Thermodynamic Models for Chemical Engineering: Design, Develop, Analyse and Optimize

Thermodynamic Models for Chemical Processes

Design, Develop, Analyze and Optimize

Jean-Noël Jaubert

Romain Privat

Series Editor

Laurent Falk

Table of Contents

Cover image

Title page

Copyright

Preface

1: Correlations for the Estimation of Thermodynamic Properties of Pure Substances in the Liquid, Perfect Gas or Vapor–Liquid States

Abstract

1.1: Introduction

1.2: Thermodynamics of the vapor–liquid equilibrium of a pure substance: what should be remembered

1.3: Correlations for the saturated vapor pressure of pure substances

1.4: Equations that can be used to correlate the molar volumes of pure liquids

1.5: Equations that can be used to correlate the molar volumes of saturated gases

1.6: Equations that can be used to correlate the enthalpies of vaporization

1.7: Equations used to correlate the heat capacity at constant molar pressure, molar enthalpy or molar entropy of an incompressible liquid

1.8: Equations that can be used to correlate the molar heat capacity at constant pressure, molar enthalpy or molar entropy of a perfect gas

1.9: Density of a pure substance

1.10: Prediction of the thermodynamic properties of pure substances

2: Estimation of Thermodynamic Properties of Pure Substances Using an Equation of State: Overview of Available Models and Calculation Procedures

Abstract

2.1: Volumetric equation of state: a definition

2.2: General overview of the volumetric equations of state

2.3: Presentation of usual volumetric equations of state

2.4: Practical use of volumetric equations of state

2.5: Calculation of state properties using a volumetric equation of state

2.6: Vapor–liquid equilibrium calculation using a pressure-explicit equation of state: illustration with cubic equations of state

2.7: Overall summary: criteria for selecting an equation of state for modeling of the thermodynamic properties of a given pure fluid

3: Low-Pressure Vapor–Liquid and Liquid–Liquid Equilibria of Binary Systems: Activity-Coefficient Models

Abstract

3.1: Introduction

3.2: Classification of fluid-phase behaviors of binary systems at low pressure and low temperature

3.3: Condition of equilibrium between fluid phases of binary systems

3.4: Vapor–liquid equilibrium relationship at low pressure

3.5: Activity coefficients: definition and models

3.6: Calculation of the vapor–liquid equilibrium of binary systems at low temperature and low pressure

4: Estimation of the Thermodynamic Properties of Mixtures from an Equation of State: An Overview of Models and Calculation Procedures

Abstract

4.1: The phase-equilibrium condition and the φ-φ approach

4.2: General presentation of the usual volumetric equations of state applicable to mixtures

4.3: Virial expansions

4.4: Cubic equations of state

4.5: Equations of state based on the statistical associating fluid theory (SAFT)

4.6: Specific equations of state for particular mixtures

4.7: Practical use of the equations of state for mixtures

5: General Summary: Decision Tree to Select a Thermodynamic Model in Order to Simulate or Design a Chemical Process

Abstract

5.1: Selection of thermodynamic models for representation of pure substances

5.2: Selection of thermodynamic models for representation of mixtures

References

Index

Copyright

First published 2020 in Great Britain and the United States by ISTE Press Ltd and Elsevier Ltd

Apart from any fair dealing for the purposes of research or private study, or criticism or review, as permitted under the Copyright, Designs and Patents Act 1988, this publication may only be reproduced, stored or transmitted, in any form or by any means, with the prior permission in writing of the publishers, or in the case of reprographic reproduction in accordance with the terms and licenses issued by the CLA. Enquiries concerning reproduction outside these terms should be sent to the publishers at the undermentioned address:

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Notices

Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary.

Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility.

To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein.

For information on all our publications visit our website at http://store.elsevier.com/

© ISTE Press Ltd 2021

The rights of Jean-Noël Jaubert and Romain Privat to be identified as the authors of this work have been asserted by him in accordance with the Copyright, Designs and Patents Act 1988.

British Library Cataloguing-in-Publication Data

A CIP record for this book is available from the British Library

Library of Congress Cataloging in Publication Data

A catalog record for this book is available from the Library of Congress

ISBN 978-1-78548-209-0

Printed and bound in the UK and US

Preface

Jean-Noël Jaubert; Romain Privat May 2020

This book is not a course book but a vademecum aimed primarily at users of process simulation software. It provides, in a condensed form, the methods governing the choice of a thermodynamic model for a targeted application and reminds the reader of the essential concepts on which these methods are based. At the time of publication (2020), this book was up to date with the main models of practical interest for the engineer and the researcher.

Finally, because we are convinced that, in order to use these models properly, it is important to understand – at the very least – how to carry out the calculations of the properties of interest that result from them, we will also refer to the major points.

Happy reading!

1: Correlations for the Estimation of Thermodynamic Properties of Pure Substances in the Liquid, Perfect Gas or Vapor–Liquid States

Abstract

A correlation is a mathematical expression, usually simple, of a physico-chemical property y as a function of one or several variables x. In this chapter, dedicated to pure substances, two types of properties are considered

Keywords

Antoine equation; Clapeyron equation; Enthalpy; Entropy; Isotherms; Molar heat capacity; Phase-intensive variables; Saturated vapor pressure; Thermodynamics; Vapor–liquid equilibrium

1.1: Introduction

A correlation is a mathematical expression, usually simple, of a physico-chemical property y as a function of one or several variables x. In this chapter, dedicated to pure substances, two types of properties are considered:

−properties depending on the temperature: for example, the heat capacity at constant pressure of a liquid pure substance (assumed to be incompressible), the saturated vapor pressure of a pure substance, the density of a liquid pure substance (assumed to be incompressible), etc. In these cases, the variable of the correlations is x = T;

−constant properties (which do not depend on the temperature): forexample, the normal boiling point, the critical pressure, the acentric factor, etc.

We will look at which principal correlations can be used for the pure-substance thermodynamic properties that depend on the temperature T. This chapter will end with a brief presentation of the methods that allow us to predict the constant properties and those depending on T using only knowledge of the chemical structure of pure substances. The variables x of correlations then become structural information (as well as T in the case of properties that depend on the temperature).

The T-dependent properties that are taken into consideration in this chapter are:

−the characteristic properties of the vapor–liquid equilibrium of a pure substance: saturated vapor pressure Psat(T), molar enthalpies of a boiling liquid hLsat(T) and of saturated vapor hGsat(T), molar enthalpy of vaporization ΔvapH(T) = hGsat(T) – hLsat(T), molar heat capacity at constant pressure of the boiling liquid cP,Lsat(T), densities of the boiling liquid ρLsat(T) or of the saturated gas ρGsat(T);

−properties of a pure perfect gas: molar enthalpy h•(T), molar heat capacity at constant pressure cP•(T);

−properties of a subcooled liquid¹: molar enthalpy hLpure(T), molar heat capacity at constant pressure cLpure(T), volumetric mass ρLpure(T). Here, we assume that pure subcooled liquids are incompressible; in other words, their properties are not affected by the pressure.

Note

Properties of a non-perfect gaseous pure substance cannot be described by the correlations presented in this chapter. Suitable methods (mainly based on equations of state) are presented in the following chapters.

1.2: Thermodynamics of the vapor–liquid equilibrium of a pure substance: what should be remembered

1.2.1: Phase-intensive variables and global-intensive variable

The intensive state of a two-phase system can be described by two sets of variables:

−phase-intensive variables, which are the intensive variables specific to one of the two phases of the system, for example, the temperature of the liquid phase, the pressure of the gas phase, the density of the liquid, the molar heat capacity of the gas phase at constant pressure, etc.;

−global-intensive variables that are not specific to a given phase but which instead characterize the two-phase system as a whole (i.e. the whole system). As an example, we cite the molar proportion of the gas phase (defined as the quantity of matter present in the gas phase divided by the global quantity of matter in the system, i.e. the sum of the quantities of matter in the liquid and gas phases), the global density (defined as the global mass of the system, i.e. mliquid + mgas, divided by the global volume, i.e. Vliquid + Vgas, etc.

Note

As explained in the following, at the vapor–liquid equilibrium, the two phases have the same temperature (T L = T G ), the same pressure (P L = P G ) and each component has the same chemical potential in each phase (μ i,L = μ i,G ). Thus, the temperature, pressure and chemical potential of a component i are both phase-intensive and global-intensive variables.

Since the extensive properties are additive, the global extensive properties of a two-phase system are obtained by adding the extensive properties of the two phases:

   [1.1]

Consequently, the relationship between the molar properties of the phases that