Basic Principles and Calculations in Chemical Engineering

Welcome to Basic Principles and Calculations in Chemical Engineering. Several tools exist in the book in addition to the basic text to aid you in learning its subject matter. We hope you will take full advantage of these resources. Learning Aids 1. Numerous examples worked out in detail to illustrate the basic principles 2.


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CHAPTER 11 HUMIDITY (PSYCHROMETRIC) CHARTS AND THEIR USE 11.1 Terminology 11.2 The Humidity (Psychrometric) Chart 11.3 Applications of the Humidity Chart PART V SUPPLEMENTARY MATERIAL CHAPTER 12 ANALYSIS OF THE DEGREES OF FREEDOM IN STEADY-STATE PROCESSES CHAPTER 13 HEATS OF SOLUTION AND MIXING CHAPTER 14 THE MECHANICAL ENERGY BALANCE CHAPTER 15 LIQUIDS AND GASES IN EQUILIBRIUM WITH SOLIDS CHAPTER 16 SOLVING MATERIAL AND ENERGY BALANCES USING PROCESS SIMULATORS (FLOWSHEETING CODES) CHAPTER 17 UNSTEADY-STATE MATERIAL AND ENERGY BALANCES A ANSWERS TO SUPPLEMENTAL QUESTIONS AND PROBLEMS 829 B ATOMIC WEIGHTS AND NUMBERS C TABLE OF THE PITZER Z FACTORS D HEATS OF FORMATION AND COMBUSTION E ANSWERS TO SELECTED PROBLEMS
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2.7 Choosing a Basis 2.8 Density and Specific Gravity 2.10 Temperature 2.11 Pressure and Hydrostatic Head 2.12 Flow Rate PART II MATERIAL BALANCES CHAPTER 3 MATERIAL BALANCES 3.1 Introduction to Material Balances 3.2 A General Strategy for Solving Material Balance Problems CHAPTER 4 MATERIAL BALANCES WITHOUT REACTION CHAPTER 5 MATERIAL BALANCES INVOLVING REACTIONS 5.1 Stoichiometry 5.2 Terminology for Reaction Systems 5.3 Species Mole Balances 5.4 Element Material Balances 5.5 Material Balances for Combustion Systems CHAPTER 6 MATERIAL BALANCES FOR MULTI-UNIT SYSTEMS 6.1 Primary Concepts 6.2 Sequential Multi-Unit Systems 6.3 Recycle Systems 6.4 Bypass and Purge 6.5 The Industrial Application of Material Balances
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PART III GASES, VAPORS, AND LIQUIDS CHAPTER 7 IDEAL AND REAL GASES 7.1 Ideal Gases 7.2 Real Gases: Equations of State 7.3 Real Gases: Compressibility Charts 7.4 Real Gas Mixtures CHAPTER 8 MULTIPHASE EQUILIBRIUM 8.1 Introduction 4118.2 Phase Diagrams and the Phase Rule 8.3 Single Component Two-Phase Systems (Vapor Pressure) 4258.4 Two-Component Gas/Single-Component Liquid Systems 4368.5 Two Component Gas/Two Component Liquid Systems 4558.6 Multicomponent Vapor-Liquid Equilibrium PART IV ENERGY CHAPTER 9 ENERGY BALANCES 9.1 Terminology Associated with Energy Balances 9.2 Types of Energy to Be Included in Energy Balances 4969.3 Energy Balances without Reaction CHAPTER 10 ENERGY BALANCES: HOW TO ACCOUNT FOR CHEMICAL REACTION 59710.1 The Standard Heat (Enthalpy) of Formation 10.2 The Heat (Enthalpy) of Reaction 10.3 Integration of Heat of Formation and Sensible Heat 61410.4 The Heat (Enthalpy) of Combustion
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PREFACE READ ME ACKNOWLEDGMENTS ABOUT THE AUTHORS PART I INTRODUCTION CHAPTER 1 WHAT ARE CHEMICAL ENGINEERING AND BIOENGINEERING? 1.1 Introduction 1.2 A Brief History of Chemical Engineering 1.3 Where Do Chemical and Bioengineers Work? 1.4 Future Contributions of Chemical and Bioengineering 7CHAPTER 2 INTRODUCTORY CONCEPTS 2.1 Systems of Units 2.2 Conversion of Units 2.3 Dimensional Consistency 2.4 Significant Figures 2.5 Validation of Results 2.6 The Mole and Molecular Weight
Chapter 1 What Are Chemical Engineering and Bioengineering?
low-producing oil and natural-gas reservoirs.Preliminary tests show that contrary to expectations, only 20% maxi- precipitates form carbonate minerals, but the majority of the dissolves in water. Trapping CO in minerals would be more secure, but Other suggestions for the reduction of CO emissions include permanent reduction in demand, chemical reaction, various solvents, use of pure O as the Chemical Engineering Progress, 33–41 (April, 2009), and F. Princiotta, “Mitigating Global Climate Change through Power-Generation Technology,” Chemical Engineering Progressber, 2007), who have a large list of possible avenues of approach. The bottom emissions reduction is not just a matter of solving technical problems but a matter of cost and environmental acceptance. Based on the nature of these challenges, it is easy to see that chemical and bioengineers will be intimately involved in these efforts to find effective solutions.The chemical engineering profession evolved from society’s need for products and energy. Today and into the future, chemical and bioengineers will con-tinue to meet society’s needs using their process knowledge, their knowledge of fundamental science, and their problem-solving skills.In this chapter we reviewed the history of chemical engineering and presented information on the current and projected future status of the profession.Glossary The chemical and refining industries.Computer-aided design (CAD) packages Software programs that are used to design and/or analyze systems including chemical processes.Web Sitewww.pafko.com/history/h_whatis.html
1.4 Future Contributions of Chemical and Bioengineering
A bioengineer uses engineering expertise to analyze and solve problems in chemistry, biology, and medicine. The bioengineer works with other engineers as well as physicians, nurses, therapists, and technicians. Biomedical engineers may be called upon in a wide range of capacities to bring together knowledge from many technical sources to develop new procedures, or to con-duct research needed to solve problems in areas such as drug delivery, body imaging, biochemical processing, innovative fermentation, bioinstrumentation, biomaterials, biomechanics, cellular tissue and genetics, system physiology, and so on. They work in industry, hospitals, universities, and government reg-ulatory agencies. It is difficult to find valid surveys of specific companies or topics to classify bioengineering graduates’ ultimate locations, but roughly speaking, one-third of graduates go to medical school, one-third continue on to graduate school, and one-third go to work in industry with a bachelor’s degree.1.4 Future Contributions of Chemical and BioengineeringThe solution of many of the pressing problems of society for the future (e.g., global warming, clean energy, manned missions to Mars) will depend significantly on chemical and bioengineers. In order to more fully explain
Table 1.1 Chemical Engineering Employment by Sector (from AIChE Surveys)19962000200220052007Chemical, industrial gases, rubber, soaps, 33.3 32.5 25.2 28.1 25.5Food, ag products, ag chemical 4.5 5.1 5.6 5.7 5.0Energy, petroleum, utilities 14.1 1.9 5.1 4.5 3.7Electronics, materials, computers 1.4 1.9 5.1 4.5 3.7Equipment design and construction 13.8 12.6 10.6 12.6 14.3Environmental, health, and safety 6.4 4.7 4.4 4.2 3.4Aerospace, automobile 1.1 0.9 1.8 2.0 2.1Research and development 3.9 3.8 4.4 4.2 3.4 3.6 3.6 3.5 3.7 4.4 1.5 2.2 2.4 4.4 3.7Pharmaceutical, health care 4.2 6.5 6.1 8.4 7.6Professional (including education) 4.7 4.5 8.6 7.0 8.4 7.4 8.6 9.6 - 1.5
1.4 Future Contributions of Chemical and Bioengineering
to capture 80% to 95% of CO from combustion gases; the CObe condensed into a liquid that would be transported and stored somewhere indefinitely where it could not leak into the atmosphere. If several hundreds or thousands of CCS systems were deployed globally this century, each capturing 1 to 5 metric tons of CO per year collectively, they could contrib-ute between 15% and 55% of the worldwide cumulative mitigation effort.However, the engineering challenges are significant. First, CCS is an energy-intensive process, so power plants require significantly more fuel to generate each kilowatt-hour of electricity produced for consumption. Depending on the type of plant, additional fuel consumption ranges from 11% to 40% more—meaning not only in dollars, but also in additional fossil fuel that would have to be removed from the ground to provide the power for the capture and sequestration, as well as additional COtration by doing so. Current carbon-separation technology can increase the price tag of producing electricity by as much as 70%. Put another way, it the problem. The U.S. Department of Energy is working on ways to reduce the expenses of separation and capture.By far, the most cost-effective option is partnering CCS not with older combined-cycle (IGCC) or oxygenated-fuel (oxyfuel) technology. There is also a clear need to maximize overall energy efficiency if CCS itself is not merely going to have the effect of nearly doubling both demand for fossil fuels and the resultant CO has been captured as a fairly pure stream, the question is what to do with it that is economical. In view of the large quantity of COthat must be disposed of, disposal, to be considered a practical strategy, has Any release of gas back into the atmosphere not only would negate the environmental benefits, but it could also be deadly. In large, concentrated quantities, carbon dioxide can cause asphyxiation. Researchers are fairly confident that underground storage will be safe and effective.This technology, known as carbon sequestration, is used by energy firms as an oil-recovery tool. But in recent years, the Department of Energy has broadened its research into sequestration as a way to reduce emissions. And the energy industry has taken early steps toward using sequestration to capture emissions from power plants.Three sequestration technologies are actively being developed: storage in saline aquifers in sandstone formations [refer to S. M. Benson and T. Surles, “Carbon Dioxide Capture and Storage,” Proceed. IEEE(2006)], where the CO
Chapter 1 What Are Chemical Engineering and Bioengineering?
the role of chemical and bioengineers and to illustrate the role of chemical and bioengineers in solving society’s technical problems, we will now consider some of the issues associated with carbon dioxide capture and sequestration, which is directly related to global warming.Because fossil fuels are less expensive and readily available, we would like to reduce the impact of burning fossil fuels for energy, but without significantly increasing the costs. Therefore, it is imperative that we develop low-cost COcapture and sequestration technologies that will allow us to do that.An examination of Figure 1.1 shows the sources of COtion is the number-one source. Transportation sources are widely distrib-uted. No doubt power generation would be the most fruitful.Carbon capture and storage (CCS) is viewed as having promise for a few decades as an interim measure for reducing atmospheric carbon emis-sions relatively quickly and sharply while allowing conventional coal-fired power plants to last their full life cycles. But the energy costs, the disposal the overall consumption of fossil fuels (because of the increased consump-tion of energy to collect and sequester CO, more power plants have to be built so that the final production of net energy is the same) all suggest that One interim measure under serious consideration for CCS that might allow existing conventional coal-fired power plants to keep producing until technologies. An existing plant could be retrofitted with an amine scrubber Major sources of carbon dioxide emissions in the United States excluding agriculture
Electric PowerGeneration 42%Transportation 33%Industrial 15%Residential 6%Commercial 4%
Chapter 1 What Are Chemical Engineering and Bioengineering?
Globalization of the CPI markets began in the mid-1980s and led to increased competition. At the same time, developments in computer hardware made it possible to apply process automation (advanced process control, or APC, and optimization) more easily and reliably than ever before. These automation projects provided improved product quality while increasing production rates and overall production efficiency with relatively little capi-investment. Because of these economic advantages, APC became widely accepted by industry over the next 15 years and remains an important factor Beginning in the mid-1990s, new areas came on the scene that took advantage of the fundamental skills of chemical engineers, including the microelectronics industry, the pharmaceutical industry, the biotechnology industry, and, more recently, nanotechnology. Clearly, the analytical skills and the process training made chemical engineers ideal contributors to the development of the production operations for these industries. In the 1970s, and government. By 2000, that number had dropped to 50% because of increases in the number taking jobs with biotechnology companies, phar-maceutical/health care companies, and microelectronics and materials companies. The next section addresses the current distribution of jobs for 1.3 Where Do Chemical and Bioengineers Work?Table 1.1, which lists the percentages of all chemical engineers by employment sector between 1996 and 2007, shows that the percentage of chemical engi-neers in these developing industries (pharmaceutical, biomedical, and micro-electronics industries) increased from 7.1% in 1997 to 19.9% in 2005.Chemical engineers are first and foremost process engineers. That is, chemical engineers are responsible for the design and operation of processes that produce a wide range of products from gasoline to plastics to composite chemical engineers work for environmental companies, government agen-cies including the military, law firms, and banking companies.The trend of chemical engineering graduates taking employment in industries that can be designated as bioengineering is a new feature of the twenty-first century. Not only have separate bioengineering or biomedical to reflect the research and fresh interests of students and faculty.
1.2 A Brief History of Chemical Engineering the demand for process engineers in the CPI began to increase. As ichemistry programs grew, they eventually formed separate degree-granting programs as the chemical engineering departments of today.The acceptance of the “horseless carriage,” which began commercial production in the 1890s, created a demand for gasoline, which ultimately fueled exploration for oil. In 1901, a Texas geologist and a mining engineer led a drilling operation (the drillers were later to be known as “wildcatters”) that brought in the Spindletop Well just south of Beaumont, Texas. At the time, Spindletop produced more oil than all of the other oil wells in the United States. Moreover, a whole generation of wildcatters was born, result-ing in a dramatic increase in the domestic production of crude oil, which cre-ated a need for larger-scale, more modern approaches to crude refining. As a result, a market developed for engineers who could assist in the design and operation of processing plants for the CPI. The success of oil exploration was to some degree driven by the demand for gasoline for the automobile indus-try, but ultimately the success of the oil exploration and refining industries led to the widespread availability of automobiles to the general population because of the resulting lower cost of gasoline.cal tools available to them and largely depended upon their physical intu-ition to perform their jobs as process engineers. Slide rules were used to perform calculations, and by the 1930s and 1940s a number of nomographs were developed to assist them in the design and operation analysis of processes for the CPI. Nomographs are charts that provide a concise and convenient means to represent physical property data (e.g., boiling point temperatures or heat of vaporization) and can also be used to provide sim-plified solutions of complex equations (e.g., pressure drop for flow in a pipe). The computing resources that became available in the 1960s were the beginnings of the computer-based technology that is commonplace today. For example, since the 1970s computer-aided design (CAD)ages have allowed engineers to design complete processes by specifying only a minimum amount of information; all the tedious and repetitive cal-culations are done by the computer in an extremely short period of time, allowing the design engineer to focus on the task of developing the best possible process design.During the period 1960 to1980, the CPI also made the transition from an industry based on innovation, in which the profitability of a company depended to a large degree on developing new products and new process-ing approaches, to a more mature commodity industry, in which the finan-cial success of a company depended on making products using established technology more efficiently, resulting in less expensive products.
Chapter 1 What Are Chemical Engineering and Bioengineering?you were adept at math and chemistry and/or biology? In fact, most pro-spective engineers choose this field without fully understanding the profession (i.e., what chemical and bioengineers actually do and what they are capable of Chemical and bioengineers today hold a unique position at the inter-face between molecular sciences and macroscopic (large-scale) engineering. They participate in a broad range of technologies in science and engineering projects, involving nanomaterials, semiconductors, and biotechnology. Note plinary groups, each member contributing his or her own expertise.1.2 A Brief History of Chemical EngineeringThe chemical engineering profession evolved from the industrial applications of chemistry and separation science (the study of separating components from mixtures), primarily in the refining and chemical industry, which we will refer to here as the cal process was implemented in 1823 in England for the production of soda ash, which was used for the production of glass and soap. During the same time, advances in organic chemistry led to the development of chemical pro-cesses for producing synthetic dyes from coal for textiles, starting in the 1850s. In the latter half of the 1800s a number of chemical processes were imple-mented industrially, primarily in Britain.And in 1887 a series of lectures on chemical engineering which summarized industrial practice in the chemical industry was presented in Britain. These lectures stimulated interest in the United States and to some degree led to the formation of the first chemical engineering curriculum at braced the field of chemical engineering by offering fields of study in this area. In 1908, the American Institute of Chemical Engineers was formed and since then has served to promote and represent the interests of the chemical engineering community.Mechanical engineers understood the mechanical aspects of process operations, including fluid flow and heat transfer, but they did not have a background in chemistry. On the other hand, chemists understood chemis-try and its ramifications but lacked the process skills. In addition, neither separation science, which is critically important to the CPI. In the United States, a try departments were training process engineers by offering degrees in industrial chemistry, and these served as models for other departments as
1.1 Introduction 1.2 A Brief History of Chemical Engineering 1.3 Where Do Chemical and Bioengineers Work? 1.4 Future Contributions of Chemical and Bioengineering 1.5 Conclusion Your objectives in studying this chapter are to be able to Appreciate the history of chemical engineering and bioengineering Understand the types of industries that hire chemical and bioengineers Appreciate the diversity of the types of jobs in which chemical Understand some of the ways in which chemical and bioengineers can contribute in the future to the resolution of certain of society’s problems
In this chapter we will present some features of the professions of chemical and bioengineering. First, we will present an overview of the history of these fields. Next, we will consider where graduates of these programs go to work. Finally, we will present types of projects in which chemical and bioengineers might participate now and in the future.Why did you choose to work toward becoming a chemical or bioengineer? Was it the starting salary? Did you have a role model who was a chemical or bioen-gineer, or did you live in a community in which engineers were prominent? Or were you advised that you would do well as a chemical or bioengineer because
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American Petrofina Foundation Centennial Professor Emeritus in Chemical Engineering at the University of Texas, where he taught for 42 years. He received his B.S. from MIT in 1947 and his Ph.D. from the University of Washington in 1957. He was the author of 11 books and over 200 articles on the topics of process analysis, fault detection, and optimization, and served as President of the CACHE Corporation (Computer Aids for Chemi-cal Engineering Education) as well a Director of the AIChE. His book, has been recognized by the earned his B.S. in 1969 and his M.S. in 1972, both from the University of Texas at Austin. In 1977, he earned his Ph.D. from the Univer-sity of California at Berkeley. Dr. Riggs was a university professor for 30 years, the first five years being spent at West Virginia University and the re-mainder at Texas Tech University. He was appointed Professor Emeritus of Chemical Engineering at Texas Tech University after he retired in 2008. variety of capacities. His research interests centered on advanced process control and online process optimization. During his academic career he served as an industrial consultant and founded the Texas Tech Process Control and Optimization Consortium, which he directed for 15 years. Dr. Riggs is the author of two other popular undergraduate chemical engi-neering textbooks: An Introduction to Numerical Methods for Chemical EngineersSecond Edition, and Chemical and Bio-Process Control, Third Edition. He currently resides near Austin in the Texas Hill Country.
We are indebted to many former teachers, colleagues, and students who directly or indirectly helped in preparing this book, and in particular the present edition of it. We want to thank Professor C. L. Yaws for his kindness in making available the physical properties software database that is the basis of the physical properties package in the CD that accompanies our book, and also thanks to Professors M. B. Cutlip and M. Shacham who gra-ciously made the Polymath software available. Far too many instructors using the text have contributed their corrections and suggestions to list them by name. Any further comments and suggestions for improvement of this textbook would be appreciated.
How can you make the best use of this book? Read the objectives before and after studying each section. Read the text, and when you get to an example, first cover up the solution and try to solve the stated problem. Some people, those who learn by reading concrete examples, might look at the examples first and then read the text. After reading a section, solve the self-assessment problems at the end of the section. The answers are in Appendix A. After completing a chapter, solve a few of the problems listed at the end of the chapter. R. P. Feynman, the Nobel laureate in physics, made the point: “You do not know anything until you have practiced.” Whether you solve the problems using hand calculators or computer programs is up to you, but use a systematic approach to formu-lating the information leading to a proper solution. Use the supplement on the CD in the back of the book (print it out if you need to) as a source of examples of additional solved problems with which to practice solving problems.
You will find that skipping the text and jumping to equations or examples to solve problems may work sometimes but in the long run will lead to frustration. Such a strategy is called “formula-centered” and is a very poor way to approach a problem-solving subject. By adopting it, you will not be able to generalize, each problem will be a new challenge, and the interconnections among essen-tially similar problems will be missed.Various appropriate learning styles (information processing) do exist; hence you should reflect on what you do to learn and adopt techniques best suited to you. Some students learn through thinking things out in solitary study. Others prefer to talk things through with peers or tutors. Some focus best on practical examples; others prefer abstract ideas. Sketches and graphs used in explanation usually appeal to most people. Do you get bored by going over the same ground? You might want to take a battery of tests to assess your learning style. Students often find such inventories interesting and helpful. Look in the CD that accompanies this book to read about learn-Whatever your learning style, what follows are some suggestions to enhance learning that we feel are appropriate to pass on to you.Each chapter in this book will require three or more hours to read, as-similate, and practice your skills in solving pertinent problems. Make al-lowance in your schedule so that you will have read the pertinent mate-understanding what your professor is discussing, you will be able to ble, but it is one of the most efficient ways to spend your study time.If you are enrolled in a class, work with one or more classmates, if permit-ted, to exchange ideas and discuss the material. But do not rely on some-Learn every day. Keep up with the scheduled assignments—don’t get be-hind, because one topic builds on a previous one.Seek answers to unanswered questions right away.Employ active reading; that is, every five or ten minutes stop for one or ideas. Write a summary on paper if it helps.
11. A CD that includes some valuable accessories:Polymath—an equation-solving program that requires minimal expe-rience to use. Polymath is provided with a 15-day free trial. Details on the use of Polymath are provided. A special web site gives signifi-cant discounts on educational versions of Polymath for various time periods: 4 months, 12 months, and unlimited use: www.polymath-software.com/himmelblauSoftware that contains a physical properties database of over 700 A Supplementary Problems Workbook with over 100 completely solved problems and another 100 problems with answers.The workbook contains indexed descriptions of process equipment and animations that illustrate the functions of the equipment. You can ing on the page number.Problem-solving suggestions including checklists to diagnose and overcome problem-solving difficulties that you experience. f. Additional chapters and appendixesA set of steam tables (properties of water) in both SI and American Engineering units in the pocket in the back of the bookScan through the book now to locate these features.You cannot put the same shoe on every foot.Publilius Syrusthat almost all people learn by practicing and reflecting, and not by watching and listening to someone else telling them what they are supposed to learn. “Lecturing is not teaching and listening is not learning.” You learn by doing.Do not equate memorizing with learning. Recording, copying, and outlining notes or the text to memorize problem solutions will be of little help in really understanding how to solve material and energy balance problems. Practice will help you to be able to apply your knowledge to problems that you have not seen before.
Welcome to Basic Principles and Calculations in Chemical Engineering. subject matter. We hope you will take full advantage of these resources. Numerous examples worked out in detail to illustrate the basic principlesA consistent strategy for problem solving that can be applied to any problemFigures, sketches, and diagrams to provide a detailed description and reinforcement of what you readA list of the specific objectives to be reached at the beginning of each Self-Assessment Tests at the end of each section, with answers so that you can evaluate your progress in learningA large number of problems at the end of each chapter with answers for about a third of them provided in Appendix EThought and discussion problems that involve more reflection and con-sideration than the problem sets cited in item 6Appendixes containing data pertinent to the examples and problemsSupplementary references for each chapterA glossary following each section
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PREFACEThis book is intended to serve as an introduction to the principles and tech-niques used in the field of chemical engineering as well as biological, petro-leum, and environmental engineering. Although the range of subjects deemed to be in the province of chemical engineering has broadened over the last twenty years, the basic principles of this field of study remain the same. This book presents the foundation of specific skills and information that are required for the successful undergraduate and postgraduate study of chemi-cal engineering as well as the professional practice of chemical engineering. Moreover, your remaining chemical engineering classes will rely heavily on problems as well as the application of material and energy balances. One can view the study of the field of chemical engineering as a tree with material and energy balances being the trunk and the subjects of thermodynamics, fluid flow, heat transfer, mass transfer, reactor kinetics, process control, and process design being the branches off the trunk. From this perspective, it is formulate and solve material and energy balance problems. More important, you should learn to systematically formulate and solve all types of problems using the methods presented in this text. In addition, this text serves to introduce you to the breadth of processes that chemical engineers work with, from the types of processes found in the refining and chemical industries to those found in bioengineering, nanoengineering, and the microelectronics industries. While the analysis used in this book will be based largely on a macroscopic scale (i.e., representing a complex system as a uniform system), your later engineering courses will teach you how to formulate microscopic material and energy balances that can be used to more completely describe
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This book is dedicated to the memory of
Many of the designations used by manufacturers and sellers to distinguish their products are claimed as trademarks. Where those designations appear in this book, and the publisher was aware of a trademark The authors and publisher have taken care in the preparation of this book, but make no expressed or implied warranty of any kind and assume no responsibility for errors or omissions. No liability is assumed for programs contained herein.The publisher offers excellent discounts on this book when ordered in quantity for bulk purchases or special sales, which may include electronic versions and/or custom covers and content particular to your business, training goals, marketing focus, and branding interests. For more information, please contact:[email protected] us on the Web: informit.com/phLibrary of Congress Cataloging-in-Publication DataHimmelblau, David Mautner, 1923-2011 Basic principles and calculations in chemical engineering.—8th ed. / David M. Himmelblau, p. cm. Includes bibliographical references and index. ISBN 0-13-234660-5 (hardcover : alk. paper) 1. Chemical engineering—Tables. I. Riggs, James B. II. Title. TP151.H5 20122011045710All rights reserved. Printed in the United States of America. This publication is protected by copyright, and permission must be obtained from the publisher prior to any prohibited reproduction, storage in a retrieval system, or transmission in any form or by any means, electronic, mechanical, photocopying, recording, or likewise. To obtain permission to use material from this work, please submit a written request to Pearson Education, Inc., Permissions Department, One Lake Street, Upper Saddle River, New Jersey 07458, or you may fax your request to (201) 236-3290.Text printed in the United States on recycled paper at Edwards Brothers Malloy in Ann Arbor, Michigan.Executive Editor: Bernard GoodwinProject Editor: Elizabeth RyanCopy Editor: Barbara WoodProofreader: Linda Begley Publishing Coordinator: Michelle HousleyCover Designer: Alan ClementsCompositor: LaserWords
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The Prentice Hall International Seriesin the Physical and Chemical Engineering Sciences had its auspicious beginning in 1956 under the direction of Neal R. Amundsen. The series comprises the most widely adopted college textbooks and supplements for chemical engineering education. Books in this series are written by the foremost educators and researchers in the field of chemical engineering.
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Prentice Hall International Series in the Physical and Chemical Engineering Sciences
Basic Principles and Calculations Eighth Edition
xiv Preface
microscopic balance you only have to apply the balances presented in this textbook to a very small volume inside the process of interest.This text is organized as follows: Part I Introduction: background information (Chapters 1–2) Part II Material Balances: how to formulate and solve material balances  Part III Gases, Vapors, and Liquids: how to describe gases and liquids  Part IV Energy: how to formulate and solve energy balances (Chapters 9–11)Expecting to “absorb” the information and skills in this text by reading and listening to lectures is a bit naïve. It is well established that one learns by doing, that is, applying what you have been exposed to. In this regard, our text offers a number of resources to assist you in this endeavor. Probably the most important resources for your study of this material are the Self- Assessment Tests at the end of each section in the book. In particular, the Assessment questions and problems are particularly valuable because by answering them and comparing your answers to the answers posted in Appendix A, you can determine what it is that you do not fully understand, which is quite an important piece of information. A number of valuable resources are provided to you on the CD that accompanies this book, which includes the physical property software, which provides timesaving access to physical properties for over 700 compounds and elements; Polymath for solving sets of equations, which comes with a 15-day free trial; and the Supplemental Problems Workbook with over 100 solved problems and pro-cess equipment descriptions. For more specific information on the resources available with this textbook and the accompanying CD, refer to the “Read It is our sincere hope that this textbook and materials not only inspire you to continue to pursue your goal to become a chemical engineer, but also make your journey toward that goal easier.Jim RiggsAustin, Texas
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F PHYSICAL PROPERTIES OF VARIOUS ORGANIC AND INORGANIC SUBSTANCES G HEAT CAPACITY EQUATIONS H VAPOR PRESSURES I HEATS OF SOLUTION AND DILUTION J ENTHALPY-CONCENTRATION DATA K THERMODYNAMIC CHARTS L PHYSICAL PROPERTIES OF PETROLEUM FRACTIONS M SOLUTION OF SETS OF EQUATIONS N FITTING FUNCTIONS TO DATA
Absolute pressure (psia), 68, 71–72, 468Absolute temperature, 60Adiabatic reaction, 622–626Adiabatic systems, energy balances, nition, 757practice problems, 766–767curves for, 757–759 tting to experimental data, 760Freundlich, 758–761Langmuir, 759–761Air, average molecular weight, Answers to questions and problems, Armour’s laws of ignorance, 130Atmospheric pressure, 70Average molecular weight, Azeotropes, 459Barometric pressure, 68 nition, 44practice problems, 90–91
refer to pages in Chapters 12 through 17, and Appendixes F through N, which are located on the CD that accompanies this book. Pages in the problem Workbook are indexed separately, and that index will be found in the Workbook itself as well as proceeding this index..
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Index 945
Weight Well-mixed system, 317Wet basis, 234Wet-bulb line, 658–659Wet-bulb temperature, 654–655Work (in a batch process, 732–733in energy balances, 501–507 ow, 502–503Working in chemical/bioengineering, Yield, 204–205 Compressibility
Thin  lm deposition, 426–427ThOD (theoretical oxygen demand), Tie components, 175TOD (total oxygen demand), 245Total system volume, 421Transient state. Triple point, 414Two component gas/single-component practice problems, 476–481Two component gas/two-component azeotropes, 459ideal solution relations, 455–457-value (vapor-liquid equilibrium practice problems, 481–485Raoult’s law, 455–457vapor-liquid equilibria phase Two-phase regions, 418 (internal energy), 511–513 ed, 135UNIFAC method, 376 nition, 729Unsteady-state processes, de110–111Unsteady-state processes, energy modeling a calcination process, practice problems, 820–826Unsteady-state processes, energy balances without reactionsUnsteady-state processes, material oscillating reactions, 812–814overview, 800–804practice problems, 820–826Vacuum, 68, 72–73Validating results, 36–37van der Waals’ equation, 25, 368Vapor, 413Vapor pressure, 415, Vaporizationat constant temperature, 417–418 nition, 416Vapor-liquid equilibria phase diagrams, Variables for degree-of-freedom analysis, steady-state processes, Vendors of commercial simulators, Virial equations, 369Volumetric  ow rate, 78, 356Water properties, 427–429Watson’s equation, 523
Index 943
nition, 598overview, 598–603practice problems, 643–644Standard state, 598 nition, 349energy balances, 492–493State variables, energy balances, 493closed systems, energy balances without reactions, 541–542energy balances, 492open systems, energy balances without reactions, 546–557processes/systems, 108–110 cients, 192Stoichiometric quantity, 192Stoichiometry, de nition, 190Stoichiometry, solving problems withbalancing a reaction equation for a biological reaction, 193calculating the mass of reactants, 194for multiple reactions, 195–197practice problems, 248–253Stream variables for degree-of-freedom analysis, steady-state processes, 685Streptomycin extraction, 160–162Sublimation pressure, 416Sugar recovery process, 284–287Supercritical  uids, 373Supercritical region, 416Superheated steam properties, 428–429Superheated vapor, 416Surroundings, energy balances, 492extent of reaction, 198general energy balance, 544 nition, 108energy balances, 492steady-state, 108–110unsteady-state, 110–111 AE system practice problems, 82TemperatureFahrenheit (practice problems, 94–95relative scale, 60standard conditions of, 60Theoretical air (oxygen), 234Theoretical reaction.
Saturated liquid/vapor, 416Saturated water properties, 427–428S.C. (standard conditions), 352–354Selectivity, 203–204Semi-batch processes, 111Separation with gas chromatographic AE system of units, 13 nition, 13pre xes, 14 cant  gures, 29–36, 88 Process simulation.Single phase enthalpy, 514liquid water properties, 429practice problems, 472–476prediction via equations, 425–427saturated water properties, 427–428superheated steam properties, thin  lm deposition, 426–427vapor pressuresreference substance, 433from reference substance plots, from tables, 427–432Once-through conversion. nition, 81Solution at in nite dilution, heats of, balance with reactions.bioreactor analysis, 221–224degree-of-freedom analysis, 693multiple-reaction processes, 216–224practice problems, 258–261single-reaction processes, 210–214for a speci ed fraction conversion, c gravitycalculating density, 51–52 nition, 50–52practice problems, 91Speci c volume, de nition, 50Standard atmosphere, 70Standard conditions (S.C.), 352–354Standard conditions of temperature, 60Standard heat of combustion, 635, Standard heat of formationconverting from standard heat of
Index 941
balance with reactions.degree of completion, 203excess reactants, 201–202extent of reaction, 198–201limiting reactants, 201–202maximum extent of reaction, 201–202practice problems, 253–258selectivity, 203–204acentric factor, 375compressibility factor, 373, 378–383corresponding states, 373group contribution method, 376ideal critical speci c volume, 379ideal reduced volume, 379internal energy, 514mixtures, 384–386, 408–410pseudoreduced ideal volume, 385pseudoreduced variables, 385reduced variables, 373supercritical  uids, 373UNIFAC method, 376Real gases, compressibilitycompressibility charts, 377–383, Real gases, pressure calculationscompressibility factor, 382–383real gas mixtures, 385–386compressibility factor, 380–382real gas mixtures, 385–386Recycle stream, 290–291 ltration, 294–297fresh feed, 291gross product, 291once-through conversion, 297overall (net) product, 291practice problems, 328–343process feed, 291with reaction, 297–303recycle stream, 290–291re ux, 293without reaction, 293–297Reference state, 598Reference substance, 433Reference substance plots, 432–435, ux, 293 ciency, 737Relative error, 81Relative humidity, 654, 656humidity.Relative temperature, 60Required air (oxygen). Theoretical air.Reversible processes, 729 cant  gures, 30
Pressure (barometric, 68 nition, 65differences, calculating, 74–75gauge pressure, 68hydrostatic, 66–68, 95–97practice problems, 95–97standard atmosphere, 70Problem solving, novices Process analysis, material balance, Process feed, recycle systems, 291Process  owsheets, 268–270Process matrix, 777Process optimization, material balance, Process simulation nition, 768modular-based method, 772, overview, 768–773practice problems, 782–799process matrix, 777vendors of commercial simulators, Process simulators, material balance, 314Processesbatch, 111continuous, 111 ciency, 737ideal reversible, 729–735irreversible, 729reversible, 729semi-batch, 111steady-state, 108–110unsteady-state, 110–111 Process Properties nition, 349liquid water, 429saturated water, 427–428Properties, physicalinorganic substances, organic substances, petroleum fractions, Pseudo steady-state processes/systems, Pseudoreduced ideal volume, 385Pseudoreduced variables, 385psia (absolute pressure), 68, 71–72, psig (gauge pressure), 68Psychrometric charts. Psychrometric line. Wet-bulb line.mechanical energy balance, 744–746Quality, 418Quasi steady-state processes/systems, Raoult's law, 455–457biological reaction, 193
Index 939
source, 243 ow systems. nonlinear. Corrected.Once-through conversion, recycle Open processes, 108 nition, 108energy balances, 492general energy balance, 542–546Open systems, energy balances without reactionsgeneral energy balance, 542–546Organic substances, physical properties ce coef cients, 742Oscillating reactions, unsteady-state process material balances, Overall conversion, recycle systems, 297Overall process, 274Overall (net) product, recycle systems, ed, 135Paniker, P. K. N., 49Path variables, energy balances, (potential energy), 508–511de nition, 350, 421energy balances, 492overview, 413–419practice problems, 470–472vapor-liquid equilibria, 457–459Phase rule, 419–424, 470–472 ciency, 738Potential energy (), 508–511Pound force, 21–23Power, de nition, 502Pressure relative, 68, 71–72atmospheric pressure, 70
Mechanical energy balance ce coef cients, 742overview, 740–742pumping water, 744–746Methane, generating electricity from, effects on energy balances, Mixtures, gases, 384–386, 408–410Modular-based process simulation, Molar  ow rate, 78 nition, 41–42overview, 38–42practice problems, 89–90converting to/from mass, 38–39 nition, 37practice problems, 89–90systems; Two component gas/Two component gas/two-degrees of superheat, 416equilibrium pressure, 415freezing, 416intensive properties, 421phase rule, 419–424quality, 418saturated liquid/vapor, 416sublimation pressure, 416supercritical region, 416superheated vapor, 416two-phase regions, 418vapor, 413vapor pressure, 415Nanotechnology, 20Nitrogenfor cell growth, 56–57
Index 937
with reaction, 282–284sugar recovery process, 284–287without reaction, 278–282Material balance problems, solvingArmour’s laws of ignorance, 130degree-of-freedom analysis, nonlinear, 139overview, 123–124practice problems, 154–158problem statement, 124–125sketch the process, 126Material balance with reactions. balancing a reaction equation for a biological reaction, 193calculating the mass of reactants, hydrocracking, 230–232for multiple reactions, 195–197Material balance with reactions, cellular product, 244extracellular product, 244 ue gas, 234generating electricity from methane, nitrogen source, 243overview, 233practice problems, 261–266theoretical air (oxygen), 234ThOD (theoretical oxygen demand), TOD (total oxygen demand), 245Material balance without reactionpractice problems, 181–188separation with gas chromatographic streptomycin extraction, 160–162Maximum extent of reaction, 201–202 ciency, 737Mechanical energy, 749
Irreversible processes, 729Isobaric systems, energy balances, Isochoric systems, energy balances, Isothermal systems, energy balances, (kinetic energy), 507–508Korean Air Lines freighter crash, 12-value (vapor-liquid equilibrium ratio), Law of corresponding states. Corresponding states.Least squares application, Limiting reactants, 201–202 Equations, linear.Liquid water properties, 429Manometer, 71–72Mars Climate Orbiter, 17converting to/from moles, 38–39Mass  ow rate, 78Mass of reactants, calculating, 194bank statement analogy, 102–103combined with energy balances, nition, 102 owsheeting codes. Process for multiple components, 112–119practice problems, 147–154process analysis, 314process optimization, 314process simulators, 314bypass streams, 306–309, 343–345overall process, 274practice problems, 318–328process  owsheets, 268–270purge streams, 306–307, 309–312,
Index 935
Standard heat of practice problems, 724–727 cation, 517solution at in nite dilution, 710Henry’s law, 457HHV (higher (gross) heating value), Home heating, humidity charts for, 667Howe’s law, 124Humidi cation, 659–665, 668–669Humidity, 654 nition, 657dry-bulb temperature, 654 cation, 659–665humidity, 654practice problems, 674–677properties of moist air, 663–665relative humidity, 654, 656wet-bulb temperature, 654–655 cation, 668–669practice problems, 677–680Hydrocarbon vapor, enthalpies of, Hydrocracking, 230–232Hydroelectric plants, ef ciency, Hydrostatic head, 66–68, 95–97Ideal critical speci c volume, 379Ideal gas law, 351–357Ideal gas mixtures, 357–360internal energy, 514practice problems, 391–403S.C. (standard conditions), 352–354volumetric  ow rate, 356Ideal reduced volume, 379Ideal reversible processes, 729–735Ideal solution relations, 455–457Incremental (differential) heat of Inorganic substances, physical properties of, Intensive properties, 421Internal energy (), 511–513
Equilibrium pressure, 415Equilibrium state, energy balances, 492Error checking. Validating results. ed, 135Excess reactants, 201–202Exothermic reactions, 598Extent of reaction, 198–201Extracellular product, 244Extraction processes, de nition, 412Fahrenheit ( Process Process simulators.Fluid warmer, 550–551Force, de nition, 21Freezing, 416Frequent  ier miles, converting to U.S. Fresh feed, recycle systems, 291Freundlich isotherms, 758–761Functions,  tting to data, Variables.Gas chromatographic column, density, 356–357partial pressure, 357speci c gravity, 357118–119Gauge pressure (psig), 68General energy balancefor multi-reaction processes, for multi-unit processes, 629–634Generalized compressibility. Compressibility charts.Gibbs’ phase rule, 421, Gordon’s law, 124Green chemistry, 605–606Gross product, recycle systems, 291Group contribution method, 376 uids, 746), in energy balances, 497–501Heat capacity, 511–513, 518–522 ciency, 737Heat reaction, 603–614, 645–650Heat transfer, 497–498
Index 933
overview, 514–518Energy balances, properties nition, 492Energy balances, types of energyheat capacity, 511–513, 518–522 cation, 517internal energy (), 511–513kinetic energy (potential energy (), 508–511practice problems, 572–580Energy balances without reactionsconservation of energy, 530–532general energy balance for open practice problems, 580–595Energy conservation. of energy.of hydrocarbon vapor, of nitrogen, ), energy balances Standard heat of overview, 514–518Equation-based process simulation, c equationsdegree-of-freedom analysis, steady-state processes, 685–687dimensional consistency, 25–27phase rule, reaction, linear, nonlinear, reaction, nonlinear, 139 linear, 139
nition, 416Difference equations, 104Differential equations, 105dimensionless groups, 26nondimensional groups, 26overview, 25practice problems, 85–88van der Waals’ equation, 25Dimensionless groups, 26 nition, 412ef ciency of recovery, 115–116micro-dissection, 31–34Dry-bulb temperature, 654COP (coef cient of performance), 737 nition, 735–736energy conservation, 737hydroelectric plants, 736processes, 737refrigeration cycle, 737Electricity, generating from methane, degree-of-freedom analysis, 691–692overview, 226–232practice problems, 261Endothermic reactions, 598Energy, de nition, 497Energy balances. energy balance.conservation of energy, 499–500, owsheeting codes. Process mixing, effects of, 715–722practice problems, 569–572surroundings, 492Energy balances, energy caused by reactionsadiabatic reaction, 622–626endothermic reactions, 598exothermic reactions, 598heat reaction, 603–614, 645–650reference state, 598standard heat of combustion, 635standard heat of formation, 598–603, standard state, 598Energy balances, enthalpy (
Index 931
Compressibility charts, 377–383, Compressibility factor, 373, 378–383Computer-aided design (CAD), 5 nition, 55practice problems, 91–94at constant temperature, 417–418 nition, 415Conservation of energy, energy Continuous  ltration, recycle systems, Continuous processes, 111 c conversionsfrequent  ier miles to U.S. miles, 23nanotechnology, 20overview, 17 pound force, 21–23practice problems, 83–85reaction systems, 203temperature, 62–64 nition, 17pressure, 66Cooling, humidity charts for, 668–669Cooling towers, humidity charts for, COP (coef cient of performance), Corrected, 389Corresponding states, 373CPI (chemical process industries), 4–6Dalton’s law, 357–358 cant  gures.Degree of completion, 203Degree-of-freedom analysis nition, 135processes using element balances, processes using species balances, Degree-of-freedom analysis, steady-state processesnumber of degrees, 684overview, 684–687practice problems, 700–707process speci cation, 690–691stream variables, 685Degrees of superheat, 416 nition, 49overview, 49–54practice problems, 91from relative humidity, 656
Batch processes nition, 111unsteady-state processes, 810–812work performed by, 732–733Benedict-Webb-Rubin (BWR) equation, Bioreactor analysis, 221–224 nition, 415BWR (Benedict-Webb-Rubin) equation, CAD (computer-aided design), 5Calcination process, modeling, 816–817Careers in chemical/bioengineering, CCS (carbon capture and storage), 8–10117–118Cellular product, 244Centrifuges, concentrating cells, 117–118Checking for errors. Validating results.Chemical process industries (CPI), 4–6Citric acid production, 626–629Closed processes, 108Coef cient of performance (COP), cellular product, 244extracellular product, 244 ue gas, 234generating electricity from methane, nitrogen source, 243overview, 233practice problems, 261–266theoretical air (oxygen), 234ThOD (theoretical oxygen demand), TOD (total oxygen demand), 245Combustion temperature. reaction. nition, 40Compressibility, real gasescompressibility charts, 377–383,

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