Parameters affecting product formation in the gamma radiolysis of aqueous benzene solutions

246 Pages·2001·8.6 MB·English

by  Land, Larry Lee

PARAMETERSAFFECTINGPRODUCT
FORMATIONINTHEGAMMARADIOLYSISOF
AQUEOUSBENZENESOLUTIONS
By
LARRYLEELAND
ADISSERTATIONPRESENTEDTOTHEGRADUATESCHOOL
OFTHEUNIVERSITYOFFLORIDAINPARTIALFULFILLMENT
OFTHEREQUIREMENTSFORTHEDEGREEOF
DOCTOROFPHILOSOPHY
UNIVERSITYOFFLORIDA
2001
Thisdissertationisdedicatedtomywife,CynthiaIsabelMendozaLand. Withoutyour
unendingloveandcontinuoussupport,thecompletionofthisworkwouldnothavebeen
possible.
ACKNOWLEDGMENTS
Thewriterwouldliketoexpressheartfeltgratitudewithoutlimitto
ProfessorRobertJ.Hanrahanforhisuntiringsupportandcountlesssuggestionsthat
immenselyaidedinmakingthisprojectasuccess. Thewriterwouldalsoliketosay
thankstoProfessorM.L.Mugaforhisquickwitandhisintroductionofthewritertothe
worldofcrosswordpuzzles. Thewriterwouldliketoshowappreciationto
Dr.KathrynR.Williamsforherfriendshipdownthroughtheyearsandtheuseofher
analyticalinstrumentation.
Onamorepersonalnote,thewriterwouldliketoofferthankstoseveralspecial
peoplewhoseacquaintanceshipsmadegraduateschoolbothenjoyableandmemorable:
SusanRasmussenPursley,CraigHoag,DavidMiko,LisaSpurlockandMarkStoy. Ifeel
thatIamabetterpersonforhavingknowneachofyou.
in
TABLEOFCONTENTS
page
ACKNOWLEDGMENTS
iii
LISTOFTABLES vi
LISTOFFIGURES viii
ABSTRACT xiii
CHAPTERS
1 INTRODUCTION 1
PurposeoftheProject 1
ScopeoftheProject 3
2 INTERACTIONOFRADIATIONWITHMATTER 4
ProductionandDecayofCobalt-60 4
PhotonandParticleInteractionswithMatter 6
GammaRadiolysisofWater 19
3 DOSIMETRYANDTHEFRICKEDOSIMETER 30
GeneralBackground 30
FrickeDosimetry 33
ApplicationofFrickeDosimetry 37
4 PRELIMINARYINVESTIGATIONSINTOTHEAQUEOUSBENZENE
SYSTEM 62
TestTubeGeometry,GeometryA 62
Screw-TopVialGeometry,GeometryB 72
OpenTubeEvaporationStudy 74
5 ANALYTICALMETHODSFORC02QUANTITATION 77
Trapping/TitrationExperiment 77
GasChromatographyExperiment 91
IV
6 GAMMAIRRADIATIONOFAQUEOUSBENZENESOLUTIONS 104
LowDoseRateExperimentsforInitialProductDetermination 104
HighDoseRateExperimentsforCO2Production 115
GC-MSExperimentsforQualitativeDeterminationofTraceProducts 118
7 MECHANISMANDDISCUSSION 160
EffectofHeadspaceVolume 160
EffectofHeadspaceGas 170
ReactionsofBenzenewithRadicalTransients 183
DiscussionofReactionMechanism 187
ApplicationofMechanismstoOurSystems 198
8 CONCLUSIONANDFUTUREWORK 217
SummaryofResults 217
ImplicationsforDetoxificationApplicability 218
FutureWork 219
LISTOFREFERENCES 220
BIOGRAPHICALSKETCH 230
v
LISTOFTABLES
Table Page
1. TypicalreactionsinvolvedintheCobalt-60gammaradiolysisofwater 23
2. MainreactionsintheFrickedosimeter 34
3. RepresentativeFrickeexperimentaldatausingeachofthethreesamplegeometries.
ThedateonwhicheachrepresentativeFrickeexperimentwasperformedislisted
alongwiththedoserate,DR,invariousunits 57
4. Aportionofadecaycorrectiontableshowingtheadditionaltimeneededinthe
irradiatorasthesourcedecayed 61
5. ListingofconcentrationsofstandardHC1,NaOHandNa2C03solutionsfor
titrationexperiments 81
6. Listingofvolumesandconcentrationsofeachsolutionusedforthethreepseudo-
unknowntitrationexperiments 82
7. Listingoftheresultsfromthethreepseudo-unknowntitrationtrappingexperiments
fordeterminationofradiolyticallyproducedCO2 91
8. Resultsfromthethreepseudo-unknownCO2headspaceexperimentsanalyzedby
gaschromatography 103
9. ListingofpmolesofcompoundinsolutionversusdoseinMradfortheshortair
system 1 114
10. ListingofpmolesofcompoundinsolutionversusdoseinMradforthelong
oxygensystem(LOD=LimitofDetection) 114
11. Lsiyssttienmg(ofLpOmDol=eLsiomiftcoofmpDeotuencdtiionn)solutionversusdoseinMradforthelongair 115
12. ListingofpmolesofcompoundinsolutionversusdoseinMradforthelong
nitrogensystem(LOD=LimitofDetection) 115
13. ListingofumolesofCO2versusdoseinMradforeachofthefoursystems
(LOD=LimitofDetection) 117
14. ExperimentalparametersforgeometryBgaschromatographyexperiments
GCMS1-GCMS5 120
15. ExperimentalparametersforgeometryCgaschromatographyexperiments
GCMS6-GCMS10 122
16. MassspectraldataforexperimentGCMS1 129
17. MassspectraldataforexperimentGCMS2 131
18. MassspectraldataforexperimentGCMS3 134
19. MassspectraldataforexperimentGCMS4 136
20. MassspectraldataforexperimentGCMS5 138
21. MassspectraldataforexperimentGCMS6 140
22. MassspectraldataforexperimentGCMS7 142
23. MassspectraldataforexperimentGCMS8 144
24. MassspectraldataforexperimentGCMS9 146
25. MassspectraldataforexperimentGCMS10 148
26. MassspectraldataforexperimentGCMS11 150
27. MassspectraldataforexperimentGCMS12 153
28. MassspectraldataforexperimentGCMS13 157
29. MassspectraldataforexperimentGCMS14 159
30. ListingofinitialG-valuesforbenzeneandquantifiedradiolysisproductsforthe
shortairandlongairsystems 170
31. Lliosntginogxyogfeinn,itilaolnGg-aviarlaunedslfoorngbennitzreongeenansdysqtueamnsti(fiLeOdDra=diLoliymsiitsopfroDdeutcetcstifoonr)the181
32. Ratesofproduction,R,ofradicalandmolecularproductsduringthefour
experimentsusinggeometryB 203
33. Airbornetoxicitylimits(TL)forbenzeneandidentifiedproducts 212
vii
LISTOFFIGURES
Figure Page
1. D1e.1c7ayMediVagarnadm1o.f33CoMbealVt-p6r0osdhuocewdinigntchaesctawdoegammaphotonsofenergies 5
2. Adiagramofthephotoelectriceffectshowingtheeventsthatoccur 10
3. AdiagramoftheComptoneffectindicatingthedeflectionanglesofthescattered
gammaphoton,0,andtheejectedelectron,(J>,fromthepathoftheincidentgamma
photon,y 11
4. Adiagramofpairproductionshowingtheproductionofanelectron/positronpair
andtheresultingemissionofannihilationradiationatanangleof180°relativeto
eachother 14
5. Theradiationchemistrytimescaleshowingthepertinentreactionsthatoccurwithin
eachstage 20
6. Cross-sectionoftheCobalt-60gammairradiator 38
7. Asideviewofthewagon-wheelsampleholderusedingeometryAshowingthe
spacingbetweenplates 41
8. Topviewofthewagon-wheelsampleholderusedingeometryAshowingthe
relativedistancesfromthesourceholetotheinnerandoutersampleholes 42
9. Topviewofthesolidaluminumsampleholderrestingonthesolidaluminumplate.
Theholderisaffixedusingbrackets. Ahandleispresentonthebottomoftheplate
toaidininsertionandremoval 44
10. Cutawayviewofthesolid-blockaluminumsampleholdershowingtherelative
positionsofthebottomsofthesamplecellsandthesourcerod 45
11. Topviewofthesolid-blockaluminumsampleholderusedingeometryCshowing
thefoursamplepositionsandthesourcetosampledistancesusedfortotal
irradiatorcalibration 46
12. FrickeplotfortheinnersamplepositionusinggeometryA. Thisexperimentwas
performedon10/93andresultedinadoserateof7023.2rad/min 49
viii
13. FrickeplotfortheinnerandoutersamplepositionsusinggeometryB. This
experimentwasperformedon4/94andresultedinadoserateof5782.2rad/minfor
theinnersampleposition,and1421.1rad/minfortheoutersampleposition 50
14. Frickeplotforsampleposition1usinggeometryC. Thisexperimentwas
performedon5/99andresultedinadoserateof24591rad/min 51
15. Frickeplotforsampleposition2usinggeometryC. Thisexperimentwas
performedon5/99andresultedinadoserateof5721.2rad/min 52
16. Frickeplotforsampleposition3usinggeometryC. Thisexperimentwas
performedon5/99andresultedinadoserateof1660.0rad/min 53
17. Frickeplotforsampleposition4usinggeometryC. Thisexperimentwas
performedon5.99andresultedinadoserateof245.48rad/min 54
18. PlotofdoserateversussourcetosampledistanceforgeometryC. Thisexperiment
resultedintotalcalibrationoftheirradiator 58
19. PlotofdoserateversusthereciprocalofsquaredistanceforgeometryC. This
experimentresultedintotalcalibrationoftheirradiator 59
20. Chemicalstructuresofbenzene,phenol,2-phenylphenolandbiphenyl 66
21. SolutionbenzeneconcentrationversustimeofirradiationforgeometryAforthe
firsttwohoursofirradiation 67
22. PhenolconcentrationversustimeofirradiationforgeometryAforthefirsttwo
hoursofirradiation 68
23. 2-PhenylphenolconcentrationversustimeofirradiationforgeometryAforthefirst
twohoursofirradiation 69
24. BiphenylconcentrationversustimeofirradiationforgeometryAforthefirsttwo
hoursofirradiation 70
25. Apparentsolutionbenzeneconcentrationversustimeofirradiationexhibiting
improbablebehavior 71
26. Solutionbenzeneconcentrationversusthelengthoftimethevialhadstood
uncappedonthebenchtop 76
27. P5.s0e0u0dom-muonlkensoCwnO3ti2t-raatnidon6e.x0p7e0rmimmeonltes1:OpHH-pulsoitnfgo0r.t9h1e2t7itMratHioCn1ofastitrant 83
28. P5.s0e0u0dom-muonlkensowCnO3ti2t-raatnidon6e.x0p7e0rmimmeonltes1:OSHe-counsdindger0i.v9a1t2i7veMplHotC1forasthteittriatnrtationo8f4
IX
0 0 0
29. Pseudo-unknowntitrationexperiment2: pHplotforthetitrationof
0.5000mmolesCOs2'and0.6070mmolesOH-using0.04564MHC1astitrant...85
30. Pseudo-unknowntitrationexperiment2: Secondderivativeplotforthetitrationof
0.5000mmolesCO32”and0.6070mmolesOH~using0.04564MHC1astitrant...86
31. P5.s0e0u0dxo1-u-n2kmnmoowlnetsitCraOti3o2n'eaxnpder6i.m0e7n0tx13:-p2HmmpololtefsorOtHhe-tuistirnagti4on.5o6f4x1 -3MHC1
astitrant 87
32. Pseudo-unknowntitrationexperiment3: Secondderivativeplotforthetitrationof
5.000xl0-2mmolesCO32-and6.070xl0-2mmolesOH'using4.564xl0~3MHC1
astitrant 88
33. Gaschromatographyaircalibrationplotindicatingthenormalizedpeakareaversus
lamolesofinjectedair 96
34. GaschromatographyCO2calibrationplotindicatingthenormalizedpeakarea
versuspmolesofinjectedCO2 97
35. Diagramshowingheadspacegastransferinprogress. Thelargesyringecontains
acidsolutionthatisaddedtothevialastheheadspaceiswithdrawnintothesmaller
syringe 100
36. Atypicalchromatogramofasamplecontainingair(N2/O2)andCO2 102
37. Crosssectionofthe500mLroundbottomflaskmodifiedforuseasanirradiation
vessel 123
38. GC-MSchromatogramforexperimentGCMS1 128
39. GC-MSchromatogramforexperimentGCMS2 130
40. GC-MSchromatogramforexperimentGCMS3 133
41. GC-MSchromatogramforexperimentGCMS4 135
42. GC-MSchromatogramforexperimentGCMS5 137
43. GC-MSchromatogramforexperimentGCMS6 139
44. GC-MSchromatogramforexperimentGCMS7 141
45. GC-MSchromatogramforexperimentGCMS8 143
46. GC-MSchromatogramforexperimentGCMS9 145
47. GC-MSchromatogramforexperimentGCMS10 147
x