The Clausius inequality implications for nonequilibrium thermodynamic steady states with NE

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1、TheClausiusinequality:implicationsfornonequilibriumthermodynamicsteadystateswithNEMDcorroborationChristopherGunaseelanJesudasonChemicalPhysicsDivision,ChemistryDepartment,UniversityofMalaya50603KualaLumpur,Malaysiaemail:jesu@um.edu.myAbstract:TheClausiusinequalityforclosed

2、systemswasdeducedfromtheRiemannintegrationofclosedCarnotcycleloopsforirreversibletransitions.ThecorrespondinginequalitiesfortherecentlydevelopedopensystemCarnotcyclesarederivedhereandtheirpropertiesindicatethatnonewnonequilibriumentropyresultsfromthemashasbeenproposedovert

3、hedecades.Itisproventhatasequenceofpointsalonganon-equilibriumstatespacemusthaveexcessvariablesaugmentingthosefortheequilibriumsituation,therebyprovingthatthePrincipleofLocalEquilibrium(PLE)usedextensivelytodescribenonequilibriumsystemsisonlyanapproximation.Todemonstrateth

4、ebreakdownofthePrinciple,verificationofthetheorem,andthepresenceofnewphenomena,anabinitiosteadystatesimulationofasimpledimerreaction2A↔Aundernonequilibriumconditionswasperformedandtheresults2comparedtotheequilibriumconditionstoshowtheregimeofbreakdownofthePrinciple.Thenove

5、ldimerreactionpresentedhasacyclicalpathwayfoundinmanynaturalprocesses,suchaslaserphotochemistry.Itissuggestedthatsuchreactionpathwayscanexistandawaitsexperimentalverification.Anewalgorithmtoconservemomentumandenergyatthepotentialswitchesofthedimerisappliedeffectively.Newat

6、omicandmolecularfluxflowsnotpresentunderequilibriumconditionsareshowntoexist,wherethenetrateofreactionalongthecellisnotzerobutsmall,unlikethezerorateequilibriumrequirement,leadingtothefluxpresence.Theequilibriumconstantisalsoshiftedfromthevalueatthermodynamicalequilibrium.

7、Unlessreinterpreteddifferently,itisshownthattheso-calledCuriesymmetryprinciple,fundamentalindecidingonthefeasibilityofflux-forcecouplingsinboththeoryandexperimentinallphysicaltheories,cannotapplytosuchexperimentalresults.Hence,afargreaterfreedominselectingappropriateforce-

8、fluxcouplingsisindicatedthanwouldbethecaseiftheCurieprinciple,ascommonlyinterpretedisadop