FACULTAD DE MINAS UNIVERSIDAD NACIONAL DE COLOMBIA

THERMODYNAMICS OF MATERIALS
Lectures Room M3-212, Tuesday - Thursday: 10:00-12:00 am Instructor Germán
Sierra (geasierraga@unal.edu.co) Office hours: Text: Lecture notes/copies +
Introduction to the Thermodynamics of Materials, D.R.
Gaskell, McGraw-Hill, 4th edition. Chemical Thermodynamics of Materials. S. Stolen, T.
Grande. Ed. Wiley.
Course Description The course covers the fundamentals of classical thermodynamics
focusing on the first law of thermodynamics and its applications to the calculations of heat
involved in various materials processes such as chemical reactions and phase
transformations. Second law of thermodynamics and the concept of entropy are then
introduced. The application of maximum work theorem to engine efficiency is briefly
discussed. Various thermodynamic potentials are defined to determine the equilibrium of a
system under various thermodynamic conditions, with an emphasis on the Gibbs free energy
functions at constant temperature and pressure conditions. The relationships among
thermodynamic properties are derived using the Maxwell relations. Phase diagrams of single-
component systems are constructed from the Gibbs free energy function, and the Clapeyron
equation is applied to describe the phase boundaries. Applications of thermodynamics to the
determination of chemical equilibrium are also discussed. The last part of the course is
focused on the solution thermodynamics and its application to binary phase-diagrams. The
course of Thermodynamics of Materials, discusses application of thermodynamics to
materials science and engineering.
Course Outline 0. Introduction. The Concept of system, state, types of properties,
thermodynamic processes, Ideal gases, Dalton’s law of partial pressures, Real gases, External
energy and internal energy, heat, work. (01 week).
1. The first thermodynamic law and its applications. The First Law, enthalpy. Special
conditions: constant volume (isochoric), constant temperature,
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(isothermal) constant pressure (isobaric), adiabatic. Heat capacity at constant volume and
pressure for gases and solids. Relation between Cp and CV, the temperature dependence of
heat capacity. Enthalpy of physical transformations and chemical reactions, Sensible and
latent heats, Hess'law, Temperature dependence of the enthalpy of reaction, KIRCHOFF's
equiation. (02 weeks).
2. 2nd law of thermodynamics. Carnot cycle, Clausius statement, Kelvin Plank statement,
Spontaneous or natural processes, Reversible and non-reversible processes. The second law
and the definition of entropy. Calculation of entropy changes. Volume, presion and
Temperature dependence of the entropy. Third Law of Thermodynamics. Entropy of
reaction, Combined 1st and 2nd laws. (01 weeks) (20%)
3. Auxiliary Functions and Thermodynamic Relations. Euler reciprocity relation, definition
and meaning of Gibbs free energy, Spontaneous Evolution and Equilibrium Condition,
definition of Helmholtz free energy. Gibbs free energy of mixing, definition of chemical
potential, Fugacity and activity. Gibbs- Helmholtz relation. Maxwell’s Relations,
fundamental equation. Gibbs free energy of reaction, Temperature dependence of the Gibbs
free energy of reaction, presion dependence of the Gibbs free energy of reaction.(02 weeks)
4. Thermochemistry. Definition of combustion, formation, reduction and dissolution heat
reaction. Enthapy, entropy and Gibbs free energy changes in chemical reactions.
Temperature dependence of the enthalpy, entropy and Gibbs free energy of reaction. Mass
and energy balance in steady-flow systems (close and open systems) (02 weeks)
5. Phase equilibrium in a one component system. The variation of Gibbs free energy with
temperature at constant pressure, The variation of Gibbs free energy with pressure at constant
temperature, Equilibrium between the vapor phase and a condensed phase, solid-solid
equilibrium, Clausius Clapleyron equation, Phases and Gibbs phase rule, 1 component phase
diagrams. Super-Critical Properties. (02 week)
6. Reaction equilibrium.
a) in gaseous systems. Reaction equilibria; equilibrium constants, Pressure and Temperature
Dependences of Equilibrium Le Chatelier’s principle b) reaction involving condensed phases
and gaseous phase . ELLINGHAM diagrams (04 weeks)
7. Thermodynamics of solutions; Raoult's law; ideal solutions, activity, chemical potential,
Measurement of vapor pressure. Gibbs energy of mixing. The Gibbs- Duhem equation.
Graphical determination of the partial molar Gibbs energy of
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mixing. Gibbs free energy formation of a solution, the heat of formation of an ideal solution,
entropy of formation of an ideal solution. (01 wekks)
Course Objectives:
1. To provide an understanding of the classical thermodynamic approach to the energetic of
complex systems. 2. To provide a foundation for the application of the principles of
thermodynamics hydrometallurgical reaction and mineral transformation. 3. To provide a
consistent picture of thermodynamics concepts when applied to phase equilibria. 4. To
provide understanding key factors affecting the phase diagrams of one, two and three
component materials systems.
Assessment Assignments: 10%. Exams: 80%. There will be 4 exams during the semester, all
equally weighted.
Reference Material
1. D. R. Gaskell, Introduction to the Thermodynamics of Materials, 4th Edition, Taylor
& Francis, 2003. 2. S. Stolen, T. Grande and N. L. Allan: Chemical Thermodynamics of
Materials. Wiley,
Chichester, 2004. 3. J. Ganguly, Thermodynamics in Earth and Planetary Sciences.
Springer. 4. L. Cemic , Thermodynamics in Mineral Sciences. Springer 5. G. W. Castellan,
Physical Chemistry, 3rd Ed., Addison-Wesley, Reading, MA, 1983 6. Ira. N. Levine, Physical
Chemistry. McGraw-Hill 7. J.M. Smith. Introducción a la Termodinámica en Ingeniería
Química. McGRAW-HILL 8. D.V. Ragone, Thermodynamics of Materials, Volumes 1& 2,
John Wiley & Sons, Inc.,
1995 9. O. Kubashevski, C.B. Alcock, and P.J. Spencer, Materials Thermochemistry,
 Pergamon Press, 1993. 10. M. J. Moran, Fundamentals of Engineering Thermodynamics.
Wiley 5th Edition 11. Lupis, C.H.P. Chemical Thermodynamics of Materials, North-
Holland, 1983 12. Ragone, D.V. Thermodynamics of Materials, Volumes 1& 2, John Wiley
& Sons,
Inc., 1995
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