in a system at equilibrium: Maxwell's relations; the Gibbs-Helmholtz equation. The chemical potential. Phase equilibrium. Equilibrium for a chemical reaction. Chemical reactions in ideal gas mixtures. Van't Hoff's equation. The phase rule. One-component phase equilibrium: phase diagrams; critical point. Enthalpy and entropy of phase changes; Trouton's rule. Clapeyron's equation: liquid-vapour, solid-vapor and solid-liquid equilibria. Solid-solid transition phase and polymorphism. Higher-order phase transitions. Real gases: the approximate state equations of van der Waals and of Redlich-Kwong; the virial equation; the law of corresponding states. Solutions: partial molar quantities; mixing quantities. Ideal solutions and their thermodynamic properties; Raoult's law. Ideally diluted solutions: Henry's law. Non ideal solutions: activity and activity coefficient; the two conventions for standard states. The Gibbs-Duhem equation; activity coefficients for non volatile solutes. Solutions of electrolytes: the ionic strength and the Debye-Hueckel theory for the activity coefficients; Davies' extension. Non ideal gas mixtures: the fugacity. Chemical reactions in non ideal systems: reactions in non electrolyte solutions; reactions in electrolyte solutions; the "salt" effect; the common ion effect. Colligative properties: vapour pressure lowering, freezing point depression, boiling point elevation; osmotic pressure. Two-component liquid-vapour equilibrium: ideal and non ideal solutions; fractional distillation; theoretical plates; azeotrope. Two-component liquid-liquid equilibrium. Two component solid-liquid equilibrium; eutectic point. Electrochemical cells (hints): galvanic and electrolytic cells. Nernst's equation; standard electrode potentials; reference electrode; concentration cells; fuel cells.
Didactic methods
- The course is focused on lectures dealing with the fundamentals of chemical kinetics and laboratory experiments, suitably illustrated prior to the beginning of practical sessions. Students are required to write a concise report for each experience, in which, beside the presentation of data and of their elaboration, an interpretation of observed phenomena is required, based on knowledge obtained from relevant lectures
Learning assessment procedures
- Learning level is preliminarily verified during the discussion of the laboratory experiments, and by report delivery, required at the end of each experiment. Two partial written exams are enabled by middle and end of the course or, in alternative, a final written test, required by the students before the final verification by oral test. Both during the written and during the oral exam several questions are provided to the student, usually numerical exercises by written test and theoretical explanations by oral one. The questions are designed in order to verify the theoretical knowledge of the basic principles of thermodynamics, their implications; their application for chemical- physical and chemical reactions interpretation; phase transitions, properties of mixtures and the chemical equilibrium and their implications in real systems and materials science.
Reference texts
- P. Atkins, J. De Paula - "Physical Chemistry", Oxford, UK
