Chemical, Biochemical, and Engineering Thermodynamics

914 Pages·2006·39.19 MB·English

by  Stanley I. Sandler

Chemical, Biochemicai,
and Engineering
Tlzermoc!gnarnic
Fourth Edition
Stanley I. Sandlel-
if
Uiril.er.;it?. ~rlo~ctrrr.
John IViIey LO Sons, Jnc.
I
i
..
ASSOCIATE PUBLISHER Dan S;~yre
:\CQL'lSl'rlOSS EDl'lU!l Jcnoifer \\;.lter
EDITORIAL .ASSISTAS1 Slarv blor.1r1-hlcGce
-
ILLUSTRATION COORDIS4TOK 1,l:try A11113
DESIGNER Hope bl~llsr
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Library oiCungress Cat;,lonin.-is-Peblicil~ion Dat;t
Sandler. Stanley I.. 1940-.
Chemical. biochemical, and engineering thrmodynan~ic/s Stanly I. Sandler--4lh cd.
p. cm.
Rev. Ed. of: Chemical and engineering thermodynamics. 3rd ed. c1999.
Includes index
- ISBN-13: 978-0-471-66174-0( clolh : acid-free paper)
ISBN-10: 0-471-66174-0 (clolh :n cid-free paper)
I. ne~modynamics-Texrbookr2. . Chemical enginecring-Teslbooks. 3. Biochemical
engineering-Textbook;. 1. Sandler, Stanley I.. 1940- Chemical and engineering
thcrmodynanics. II. Title.
QD504.S25 2W6
541.3'69-dc22
2055054235
Printed in the United States of America
rroii; oilier coili-ses you may be used to solving algebraic equations that have only a single correct ansqser. The
si!;:.:;i,;ii here is the u~ieco ntinually faced by practicing engineers of [needing to solve a problem even tliougll 1112
c!?;.:.iptio~i OF the properties is imperfect. and a choice of equation oistate or activity coefficient model [uust be
~iiacl?.( SOIIIg~l~.i dnncei n making such choices for ~n~ixtoreiss given in Sec. 9.1 I.)
Tiit iecoiid pi-ohli.[n is that the equations of state and activit: cozilicient n~odelsu sed in thermodynamics
:(re !i~iil inear algebr.~ise quations; so that computations in\.olving tlien~c an be difficult. It is for this reason that
I provide a collectioi~o f computer aids on the CD-ROM accompanying this book. Incl~tdedo n this CD-ROhsI
are .\I.ATHC.AD woltilieets, Visual Basic programs (as code and staild-alone executable modules), MATLAB
pro:riinls i;is code and esselltially stand-alone programs). and older DOS Basic programs (as code and stand-
:lions execii~ibiep ro:riims). These computer aids are described it1 .Appendix B. I recommend the use of the
hi ATHCAD \\~orksli~e(tass the form of the code is the same as that in which the equations are normally written
so that it is t:isily u~iderstouda, nd it is easy to make changes) or the Visual Basic progralns (as they are simple to
LIS:l~nd h;~\.en ice :r;~phics). To use the IMATHCAD worksheets. the AIATHCAD engine is required. A 120-day
cv:lIi~niion\ .ersion of [his soft\\.are is included on the CD-ROM. The Visual Basic programs do:iot require any
other soitu.nre: ho\verer. the Visual Basic compiler is needed if you wish to change the prog&ms. To run the
M.ATLAB pro~r;i1iisy ou need to itistall the MCR libn~rya. lso on the CD-ROM: the complete MATLAB prosram
is ncedscl to ~n;~kancy changes.
I liave alw provided .;e\,erul instrnctional aids to help you in your study of thermodynamics using this book.
First. every cliilptei- begirls with instructional objectives listing tlic iiiiportant items to be learned. I suggesi
rcadiiig these objectives before starting a chapter, and then revie\cin: them while preparing for examinations.
Second. important erjo:[tions in the book are shown in boxes. and the really important equationsnlso are indicated
by name or description in the margin. Third, there are many problems at the end of each chapter (or, in the case
of Chapters I0 though 12, at, the end of each section) for you to hone your problem-solving skills. Finally. in
Appcndin C there are answers to selected problems. However. on& the final answers appear, not the complete
.;iilu~ionw ith ilie steps to get to that answer. Keep in mind [hat you may be solving a problem correctly. bur get
n slightly different nunierical answer than the one I h\,e provided because you read a graph of thermodynamic
properties slightly differently than I did. or used a correct but different equation of state or activity coefficient
model than I did. So if your answer and [nine differ only sli$htly. it is likely that both are correct.
Good luck in your study of thermodynamics.
Srotzle? 1. Sn~irller
Nelvnrk. Deln~cf~re
J11nr 10. 2005
ACKXOWLEDGMENTS
I wdnr to thank a collection of people who have contributed to this book in many important ways. First, and
loremost, niy Family, who have put up with me closeted in my office, typing away on my computer instead
of spending time with them. Next are my faculty colleagues, present and former,who have supported me in
(his book writing acti~ityin so many, many ways, including providing many useful comments, criticisms, and
su$!gestions. Special thanks go to Michael Paulaitis and Norman Wagner. who have contributed problems to this
edition, and to Abraham Lenhoff, who both provided problems and corrected my many initial errors in Chapter
15. I am also pleased to acknowledge Jiirgen Gmehling of the University Oldenburg (Germany) and the UNIFAC
Consortium for providing the group information and parameters for use in a proglam that accompanies this book.
Finally, I wish to acknowledge the contributions of the students, both at the University of Delaware and (by e-
mail) worldwide, who have used previous versions of the book and who have pointed out errors and rypos, and
asked questions, that have resulted in some of the changes you see in this edition.
SfonleyI . Sandier
May 10,2005
i
.
:I\ ailable. 1 5ltggest l~ocio \,eriit," the hlloiving cliapte~iln~d sectintis:
Sei. 9.9 Chapter 14
S c c ~I 1 .3. I I .A. and I I .5 Chepter 1.i. if ilierc is no interchi iii >i~~citctilicoi
Cliapter 17 sngineeriiig
One-seincsler graduate thermo(l!.na~i~icsc out-se
l<evit\\*1 i1itclio f (he ~ii;iteriiiIi t1 this l,c,ok ill ahoi~5t )p trcctit ojtll* setne,~tci-1.1 hlisttriiig ~.t<?. :III~~ IP:II I>SCI\i clc
iin iiitro(!i~ctioiit o st;![iitical tii~cli:iiiii.si t1 11ie retiiaitider of the coi.tr~c.
FOR STUDENTS
.ipplictl Ihermodynaiiiics. as considered in this textbook. is one of tile sitl,iects thiit is ill: i..'a~i~l:ii;iiu~in- thc
~xtcticeo f chemical engineering. A major par1 of tile equipment and operatiti: costs ol'pi-~?ic~.;Jcc>\, cl~)pebdy
cli~tiiic:il engineers is based on desigii niethod [liar use the principles of applied thermoii:. ~?:~tnics\\.; liilc lhi:
\\ill be tleniotisu-ated it1 courses you \\.ill wke in mass transfer. rrc~ctione iifiiiecritig. ittiil pi;'.ies\ di.igti. \i~tiic
hrii.l'itiirodt~c~oreys amples are provided in ihis buok.
.At iliis ~pointi n yot~redt~ca[ioy~niu. 1i:tve pruhahly heen exposed to soins n5pccis ol'tli~.riiiiki!i n:~iiiici~n coitise\
iii ;eticritI clie~iiistry.p liysicd cheniistry ittid pliysics. !My reco~iiiiic~icl~ttiiso i~lii; ~t ),II~Ic o;ii~~l~ioter~l~c i\\ hi11
!.oil have '.learned aboitt thertiiodyn;itiiics in tltoze coirrscs. 711; not;ttion in this I~oel;i h iiii'fei.ctl1. 11111I ~iili~ll
incve like rliat in other chetliicai ensinrering courses. Also. in those n o n - e i n c ourxi.~t.h crtiiodynanlicr
ira\ usually iipplied only to a closed sysietn (for example, a tixcd niitss of a substaticei. iihile eii:i~lcr.rin:
i~pplicarionsg enerally involve open sysretiis. that is, [hose with riii~ssi lows into atidlor oilt i ~thie s!.ilctn. Also.
you tiixy Iiave been introduced to entropy using 11 device such as ;i Carnot cycle. Please iii~iiiediatclyt xpilngi:
froti1 your iiiilid the connection betweeii entropy and such deviccs. Entrap);. like eilergy, is a wry gcncral cvlicept.
independent of any such device. Ho\\,eser. entropy is differeiib froni energy 1:tnd nionicntuiiii iii tlii~ti l is 1101 it
cotiscr\'etl property. Energy is conserved. entropy is not.
.A5 you will see (in Ch;iptcr 4). evetl tIio~t:h it is a non-co~iservedp roperly. entropy ii ti.r-)-i ~iip~'rta~Fiol.r
ci~inplei,f two metnl blocks, one hot and another cold, are put into cotitoci \villi eilcli olhcr. the COIICC~o~r
enrropy leads us to [lie conclusion that after a while, the two blocks will be ai the same tei!ip;.ci!i~rc. tvliich is in
agreement with our experience. Horuever. [he principle of enerzy con.serv:~tiunt ells us only ihct the iuiol encrgy
of the system finally \\.ill equal the totiil energ initially, not that the blocks need to be ;it tile hilriir tcni]:ernture.
This is an illustration of how we freqitenrly have to use both the concepts of energy coiiseriaiion :inti cnlropy
(and in open systems [hat total ninss cat] not be created or destroyed) to solve problems in thsriiiudgn;imics.
There are two general ways in which themiodynamics is used. Onc is the calculation of heat and n~ork( or
more generally, energy) flows-for example, in determining the conversion of heat to work in v;ir;ous types of
engines, determining the heat flows accompanyin; chemical reactions, or in changes froni one state of system
to another. The second important type of thermodynainic calculation is the determination the equilibriutn stare.
[br example, in calculating the equilibrium compositions of the vapor and liquid of a comples mixture needed
in order to design a mahod for purifying the components. or the equilibrium-;omposition of a chemically
reacting system. You should be able to do all such calculations after completing the material in this textbook, as
well as some computations relating to biochemical processing, safety, and the distributioti of chemicals in the
environment.
Chemical engineering, and chemical engineering thermodyna~nicsi n this book, deals wiih real substances,
and therein lie two of the difficulties. The first is that the properties of real substances are not completely knowti
from experiment at all temperatures and pressures (and for mixtures at all compositions) and are approximately
described by model equations-for example, a volumetric equation of state that interrelates pressure, volume,
and temperature (the ideal gas equation of state applies only to gases at very low pressuresj. or equations that
relate activity coefficients to composition. Any one of several different equations may be used to describe a pure
substance or mixture, and each will result in a slightly different answer in solving a problem. However, within
the accuracy of the underlying equations, all the solutions are likely to be correct. This may be disconcerting, as
New to This Edition v
level in other core undergr:~du;~teco~irsiens c hemical engineering (i.e.. rarely is kinetic theory introduced in Illlid
iiiechanics 01. mass transfer courses). 1 do believe expolure to statistical and quantum mechanics is important.
and that is why the physical chemistry course that deals with theseshould be retained.
NEW TO THIS EDITION
This foilrth edition of C%o!ricnl rirrd Eirginceri~rgT l1ei~71o(l~ii(ii1rricern.a med Clirnricnl. Bioi.Iren~ic~r~t~l.i dO i-
giircerin!: Tlieni~orl~~irr~riisi cax s.i gnificant re\.ision to the previous editions. The most e\.idenr clia~~a~ree [sli e
increase in the number of cliaptcrs fl'oni 9 to 15. and the inclusion of nlaterial on some of the bincheniicill uppli-
cations of thermodynamics: but a number of additional changes have been made to en:~ble this test to c<>i~tinue
to evolvc as a teaching and learning tool.
I~~.riri~rrioo~l?~iercrr/i ~~eo.sn d nornrioir. Tvo items Iia\;e been added at the beginning of each chilj~terT. he
tint is a list of instructional objectives. This provides students with my expectations for what they should
learn from the chapter. and can serve as a checklist that they can use to monitor prozress in tlicir studies
(especially for esamin;ltions). The second is a list oi [he important new notation introduced in that chapten
This is iiieililt to provide ;In eils). rel'erence for students and to indicate the import;tnt quantities hein?
inlri)d~icetiln the chxpter.
Nio~~berrifclrnpre,i:~~r ct-co.sedfi~9~ ~ror ,I >. The increase in the number of the chiipters \\-as doiic largely
to reduce the length of some chapters to units more easily digestible by student?. Thus. itic content of the
very long Chapter S of the previous editions. dealins with all types of phase equilibria. in this new edition
h;~sb een separated into Chapter 10. which considers only vapor-liquid equilibrium: Chi~pterI I. which
discusses other types of tluid-phase equilibria (liquid-liquid, vapor-liquid-liquid. si~percriric~eslt racrion.
etc.): and Chctpter 12. on phase eqoilibna involving a solid. Similarly, the two subjects of the previous
Chapter 9, chemic;il reaction equilibria and the energy balances on reacting systems, ha.\ becii split into
Chiipters 13 and 14. ~lsot,h e content of Chapters 1 and 3 of the previous edition hiis bee11 rcorgiinized
into four chapters. tlaving the book organized in this way should make it easier for the professor to choose
among the material to be covered. if he or she decidcs to do so.
* Marrri(11 relnrrd ro bioclie~~ricra~l l~plicr~riuoif isr hrr~rior!,nrinrics. The only new chapter is Chaptcr 15.
dealing with biochemicnl processes. though a number of biochemical examples also appear in Chapiers
I I and 12, and elsewhere in the book. The new Chapter 15 deals with the application of ther~nodyiiamics
to some biochemical processes. Since pH is important in many such processes. the first section of this
chapter deals with this subject. It should be a review. perhaps in a little more depth, of what the stude~iht as
learned in courses in general and physical chemistry. Section 15.2 discusses how pH affects the ionization
of biochemicals. including how the charge on a protein changes with pH. Section 15.3 deals with the
solubilities of weak. acids and bases as a function of pH, and the role this can play in the formulittion
of pharrnaceuticals. Ligand binding, a different typs of biochemical reaction, is considered in Sec. 15.4,
with some detail on the unique case of oxygen binding to the four-site hemoglobin molecule that makes
our form of life possible. Other biochemical reactions are considered in Sec. 15.5, including the unfolding
(denaturation) of,proteins as a function of temperature and pressure. The ultracentrifugation of proteins is
considered briefly in Sec. 15.6, and Sec. 15.7 contains a discussion of Gibbs-Donnan osmotic equilibrium
and how this is affected by pH. The coupling of chemical reactions, with particular attention to the .4TP-
ADP reaction, is considered in Sec. 15.8. There the discussion is a very macroscopic one, ignoring the
details of the metabolic pathways, which are best considered in a biochemistry course. This chapter and the
book conclude with the thermodynamic analysis of a fermenter, including the second law (or availability)
constraint that applies to biochemical reactions and the operation of fennenters.
Brief introdltctions (nnd simple e.rnrnples) of advnnced nnd emerging applications of tliennod~nmnics.
Thermodynamics is central to the practice of chemical engineering and to the cuniculum; for example,
phase equilibria is the basis for most separation and purification processes, and energy balances are needed
in many areas, including reactor design. However, in my teaching experience, I have found that students do
\,i Preface
not appreciate this connection until later in their studies. and many feel that thermodynamics is too abstract
while they are studying this subject. I have tried to dispel this notion by providing some brief introdoctions
(and simple examples) of the applications of thermodynamics to subjects chemical engineering students
will encounter later in their studies. For example. in Sec. 10.1, on vapor-liquid equilibria of ideal mixtures.
[here is also a brief introduction to distillation ronly several pages in length, and a simple McCabe-Thiele
type discussion): this is intended to motivate an understanding of vapor-liquid equilibrium, not meant to
rcplace a course in mass transferoperations. Disrillation is ievisited briefly in Sec. 10.2, on the vapor-liquid
equilibrium of nonideal mixtures. to explain why azeotropes cause difficulties in distillation, and one way
to deal with this. Additional "practical considerations" include brief esa~npleso n Rayleigh distillation, air
stripping (to remove radon from ground water). staged liquid-liquid extraction, and others. Also. in Chapter
12 there is a bt-ief introduction to the rherrnodynarnicc of the new field of product engineering. These
introductions are all short and designed merely to motiv3te the student's interest in thermodynamics. and to
provide an introducrion to courses that will follow in the fhemical engineering curriculum. Other practical
applications that appeared in the previous editions. such as the liquefaction of gases, computing heat loads
on chemical I-eactors. and the application of thermodynamics to safety and environmental problems. have
been retained.
lle.scril>rio~z.osf lobnrnro~-?e.q r~il~nrenCr.h apter I0 also includes brief descriptions of the types of laboratory
cquipz~lent1 1sedt o measure fluid phase equilibria. so that students will have a better understandin: of ho\v
such darn are obtained. and so they gain some familiarity with the equipment they (nay encounter in typical
junior and senior level laboratory courses.
Help irt choosing rlre nl~propriorerl zernzorlynaniic ntorl~iln solving prable~nro, nd in rfsirzg proces.7 sin~rrln-
ro,:x. I have put more emphasis on helping students choose the appropriate thermodynamic moGel for their
sepal-ations and design courses. and on the use of process simulators. such as Aspen, Hysys, SimSci, and
Chemcad. This is especially evident in Sec. 9.1 1.
Conirecrio!r.s ivirlr orher courses bz rile cirrric~rllrnr.I believe that as educators, we should consider each of
our courses to be a tree with roots and branches in othsr parts of the chemical engineering curric'ulum.
rather than a silo of knowledge disconnected from the rest. It is for this reason in this book that I have made
connections to courses in fluid mechanics, separations processes, reactor design, as well as the new chapter
related to biochemical engineering:
New problen~sa nd ill~urrarior~sA. lmost 200 new or revised problems and new illustrations have been
included.
Arrs+versr o selecred probleins. I have also added an appendix with answers to selected problems that stu-
dents can use to check their work. However, it is only the final answers that are provided, not the complete
solution. Students should use these answers with some discretion. Unlike a simple algebra problem, for
which there will be an exact solution, here students should remember that if they read a thermodynamic
property chart somewhat differently than I have. they will get a slightly different answer. Likewise. if they
use one equation of state in the solution and I have used another, or if they used one activity coefficient
model and I have used another, the final answers will be somewhat different. Therefore, except for the sim-
plest problems (for example, those involving ideal gases), a student may not get the exact same answers I
did.
IUPAC norarion. Another, lesser change I have made in this revision, largely suggested by my European
colleagues, is to adopt some of the thermodynamic notation recommended by the International Union of
Pure and Applied Chemistry (IUPAC). However, I have not been consistent in doing this, as I have found
that some of the IUPAC-recommended notation did not meet my needs and might he confusing to the
student.
Updated cornpritational tools. As in previous editions, I provide many opportunities for the use of personal
computers in problem solving. The thud edition of this book included MATHCAD worksheets and DOS-
based Basic language (and compiled) programs. To these programs I have added Windows-friendly Visual
Basic versions of those earlier programs that are easier to use and have greater capabilities. There is also a
new Visual Basic pure-component database that can be used as a stand-alone program or accessed by the
equation-otlstate and UNIFAC prosrams to import the needed parameters. Also. the UNIF.AC prograni has
. been updated to the latest version (as of the beginning of 2005) with the most recsntly ptiblisllec!
. parameters. Several MATLAB programs have also been added. I have used the CD-ROLI sylnihol in
I :, the margin. as here. to indicate \i,lien reference is made to using one or mol-e of thehi. prograin>. ant1
~-
to suggest to the professor and student when these PI-~gramcs;k n be used in prohletii hot\ iog.
These programs and worksheets are included in the CD-ROM that eccon~paniest his hoclk. :inti they can
also be downloaded from the Web site
w~v\v.wiley.com/collegels;indler. It is my intention to add to and update these progrxns on rliis \\-e!, sill..
Appendix B on tlie CD-RON and Web site describes the use of these prosrams :nntl \vorli.;lissis. and pro-
vides installation instructions for their use. While there is no necessity to use these compotntionrd :lids to
learn thermodynamics with this book. their availability greatly facilitates the solution of ininn!. interesting
and practical problems that \\zould otherwise be possible only after tedious progrinm~ning.
MATHOID 1.3. A 120-day trial version of M.4THCAD 13 is included on the CD-ROM that i~ccornpniiies
this text.
ADDITIONAL FEiY1'URES
~Mrrrgi~11r ore.s. The margin notes I h;lve added are meant to elliphasize the coticepts I heliere to be iiiiport~nr.
as well ;IS io make it easier for the student to find those concepts again at a later time. Since I frquently \vrite
\notes in the margins of books that I use. I wanted to provide a place for students to add notes of their oxn.
Bo.rc:d eqlrotio11.r. 1 have placed boxes around important equatiorls so that the reader can u;~*il!. identiw the
equations !hat are the end results of sometimes quite detailed analysis. It is hoped t1i:lt in this \va! the student
will casily see tlie important tree in \\,hat may appear to be a forest of equations.
De,sc~-ij~iirvietl esfor illt~.srrc~riorrI.s h. ave provided a short title or description to indicue wiiat i\ no he li.arncd
li-on1 or seen in each illustration.
Reolisric /I~o~/~IIRIc.asl.i stic problems are employed to familiarize students with the typcs of cl~;~llen:es they
will encounter in industry and graduate research.
Ir~irorl~~croifo ~etn viron111o~1r~rr1rt1l si(fet? applicaiiorls of rherri~orlyt~otnicsA. n introduction lo these topics
provides course material useful for ABET accreditation.
SI lr~rit.s.S I units are used throughout
STUDENT RESOURCES
The following resources are available from the book Web site at
www.wiley.com/college/sandler. Visit the Student section of.the Web site.
MATHCAD worksheets to solve,pure-fluid and mixture thermodynamics problems
* Visrrnl Basic programs that run in the Windows environment to solve pure fluid and mixture therrnodyna~n-
ics problems and to obtain graphs of the results
DOS-based programs (from the third edition) that can easily be modified by students with access to an
inexpensive Basic compiler
MATLAB programs and library to solve problems in the thermodynamics of pure fluids and mixtures
Adobe PDF versions of important dr~mg raphs that students can enlarge, print out, use in problem solving
and then hand in as part of their homework assignments.
These resources are also available on the CD-ROM accompanying the text. Updates to these resources will be
included on the Web site.
iYSTRCCTOR RESOURCES
:\I1 student resoorce.; lire also a\sailableon tlie Instructorstction of the \i'eb site at ~~\\~\!~.wiley.con~/coII~gei~rl~iclIer.
Tlic follo\\ring itpplements are available only to inrrocrors who adopt rlic let:
* So/rriioiic11.i1i~iriol4: 11 solutions available as Word docitments. and many solutions also available as MATFI-
C,-\D \\,orksliee~s
Ii~icipcg n1ler;v ~!irc.~rfigrrr'e.s
Tc..ri,h,?rrre.c Or Po~vrrPoirtr,fon,,nr
All important ad\.;itntage of the MATHCAD worksheets is that a faculty meniber can create variations to the
p:.oblenls in this book by changing the conditions or inpitr parameters in the \vorkshre~a, nd inimcdi;~telyo ht:;iii
111- atis\vrr to tlie revised problem. In this way the recycling of problem s~lutionsc an be ininimized. Also. the
ability to change paranteters in a MATHCAD worksheet :illows "\\*hat if" questions to be answered quickly. For
cs;ttnple. the questioli of how the phase behaviorchanses in a mixture with chanses in temperature or pressure is
~~uickalyns wered by changing a parameter or input \.ariabIe in :I MATHC.AD tvorksheet. These instroctor-only
rehoorce\ ;~rcp assu.ord-protected. Visit the Instructor section of the book Web site to register for a password to
:tcccss tliil\c tii:itct-ials.
I'KOPOSEI) SYLLABI
.As with tilost texrhooks, there is more material here than can be co\,ered in a two-semester or [\YO-quartsr
COLI~TShi~s .a llows the instrucror to tailor the course to his or her interests. and to the needs of the curriculunl.
The material not covered in class should still be useful to students as reference m;~terialf or other courses in the
curriculum. and For use later in their professional careers. Some su::ested syllabi are given next.
Two-semester undergraduate chemical engineering therniodynanlics ctiurse
Cover as iiiuch of rlic hook as possible. If omissions are necessary. I would !lor cover the following n1;iterial:
Secs. 2.4 a;id 3.6 Secs. 12.3, 12.4. and 11.5
Secs. 6.9 and 6.10 Chapter I4
Src. 9.9 Chapter 15. if there is no interest in biochemical
engineerin:
Two-quarter undergradttate chemical engineering thermodynamics course
I suggest rlor covering the following chapters and sections:
Secs. 2.4 and 3.6 Sec. 9.9
Sec. 5.3 Secs. 12.3, 12.4, and 12.5
Secs. 6.6.6.9. and 6.10 Chapter 14
Sec. 7.8 Chapter 15. if there is no interest in biochemical
engineering
One-semester undergraduate chemical engineering thermodynamics course following a one-semester gen-
eral or mechanical engineering course
I suggest quickly reviewing the notation in Chapters 2, 3, and 4, and then starting with Chapter 8. With the
limited time available, I suggest nor covering the following chapters and sections:
Sec. 9.9 Chapter 14
Secs. 12.3, 12.4, and 12.5 Chapter 15, if there is no interest in biochemical
engineering
One-quarter undergraduate chemical engineering thermodynamics course follolving a general or me-
chanical engineering thermodynamics course
Quickly review the notation in Chapters 2.3, and4, and then go directly to Chapter 8. With the very limited time
To Judith,
Catherine,
Joel,
And Michael
About the Author.
STANLEY I. SANDLER earned the B.Ch.,E. degree in 1962 from the City College of
New York, and the Ph.D. in chemical engineering from the University of Minnesota in
1966. He washen a National Science Foundation Postdoctoral Fellow at the Institute
for Molecular Physics at the University of Maryland for the 1966-67 academic year.
He joined the faculty of the University of Delaware in 1967 as an assistant proFessor.
and was promoted to associate professor in 1970, professor in 1973, and Henry Beiin
du Pont Professor of Chemical Engineering in 1982. He was department chairman from
1982 to 1986. He currently is also professor of chemistry and biochemistry at the Uni-
versity of Delaware-and founding directoi of its Center for Molecular and Engineering
Thermodynamics. He has been a visiting professor at Imperial College (London), the
Technical University of Berlin, the University of Queensland (Australia), the Univer-
sity of Califoinia-Berkeley, and the University of Melbourne (Australia).
. In addition to this book, Professor Sandler is the author of 325 research papers and
a monograph, and he is the editor of a book on thermodynamic modeling and five
conference proceedings. He is also the editor of the AIChE Journal. Among hjs many
awards and honors are a Faculty Scholar Award (1971) from the Camille and Henry
Dreyfus Foundation; a Resea~chF ellowship (1980) and a U.S. Senior Scientist Award
(1988):.from the Alexander von Humboldt Foundation (Germany); the 3M Chemical
Engineering Lectureship Award (1988) from the American Society for Engineering
Educauon; the Professional Progress (1984). Warren K. Lewis (1996). and Founders
(2004) &wards from the American Institute of Chemical Engineers; the E. V. Murphree
Award.(1996) from the American Chemical Society, the Rossini Lectureship Award
(1997)-from.the International Union of Pure and Applied Chemistry, and election to
the U.S. National Academy of Engineering (1996). He is a Fellow of the American
Institute of Chemical Engineers and the Institution of Chemical Engineers (Britian and
Ausdia), and a Chartered Engineer.
Preface
ISTEZDED AUDIENCE AND OBJECTIVES
Tliis bouk is intended as the text for a course in thermodynamics for undergraduate students in chemical en-
sitleerin:. It has been used in this manner at the University of Delaware for more than 20 years, originaily in
a cot~rrcf or third-year students and currently for use by sophomores. I had two objectives in \\,titin2 the firs!
etlilioii of !his hook. which have been irerained in the succeeding editions. The first was to develop a inodern ap-
plied tiieriii~tlynaiiiicst ext. especially for chemical engineering students. that wns relevant to other parts of the
c~~rrii.r~i~~i~i-spccitici~cIoluyr -ses in separations processes. chemical reitctor an;~lysi,s.a nd process deri$tl. The
olher ohicctivr was to organize and present mnteriill in suflicient detail and in such a way that the stuclent C;III
oh!;iin a good u~irle~-st;~ndoifn gth e principles of thermodynamics and ;I proficiency in applying these principles
ro ths solt~tiono f;l~;tr ge variety of energy How and equilibrium problems.
Thouzh this is designed to be an undergraduate texrbook, 1 also use the material in this book when I :each the
otie-seniestergraduate thermodynamicscourse. I am frequently asked what I teach in that course. as the graduate
thermodynamics course in different schools is probiibly the least defined ;tnd most heterogeneous course in
zraduare programs. When I teach graduate thermodynamics. I go through much of' the materi;tl in this book in
;
about 60 percent of the semester, a hlisteriilg pace, and then provide an introduction to statistical mechat~icsi n
the remainder of the course.
Chemical engineering faculties are increasingly examining their curricula to find space to add new subjects.
such as biochemical engineering, and at the same time to meet institutional requirements of reduced credit hours.
I believe that breadth is more important than redundancy, especially when redundancy has little positive effect.
It is very important that we keep the right balance between breadth and depth, and critically examine the need
for redundancy in our core program. If we omit introducing our students to some area, we make it much more
difficult for them to independently learn about this subject later in their careers, since they will start without any
basic knowledge, or without even knowing the nomenclature. Thermodynamics, in some form. is typically pre-
sented to students in general chemistry, physical chemistry, and physics courses, before the chemicdl engineering
course. I believe this redundancy has had little positive, and perhaps even a negative, effect. Because of the types
of systems considered (open systems in chemical engineering, but only simple closed systems elsewhere), and
frequently the use of quite different notation among the different subject areas, I find that chemical engineering
students are more confused by this redundancy than aided by it. Therefore, when I teach undergraduates I begin
by telling them to forget what they have been taught about thermodynamics elsewhere.
Consequently, I suggest that thermodynamics should he studied only in the general chemistry course and in a
chemical engineering thermodynamics course, eliminating the physical chemistry and physics exposures. As this
textbook contains sufficient information on colligative properties for chemical engineers, I suggest eliminating , .
the One-semester course of the physical chemistry program (retaining thecourse on statistical mechanics and
quantum mechanics), and perhaps reducing by one credit the physics course most chemical engineering students
I
take by eliminating thermodynamics there as weU. I
I am also frequently asked why I have not included statistical mechanics in this book or in my undergraduate !
course. This is an especially poignant question for me, since statistical mechanics.is one of my research areas.
My answer is as follows. I6nd that students have sufficient difficulty with macroscopic thermodynamics and i
its application that moving to the microscopic or statistical mechanics level adds little, except perhaps some
1
confusion, and usually detracts from the flow of the course. Further, we generally do not go to the molecular
I
!