Chemistry

ANDREA CICCIOLI

General Educational Target

To complete the education and training of students in the field of physicochemical thermodynamics at a graduate level



Specific Educational Targets


A) Knowledge and understanding. This class is aimed at giving students a body of knowledge that can be summarized by four points: 1) to deepen the understanding of fundamentals of thermodynamics (that students were introduced to in the Chimica Fisica I class during the undergraduate course) with special emphasis on the second law of thermodynamics, which is presented by an approach based on the concept of entropy production as the driving force for the irreversible processes; 2) to illustrate the thermodynamic treatment of one-component or fixed-composition systems with a systematic and mathematically rigorous approach, by deriving the total differentials of all the thermodynamic functions involved in physicochemical problems; 3) to extend the thermodynamic treatment to processes and systems more complex than those addressed by students in the elementary courses: real gases, multicomponent real solutions and phase diagrams, heterogeneous chemically reactive systems, high-pressure phenomena, systems with curved interfaces, etc.; 4) to illustrate the basic aspects of the most important experimental techniques used to determine thermodynamic properties.

B) Applying knowledge and understanding. With regard to the ability in applying the above reported contents, a part of the classes is intended to enable students 1) to solve practical problems of applied thermodynamics and thermochemistry, such as to calculate heat, work, and changes of thermodynamic functions in reversible and irreversible processes, to evaluate the driving force of irreversible processes, the mixing properties in multicomponent solutions, the equilibrium phases and their compositions in reactive and non-reactive systems, to read and discuss two- and three-component phase diagrams, etc. and 2) to give students a good command of the mathematical handling of thermodynamic functions and expressions, enabling them to derive autonomously other relations useful in solving specific physicochemical problems.

Advanced understanding of the fundamentals of thermodynamics; solving problems in applied and chemical thermodynamics; manipulation of thermodynamic formalism so as to derive autonomously further relations useful to handle specific problems in the thermodynamics of materials

Fundamentals of differential and integral calculus (requested)
Functions of one variable (requested)
Functions of two variables (recommended)
Fundamentals of classic dynamics and electromagnetism (recommended)
Fundamentals of quantum mechanics and statistical thermodynamics (recommended)

Fundamentals of thermodynamics: general aspects and definitions. Thermodynamics variables and functions. Reversible and irreversible processes. Thermodynamic Equilibrium. First and second law. Clausius inequality. Degradation and dissipation of energy. The classic approach to the second law: the heat engines. Combined form of first and second law in terms of S, U, H, G, A. Spontaneous internal processes. Entropy production as driving force of irreversible processes. Equilibrium criteria. Thermal, hydrostatic, material equilibrium. Thermodynamic potentials. Chemical affinity and chemical equilibrium.
One component and fixed-composition systems. Thermodynamic functions and their total differentials. Maxwell's equations. The phase rule. One-component phase diagrams. Clapeyron and Clausius-Clapeyron equations. G(P,T) surfaces. Common tangent method and T-V phase diagrams. The lever rule. The effect of curved interfaces.
Real gases. Compressibility factor. Equations of State: van der Waals, Redlich-Kwong, virial EOS. Critical parameters. Condensation of real gases: the Maxwell construction. The corresponding states. The fugacity. Gas mixtures. The Lewis-Randall rule. Intermolecular potentials and EOS.
Thermodynamics of solutions. Homogeneous functions and Euler's theorem. Gibbs-Duhem equations. Ideal solutions. Standard state. Fugacity and activity. Regular solutions. The quasichemical model. Intermidiate phases and line compounds. Tie-lines. Two-component phase diagrams. Miscibility gaps. Eutectic, peritectic, montectic systems. Ellingham-Richardson diagrams. Volatility diagrams.
Continuous systems. Thermodynamic Equilibrium under external fields.
Experimental methods for the determination of thermodynamic properties and phase diagrams. Calorimetric, electrochemical and tensimetric techniques. Use of thermochemical tabulations for the prediction of chemical processes.

* R. DeHoff, Thermodynamics in Materials Science, 2nd Edition, CRC - Taylor & Francis, 2006.

*,** K. Denbigh, The Principles of Chemical Equilibrium, 3rd ed., Cambridge University Press, 1971. (see also 4th ed., 1981)

* D. Kondepudi, Introduction to Modern Thermodynamics 1ed., Wiley, 2008.

I. Prigogine, D. Kondepudi, Modern Thermodynamics: From Heat Engines to Dissipative Structures, 2nd Edition, Wiley, 2014.


* I.N. Levine, Physical Chemistry, 6th ed. Mc Graw Hill, 2009.


** H.C Van Ness, Understanding Thermodynamics, Dover Publications, 1969.



______________________________________________________________________
* Available from "Biblioteca Illuminati", the main library in the Chemistry department (and from A. Ciccioli)
** Available from the main library of the Physics department (and from A. Ciccioli)

More advanced textbooks:

** Mats Hillert, Phase Equilibria, Phase Diagrams and Phase Transformations, 2nd Edition, Cambridge University Press, 2009 (presso la biblioteca di fisica c'è solo la prima edizione).

*** C.H.P. Lupis, Chemical Thermodynamics of Materials, Elsevier, 1983.

Further Readings:

*** David R. Gaskell, Introduction to the Thermodynamics of Materials, 5th edition, Taylor & Francis, 2008. Oppure: 4th edition, Taylor & Francis, 2003.
* I.M. Klotz, R. M. Rosenberg, Chemical Thermodynamics : Basic Concepts and Methods. 7th Ed., Wiley, 2008.
K.S. Pitzer (Lewis-Randall), Thermodynamics, 3rd edition, McGraw Hill, 1995.
Any good textbook of general physical chemistry: McQuarrie, Engel-Reid, Atkins, ecc.

______________________________________________________________________
* Available from "Biblioteca Illuminati", the main library in the Chemistry department (and from A. Ciccioli)
** Available from the main library of the Physics department (and from A. Ciccioli)
*** Available from A. Ciccioli

Classroom-taught lessons, including excercises
PC-aided excercises

Attendance is recommended.

Written exam based on numerical excercises and theoretical problems/questions. Solutions should be well-discussed in a concise but exhaustive manner.
The oral exam is optional