7/15/2016

Entropy of a Gas

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Thermodynamicsisabranchofphysicsthatdealswiththeenergyandworkofasystem.Inaerodynamics,wearemost
interestedinthermodynamicsinthestudyofpropulsionsystemsandunderstandinghighspeedflows.Thefirstlawof
thermodynamicsindicatesthatthetotalenergyofasystemisconserved.Totalenergyincludesthepotentialandkinetic
energy,theworkdonebythesystem,andthetransferofheatthroughthesystem.Thesecondlawofthermodynamics
indicatesthat,whilemanyphysicalprocessesthatsatisfythefirstlawarepossible,theonlyprocessesthatoccurinnature
arethoseforwhichtheentropyofthesystemeitherremainsconstantorincreases.
Entropy,liketemperatureandpressure,canbeexplainedonbothamacroscaleandamicroscale.Sincethermodynamics
dealsonlywiththemacroscale,thechangeinentropydeltaSisdefinedheretobetheheattransferdeltaQintothe
systemdividedbythetemperatureT:
deltaS=deltaQ/T
Duringathermodynamicprocess,thetemperatureTofanobjectchangesasheatQisappliedorextracted.Amorecorrect
definitionoftheentropySisthedifferentialformthataccountsforthisvariation.
dS=dQ/T
Thechangeinentropyisthentheinverseofthetemperatureintegratedoverthechangeinheattransfer.Forgases,there
aretwopossiblewaystoevaluatethechangeinentropy.Webeginbyusingthefirstlawofthermodynamics:
dE=dQdW
whereEistheinternalenergyandWistheworkdonebythesystem.Substitutingforthedefinitionofworkforagas.
dQ=dE+pdV
wherepisthepressureandVisthevolumeofthegas.IfweusethedefinitionoftheenthalpyHofagas:
H=E+p*V
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7/15/2016

Entropy of a Gas

Then:
dH=dE+pdV+Vdp
Substituteintothefirstlawequation:
dQ=dHVdppdV+pdV
dQ=dHVdp
isanalternatewaytopresentthefirstlawofthermodynamics.Foranidealgas,theequationofstateiswritten:
p*V=R*T
whereRisthegasconstant.Theheattransferofagasisequaltotheheatcapacitytimesthechangeintemperaturein
differentialform:
dQ=C*dT
Ifwehaveaconstantvolumeprocess,theformulationofthefirstlawgives:
dE=dQ=C(constantvolume)*dT
Similarly,foraconstantpressureprocess,theformulationofthefirstlawgives:
dH=dQ=C(constantpressure)*dT
Ifweassumethattheheatcapacityisconstantwithtemperature,wecanusethesetwoequationstodefinethechangein
enthalpyandinternalenergy.Ifwesubstitutethevalueforpfromtheequationofstate,andthedefinitionofdEinthefirst
energyequation,weobtain:
dQ=C(constantvolume)*dT+R*TdV/V
SimilarlysubstitutingthevalueofVfromtheequationofstate,andthedefinitionofdHweobtainthealternateform:
dQ=C(constantpressure)*dTR*Tdp/p
SubstitutingtheseformsfordQintothedifferentialformoftheentropyequationgives::
dS=C(constantvolume)*dT/T+R*dV/V
and
dS=C(constantpressure)*dT/TR*dp/p
Theseequationscanbeintegratedfromcondition"1"tocondition"2"togive:
S2S1=Cv*ln(T2/T1)+R*ln(V2/V1)
and
S2S1=Cp*ln(T2/T1)R*ln(p2/p1)
whereCvistheheatcapacityatconstantvolume,Cpistheheatcapacityatconstantpressure,andlnisthesymbolforthe
logarithmicfunction.
Ifwedividebothequationsbythemassofgas,wecanobtainintrinsic,or"specific"formsofbothequations:
s2s1=cv*ln(T2/T1)+R*ln(v2/v1)
and
s2s1=cp*ln(T2/T1)R*ln(p2/p1)
wherecpandcvarethespecificheatcapacities.Dependingonthetypeofprocessweencounter,wecannowdetermine
thechangeinentropyforagas.
Theseequationscanbeabitconfusing,becauseweusethespecificheatatconstantvolumewhenwehaveaprocessthat
changesvolume,andthespecificheatatconstantpressurewhentheprocesschangespressure.Toclarifymatters,let'slook
atthefirstequation:
s2s1=cv*ln(T2/T1)+R*ln(v2/v1)
Ifwehaveaconstantvolumeprocess,thesecondtermintheequationisequaltozero,sincev2/v1=1.Wecanthen
determinethevalueofthespecificheatfortheconstantvolumeprocess.Butifwehaveaprocessthatchangesvolume,the
secondtermintheequationisnotzero.Wecanthinkofthefirsttermoftheequationasthecontributionforaconstant
volumeprocess,andthesecondtermastheadditionalchangeproducedbythechangeinvolume.Asimilartypeof
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