Conceptual Model for Diffusion

Diffusionisdefinedasthenettransportduetorandommotion.Amodelfordiffusive
fluxcanbeconstructedfromthefollowingsimpleexample.Consideraonedimensional
systemwithmotionintheXdirectiononly.AninterfaceBB'separatestworegionsof
differentconcentration, C1 and C2 =particles/volumeontheleftandrightsideofthe
interface,respectively.Themotionofeachparticleisaonedimensionalrandomwalk.
Ineachtimeinterval, t ,eachparticlewillmoveadistance X ,movingright(+ X
)orleft( X )withequalprobability.

B
X

C1

C2

B'

A , area of interface

Withineachtimestep,anyparticlewithinadistance X oftheinterfaceBB'hasa50%
probabilityofcrossingoverthatinterface.Thenumberofparticleswiththepotentialto
cross BB' fromlefttoright(positivemassflux)is(C1 X A),where A istheareaof
interface BB'. Onaveragehalfofthesetakeapositivestepandcrosstheinterfacein
time t ,suchthatthefluxlefttorightis(0.5 C1 X A). Similarly,thenumberof
particlescrossingrighttoleftin t (negativemassflux)willbe(0.5 C2 X A). The
resultingmassflux,qX,,is

0.5XA(C1 C2)
.
t
IfC(X)iscontinuous,then C 2 C1 X C
(5)

(6)

qx

q x [

X 2
C
C
.
]A
DA
2t
X
X

,and(1)becomes

D ~ (1 2) X 2 t isthecoefficientofdiffusion,ordiffusivity,anditunitsare[length2

time1].Thediffusivityofachemicalmoleculeinagivenfluiddependsontheeasewith
whichthemoleculecanmove,specifically,howfar, X ,themoleculecanmoveina
giventimeinterval.Theeaseofmolecularmotion,andthusthediffusivityofaparticular
chemical,willdependonthemoleculesizeandpolarity,thetypeoffluidandthe
temperature.
Equation(2)isamathematicalexpressionofFick'sLaw.Fick'sLawstatesthattheflux
ofsolutemasscrossingaunitarea,A,perunittime, t ,inagivendirection,e.g.X,is
proportionaltothegradientofconcentrationinthatdirection, C X ,andiscounter
gradient,i.e.thenetfluxisdowngradient.Becausethefluxinanydirectionis
proportionalonlytotheconcentrationgradientinthatdirection,Fick'sLawcanbe
directlyextendedtothreedimensions.
(3)

q = - D C = ( q x , q y , q z ) ( D

C
C
C
, D
, D
).
X
Y
Z

Notethatformoleculardiffusion,consideredhere,thecoefficientfordiffusionis
isotropic,i.e.thesameinalldirections.
Diffusion from a point source
ConsideracloudofNparticles(andtotalmassM)releasedatX=0andt=0.Underthe
actionofmoleculardiffusion,thecloudwillslowlyspread.Weusetherandomwalk
modeltopredictthedistributionofparticle(mass)concentration,C(X,t).Note,thatif
weassumeaunitmassperparticle,wecanconvenientlyinterchangeN=M.For
simplicityweagainconsideraonedimensionalsystem,withthesamerulesofrandom
motiondescribedabove,i.e.ateachtimestep, t ,eachparticlewillmoveeither+ X
or X withequalprobability.Overtimeeachparticlewillmoveabitforward
andabitbackward.Theprobablelocationofanindividualparticleaftermanysuchsteps
canbepredictedwiththeCentralLimitTheorem(seeanybasicstatisticstext).
Specifically,inthelimitofmanysteps,theprobabilitythataparticlewillbelocated
betweenm X and(m+1) X approachesanormaldistributionwithzeromeananda
standarddeviationof
(4) 2Dt ,
where,asabove,
(5) D (1 2) X 2 t .
TheprobabilitythataparticleendsupbetweenXandX+ X is

(6)

p(X,t)X

1
X2
exp(
)X
2
2 2

1
X2
exp(
)X .
4Dt
4Dt

NowconsiderthefullcloudofNparticles.Atanytimet,thenumberofparticles
betweenXandX+ X isexpectedtoben(X,t)=Np(X,t) X .Thus,theconcentration,
C,atpositionXisC(X,t)n(X,t)/(A X ),whereAistheconstantcrosssectionofthe
onedimensionalsystem.ExchangingMforN,theconcentrationdistribution,C(X,t),is
(7)

C( X , t)

M
A 4Dt

exp( X 2 / 4 Dt ) =[mass/length3]

Asnotedabove,thisdistributionisthenormaldistributionwithzeromeanandstandard
deviation, 2Dt ,whichshouldbefamiliartoyoufromanybasicstatisticscourse.
Briefly,thedistributionformsabellcurve,asshownbelow.Atanytime,sixtyeight
percentofthetotalmass(totalnumberofparticles)fallswithin ofthemeanposition
(X=0).Ninetyfivepercentofthemassfallswithin2 ofthemeanposition.And,
99.7%fallswithin3 ofthemeanposition.Basedontheselimits,ithasbecome
commontodefinetheextentofaconcentrationpatchbasedonthecontourthatincludes
ninetyfivepercentofthetotalmass,i.e.thecontourat2 fromthecenter.Withthis
conventionthelengthofadiffusingcloud,L,isoftentakenasL=4 .

C
Cmax
0.61 Cmax
68%
95%

-3 -2 -

+2 +3

Itisalsousefultonotethattheconcentrationlevelatonestandarddeviationfromthe
cloudcenteris61%ofthemaximumconcentration,i.e.C(X= )=0.61Cmax,where
Cmaxistheconcentrationatthecenterofthecloud.Thisvalueprovidesausefulwayto
rapidlydefinethestandarddeviationofaparticle(species)cloud.
ExampleofRandomWalkProcess:

Thisanimationshowsthemotionof500particlesinaonedimensionalrandomwalkwith
stepsize X =1intime t =1.Att=0theparticlesarelocatedatX=0.Thisrandom
walkanimationmimicstheeffectofFickianDiffusion.Asyouwatchtheanimation,
considerthefollowing.
GraphofAbsoluteParticleLocation(lowerleftwindow).
Thisgraphshowsthenumberofparticleslocatedateachpositionofthexaxis.The
numberofparticlesperlocationisanalogoustoaconcentration.
1) Overtimehowdoesthepeakparticlenumber,N,(concentration,C)changeunderthe
influenceofrandomparticlemotion(diffusion)?
2) Overtimehowdoesthegradientinparticlenumber(concentration),i.e.dN/dX
(dC/dX)changeundertheinfluenceofrandomparticlemotion(diffusion)?
3) Whatisthesignoftheparticlenumber(concentration)gradient(dN/dX)forX>0?
Considertheanimationofindividualparticlemotion(uppermostwindow).ForX>0,
isthenetparticlefluxpositive(totheright)ornegative(totheleft)?Isthedirection
offluxupgradientofdowngradient?Istherelationshipbetweenthedirectionof
fluxandtheconcentrationgradientconsistentwithFick'sLaw(equation3)?
4) Estimatethediffusioncoefficient,D,usingequation(4)above,andthevaluesof
givenintheupperleftcornerofthisgraph.Notethatyoucanpausetheanimation.
HowdoestherealizedvalueofDcomparewiththetheoreticalvaluegivenin
equation(5).Notethatnospecificunitsaregivenhere,suchthatDwillsimplyhave
unitL2T1,whereLisanarbitrarylengthunitandTisthearbitrarytimeunit.
GraphofParticleLocationinTermsof.
Thisgraphplotsthedistributionofparticlelocationwiththepositionnormalizedbythe
standarddeviation, .ThesolidcurveistheGaussiandistribution.
5) Notethatatearlytime(firstfewtimesteps)therealdistributionofparticlesdoesnot
approximateaGaussiandistributionverywell.ThisisbecausetheGaussian
distributionisonlyvalidafterasufficientnumberofsteps(CentralLimitTheorem).
Usetheanimationtoestimatehowmanystepsarerequiredforthedistributionto
consistentlyfittheGaussiandistribution.

Conclusion - Key Aspects of Diffusion

(7) Diffusionisthenetfluxduetorandommotion.
(8) Diffusivefluxisproportionalbutoppositeinsigntothegradientofconcentration.
(9) Diffusionactstodiluteconcentrationandreducegradientsofconcentration.