self-heating substances and mixtures · 2. self-heating substances and mixtures information a...

Self-HeatingSubstancesandMixturesChemicalClassStandardOperatingProcedure

Rev.Date:2017-03-28

Self-HeatingSubstancesandMixtures

H251H252

Examples:magnesiumethoxide,sodiumethoxide,sodiumtert-butoxide,potassiummethoxide,titaniumsulfide

Note:BeforehandlinganySelf-HeatingSubstances,researchersmustalsoreadandsignthe“QuenchingofSelf-

HeatingSubstancesandMixtures”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

This SOP covers theprecautions and safehandlingprocedures for theuseof Self-Heating SubstancesandMixtures.

ForalistofSelf-HeatingSubstancesandMixturescoveredbythisSOPandtheiruse(s),seethe“ListofChemicals”.ProceduresdescribedinSection12applytoallmaterialscoveredinthisSOP.Achangetothe“ListofChemicals”doesnotconstituteachangeintheSOPrequiringrevieworretraining.

Ifyouhavequestionsconcerningtheapplicabilityofanyrecommendationorrequirementlistedinthisprocedure,contactthePrincipalInvestigator/LaboratorySupervisororthecampusChemicalHygieneOfficeratucbcho@berkeley.edu.


Rev.Date:2017-03-28

2. Self-HeatingSubstancesandMixturesInformation

Aself-heatingsubstanceisdefinedasfollows:asolidorliquidormixture,otherthanapyrophoricliquidorsolid,which,byreactionwithairandwithoutenergysupply, is liabletoself-heat;thissubstanceormixturediffersfromapyrophoricliquidorsolidinthatitwilligniteonlywhenlargeamount(kilograms)andafterlongperiodsoftime(hoursordays).

3. PotentialHazards/Toxicity

Self-heating of a substance or mixture is a process where the gradual reaction of that substance ormixturewithoxygeninairgeneratesheat.Iftherateofheatproductionexceedstherateofheatloss,thenthetemperatureofthesubstanceormixturewillrisewhich,afteraninductiontime,mayleadtoself-ignitionandcombustion.

Thefirehazardpresentedbyself-heatingsubstancesisduetofourinter-relatedfactors:

• Volumeofmaterialpresent

• Rateatwhichthematerialselfreacts

• Temperatureofthesurroundings/insulatingfactors

• Availabilityofoxygen/moisture

TheGHS establishes two categories for self-heating substances ormixtures. Category 1materials aremorereactiveandselfheatmorereadilyandinsmalleramountsthancategory2materials.

TheGloballyHarmonizedSystemofClassificationandLabelingofChemicals(GHS)designatesself-heatingsubstancesandmixturesbyoneormoreofthefollowingHcodes:

H251Self-heating;maycatchfire

H252Self-heatinginlargequantities;maycatchfire

It is thePrincipal Investigator’s responsibility toensure activity-specific laboratory procedures and/orprocessesaretakenintoaccountwhenusingthisChemicalClassSOP.Please,reviewtheSDSofanychemicalbeforeuse(seeSection11–SDSLocation)

4. EngineeringControls

The following is the set of engineering controls that are required when working with Self-HeatingSubstances:

• WorkwithSelf-HeatingSubstances–theworkmustbeconductedinafumehoodunlessothercontrolsaredesignatedinthelab-specificProtocol/Proceduresection.Sashheightmustbekeptaslowaspossibletoavoidescapingfumesandprovideaphysicalbarrier.

• Removeany flammables (squirtbottles,solvents,oilbath)andcombustibles (Kimwipes,papertowels)fromtheworkarea.

• LaboratoriesandroomswhereSelf-HeatingSubstancesareusedmusthavegeneralroomventilationthatisnegativepressurewithrespecttothecorridorsandexternalenvironment.Thelaboratory/roomdoormustbekeptclosedatalltimes.


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5. PersonalProtectiveEquipment

Ataminimum,thefollowingPPEmustbewornatalltimes.

EyeProtection

A. ANSIZ87.1-compliantsafetyglasseswithsideshields,orchemicalsplashgoggles.

• Ordinary prescription glasses will NOT provide adequate protection unless they alsomeetANSIstandardandhavecompliantsideshields.

B. If the potential for explosion/splashing exists, and adequate coverage is not provided by thehoodsash,afaceshieldmustbeworn.

SkinProtection

A. Flame-resistantlabcoat(NomexIIIA,NFPA2112)mustbewornwhenworkingwithSelf-HeatingSubstances.

B. Glovesarerequiredwhenhandlinghazardouschemicals.

• RefertospecificchemicalSDSforinformationongloveselection.

• Foradditionalinformationongloveselection,goto:

http://ehs.berkeley.edu/hs/63-laboratory-safety/94-glove-selection-and-usage.html

C. 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

Ifskincontactoccurs,and/orskinorclothingareonfire,immediatelydrenchinthesafetyshowerwithcopiousamountsofwaterfornolessthan15minutestoremoveanyremainingcontaminants.Ifpossibletodosowithoutfurtherinjury,removeanyremainingjewelryorclothing.

Incaseofeyecontact


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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.

Ifinhaled

Moveintofreshair.

Needlestick/punctureexposure

Wash theaffectedareawithantiseptic soapandwarmwater for15minutes. Formucousmembraneexposure such as eyes,mouth and/or nose, flush the affected area for 15minutes using an eyewashstation.

7. SpecialHandling,Storage,andDisposalRequirements

Self-HeatingSubstanceschemicalscanbehandledandstoredsafelyaslongasallexposuretomoistureorotherincompatiblechemicalsisminimized.NeverleaveacontainerwitharesidueofaSelf-HeatingSubstancematerialopentotheatmosphere.

Lab-specific informationonhandling and storagemaybe included in Section12 - Protocol/Proceduresection.

Precautionsforsafehandling

• Only use if the area is properly equippedwith a properly operating eyewash/safety showerwithintensecondsoftravel.

• Workawayfromanywatersourcesorwherethereisthepotentialofwatersplash.• Eliminateorsubstituteforalesshazardousmaterialwhenpossible.• Designyourexperimenttousetheleastamountofmaterialpossibletoachievethedesired

result.• DonotexceedthescaleofproceduresspecifiedinProtocol/Proceduresectionwithoutapproval

ofthePI.• Verifyyourexperimentalset-upandprocedurepriortouse.• Knowthelocationofthenearesteyewash,safetyshowerandfireextinguisherbeforebeginning

work.• Uponleavingtheworkarea,removeanypersonalprotectiveequipmentwornandwashhands.• Attheendofeachproject,thoroughlydecontaminatetheworkareaaccordingtothematerial

beinghandled.

Conditionsforsafestorage

• Storeinalocationseparatedfrombases,oxidizingandotherincompatiblematerials.• Never allowproduct to get in contactwithwater orwater-based compounds during storage.

Keep inadryplace(suchasadesiccatororadryboxorglovebox) freeofmoisture/humidityandawayfromsourcesofheat.

• Do not leave the container near a lab sink, emergency eyewash, or safety shower or on thebenchtop-evenmomentarily.


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• Ensurethatasufficientprotectivesolvent,oil,kerosene,orinertgasremainsinthecontainerwhilethematerialisstored.

Disposal • Any unused or unwanted Self-Heating Substances must be destroyed by following the

Quenching of Self-Heating Substances SOP. If you have large quantities of unreacted Self-HeatingSubstances,contactEH&Sforguidanceondisposaloptions.

• Wastematerialsgeneratedmustbetreatedasahazardouswaste.• TheemptycontainermustberinsedthreetimeswithaCOMPATIBLEsolvent;leaveitopenin

thebackofthehoodovernight.Solventrinsesandwaterrinsemustbedisposedofashazardouswaste.

• Asanalternative,unrinsedemptycontainerscanbedisposedofthroughEH&Sashazardouswaste.Theunrinsedemptycontainersmustbecapped.

• Donotmixwithincompatiblewastestreams.• Decontaminationofcontainersinordertousethemforotherpurposesisnotpermitted.

8. ChemicalSpillandManagingAnySubsequentFire

Self-HeatingSubstancesSpillResponse

• Inthecaseofaspill,announcethesituationloudlyintheimmediateareaandhaveanynearbypersonsmovetoasafelocation.

• Immediatelyeliminate/removeallnearbyignitionsources.• Ifspilloccursinafumehood,coverwithMet-L-X,drysand,orothernon-combustiblematerial,

closethehoodsashandifpresent,presstheredpurgebutton.• If a spilloccursoutsidea fumehood, coverwithMet-L-X,dry sand,orothernon-combustible

material,andstandawayfromthespill.• Locateandhaveaproperfireextinguisher(drychemical-based)readyincaseofignition/fire.• Useclean,non-sparkingtoolstocollectabsorbedmaterialandplaceintoloosely-coveredmetal

orplasticcontainersreadyfordisposal.• Ifyoucannotassessthesituationwellenoughtobesureofyourownsafety,donotapproach

thespill.• Keepothersfromenteringcontaminatedarea(e.g.,usecautiontape,barriers,etc.).• Reportthespillto510-642-3073.

Self-HeatingSubstancesFireResponse

• Call911(fromacellphone:510-642-3333)forassistancewithallfires,evenifextinguished.• If the spill ignites, and if you are trained and you feel comfortable to do so, consider

extinguishing the fire with an appropriate fire extinguisher. Use only dry chemical fireextinguishers(classesABCorD).

• AcanofMet-L-Xordrysandintheworkarea,withinarm’sreach,mightbehelpfultoextinguishanysmallfireasitcansmothertheflames.

• DonotusewatertoextinguishaSelf-HeatingSubstancefireasitmayenhancetheintensityofthe fire. An exception to thiswould be in the case of skin contact or ignited clothing/skin. Inthesecasesrinsinganyunreactedchemicaloffisofprimaryimportance.

9.CleaningandDecontamination


Rev.Date:2017-03-28

Lab-specificinformationondecontaminationmaybeincludedinSection12-Protocol/Procedure.

• WearingproperPPE,laboratoryworksurfacesmustbecleanedattheconclusionofeachprocedureandattheendofeachworkday.

• Decontaminateallequipmentbeforeremovingfromadesignatedarea.

10.HazardousWasteDisposal

LabelWaste

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

DisposeofWaste

• Disposeofregularlygeneratedchemicalwastewithin6months.

• ContactEH&Sat642-3073ifyouneedassistance.

11.SafetyDataSheet(SDS)Location

SDScanbeaccessedonlineathttp://ucsds.com


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12. Protocol/Procedure-Self-HeatingSubstancesandMixturesProcedure/Use Scale Engineering

Controls/EquipmentPPE(eye,face,gloves,clothing) ProcedureStepsandSpecialPrecautionsfor

thisProcedure1.UsingSelf-heatingsolidasareagent.

Upto10gofsolidassuppliedinthereagentbottle.RemembertoobtainPIapprovalifhigherscaleisnecessary.Documentthisapprovalinyournotebook

ConductinacleanfumehoodwiththesashaslowaspossibleusingSchlenktechniques,oraninertatmosphereglovebox.

EyeProtection:Weartight-fittingsafetygogglesorsafetyglasseswithsideshields.FaceProtection:Faceshieldsaretobeusedwhenthereisnoprotectionfromthehoodsash.HandProtection:Confirmcompatibilityofglovematerialwithchemicalbeingused.Generalguidance(unlessotherwisespecifiedinthespecificSDS):Nitrileglovesmustbeusedtopreventincidentalcontact.Forspillhandlingorforpotentialcontactwithlargerquantities,usedoublenitrileorheaviergaugenitrileorneoprenegloves.Glovesmustbeinspectedpriortouse.Washanddryhandsafteruse.Clothing:WearNomexIIIA(NFPA2112)labcoat;fulllengthpantsorequivalent;andclose-toedandclose-heeledshoes.

GeneralProcedureforSelf-HeatingCompounds:Mostself-heatingcompoundsreactwithatmosphericoxygenormoisturetoliberateflammableproductsexothermically.However,thisreactionoccurssoslowlythattheyaresufficientlystabletohandleinairinsmallquantitiesorforbriefperiodsoftime.Examplesincludemanymetalsulfidesoralkoxidessuchassodiumsulfideorsodiumtert-butoxideandsomeoxidatively-orthermally-unstablecompoundssuchasfinely-dividedelementalcarbon.Addtheseself-heatingreagentstoreactionsinportionsinameasuredandcontrolledmanner.Storetheminsealedcontainersawayfrommoistureandheat(andunderinertgas,ifneeded).Monitorreactionsfortheformationofgas(suchasH2S),whichcouldbeindicativeofairorwaterintrusion.Avoidvigorousoruncontrolledexothermicreactionsandthebuildupofpressurewithinareactionvessel.Coolifnecessary.Adequateventilation(pressurebubbleronSchlenkmanifoldoranequilibratingballoon)hastobeusedtopreventdangerousoverpressurization.

Notes AnydeviationfromthisSOPrequiresapprovalfromPI.


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Procedure/Use Scale Engineering

Controls/EquipmentPPE(eye,face,gloves,clothing) Procedure Steps and Special Precautions

forthisProcedure2.TransferringofliquidSelf-HeatingChemicalsorsolutionsofSelf-HeatingChemicals.

Upto10g(opentransfer)ofaself-heatingneatliquid;orUpto100gofself-heatingmaterialasaneatliquidorinsolution,upto200mLtotaltransferredvolume,assuppliedinthereagentbottle.RemembertoobtainPIapprovalifhigherscaleisnecessary.Documentthisapprovalinyournotebook

ConductinacleanfumehoodwiththesashaslowaspossibleusingSchlenktechniqueswhenappropriate,oraninertatmosphereglovebox.

EyeProtection:Weartight-fittingsafetygogglesorsafetyglasseswithsideshields.FaceProtection:Faceshieldsaretobeusedwhenthereisnoprotectionfromthehoodsash.HandProtection:Confirmcompatibilityofglovematerialwithchemicalbeingused.Generalguidance(unlessotherwisespecifiedinthespecificSDS):Nitrileglovesmustbeusedtopreventincidentalcontact.Forspillhandlingorforpotentialcontactwithlargerquantities,usedoublenitrileorheaviergaugenitrileorneoprenegloves.Glovesmustbeinspectedpriortouse.Washanddryhandsafteruse.Clothing:WearNomexIIIA(NFPA2112)labcoat;fulllengthpantsorequivalent;andclose-toedandclose-heeledshoes.

GeneralRemarks:Mostself-heatingcompoundsreactwithatmosphericoxygenormoisturetoliberateflammableproductsexothermically.However,thisreactionoccurssoslowlythattheyaresufficientlystabletohandleinairinsmallquantitiesorforbriefperiodsoftime.Examplesincludeneatliquidssuchascobaltcarbonylorsolutionsorsuspensionsofsolidself-heatingchemicalssuchaslithiumethoxide.Addtheseself-heatingreagentstoreactionsinportionsinameasuredandcontrolledmanner.Protectthemfromairandmoistureduringstorageandminimizehandlingtimeinair.Whenpossible,quicklyfillasyringeorflaskwiththereagentandsubsequentlytransferitusingstandardairfreetechniques.Monitorreactionsfortheformationofgas(suchasCO),whichcouldbeindicativeofairorwaterintrusion.Avoidvigorousoruncontrolledexothermicreactionsandthebuildupofpressurewithinareactionvessel.Coolifnecessary.Adequateventilation(pressurebubbleronSchlenkmanifoldoranequilibratingballoon)hastobeusedtopreventdangerousoverpressurization.ConsiderationsforLarger-ScaleUseofSelf-HeatingCompounds1:

1AldrichTechnicalBulletin,AL-134HandlingAir-SensitiveReagents


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Smallquantities(<10g)ofliquidself-heatingchemicalsorsolutionsofself-heatingchemicalscanbedispensedinair,buttypicallydegradefromrepeatedatmosphericexposure.Forlargerquantities(>10g),airfreetransferssuchasbycannulaarerecommendedtoprotectyouandthereagent.Disposableplasticsyringeslargerthan20mLareNOTappropriatefortransferringself-heatingmaterials.Inserttheneedle(nolargerthan20gauge)throughtheholeinthemetalcap.Useplasticsyringesandneedlesonlyonce.Ifusedmorethanonce,therubbergasketofaplasticsyringemayswellupleadingtoajammedsyringe.Drawthesyringeplungerslowly,checkingforleaks.Ifthesyringeispulledtoohard,thewater-reactiveliquidcancomeoutthebackofthesyringeontotheresearcher.Orientthesyringeinsuchawaythatanaccidentalspillwillbedirectedawayfromyou.Neveroverfillthesyringe;fillthesyringehalffull,evenifyouneedtomakemultipletransfers.Thepressureinbottlesofmoisturesensitivechemicalsmustbetightlycontrolled.Drawoutwaterreactiveliquidonlyinthepresenceofaflowofinertgastopreventairfromenteringthereagentcontainer.Theplasticcaponthereagentcontaineristobereplacedaftereachuse.Forextendedstorageofunusedreagents,usethesolidplasticcap,orequipthebottlewithasure-sealcaporequivalent.Donotapplytapetothemetalsurfaceofthesure-sealcap;thisisthesurfacethatmakesasealwiththeplasticcap.For


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reagentsthatarestableatambienttemperature,itispreferabletoavoidstoringtheminthefridgetoavoidcondensationandthermalexpansion/contractionoftheseals.Storethemsealedinacool,dryplacelikeadessicator.Clampthereagentbottletopreventitfrommoving.Clamp/securethereceivingvesseltoo.-ReagentTransferwithSyringe-Thesyringetransferofliquidreagentsisreadilyaccomplishedbyfirstpressurizingthesure-sealreagentbottlewithinertgasfollowedbyfillingthesyringe.Theinertgaspressureisusedtoslowlyfillthesyringewiththedesiredvolumeplusaslightexcess(tocompensateforgasbubbles)ofthereagent.Notetheinertgaspressurepushestheplungerbackasthereagententersthesyringe.Donotpullbacktheplungerasthistendstocauseleaksandcreatesgasbubbles.Theexcessreagentalongwithanygasbubblesisforcedbackintothereagentbottle.Theaccuratelymeasuredvolumeofreagentinthesyringeisquicklytransferredtothereactionapparatusbypuncturingarubberseptumonthereactionflaskoradditionfunnel.Followingitsuse,asyringecontainsamountofresidualreagent.ItisadvisabletorinseoutthereactivereagentbyfirstplacingafewmillilitersofthesamesolventthatwasusedforthereactioninasmallErlenmeyerflaskinthehood.Keepingtheneedletipunderthesolventatalltimes,nomorethanhalfthesolventisthen


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drawnintothesyringe.ThesolventplusdissolvedresidualreagentisejectedfromthesyringebackintothesameErlenmeyerflask.Repeatthisrinsetreatmentatleastthreetimes.Thewashsolutioncanbesafelycombinedwithotherwastesolventsandthesyringemaybefurthercleanedwithwaterandacetone.

-ReagentTransferwithCannula(Double-TippedNeedle)-Usealongflexibleneedlethatisonetothreefeetlongtotransferliquidviathecannulamethod.Thedouble-tippedneedletechniquemustbeusedwhentransferring20mLormoreatonce.Pressurizethesure-sealbottlewithnitrogenand


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theninsertthedouble-tippedneedlethroughtheseptumintotheheadspaceabovethereagent.Nitrogenwillpassthroughtheneedle.Inserttheotherendthroughtheseptumatthegraduatedadditionfunnelonthereactionapparatus.Pushtheneedleintotheliquidinthesure-sealreagentbottleandtransferthedesiredvolume.Thenwithdrawtheneedletoabovetheliquidlevel.Allownitrogentoflushtheneedle.Removetheneedlefirstfromthereactionapparatusandthenfromthereagentbottle.Foranexactmeasuredtransfer,conveyfromthesure-sealbottletoadrynitrogenflushedgraduatedcylinderfittedwithadouble-inletadapter.Transferthedesiredquantityandthenremovetheneedlefromthesure-sealbottleandinsertitthroughtheseptumonthereactionapparatus.Applynitrogenpressureasbeforeandthemeasuredquantityofreagentisaddedtothereactionflask.Afteruse,thedouble-tippedneedleisflushedfreeofreagentwithnitrogeninthetransfersystem,andthenimmediatelyremovedandplacedinacleansink.Withwaterrunninginthesinkandinthecompleteabsenceofflammablesolventsandvapors,thedouble-tippedneedlecanberinsedwithwater.Whennoactivityintherinsewaterisobserved,acetonefromasqueezebottlecanbeflushedthroughtheneedle.


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Notes AnydeviationfromthisSOPrequiresapprovalfromPI.


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13.DocumentationofTraining(signatureofallusersisrequired)• PriortoconductinganyworkwithSelf-HeatingSubstancesdesignatedpersonnelmustprovide

training to his/her laboratory personnel specific to the hazards involved in working with thesubstance(s),workareadecontamination,andemergencyprocedures.

• ThePrincipalInvestigatormustprovidehis/herlaboratorypersonnelwithacopyofthisSOPandacopyoftheSDSprovidedbythemanufacturer.

IhavereadandunderstandthecontentofthisSOP:Name Signature Identification Date


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ListofChemicals

Chemical(s) Chemical(s) Chemical(s)Azodicarboxamide Bariumisopropoxide CalciumisopropoxideCarbon-13C Cobaltcarbonyl FormamidinesulfinicacidLithiumethoxide Lithiumisopropoxide LithiummethoxideLithiumtert-butoxide Magnesium MagnesiumethoxideMagnesiumsulphide N,N-Dimethyl-4-nitrosoaniline Potassium(poly)sulfidePotassiumethoxide Potassiumisobutoxide PotassiummethoxideSelectfluor(R)fluorinatingreagent Selectfluor(R)IIreagent SodiumethoxideSodiumhydrosulfite Sodiummethoxide SodiumsulfideSodiumtert-butoxide Sodiumtert-pentoxide StrontiumisopropoxideTitanium(IV)sulfide

self-heating substances and mixtures · 2. self-heating substances and mixtures information a...

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