欢迎来到天天文库
浏览记录
ID:37659436
大小:196.66 KB
页数:15页
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:TheClausiusinequalityforclosedsystemswasdeducedfromtheRie
2、mannintegrationofclosedCarnotcycleloopsforirreversibletransitions.ThecorrespondinginequalitiesfortherecentlydevelopedopensystemCarnotcyclesarederivedhereandtheirpropertiesindicatethatnonewnonequilibriumentropyresultsfromthemashasbeenproposedoverthedecades.Itisproventhatasequenceofpointsalonganon-equ
3、ilibriumstatespacemusthaveexcessvariablesaugmentingthosefortheequilibriumsituation,therebyprovingthatthePrincipleofLocalEquilibrium(PLE)usedextensivelytodescribenonequilibriumsystemsisonlyanapproximation.TodemonstratethebreakdownofthePrinciple,verificationofthetheorem,andthepresenceofnewphenomena,an
4、abinitiosteadystatesimulationofasimpledimerreaction2A↔Aundernonequilibriumconditionswasperformedandtheresults2comparedtotheequilibriumconditionstoshowtheregimeofbreakdownofthePrinciple.Thenoveldimerreactionpresentedhasacyclicalpathwayfoundinmanynaturalprocesses,suchaslaserphotochemistry.Itissuggeste
5、dthatsuchreactionpathwayscanexistandawaitsexperimentalverification.Anewalgorithmtoconservemomentumandenergyatthepotentialswitchesofthedimerisappliedeffectively.Newatomicandmolecularfluxflowsnotpresentunderequilibriumconditionsareshowntoexist,wherethenetrateofreactionalongthecellisnotzerobutsmall,unl
6、ikethezerorateequilibriumrequirement,leadingtothefluxpresence.Theequilibriumconstantisalsoshiftedfromthevalueatthermodynamicalequilibrium.Unlessreinterpreteddifferently,itisshownthattheso-calledCuriesymmetryprinciple,fundamentalindecidingonthefeasibilityofflux-forcecouplingsinboththeoryandexperiment
7、inallphysicaltheories,cannotapplytosuchexperimentalresults.Hence,afargreaterfreedominselectingappropriateforce-fluxcouplingsisindicatedthanwouldbethecaseiftheCurieprinciple,ascommonlyinterpretedisadop
此文档下载收益归作者所有