Thermodynamics

Thermodynamics

Jean-Paul Duroudier

Industrial Equipment for Chemical Engineering Set

coordinated by

Jean-Paul Duroudier

Table of Contents

Cover image

Title page

Dedication

Copyright

Preface

1: A Logical Presentation of Thermodynamics

Abstract

1.1 Concepts in thermodynamics

1.2 Tenets of thermodynamics

1.3 First law of thermodynamics and internal energy

1.4 Second law and entropy

1.5 Gibbs energy and Euler’s theorem

1.6 Values of state. Thermodynamic potentials

1.7 Use of the concept of entropy – thermal machines and entropy analysis

1.8 Gibbs–Duhem and Gibbs–Helmholtz equations

1.9 Entropy and statistical physics

2: Equations of State and Fugacities

Abstract

2.1 Perfect gases

2.2 Mixture of perfect gases

2.3 Real chemical species in the pure state

2.4 Properties of real mixtures

2.5 Characterization of crude-oil-based mixtures

2.6 Conclusion

3: Solution Activity Coefficients

Abstract

3.1 Mixtures in the liquid state (non-electrolytes)

3.2 Equilibrium between crystal and solution

3.3 Electric field of Debye and Hückel [DEB 23]

3.4 Two approximate calculation methods (electrolytes) [MEI 80] and [HEL 81]

3.5 Osmotic coefficient (electrolytes), [MEI 80] and [HEL 81]

3.6 Cruz and Renon’s theoretical and practical review [CRU 78]

4: Laws Governing the Transfer of Material and Heat Between Two Immiscible Fluids Electrolytes and their Diffusion

Abstract

4.1 Fick’s law [FIC 55]

4.2 Maxwell–Stefan equations

4.3 Matrix resolution of the M.–S equations

4.4 Simultaneous transfers of material and heat

4.5 Diffusion of electrolytes

4.6 Determination of diffusivities

4.7 Concepts concerning batteries and electrolytic cells

5: Calculation of the Equilibrium Between Two Fluids

Abstract

5.1 General

5.2 Representation of liquid–vapor equilibria

5.3 Calculation of the equilibria between two fluids

5.4 A limiting case: Henry’s law

5.5 Liquid–liquid equilibrium: general points and representations

5.6 Calculation of liquid–liquid equilibria: binary mixtures

5.7 Ternary mixtures

5.8 Equilibria in the supercritical domain

Appendix 1: Indefinite Integrals Useful for the Calculation of the Functions of State on the Basis of a Cubic Equation

A1.1 Expression of the cubic equation

A1.2 Expressions of the integrals

Appendix 2: Solving Third- and Fourth-degree Equations: Searching for Dimensioless Groups

A2.1 Third-degree equation

A2.2 Fourth-degree equation

A2.3 Finding dimensionless groups expressing a physical law

Appendix 3: A Few Important Identities

A3.1 Theorem of reciprocity

A3.2 Closed-loop derivation

A3.3 Cascaded derivation

A3.4 Rational fractions and simple elements

Appendix 4: A Few Expressions for Partial Vapor Pressures

A4.1 Henry’s constant

A4.2 Empirical formulae

Appendix 5: Numerical Calculation of the Solution to F(X) = 0

Appendix 6: Jacobian Method

Appendix 7: Characteristics of Various Gases

Appendix 8: The CGS Electromagnetic System

A8.1 Potential in the international system (SI) and in the CGS electromagnetic system

A8.2 Other units in SI and CGSEM

Appendix 9: Resistance, Conductance, Diffusance

Bibliography

Index

Dedication

There are no such things as applied sciences, only applications of science

Louis Pasteur (11 September 1871)

Dedicated to my wife, Anne, without whose unwavering support, none of this would have been possible.

Copyright

First published 2016 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 2016

The rights of Jean-Paul Duroudier to be identified as the author 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 978-1-78548-176-5

Printed and bound in the UK and US

Preface

The observation is often made that, in creating a chemical installation, the time spent on the recipient where the reaction takes place (the reactor) accounts for no more than 5% of the total time spent on the project. This series of books deals with the remaining 95% (with the exception of oil-fired furnaces).

It is conceivable that humans will never understand all the truths of the world. What is certain, though, is that we can and indeed must understand what we and other humans have done and created, and, in particular, the tools we have designed.

Even two thousand years ago, the saying existed: faber fit fabricando, which, loosely translated, means: "c’est en forgeant que l’on deviant forgeron" (a popular French adage: one becomes a smith by smithing), or, still more freely translated into English, practice makes perfect. The artisan (faber) of the 21st Century is really the engineer who devises or describes models of thought. It is precisely that which this series of books investigates, the author having long combined industrial practice and reflection about world research.

Scientific and technical research in the 20th century was characterized by a veritable explosion of results. Undeniably, some of the techniques discussed herein date back a very long way (for instance, the mixture of water and ethanol has been being distilled for over a millennium). Today, though, computers are needed to simulate the operation of the atmospheric distillation column of an oil refinery. The laws used may be simple statistical correlations but, sometimes, simple reasoning is enough to account for a phenomenon.

Since our very beginnings on this planet, humans have had to deal with the four primordial elements as they were known in the ancient world: earth, water, air and fire (and a fifth: aether). Today, we speak of gases, liquids, minerals and vegetables, and finally energy.

The unit operation expressing the behavior of matter are described in thirteen volumes.

It would be pointless, as popular wisdom has it, to try to reinvent the wheel – i.e. go through prior results. Indeed, we well know that all human reflection is based on memory, and it has been said for centuries that every generation is standing on the shoulders of the previous one.

Therefore, exploiting numerous references taken from all over the world, this series of books describes the operation, the advantages, the drawbacks and, especially, the choices needing to be made for the various pieces of equipment used in tens of elementary operations in industry. It presents simple calculations but also sophisticated logics which will help businesses avoid lengthy and costly testing and trial-and-error.

Herein, readers will find the methods needed for the understanding the machinery, even if, sometimes, we must not shy away from complicated calculations. Fortunately, engineers are trained in computer science, and highly-accurate machines are available on the market, which enables the operator or designer to, themselves, build the programs they need. Indeed, we have to be careful in using commercial programs with obscure internal logic which are not necessarily well suited to the problem at hand.

The copies of all the publications used in this book were provided by the Institut National d’Information Scientifique et Technique at Vandœuvre-lès-Nancy.

The books published in France can be consulted at the Bibliothèque Nationale de France; those from elsewhere are available at the British Library in London.

In the in-chapter bibliographies, the name of the author is specified so as to give each researcher his/her due. By consulting these works, readers may gain more in-depth knowledge about each subject if he/she so desires. In a reflection of today’s multilingual world, the references to which this series points are in German, French and English.

The problems of optimization of costs have not been touched upon. However, when armed with a good knowledge of the devices’ operating parameters, there is no problem with using the method of steepest descent so as to minimize the sum of the investment and operating expenditure.

1

A Logical Presentation of Thermodynamics

Abstract

There are four states of aggregation: gas, liquid, solid and plasma.

Keywords

Aggregation; Enthalpy; Entropy; Euler’s theorem; Gibbs–Duhem equation; Gibbs energy; Holonomicity; Parameters; Pfaff formula; Reciprocity theorem; Thermodynamics

1.1 Concepts in thermodynamics

1.1.1 States of aggregation of material

There are four states of aggregation: gas, liquid, solid and plasma.

In the discussions herein, we shall only consider the first three.

1.1.2 Phases and components

A material is said to be homogeneous if all of its properties vary contiguously. It is said to be uniform if all its properties have the same value throughout.

A homogeneous piece of material constitutes what is called a phase. The number of phases that may be found in nature is, if not limitless, at least very large, because there are a considerable number of chemical species of which they may be composed.

A piece of material is said to be heterogeneous if its properties exhibit discontinuities. However, within a heterogeneous ensemble, there are homogeneous domains which make up phases.

An ensemble – be it homogeneous or heterogeneous – is often said to be either single- or poly-phase.

The terms component and element denote any species involved in the composition of a homogeneous or heterogeneous mixture, whose quantity may vary independently of the other components. The proportions of the different components of a mixture are often defined in concentrations (kmol.m− 3 or kg.m− 3) or in fractions, also known as titers (molar, gravimetric or volumetric).

1.1.3 Thermodynamic system: variables and functions of state

A thermodynamic system is a material ensemble whose state is defined by so-called variables of state (composition, pressure, temperature, etc.). These variables are independents. The other variables defining the state are the functions of state, which are obtained from the variables of state by using the equations of state.

Instead of system, we sometimes employ the term physical agent.

1.1.4 Variables and intensive or extensive functions (parameters)

We distinguish between:

– intensive parameters, which do not depend on the size of the physical agent (pressure, temperature, titers, etc.…),

– extensive parameters, whose value is proportional to the size of the system (mass, number of particles or molecules, energy, volume, etc.).

1.1.5 Isolated, open and closed systems

An isolated system is a system which exchanges nothing with its environment, and whose boundary is immovable.

A system is open or closed depending on whether or not it exchanges material with the outside world.

In statistical physics, isolated systems are described by the microcanonical ensemble. A closed system (which exchanges energy but not material with the outside world) is described by the canonical ensemble. A system which exchanges both energy and material with its environment is described by the large canonical ensemble.

1.1.6 Energy and evolution of a system. The concept of work

Essentially, in thermodynamics, we study the consequences in terms of energy of the changes occurring in a system, drawing inspiration from elementary mechanics (the mechanics of simple machines). We characterize the work created from a potential energy by the product of a generalized force Xi by a generalized displacement xi. The conjugate values Xi and xi are linked by an equation of state, and there are as many equations of state as there are types of work. Conventionally, the generalized forces are counted positively, and so too is any work