73514 - Thermodynamics Of Energy And Materials M

Learning outcomes

Knowledge about thermodynamic properties of fluids and materials and their use in phase equilibrium and reaction problems. Knowledge about the fundamentals of thermodynamic analysis for energy and process industry applications.

Course contents

1. Introduction / Course Overview

This course begins with a brief review of fundamental thermodynamic concepts, ensuring a solid foundation for more advanced topics. The key areas covered in the introduction include:

• Basic Thermodynamic Quantities: A recall of essential properties such as enthalpy, internal energy, specific heat capacities, and their physical significance in thermodynamic systems.
• PVT Behavior of Pure Substances and the Ideal Gas Law: Review of the relationships among pressure (P), volume (V), and temperature (T) for pure substances, including ideal gas behavior and the limitations of the ideal gas law.
• The First Law of Thermodynamics: Re-examination of the first law for both closed and open systems, including its application in solving simple energy balance problems involving heat and work interactions.

2. Second Law of Thermodynamics and Its Applications

This section focuses on the consequences and applications of the Second Law of Thermodynamics, including its role in defining system behavior, evaluating thermodynamic properties, and guiding energy conversion efficiency. The key topics include:

2.1 Derivation of Constitutive Equations:

• Combined use of the First and Second Laws to derive Gibbs and Maxwell relations.
• Application of Gibbs–Maxwell relationships to calculate thermodynamic properties.
• Development and interpretation of state diagrams and property relationships.
• Stability of equilibrium and system evolution based on thermodynamic constraints.
• Conditions for phase equilibrium, particularly liquid–vapor equilibrium.

2.2 Thermodynamic Models for Pure Components:

• Use of Cubic Equations of State (EoS) and generalized correlations for gases and liquids.
• Evaluation of thermodynamic properties for pure substances.
• Solving practical problems involving real fluid behavior.

2.3 Energy Conversion and Work:

• Concepts of ideal work, lost work, minimum work input, and maximum work output.
• Definition and application of exergy for efficiency analysis.
• Thermodynamic analysis of engineering cycles, including:

• Compressible flow systems
• Compressors
• Power cycles (e.g., Rankine)

• Refrigeration cycles

3.Multicomponent Systems and Advanced Equilibria

This section extends thermodynamic principles to mixtures and chemically reacting systems, with a focus on non-ideal behavior in multicomponent systems.

3.1 Ideal and Non-Ideal Mixtures

• Definition and evaluation of excess properties (e.g., excess enthalpy, excess Gibbs energy).
• Energy balances in non-ideal mixtures.
• Mixing enthalpy and use of enthalpy–concentration charts.

3.2 Thermodynamic Models for Non-Ideal Mixtures

• Description of non-ideal behavior using:
  • Fugacity
  • Activity
  • Activity coefficients
• Methods for the estimation and calculation of these quantities.

3.3 Multiphase Equilibria

• General multiphase equilibrium conditions based on chemical potential equality.
• Vapor–Liquid Equilibrium (VLE):
  • Qualitative behavior
  • Ideal models (e.g., Raoult's Law)
• Liquid–Liquid and Vapor–Liquid–Liquid Equilibrium (VLLE):
  • Use of non-ideal models (e.g., NRTL, UNIQUAC).

3.4. Chemical Reaction Equilibrium

• Derivation of the general equilibrium condition from thermodynamic principles (minimization of Gibbs energy).
• Analysis of temperature and pressure effects on chemical equilibrium.
• Example applications:
  • Non-ideal reacting systems
  • Systems involving pure solid phases
  • Systems with liquid and solid phase coexistence
• Treatment of multiple simultaneous reactions in equilibrium.

Readings/Bibliography

Suggested Textbooks:

• S. I. Sandler, Chemical and Engineering Thermodynamics, 3rd Edition, Wiley and Sons, 1999.

• J. M. Smith, H. C. Van Ness, and M. M. Abbott, Introduction to Chemical Engineering Thermodynamics, 7th Edition, McGraw-Hill Education, 2005.

These textbooks contain most of the theory and results considered in the course.

Additional references that provide further insight include:

• R. C. Reid, J. M. Prausnitz, and B. E. Poling, The Properties of Gases and Liquids, McGraw-Hill, New York, 1987.

• J. M. Prausnitz, R. N. Lichtenthaler, and E. G. de Azevedo, Molecular Thermodynamics of Fluid-Phase Equilibria, 3rd Edition, Prentice Hall, New Jersey, 1999 — particularly focused on various thermodynamic models.

• E. Winterbone, Advanced Thermodynamics for Engineers, Elsevier, 1996 — for examples on the use of exergy in the analysis of thermodynamic processes.

Teaching methods

Lectures

Assessment methods

The course assessment consists of a written examination followed by an oral examination.

Written examination. The written examination consists of solving between one and three exercises covering the main topics of the course. Half of the available points will be allocated to the thermodynamics of pure substances, covering Topics 1 and 2 of the course, while the remaining points will be allocated to the thermodynamics of mixtures, covering Topic 3.

The written examination will take place in LAB6 and must be completed using the laboratory computers. The use of personal laptops, tablets, mobile phones, or other personal electronic devices is not permitted. Students may use their own programs, which can be transferred to the laboratory computers via a USB drive. Internet access will not be available during the examination.

Students may consult their personal notes, course slides, and the course textbook.

To pass the written examination, students must obtain a minimum score of 16 out of 30.

Oral examination. The oral examination consists of a review and discussion of the written examination, followed by questions of a theoretical and/or practical nature on the topics covered during the course. It typically includes two questions and carries greater weight than the written examination, accounting for approximately two-thirds of the final grade.

Students must complete the oral examination within the two examination sessions following the session in which they passed the written examination. Students who do not meet this deadline or who fail the oral examination twice must retake and pass the written examination before attempting the oral examination again.

Teaching tools

The slides presented during the lessons, as well as other supporting materials (exercises, mock exams, etc.), will be made available on the course website during the semester

Office hours

See the website of Alessandro Zambon