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Ideal gas law - Wikipedia, the free encyclopedia

Idealgaslaw
FromWikipedia,thefreeencyclopedia

Theidealgaslawistheequationofstateofahypotheticalidealgas.
Itisagoodapproximationtothebehaviorofmanygasesundermany
conditions,althoughithasseverallimitations.Itwasfirststatedby
mileClapeyronin1834asacombinationofBoyle'slaw,Charles's
lawandAvogadro'sLaw.[1]Theidealgaslawisoftenwrittenas:

wherethelettersdenotepressure,volume,amount(inmoles),ideal
gasconstant,andtemperatureofthegas,respectively.
Itcanalsobederivedmicroscopicallyfromkinetictheory,aswas
achieved(apparentlyindependently)byAugustKrnigin1856[2]
andRudolfClausiusin1857.[3]

Contents
1Equation
1.1Commonform
1.2Molarform
1.3Statisticalmechanics
2Applicationstothermodynamicprocesses
3Deviationsfromidealbehaviorofrealgases
4Derivations
4.1Empirical
4.2Theoretical
4.2.1Kinetictheory
4.2.2Statisticalmechanics
5Seealso
6References
7Furtherreading
8Externallinks

Isothermsofanidealgas.Thecurved
linesrepresenttherelationship
betweenpressure(onthevertical,y
axis)andvolume(onthehorizontal,
xaxis)foranidealgasatdifferent
temperatures:lineswhicharefurther
awayfromtheorigin(thatis,lines
thatarenearertothetoprighthand
cornerofthediagram)represent
highertemperatures.

Equation

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Thestateofanamountofgasisdeterminedbyitspressure,volume,andtemperature.Themodernformofthe
equationrelatesthesesimplyintwomainforms.Thetemperatureusedintheequationofstateisanabsolute
temperature:intheSIsystemofunits,Kelvin.[4]

Commonform
Themostfrequentlyintroducedformis

where:
Pisthepressureofthegas
Visthevolumeofthegas
nistheamountofsubstanceofgas(alsoknownasnumberofmoles)
Ristheideal,oruniversal,gasconstant,equaltotheproductoftheBoltzmannconstantandtheAvogadro
constant.
Tisthetemperatureofthegas
InSIunits,Pismeasuredinpascals,Vismeasuredincubicmetres,nismeasuredinmoles,andTinKelvin
(TheKelvinscaleisashiftedCelsiusscalewhere0.00Kelvin=273.15degreesCelsius,thelowestpossible
temperature).Rhasthevalue8.314JK1mol1or0.08206Latmmol1K1or2caloriesifusingpressure
instandardatmospheres(atm)insteadofpascals,andvolumeinlitresinsteadofcubicmetres.

Molarform
Howmuchgasispresentcouldbespecifiedbygivingthemassinsteadofthechemicalamountofgas.
Therefore,analternativeformoftheidealgaslawmaybeuseful.Thechemicalamount(n)(inmoles)isequal
tothemass(m)(ingrams)dividedbythemolarmass(M)(ingramspermole):

Byreplacingnwithm/M,andsubsequentlyintroducingdensity=m/V,weget:

DefiningthespecificgasconstantRspecificastheratioR/M,

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Thisformoftheidealgaslawisveryusefulbecauseitlinkspressure,density,andtemperatureinaunique
formulaindependentofthequantityoftheconsideredgas.Alternatively,thelawmaybewrittenintermsof
thespecificvolumev,thereciprocalofdensity,as

Itiscommon,especiallyinengineeringapplications,torepresentthespecificgasconstantbythesymbolR.In
suchcases,theuniversalgasconstantisusuallygivenadifferentsymbolsuchasRtodistinguishit.Inany
case,thecontextand/orunitsofthegasconstantshouldmakeitclearastowhethertheuniversalorspecific
gasconstantisbeingreferredto.[5]

Statisticalmechanics
Instatisticalmechanicsthefollowingmolecularequationisderivedfromfirstprinciples:

wherePistheabsolutepressureofthegasmeasuredinPascalsNisthenumberofmoleculesinthegiven
volumeV.ThenumberdensityisgivenbytheratioN/V.numberdensityinthegasmeasuredin1/(meters
cubed)kBistheBoltzmannconstantrelatingtemperatureandenergyandTistheabsolutetemperature.
Thenumberdensitycontraststotheotherformulation,whichusesn,thenumberofmolesandV,thevolume.
ThisrelationimpliesthatR=NAkBwhereNAisAvogadro'sconstant,andtheconsistencyofthisresultwith
experimentisagoodcheckontheprinciplesofstatisticalmechanics.
Fromthiswecannoticethatforanaverageparticlemassoftimestheatomicmassconstantmu(i.e.,the
massisu)

andsince=mn,wefindthattheidealgaslawcanberewrittenas:

InSIunits,PismeasuredinpascalsVincubicmetresYisadimensionlessnumberandTinKelvin.khas
thevalue1.381023JK1inSIunits.

Applicationstothermodynamicprocesses
Thetablebelowessentiallysimplifiestheidealgasequationforaparticularprocesses,thusmakingthis
equationeasiertosolveusingnumericalmethods.

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Athermodynamicprocessisdefinedasasystemthatmovesfromstate1tostate2,wherethestatenumberis
denotedbysubscript.Asshowninthefirstcolumnofthetable,basicthermodynamicprocessesaredefined
suchthatoneofthegasproperties(P,V,T,orS)isconstantthroughouttheprocess.
Foragiventhermodynamicsprocess,inordertospecifytheextentofaparticularprocess,oneofthe
propertiesratios(whicharelistedunderthecolumnlabeled"knownratio")mustbespecified(eitherdirectly
orindirectly).Also,thepropertyforwhichtheratioisknownmustbedistinctfromthepropertyheldconstant
inthepreviouscolumn(otherwisetheratiowouldbeunity,andnotenoughinformationwouldbeavailableto
simplifythegaslawequation).
Inthefinalthreecolumns,theproperties(P,V,orT)atstate2canbecalculatedfromthepropertiesatstate1
usingtheequationslisted.
Process
Isobaricprocess
Isochoricprocess
(Isovolumetricprocess)
(Isometricprocess)
Isothermalprocess

Isentropicprocess
(Reversibleadiabatic
process)

Constant
Pressure

Volume

Temperature

Entropy[a]

Known
ratio

PVn

T2

P2=P1

V2=V1(V2/V1)

T2=T1(V2/V1)

T2/T1

P2=P1

V2=V1(T2/T1)

T2=T1(T2/T1)

P2/P1

P2=P1(P2/P1)

V2=V1

T2=T1(P2/P1)

T2/T1

P2=P1(T2/T1)

V2=V1

T2=T1(T2/T1)

P2/P1

P2=P1(P2/P1)

V2=V1/(P2/P1)

T2=T1

V2/V1

P2=P1/(V2/V1) V2=V1(V2/V1)

T2=T1

P2/P1

P2=P1(P2/P1)

V2/V1

P2=P1(V2/V1)

V2=V1(V2/V1)

P2=

V2=

V2=V1(P2/P1)
(1/)

P1(T2/T1)/(1) V1(T2/T1)1/(1)
V2=V1(P2/P1)

P2/P1

P2=P1(P2/P1)

V2/V1

P2=P1(V2/V1)n V2=V1(V2/V1)

T2/T1

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V2

V2/V1

T2/T1

Polytropicprocess

P2

P2=

(1/n)

V2=

P1(T2/T1)n/(n1) V1(T2/T1)1/(1n)

T2=T1(P2/P1)(
1)/

T2=T1(V2/V1)(1
)

T2=T1(T2/T1)
T2=T1(P2/P1)(n
1)/n

T2=T1(V2/V1)
(1n)

T2=T1(T2/T1)

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^a.Inanisentropicprocess,systementropy(S)isconstant.Undertheseconditions,P

1V1 =P2V2 ,where

isdefinedastheheatcapacityratio,whichisconstantforacalorificallyperfectgas.Thevalueusedforis
typically1.4fordiatomicgaseslikenitrogen(N2)andoxygen(O2),(andair,whichis99%diatomic).Also
istypically1.6formonatomicgaseslikethenoblegaseshelium(He),andargon(Ar).Ininternalcombustion
enginesvariesbetween1.35and1.15,dependingonconstitutiongasesandtemperature.

Deviationsfromidealbehaviorofrealgases
Theequationofstategivenhereappliesonlytoanidealgas,orasanapproximationtoarealgasthatbehaves
sufficientlylikeanidealgas.Thereareinfactmanydifferentformsoftheequationofstate.Sincetheideal
gaslawneglectsbothmolecularsizeandintermolecularattractions,itismostaccurateformonatomicgasesat
hightemperaturesandlowpressures.Theneglectofmolecularsizebecomeslessimportantforlower
densities,i.e.forlargervolumesatlowerpressures,becausetheaveragedistancebetweenadjacentmolecules
becomesmuchlargerthanthemolecularsize.Therelativeimportanceofintermolecularattractionsdiminishes
withincreasingthermalkineticenergy,i.e.,withincreasingtemperatures.Moredetailedequationsofstate,
suchasthevanderWaalsequation,accountfordeviationsfromidealitycausedbymolecularsizeand
intermolecularforces.
Aresidualpropertyisdefinedasthedifferencebetweenarealgaspropertyandanidealgasproperty,both
consideredatthesamepressure,temperature,andcomposition.

Derivations
Empirical
Theidealgaslawcanbederivedfromcombiningtwoempiricalgaslaws:thecombinedgaslawand
Avogadro'slaw.Thecombinedgaslawstatethat

whereCisaconstantwhichisdirectlyproportionaltotheamountofgas,n(Avogadro'slaw).The
proportionalityfactoristheuniversalgasconstant,R,i.e.C=nR.
Hencetheidealgaslaw

Theoretical
Kinetictheory
Mainarticle:kinetictheory

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Theidealgaslawcanalsobederivedfromfirstprinciplesusingthekinetictheoryofgases,inwhichseveral
simplifyingassumptionsaremade,chiefamongwhicharethatthemolecules,oratoms,ofthegasarepoint
masses,possessingmassbutnosignificantvolume,andundergoonlyelasticcollisionswitheachotherand
thesidesofthecontainerinwhichbothlinearmomentumandkineticenergyareconserved.
Statisticalmechanics
Mainarticle:Statisticalmechanics
Letq=(qx,qy,qz)andp=(px,py,pz)denotethepositionvectorandmomentumvectorofaparticleofan
idealgas,respectively.LetFdenotethenetforceonthatparticle.Thenthetimeaveragedpotentialenergyof
theparticleis:

wherethefirstequalityisNewton'ssecondlaw,andthesecondlineusesHamilton'sequationsandthe
equipartitiontheorem.SummingoverasystemofNparticlesyields

ByNewton'sthirdlawandtheidealgasassumption,thenetforceofthesystemistheforceappliedbythe
wallsofthecontainer,andthisforceisgivenbythepressurePofthegas.Hence

wheredSistheinfinitesimalareaelementalongthewallsofthecontainer.Sincethedivergenceofthe
positionvectorqis

thedivergencetheoremimpliesthat

wheredVisaninfinitesimalvolumewithinthecontainerandVisthetotalvolumeofthecontainer.

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Puttingtheseequalitiestogetheryields

whichimmediatelyimpliestheidealgaslawforNparticles:

wheren=N/NAisthenumberofmolesofgasandR=NAkBisthegasconstant.

Seealso
Combinedgaslaw
VanderWaalsequation
Boltzmannconstant
Configurationintegral
Dynamicpressure
Internalenergy

References
1. Clapeyron,E(1834)."Mmoiresurlapuissancemotricedelachaleur".Journaldel'colePolytechnique(in
French) XIV:15390.FacsimileattheBibliothquenationaledeFrance(pp.15390).
(http://gallica.bnf.fr/ark:/12148/bpt6k4336791/f157.table)
2. Krnig,A.(1856)."GrundzgeeinerTheoriederGase".AnnalenderPhysikundChemie(inGerman) 99(10):
31522.Bibcode:1856AnP...175..315K.doi:10.1002/andp.18561751008.FacsimileattheBibliothquenationale
deFrance(pp.31522).(http://gallica.bnf.fr/ark:/12148/bpt6k15184h/f327.table)
3. Clausius,R.(1857)."UeberdieArtderBewegung,welchewirWrmenennen".AnnalenderPhysikundChemie
(inGerman) 176(3):35379.Bibcode:1857AnP...176..353C.doi:10.1002/andp.18571760302.Facsimileatthe
BibliothquenationaledeFrance(pp.35379).(http://gallica.bnf.fr/ark:/12148/bpt6k15185v/f371.table)
4. "EquationofState".
5. MoranandShapiro,FundamentalsofEngineeringThermodynamics,Wiley,4thEd,2000

Furtherreading
DavisandMastenPrinciplesofEnvironmentalEngineeringandScience,McGrawHillCompanies,
Inc.NewYork(2002)ISBN0072350539
Websitegivingcreditto(http://www.gearseds.com/curriculum/learn/lesson.php?id=23&chapterid=5)
BenotPaulmileClapeyron,(17991864)in1834

Externallinks

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Configurationintegral(statisticalmechanics)
(http://clesm.mae.ufl.edu/wiki.pub/index.php/Configuration_integral_%28statistical_mechanics%29)
whereanalternativestatisticalmechanicsderivationoftheidealgaslaw,usingtherelationshipbetween
theHelmholtzfreeenergyandthepartitionfunction,butwithoutusingtheequipartitiontheorem,is
provided.
OnlineIdealGaslawCalculator(http://easycalci.com/idealgaslawcalculator/)
Retrievedfrom"https://en.wikipedia.org/w/index.php?title=Ideal_gas_law&oldid=682991801"
Categories: Gaslaws Idealgas Equationsofstate
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