Table Of Content% ', -<,4.
FLUID-FLUIDINTERFACESANDTHEEFFECTOFINTERFACIALPHENOMENA
ONCHEMICALTRANSPORTINPOROUSMEDIAWITHMULTIPLEFLUIDS
,
By
HEONKIKIM
ADISSERTATIONPRESENTEDTOTHEGRADUATESCHOOL
OFTHEUNIVERSITYOFFLORIDAINPARTIALFULFILLMENT
OFTHEREQUIREMENTSFORTHEDEGREEOF
DOCTOROFPHILOSOPHY
UNIVERSITYOFFLORIDA
DECEMBER1998
ACKNOWLEDGMENTS
Iwouldliketoexpressmydeepgratitudetomyadvisors,DrsMichaelD.Annable
andP. SureshC.Rao,fortheirencouragement,supportanddirectionthroughoutthis
research.
IwouldliketothankDrsWilliamR.Wise,PaulA.Chadik,KirkHatfieldandKurt
D.Pennellfortheirhelpfulcommentsandvaluablesuggestionsduringpastthreeyears.
Iwouldalsoliketoextendmydeepappreciationtomycolleagues,JimJawitz,Randy
andGloriaSillan,ClaireShukla,ClaytonClark,andDr.Chenwhohavewatchedthe
progressofthisresearchandwerealwayswillingtotakepartindiscussionsforbetter
understandingofcontaminanthydrology.
IwouldespeciallythankMs.IrenePoyerforhergreatsupportinthelab. Without
herhelp,thisworkwouldnothavebeenachieved.
ThesupportfromDr.ChangWhanKimatYonseiUniversityinKoreasinceasearly
as1987ineveryaspect,isgreatlyappreciated.
Myveryspecialthanksgotomywife,Hea-young,Ryu,andmydaughter,Jeong-Yon,
whoselove,encouragementandperseverancehavegivenmestrengthduringmygraduate
studies. Finally,consistentsupportfrombothofmyparentsandparents-in-law,mentallyas
wellasfinancially,isgreatlyappreciated.
ii
TABLEOFCONTENTS
ACKNOWLEDGMENTS
ii
LISTOFFIGURES vi
ABSTRACT x
CHAPTERS
1. INTRODUCTION 1
ResearchObjectivesandOrganization 3
SurfaceExcessofOrganicChemicals 5
ModelsforInterfacialAreaEstimation 8
ThermodynamicModels 8
Semi-EmpiricalModels 10
IdealPorousSystem-PendularRingModel 14
MassTransferModel 16
2. INFLUENCEOFAIR-WATERINTERFACIALADSORPTIONANDGAS-
PHASEPARTITIONINGONTHETRANSPORTOFORGANIC
CHEMICALSINUNSATURATEDPOROUSMEDIA 19
Introduction 19
TheoreticalBackground 21
MaterialsandMethods 25
Materials 25
MiscibleDisplacementExperiments 26
SurfaceTensionMeasurements 28
ResultsandDiscussion 29
RetardationofChemicals 29
EstimationofAir-WaterInterfacialArea 33
Summary 34
iii
3. GASEOUSTRACERAPPLICATIONFORTHEESTIMATIONOFAIR-
WATERINTERFACIALAREAS,INTERFACIALMOBILITY,AND
WATERCONTENTSINPARTIALLYSATURATEDPOROUSMEDIA 44
Introduction 44
MaterialsandMethods 47
DataAnalysis 49
ResultsandDiscussion 50
Water-PartitioningTracer 50
InterfacialTracer 51
Summary 56
4. EFFECTSOFWATER-PARTITIONINGANDAIR-WATERINTERFACIAL
ADSORPTIONONTHEGASEOUSTRANSPORTOFORGANIC
CONTAMINANTSINUNSATURATEDPOROUSMEDIA 65
Introduction 65
TheoreticalBackground 67
MaterialsandMethods 68
Materials 68
MiscibleDisplacementExperiments 69
ResultsandDiscussion 71
Summary 75
5. EXPERIMENTALEVALUATIONOFTHEQUANTITATIVEVALIDITY
OFINTERFACIALTRACERS 85
Introduction g5
TheoreticalBackground 87
SurfactantAdsorptionattheNAPL-WaterInterface 87
InterfacialTracerDisplacementExperiment-InterfacialArea
Calculation 89
ComparisonofIsotherms 90
MaterialsandMethods 91
Materials 91
ColumnDisplacementExperiments 92
InterfacialTensionMeasurement 93
ResultsandDiscussion 94
NAPL-WaterInterfacialArea 94
InterfacialAdsorptionIsotherm 97
Summary 99
iv
6. TRIAMNPSAPCOTROTFONFOINN-TEEQRUFIALCIIBARLIUAMNDSOWRAPTTEIRO-NPAARNTDINTOINONLIINNGEATRRACERS:
ADSORPTIONISOTHERM 107
Introduction 107
TheoreticalBackground 109
Two-RegionModel 109
Two-SiteModel 112
NonlinearIsotherm 113
TemporalMomentAnalysis 114
Experimental 116
ResultsandDiscussion 116
GaseousTransport 116
AqueousTransport 122
EffectofPulseSizeontheReteirdationFactor 125
Summary 127
7. CONCLUSIONSANDRECOMMENDATIONS 144
Conclusions 144
Recommendations 147
APPENDIX 149
REFERENCES 152
BIOGRAPHICALSKETCH 159
V
LISTOFFIGURES
Figure
1-1 ThelogA^,„,-log relationshipfororganiccompounds;K,„-surface
adsorptioncoefficient(watertoair-waterinterface),centimeter;K^,„-octanol
waterpartitioningcoefficient(dimensionless);datafromHoffetal.(1993b),
Valsaraj(1994) 18
2-1 Detailedcolumnconfigurationfortheunsaturatedcolumnexperiments 37
2-2 Experimentalset-upforunsaturatedcolumnexperiments 38
2-3 Breakthroughcurvesforbromideandfouralcoholsatthreedifferentwater
contents 39
2-4 Breakthroughcurvesforthetransportofaromaticcompoundsandbromide;
Cl-chloro:bnz-benzene:eth-ethyl:pnl-phenol 40
2-5 Effectofwatersaturationonthetotalretardationfactors(R,)ofalcohols(a),
andaromaticcompounds(b). Alltheretardationsources(soilsorption,gaseous
partitioning,andair-waterinterfacialadsorption)weretakenintoaccountfor
thepredictedcurves(solidlines);nonanol,m-alcoholmixturesolutions:
s-singlecomponentsolution;notationforaromaticcompoundsisthesame
asinFig.2-4 41
C
2-6 Measuredsurfacetensionsof«-octanoland«-nonanol; representsthe
influentalcoholconcentrationusedduringthecolumnexperiments 42
2-7 Correlationofthespecificair-waterinterfacialareas(a)calculatedfromthe
retardationof«-octanol(inmixture)and«-nonanol(inmixture(m)andsingle-
component solution(s))withthedegreeofwatersaturation{SJ;anempirical
curvefromSDBSdisplacementexperimentsbyKimetal.(1997)wereoverlaid
forcomparison;verticallinesrepresentdatafromoneexperimentwithasuite
ofalcohols 43
vi
3-1 Experimentalsetupforgaseousinterfacialandwater-partitioningtracer
experiments 59
3-2 Breakthroughcurvesofthewater-partitioningtracersatdifferentwater
saturations;tracerconcentrationwasnormalizedsothatthetotalmassof
appliedtracersforalltheexperimentsatdifferentwatersaturationswas
reducedto0.1porevolume 60
3-3 Themeasuredvolumetricwatercontentwithrespecttotheactualwatercontent
estimatedbycolumnweight:solidline-ideal1:1line 61
3-4 Breakthroughcurvesofthegaseousinterfacialtracer(«-decane)atdifferent
watersaturations;tracerconcentrationwasnormalizedsothatthetotalmass
of«-decaneforalltheexperimentsatdifferentwatersaturationswasreducedto
0.1porevolume;insetgraphforthemethaneBTCsattwodifferentwater
saturations 62
3-5 Measuredspecificair-waterinterfacialareas(a,)usinggaseousandaqueous
interfacialtracers;SDBS(Kim,etal.,1997):alcohols(fromChap.2):
regressioncurve(n-decane):a,=-196.0InS^.-58.9(r^=0.978) 63
3-6 Theratioofinterfacialvelocitytothebulkpore-watervelocity(a)withthe
observedsodiumdodecylbenzenesulfonate(SDBS)retardationfactors
(Kimetal.,1997)andthehypotheticalretardationfactorsofSDBSestimated
basedonthespecificair-waterinterfacialareas(a,) measuredbygaseous
interfacialtracer(«-decane)experiments 64
4-1 Thebreakthroughcurvesofn-nonaneandchlorobenzeneatdifferentwater
saturations(medium:DoverAFBsoil) 78
4-2 Estimatedspecificair-waterinterfacialareasofthecolumnspackedwith
DoverAFBsoilandacleansandinwatersaturationrangeof5-55% 79
4-3 ObservedandpredictedtotalretardationfactorsofVOCsforDoverAFBsoil.
Thecomponents{^)ofpredictedtotalretardationfactorofchlorobenzenewere
shownwiththeobservedtotalretardationfactor 80
4-4 Thefractionsofpredictedtotalretardationfactorsof/^-xylenefortheDover
AFBsoilandcleansand. Thefractionalretardationfactors(f)werenormalized
withrespecttothepredictedtotalretardationfactors,whichwerereduced
tounity 81
vii
4-5 Thefractionif,)ofpredictedtotalretardationfactorsofinterfacial(air-water)
adsorptionforVOCsusedinthisstudy 82
4-6 ComparisonofVOCbreakthroughcurvesatwatersaturationof0.117:dual-
mixtureinjection;solo-singlecomponentinjection 83
4-7 Breakthroughcurvesof«-heptaneatwatersaturationof0.146withdifferent
injectionvolumes;thevolumeof«-heptaneandairmixturetakenfromthe
headspaceinthesamplepreparationvial,usedastheinputpulse 84
5-1 Schematicdiagramoftheexperimentalset-up 101
5-2 InterfacialtensionsbetweenNAPL-surfactantaqueoussolutions 102
5-3 Breakthroughcurvesofinterfacialtracers:(a)SDBS(CMC=2.2mM),
«-decanecolumn;(b)CPC(CMC=0.9mM),«-decanecolumn;(c)SDBS,
PCEcolumn 103
5-4 RetardationfactorsofSDBSandCPCasafunctionoftracerinfluent
concentrationsfromn-decaneglassbeadcolumnexperiments 105
5-5 InterfacialadsorptionisothermsofSDBSandCPCcalculatedfrominterfacial
tensiondataandtheGibbsequation(solidline),andcolumn(«-decane)
experimentdata 106
6-1 Breakthroughcurvesoftheinterfacialtracers;DoverAFBsoil,watersaturation
0.15 132
6-2 Breakthroughcurvesofmethaneatdifferentpore-gasvelocities,sandcolumn,
watersaturation0.31 133
6-3 Thenormalized,temporal,centralmomentsofvolatileorganicchemicalswith
respecttotheretardationfactor 134
6-4 Normalizedbreakthroughcurvesofmethylenechloride(gaseouswater-
partitioningtracer)atdifferentwatercontents,sand 135
6-5 Thechangeofthenormalized,temporal,centralmomentsofmethylenechloride
(water-partitioningtracer)withvolumetricwatercontentchange 136
6-6 FittedBTCsofmethylenechlorideusing2-sitemodel;squares-observeddata,
solidline-fitting;(a)watercontent0.070,(b)watercontent0.141,(c)water
content0.184 137
viii
sir—
6-7 Thebreakthroughcurvesoftracers:(a)bromide,(b)CPC0.0596mM,(c)CPC
0.199 mM;porewatervelocity0.9cm/min.;rectangle-frontsideofBTC,
closedtriangle-backsideofBTC,opentriangle-invertedbacksideofBTC. 138
6-8 NormalizedbreakthroughcurvesofCPCwithdifferentinputconcentrations,
glassbeadcolumn,coatedwithn-decane;datafromChap.5 139
6-9 TheadsorptionisothermofCPCatthe«-decane-waterinterfaceat22°C(a);
andregressionresultusingFreundlichisothermmodel(Eq.6-27)fortheCPC
concentrationuptothesaturationpoint(CPCconc.=5xl0"^mol/cm^)(b):
squares-observeddata;solidline-regression 140
6-10 BreakthroughcurvesofCPC:(a)observed,C„=0.056mM,(b)simulatedBTC
usingequilibrium,nonlinearisotherm,2-sitemodel,A^=0.353(Freundlich
isothermmodel),(c)simulatedBTCusingequilibrium,linearisothermmodel,
(d)fittedBTCusingnon-equilibrium,nonlinearisotherm(iV=0.353),
2-sitemodel,/?=0.52,<y=1.33:allBTCshavethesameretardationfactorof
3.21 141
6-11 BreakthroughcurvesofCPC;thefittingparameters(/?andco)forthefrontal
sideoftheBTCwereusedtopredictthebacksideofBTC 142
6-12 BreakthroughcurvesofCPC;thesizeofinputpulseisnotcorrected;
influentconcentrationsareshowninTable6-3 143
ix
AbstractofDissertationPresentedtotheGraduateSchool
oftheUniversityofFloridainPartialFulfillmentofthe
RequirementsfortheDegreeofDoctorofPhilosophy
FLUID-FLUIDINTERFACESANDTHEEFFECTOFINTERFACIALPHENOMENA
ONCHEMICALTRANSPORTINPOROUSMEDIAWITHMULTIPLEFLUIDS
By
HEONKIKIM
December1998
Chairman:MichaelD.Annable
Cochairman:P.SureshC.Rao
MajorDepartment:EnvironmentalEngineeringSciences
Thephysicalmorphologyandquantityoftheinterfacesbetweenimmisciblefluids
inporousmediaisofgreatinterestinsubsurfacecontaminanthydrology. Althoughthe
quantityoffluid-fluidinterfacialareasinporousmediacontaminatedwithwater-immiscible
fluidshasbeenrecognizedasacontrollingfactorofmanyphysico-chemicalprocesses,
experimentaltechniquestomeasurethisquantityhavenotbeenavailableuntilaninterfacial
tracermethodwasdevelopedin1995. Theobjectivesofthisstudyare(1)tovalidatethe
interfacialtracertechniqueinbothaqueousandgaseousapplications,(2)tocharacterizethe
effectofinterfacialadsorptionoforganiccontaminantsatthefluid-fluidinterfacesontheir
aqueousandgaseoustransport,(3)andtoinvestigatethenon-ideal behaviorofchemical
X
