Physical Chemistry 1
(course in Italian)
see also https://www.unimi.it/it/corsi/insegnamenti-dei-corsi-di-laurea/2023/laboratorio-di-chimica-fisica-i
Learning objectives
The course will combine the basic aspects of chemical thermodynamics with experimental experiences aimed at the collection and handling of data and the estimation of the error on the thermodynamic parameters obtained.
Expected learning outcomes
The student will learn the principles that allow to interpret and quantitatively predict the behavior and reactivity of simple chemical systems (pure substances, simple mixtures, solutions) as a function of the physical chemical boundary conditions. In the laboratory, the student will experimentally verify what is illustrated in class and learns how to handle data and by drawing up a report accompanied by graphs and numerical calculations. The practical activities also allow the students to develop collaborative skills and problem-solving skills.
Course syllabus
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).
During the Experimental Laboratory physico-chemical parameters are determined (ΔU, ΔH, equilibrium constants, CMC of surfactants) through the elaboration of different measurements (calorimetry, spectrophotometry, conductivity, vapor tension) on the grounds of thermodynamic relations.
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).
During the Experimental Laboratory physico-chemical parameters are determined (ΔU, ΔH, equilibrium constants, CMC of surfactants) through the elaboration of different measurements (calorimetry, spectrophotometry, conductivity, vapor tension) on the grounds of thermodynamic relations.
Prerequisites for admission
The student should be familiar with derivative and integral calculus. Further he/she should be able to perform calculationd and diagrams by the Program Excel.
Teaching methods
Class room lessons combined with numerical exercises and laboratory experiments performed together with the teacher and the assistants.
Bibliography
P. W. Atkins, J. de Paula - Physical Chemistry - 9th ed. (2011) Oxford University Press.
Teaching material provided by the professor.
Teaching material provided by the professor.
Assessement methods and criteria
The assessment method is an oral examination combined with the solution of simple exercises. During the exam the student discusses the laboratory experiments and the thermodynamic principles underlying the experiments.
The final mark is also determined by the evaluation of the Laboratory Relation.
The final mark is also determined by the evaluation of the Laboratory Relation.
