MeasurementsofElementaryRateConstants, IgnitionDelaysandSpeciesHistoriesinShockTubes

R.K.Hanson,D.F.Davidson StanfordUniversity
1st InternationalWorkshoponFlameChemistry July2829,2012

ShockTube/LaserApproach AdvancesinMethodology ElementaryReactionRateStudies MultiSpeciesTimeHistories

Kinetics Shock Tube1 (30atm)

Kinetics Shock Tube2 (30atm)

StanfordShockTubes
Aerosol Shock Tube (10atm)

High Pressure Shock Tube (500atm)

NewConstrainedReactionVolume(CRV)Facility
2Configurations
Sliding Valve

CRV1
GasPhase Experiments to100atm

Constrained ReactionVolume

CRV2
Aerosol Experiments to100atm Aerosol GenerationTank

Firstuseof tunable dyelasers inshock tubes (1982) Ultrafast lasersusedto extendUV tuningrange (2009)

StanfordLaserDiagnostics
Ultraviolet CH3 216nm NO225nm O2 227nm HO2 230nm OH306nm NH336nm Visible CN 388nm CH431nm NCO440nm NO2472nm NH2597nm HCO614nm Infrared H2O2.5m CO22.7m CH4 3.4m CH2O3.4m CO4.6m NO5.2m C2H410.5m

Newlasers allowsimple accesstomidIR (200710)

LaserAbsorptionYieldsHighSensitivity
RepresentativeDetectionLimits:PolyatomicMolecules
1000

CO2
Detection Limit [ppm]
100 10 1 0.1 0.01 1000

CH2O C2H4 H2O

NH2 CH3

1atm,15cm,1MHz
1500 2000 2500 3000

Temperature [K]

Polyatomicmolecules@1500K:2200ppm
5

LaserAbsorptionYieldsHighSensitivity
RepresentativeDetectionLimits:DiatomicMolecules
1000

1atm,15cm,1MHz

Detection Limit [ppm]

100 10

CO OH
subppm sensitivityfor OH,CH,CN

CH
0.1 0.01 1000 1500 2000 2500

CN
3000

Temperature [K]

Diatomicmolecules@1500K: subppmdetectivitiy forUVabsorbers ppmdetectivity forIRabsorbers

AdvancesinShockTube Methodology
1. Improveduniformitywithdriverinserts 2. Longertesttimeswithtailoredgas mixtures&extendeddriver 3. Reactivegasmodeling: problemandsolutions

ImprovementinReflectedShockTemperatureUniformity UsingDriverInserts
Conventionalshocktube operationcanprovide nearidealuniformflows for13ms But,boundarylayersand attenuation inducedP/dt anddT/dt atlongertimes

dP/dt = 3%/ms dT/dt = 1.2%/ms

ImprovementinReflectedShockTemperatureUniformity UsingDriverInserts These effectsreduce ignitiondelaytimes relativetoConstantPcase Solution:DriverInserts

dP/dt = 3%/ms dT/dt = 1.2%/ms

VRS Driverinsertsmodifyflowtoachieve uniformTandPatlongtesttimes

P5 T5

ImprovementinReflectedShockTemperatureUniformity UsingDriverInserts
Result:dP/dt = 0priorto ignition Properign forcomparison withConstantPsimulations

VRS

P5 T5

10

LongerTestTimesAchievablewith TailoredGasMixtures&ExtendedDriverSections Conventionalshocktubeoperation:~13mstesttime

NooverlapwithRCMoperation~10150mstesttime
1000 2500K 1000K 625K 10atm 100 10 1 0.1 0.01 1E-3 Unmodified Stanford ST RCM

10

Test Time, Ignition Time [ms]

n-Dodecane/Air

=1
0.4 0.8 1.2 1.6

1000/T [1/K]
11

LongerTestTimesAchievablewith TailoredGasMixtures&ExtendedDriverSections Longerdriverlengthandtailoredgasmixtures canprovidelongertesttimes(>40ms)

1000 2500K 1000K 625K 10atm 100 10 1 0.1 0.01 1E-3 RCM Modified ST Unmodified Stanford ST

Test Time, Ignition Time [ms]

n-Dodecane/Air

=1
0.4 0.8 1.2 1.6

2xDriverExtension

1000/T [1/K]

ShocktubesnowcanoverlapwithRCMs

12

FirstUseofLongTestTimeFacility: LowPressurenHeptaneIgnitionintheNTCregime
Testtime=45ms at725K
Relative Pressure
6
2nd Stage Ignition

n-Heptane/21%O2/Ar
=1, 725K, 2.9 atm

Enablesfirstlowpressure (~3atm)nheptaneignition datainNTCregime Clearevidenceof2stage ignition:1 =8ms,2 =20ms Nextstep:adddriverinsertsto removedP/dt &dT/dt

4 3 2 1 0

1st Stage Ignition

Reactive Mix

Non-Reactive Mix w/o Inserts

Test time = 45 ms
OH Emission

10

20

30

40

50

Time [ms]

Howdothe3atm data comparetohighPdata?

13

LowPressure,LowTemperatureStudies: NewResultsfornHeptaneintheNTCRegime
100

1000K

833K

714K

625K

n-Heptane/21%O2/Ar,N2 =1 Ignition Delay Times [ms]

3 atm
10

12 atm

40 atm 55 atm
0.1 1.0 1.2 1.4 1.6

Stanford Aachen

1000/T [1/K]

Previous1255atm data New3atm data Howdomeasurementscomparewithcurrentmodels?

14

LowPressure,LowTemperatureStudies: NTCHeptane,ComparisonwithModel
100

1000K

833K

714K

625K

n-Heptane/O2/Ar/N2 =1 Ignition Delay Times [ms]

3 atm
10

12 atm

40 atm

Solid: LLNL C7 Model

1.6

0.1 1.0 1.2 1.4

1000/T [1/K]

LLNLC7(2000)modelperformsreasonablywellathighP FurthertestsneededatlowP Revealsvalueoflongtesttimeexperiments

15

ReactiveGasdynamics Modeling:AProblem
Mostcurrentreflectedshockmodelingassumes ConstantVolumeorConstantPressure But: Exothermic energyreleaseduringoxidationor endothermic coolingduringpyrolysischangesT&P behindreflectedshocks notaConstantVorConstantPprocess! Example:HeptaneIgnition
16

EffectofEnergyReleaseonPProfiles: nHeptaneOxidation
5

0.4% Heptane/4.4% O2/Ar, =1

4

1380K, 2.3 atm

Pressure [atm]

3
2

Measured SidewallP ConstantP Model

ign
0

0 -100

100

200

300

400

500

600

Time [us]

Howdoesthiscomparewithmodels? NotaconstantPprocess!
17

EffectofEnergyReleaseonPProfiles: nHeptaneOxidation
5

0.4% Heptane/4.4% O2/Ar, =1

4

1380K, 2.3 atm

ConstantV Model Measured SidewallP

Pressure [atm]

3
2

ign
0

ConstantP Model

0 -100

100

200

300

400

500

600

Time [us]

Howdoesthiscomparewithmodel? NotaconstantPprocess! NotaConstantVprocess,evenfor0.4%fuel! Sohowcanentireprocessbemodeled?

18

3ProposedSolutionstoEnableModelingthrough EntireCombustionEvent
1. Minimizefuelloadingtoreduceexothermically or endothermicallydrivenTandPchanges
enabledbyhighsensitivitylaserdiagnostics

2. Modifiedgasdynamics modelingtoaccountfor PandTchangeduringcombustion

workinprogress(butcomputationallyintensive:1D,3D)

3. Usenewconstrainedreactionvolumeconceptto minimizepressureperturbations
enablesconstantP(orspecifiedP)modeling

Examples:

1)Useofdilutereactivemixtures 2)Useofconstrainedreactionvolume
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Example1:BenefitofDiluteMixtures 3PentanoneOxidation
LowFuelLoadingExperiment
2.0

OHMoleFraction
150

1.5

OH Mole Fraction [ppm]

Const. H P Model
100

Pressure [atm]

1.0

OH Data
50

0.5

400 ppm 3-Pentanone/O2/Ar 1486 K, 1.52 atm, =1

0.0 0 500 1000 1500

TfinalTInitial =45K
0 0 500 1000 1500

Time [s]

Time [s]

Pressurenearlyconstantthroughoutexperiment GoodagreementbetweenConstantH,Pmodelandexpt. Modelsuccessfullyincludestemperaturechange

20

Example2:ConstrainedReactionVolumeApproach HydrogenIgnitionat950K
ConventionalShockTube
PreShock HeliumTestMixture PostShock

ConstrainedReactionVolume
PreShock HeliumNonReactiveMixTM PostShock

Reflected ShockWave

LargeRegionof EnergyRelease

SmallRegionof EnergyRelease

Largereactionvolumegiveslargeenergyrelease P&T CRVgivesreducedenergyrelease nearconstantP

21

Example2:ConstrainedReactionVolumeApproach HydrogenIgnitionat950K
ConventionalShockTube
8

ConstrainedReactionVolume
8

4%H2-2%O2-Ar Normal Filling 979K, 3.44 atm

Pressure [atm]

4% H2-2%O2-Ar CRV = 4 cm 956K, 3.397 atm

Ignition Pressure

Pressure [atm]

Pressure

Emission
0 0 1 2 3 4 5
0 0 1 2 3

Emission

Time [ms]

Time [ms]

ConventionalSTexhibitslargepressurechange! CRVpressurenearlyconstantthroughoutexperiment! Allowskineticsmodelingthroughignitionandcombustion!

22

ElementaryReactionRate Determinations
Goal Neardirectdeterminationofrate constantsforspecificreactions Examples OH+ketones:
acetone,2butanone,2 &3pentanone

OH+alkanes OH+butanol isomers OH+methylesters

23

ExperimentalStrategy
TBHPusedasapromptOHprecursor UsefulTrange(850to1350K) PioneeredbyBott andCohen(1984) AlsousedatArgonne Fuelinexcess,pseudofirstorderexperiment

fast upon shock heating

+
tertbutylhydroperoxide Acetone

24

Representative3Pentanone+OHData: 1188Kand1.94atm
20

OH Mole Fraction [ppm]

15

211 ppm 3-Pentanone / Ar 17 ppm TBHP 1188 K, 1.94 atm

OH Sensitivity

1 0 -1 -2 -3

10

Current Study 13 3 -1 -1 1.23x10 cm mol s

3-Pent+OH=Products CH3+OH=CH2*+H2O C2H5=C2H4+H

0 50 100

0 0 50 100

-4

Time [s]

Time [s]

Highqualitydataallowshighprecisioncomparisonwithmodel Sensitivityanalysisconfirmspseudofirstorderbehavior Neardirectdeterminationofreactionrateconstant!

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Resultsfor3Pentanone+OH Products
1429K 1E14 1250K 1111K 1000K 909K 833K

3-Pentanone + OH = Products

k [cm k [cm mol mol s s ]]

-1 -1 3 3

-1 -1

1E13

+/ 20%
Current Study Serinyel et al. - NUI Galway (2010)
1E12 0.7 0.8 0.9 1.0 1.1 1.2

1000/T [1/K]

Nootherhightemperaturedataavailable NUImodel(Serinyel etal.)inexcellentagreement

26

Summary:OH+KetonesProducts
1429K 1250K 1111K 1000K 909K 833K

Ketone + OH = Products kKetone + OH [cm mol s ]

-1 -1 3

1E13

Acetone 2-Butanone 3-Pentanone 2-Pentanone

Lines: Modified SAR (SAR x 0.75)

1E12 0.7 0.8 0.9 1.0 1.1 1.2

1000/T [1/K]

HowdodatacomparewithStructuralActivityRelationship(SAR)model? Dataagreewithin25%withSARestimatedrateconstants Similarmeasurementsperformedwithmethylesters 27

Summary:OH+Methyl Esters Products

1429K 1250K 1111K 1000K 909K 833K

Methyl Ester + OH = Products

kMethyl Ester + OH [cm mol s ]
-1 -1 3

1E13

1E12 0.7

MButanoate MPropanoate MFormate MAcetate Lines: Modified SAR (SAR x 0.75)

0.8 0.9 1.0 1.1 1.2

1000/T [1/K]

Dataagreewithin25%withSARestimatedrateconstants Currentwork:OH+aldehydes,alcohols
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MultiSpeciesTimeHistories
Motivation Multispeciesprovidegreaterconstraint onmechanismrefinement/evaluation RecentWork
Ketones:Acetone,Butanone,3Pentanone Alcohols:1,2,tert,&isoButanol Alkanes:nHexadecane Esters:MethylFormate,MA,MP,MB,EP
29

MultiSpeciesApproach:3PentanonePyrolysis
300
1.2

1% 3-Pentanone / Ar

3-Pentanone Mole Fraction [%]

=3.39m
0.8

CH3 Mole Fraction [ppm]

3Pent

0.1% 3-Pentanone / Ar
.

200

=216nm
1346 K, 1.67 atm

CH3

0.4

100

1323 K, 1.32 atm

0.0 0 500 1000

0 0 100 200

Time [s]

Time [s]

2.0

0.25% 3-Pentanone / Ar
3000

1% 3-Pentanone / Ar C2H4 Mole Fraction [%]

1.5

CO Mole Fraction [ppm]

1325 K, 1.60 atm

2000

1343 K, 1.60 atm

1.0

1000

0 0 500

=4.6m
1000

CO

0.5

=10.5m
0.0 0 500 1000

C2H4
1500

Time [s]

Time [s]

ExcellentSNR,highsensitivitydata

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ComparisonwithSerinyel etal.(2010)GalwayNUI
300
1.2

1% 3-Pentanone / Ar
Serinyel et al.

3-Pentanone Mole Fraction [%]

CH3 Mole Fraction [ppm]

3Pent

0.1% 3-Pentanone / Ar
Serinyel et al.

CH3
1346 K, 1.67 atm

200

0.8

0.4

100

1323 K, 1.32 atm

0.0 0 500 1000

0 0 100 200

Time [s]

Time [s]

2.0

0.25% 3-Pentanone / Ar
3000 Serinyel et al.

CO
1325 K, 1.60 atm

1% 3-Pentanone / Ar C2H4 Mole Fraction [%]

1.5

CO Mole Fraction [ppm]

C2H4
1343 K, 1.60 atm

2000

1.0

1000

0.5

0 0 500 1000

0.0 0 500 1000 1500

Time [s]

Time [s]

TwoDifferences:1)3Pdecompositionrate;2)CO/C2H4 yields

31

3PDataEnablesRevisionofDecompositionRate
3PentanoneSensitivity
100000

ArrheniusPlot:3PentProducts
1429K 1250K 1111K

3-Pentanone = Products 1.6 atm

10000

ktotal [1/s]

1000

100

Serinyel et al. (2010)

2Channels
10

1 0.7

0.8

0.9

1000/T [1/K]

3Pdatashow strongsensitivities tok1 +k2

Revisedktotal 3.5xSerinyel etal.rate COyieldsstillnotcorrect!

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COYieldResolvedthroughUseofOAtomBalance
3PandCOdatayieldtotalOatoms
1.0

Oatomconcentrationat1.5ms LaserAbsorption
3Pentanone: CO: Sum: 23% 69% 92%

0.8

1% 3-Pentanone / Ar 1248 K, 1.6 atm

Mole Fraction [%]

CO
3-Pentanone
0.6

0.4

Simulation(withnewk1+k2)
3Pentanone: 23% CO: 43% CH3CHCO: 27% Sum:93%

0.2

0.0 0 500 1000 1500

Time [s]

Modelunderpredicts COandoverpredicts methylketene Why?Methylketenedecompositionpathwaymissinginmechanism IntroduceCH3CHCO C2H4 +CO(assumek thesameasketenedecomp.)

33

RevisedModelImproves3PSimulations
FinalModificationstoSerinyel etal. 3PentanoneMechanism Reviseddecompositionrate: 3pentanone products Additionalreaction: methylketene C2H4 +CO

CH3

0.25% 3-Pentanone / Ar.

3000

CO Mole Fraction [ppm]

CO
1403 K, 1.57 atm 1325 K, 1.60 atm 1272 K, 1.64 atm

C2H4

2000

1000

1215 K, 1.68 atm

0 0 500 1000

Time [s]

Goodagreementwith3P,CH3,CO,andLowTC2H4 timehistories

34

OngoingWork
Diagnostics development & spectroscopy:
aldehydes (CH2O, CH3CHO) alkyl radicals (C2H5) methyl esters (methyl formate) Alkenes (C3H6, C4H8)

Continued improvement of shock tube methods:

constrained reaction volume

Direct measurement of elementary reactions:

OH + oxygenates (aldehydes, ethers, alcohols) decomposition of oxygenates CH3, HO2 reactions with HC
35

Acknowledgements
ARO,AFOSR,DOE,NSF Students: Genny Pang,MattCampbell,WeiRen,BrianLam,SijieLi, SreyashiChakraborty

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