1

SimpleAnalysisofHeatConductionin
IITKanpur Nobulkflow Gases(hardspheremodel)
Assumehomogeneousgasconsistingofrigid
nonattractingmolecules(hardspheres)
Temperaturegradientissufficientlysmall,
thatthetemperatureisessentiallylinearover
severalmeanfreepaths()
Theonlyenergystoragemodeismolecular
translation
xa x x+a Fromkinetictheoryofgases
T(xa) ~100nm molecule
~0.4nm diameter
T(x) [n]~1025
positive negative
meanfreepathistheaveragedistanceamolecule
T(x+a)
netdiffusion willtravelbeforecollidingwithanothermolecule
a a Avagadro number
xa x x+a
NA =6.02 1026 molecules/kmol idealgaslaw
Ru =8314J/kmolK molecules universal Boltzmann
kB =1.38 1023 J/K /m3 gasconstant constant
[ref]R.ByronBird,WarrenE.Stewart,EdwinN. Lightfoot,TransportPhenomena,Wiley,2007
 2

HeatConductioninGases(hardspheremodel)
IITKanpur distance,y

a a
xa x x+a
Fromkinetictheoryofgases
a

averageperpendiculardistancefromplaneof
lastcollisiontoplanewherenextcollisionoccurs

/ /
numberofmoleculescrossingx,
originatingfrom(xa),samefor
mean (x+a)(perunittimearea)
massofa molecular
molecular Note:nocollisionbetween(xa)or
molecule weight
speed (x+a)andx
 3

HeatConductioninGases (hardspheremodel)
netheatdiffusion
IITKanpur
T(xa) diffusion
T(x)
(+)ve ()ve
T(x+a)
a a
xa x x+a
Hardspheremodel:Onlyenergystorageistranslationalkineticenergy,norotationalor
vibrationalenergy(e.g.monoatomicgasesHe,Ar)(internalenergy=translationalkineticenergy)
meaninternalenergyofmolecules
heatflux originatingat(xa)plane

_ per molecule

_mass per kg

meantranslationalkinetic massspecificheat
energyofmolecules
 4

HeatConductioninGases(hardspheremodel)
IITKanpur

2 /
idealgaslaw

c
c

k,thermalconductivity
Fourierslawof
heatconduction
 5

ThermalConductivityofGases
Example Helium@273K: (hardspheremodel)
IITKanpur
k(tabulated)=0.141W/mK

~ =2.551 1010 m,0.2551nm

m=MW/NA =4/ 6.02 1026 =6.64 1027 kg
~ =1202m/s
[n]=2.69 1025 molecules/m3 (@1atm)
/
~ =1.286 107 m,128.6nm
=0.179kg/m3 Notethatintermolecularforces
c =3117.75J/kgK wereneglectedandfastermolecules
~ ~
(higherKE)crossaplanemore
smallvariation2.55A k(theory)=0.029W/mK frequentlythanslowerones
/ Forpolyatomicgases(alsohavingrotationalandvibrational

~ modesofenergystorage)similaranalysiscanbeusedwhere
themeanenergy(meaninternalenergypermolecule,U)is
independentofP considered:
increaseswithT
(U)xa =(U)x a and(U)x+a =(U)x +a (Taylorseriesexpansion)
higherforlowerMW
/ /
_ _
 6
MolecularCollisionModels
IITKanpur

attraction
repulsion r
Epot

Epot
r r

collision
collision

distance
distance

4
LennardJones(LJ)Model HardSpheremodel, canbe
takenfromLJtabulatedproperties

LJmodelapproximatesintermolecularinteraction
attractive ()ve
force=dEpot/dr
repulsive (+)ve
 7
PropertiesLJModel
IITKanpur

smallvariation

smallvariation
[ref]AnIntroductiontoCombustion ConceptsandApplicationsbyStephenR.Turns,ThirdEdition,TataMcGrawHill
NewDelhi,2012.
 ThermalConductivityofaSolid
IITKanpur
Solidiscomprisedofatomsboundinaperiodicarrangementcalledalatticeandfree
electrons
Transportofenergyismostlyduetotwoeffects:
1. Migrationoffreeelectrons
2. Latticevibrationalwaves(orsoundwaves),particlelikephenonmenon
phonons
Inpuremetals,theelectroncontributiontoheatconductiondominateswhileinnon
metalsthephononcontributiondominates
Similaranalysisasthatdoneforthegasesconsideringcarriers aselectronsorphonons

isthespecificheatcapacityperunitvolume(J/m3K)
meanspeedofthecarrier(m/s)
meanfreepathofthecarrier(m)

8
 ThermalConductivityofNonmetallic
IITKanpur Solids
Ininsulatingsolidstherearenofreeelectrons,theheatistransportedbyphonons
(carrier=phonon) ~constant

Atlowtemperature (T<0.1D,D =Debyetemperature)

Phononheatcapacity(perunitvolume):

~
Phononspeed(equaltothesoundvelocity):
~
Themeanfreepathofaphononislimitedby
scatteringfromtheboundariesofthe ~T3
specimen: ~ ,
[ref]TerrellL.Hill,AnIntroductionto
(scatteringbyotherphononsislimiteddue StatisticalThermodynamics,Dover,1986
toverylowphonondensity)
~
Notethatthisbehaviorismostlyapplicable
atverylowtemperatures<100Kfor
D =2200K(fordiamond) 9
 ThermalConductivityofNonmetallic
IITKanpur Solids
(carrier=phonon)
atmoderateandhightemperature (T~> D)
Phononheatcapacity(perunitvolume):

~ ,

3 (Dulong andPetitLaw)

Phononspeed(equaltothesoundvelocity):
~
Themeanfreepathofaphononislimitedby
scatteringfromotherphonons:
Numberdensityofphononisdirectlyproportional
totemperature: ~
~ , ~ ~ /
Theregularityofthelatticearrangementhasan
importanteffectonk(duetophonons)withcrystalline
(wellordered)materialslikequartzhavinghigherthermal
conductivitythanamorphousmaterialslikeglass
10
[ref]PhilipD.Thacher,EffectofBoundariesandIsotopesontheThermalConductivityofLiF,PhysicalReview,v156,1967
 ThermalConductivityofMetalsandAlloys
(impurityscattering)
IITKanpur

Inmetalsandalloys,theheatispredominantlytransportedbyfreeelectrons
(carrier=electrons)

Electronheatcapacity(perunitvolume):
~
Electronspeed(equaltotheFermivelocity): ~

Atverylowtemperature(T<<0.1D):numberdensityofphononsismuchlowerthanthe
numberdensityoftheimpurities impurityscatteringofelectronsispredominant,
scatteringoccursatspecimenboundaries,crystalfaults(dislocations,foreignatomssuch
asimpuritiesorcomponentsofalloys)
Themeanfreepathofaelectronsisessentiallylimitedbyscatteringfromtheimpurities:
~ , ,

Forimpurityscattering: ~
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[ref]F.Reif,FundamentalsofStatisticalandThermalPhysics,1965,McGrawHill
 ThermalConductivityofMetalsandAlloys
(phononscattering)
IITKanpur
(carrier=electrons)
Electronheatcapacity(perunitvolume):
~
Electronspeed(equaltotheFermivelocity): ~
Atlowtemperatures(T~0.1D):scatteringofelectronsbyphononsbecomes
predominant(electronelectronscatteringisinsignificant)
Themeanfreepathofaelectronsisessentiallylimitedbyscatteringfromthephonons:
~ ~ Forphononscattering: ~

Moregenerallyelectronsarescatteredindependently
bybothimpuritiesandphononsatthesametime
hence,thermalresistivity(reciprocalofthermal
conductivity)adds: ~ Highpurity
Forbothimpurityandphononscattering:
~ Lowpurity
Atmoderatetemperatures(T~D):
Themeanfreepathofaelectronsisessentially
limitedbyscatteringfromthephonons:
~ ~ ~ D (Li)=430K 12

 ThermalconductivityofSolids
IITKanpur

Electroncontribution
Phononcontribution

Forcrystallinenonmetallicsolidssuchasdiamondkphonon canbequitelarge(2300W/mK),
exceedingvaluesofkelectron associatedwithgoodconductorssuchasaluminum(202W/m
K)(canbeusedtodistinguishdiamondfromfakestones!)
Whenbothelectronsandphononscontributionareappreciablethentheircontributions
canbeadded(astheyoperateinparallel)andthethermalconductivitymaybeexpressed
as:
k=kelectron +kphonon
Temperaturedependenceofthermalconductivityofmetals,metalalloysandnonmetallic
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solidsiscomplicatedandforanumberofmaterialsauniformtrendisnotdisplayed
 ThermalConductivityofLiquids
IITKanpur
Bridgmanssimpletheory:
Moleculesarrangedincubiclatticewithcentertocenterspacing(1/[n])1/3,[n]isthe
numberofmoleculesperunitvolume,thisspacingisthecollisiondistance(~)
Energytobetransferredfromonelatticeplanetothenextatsonicvelocity(vs)oftheliquid
Developmentisbasedonreinterpretationofthehardspheregasmodel
,
3

_

/ a=(1/[n])1/3
3 Bridgmansequation

ismeanmolecularspeedinxdirectionandistakenasthesonicspeed(vs)
aisthethe distancethatenergytravelsbetweentwosuccessivecollisionswhichistaken
asthelatticespacinga
Velocityoflowfrequency Canbeobtainedfrom
soundcanbeshowntobe: isothermalcompresibility:
_ _ 1
_ _
Forliquidmetalsthecontributionfromfreeelectrontransportissignificantandthermal
conductivityisconsiderablehigherascomparedtononmetallicliquids 14
[ref]R.ByronBird,WarrenE.Stewart,EdwinN. Lightfoot,TransportPhenomena,Wiley,2007
 Thermalconductivity
[ref]F.P.Incropera,2013
IITKanpur

@STP

Experimentalmeasurementsmaybemadetodeterminethermalconductivity
Forgasesthermalconductivitymaybepredictedusingkinetictheory,forliquids
andsolidsalsotheoriesareavailabletopredictthermalconductivity,however,
theyarecomplicatedandmanyopenquestionsstillremain
ksilver =410W/mK,kco2 =0.0146W/mK,kdiamond =2300W/mK(@0C)
Generally:ksolid >kliquid >kgas (mainlyduetodifferenceinintermolecularspacing)
Generally:kmetal >knonmetal (duetoavailabilityoffreeelectronsinmetals)
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 Thermalconductivity
k=k0(1+T), isgenerallysmallandnegativefor
mostsolidsandliquidsandispositiveforgases
IITKanpur
[ref]F.P.Incropera,2013

Solids Liquids(nonmetallic),saturatedcondition Gases(normalpressure)

Thermalconductivityofgasesincreaseswithincreaseintemperatureandishigherforlighter
molecules,itisindependentofpressure
Thermalconductivityofnonmetallicliquidsandsolidsmayincreasebutmostlydecreaseor
remainssamewithtemperature
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