Introductory Chemical Engineering Thermodynamics / Edition 1

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Overview

1138F-0

Includes extensive coverage of process simulation models

A practical, up-to-date introduction to applied thermodynamics

Introductory Chemical Engineering Thermodynamics will help students master the fundamentals of applied thermodynamics as practiced today: with a molecular perspective and extensive use of process simulation.

The book begins by introducing energy and entropy balances that are at the heart of processing engineering calculations. Understand the ideal gas law and thermodynamic tables. Learn important equation of state techniques for calculating thermodynamic properties including virial and cubic equations of state and the underlying theories behind them. Coverage includes:

  • Closed systems, open systems, and steady-state systems
  • Process thermodynamics, including the Carnot and Rankine cycles; Rankine modifications, refrigeration, liquefaction, internal combustion and fluid-flow
  • Departure functions and the role of enthalpy and entropy properties
  • Generalizing classical thermodynamics to any fluid
  • Fluid phase equilibria in mixtures, including multicomponent systems, fugacities, activity models, and liquid-liquid phase equlibria
  • Comparisons of thermodynamic models that help readers choose the most meaningful approach to each problem

Introductory Chemical Engineering Thermodynamics presents extensive practical examples, especially in its coverage of non-ideal mixtures, which addresses water contamination via hydrocarbons, polymer blending/recycling, oxygenated fuels and other contemporary issues.

Throughout, the book makes use of models and equations that may be worked with low-cost calculators and spreadsheet software. Useful appendices include a glossary; problem-solving strategies and software; relevant basic mathematics; and pure component properties.

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Editorial Reviews

Booknews
The four units of this textbook address first and second laws, generalized analysis of fluid properties, fluid phase equilibria in mixtures, and reacting systems. Appendices summarize models for process simulators, and computer programs for calculators, spreadsheets and Fortran. ^^^^ Annotation c. by Book News, Inc., Portland, Or.
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Product Details

Meet the Author

J. RICHARD ELLIOTT is Associate Professor of Chemical Engineering at the University of Akron in Akron, OH. His research interests include thermodynamics of hydrogen bonding, molecular simulations, and PRISM theory; thermodynamics of supercritical fluids and hydrocarbon processing; and experimental phase equilibium measurements. He holds a Ph.D. from Pennsylvania State University.

CARL T. LIRA is Associate Professor in the Department of Chemical Engineering at Michigan State University, specializing in the thermodynamics of complex systems. He holds a Ph.D. from the University of Illinois.

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Read an Excerpt

Preface

"No happy phrase of ours is ever quite original with us; there is nothing of our own in it except some slight change born of our temperament, character, environment, teachings and associations."
Mark Twain
Thank you for your interest in our book. We have developed this book to address ongoing evolutions in applied thermodynamics and computer technology. Molecular perspective is becoming more important in the refinement of thermodynamic models for fluid properties and phase behavior. Molecular simulation is increasingly used for exploring and improving fluid models. While many of these techniques are still outside the scope of this text, these new technologies will be important to practicing engineers in the near future, and an introduction to the molecular perspective is important for this reason. We expect our text to continue to evolve with the chemical engineering field.

Computer technology has made process simulators commonplace in most undergraduate curriculums and professional work environments. This increase in computational flexibility has moved many of the process calculations from mainframe computers and thermodynamic property experts to the desktop and practicing engineers and students. This increase in computational ability also increases the responsibility of the individuals developing process simulations to choose meaningful models for the components in the system because most simulators provide even more options for thermodynamic models than we can cover in this text. We have included background and comparison on many of the popular thermodynamic models to address this issue.

Computationaladvances are also affecting education. Thus we have significant usage of equations of state throughout the text. We find these computational tools remove much of the drudgery of repetitive calculations, which permits more class time to be spent on the development of theories, molecular perspective, and comparisons of alternative models. We have included FORTRAN, Excel spreadsheets, TI85, and HP48 calculator programs to complement the text. The programs are summarized in the appendices.
  • Solutions to cubic equations of state are no longer tedious with the handheld calculators available today for about $100. We provide programs for calculation of thermodynamic properties via the Peng-Robinson equation, vapor pressure programs, Peng-Robinson K-ratios and bubble pressures of mixtures, and van Laar and UNIFAC activity coefficients as well as several other utility programs. Our choice of the HP48 calculator is due to its being one of the first to provide a computer interface for downloading programs from a PC and provide calculator-to-calculator communication, which facilitates distribution of the programs. If all students in the class have access to these engineering calculators, as practiced at the University of Akron, questions on exams can be designed to apply to these programs directly. This obviates the need for traditional methods of reading charts for departure functions and K-ratios and enables treatment of modern methods like equations of state and UNIFAC.
  • Spreadsheets have also improved to the point that they are powerful tools for solving engineering problems. We have chosen to develop spreadsheets for Microsoft® Excel because of the widespread availability. Certainly Mathcad®, Mathematica®, and other software could be used, but none has the widespread availability of spreadsheets. We have found the solver within Excel to provide a good tool for solving a wide variety of problems. We provide spreadsheets for thermodynamic properties, phase and reaction equilibria.
  • High-level programming is still necessary for more advanced topics. For these applications, we provide compiled programs for thermodynamic properties and phase behavior. For an associating system, such as an alcohol, we provide the ESD equation of state. These programs are menu-driven and do not require knowledge of a computer language.

    In a limited number of instances, we provide FORTRAN source code. We provide FORTRAN code because of our own abilities to program faster in FORTRAN, although other languages are finding increasing popularity in the engineering community. We have tried to avoid customization of the code for a specific FORTRAN compiler, which improves portability to other operating platforms but also limits the "bells and whistles" that a specific interface could provide. These programs provide a framework for students and practicing engineers to customize for their own applications.
Energy and entropy balances are at the heart of process engineering calculations. We develop these approaches first using the ideal gas law or thermodynamic tables, then revisit the topics after developing equation-of-state techniques for thermodynamic properties. We are well aware of the concern that students often apply the ideal gas law inappropriately. Therefore we clearly mark equations using the ideal gas law or assuming a temperature-independent heat capacity. From a pedagogical standpoint, we are faced with the issues of developing first and second law balances, equations of state (and their departure functions) for fluid properties, and then combining the principles. We have found it best that students quickly develop ability and confidence in application of the balances with simple calculational procedures before introducing the equation of state. The balance concepts are typically more easily grasped and are essential for extension to later courses in the curriculum. Another benefit of this approach is that the later development of the equation of state can be directly followed by departure functions, and the reasons for needing properties such as enthalpy and entropy are well understood from the earlier emphasis on the balances. This enables students to focus on the development of the departure functions without being distracted by not completely understanding how these properties will be used.

Fugacity is another property which is difficult to understand. We have tried to focus on the need for a property which is a natural function of T and P, and also stress how it is related to departure functions. There are many ways to calculate fugacities (which provides many trees to block the view of the forest), and we have tried to provide tables and diagrams to show the inter-relations between fugacity coefficients, activity coefficients, ideal gases, ideal solutions, and real solutions.

A distinct feature of this text is its emphasis on molecular physics at the introductory level. Our perspective is that this background must be made available to students in an integrated manner, but it is up to instructors to decide the level of emphasis for the entire spectrum of their students. We have organized this material such that it may be covered as a supplementary reading assignment or as a homework and test assignment. With the latter emphasis, it is possible to formulate a graduate course based on this text.

Throughout the text, we have used text boxes to highlight important statements and equations. Boxed equations are not always final results of derivations. In some cases, the boxes highlight mathematical definitions of important intermediate results that might be useful for homework problems.

We consider the examples to be an integral part of the text, and we use them to illustrate important points. In some cases, derivations and important equations are within an example because the equations are model-specific (e.g., ideal gas). Examples are often cross-referenced and are therefore listed in the table of contents.

There are many marginal notes throughout the text. Where you find an EXCLAMATION POINT icon, it means that an important point is made, or a useful equation has been introduced. Where you find an HP or TI icon, it means that a calculator program is available to assist in calculations. The calculator programs are sometimes not necessary, but extremely helpful. Where you find a DISK icon, it means that an Excel spreadsheet or a compiled program is available. In some cases, the program is simply convenient, but typically you will find that these calculations are tedious without the program. For calculator or PC icons, the program names are given by the icons. See the computer appendix or the readme files for specific program instructions.

We periodically update computer software and the computer appendix. The latest software is available from our website http://www.egr.msu.edu/~lira/thermtxt.htm. We hope you find our approaches helpful in your learning and educational endeavors. We welcome your suggestions for further improvements and enhancements. You may contact us easily at the email addresses below. Unfortunately, we will be unable to personally respond to all comments, although we will try.

Notes to Students

Computer programs facilitate the solution to homework problems, but should not be used to replace an understanding of the material. Always understand exactly which formulas are required before turning to the computer. Before using the computer, we recommend that you know how to solve the problem by hand calculations. If you do not understand the formulas in the spreadsheets it is a good indication that you need to do more studying before using the program so that the structure of the spreadsheet will make sense. When you understand the procedures, it should be obvious which spreadsheet cells will help you to the answer, and which cells are intermediate calculations. It is also helpful to rework example problems from the text using the software.

Acknowledgments

We would like to thank the many people who helped this work find its way to the classroom. We express appreciation to Professors Joan Brennecke, Mike Matthews, Bruce Poling, Ross Taylor, and Mark Thies, who worked with early versions of the text and provided suggestions for improve-ment. We are also greatly indebted to Dave Hart for proofreading an early version. There are many students who suffered through error-prone preliminary versions, and we thank them all for their patience and vision of the common goal of an error-free book. CTL would like to thank Ryoko Yamasaki for her work in typing many parts of the manuscript and problem solutions. CTL also thanks family members Gail, Nicolas, and Adrienne for their patience while the text was prepared, as many family sacrifices helped make this book possible. JRE thanks family members Guliz, Serra, and Eileen for their similar forbearance. We acknowledge Dan Friend and NIST, Boulder for contributions to the steam tables and thermodynamic charts. Lastly, we acknowledge the influences of the many authors of previous thermodynamics texts. We hope we have done justice to this distinguished tradition, while simultaneously bringing deeper insight to a broader audience.

Carl T. Lira, Michigan State University, lira@egr.msu.edu
J. Richard Elliott, University of Akron, dickelliott@uakron.edu"
Read More Show Less

Table of Contents

Preface
Notation
Unit I First and Second Laws
Ch. 1 Introduction
Ch. 2 The Energy Balance
Ch. 3 Entropy
Ch. 4 Thermodynamics of Processes
Unit II Generalized Analysis of Fluid Properties
Ch. 5 Classical Thermodynamics - Generalization to any Fluid
Ch. 6 Engineering Equations of State for Pvt Properties
Ch. 7 Departure Functions
Ch. 8 Phase Equilibrium in a Pure Fluid
Unit III Fluid Phase Equilibria in Mixtures
Ch. 9 Introduction to Multicomponent Systems
Ch. 10 Phase Equilibria in Mixtures by an Equation of State
Ch. 11 Activity Models
Ch. 12 Liquid-Liquid Phase Equilibria
Ch. 13 Special Topics
Phase Behavior
Solid-Liquid Equilibrium. Residue Curves
Ch. 14 Reacting Systems
Ch. 15 Molecular Association and Solvation
Glossary
App. A Summary of Computer Programs
App. B Mathematics
App. C Strategy for Solving VLE Problems
App. D Models for Process Simulators
App. E Pure Component Properties
Index
Read More Show Less

Preface

Preface

"No happy phrase of ours is ever quite original with us; there is nothing of our own in it except some slight change born of our temperament, character, environment, teachings and associations."
Mark Twain
Thank you for your interest in our book. We have developed this book to address ongoing evolutions in applied thermodynamics and computer technology. Molecular perspective is becoming more important in the refinement of thermodynamic models for fluid properties and phase behavior. Molecular simulation is increasingly used for exploring and improving fluid models. While many of these techniques are still outside the scope of this text, these new technologies will be important to practicing engineers in the near future, and an introduction to the molecular perspective is important for this reason. We expect our text to continue to evolve with the chemical engineering field.

Computer technology has made process simulators commonplace in most undergraduate curriculums and professional work environments. This increase in computational flexibility has moved many of the process calculations from mainframe computers and thermodynamic property experts to the desktop and practicing engineers and students. This increase in computational ability also increases the responsibility of the individuals developing process simulations to choose meaningful models for the components in the system because most simulators provide even more options for thermodynamic models than we can cover in this text. We have included background and comparison on many of the popular thermodynamic models to address this issue.

Computational advances are also affecting education. Thus we have significant usage of equations of state throughout the text. We find these computational tools remove much of the drudgery of repetitive calculations, which permits more class time to be spent on the development of theories, molecular perspective, and comparisons of alternative models. We have included FORTRAN, Excel spreadsheets, TI85, and HP48 calculator programs to complement the text. The programs are summarized in the appendices.
  • Solutions to cubic equations of state are no longer tedious with the handheld calculators available today for about $100. We provide programs for calculation of thermodynamic properties via the Peng-Robinson equation, vapor pressure programs, Peng-Robinson K-ratios and bubble pressures of mixtures, and van Laar and UNIFAC activity coefficients as well as several other utility programs. Our choice of the HP48 calculator is due to its being one of the first to provide a computer interface for downloading programs from a PC and provide calculator-to-calculator communication, which facilitates distribution of the programs. If all students in the class have access to these engineering calculators, as practiced at the University of Akron, questions on exams can be designed to apply to these programs directly. This obviates the need for traditional methods of reading charts for departure functions and K-ratios and enables treatment of modern methods like equations of state and UNIFAC.
  • Spreadsheets have also improved to the point that they are powerful tools for solving engineering problems. We have chosen to develop spreadsheets for Microsoft® Excel because of the widespread availability. Certainly Mathcad®, Mathematica®, and other software could be used, but none has the widespread availability of spreadsheets. We have found the solver within Excel to provide a good tool for solving a wide variety of problems. We provide spreadsheets for thermodynamic properties, phase and reaction equilibria.
  • High-level programming is still necessary for more advanced topics. For these applications, we provide compiled programs for thermodynamic properties and phase behavior. For an associating system, such as an alcohol, we provide the ESD equation of state. These programs are menu-driven and do not require knowledge of a computer language.

    In a limited number of instances, we provide FORTRAN source code. We provide FORTRAN code because of our own abilities to program faster in FORTRAN, although other languages are finding increasing popularity in the engineering community. We have tried to avoid customization of the code for a specific FORTRAN compiler, which improves portability to other operating platforms but also limits the "bells and whistles" that a specific interface could provide. These programs provide a framework for students and practicing engineers to customize for their own applications.
Energy and entropy balances are at the heart of process engineering calculations. We develop these approaches first using the ideal gas law or thermodynamic tables, then revisit the topics after developing equation-of-state techniques for thermodynamic properties. We are well aware of the concern that students often apply the ideal gas law inappropriately. Therefore we clearly mark equations using the ideal gas law or assuming a temperature-independent heat capacity. From a pedagogical standpoint, we are faced with the issues of developing first and second law balances, equations of state (and their departure functions) for fluid properties, and then combining the principles. We have found it best that students quickly develop ability and confidence in application of the balances with simple calculational procedures before introducing the equation of state. The balance concepts are typically more easily grasped and are essential for extension to later courses in the curriculum. Another benefit of this approach is that the later development of the equation of state can be directly followed by departure functions, and the reasons for needing properties such as enthalpy and entropy are well understood from the earlier emphasis on the balances. This enables students to focus on the development of the departure functions without being distracted by not completely understanding how these properties will be used.

Fugacity is another property which is difficult to understand. We have tried to focus on the need for a property which is a natural function of T and P, and also stress how it is related to departure functions. There are many ways to calculate fugacities (which provides many trees to block the view of the forest), and we have tried to provide tables and diagrams to show the inter-relations between fugacity coefficients, activity coefficients, ideal gases, ideal solutions, and real solutions.
A distinct feature of this text is its emphasis on molecular physics at the introductory level. Our perspective is that this background must be made available to students in an integrated manner, but it is up to instructors to decide the level of emphasis for the entire spectrum of their students. We have organized this material such that it may be covered as a supplementary reading assignment or as a homework and test assignment. With the latter emphasis, it is possible to formulate a graduate course based on this text.

Throughout the text, we have used text boxes to highlight important statements and equations. Boxed equations are not always final results of derivations. In some cases, the boxes highlight mathematical definitions of important intermediate results that might be useful for homework problems.

We consider the examples to be an integral part of the text, and we use them to illustrate important points. In some cases, derivations and important equations are within an example because the equations are model-specific (e.g., ideal gas). Examples are often cross-referenced and are therefore listed in the table of contents.

There are many marginal notes throughout the text. Where you find an EXCLAMATION POINT icon, it means that an important point is made, or a useful equation has been introduced. Where you find an HP or TI icon, it means that a calculator program is available to assist in calculations. The calculator programs are sometimes not necessary, but extremely helpful. Where you find a DISK icon, it means that an Excel spreadsheet or a compiled program is available. In some cases, the program is simply convenient, but typically you will find that these calculations are tedious without the program. For calculator or PC icons, the program names are given by the icons. See the computer appendix or the readme files for specific program instructions.

We periodically update computer software and the computer appendix. The latest software is available from our website http://www.egr.msu.edu/~lira/thermtxt.htm. We hope you find our approaches helpful in your learning and educational endeavors. We welcome your suggestions for further improvements and enhancements. You may contact us easily at the email addresses below. Unfortunately, we will be unable to personally respond to all comments, although we will try.

Notes to Students

Computer programs facilitate the solution to homework problems, but should not be used to replace an understanding of the material. Always understand exactly which formulas are required before turning to the computer. Before using the computer, we recommend that you know how to solve the problem by hand calculations. If you do not understand the formulas in the spreadsheets it is a good indication that you need to do more studying before using the program so that the structure of the spreadsheet will make sense. When you understand the procedures, it should be obvious which spreadsheet cells will help you to the answer, and which cells are intermediate calculations. It is also helpful to rework example problems from the text using the software.

Acknowledgments

We would like to thank the many people who helped this work find its way to the classroom. We express appreciation to Professors Joan Brennecke, Mike Matthews, Bruce Poling, Ross Taylor, and Mark Thies, who worked with early versions of the text and provided suggestions for improve-ment. We are also greatly indebted to Dave Hart for proofreading an early version. There are many students who suffered through error-prone preliminary versions, and we thank them all for their patience and vision of the common goal of an error-free book. CTL would like to thank Ryoko Yamasaki for her work in typing many parts of the manuscript and problem solutions. CTL also thanks family members Gail, Nicolas, and Adrienne for their patience while the text was prepared, as many family sacrifices helped make this book possible. JRE thanks family members Guliz, Serra, and Eileen for their similar forbearance. We acknowledge Dan Friend and NIST, Boulder for contributions to the steam tables and thermodynamic charts. Lastly, we acknowledge the influences of the many authors of previous thermodynamics texts. We hope we have done justice to this distinguished tradition, while simultaneously bringing deeper insight to a broader audience.

Carl T. Lira, Michigan State University, lira@egr.msu.edu
J. Richard Elliott, University of Akron, dickelliott@uakron.edu"
Read More Show Less

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