Escolar Documentos
Profissional Documentos
Cultura Documentos
OnsagerreciprocalrelationsWikipedia,thefreeencyclopedia
Onsagerreciprocalrelations
FromWikipedia,thefreeencyclopedia
Inthermodynamics,theOnsagerreciprocalrelationsexpresstheequalityofcertainratiosbetweenflowsand
forcesinthermodynamicsystemsoutofequilibrium,butwhereanotionoflocalequilibriumexists.
"Reciprocalrelations"occurbetweendifferentpairsofforcesandflowsinavarietyofphysicalsystems.For
example,considerfluidsystemsdescribedintermsoftemperature,matterdensity,andpressure.Inthisclassof
systems,itisknownthattemperaturedifferencesleadtoheatflowsfromthewarmertothecolderpartsofthe
systemsimilarly,pressuredifferenceswillleadtomatterflowfromhighpressuretolowpressureregions.Whatis
remarkableistheobservationthat,whenbothpressureandtemperaturevary,temperaturedifferencesatconstant
pressurecancausematterflow(asinconvection)andpressuredifferencesatconstanttemperaturecancauseheat
flow.Perhapssurprisingly,theheatflowperunitofpressuredifferenceandthedensity(matter)flowperunitof
temperaturedifferenceareequal.ThisequalitywasshowntobenecessarybyLarsOnsagerusingstatistical
mechanicsasaconsequenceofthetimereversibilityofmicroscopicdynamics(microscopicreversibility).The
theorydevelopedbyOnsagerismuchmoregeneralthanthisexampleandcapableoftreatingmorethantwo
thermodynamicforcesatonce,withthelimitationthat"theprincipleofdynamicalreversibilitydoesnotapply
when(external)magneticfieldsorCoriolisforcesarepresent",inwhichcase"thereciprocalrelationsbreak
down".[1]
Thoughthefluidsystemisperhapsdescribedmostintuitively,thehighprecisionofelectricalmeasurementsmakes
experimentalrealisationsofOnsager'sreciprocityeasierinsystemsinvolvingelectricalphenomena.Infact,
Onsager's1931paper[1]referstothermoelectricityandtransportphenomenainelectrolytesaswellknownfromthe
19thcentury,including"quasithermodynamic"theoriesbyThomsonandHelmholtzrespectively.Onsager's
reciprocityinthethermoelectriceffectmanifestsitselfintheequalityofthePeltier(heatflowcausedbyavoltage
difference)andSeebeck(electricalcurrentcausedbyatemperaturedifference)coefficientsofathermoelectric
material.Similarly,thesocalled"directpiezoelectric"(electricalcurrentproducedbymechanicalstress)and
"reversepiezoelectric"(deformationproducedbyavoltagedifference)coefficientsareequal.Formanykinetic
systems,liketheBoltzmannequationorchemicalkinetics,theOnsagerrelationsarecloselyconnectedtothe
principleofdetailedbalance[1]andfollowfromtheminthelinearapproximationnearequilibrium.
ExperimentalverificationsoftheOnsagerreciprocalrelationswerecollectedandanalyzedbyD.G.Miller[2]for
manyclassesofirreversibleprocesses,namelyforthermoelectricity,electrokinetics,transferenceinelectrolytic
solutions,diffusion,conductionofheatandelectricityinanisotropicsolids,thermomagnetismand
galvanomagnetism.Inthisclassicalreview,chemicalreactionsareconsideredas"caseswithmeager"and
inconclusiveevidence.Furthertheoreticalanalysisandexperimentssupportthereciprocalrelationsforchemical
kineticswithtransport.[3]
Forhisdiscoveryofthesereciprocalrelations,LarsOnsagerwasawardedthe1968NobelPrizeinChemistry.The
presentationspeechreferredtothethreelawsofthermodynamicsandthenadded"ItcanbesaidthatOnsager's
reciprocalrelationsrepresentafurtherlawmakingathermodynamicstudyofirreversibleprocessespossible."[4]
SomeauthorshaveevendescribedOnsager'srelationsasthe"Fourthlawofthermodynamics".[5]
Contents
1 Example:Fluidsystem
1.1 Thefundamentalequation
1.2 Thecontinuityequations
https://en.wikipedia.org/wiki/Onsager_reciprocal_relations
1/5
8/18/2016
OnsagerreciprocalrelationsWikipedia,thefreeencyclopedia
1.2 Thecontinuityequations
1.3 Thephenomenologicalequations
1.4 Therateofentropyproduction
1.5 TheOnsagerreciprocalrelations
2 Abstractformulation
2.1 Proof
3 Seealso
4 References
Example:Fluidsystem
Thefundamentalequation
Thebasicthermodynamicpotentialisinternalenergy.Inasimplefluidsystem,neglectingtheeffectsofviscosity
thefundamentalthermodynamicequationiswritten:
whereUistheinternalenergy,Tistemperature,Sisentropy,Pisthehydrostaticpressure,Visthevolume, is
thechemicalpotential,andMmass.Intermsoftheinternalenergydensity,u,entropydensitys,andmassdensity
,thefundamentalequationatfixedvolumeiswritten:
Fornonfluidormorecomplexsystemstherewillbeadifferentcollectionofvariablesdescribingtheworkterm,
buttheprincipleisthesame.Theaboveequationmaybesolvedfortheentropydensity:
Theaboveexpressionofthefirstlawintermsofentropychangedefinestheentropicconjugatevariablesof and
,whichare
and
andareintensivequantitiesanalogoustopotentialenergiestheirgradientsarecalled
thermodynamicforcesastheycauseflowsofthecorrespondingextensivevariablesasexpressedinthefollowing
equations.
Thecontinuityequations
Theextensivequantities and
massiswritten:
areconservedandtheirflowssatisfycontinuityequations.Theconservationof
and,assumingthatfluidvelocitymakesanegligiblecontributiontotheenergyflow,theconservationofenergyis
simplytheconservationoftheinternalenergy:
where
isthemassfluxvectorand
https://en.wikipedia.org/wiki/Onsager_reciprocal_relations
istheheatfluxvector.
2/5
8/18/2016
OnsagerreciprocalrelationsWikipedia,thefreeencyclopedia
Theentropyisnotconservedanditscontinuityequationiswritten:
where
istherateofincreaseinentropydensityduetotheirreversibleprocessesofequilibrationoccurringin
thefluid.
Thephenomenologicalequations
Intheabsenceofmatterflows,Fourier'slawisusuallywritten:
wherekisthethermalconductivity.However,thislawisjustalinearapproximation,andholdsonlyforthecase
where
,withthethermalconductivitypossiblybeingafunctionofthethermodynamicstatevariables,but
nottheirgradientsortimerateofchange.Assumingthatthisisthecase,Fourier'slawmayjustaswellbewritten:
Intheabsenceofheatflows,Fick'slawofdiffusionisusuallywritten:
,
whereDisthecoefficientofdiffusion.Sincethisisalsoalinearapproximationandsincethechemicalpotentialis
monotonicallyincreasingwithdensityatafixedtemperature,Fick'slawmayjustaswellbewritten:
where,again,D'isafunctionofthermodynamicstateparameters,butnottheirgradientsortimerateofchange.
Forthegeneralcaseinwhichtherearebothmassandenergyfluxes,thephenomenologicalequationsmaybe
writtenas:
or,moreconcisely,
and
Therateofentropyproduction
Fromthefundamentalequation,itfollowsthat:
https://en.wikipedia.org/wiki/Onsager_reciprocal_relations
3/5
8/18/2016
OnsagerreciprocalrelationsWikipedia,thefreeencyclopedia
and
Usingthecontinuityequations,therateofentropyproductionmaynowbewritten:
and,incorporatingthephenomenologicalequations:
Itcanbeseenthat,sincetheentropyproductionmustbegreaterthanzero,theOnsagermatrixof
phenomenologicalcoefficients
isapositivesemidefinitematrix.
TheOnsagerreciprocalrelations
Onsager'scontributionwastodemonstratethatnotonlyis
positivesemidefinite,itisalsosymmetric,except
incaseswheretimereversalsymmetryisbroken.Inotherwords,thecrosscoefficients
and
areequal.
Thefactthattheyareatleastproportionalfollowsfromsimpledimensionalanalysis(i.e.,bothcoefficientsare
measuredinthesameunitsoftemperaturetimesmassdensity).
Therateofentropyproductionfortheabovesimpleexampleusesonlytwoentropicforces,anda2x2Onsager
phenomenologicalmatrix.Theexpressionforthelinearapproximationtothefluxesandtherateofentropy
productioncanveryoftenbeexpressedinananalogouswayformanymoregeneralandcomplicatedsystems.
Abstractformulation
Let
denotefluctuationsfromequilibriumvaluesinseveralthermodynamicquantities,andlet
betheentropy.Then,Boltzmann'sentropyformulagivesfortheprobabilitydistribution
function
,A=const,sincetheprobabilityofagivensetoffluctuations
is
proportionaltothenumberofmicrostateswiththatfluctuation.Assumingthefluctuationsaresmall,the
probabilitydistributionfunctioncanbeexpressedthroughtheseconddifferentialoftheentropy[6]
whereweareusingEinsteinsummationconventionand
isapositivedefinitesymmetricmatrix.
Usingthequasistationaryequilibriumapproximation,thatis,assumingthatthesystemisonlyslightlynon
equilibrium,wehave[6]
Supposewedefinethermodynamicconjugatequantitiesas
,whichcanalsobeexpressedaslinear
functions(forsmallfluctuations):
https://en.wikipedia.org/wiki/Onsager_reciprocal_relations
4/5
8/18/2016
OnsagerreciprocalrelationsWikipedia,thefreeencyclopedia
Thus,wecanwrite
where
arecalledkineticcoefficients
TheprincipleofsymmetryofkineticcoefficientsortheOnsager'sprinciplestatesthat isasymmetricmatrix,that
[6]
is
Proof
Definemeanvalues
values
at
and
offluctuatingquantities and
respectivelysuchthattheytakegiven
Notethat
Symmetryoffluctuationsundertimereversalimpliesthat
or,with
,wehave
Differentiatingwithrespectto andsubstituting,weget
Putting
intheaboveequation,
Itcanbeeasilyshownfromthedefinitionthat
,andhence,wehavetherequiredresult.
Seealso
LarsOnsager
Langevinequation
References
1.L.Onsager,ReciprocalRelationsinIrreversibleProcesses.I.,Phys.Rev.37,405426(1931)(http://prola.aps.org/abstra
ct/PR/v37/i4/p405_1)
2.D.G.Miller,Thermodynamicsofirreversibleprocesses.TheexperimentalverificationoftheOnsagerreciprocal
relations,Chem.Rev.60(1960),1537.
3.G.S.Yablonsky,A.N.Gorban,D.Constales,V.V.GalvitaandG.B.Marin,Reciprocalrelationsbetweenkineticcurves
(http://arxiv.org/pdf/1008.1056v2.pdf),EPL,93(2011)20004.
4.TheNobelPrizeinChemistry1968.PresentationSpeech.(http://nobelprize.org/nobel_prizes/chemistry/laureates/1968/pre
ss.html)
5.ForexampleRichardP.Wendt,JournalofChemicalEducationv.51,p.646(1974)"SmplifiedTransportTheoryfor
ElectrolyteSolutions"
6.Landau,L.D.Lifshitz,E.M.(1975).StatisticalPhysics,Part1.Oxford,UK:ButterworthHeinemann.ISBN97881
81477903.
Retrievedfrom"https://en.wikipedia.org/w/index.php?title=Onsager_reciprocal_relations&oldid=720689126"
Categories: Conceptsinphysics Lawsofthermodynamics Nonequilibriumthermodynamics
Thispagewaslastmodifiedon17May2016,at10:32.
TextisavailableundertheCreativeCommonsAttributionShareAlikeLicenseadditionaltermsmayapply.
Byusingthissite,youagreetotheTermsofUseandPrivacyPolicy.Wikipediaisaregisteredtrademark
oftheWikimediaFoundation,Inc.,anonprofitorganization.
https://en.wikipedia.org/wiki/Onsager_reciprocal_relations
5/5