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时间:2019-05-27
《The Clausius inequality implications for nonequilibrium thermodynamic steady states with NE》由会员上传分享,免费在线阅读,更多相关内容在行业资料-天天文库。
1、TheClausiusinequality:implicationsfornonequilibriumthermodynamicsteadystateswithNEMDcorroborationChristopherGunaseelanJesudasonChemicalPhysicsDivision,ChemistryDepartment,UniversityofMalaya50603KualaLumpur,Malaysiaemail:jesu@um.edu.myAbstract:TheClausiusinequalityforclosedsystemswasdeducedfr
2、omtheRiemannintegrationofclosedCarnotcycleloopsforirreversibletransitions.ThecorrespondinginequalitiesfortherecentlydevelopedopensystemCarnotcyclesarederivedhereandtheirpropertiesindicatethatnonewnonequilibriumentropyresultsfromthemashasbeenproposedoverthedecades.Itisproventhatasequenceofpoi
3、ntsalonganon-equilibriumstatespacemusthaveexcessvariablesaugmentingthosefortheequilibriumsituation,therebyprovingthatthePrincipleofLocalEquilibrium(PLE)usedextensivelytodescribenonequilibriumsystemsisonlyanapproximation.TodemonstratethebreakdownofthePrinciple,verificationofthetheorem,andthep
4、resenceofnewphenomena,anabinitiosteadystatesimulationofasimpledimerreaction2A↔Aundernonequilibriumconditionswasperformedandtheresults2comparedtotheequilibriumconditionstoshowtheregimeofbreakdownofthePrinciple.Thenoveldimerreactionpresentedhasacyclicalpathwayfoundinmanynaturalprocesses,suchas
5、laserphotochemistry.Itissuggestedthatsuchreactionpathwayscanexistandawaitsexperimentalverification.Anewalgorithmtoconservemomentumandenergyatthepotentialswitchesofthedimerisappliedeffectively.Newatomicandmolecularfluxflowsnotpresentunderequilibriumconditionsareshowntoexist,wherethenetrateofr
6、eactionalongthecellisnotzerobutsmall,unlikethezerorateequilibriumrequirement,leadingtothefluxpresence.Theequilibriumconstantisalsoshiftedfromthevalueatthermodynamicalequilibrium.Unlessreinterpreteddifferently,itisshownthattheso-calledCuriesymmetryprinciple,fundamentalindecidingonthefeasibili
7、tyofflux-forcecouplingsinboththeoryandexperimentinallphysicaltheories,cannotapplytosuchexperimentalresults.Hence,afargreaterfreedominselectingappropriateforce-fluxcouplingsisindicatedthanwouldbethecaseiftheCurieprinciple,ascommonlyinterpretedisadop
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