Thermodynamics and Statistical Mechanics: An Integrated Approach PDF
Preview Thermodynamics and Statistical Mechanics: An Integrated Approach
Thermodynamics and Statistical Mechanics Learnclassicalthermodynamicsalongsidestatisticalmechanicswiththisfreshapproach to the subjects. Molecular and macroscopic principles are explained in an integrated, side-by-sidemannertogivestudentsadeep,intuitiveunderstandingofthermodynamics and equip them to tackle future research topics that focus on the nanoscale. Entropy is introduced from the get-go, providing a clear explanation of how the classical thermodynamiclawsconnecttomolecularprinciples,andclosingthegapbetweenthe atomicworld andthe macroscale. Notationis streamlined throughout, withafocus on general concepts and simple models, for building basic physical intuition and gaining confidenceinproblemanalysisandmodeldevelopment. Well over 400 guided end-of-chapter problems are included, addressing conceptual, fundamental, and applied skill sets. Numerous worked examples are also provided, togetherwithhandyshadedboxestoemphasizekeyconcepts,makingthisthecomplete teachingpackageforstudentsinchemicalengineeringandthechemicalsciences. M. Scott Shell is an Associate Professor in the Chemical Engineering Department at theUniversityofCalifornia,SantaBarbara.HeearnedhisPhDinChemicalEngineering fromPrincetonin2005andiswellknownforhisabilitytocommunicatecomplexideas and teach in an engaging manner. He is the recipient of a Dreyfus Foundation New Faculty Award, an NSF CAREER Award, a Hellman Family Faculty Fellowship, a Northrop-Grumman Teaching Award, a Sloan Research Fellowship, and a UCSB DistinguishedTeachingAward. Downloaded from https:/www.cambridge.org/core. UCL, Institute of Education, on 11 Jan 2017 at 04:35:34, subject to the Cambridge Core terms of use, available at https:/www.cambridge.org/core/terms. http://dx.doi.org/10.1017/CBO9781139028875 “This textbook presents an accessible (but still rigorous) treatment of the material at a beginning-graduate level, including many worked examples. By making the concept of entropy central to the book, Prof. Shell provides an organizing principle that makes it easierforthestudentstoachievemasteryofthisimportantarea.” Athanassios Z. Panagiotopoulos Princeton University “Otherintegratedtreatmentsofthermodynamicsandstatisticalmechanicsexist,butthis onestandsoutasremarkablythoughtfulandclearinitsselectionandilluminationofkey conceptsneededforunderstandingandmodelingmaterialsandprocesses.” Thomas Truskett University of Texas, Austin “This text provides a long-awaited and modern approach that integrates statistical mechanics with classical thermodynamics, rather than the traditional sequential approach, in which teaching of the molecular origins of thermodynamic laws and models only follows later, after classical thermodynamics. The author clearly shows how classical thermodynamic concepts result from the underlying behavior of the moleculesthemselves.” Keith E. Gubbins North Carolina State University Downloaded from https:/www.cambridge.org/core. UCL, Institute of Education, on 11 Jan 2017 at 04:35:34, subject to the Cambridge Core terms of use, available at https:/www.cambridge.org/core/terms. http://dx.doi.org/10.1017/CBO9781139028875 Cambridge Series in Chemical Engineering SERIES EDITOR ArvindVarma,PurdueUniversity EDITORIAL BOARD ChristopherBowman,UniversityofColorado EdwardCussler,UniversityofMinnesota ChaitanKhosla,StanfordUniversity AthanassiosZ.Panagiotopoulos,PrincetonUniversity GregoryStephanopoulos,MassachusettsInstituteofTechnology JackieYing,InstituteofBioengineeringandNanotechnology,Singapore BOOKS IN SERIES BaldeaandDaoutidis,DynamicsandNonlinearControlofIntegratedProcessSystems Chau,ProcessControl:AFirstCoursewithMATLAB Cussler,Diffusion:MassTransferinFluidSystems,ThirdEdition CusslerandMoggridge,ChemicalProductDesign,SecondEdition DePabloandSchieber,MolecularEngineeringThermodynamics Denn,ChemicalEngineering:AnIntroduction Denn,PolymerMeltProcessing:FoundationsinFluidMechanicsandHeatTransfer DuncanandReimer,ChemicalEngineeringDesignandAnalysis:AnIntroduction FanandZhu,PrinciplesofGas–SolidFlows Fox,ComputationalModelsforTurbulentReactingFlows Franses,ThermodynamicswithChemicalEngineeringApplications Leal,AdvancedTransportPhenomena:FluidMechanicsandConvectiveTransportProcesses LimandShin,Fed-BatchCultures:PrinciplesandApplicationsofSemi-BatchBioreactors MarchisioandFox,ComputationalModelsforPolydisperseParticulateandMultiphaseSystems MewisandWagner,ColloidalSuspensionRheology Morbidelli,Gavriilidis,andVarma,CatalystDesign:OptimalDistributionofCatalystin Pellets,Reactors,andMembranes NobleandTerry,PrinciplesofChemicalSeparationswithEnvironmentalApplications OrbeyandSandler,ModelingVapor–LiquidEquilibria:CubicEquationsofStateandtheir MixingRules Petyluk,DistillationTheoryanditsApplicationstoOptimalDesignofSeparationUnits RaoandNott,AnIntroductiontoGranularFlow Russell,Robinson,andWagner,MassandHeatTransfer:AnalysisofMassContactorsand HeatExchangers Schobert,ChemistryofFossilFuelsandBiofuels Sirkar,SeparationofMolecules,MacromoleculesandParticles:Principles,Phenomenaand Processes Slattery,AdvancedTransportPhenomena Varma,Morbidelli,andWu,ParametricSensitivityinChemicalSystems Downloaded from https:/www.cambridge.org/core. UCL, Institute of Education, on 11 Jan 2017 at 04:35:34, subject to the Cambridge Core terms of use, available at https:/www.cambridge.org/core/terms. http://dx.doi.org/10.1017/CBO9781139028875 Downloaded from https:/www.cambridge.org/core. UCL, Institute of Education, on 11 Jan 2017 at 04:35:34, subject to the Cambridge Core terms of use, available at https:/www.cambridge.org/core/terms. http://dx.doi.org/10.1017/CBO9781139028875 To Janet, Mike, Rox, and the entire Southern Circus Downloaded from https:/www.cambridge.org/core. UCL, Institute of Education, on 11 Jan 2017 at 04:35:34, subject to the Cambridge Core terms of use, available at https:/www.cambridge.org/core/terms. http://dx.doi.org/10.1017/CBO9781139028875 Downloaded from https:/www.cambridge.org/core. UCL, Institute of Education, on 11 Jan 2017 at 04:35:34, subject to the Cambridge Core terms of use, available at https:/www.cambridge.org/core/terms. http://dx.doi.org/10.1017/CBO9781139028875 Thermodynamics and Statistical Mechanics An Integrated Approach M. SCOTT SHELL UniversityofCalifornia,SantaBarbara Downloaded from https:/www.cambridge.org/core. UCL, Institute of Education, on 11 Jan 2017 at 04:35:34, subject to the Cambridge Core terms of use, available at https:/www.cambridge.org/core/terms. http://dx.doi.org/10.1017/CBO9781139028875 UniversityPrintingHouse,CambridgeCB28BS,UnitedKingdom CambridgeUniversityPressispartoftheUniversityofCambridge. ItfurtherstheUniversity’smissionbydisseminatingknowledgeinthepursuitof education,learningandresearchatthehighestinternationallevelsofexcellence. www.cambridge.org Informationonthistitle:www.cambridge.org/9781107656789 ©M.ScottShell2015 Thispublicationisincopyright.Subjecttostatutoryexception andtotheprovisionsofrelevantcollectivelicensingagreements, noreproductionofanypartmaytakeplacewithoutthewritten permissionofCambridgeUniversityPress. Firstpublished2015 PrintedintheUnitedKingdombyTJInternationalLtd.PadstowCornwall AcatalogrecordforthispublicationisavailablefromtheBritishLibrary LibraryofCongressCataloginginPublicationdata Shell,M.Scott(MichaelScott),1978– Thermodynamicsandstatisticalmechanics:anintegratedapproach/M.ScottShell. pagescm–(Cambridgeseriesinchemicalengineering) ISBN978-1-107-01453-4(Hardback)–ISBN978-1-107-65678-9(Paperback) 1. Thermodynamics. 2. Statisticalmechanics. I. Title. QC311.S51362014 5360.7–dc23 2014010872 ISBN978-1-107-01453-4Hardback ISBN978-1-107-65678-9Paperback Additionalresourcesforthispublicationatwww.engr.ucsb.edu/~shell/book CambridgeUniversityPresshasnoresponsibilityforthepersistenceoraccuracy ofURLsforexternalorthird-partyinternetwebsitesreferredtointhispublication, anddoesnotguaranteethatanycontentonsuchwebsitesis,orwillremain, accurateorappropriate. Downloaded from https:/www.cambridge.org/core. UCL, Institute of Education, on 11 Jan 2017 at 04:35:34, subject to the Cambridge Core terms of use, available at https:/www.cambridge.org/core/terms. http://dx.doi.org/10.1017/CBO9781139028875 Contents Preface pagexv Referencetables xvii TableA Countingandcombinatoricsformulae xvii TableB Usefulintegrals,expansions,andapproximations xvii TableC Extensivethermodynamicpotentials xviii TableD Intensiveper-particlethermodynamicpotentialsfor single-componentsystems xviii TableE Thermodynamiccalculusmanipulations xix TableF Measurablequantities xx TableG Commonsingle-componentstatistical-mechanicalensembles xxi TableH Fundamentalphysicalconstants xxii 1 Introduction and guide for this text 1 2 Equilibrium and entropy 6 2.1 Whatisequilibrium? 6 2.2 Classicalthermodynamics 7 2.3 Statisticalmechanics 11 2.4 Comparisonofclassicalthermodynamicsandstatisticalmechanics 14 2.5 Combinatorialapproachestocounting 15 Problems 18 3 Energy and how the microscopic world works 21 3.1 Quantumtheory 21 3.2 Theclassicalpicture 25 3.3 Classicalmicrostatesillustratedwiththeidealgas 29 3.4 Rangesofmicroscopicinteractionsandscalingwithsystemsize 32 3.5 Frommicroscopictomacroscopic 34 3.6 Simpleandlatticemolecularmodels 37 3.7 Asimpleandwidelyrelevantexample:thetwo-statesystem 38 Problems 41 4 Entropy and how the macroscopic world works 50 4.1 Microstateprobabilities 50 4.2 Theprincipleofequalaprioriprobabilities 51 4.3 Ensembleaveragesandtimeaveragesinisolatedsystems 54 4.4 Thermalequilibriumuponenergyexchange 58 4.5 Generalformsforequilibriumandtheprincipleofmaximumentropy 65 4.6 Thesecondlawandinternalconstraints 69 4.7 Equivalencewiththeenergy-minimumprinciple 70 Downloaded from https:/www.cambridge.org/core. UCL, Institute of Education, on 11 Jan 2017 at 04:35:34, subject to the Cambridge Core terms of use, available at https:/www.cambridge.org/core/terms. http://dx.doi.org/10.1017/CBO9781139028875
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