Advanced Thermodynamics

This is a 4 ECTS course composed of lecture hours, self-study, six assignments, and a final examination.

Chemical thermodynamics dictates the behaviour and performance of materials and processes for a wide range of applications, and is central to many fields of relevance for chemical engineers. This course will address advanced macroscopic thermodynamics and will introduce statistical thermodynamics that makes the link between the atomic (molecular) and macroscopic scales. It will cover both the thermodynamics of materials (Part I) and thermodynamics of process engineering (Part II).

Part I: Thermodynamics of materials
The first part of the course will introduce key experimental techniques used for the determination of thermodynamic properties and phase diagram equilibria, including calorimetry and mass spectrometry techniques. While classical thermodynamics and its experimental methods deal mostly with the macroscopic scale and are well adapted for condensed matter (solids and liquids), they are not always well suited for the determination of thermodynamic properties of gases, which require knowledge of the internal energy at the atomic (molecular) scale and the use of statistical methods. This course will thus also introduce the basis of statistical thermodynamics and statistical-mechanical evaluation of thermodynamic properties (e.g. heat capacity, entropy) of gases. Furthermore, more general thermodynamic modelling methods based on Gibbs energy minimization will be introduced, as well the development of multi-component thermodynamic databases, that integrate the experimental and statistical information as input for their development and optimization. The understanding and proper use of such databases is key to predict the performance of modern materials.

Part II: Thermodynamics of process engineering
The second part of the course bridges the gap between the theory of classical thermodynamics and the practice of chemical and process engineering. Reliable values of properties of fluids are necessary to design an industrial process, such as separation units and reactors. Often experimental data are limited, and estimations and predictions are necessary. This part of the course will focus on estimation methods, and, this is key, expects the student to achieve the ability to critically assess the reliability of their estimated values. The focus is on PVT and thermodynamic properties of gasses and liquid, as pure component and mixtures, and their phase equilibria. Many of these methods rely heavily on empirical formulations, but the most reliable ones often have a theoretical basis. As the physical properties of every substance are based on their molecular structure, often such theory is molecular based. Where relevant, such theory will be covered. The course will first focus on pure components properties, low pressure vapour-liquid equilibria, high pressure vapour-liquid equilibria and reaction equilibria. The course will cover estimations of vapour pressure, heat of vaporisation, activity and fugacity coefficient models, equations of state, enthalpy and entropy of formation at relevant temperature and pressures.

The course will finally stress the importance and use of theoretical and experimental data, as well as thermodynamic databases in various fields of relevance for chemical engineers through practical assessments and case studies.