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SafeHandlingofPyrophoric(PP)Reagents
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PurposeThisPowerPointpresenta0onoffersadetaileddescrip0ononthesafehandling,useandstorageofpyrophoricliquids.Theinforma0onprovidedcanassistlabpersonnelwithconduc0ngariskassessment,traininganddevelopinganSOPbeforeusingpyrophoricliquidssuchastert-Butyllithium,diethylzincetc.
Disclaimer:ThisSafetyGuidelinesdocument/SOPwaspreparedexclusivelyfortheuseofUniversityofWisconsin-Madisonstudents,staffandfacultyengagedinacCviCesrelatedtotheireducaCon,research,and/oremployment.ThecontentisintendedtoprovidesafeoperaConalpracCcescurrentlybelievedtorepresentbestpracCcesintheuseandhandlingofchemicalsinvolvedintheprocess,andisnotintendedtoreplacehands-onpracCcaltraininginthetechniquesdescribed.ItremainstheresponsibilityofthePrincipalInvesCgatortoassurethathis/herco-workersareproperlytrainedonhazardmanagement,whichmayincludeadaptaConcontainedwithinthisdocumenttomeetspecificneedstoaddressspecifichazardsinaparCcularexperimentinalaboratory.Referencetoanyspecificcommercialproduct,process,orservicebytradename,trademark,manufacturer,orotherwise,doesnotimplyitsendorsementorrecommendaConbyUniversityofWisconsin-Madison.
Preparedby:TilakChandra,Ph.D.
HazardsA=ributedtothePPReagentManipula?ons
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Pyrophoricreagentsignitespontaneouslywhenexposedtoair,andcancauseseverecaus?cinjuriesorburnsoncontactwithskin,eyesandmucousmembranesastheyreactwithmoistureresul0nginthegenera0onofalkalinehydroxide.Fumesarisingfromthecombus0onofPPcompoundsaremainlylithiumoxideandlithiumhydroxide.Theyalsohaveaburning(caus0c)effect.
EngineeringControls
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Becauseofthedangersofreac0vity(spontaneousigni0on),specialprecau0onsmustbeengagedwhenworkingwithpyrophoricreagents.Allopera0onswithsolidandconcentratedreagentsshouldbeperformedinaproperlyfunc0onalchemicalfumehood.Afireex0nguisher,emergencysafetyshowerandeyewashshouldbereadilyavailablewithin10secondtravel0me.Smallscalepyrophoricmanipula0onscanbecarriedouteasilyinaglovebox,theyprovideexcellentinertatmosphereforpyrophoricchemicals.
Administra?veControlsAvoidworkingalonewhileconduc0ngexperimentwithPPreagents.Thebuddysystemprovidesaddedprotec0onintheeventofanemergency.Knowexactloca0onofeyewashsta0on,safetyshowerandfireex0nguishersbeforestar0ngexperiment.
PersonalProtec?veEquipment
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EyeProtec?onSafetyglassesorgogglesshouldalwaysbeworntoprotecttheeyesfromthecorrosivityofPPcompounds.Addi0onaleyeprotec0on,providedbyafaceshield,isrecommendedinexperimentswherehighervolumesofPPreagentsareemployedandPPsolu0onsarepressurized,forinstanceinordertotransferthemviatubing.BodyProtec?onAlong-sleevedfire-resistantlaboratorycoatwhichisclosedshouldbewornatall0meswhenworkingwithpyrophoricchemicals.Inaddi0on,itisrecommendedtowearfire-resistantclothingunderneath,asopposedtosynthe0cclothingnotintendedtobefireresistantwhileworkingwithpyrophoricchemicals.GlovesNitrileglovesareacceptableformanipula0ngPPreagentsinagenerallaboratoryopera0onbuttheyarecombus0ble.DryandcleanNomex®glovesserveforprotec0onofthehands.
Fig.1
LaboratoryScaleChecklistBeforeWorkingwithPyrophoric(PP)Reagents
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Items Y NSecurelatestversionofSDS/MSDSofPPsolu0onofinterestfromvendor
ReadlatestversionofSDSofPPsolu0onofinterestfromvendor
Aresafetyglasses,gogglesandfaceshieldavailable?
Isaflameresistantlabcoatorcoverallsavailable?
AreglovesofViton®ornitrileavailable?
Areextendedsleeveglovesavailable?
Areleather,closedtoeshoesavailable?
IsanappropriatelysizedboYletotesafetycarrieravailable?
IsaClassBfireex0nguisheravailable?
Knowtheloca0onofnearesteyewashandsafetyshower?
DidyouordertheminimumamountofPPsolu0onnecessaryfortheexperiment?
HasthePPsolu0onboYlebeenstoredat<10oCina0ghtlyclosedcontainer?
Isasuitablelaboratoryfumehoodavailabletoconducttheexperiment?
IsthehoodfreefromcluYer(solventboYles,samples,combus0blematerials)?
Permissionfrom:Org.ProcessRes.Dev.2014,18,1192−1210 Cont.
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Items Y NIsinertgas(drynitrogenorargon)availableinthehood?
Isaninertgasdeliverysystem(Schlenkline)ormanifoldavailableinthehood?
Isaglasswaredryingovenorheatgunavailabletodrytheequipment?
Isaglassdesiccatoravailableofsufficientsizetoallowthedryglasswaretocooltoroomtemperature?
Isavacuumpumpavailable,toevacuatetheequipment,ifthistechniqueisselected?
IsanexplosionproofrefrigeratororcoldroomavailabletostorePPsolu0on?
Haveyoualertedyourlabmates/co-workersthatyouwillbehandlingPPsolu0ons?
Haveyourehearsedyouremergencyresponseprocedure?
Aretheretwoinertgasbubblersavailable?
Isthereasyringeavailablewithasufficientlylongneedle?Or,isthereacannulaavailable?
Hasalltheequipmentbeendriedinanovenat125oCforatleastfourhours?
Wastheequipmentassembledhotandallowedtocooltoroomtemperatureinstreamofinertgas?
Isthereametalbowlunderthereac0onflaskasasecondarycontainment?
Issufficient0meavailabletocompletetheexperiment?
Isaco-workeravailableduringthePPtransfer?
Isthereaninertgaspurgeonduringtheen0reexperiment?
Methods:Small/LargeGlassAssemblyDrying
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Smallflasksandacondenserareeasytodryinanovenandcoolunderacalciumchloridedesiccator,butalargescaleassembly(condenser,1litflaskanddroppingfunnel)cannotbedriedinadesiccator.Aheatgunandvacuumisappropriateforsuchassembly.ASerassemblingtheset-upinafumehood,connecttheassemblytoavacuumusingasuitabletakeoff.ASchlenkline(SL)isappropriateforthisdryingwherenitrogenisusedasaninertgas.HeattheassemblyusingaheatgunandconCnuouslyevacuatetheassembly.DonotheatTygon®tubesusedforchilledwaterfiWed to the condenser and Keck Clips during the dryingprocess.Keck®clipslosetheirholdingcapacityiftheyareheatedunderhightemperatureorusedincorrectly.
(Fig.2)
SafetyMeasures&Techniques
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• Inthefirststepcleananddryglasswareinanovenabove120oCfor4horusingaheatgunthencoolinaglassdesiccatoroveranhydrouscalciumchloride.• Inspectyourglasswareandreac0onset-upforanydeepnotchingstarcracks,oranycrackingatallintheflasks,youshouldreplaceitimmediatelyiftheglasswareiscracked.• Useasecondarycontainmenttosupportthereac0onflaskincaseofanyemergencyorotherpurposessuchashea0ngandcooling.• DonotcannulatePPreagentsoranypyrophoricchemicalstoanyopenglassware.• Thehoodsashshouldbeclosedasmuchaspossibleduringthetransferopera0onandreac0on,toprovideanaddi0onallevelofpersonnelprotec0on.
TechniquesforTransferringtert-Butyllithium(fortransferring>10mLDoubleTippedNeedle/CannulaMethod)
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Reac?onassemblyforlarge-scalepyrophoricreagenttransfer
Small-scalepyrophoricreagenttransfer
(Fig.3a)(Fig.3b)
TransferringPyrophoricReagentswithaSyringe
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Transferofpyrophoricreagentsviasyringeisconvenient,butshouldnotbeusedformorethan10mL.Youwillneedasmallposi0vepressureinthereagentboYleinordertodrawthereagentintosyringe.EnsurethatexcesspressureisreleasedthroughthemineraloilbubblerthatisaYachedtothegasline.SLequippedwithapressurereleasesystem,wheretheinertgaslineisventedthroughanoilbubblerisagoodop0on.
Fig.4fillingsyringewithslightN2pressure
I. ItisrecommendedthatthesyringebeatleasttwicethevolumeofthePPtobedispensed.II. Thesyringeshouldbedriedinanovenat125°Cforatleast4h,placedinadesiccator(smallglassitems)tocooltoambienttemperature,andthenpurgedwithastreamofinertgas(plas0csyringecanbedriedinadesiccatorwithouthea0ng).
PyrophoricReagentsTransferwithSyringe
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I. Inserttheneedle,connectedtotheinertgasline(bubbler),throughtheseptumintotheheadspaceabovethereagentmaintainingasmallposi0vepressureinsidetheSure/SealTMpyrophoricreagentboYle.(neverover-pressurizereagentbo@lecontainingPPreagents).
II. Insertneedleofaluer-locksyringethroughtheseptumintothereagentboYle.
III. Pulltheplungerbackslowlytofillthesyringewiththerequiredvolumeofreagent.Alwayskeeptheplungerinyourgraspandavoidpullingbacktheplungerquicklyasthisac0oncausesleaksandbuildsgasbubbles.
IV. OncetherequiredvolumeisaYained,slowlypullupthesyringeneedlefromthepyrophoricreagenttotheoverheadspaceabovetheliquid.
V. Pulltheplungerupslowlyandallowtheinertgastopushthereagenttrappedintheneedleintothesyringe.
VI. Shuttheinertgaslineoffandslowlypulltheneedleoutfromtheassemblytocompletethetransfer.
VII. Rinsesyringeandneedlewithanon-reac0ngsolventajertransferringreagent,andquenchtheresidueunderaninertatmosphereusingisopropanol.
PyrophoricLiquidTransfer:CannulaMethod
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• SecuretheboYlewithclampthenslightlypressurizetheSure/SealTMboYlewithnitrogenorargon.Insertthedouble-0ppedneedlethroughtheseptumintotheheadspaceabovethereagent.Nitrogenwillpassthroughtheneedle(Fig.5a).
• Inserttheotherendthroughtheseptumatthegraduateddroppingfunnel(Fig.5b)ofthereac0onapparatuswhichmustbeequippedwithagaslinetoabubblerorcalciumchlorideguardtube.
• Pre-measurethevolumeyourequireintoanaddi0onfunnel,markitcorrectlythendrytheglasswarethoroughlyasyourset-upunderinertgasoroven.Donotover-pressurizethereagentboYleanduseofSchlenklinenitrogenisrecommended.
Cont.
PyrophoricLiquidTransfer:CannulaMethod
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• PushtheneedleintotheliquidintheSure/SealreagentboYleandtransferthedesiredvolume(Fig.5c).Tocontroltheflowrate,fitaLuerlockTMsyringevalveconnec0ngtwoelongatedneedles.
• Thenwithdrawtheneedletoabovetheliquidlevel(headspace,5d).Allownitrogentoflushtheneedleorcannula(Fig.5a&5d).Takeouttheneedlefromthereac0onapparatusfirstandthenfromthereagentboYle(Fig.5e).
Cont.
PyrophoricLiquidTransfer:CannulaMethod
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StorageofPPReagents
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Alwaysstorepyrophoricchemicalsunderaninertatmosphere.ProcuresmallestvolumeofPPreagentforuse.PPreagentswilldegradeover0me.Avoidareaswithheat/flames,oxidizers,andwatersources.BoYleswithpyrophoricmaterialsmustbeclearlylabeledwiththecorrectchemicalname(fullnameandnoacronym)andhazardwarning.Storeincool,dryandwell-ven0latedareaawayfromincompa0blematerials(RTstablePPReagents).“Usealabsafe”Refrigeratorforstoringtemperaturesensi0vePPreagents.NeverallowPPreagentstogetincontactwithmoistureduringstorage.Keepcontainers?ghtlyclosed.Neverreturnexcessreagenttotheoriginalcontainer.
ManagingSpillsInvolvingPPReagents
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Forsmallspillsinsidechemicalfumehood,usedrysand/lime,orothernon-combus0bleMaterialforcoveringthespillmaterial,closethehoodsash.Ifaspilloccursoutsideafumehoodandyouareunabletohandlethespillcallimmediately911.
DisposalofPyrophoricReagents
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Largequan0tyofPPreagentshouldbedisposedofthroughsafetydept.SmallamountsofunusedorunwantedPPmaterialsmustbedestroyedbycarefulquenchingoftheresidue.Transferthematerialstoanappropriatereac0onflaskforHydrolysisorneutraliza0on.Dilutesignificantlywithanunreac0vesolventsuchasheptaneortolueneandplacetheflaskinanicewatercoolingbath.Slowlyaddisopropanoltoquenchpyrophoricmaterials.Uponcomple0on,addmethanolasamorereac0vequenchingagenttoensurecomple0on.Finally,addwaterdrop-wisetomakesuretherearenopocketsofreac0vematerials.AVOIDlowboilingdiluentssuchasetherandpentanethattendtocondensewateruponevapora0on.Donotleavecontainerswithresiduesofpyrophoricmaterialsopentotheatmosphereduetouncontrolledigni0on.Transferneutralizedmixtureintosolventcarboy*fordisposalpurpose.*Beforetransferringquenchedmaterialintosolventcarboy,makesurethereisnoreacCvePPreagentpresent(firehazards).
References
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• Org.ProcessRes.Dev.18,2014,1192−1210.• hYps://www.pnl.gov/main/publica0ons/external/technical_reports/PNNL-18668.pdf• Methodsforthesafestorage;handling;anddisposalofpyrophoricliquidsandsolidsinthelaboratoryJ.Chem.Health&Saf.18(1),2011,5-10.• Managementof0me-sensi0vechemicals(III):stabiliza0onandTreatmentJ.Chem.HealthSaf.,13(1)2006,24-
29.• hYp://www.sigmaaldrich.com/content/dam/sigma-aldrich/docs/Aldrich/Bulle0n/al_techbull_al134.pdf• hYp://www.sigmaaldrich.com/content/dam/sigma-aldrich/docs/Aldrich/Bulle0n/al_techbull_al164.pdf• hYp://www.sigmaaldrich.com/MSDS/MSDS/DisplayMSDSPage.do?
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