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HeatcapacityratioWikipedia,thefreeencyclopedia

Heatcapacityratio
FromWikipedia,thefreeencyclopedia

Inthermalphysicsandthermodynamics,
theheatcapacityratiooradiabatic
indexorratioofspecificheatsor
Poissonconstant,istheratiooftheheat
capacityatconstantpressure( )toheat
capacityatconstantvolume( ).Itis
sometimesalsoknownastheisentropic
expansionfactorandisdenotedby
(gamma)(foridealgas)or (kappa)
(isentropicexponent,forrealgas).The
formersymbolgammaisprimarilyused
bychemicalengineers.Mechanical
engineersusetheRomanletter .[3]

HeatCapacityRatioforvariousgases[1][2]
Temp.

Gas

181C

H2

Temp.

Gas

Temp. Gas

1.597 200C DryAir 1.398 20C

NO 1.400

76C

1.453 400C

1.393 20C

N2O 1.310

20C

1.410 1000C

1.365 181C N2 1.470

100C

1.404 2000C

1.088 15C

1.404

400C

1.387 0C

CO2 1.310 20C

Cl2 1.340

1000C

1.358 20C

1.300 115C CH4 1.410

2000C

1.318 100C

1.281 74C

1.350

1.660 400C

1.235 20C

1.320

1.195 15C

NH3 1.310

20C
20C

where, istheheatcapacityand the

specificheatcapacity(heatcapacityper
unitmass)ofagas.Suffix and refer
toconstantpressureandconstantvolume
conditionsrespectively.

He

H2O 1.330 1000C

100C

1.324 20C

CO

1.400 19C

Ne 1.640

200C

1.310 181C

O2

1.450 19C

Xe 1.660

1.760 76C

1.415 19C

Kr 1.680

1.670 20C

1.400 15C

SO2 1.290

1.399 360C

Hg 1.670

180C
20C
0C

Ar

DryAir 1.403 100C

20C

1.400 200C

1.397 15C

C2H6 1.220

100C

1.401 400C

1.394 16C

C3H8 1.130

Tounderstandthisrelation,considerthe
followingthoughtexperiment.Aclosedpneumaticcylindercontainsair.Thepistonislocked.Thepressure
insideisequaltoatmosphericpressure.Thiscylinderisheatedtoacertaintargettemperature.Sincethe
pistoncannotmove,thevolumeisconstant.Thetemperatureandpressurewillrise.Whenthetarget
temperatureisreached,theheatingisstopped.Theamountofenergyaddedequals:
,with
representingthechangeintemperature.Thepistonisnowfreedandmovesoutwards,stoppingasthe
pressureinsidethechamberequilibratestoatmosphericpressure.Wearefreetoassumetheexpansion
happensfastenoughtooccurwithoutexchangeofheat(adiabaticexpansion).Doingthiswork,airinside
thecylinderwillcooltobelowthetargettemperature.Toreturntothetargettemperature(stillwithafree
piston),theairmustbeheated.Thisextraheatamountstoabout40%morethanthepreviousamountadded.
Inthisexample,theamountofheataddedwithalockedpistonisproportionalto ,whereasthetotal
amountofheataddedisproportionalto .Therefore,theheatcapacityratiointhisexampleis1.4.
Anotherwayofunderstandingthedifferencebetween
and isthat appliesifworkisdonetothe
systemwhichcausesachangeinvolume(e.g.bymovingapistonsoastocompressthecontentsofa
cylinder),orifworkisdonebythesystemwhichchangesitstemperature(e.g.heatingthegasinacylinder
tocauseapistontomove).
appliesonlyif
thatis,theworkdoneiszero.Considerthe
differencebetweenaddingheattothegaswithalockedpiston,andaddingheatwithapistonfreetomove,
sothatpressureremainsconstant.Inthesecondcase,thegaswillbothheatandexpand,causingthepiston
todomechanicalworkontheatmosphere.Theheatthatisaddedtothegasgoesonlypartlyintoheatingthe
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gas,whiletherestistransformedintothemechanicalworkperformedbythepiston.Inthefirst,constant
volumecase(lockedpiston)thereisnoexternalmotion,andthusnomechanicalworkisdoneonthe
atmosphere isused.Inthesecondcase,additionalworkisdoneasthevolumechanges,sotheamount
ofheatrequiredtoraisethegastemperature(thespecificheatcapacity)ishigherforthisconstantpressure
case.

Contents
1Idealgasrelations
1.1Relationwithdegreesoffreedom
2Realgasrelations
3Thermodynamicexpressions
4Adiabaticprocess
5Seealso
6References

Idealgasrelations
Foranidealgas,theheatcapacityisconstantwithtemperature.Accordinglywecanexpresstheenthalpyas
andtheinternalenergyas
.Thus,itcanalsobesaidthattheheatcapacityratiois
theratiobetweentheenthalpytotheinternalenergy:

Furthermore,theheatcapacitiescanbeexpressedintermsofheatcapacityratio( )andthegasconstant(
):
,
where istheamountofsubstanceinmoles.
Itcanberatherdifficulttofindtabulatedinformationfor
followingrelation,canbeusedtodetermine :

,since

ismorecommonlytabulated.The

Relationwithdegreesoffreedom
Theheatcapacityratio( )foranidealgascanberelatedtothedegreesoffreedom( )ofamoleculeby:

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Thusweobservethatforamonatomicgas,withthreedegreesoffreedom:
,
whileforadiatomicgas,withfivedegreesoffreedom(atroomtemperature:threetranslationalandtwo
rotationaldegreesoffreedomthevibrationaldegreeoffreedomisnotinvolvedexceptathigh
temperatures):
.
E.g.:Theterrestrialairisprimarilymadeupofdiatomicgases(~78%nitrogen(N2)and~21%oxygen(O2))
andatstandardconditionsitcanbeconsideredtobeanidealgas.Theabovevalueof1.4ishighly
consistentwiththemeasuredadiabaticindicesfordryairwithinatemperaturerangeof0to200C,
exhibitingadeviationofonly0.2%(seetablationabove).

Realgasrelations
Astemperatureincreases,higherenergyrotationalandvibrationalstatesbecomeaccessibletomolecular
gases,thusincreasingthenumberofdegreesoffreedomandlowering .Forarealgas,both and
increasewithincreasingtemperature,whilecontinuingtodifferfromeachotherbyafixedconstant(as
above, =
)whichreflectstherelativelyconstant
differenceinworkdoneduring
expansion,forconstantpressurevs.constantvolumeconditions.Thus,theratioofthetwovalues, ,
decreaseswithincreasingtemperature.Formoreinformationonmechanismsforstoringheatingases,see
thegassectionofspecificheatcapacity.

Thermodynamicexpressions
Valuesbasedonapproximations(particularly
)areinmanycasesnotsufficiently
accurateforpracticalengineeringcalculationssuchasflowratesthroughpipesandvalves.Anexperimental
valueshouldbeusedratherthanonebasedonthisapproximation,wherepossible.Arigorousvalueforthe
ratio

canalsobecalculatedbydetermining

fromtheresidualpropertiesexpressedas:

Valuesfor arereadilyavailableandrecorded,butvaluesfor
needtobedeterminedviarelations
suchasthese.Seehereforthederivationofthethermodynamicrelationsbetweentheheatcapacities.
Theabovedefinitionistheapproachusedtodeveloprigorousexpressionsfromequationsofstate(suchas
PengRobinson),whichmatchexperimentalvaluessocloselythatthereislittleneedtodevelopadatabase
ofratiosor
values.Valuescanalsobedeterminedthroughfinitedifferenceapproximation.
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Adiabaticprocess
Seealso:Adiabaticprocessandpolytropicprocess
Thisratiogivestheimportantrelationforanisentropic(quasistatic,reversible,adiabaticprocess)processof
asimplecompressiblecaloricallyperfectidealgas:

where isthepressureand isthevolume.

Seealso
Heatcapacity
Specificheatcapacity
Speedofsound
Thermodynamicequations
Thermodynamics
Volumetricheatcapacity

References
1. White,FrankM.:FluidMechanics4thed.McGrawHill
2. Lange'sHandbookofChemistry,10thed.page1524
3. Fox,R.,A.McDonald,P.Pritchard:IntroductiontoFluidMechanics6thed.Wiley

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