73498 - Thermodynamics For Chemical Engineering M

Learning outcomes

To be able to use the methodologies of general, applied and chemical thermodynamics and apply it to the analysis of chemical engineering systems and processes and to the evaluation of fluid properties, chemical and physical equilibria.

Course contents

Prerequisites: Chemical Engineering Thermodynamics (Undergraduate Level), Calculus, Numerical Methods, Physics.

The course is dedicated to students with some previous knowledge on pure components thermodynamics in order to give them further information of such discipline with focus on the tools and methods for the thermodynamic analysis of chemical processes as well as for the description and prediction of thermodynamic properties of pure substances and mixtures and of the behavior of chemical equilibria in homogeneous and multiphase systems.

Brief introduction to recall the thermodynamics for pure compounds and mixtures. First law of thermodynamics and the energy balance for pure compounds and mixtures. Definitiona and evaluation of the different thermodynamic quantities (internal energy, enthalpy and free energies).

Analysis of the second law, definition of entropy and use of the second principle in the calculation of the relationship between the state variables: Maxwell's equations for perfect fluids, and for other systems (viscosity, surface tension, etc. with internal state variable. .) application of the second law to calculate the maximum and minimum labor and for thermodynamic analysis of the processes.

Existence and stability of thermodynamic equilibria in homogeneous and heterogeneous phase for pure substances and mixtures. Mixtures thermodynamics, the Gibbs Duhem equation, partial molar quantities, sizes and quantities of excess mixing, definition of chemical potential and fugacity.

Equilibrium relationships for ideal and non-ideal systems, azeotropic systems and systems with miscibility gaps. Raoult's law generalized to Henry's Law for liquid gas or solid-liquid mixtures. Equilibria in reactive systems with single and multiple reactions, the reaction equilibrium constant and its use for the calculation of the equilibrium concentration of a reactive system.

Introduction to equations of state for the calculation of thermodynamic quantities. Ideal Gas and van der Walls equations of state. Virial equation and its evolution: the equation of Benedict Webb Rubin. The corresponding states principles and its overcoming through the introduction of correction parameters, generalized diagrams, Lee-Kesler method and generalized cubic equations of state (Peng Robinson). Introduction to Lattice fluid equations of state and to relationships derived from statistical thermodynamics. The relationships between state variables differential and P, V and T quantities and their calculation using equations of state and the deviation from ideal gas state. Group contribution methods for the estimation of pure components paramters. Extension to mixtures of the equations of state: mixing rules and methods for the calculation of binary parameters.

Models for the evaluation for the estimation of the chemical potential and the calculation of phase equilibria in multicomponent systems. Empirical and semi-empirical models ( Margules, Van Laar ), regular solutions theory and solubility parameter. Models based on the lattice fluid theory ( Flory Huggins) and on local composition ( NRTL model of Wilson. UNIQUAC and UNIFAC models).

Applications of different models considered for the description of the behaviour of real thermodynamic systems such as multicomponents phase equilibria and non ideal reactive systems with one or more phases and reactions.

Introduction to Statistical Thermodynamics

Readings/Bibliography

S. I. Sandler, "Chemical and Engineering Thermodynamics " Third Edition, Wiley and Sons (1999)

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, E. G. de Azevedo, Molecular Thermodynamics of Fluid-Phase Equilibria 3rd Edition Prentice Hall New Jersey 1999

J. M. Smith, H. C. Van Ness, Michael M. Abbott - Introduction To Chemical Engineering Thermodynamics: Chemical Engineering Thermodynamics (7th Edition) McGraw-Hill Education, 2005

Teaching methods

Classes and examples

Assessment methods

One written exam (or two intermediate written tests), that require the solution of some problems with the aid of a calculator or personal computer, and one oral exam. 

Teaching tools

Lectures on the blackboard and with slides, problems, videos, questionnaires.

Office hours

See the website of Maria Grazia De Angelis