pyrophoric materials (pyr) - university of california ... · pyrophoric materials chemical class...
TRANSCRIPT
PyrophoricMaterialsChemicalClassStandardOperatingProcedure
Rev.Date:2017-03-28
PyrophoricMaterials(PYR)
H250
Examples:tert-ButylLithium,sec-ButylLithium,n-ButylLithium,DiethylZinc,Organoaluminumcompounds(asEt3Al,Et2AlCl,EtAlCl2,Me3Al),RaneyNickelcatalyst,Palladiumcatalyst
WORKING ALONE1 is PROHIBITED while handling PYR materialsNote:Beforehandlinganypyrophoricmaterial,researchersmustalsoreadandsignthe“Quenchingof
PyrophoricMaterials”hazardousoperationSOP.
ThisSOPisnotasubstituteforhands-ontraining.
PrintacopyandinsertintoyourlaboratorySOPbinder.
Department: Chemistry
DateSOPwaswritten: Thursday,March23,2017
DateSOPwasapprovedbyPI/labsupervisor: Friday,March24,2017
PrincipalInvestigator:Name:F.Fischer
Signature:______________________________
InternalLabSafetyCoordinatororLabManager:
Name:StephenvonKugelgen
LabPhone:510.301.1058
OfficePhone:510.642.8252
EmergencyContact:Name:StephenvonKugelgen
PhoneNumber:510.301.1058
Location(s)coveredbythisSOP: TanHall674,675,676,679,680,683,684
1.Purpose
ThisSOPcoverstheprecautionsandsafehandlingproceduresfortheuseofPyrophoricMaterials(PYR).
ForalistofPYRcoveredbythisSOPandtheiruse(s),seethe“ListofChemicals”.ProceduresdescribedinSection12applytoallmaterialscoveredinthisSOP.Achangetothe“ListofChemicals”doesnotconstituteachangeintheSOPrequiringrevieworretraining.
1Whenincludedinastandardoperatingprocedure,foranydurationoftime,apersonisworkingalonewhenperformingataskinalaboratoryandtheycannotbeseenorheardbyotherworkers,andwhenassistanceisnotreadilyavailable.Inthiscontext,ataskisanyportionorsectionofanoperationorjob,anddoesnotrefertoajobinitsentirety.
PyrophoricMaterialsChemicalClassStandardOperatingProcedure
Rev.Date:2017-03-28
Ifyouhavequestionsconcerningtheapplicabilityofanyrecommendationorrequirementlistedinthisprocedure,contactthePrincipalInvestigator/LaboratorySupervisororthecampusChemicalHygieneOfficeratucbcho@berkeley.edu.
2.Physical&ChemicalProperties/DefinitionofChemicalGroup
Pyrophoricmaterialscanignitespontaneously(within5minutes)oncontactwithair,moistureintheair,oxygen,water,orotherchemicalswithreactivehydroxylgroups.Mostpyrophoricsmayalsobeclassifiedaswaterreactives.However,notallwaterreactivesarepyrophoric.ThereactionratesofpyrophoricswithairisintheorderRateSOLID<RateLIQUID≤RateGAS.
Pyrophoricsolidsgenerallysmolderbeforeigniting;pyrophoricliquidsgenerallyigniteimmediatelyonexposuretoair;pyrophoricgasesmayformjetfiresifescapingfromavesselfollowingamechanicalfailure.
Asmostpyrophoricsreactviolentlywithwater,donotallowpyrophoricmaterialstocomeincontactwithwater(exceptduringthequenchingprocess).Pyrophoricsmustbehandledunderaninertatmospherethatrigorouslyexcludesair/moisture.
3.PotentialHazardsandToxicity
Manypyrophoricsaresuppliedassolutionsinflammablesolventssuchhexane.Thehazardsofthemixture,thepyrophoricandthesolvent,mustbeconsideredtogetherandproceduresforsafehandlingmustreflectthehazardpropertiesofbothsolventandsolute.
Mostofthesematerialsaretoxicandmaycausedamagetotheliver,kidneys,andcentralnervoussystem.Safeuserequiresassessingallpotentialhazards.
AsdefinedbytheGloballyHarmonizedSystemofClassificationandLabelingofChemicals(GHS),pyrophoricsaredesignatedbythefollowingHcode:
H250CatchesfirespontaneouslyifexposetoairItisthePrincipal Investigator’s responsibility toensureactivity-specific laboratoryproceduresand/orprocessesaretakenintoaccountwhenusingthisChemicalClassSOP.Please,reviewtheSDSofanychemicalbeforeuse(seeSection11–SDSLocation)
4.EngineeringControls
Thefollowingisthesetofengineeringcontrolsrequiredwhenhandlingpyrophoricmaterials:
• Work under an inert atmosphere (e.g., argon, nitrogen) using a Schlenk line, in a glove box,vacuummanifold,oranyenclosedinertenvironment.
• If procedure is done in the fume hood, use the sash as a safety shield. For hoods with ahorizontalslidingsash,positionthesashallthewaydown,standbehindtheslidingwindowsandreacharoundtoperformthemanipulationsrequired.Forhoodswithverticalslidingsash,keepthesashaslowaspossible.
• Faceshieldsaretobeusedwhenthereisnoprotectionfromthehoodsashorwhenthehoodsashisopen.
• Remove any flammables (squirt bottles containing solvents, oil baths) and combustibles(Kimwipes,papertowels)fromtheworkarea.
PyrophoricMaterialsChemicalClassStandardOperatingProcedure
Rev.Date:2017-03-28
• LaboratoriesandroomswherePyrophoricsareusedmusthavegeneralroomventilationthatisnegativepressurewithrespecttothecorridorsandexternalenvironment.Thelaboratory/roomdoormustbekeptclosedatalltimes.
5.PersonalProtectiveEquipment
Ataminimum,thefollowingPPEmustbewornatalltimes.
EyeProtection
A. ANSIZ87.1-compliantsafetyglasseswithsideshields,orchemicalsplashgoggles.
• OrdinaryprescriptionglasseswillNOTprovideadequateprotectionunlesstheyalsomeetANSIstandardandhavecompliantsideshields.
B. Ifthepotentialforexplosion/splashingexists,andadequatecoverageisnotprovidedbythehoodsash,afaceshieldmustbeworn.
SkinProtection
A. Wearnon-syntheticclothingunderlabcoat.
B. Flame-resistant lab coat (Nomex IIIA, NFPA 2112) must be worn when working withpyrophorics.
C. Acombinationoffireresistant(FR)liners,coveredwithapairofchemical-resistantdisposablegloves (e.g.nitrileglovesor thosespecified in the specificSDS),mustbewornATALLTIMES.The following products are Approved FR Liners: Ansell Kevlar® Goldknit® Lightweight 70-200andHanzNomex®FlameResistantUtilityLinerGloves.
D. Longpants,closed-toe/closed-heelshoes,coveredlegs,andankles.
6.FirstAidProceduresandMedicalEmergencies
Intheeventofaninjury,notifyyoursupervisorimmediatelyandEH&Swithin8hours.
GototheOccupationalHealthFacility(TangHealthCenter,oncampus); ifafterhours,gotothenearestemergencyroom(AltaBates,2450AshbyAveinBerkeley);or
Call911(fromacellphone:510-642-3333)if:
• itisalifethreateningemergency;or
• younotareconfidentinyourabilitytofullyassesstheconditionsoftheenvironmentand/orthe condition of the contaminated/injured person, or you cannot be assured of your ownsafety;or
• thecontaminated/injuredpersonisnotbreathingorisunconscious.
Please remember to provide a copy of the appropriate manufacturer SDS (if available) to theemergency responders or physician. At a minimum, be ready to provide the identity/name of anyhazardousmaterialsinvolved.
Incaseofskincontact
PyrophoricMaterialsChemicalClassStandardOperatingProcedure
Rev.Date:2017-03-28
Ifskincontactoccurs,and/orskinorclothingareonfire,immediatelydrenchinthesafetyshowerwithcopious amounts of water for no less than 15 minutes to remove any remaining contaminants. Ifpossibletodosowithoutfurtherinjury,removeanyremainingjewelryorclothing.
Incaseofeyecontact
Rinse thoroughlywith plenty ofwater using an eyewash station for at least 15minutes, occasionallyliftingtheupperandlowereyelids.Removecontactlensesifpossible.
Ifswallowed
DoNOT induce vomiting unless directed otherwise by the SDS. Never give anything bymouth to anunconsciousperson.Rinsemouthwithwater.
Needlestick/punctureexposure
Washtheaffectedareawithantisepticsoapandwarmwaterfor15minutes.
Ifinhaled
Moveintofreshair.
7.SpecialHandling,Storage,andDisposalRequirements
Pyrophoricreagentscanbehandledandstoredsafelyaslongasallexposuretoatmosphericoxygenandmoistureorotherincompatiblechemicalsisavoided.Neverleaveacontainerwitharesidueofapyrophoricmaterialopentotheatmosphere.
Lab-specificinformationonhandlingandstoragemaybeincludedinSection12-Protocol/Proceduresection.
HandlingPyrophoricLiquids
• Therearetwobasictechniquestotransferpyrophoricliquids:thesyringeandthecannulaneedle(over-pressuretransfer).Thesyringemustonlybeusedforsmallquantities(lessthan20mL).Toconvenientlytransfer20mLormoreofreagentatonce,thecannulatechniquemustbeused.
• AgloveboxoraSchlenklineinafumehoodwithinertgasflowwillbenecessary.Thesure-sealcapsystemprovidesaconvenientmethodforstoringanddispensingair-sensitivereagents.
• Pyrophoricsolidsmustbetransferredunderaninertatmosphereinaglovebox.
• PyrophoricgasesmustbehandledincompliancewiththeCaliforniaFireCode,Chapter41.
• Eliminateorsubstituteforalesshazardousmaterialwhenpossible.• Designyourexperimenttousetheleastamountofmaterialpossibletoachievethedesired
result.• DonotexceedthescaleofproceduresspecifiedinProtocol/Proceduresectionwithoutapproval
ofthePI.• Verifyyourexperimentalset-upandprocedurepriortouse.• Knowthelocationofthenearesteyewash,safetyshowerandfireextinguisherbeforebeginning
work.• Uponleavingtheworkarea,removeanypersonalprotectiveequipmentwornandwashhands.
PyrophoricMaterialsChemicalClassStandardOperatingProcedure
Rev.Date:2017-03-28
• Attheendofeachproject,thoroughlydecontaminatetheworkareaaccordingtothematerialbeinghandled.
StorageofPyrophoricMaterials• Keepthematerialunderinertatmospherewhennotinuse.• Storeminimalamountsofpyrophoricchemicals.Containerscarryingpyrophoricmaterialsmust
beclearlylabeledwiththecorrectchemicalnameandhazardwarninginEnglish.
• Inertgas-filleddesiccatorsorgloveboxesaresuitablestoragelocationsformostmaterials.
• Ifpyrophoricmaterialsarereceivedinspeciallydesignedshipping,storageordispensingcontainer(suchasthesure-sealcapsystem),ensurethattheintegrityofthatcontainerismaintained.
• Takeextremecaretopreventcontainersofpyrophoricsfromleakingorbreaking.Secondarycontainmentisrequiredforstoringandtransportingpyrophoricmaterials.Usecorrosionandshatter-resistantcontainers.
• Pyrophoricchemicalsthatrequirerefrigerationmustbestoredinaflammableratedrefrigerator.Materialsshouldbeinaclearlylabeledsecondarycontaineronthetopshelfoftherefrigerator.Donotstoredmaterialsinthefridgedoor.
• Ampulesmustbestoredandtransportedinsecondarycontainers(eveningloveboxes).Takeextremecarewhilehandlingampulesoutsideoftheglovebox,keepinmindthattheseglasscontainersareveryfragile.
• Ensurethatasufficientprotectivesolvent,oil,kerosene,orinertgasremainsinthecontainerwhilethematerialisstored.
DisposalofPyrophoricReagents• Neverleaveacontainerwitharesidueofapyrophoricmaterialopentotheatmosphere.• Anyunusedorunwantedpyrophoricmaterialsmustbedestroyedbyfollowingthespecific
destructionprocedure(s)includedinyour“HazardousOperationSOP–QuenchingofPyrophoricMaterials”.Asanalternativetoquenching,rememberthatpyrophoricchemicalscanbedisposedofashazardouswaste(contactEH&Sforguidanceondisposal).
• Wastematerialsgeneratedmustbetreatedasahazardouswaste.• TheemptycontainermustberinsedthreetimeswithaCOMPATIBLEsolvent;leaveitopenin
thebackofthehoodovernight.Therinsesolventmustbetransferredinandoutofthecontainerunderaninertatmosphereusingthesyringeorcannulatechnique.Solventrinsesandwaterrinsemustbedisposedofashazardouswaste.
• Asanalternative,unrinsedemptycontainerscanbedisposedofthroughEH&Sashazardouswaste.Theunrinsedemptycontainersmustbecapped.
• Donotmixwithincompatiblewastestreams.• Decontaminationofcontainersinordertousethemforotherpurposesisnotpermitted.
8.ChemicalSpillandManagingAnySubsequentFire
PyrophoricSpillResponse• Inthecaseofaspill,announcethesituationloudlyintheimmediateareaandhaveanynearby
personsmovetoasafelocation.
PyrophoricMaterialsChemicalClassStandardOperatingProcedure
Rev.Date:2017-03-28
• Immediatelyeliminate/removeallnearbyignitionsources.
• Ifspilloccursinafumehood,coverwithMet-L-X,drysand,orothernon-combustiblematerial,closethehoodsashandifpresent,presstheredpurgebutton.
• If a spilloccursoutsidea fumehood, coverwithMet-L-X,dry sand,orothernon-combustiblematerial,andstandawayfromthespill.
• Locateandhaveaproperfireextinguisher(drychemical-based)readyincaseofignition/fire.
• Useclean,non-sparkingtoolstocollectabsorbedmaterialandplaceintoloosely-coveredmetalorplasticcontainersreadyfordisposal.
• Do not use combustible materials (paper or cloth towels) to clean up a spill, as these mayincreasetheriskofignitingthereactivecompound.
• Ifyoucannotassessthesituationwellenoughtobesureofyourownsafety,donotapproachthespill.
• Keepothersfromenteringcontaminatedarea(e.g.,usecautiontape,barriers,etc.).
• Reportthespillto510-642-3073.
PyrophoricFireResponse
• Call911(fromacellphone:510-642-3333)foremergencyassistanceandforassistancewithallfires,evenifextinguished.
• Ifthespill ignites,andifyouaretrainedandyoufeelcomfortabletodoso,extinguishthefirewithanappropriatefireextinguisher.Useonlydrychemicalfireextinguishers(classesABCorD).DonotuseaCO2extinguisher.
• AcanofMet-L-Xordrysandintheworkarea,withinarm’sreach,mightbehelpfultoextinguishanysmallfireasitcansmothertheflames.
• Donotusewatertoextinguishapyrophoricchemicalfireasitmayenhancetheintensityofthefire.Anexceptiontothiswouldbeinthecaseofskincontactorignitedclothing/skin.Inthesecases,rinsinganyunreactedchemicaloffisofprimaryimportance.
BeAWARE:Smallflamesatthetipoftheneedlescanbeproduced–expectthistooccur,anddonotpanic.ThecanofMet-L-X/sandisinthehoodtoquicklyextinguishthosesmallflames.
CarbonDioxide,Foam,Halon,andFireblanketareUNSUITABLEforextinguishingmetalalkylfires.
9.CleaningandDecontamination
Lab-specificinformationondecontaminationmaybeincludedinSection12-Protocol/Procedure.• WearingproperPPE,laboratoryworksurfacesmustbecleanedattheconclusionofeach
procedureandattheendofeachworkday.• Decontaminateallequipmentbeforeremovingfromadesignatedarea.
10.HazardousWasteDisposal
LabelWaste
PyrophoricMaterialsChemicalClassStandardOperatingProcedure
Rev.Date:2017-03-28
• Labelallwastecontainers.SeetheEH&SFactSheet,“HazardousWasteManagement”forgeneralinstructionsonproceduresfordisposingofhazardouswaste.
DisposeofWaste
• Disposeofregularlygeneratedchemicalwastewithin6months.
• ContactEH&Sat642-3073ifyouneedassistance.
11.SafetyDataSheet(SDS)Location
SDScanbeaccessedonlineathttp://ucsds.com
PyrophoricMaterialsChemicalClassStandardOperatingProcedure
Rev.Date:2017-03-28
PyrophoricMaterialsChemicalClassStandardOperatingProcedure
Rev.Date:2017-03-28
12.Protocol/Procedurefor:PyrophoricChemicals
Procedure/Use Scale EngineeringControls/Equipment
PPE(eye,face,gloves,clothing)
ProcedureStepsandSpecialPrecautionsforthisProcedure
1.Transferringof
liquidpyrophoric
chemicalsor
solutionsof
pyrophoric
chemicals.
Upto100gof
pyrophoricmaterial
asaneatliquidorin
solutionassupplied
inthereagent
bottle,uptoa
maximumof200mL
totaltransferred
volume.
Duetothehazardof
quenching,tert-
butyllithiumhasa
lowerscalelimit:
Upto20mLtert-
butyllithium
solutionassupplied
inthereagent
bottle.
Conductinaclean
fumehoodwith
thesashaslowas
possibleusingthe
Schlenck
techniques,oran
inertatmosphere
glovebox.
EyeProtection:Wearfitted
safetygogglesorsafetyglasses
withsideshields.
FaceProtection:Faceshieldsaretobeusedwhenthereisno
protectionfromthehoodsash.
HandProtection:Confirm
compatibilityofglovematerial
withchemicalbeingused.
Glovesmustbeinspectedprior
touse.Washanddryhands
afteruse.
Generalguidance:
Forindirectcontact(closed-
systemproceduressuchas
transfersviasyringeorcannula)
ANDdirectcontact(open
systemproceduressuchasspill
handling,wipingofresidual
GeneralConsiderations2:
Liquidpyrophoricchemicalsorsolutionsofpyrophoric
chemicalscanbedispensedusingasyringeforsmall
quantities(<20mL)oracannulaforlargerquantities
(≥20mL).Disposableplasticsyringeslargerthan20mL
areNOTappropriatefortransferringpyrophoric
materials.Inserttheneedle(nolargerthan20gauge)
throughtheholeinthemetalcap.
Useplasticsyringesandneedlesonlyonce.Whenused
morethanonce,therubbergasketofaplasticsyringe
mayswellupleadingtoajammedsyringe.
Drawthesyringeplungerslowly,checkingforleaks.If
thesyringeispulledtoohard,thepyrophoricliquidcan
comeoutthebackofthesyringeontotheresearcher.
Orientthesyringeinsuchawaythatanaccidentalspill
willbedirectedawayfromyou.
Neveroverfillthesyringe;fillthesyringehalffull,even
ifyouneedtomakemultipletransfers.
2AldrichTechnicalBulletin,AL-134HandlingAir-SensitiveReagents
PyrophoricMaterialsChemicalClassStandardOperatingProcedure
Rev.Date:2017-03-28
10
Rememberto
obtainPIapprovalif
higherscaleis
necessary.
Documentthis
approvalinyour
notebook
pyrophorics)withpyrophoric
material-acombinationoffire
resistant(FR)liners,covered
withapairofchemical-resistant
disposablegloves(e.g.nitrile
glovesorthosespecifiedinthe
specificSDS)),mustbewornAT
ALLTIMES.ThefollowingproductsareApprovedFRLiners:AnsellKevlar®Goldknit®Lightweight70-200andHanzNomex®FlameResistantUtilityLinerGloves.Clothing:WearNomexIIIA
(NFPA2112)labcoat;wearnon-
syntheticclothingunderlab
coat;fulllengthpantsor
equivalent;andclose-toedand
close-heeledshoes.
Thepressureinbottlesofairsensitivechemicalsmust
betightlycontrolled.Drawoutpyrophoricliquidonlyin
thepresenceofaflowofinertgastopreventairfrom
enteringthereagentcontainer.
Theplasticcaponthereagentcontaineristobe
replacedaftereachuse.Forextendedstorageof
unusedreagents,usethesolidplasticcap,orequipthe
bottlewithasure-sealcaporequivalent.Donotapply
tapetothemetalsurfaceofthesure-sealcap;thisis
thesurfacethatmakesasealwiththeplasticcap.For
reagentsthatarestableatambienttemperature,itis
preferabletoavoidstoringtheminthefridgetoavoid
condensationandthermalexpansion/contractionofthe
seals.Storethemsealedincool,dryplacelikea
dessicator.
-ReagentTransferwithSyringe-Thesyringetransferofliquidreagentsisreadily
accomplishedbyfirstpressurizingthesure-sealreagent
bottlewithinertgasfollowedbyfillingthesyringe.
Theinertgaspressureisusedtoslowlyfillthesyringe
withthedesiredvolumeplusaslightexcess(to
compensateforgasbubbles)ofthereagent.
Notetheinertgaspressurepushestheplungerbackas
thereagententersthesyringe.Donotpullbackthe
plungerasthistendstocauseleaksandcreatesgas
bubbles.
Theexcessreagentalongwithanygasbubblesisforced
backintothereagentbottle.
Theaccuratelymeasuredvolumeofreagentinthe
syringeisquicklytransferredtothereactionapparatus
bypuncturingarubberseptumonthereactionflaskor
additionfunnel.
Followingitsuse,asyringecontainsamountofresidual
reagent.Itisadvisabletorinseoutthereactivereagent
PyrophoricMaterialsChemicalClassStandardOperatingProcedure
Rev.Date:2017-03-28
11
byfirstplacingafewmillilitersofthesamesolventthat
wasusedforthereactioninasmallErlenmeyerflaskin
thehood.
Keepingtheneedletipunderthesolventatalltimes,no
morethanhalfthesolventisthendrawnintothe
syringe.
Thesolventplusdissolvedresidualreagentisejected
fromthesyringebackintothesameErlenmeyerflask.
Repeatthisrinsetreatmentatleastthreetimes.The
washsolutioncanbesafelycombinedwithotherwaste
solventsandthesyringemaybefurthercleanedwith
waterandacetone.
-ReagentTransferwithCannula(Double-TippedNeedle)-Usealongflexibleneedlethatisonetothreefeetlong
totransferliquidviathecannulamethod.
PyrophoricMaterialsChemicalClassStandardOperatingProcedure
Rev.Date:2017-03-28
12
Thedouble-tippedneedletechniquemustbeused
whentransferring20mLormore.
Pressurizethesure-sealbottlewithnitrogenandthen
insertthedouble-tippedneedlethroughtheseptum
intotheheadspaceabovethereagent.Nitrogenwill
passthroughtheneedle.
Inserttheotherendthroughtheseptumatthe
graduatedadditionfunnelonthereactionapparatus.
Pushtheneedleintotheliquidinthesure-sealreagent
bottleandtransferthedesiredvolume.
Thenwithdrawtheneedletoabovetheliquidlevel.
Allownitrogentoflushtheneedle.Removetheneedle
firstfromthereactionapparatusandthenfromthe
reagentbottle.
Foranexactmeasuredtransfer,conveyfromthesure-
sealbottletoadry,nitrogen-flushedgraduatedcylinder
fittedwithadouble-inletadapter.
Transferthedesiredquantityandthenremovethe
needlefromthesure-sealbottleandinsertitthrough
theseptumonthereactionapparatus.
Applynitrogenpressureasbeforeandthemeasured
quantityofreagentisaddedtothereactionflask.
Afteruse,thedouble-tippedneedleisflushedfreeof
reagentwithnitrogeninthetransfersystem,andthen
immediatelyremovedandplacedinacleansink.
Withwaterrunninginthesinkandinthecomplete
absenceofflammablesolventsandvapors,thedouble-
tippedneedlecanberinsedwithwater.
Whennoactivityintherinsewaterisobserved,acetone
fromasqueezebottlecanbeflushedthroughthe
needle.
PyrophoricMaterialsChemicalClassStandardOperatingProcedure
Rev.Date:2017-03-28
13
Notes AnydeviationfromthisSOPrequiresapprovalfromPI.
PyrophoricMaterialsChemicalClassStandardOperatingProcedure
Rev.Date:2017-03-28
14
Procedure/Use Scale EngineeringControls/Equipment
PPE(eye,face,gloves,clothing)
ProcedureStepsandPrecautions
2.Useofa
transitionmetal
catalyst(Pd,Ni,
Rh,Pt,Ir,Ru)fora
hydrogenation
reactionwithH2
Upto10gof
catalystas
suppliedinthe
reagentbottle.
Rememberto
obtainPI
approvalif
higherscaleis
necessary.
Documentthis
approvalin
yournotebook
Allreactionsusingthese
materialsmustbe
performedinaproperly
operatingfumehoodwith
thesashaslowaspossible
orinaninertatmosphere
glovebox.
Blastshieldsmustbeused
ifthereactionhasthe
potentialtogeneratelarge
quantitiesofgasesoris
stronglyexothermic.
Openflamesandpossible
sparkingandstatic
electricitymustbeavoided
EyeProtection:Wearfitted
safetygogglesorsafetyglasses
withsideshields.
FaceProtection:Faceshieldsaretobeusedwhenthereis
noprotectionfromthehood
sash.
HandProtection:Confirm
compatibilityofglovematerial
withchemicalbeingused.
Glovesmustbeinspectedprior
touse.Washanddryhands
afteruse.
Generalguidance:
Forindirectcontact(closed-
systemproceduressuchas
transfersviasyringeor
cannula)ANDdirectcontact
(opensystemproceduressuch
asspillhandling,wipingof
residualpyrophorics)with
pyrophoricmaterial-a
combinationoffireresistant
(FR)liners,coveredwithapair
ofchemical-resistant
disposablegloves(e.g.nitrile
glovesorthosespecifiedinthe
specificSDS)),mustbewornAT
ALLTIMES.ThefollowingproductsareApprovedFR
1)Foruseat1atmpressure(i.eH2balloon):
-First,removeairfromthereactionvesselusinga
streamofinertgasorthefreeze-pump-thawmethod.
Attachtheballoonofgasandrefilltheevacuatedflask
orbubbleuntilsaturated.Whenreactionisjudged
complete,orifmorecatalystisneeded,removedthe
balloonandreflushthesystemwithinertgasbefore
openingtotheatmosphere.
Deactivatethecatalystbyflushingtheapparatuswith
inertgasforseveralminutes.
FilteroutthecatalystthroughCelite.
BECAREFUL–DONOTDRYOUTTHECATALYST!!Have
plentyofsolventonhandsothatyoucanaddmoreto
washthefiltercakebeforeitstartstodryout.Have
alsoplentyofwateronhand.Whenyouhavefinished
washingyourfiltercake(leavingsomesolventsoit
doesn’tdryout),turnoffthevacuum,andplacethe
residueinthebackofthefumehoodforseveralhours
beforeremovingassolidwaste.
OR
BECAREFUL–DONOTDRYOUTTHECATALYST!!Have
plentyofsolventonhandsothatyoucanaddmoreto
washthefiltercakebeforeitstartstodryout.Have
alsoplentyofwateronhand.Whenyouhavefinished
washingyourfiltercake(leavingsomesolventsoit
doesn’tdryout),turnoffthevacuum.Transferthe
catalystandfiltercaketowater,andthentoyoursolid
PyrophoricMaterialsChemicalClassStandardOperatingProcedure
Rev.Date:2017-03-28
15
Liners:AnsellKevlar®Goldknit®Lightweight70-200andHanzNomex®FlameResistantUtilityLinerGloves.Clothing:WearNomexIIIA
(NFPA2112)labcoat;wear
non-syntheticclothingunder
labcoat;fulllengthpantsor
equivalent;andclose-toedand
close-heeledshoes.
waste.Don’tletthewastedryout.
2)Forpressurizedreactions:
Besurethatthedeliverypressureoftheflammablegas
iscompatiblewiththereactionapparatus.Usea
compatiblegasregulator.Insurethatthegasbeing
passedthroughthereactorisproperlyventedintothe
fumehoodandthatanyventedgasesdonotconstitute
apotentialfireorexplosionthreattocoworkersor
nearbypopulations.Takeextremecarenottoover
pressurizeglassreactors.
Notes AnydeviationfromthisSOPrequiresapprovalfromPI.
PyrophoricMaterialsChemicalClassStandardOperatingProcedure
Rev.Date:2017-03-28
16
Procedure/Use Scale EngineeringControls/Equipment
PPE(eye,face,gloves,clothing)
ProcedureStepsandPrecautions
3.Asolid
pyrophoric
materialisusedin
thelabasa
reagentina
reaction.
Examplesare
metalcarbonyls,
metalpowders,
non-metal
hydrides;metal
alloys,non-metal
sulfides.
Upto1g(vial-
to-flask
transfer)orup
to10g
(glovebox
transfer)of
solid
pyrophoric
materialas
suppliedinthe
reagentbottle.
Duetothe
difficultyof
quantitatively
transferring
pyrophoric
solidswithout
airexposure,
acceptable
scalesare
reduced
comparedto
liquid
transfers.
Rememberto
obtainPI
approvalif
higherscaleis
necessary.
Documentthis
Conductinacleanand
properlyoperatingfume
hoodwiththesashaslow
aspossibleusingthe
Schlenktechniques,oran
inertatmosphereglove
box.
Ifusingoutsideaninert
atmosphereglovebox,
ensurethereceivingvessel
isdryandablanketof
inertgasiskeptoverthe
airsensitivechemicals.
EyeProtection:Wearfitted
safetygogglesorsafetyglasses
withsideshields.
FaceProtection:Faceshieldsaretobeusedwhenthereis
noprotectionfromthehood
sash.
HandProtection:Confirm
compatibilityofglovematerial
withchemicalbeingused.
Glovesmustbeinspectedprior
touse.Washanddryhands
afteruse.
Generalguidance:
Forindirectcontact(closed-
systemproceduressuchas
transfersviasyringeor
cannula)ANDdirectcontact
(opensystemproceduressuch
asspillhandling,wipingof
residualpyrophorics)with
pyrophoricmaterial-a
combinationoffireresistant
(FR)liners,coveredwithapair
ofchemical-resistant
disposablegloves(e.g.nitrile
glovesorthosespecifiedinthe
specificSDS)),mustbewornAT
ALLTIMES.ThefollowingproductsareApprovedFR
GeneralConsiderations:
Keepthematerialunderinertatmospherewhennotin
use.Ideally,storethepyrophoricsolidinaglovebox.If
notpossible,makesuretokeepthepyrophoricsolidin
asealedcontainerunderaninertatmosphere.
Caremustbetakentopreventadangerousexothermic
reactionuponadditiontothereactionvessel.
Portionwiseadditionisoftennecessarytoprevent
uncontrollablereaction.Forcontrolledadditionsof
largerquantities,additionofthereagentasasolutionis
stronglyrecommended.Ifthisisnotpossible,useofan
airfreesolidadditionfunnelorsolidadditiontubeis
recommended.
Foranyoperationwithmorethan1gofpyrophoric
solid,ALLmanipulationsandopentransfersofthesolid
MUSTbeconductedinaninertatmosphereglovebox.
Wheneverpossible,addthereagenttoyourreactionas
asolution.
-AdditiontothereactionvesselasaSOLUTION-Weighouttheappropriatemassintoacleananddry
vesselintheglovebox.
Addslowlythedesiredamountofdrysolventunder
inertatmosphereviasyringe(<20mL)ordouble-tipped
needle-cannula(≥20mL)orintheglovebox.Once
dissolvedinanappropriatesolvent,itmaybe
manipulatedinaccordancewithProcedure1.Fordetailsonhowtotransferthesolutionwithsyringeorcannula,seeProcedure1-AdditiontothereactionvesselasaSOLID-
PyrophoricMaterialsChemicalClassStandardOperatingProcedure
Rev.Date:2017-03-28
17
approvalin
yournotebook
Liners:AnsellKevlar®Goldknit®Lightweight70-200andHanzNomex®FlameResistantUtilityLinerGloves.Clothing:WearNomexIIIA
(NFPA2112)labcoat;wear
non-syntheticclothingunder
labcoat;fulllengthpantsor
equivalent;andclose-toedand
close-heeledshoes.
Ideally,weighoutthePYRmaterialdirectlyintoyour
reactionvesselor,ifrequired,yoursolidaddition
apparatusinaninertatmosphereglovebox.Ifneeded,
sealthereactionvesselandsolidadditionapparatusin
thegloveboxandbringouttheassembledapparatus
throughthelargeantechamber.Connectittoaninert
gassupplysuchasaSchlenkline,andchargethevessel
withdry,degassedsolvent.Slowlyaddeithertheother
reagentstothepyrophoricmaterialorviseversa,being
carefultocontroltherateoftheexothermicreaction.
Forsmallerquantities(upto1g),itisacceptableto
weighouttheappropriatemassintoacleananddry
vialinaglovebox,capit,andremoveitfromthe
glovebox.Openthevialanddirectlytransferthe
contenttothereactionvesselunderagentlebackflow
ofinertgas.Becareful–Keepthereactionvesselunder
alowinertgasflowduringthistransferasitcanpush
outsomeofyourpyrophoricsolid.
Becarefultominimizedustaccumulation.Wearing
properPPE,cleanbalanceareaafterweightingthe
material.Segregateanypyrophoricmaterial-
contaminatedtrashasitisgenerated.Pyrophoric
residuesonvials,kimwipes,orweighingpapershould
beappropriatelyquenchedimmediatelyafterremoval
fromthegloveboxpriortodisposalintowaste.
SeeQuenchingofPyrophoricMaterialsSOPfordisposal
ofpyrophoricmaterial.
Notes AnydeviationfromthisSOPrequiresapprovalfromPI.
PyrophoricMaterials
ChemicalClassStandardOperatingProcedure
Rev.Date:2017-03-28
18
13.DocumentationofTraining(signatureofallusersisrequired)• Priortoconductinganyworkwithpyrophoricmaterials,designatedpersonnelmustprovidetraining
tohis/herlaboratorypersonnelspecifictothehazardsinvolvedinworkingwiththissubstance,workareadecontamination,andemergencyprocedures.
• ThePrincipalInvestigatormustprovidehis/herlaboratorypersonnelwithacopyofthisSOPandacopyofthepyrophoricmaterialSDSprovidedbythemanufacturer.
IhavereadandunderstandthecontentofthisSOP:
Name Signature Identifier Date
PyrophoricMaterials
ChemicalClassStandardOperatingProcedure
Rev.Date:2017-03-28
19
ListofChemicals
Chemical(s) Chemical(s) Chemical(s)(-)-1,2-Bis[(2S,5S)-2,5-diethylphospholano]ethane
(-)-1,2-Bis[(2S,5S)-2,5-dimethylphospholano]ethane
(+)-1,2-Bis[(2R,5R)-2,5-dimethylphospholano]ethane
2-(Diisopropylphosphino)ethylamine 2-(Di-tert-butylphosphino)ethylamine
2-(Ethylhexyl)lithium solution
2-Cyanoethyl N,N-diisopropylchlorophosphoramidite
4-Fluoro-3-methylphenylmagnesium bromide solution
4-tert-Butylphenylmagnesium bromide solution
Alane N,N-dimethylethylamine complex
Allyl(cyclopentadienyl)nickel(II) Bis(cyclopentadienyl)magnesium(II)
Bis(dimethylphosphino)methane Bis(ethylcyclopentadienyl)chromium(II)
Bis(ethylcyclopentadienyl)magnesium
Bis(ethylcyclopentadienyl)vanadium(II)
Bis(isopropylcyclopentadienyl)chromium
Bis(pentamethylcyclopentadienyl)magnesium
Bis(propylcyclopentadienyl)magnesium
Bromo(tri-tert-butylphosphine)palladium(I) dimer
Bromodimethylborane
Chlorodicyclohexylborane Cyclopentylmagnesium bromide solution
Decylmagnesium bromide solution
Dibutylchlorophosphine Dibutylzinc solution Dichloro(diisopropylamino)borane Dichloroethylphosphine Dichloromethylphosphine Dicyclohexyl(ethyl)phosphine Dicyclohexylphosphine Dicyclopentylphosphine Diethylaluminum chloride Diethylaluminum ethoxide Diethylamidosilane, Electronic
Grade, ≥99% Diethylmethoxyborane
Diethylphosphine Diisobutylaluminum chloride Diisobutylaluminum hydride Diisopropylphosphoramidous dichloride
Diisopropylzinc solution Dimethylaluminum chloride
Dimethylaluminum hydride, solution in nonane
Dimethylzinc Di-n-butylmagnesium solution
Diphenylphosphine Diphenylzinc Disodium tetracarbonylferrate dioxane complex
Di-tert-butylmethylphosphine Di-tert-butylneopentylphosphine Di-tert-butylphenylphosphine Di-tert-butylphosphine Dodecylmagnesium bromide
solution Ethylaluminum dichloride
Ethylaluminum sesquichloride Europium Hexyllithium solution Isopropylmagnesium bromide solution
Lithium dicyclohexylamide Lithium diethylamide
Lithium diisopropylamide Lithium dimethylamide Lithium pentamethylcyclopentadienide
Lithium tetramethylcyclopentadienide
Lithium triisobutyl(2,2,6,6 tetramethylpiperdino)a
L-Selectride(R) solution
Magnesiumanthracene tetrahydrofuran complex
Methyllithium solution Methylphenylphosphine
Mischmetal-nickel alloy n-Butyllithium solution Neodymium-iron-boron, alloy 30/100
PyrophoricMaterials
ChemicalClassStandardOperatingProcedure
Rev.Date:2017-03-28
20
Octylmagnesium bromide solution Octylmagnesium chloride solution Phenylethynylmagnesium bromide solution
Phenylphosphine Potassium pentamethylcyclopentadienide
Potassium tetramethylcyclopentadienide
Praseodymium R-Alpine-Borane(R) S-Alpine-Borane(R) sec-Butyllithium solution Sodium tetraethylborate Sodium tetraethylborate-d20 tert-Butyl hypochlorite tert-Butyldicyclohexylphosphine tert-Butyldiisopropylphosphine tert-Butyllithium solution tert-Butylphenylphosphine Tetradecylmagnesium chloride
solution Tetraethylammonium hydridotetracarbonylferrate
Tetraphenylbiphosphine Titanium(II) chloride
Titanium(III) chloride Tributylantimony Tributylbismuthine Tributylborane Trichlorosilane Tricyclopentylphosphine Triethylaluminum Triethylborane Triethylgallium Triethylphosphine Triisobutylaluminum Triisopropylphosphine Trimethylacetic acid, anhydride with diethylborini
Trimethylaluminum Trimethylgallium
Trimethylindium Epipure Grade Tri-n-butylphosphine Tripropylaluminum Tripropylphosphine Tris(acetonitrile)tricarbonylchromiu
m(0) Tris(butylcyclopentadienyl)erbium(III)
Tris(trimethylsilyl)phosphine Tris(trimethylsilylmethyl)borane Tri-tert-butylphosphine