Liquidsolidinterfaces Electrokine3cs

Content
Poten(alanddoublelayermodels Zetapoten(al Electrokine(cs Modifyingzetapoten(al

Chargedsurfaces
Protona(on Deprotona(on Adsorp(on Thesedeneanetchargedensity

chargedensity,chargeperunitarea[C/m2] 0electricalpoten(alatthesurface[V] !Dierencesbetweenchargeandpoten(al! Poten(alistheenergyperunitchargeJ/C=V

Chargetopoten(al
Electric field by first particle

Coulombic force on second particle

Potential energy

Chargedsurfaces
Chargedensitycreatesanelectriceld Movescounterionstowardsandcoionsaway ShieldinglayerisknownasDebyelayerorelectricaldouble layer(EDL)

Chargedsurfaces

Distance from wall

Distance from wall

Helmholzmodel
Oppositelychargedions adsorbonthesurface

Poten(alrapidlyfallstozero Distanceofclosestapproachdictatedby sizeoftheions

Helmholzmodel

Nomovementnormalto surface(ionss(ck) Sternlayer Somemovementlaterally

GouyChapmanmodel
Distribu(onofionsnearthe chargedsurface

Gradualdecayofthepoten(al

GouyChapmanSternmodel

Tworegions: Helmholzregion(Sternlayer) GouyChapmanregion

Electricpoten(al
Oncethechargedensitydistribu(on(x)is known,thepoten(alcanbederived Poissonslaw(atgeometry): 0permi[vityliquid
Providesarela(onbetweentheelectricalpoten(al andchargedensity

Helmholz
Integra(ng:

Helmholz

So,atconstant0,(x)dropslinearlywithx Fromtheslopeitfollows:

Sameresultasforcapacitanceofa atplatecondenser

GouyChapman
ChargedensityaccordingtoBoltzmannequa(on:

Ninumberofionsinvolume Nibionspervolumeinbulk zichargenumber eelectroniccharge kBoltzmannconstant Ttemperature

GouyChapman

A`ersomemath
Boundary condi(ons

GouyChapman

1/e 1/ 1/iscalledtheDebyelength(EDLthickness) Whenx=Debyelength,thepoten(alhasdroppedto36.8%(1/ e)of0

Debyelength
0permi[vityliquid eelectroniccharge Ionicstrength[molm3]

Largerionicstrength(moreions)meanssmallerDebyelength(1/)

GCSModel

xh xhouteredgeofSternlayer OuterHelmholtzplane(OHP)

Zetapoten(al

Almostiden(caltotheSternpoten(alisthezetapoten(al Itisthepoten(alatthesurfaceofshear

Electrokine(cs
Anelectriceldalongthesurfaceofachargedwall inducesthechargeintheEDLtomigrate + + + +

Itcarriestherestoftheuidbytheac(onofviscous coupling NavierStokesequa(on

10

NavierStokes

Ppressure uvelocityvector chargedensity Eelectriceldvector viscosity 0permi[vityliquid poten(al Inabsenceofpressuregradient

NavierStokes
Boundarycondi(ons replace: u(x=0)=0byu(=)=0 u(x)=Ubyu(0)=U

d 2u 0 E d 2 = dx 2 dx 2 U=

0 E 1

Usethesolu(onfor(x)togetvelocityproleU(x)

11

Electroosmo(cow

U(x) =

0 (x) E 1

Electroosmo(cow
Onlyinthenearfewnanometersofawall0 Awayfromthewall0sovelocity

Electroosmo(cmobility !Notesignofpoten(alandvelocity

12

Velocityprole
In microchannels or capillaries

10m

Changingbuerconcentra(on
Twoeects: 1. Counterionadsorp(onchanges netsurfacechargedensity 2. ThethicknessoftheEDL changesthepoten(al

13

EDLandzetapoten(al
Bindinganityofca(ons K+ > Na+ > Li+ > H+ Smallerca(onsbindstronger

Qualita(veexperiment:reten(on(memeasurementin ionexchangechromatography M2+ >>> M+ Divalentionexchangeberer thanmonovalent

14