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MaxwellBoltzmanndistributionWikipedia,thefreeencyclopedia

MaxwellBoltzmanndistribution
FromWikipedia,thefreeencyclopedia

InstatisticstheMaxwellBoltzmanndistributionisa
particularprobabilitydistributionnamedafterJames
ClerkMaxwellandLudwigBoltzmann.Itwasfirst
definedandusedinphysics(inparticularinstatistical
mechanics)fordescribingparticlespeedsinidealized
gaseswheretheparticlesmovefreelyinsidea
stationarycontainerwithoutinteractingwithone
another,exceptforverybriefcollisionsinwhichthey
exchangeenergyandmomentumwitheachotheror
withtheirthermalenvironment.Particleinthiscontext
referstogaseousparticles(atomsormolecules),and
thesystemofparticlesisassumedtohavereached
thermodynamicequilibrium.[1]Whilethedistribution
wasfirstderivedbyMaxwellin1860onheuristic
grounds,[2]Boltzmannlatercarriedoutsignificant
investigationsintothephysicaloriginsofthis
distribution.

MaxwellBoltzmann
Probabilitydensityfunction

Aparticlespeedprobabilitydistributionindicates
whichspeedsaremorelikely:aparticlewillhavea
speedselectedrandomlyfromthedistribution,andis
morelikelytobewithinonerangeofspeedsthan
another.Thedistributiondependsonthetemperature
ofthesystemandthemassoftheparticle.[3]The
MaxwellBoltzmanndistributionappliestothe
classicalidealgas,whichisanidealizationofreal
gases.Inrealgases,therearevariouseffects(e.g.,van
derWaalsinteractions,vorticalflow,relativisticspeed
limits,andquantumexchangeinteractions)thatmake
theirspeeddistributionsometimesverydifferentfrom
theMaxwellBoltzmannform.However,rarefied
gasesatordinarytemperaturesbehaveverynearlylike
anidealgasandtheMaxwellspeeddistributionisan
excellentapproximationforsuchgases.Thus,itforms
thebasisofthekinetictheoryofgases,whichprovides
asimplifiedexplanationofmanyfundamentalgaseous
properties,includingpressureanddiffusion.[4]

Cumulativedistributionfunction

Parameters

Contents
1 Distributionfunction

Support
PDF

CDF

2 Typicalspeeds
whereerfistheerrorfunction

3 Derivationandrelateddistributions
Mean
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3.1 Distributionforthemomentum
vector
3.2 Distributionfortheenergy

Mode

3.3 Distributionforthevelocityvector

Variance

4 Seealso

Skewness

5 References
6 Furtherreading

Ex.
kurtosis

7 Externallinks

Entropy

Distributionfunction
TheMaxwellBoltzmanndistributionisthe
function

where istheparticlemassand isthe

productofBoltzmann'sconstantand
thermodynamictemperature.
Thisprobabilitydensityfunctiongivesthe
probability,perunitspeed,offindingthe
particlewithaspeednear .Thisequationis
simplytheMaxwelldistribution(giveninthe
infobox)withdistributionparameter
.Inprobabilitytheorythe
MaxwellBoltzmanndistributionisachi
distributionwiththreedegreesoffreedomand
scaleparameter
.

Thespeedprobabilitydensityfunctionsofthespeedsofafew
noblegasesatatemperatureof298.15K(25C).Theyaxis
isins/msothattheareaunderanysectionofthecurve(which
representstheprobabilityofthespeedbeinginthatrange)is
dimensionless.

Thesimplestordinarydifferentialequationsatisfiedbythedistributionis:

orinunitlesspresentation:

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Typicalspeeds
Themeanspeed,mostprobablespeed(mode),androotmeansquarecanbeobtainedfrompropertiesofthe
Maxwelldistribution.
Themostprobablespeed,vp,isthespeedmostlikelytobepossessedbyanymolecule(ofthesame
massm)inthesystemandcorrespondstothemaximumvalueormodeoff(v).Tofindit,wecalculate
thederivativedf/dv,setittozeroandsolveforv:

whichyields:

whereRisthegasconstantandM=NAmisthemolarmassofthesubstance.
Fordiatomicnitrogen(N2,theprimarycomponentofair)atroomtemperature(300K),thisgives
m/s
Themeanspeedistheexpectedvalueofthespeeddistribution

Therootmeansquarespeedisthesecondordermomentofspeed:

Thetypicalspeedsarerelatedasfollows:

Derivationandrelateddistributions
Theoriginalderivationin1860byJamesClerkMaxwellwasanargumentbasedondemandingcertain
symmetriesinthespeeddistributionfunction.[2]AfterMaxwell,LudwigBoltzmannin1872derivedthe
distributiononmoremechanicalgroundsbyusingtheassumptionsofhiskinetictheory,andshowedthat
gasesshouldovertimetendtowardthisdistribution,duetocollisions(seeHtheorem).Helater(1877)
derivedthedistributionagainundertheframeworkofstatisticalthermodynamics.Thederivationsinthis
sectionarealongthelinesofBoltzmann's1877derivation,startingwithresultknownasMaxwell
Boltzmannstatistics(fromstatisticalthermodynamics).MaxwellBoltzmannstatisticsgivestheaverage
numberofparticlesfoundinagivensingleparticlemicrostate,undercertainassumptions:[1][5]

(1)

where:
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iandjareindices(orlabels)ofthesingleparticlemicrostates,
Niistheaveragenumberofparticlesinthesingleparticlemicrostatei,
Nisthetotalnumberofparticlesinthesystem,
Eiistheenergyofmicrostatei,
Tistheequilibriumtemperatureofthesystem,
kistheBoltzmannconstant.
Theassumptionsofthisequationarethattheparticlesdonotinteract,andthattheyareclassicalthismeans
thateachparticle'sstatecanbeconsideredindependentlyfromtheotherparticles'states.Additionally,the
particlesareassumedtobeinthermalequilibrium.ThedenominatorinEquation(1)issimplyanormalizing
factorsothattheNi/Naddupto1inotherwordsitisakindofpartitionfunction(forthesingleparticle
system,nottheusualpartitionfunctionoftheentiresystem).
Becausevelocityandspeedarerelatedtoenergy,Equation(1)canbeusedtoderiverelationshipsbetween
temperatureandthespeedsofgasparticles.Allthatisneededistodiscoverthedensityofmicrostatesin
energy,whichisdeterminedbydividingupmomentumspaceintoequalsizedregions.

Distributionforthemomentumvector
Thepotentialenergyistakentobezero,sothatallenergyisintheformofkineticenergy.Therelationship
betweenkineticenergyandmomentumformassivenonrelativisticparticlesis

(2)

wherep2isthesquareofthemomentumvectorp=[px,py,pz].WemaythereforerewriteEquation(1)as:

(3)

whereZisthepartitionfunction,correspondingtothedenominatorinEquation(1).Heremisthemolecular
massofthegas,TisthethermodynamictemperatureandkistheBoltzmannconstant.Thisdistributionof
Ni/Nisproportionaltotheprobabilitydensityfunctionfpforfindingamoleculewiththesevaluesof
momentumcomponents,so:

(4)

Thenormalizingconstantc,canbedeterminedbyrecognizingthattheprobabilityofamoleculehavingsome
momentummustbe1.Thereforetheintegralofequation(4)overallpx,py,andpzmustbe1.
Itcanbeshownthat:

(5)

SubstitutingEquation(5)intoEquation(4)gives:

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(6)

Thedistributionisseentobetheproductofthreeindependentnormallydistributedvariables , ,and ,
withvariance
.Additionally,itcanbeseenthatthemagnitudeofmomentumwillbedistributedasa
MaxwellBoltzmanndistribution,with
.TheMaxwellBoltzmanndistributionforthe
momentum(orequallyforthevelocities)canbeobtainedmorefundamentallyusingtheHtheoremat
equilibriumwithinthekinetictheoryframework.

Distributionfortheenergy
Theenergydistributionisfoundimposing

(7)

where
istheinfinitesimalphasespacevolumeofmomentacorrespondingtotheenergyinterval
.
Makinguseofthesphericalsymmetryoftheenergymomentumdispersionrelation
,this
canbeexpressedintermsof
as

(8)

Usingthen(8)in(7),andexpressingeverythingintermsoftheenergy ,weget

andfinally

(9)

Sincetheenergyisproportionaltothesumofthesquaresofthethreenormallydistributedmomentum
components,thisdistributionisagammadistributioninparticular,itisachisquareddistributionwiththree
degreesoffreedom.
Bytheequipartitiontheorem,thisenergyisevenlydistributedamongallthreedegreesoffreedom,sothatthe
energyperdegreeoffreedomisdistributedasachisquareddistributionwithonedegreeoffreedom:[6]

where istheenergyperdegreeoffreedom.Atequilibrium,thisdistributionwillholdtrueforanynumber
ofdegreesoffreedom.Forexample,iftheparticlesarerigidmassdipolesoffixeddipolemoment,theywill
havethreetranslationaldegreesoffreedomandtwoadditionalrotationaldegreesoffreedom.Theenergyin
eachdegreeoffreedomwillbedescribedaccordingtotheabovechisquareddistributionwithonedegreeof
freedom,andthetotalenergywillbedistributedaccordingtoachisquareddistributionwithfivedegreesof
freedom.Thishasimplicationsinthetheoryofthespecificheatofagas.
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TheMaxwellBoltzmanndistributioncanalsobeobtainedbyconsideringthegastobeatypeofquantum
gas.

Distributionforthevelocityvector
Recognizingthatthevelocityprobabilitydensityfvisproportionaltothemomentumprobabilitydensity
functionby

andusingp=mvweget

whichistheMaxwellBoltzmannvelocitydistribution.Theprobabilityoffindingaparticlewithvelocityin
theinfinitesimalelement[dvx,dvy,dvz]aboutvelocityv=[vx,vy,vz]is

Likethemomentum,thisdistributionisseentobetheproductofthreeindependentnormallydistributed
variables

,and ,butwithvariance

.ItcanalsobeseenthattheMaxwellBoltzmannvelocity

distributionforthevectorvelocity[vx,vy,vz]istheproductofthedistributionsforeachofthethree
directions:

wherethedistributionforasingledirectionis

Eachcomponentofthevelocityvectorhasanormaldistributionwithmean
standarddeviation

and

,sothevectorhasa3dimensionalnormaldistribution,a

particularkindofmultivariatenormaldistribution,withmean

andstandarddeviation

.
TheMaxwellBoltzmanndistributionforthespeedfollowsimmediatelyfromthedistributionofthevelocity
vector,above.Notethatthespeedis

andthevolumeelementinsphericalcoordinates
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where and arethe"course"(azimuthofthevelocityvector)and"pathangle"(elevationangleofthe

velocityvector).Integrationofthenormalprobabilitydensityfunctionofthevelocity,above,overthecourse
(from0to )andpathangle(from0to ),withsubstitutionofthespeedforthesumofthesquaresofthe
vectorcomponents,yieldsthespeeddistribution.

Seealso
MaxwellBoltzmannstatistics
MaxwellJttnerdistribution
Boltzmanndistribution
Boltzmannfactor
Rayleighdistribution
Kinetictheory

References
1. StatisticalPhysics(2ndEdition),F.Mandl,ManchesterPhysics,JohnWiley&Sons,2008,ISBN9780471915331
2. See:
Maxwell,J.C.(1860)"Illustrationsofthedynamicaltheoryofgases.PartI.Onthemotionsandcollisions
ofperfectlyelasticspheres,"(http://books.google.com/books?id=
YU7AQAAMAAJ&pg=PA19#v=onepage&q&f=false)PhilosophicalMagazine,4thseries,19:1932.
Maxwell,J.C.(1860)"Illustrationsofthedynamicaltheoryofgases.PartII.Ontheprocessofdiffusionof
twoormorekindsofmovingparticlesamongoneanother,"(http://books.google.com/books?
id=DIc7AQAAMAAJ&pg=PA21#v=onepage&q&f=false)PhilosophicalMagazine,4thseries,20:2137.
3. UniversityPhysicsWithModernPhysics(12thEdition),H.D.Young,R.A.Freedman(Originaledition),
AddisonWesley(PearsonInternational),1stEdition:1949,12thEdition:2008,ISBN(10)0321501306,ISBN
(13)9780321501301
4. EncyclopaediaofPhysics(2ndEdition),R.G.Lerner,G.L.Trigg,VHCpublishers,1991,ISBN
(Verlagsgesellschaft)3527269541,ISBN(VHCInc.)0895737523
5. McGrawHillEncyclopaediaofPhysics(2ndEdition),C.B.Parker,1994,ISBN0070514003
6. Laurendeau,NormandM.(2005).Statisticalthermodynamics:fundamentalsandapplications.Cambridge
UniversityPress.p.434.ISBN0521846358.,AppendixN,page434(http://books.google.com/books?
id=QF6iMewh4KMC&pg=PA434)

Furtherreading
PhysicsforScientistsandEngineerswithModernPhysics(6thEdition),P.A.Tipler,G.Mosca,
Freeman,2008,ISBN0716789647
Thermodynamics,FromConceptstoApplications(2ndEdition),A.Shavit,C.Gutfinger,CRCPress
(TaylorandFrancisGroup,USA),2009,ISBN(13)9781420073683
ChemicalThermodynamics,D.J.G.Ives,UniversityChemistry,MacdonaldTechnicalandScientific,
1971,ISBN0356037363
ElementsofStatisticalThermodynamics(2ndEdition),L.K.Nash,PrinciplesofChemistry,Addison
Wesley,1974,ISBN0201052296
Ward,CA&Fang,G1999,'Expressionforpredictingliquidevaporationflux:Statisticalratetheory
approach',PhysicalReviewE,vol.59,no.1,pp.42940.
Rahimi,P&Ward,CA2005,'KineticsofEvaporation:StatisticalRateTheoryApproach',Int.J.of
Thermodynamics,vol.8,no.9,pp.114.

Externallinks
"TheMaxwellSpeedDistribution"
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(http://demonstrations.wolfram.com/TheMaxwellSpeedDistribution/)fromTheWolfram
DemonstrationsProjectatMathworld
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Boltzmann_distribution&oldid=691569503"
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Particledistributions
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