CHEMISTRY II-PHYSICAL CHEMISTRY

This course of the Environmental Science programme, L-32 is part of the core set off courses, to be attended by all students. The main objective of the programme is to provide to graduates a systemic view of the environment. The specific objective, pertinent to this course, is the development of graduate's capacity of analysing environmental processes, with the aim of promoting environemntal quality and sustainable development. In this context, the objectives of this course are: 1) to provide the theoretical basis for understanding energy issues; 2) to develop the capacity of interpreting complex environmental processes, such as the fate of pollutants, on the basis of the Laws of Classical Thermodynamics.

Attending the classes and thoroughly studying the course notes and reading materials will enable students to achieve the following results.
Knowledge and comprehension
To understand the First and Second Law of Classical Thermodynamics and the state functions to understand how these Laws can be stated, in relation to different thermodynamic systems, by means of state functions, such as the Internal Energy, U, the Entropy, S, and the thermodynamic potentials, Free Energy, F, Entalpy, H, Gibbs free Energy. To grasp the concept of energy quality, connected to U and S, and the related function Exergy.
Capacity of applying knowledge and comprehension
To be able to calculate the efficiency of energy conversions and to estimate the maximum work which can be obtained from a thermodynamic system. To be able to derive the main Laws which govern the distribution of matter and energy in environmental systems. Based on these Laws, to be able to make qualitative predictions about the fate of pollutants in the environment.
Assessment capacity
To be able to assess the value of different energy typologies, and, on this basis, the perspectives for increasing energy efficiency. Assessing, at a qualitative level, risks related to the dispersion of pollutants in the environment.

Basic calculus: real functions of real variables, ordinary and partial derivatives, basic integrals.
Basic Mechanic concept: energy, work, conservation of mechanic energy.

Thermodynamic systems and variables. Thermodynamic processes. Internal Energy, U. U of an ideal gas.
The First Law of Thermodynamics. Thermal energy. Application of the First Law to isocoral, isothermal and isobaric processes concerning an ideal gas.
Entropy, S, and absolute temperature, T. Calculation of Entropy changes associated to thermodynamic processes, e.g. heating/cooling, changed in gas volume, phase transition.
The Second Law of Thermodynamics. Clausius inequality. Lord Kelvin and Clausius statements. Conversion of thermal energy into mechanical energy. Carnot heat engine. Carnot theorem.
Entropy and energy quality. Efficiency of a heat engine. Entropy content and energy quality. Efficiencies of the most relevant energy conversions.
Useful energy and Exergy. Exergy sources. Overview of worldwide sources and main uses. Towards a more rational use of exergy sources.
Gibbs fundamental equation. The virtual variation method and its application to Thermodynamic equilibria. Heterogeneous equilibrium conditions for isolated systems.
Thermodynamic potentials. Spontaneous processes at constant temperature: Free energy, F. Spontaneous processes at constant temperature and pressures: Gibbs free energy, G. Entalpy, H: is physical meaning. The fundamental relationship of Chemical Thermdynamics.
Phase equilibria. Conditions of heterogeneous eEquilibrium at constant temperature and pressure. Chemical potential. Changes of H, S and G with temperature at constant pressure for a pure chemical. The Third Law Thermodynamics. Phase transition: Entalpy and Entropy changes. Claperyron and Clausius-Clapeyron equations. State diagrams for one component. Triple points and Gibbs phase rule. State diagram of water.
Gas mixture. Chemical potential of an ideal gas at constant temperature. Gibbs free energy of a gas mixture. Changes in Gibbs free enrgy and entropy in mixing processes.
Real gases. Molarquantities. Graphic representation of mixing processes for binary mixtures. Chemical potential o a real gas. Fugacity. Critical temperature. Gas and vapours.
Solutions. Chemical potential of a pure liquid. Perfect and ideal solutions. Raoult and Henry Laws. Real solutions. Gibbs free energy, Entalpy and Entropy changes for a real solution. Solubility
Partitioning equilibria. Nernst Law. Octanol-water partition coefficient and its relevance in determining the fate of a pollutant in the environment. Relationship between Henry and Nernst constant and Gibbs free energy changes in partition and solution processes. Gibbs-Helmoltz equation. Calculation of changes in dissolved oxygen solubility with water temperature. Colligative properties
Chemical equilibria. Spontaneus chemical reaction and decrease in G. Equilibrium conditions for a homogeneous chemical reaction: the Guldberg and Waage Law of mass action. Effects of temperature and pressure on chemical equilibria.

Lecture notes, 8 chapters, approximately 215 pages, provided by the professor.

The achievement of the learning objectives if verified by means of a written test, which consists in three questions, which aims at ascertaining that a student has understood the main theoretical background and is able to use t for solving simple problems. Therefore, the questions concern the definition of fundamental concepts, the derivation of Laws, which are verifiable by means of experiments, from the above, the solution of simple numerical problems.

Lectures, based on the notes which are provided weekly to the students, in which power point presentations will also be used. The relevance of all topics in understanding environmental processes and energy issues are illustrated is underlined and illustrated by means of examples. Simple numerical problems, similar to those proposed in the final test, are discussed

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