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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
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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

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istheheatfluxvector.

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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,

wheretheentropic"thermodynamicforces"conjugatetothe"displacements" and are


and
istheOnsagermatrixofphenomenologicalcoefficients.

and

Therateofentropyproduction
Fromthefundamentalequation,itfollowsthat:

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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):
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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.

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