THERMODYNAMICS AND THE DESTRUCTION OF ......Thermodynamics and the Destruction of Resources Edited...

THERMODYNAMICS AND THE DESTRUCTIONOF RESOURCES

This book is a unique, multidisciplinary effort to apply rigorous thermodynamics fun-damentals to problems of sustainability, energy, and resource uses. Applying thermody-namic thinking to problems of sustainable behavior is a significant advantage in bringingorder to ill-defined questions with a great variety of proposed solutions, some of whichare more destructive than the original problem. The chapters are pitched at a levelaccessible to advanced undergraduate and graduate students in courses on sustainability,sustainable engineering, industrial ecology, sustainable manufacturing, and green engi-neering. The timeliness of the topic and the urgent need for solutions make this bookattractive to general readers as well as specialist researchers. Top international figuresfrom many disciplines, including engineers, ecologists, economists, physicists, chemists,policy experts, and industrial ecologists, make up the impressive list of contributors.

Bhavik R. Bakshi holds a dual appointment as a Professor of Chemical and BiomolecularEngineering at The Ohio State University (OSU) in Columbus, Ohio; and Vice Chancel-lor and Professor of Energy and Environment at TERI University in New Delhi, India.He is also the Research Director of the Center for Resilience at OSU. From 2006 to 2010,he was a Visiting Professor at the Institute of Chemical Technology in Mumbai, India.He has published more than 100 articles in areas such as process systems engineeringand sustainability science and engineering.

Timothy G. Gutowski is Professor of Mechanical Engineering at the MassachusettsInstitute of Technology (MIT) in Cambridge, Massachusetts. He was the Director ofMIT’s Laboratory for Manufacturing and Productivity (1994–2004) and the AssociateDepartment Head of Mechanical Engineering (2001–2005). From 1999 to 2001, he wasChairman of the National Science Foundation and Department of Energy’s Panel onEnvironmentally Benign Manufacturing. He is the author of the book Advanced Com-posites Manufacturing, holds seven patents and patent applications, and has authoredmore than 150 technical publications.

Dušan P. Sekulić is Professor of Mechanical Engineering at the University of Kentuckyin Lexington, Kentucky, and a Fellow of the American Society of Mechanical Engineers.Dr. Sekulić is a Consulting Professor at the Harbin Institute of Technology in Harbin,China. He is the author of more than 150 research publications, more than a dozenbook chapters, and the book Fundamentals of Heat Exchanger Design (jointly withR. K. Shah), which was published in both the United States and China. He is editor ofthe books Advances in Brazing: Science, Technology and Applications and Handbook ofHeat Exchanger Design.

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Cambridge University Press978-0-521-88455-6 - Thermodynamics and the Destruction of ResourcesEdited by Bhavik R. Bakshi, Timothy G. Gutowski and Dusan P. SekulićFrontmatterMore information

http://www.cambridge.org/9780521884556http://www.cambridge.orghttp://www.cambridge.org

Thermodynamics and the Destructionof Resources

Edited by

Bhavik R. BakshiThe Ohio State University and TERI University

Timothy G. GutowskiMassachusetts Institute of Technology

Dušan P. SekulićUniversity of Kentucky




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Thermodynamics and the destruction of resources / edited byBhavik R. Bakshi, Timothy G. Gutowski, Dušan P. Sekulić.

p. cm.Includes bibliographical references and index.ISBN 978-0-521-88455-6 (hardback)1. Power resources. 2. Energy consumption. 3. Conservation of naturalresources. 4. Thermodynamics. I. Bakshi, Bhavik R. II. Gutowski,Timothy George Peter. III. Sekulić, Dušan P.TJ163.2.T428 2011620 – dc22 2010043695

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“I suggest that we are thieves in a way. If I take anything thatI do not need for my own immediate use and keep it I thieve itfrom somebody else. I venture to suggest that it is the fundamentallaw of Nature, without exception, that Nature produces enough forour wants from day to day, and if only everybody took enough forhimself and nothing more, there would be no pauperism in thisworld, there would be no more dying of starvation in this world.But so long as we have got this inequality, so long we are thieving.”

M. K. Gandhi, All Men Are Brothers,Navjeevan Trust Publication, Ahmedabad, 1960

“Then I say the earth belongs to each . . . generation during itscourse, fully and in its own right. The second generation receives itclear of the debts and encumbrances, the third of the second, andso on. For if the first could charge it with a debt, then the earthwould belong to the dead and not to the living generation. Then,no generation can contract debts greater than may be paid duringthe course of its own existence.”

Thomas Jefferson, letter written on Sept. 6, 1789

“Does the educated citizen know he is only a cog in an ecologicalmechanism? That if he will work with that mechanism, his mentalwealth and his material wealth can expand indefinitely? But if herefuses to work with it, it will ultimately grind them to dust. Ifeducation does not teach us these things, then what is educationfor?”

A. Leopold, A Sand County Almanac,The Oxford University Press, New York, 2001




Contents

Contributor List page xi

Foreword by Herman E. Daly xv

Foreword by Jan Szargut xvii

Preface xxi

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1Bhavik R. Bakshi, Timothy G. Gutowski, and Dušan P. Sekulić

PART I. FOUNDATIONS

1. Thermodynamics: Generalized Available Energy and Availabilityor Exergy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15Elias P. Gyftopoulos

2. Energy and Exergy: Does One Need Both Concepts for a Study ofResources Use? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45Dušan P. Sekulić

3. Accounting for Resource Use by Thermodynamics . . . . . . . . . . . . . . . 87Bhavik R. Bakshi, Anil Baral, and Jorge L. Hau

PART II. PRODUCTS AND PROCESSES

4. Materials Separation and Recycling . . . . . . . . . . . . . . . . . . . . . . . . . 113Timothy G. Gutowski

5. An Entropy-Based Metric for a Transformational TechnologyDevelopment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133Dušan P. Sekulić

6. Thermodynamic Analysis of Resources Used in ManufacturingProcesses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163Timothy G. Gutowski and Dušan P. Sekulić

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viii Contents

7. Ultrapurity and Energy Use: Case Study of SemiconductorManufacturing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190Eric Williams, Nikhil Krishnan, and Sarah Boyd

8. Energy Resources and Use: The Present Situation, PossibleSustainable Paths to the Future, and the ThermodynamicPerspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212Noam Lior

PART III. LIFE-CYCLE ASSESSMENTS AND METRICS

9. Using Thermodynamics and Statistics to Improve the Quality ofLife-Cycle Inventory Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235Bhavik R. Bakshi, Hangjoon Kim, and Prem K. Goel

10. Developing Sustainable Technology: Metrics FromThermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249Geert Van der Vorst, Jo Dewulf, and Herman Van Langenhove

11. Entropy Production and Resource Consumption in Life-CycleAssessments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265Stefan Gößling-Reisemann

12. Exergy and Material Flow in Industrial and Ecological Systems . . . . . 292Nandan U. Ukidwe and Bhavik R. Bakshi

13. Synthesis of Material Flow Analysis and Input–Output Analysis . . . . . 334Shinichiro Nakamura

PART IV. ECONOMIC SYSTEMS, SOCIAL SYSTEMS, INDUSTRIALSYSTEMS, AND ECOSYSTEMS

14. Early Development of Input–Output Analysis of Energy andEcologic Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 365Bruce Hannon

15. Exergoeconomics and Exergoenvironmental Analysis . . . . . . . . . . . . 377George Tsatsaronis

16. Entropy, Economics, and Policy . . . . . . . . . . . . . . . . . . . . . . . . . . . 402Matthias Ruth

17. Integration and Segregation in a Population – aThermodynamicist’s View . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 429Ingo Müller

18. Exergy Use in Ecosystem Analysis: Background and Challenges . . . . 453Roberto Pastres and Brian D. Fath




Contents ix

19. Thoughts on the Application of Thermodynamics to theDevelopment of Sustainability Science . . . . . . . . . . . . . . . . . . . . . . . 477Timothy G. Gutowski, Dušan P. Sekulić, and Bhavik R. Bakshi

Appendix: Standard Chemical Exergy 489

Index 495




Contributor List

Bhavik R. Bakshi,William G. Lowrie Department of Chemical and Biomolecular Engineering,The Ohio State University,Columbus, Ohio, andDepartment of Energy and Environment,TERI University,New Delhi, India

Anil Baral,The International Council on Clean Transportation,Washington, D.C.

Sarah Boyd,Department of Mechanical Engineering,University of California,Berkeley, California

Jo Dewulf,Department of Sustainable Organic Chemistry and Technology,Ghent University,Ghent, Belgium

Brian D. Fath,Department of Biological Sciences,Towson University,Towson, Maryland

Prem K. Goel,Department of Statistics,The Ohio State University,Columbus, Ohio

Stefan Gößling-Reisemann,Faculty of Production Engineering,University of Bremen,Bremen, Germany

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xii Contributor List

Timothy G. Gutowski,Department of Mechanical Engineering,Massachusetts Institute of Technology,Cambridge, Massachusetts

Elias P. Gyftopoulos,Department of Nuclear Science and Engineering, andDepartment of Mechanical Engineering,Massachusetts Institute of Technology,Cambridge, Massachusetts

Bruce Hannon,Department of Liberal Arts and Sciences,University of Illinois-Urbana,Urbana-Champaign, Illinois

Jorge L. Hau,Catalyst Lend Lease,London, United Kingdom

Hangjoon Kim,Department of Statistics,The Ohio State University,Columbus, Ohio

Nikhil Krishnan,McKinsey & Company,New York, New York

Noam Lior,Department of Mechanical Engineering and Applied Mechanics,University of Pennsylvania,Philadelphia, Pennsylvania

Ingo Müller,Institute for Process Engineering,Technical University Berlin,Berlin, Germany

Shinichiro Nakamura,Graduate School of Economics,Waseda University,Tokyo, Japan

Roberto Pastres,Department of Physical Chemistry,University of Venice,Venice, Italy

Matthias Ruth,A. James Clark School of Engineering and School of Public Policy,University of Maryland,College Park, Maryland




Contributor List xiii

Dušan P. Sekulić,Department of Mechanical Engineering,University of Kentucky,Lexington, Kentucky

George Tsatsaronis,Institute for Energy Engineering,Technical University Berlin,Berlin, Germany

Nandan U. Ukidwe,Saflex Technology at Solutia Inc.,Springfield, Massachusetts

Geert Van der Vorst,Department of Sustainable Organic Chemistry and Technology,Ghent University,Ghent, Belgium

Herman Van Langenhove,Department of Sustainable Organic Chemistry and Technology,Ghent University,Ghent, Belgium

Eric Williams,School of Sustainable Engineering and the Built Environment andSchool of Sustainability,Arizona State University,Tempe, Arizona




Foreword

Herman E. Daly

The first and second laws of thermodynamics should also be called the first andsecond laws of economics. Why? Because without them there would be no scarcity,and without scarcity, no economics. Consider the first law: if we could create usefulenergy and matter as we needed it, as well as destroy waste matter and energy asit got in our way, we would have superabundant sources and sinks, no depletion,no pollution, more of everything we want without having to find a place for stuffwe don’t want. The first law rules out this direct abolition of scarcity. But considerthe second law: even without creation and destruction of matter-energy, we mightindirectly abolish scarcity if only we could use the same matter-energy over and overagain for the same purposes – perfect recycling. But the second law rules that out.So it is that scarcity and economics have deep roots in the physical world, as well asdeep psychic roots in our wants and desires.

Economists have paid much attention to the psychic roots of value, but not somuch to the physical roots. Generally they have assumed that the biophysical worldis so large relative to its economic subsystem that the physical constraints (the lawsof thermodynamics) are not binding. But they are always binding to some degreeand become very limiting as the scale of the economy becomes large relative to thecontaining biophysical system. Therefore attention to thermodynamic constraintson the economy, indeed to the entropic nature of the economic process, are nowcritical – as first emphasized by Nicholas Georgescu-Roegen in his magisterial TheEntropy Law and the Economic Process (1971). The present volume is a welcomeand worthy contribution to this important and continuing endeavor. It deservesstudious attention.

University of Maryland

xv




Foreword

Jan Szargut

Human production activity is based on natural resources. Their usefulness resultsfrom the ability to be transformed into useful products necessary for humans. Thatability may be evaluated by means of the laws of thermodynamics that expressnot only the conservation of energy but also its tendency to be dissipated. Thedissipation of energy (resulting in entropy generation) decreases its usefulness andreduces its ability to be transformed into useful products. The mentioned ability maybe evaluated by means of the maximum work attainable in a reversible transition tothe equilibrium with the environment embracing that part of nature that belongs tothe area of human production activity. That quantity is usually called “exergy.”

A considerable part of the natural resources utilized by humans belongs to thenonrenewable ones (organic and nuclear fuels, ores of metals, inorganic minerals).The usefulness of nonrenewable resources results from their chemical composition.The chemical exergy can be accepted as a general quality measure of the mentionedresources because it expresses the maximum work attainable during the transitionto equilibrium with a dead environment.

However, equilibrium with the natural environment is not possible, because itdoes not appear in the real natural environment. As proved by Ahrendts [1], theconcentration of free oxygen in an equilibrium environment would be very smallbecause the prevailing part of oxygen would be bound with nitrogen in nitrates.Fortunately the formation of nitrates is kinetically blocked, and they appear veryseldom in nature.

To find a real but possibly low reference state for chemical exergy, the conceptof reference substances is introduced [2]. For every chemical element, an individ-ual reference substance that is most common in the real environment is accepted.The reference substances are mutually independent, and therefore the problem ofequilibrium between them does not exist. To facilitate the use of chemical exergy,the concept of normal chemical exergy is introduced. It is defined at normal envi-ronmental temperature and pressure and mean concentration in the environment,resulting from the geochemical data.

Gaseous components of air, solid components of the external layer oflands, and ionic or molecular components of seawater are assumed as reference

xvii




xviii Foreword

substances. The general calculation of chemical exergy may be performed in threesteps:

1. calculation of normal chemical exergy of reference substances,2. calculation of normal chemical exergy of chemical elements,3. calculation of normal chemical exergy of chemical compounds.

The exact calculation of chemical exergy of gaseous reference substances is easy,because the considered components of atmospheric air may be treated as compo-nents of an ideal solution. The calculation of normal chemical exergy of elementshaving reference substances dissolved in seawater can be made with sufficient accu-racy in the case of monocharged and bicharged ions or molecular substances. Thecalculation method was elaborated by Szargut and Morris [3]. In the case of solidreference substances, an exact calculation is not possible because they appear inthe form of multicomponent solid solutions. An approximate method to evaluatethe chemical exergy in such cases was suggested [4]. It is based on the assumptionthat solid reference substances can be treated as components of an ideal solution.The concentration of solid reference substances in the environment results fromgeochemical data about the total content of the considered chemical element in thesolid environment and about its fraction presumably appearing in the form of areference substance.

The exhaustion of nonrenewable natural resources can be dangerous for thefuture of humankind. As a measure of the depletion of nonrenewable resources,the concept of thermoecological cost (TEC) was introduced [5]. It expresses thecumulative exergy consumption of the nonrenewable resources in the total chain ofprocesses leading to the considered useful product. The prefix “thermo” indicatesthat this kind of cost is expressed in exergy units, not in monetary units. The valuesof TEC can be used for the selection of the production technology and for the deter-mination of optimum design and operation parameters if the minimum depletion ofthe nonrenewable resources represents the objective function.

The calculation of TEC can be performed by means of a set of balance equations.Each of them contains the TEC of the following delivered components: the useddomestic raw materials and semifinished products, the wear of the machines andinstallations used in the considered production process, the imported raw materialsand semifinished products, the immediate consumption of nonrenewable exergyextracted from nature, and the compensation cost of losses that are due to theemission of deleterious products. On the side of products of the considered process,there appear to be TECs of the major products and of the useful by-products. TheTEC of the useful by-product should be expressed by the value of the TEC ofmajor products fabricated in another process. The substitution ratio between theby-product and the replaced major product should be taken into account. The valueof the TEC of imported semifinished products can be determined by taking intoaccount the fact that the financial means for import are gained by export. Hence theTEC value of the imported semifinished product results from its monetary cost andfrom the mean TEC value of the monetary value of exported goods.

The set of balance equations should be formulated and solved only for thesemifinished products used in other production processes. If the considered useful




Foreword xix

product is not used in other production processes (or used in a very small portion),its TEC may be determined individually by means of a sequence method, whichbegins in the final step of the production chain and goes back through all the stepsuntil the semifinished products considered in the mentioned balance equations areobtained.

The values of the TEC depend mainly on the technology of electricity productionand on the transportation system applied in the considered region or country.

Jan Szargut, full member of thePolish Academy of Sciences,Silesian University of Technology,Gliwice, Poland

REFERENCES

[1] J. Ahrendts, Die Exergie chemisch reaktionsfähiger Systeme (VDI-Forschu-ngsheft 579, Düsseldorf, 1977).

[2] J. Szargut, “Chemical exergies of the elements” Appl. Energy 32, 269–285 (1989).[3] J. Szargut and D. R. Morris, “Calculation of the standard chemical exergy of

some elements and their compounds based upon sea water as the datum levelsubstance,” Bull. Polish Acad. Sci. Tech. Sci. 33(5–6), 293–305 (1985).

[4] J. Szargut, “Standard chemical exergy of some elements and their compounds,based upon the concentration in Earth’s crust,” Bull. Polish Acad. Sci. Tech. Sci.35(1–2), 53–60 (1987).

[5] J. Szargut, “Depletion of the unrestorable natural exergy resources,” Bull. PolishAcad. Sci. Tech. Sci. 45(2), 241–250 (1997).




Preface

This book is intended to bring together a wide range of theoretical and experimen-tal results from many different disciplines, all addressing sustainability issues usingthermodynamic arguments. The disciplines involved include mechanical and chem-ical engineering, physics, economics, geography, ecology, and industrial ecology.The contributors from Japan, Europe, and the United States are all to some extentspeaking one language, albeit with different applications, construction of arguments,and degree of rigor.

We believe that it is time for a book like this to introduce the fundamentals andapplications of thermodynamics to demonstrate the richness and broad applicabilityof thermodynamic principles and the essential role that it can play in quantifyingthe impact of human activities on natural resources and the environment. Our goalhas been to assemble a collection of chapters written by authorities in their ownfields who share thermodynamics-inspired approaches to a diverse set of topics.Although there are many obstacles to presenting all of these different areas in aunified way, we believe we have succeeded in bringing together in one book aglimpse of the breadth of applications that can be considered from a thermodynamicperspective. Different chapters keep quite visible the flavor of a particular discipline,although some cross-fertilization and trans-disciplinary approaches to the issues aredemonstrated. So, our ultimate goal has evolved into a promotion of the use ofa rigorous science/engineering discipline (thermodynamics) not to solve problemsbeyond its realm but to assist in understanding the problem at hand, to define wellthe system considered, to implement conservation principles, and to appropriatelymerge such an approach with other disciplines. The task of establishing a unifiedapproach to what some call sustainability science must be left for the future. We willbe satisfied if this contribution becomes one of the building blocks along the path toachieving that goal.

This book is intended for professionals in diverse fields interested in resolvingsustainability issues. In addition, graduate and senior-level undergraduate studentsacross disciplines, particularly those that already have an introductory course in ther-modynamics, may find this book useful for helping them appreciate and understandthe broad relevance of thermodynamic principles.

Putting this book together has been a pleasure for us in large part because of allof the gifted, enthusiastic people with whom we have had the opportunity to work.

xxi




xxii Preface

We must start by thanking our 23 co-authors and contributors who provided theirauthoritative works to us in a timely manner and put up with our occasionally unrea-sonable requests and nagging. We would like to thank the professional organizationsthat hosted several of our special sessions on various aspects of thermodynamics andsustainability, particularly the American Chemical Society Green Chemistry andEngineering Conference (where the idea for this book was first launched in 2005)and the Institute of Electrical and Electronics Engineers annual symposia on elec-tronics and the environment, now called the International Symposium on SustainableSystems and Technologies.

It was a pleasure to work with Peter Gordon of Cambridge University Pressand Victoria Danahy and Peter Katsirubas of Aptara on editing this complex text.We must also acknowledge the important role played by Skype in allowing us tocontinue developing this book even when we were in distant corners of the globe.

We would like to express our gratitude to several colleagues and good friendsincluding Dr. Joseph Fiksel of Ohio State University for insight into the close connec-tion between sustainability issues and business decision making, Professor RichardGaggioli of Marquette University, Elias Gyftopoulos and Seth Lloyd of the Mas-sachusetts Institute of Technology, and Ingo Müller of the Technical UniversityBerlin for many fruitful discussions involving thermodynamics. We also thank Dr.Robert Gregory of the University of Kentucky for discussing everything else butthermodynamics. A number of years of joint work with our students (too numerousto mention by name) merits a word of appreciation.

Finally, the authors would like to acknowledge the roles by their wives MamtaBakshi, Jane Gutowski, and Gorana Sekulić, and their children, Harshal Bakshi,Laura and Ellie Gutowski, and Višnja and Aleksandar Sekulić. Their assistance andunderstanding provided continuous support for completing the book.

Bhavik R. BakshiTimothy G. GutowskiDušan P. Sekulić




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