Pyrophoric Materials (PYR) - University of California ... · Pyrophoric Materials Chemical Class Standard Operating Procedure Rev. Date: 2017-03-28 Pyrophoric Materials (PYR) H250

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.


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.


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


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.


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.


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


Rev.Date:2017-03-28

• Labelallwastecontainers.SeetheEH&SFactSheet,“HazardousWasteManagement”forgeneralinstructionsonproceduresfordisposingofhazardouswaste.

DisposeofWaste

• Disposeofregularlygeneratedchemicalwastewithin6months.

• ContactEH&Sat642-3073ifyouneedassistance.

11.SafetyDataSheet(SDS)Location

SDScanbeaccessedonlineathttp://ucsds.com


Rev.Date:2017-03-28


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


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


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.


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.


Rev.Date:2017-03-28

13

Notes AnydeviationfromthisSOPrequiresapprovalfromPI.


Rev.Date:2017-03-28

14



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



withsideshields.

FaceProtection:Faceshieldsaretobeusedwhenthereis

noprotectionfromthehood

sash.






afteruse.

Generalguidance:



transfersviasyringeor

cannula)ANDdirectcontact

(opensystemproceduressuch

asspillhandling,wipingof

residualpyrophorics)with

pyrophoricmaterial-a

combinationoffireresistant

(FR)liners,coveredwithapair

ofchemical-resistant




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


Rev.Date:2017-03-28

15

Liners:AnsellKevlar®Goldknit®Lightweight70-200andHanzNomex®FlameResistantUtilityLinerGloves.Clothing:WearNomexIIIA

(NFPA2112)labcoat;wear

non-syntheticclothingunder

labcoat;fulllengthpantsor


close-heeledshoes.

waste.Don’tletthewastedryout.

2)Forpressurizedreactions:

Besurethatthedeliverypressureoftheflammablegas

iscompatiblewiththereactionapparatus.Usea

compatiblegasregulator.Insurethatthegasbeing

passedthroughthereactorisproperlyventedintothe

fumehoodandthatanyventedgasesdonotconstitute

apotentialfireorexplosionthreattocoworkersor

nearbypopulations.Takeextremecarenottoover

pressurizeglassreactors.



Rev.Date:2017-03-28

16



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.



withsideshields.

FaceProtection:Faceshieldsaretobeusedwhenthereis

noprotectionfromthehood

sash.






afteruse.

Generalguidance:



transfersviasyringeor

cannula)ANDdirectcontact

(opensystemproceduressuch

asspillhandling,wipingof

residualpyrophorics)with

pyrophoricmaterial-a

combinationoffireresistant

(FR)liners,coveredwithapair

ofchemical-resistant




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-


Rev.Date:2017-03-28

17

approvalin

yournotebook

Liners:AnsellKevlar®Goldknit®Lightweight70-200andHanzNomex®FlameResistantUtilityLinerGloves.Clothing:WearNomexIIIA

(NFPA2112)labcoat;wear

non-syntheticclothingunder

labcoat;fulllengthpantsor


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.


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


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


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

Documents

Pyrophoric Materials (PYR) - University of California ... · Pyrophoric Materials Chemical Class Standard Operating Procedure Rev. Date: 2017-03-28 Pyrophoric Materials (PYR) H250