Introductory Chemical Engineering Thermodynamics

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9780130113863: Introductory Chemical Engineering Thermodynamics

For undergraduate courses in Applied Thermodynamics. Written in a style and at a level that is accessible to undergraduates, this introduction to applied thermodynamics covers the first and second law for process applications, molecular concepts, equations of state, activity models, and reaction equilibria--all in a tightly integrated, pedagogical progression of topics. It addresses the on-going evolution in applied thermodynamics and computer technology, and integrates several widely-accessible computational tools to allow exploration of model behavior-- e.g., programs for HP and TI calculators, Microsoft Excel spreadsheets, and PC's. Includes background and comparison on many of the popular thermodynamic models.

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From the Author:

Dear Readers, Thank you for your comments and criticisms. We welcome this opportunity to respond. We would like to begin by clarifying a couple of points. First, our text does cover chemical reaction equilibria in detail (Chapters 14 and 15). In addition to deriving the fundamental equations from first principles, we present examples, practice problems, and homework problems covering single reactions in a single phase, multiple reactions in a single phase, multiple reactions between vapor and liquid phases, and electrolyte reactions with partitioning between vapor and liquid phases. We also cover energy balances for reacting systems. The coverage of reacting systems is comparable with other introductory chemical engineering textbooks. Regarding inclusion of additional examples and resources, it is very valuable to refer you to the text's web site. Amazon prohibits us from giving the link but you can find it if you search for “Introductory Chemical Engineering Thermodynamics”. We are continually supplementing our textbook through updates on this web site. You will find sample tests for each unit, supplemental homework problems, review modules, abbreviated presentation slides, computer spreadsheets and programs, virtual guided tours through real plants and equipment, links to phase diagrams, on-line databases, and many more resources. At present, we are developing review modules that carefully lead students through key concepts with reinforcing examples. By using the web efficiently, we hope to provide effective supplements for review and self-study. We hope that you will find these comments and our web resources to be useful. Please keep those Amazon suggestions and criticisms coming.

J.R. Elliott
C.T. Lira

From the Inside Flap:

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. 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 egr.msu/~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
J. Richard Elliott, University of Akron, dickelliott@uakron"

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