Bromine handling and safety

1. Bromine Handling & Safety
Bromine,Br2,isthe only non-metallicelementthatisliquidat ordinarytemperaturesandpressures.Ithasa dark,
amber-redcolorand an intenselyirritating odour.
Bromine exposure,eitherbyliquidcontactor vapor inhalation, representsahazardwiththe potential of serious
injuryor death.The liquidrapidlyattacksskinandothertissuestoproduce irritationand necrosis.Comparatively
lowconcentrationsof vaporare quite painful andare highlyirritatingtothe eyesandthe entire respiratorytract.
Excessive exposuretoacutelydangerousconcentrationswill resultin seriousinflammationandedema,frequently
followedbypneumonia.
Excessive exposuretolowconcentrations,althoughnotacutelydangerous, will resultininflammatoryreactionsin
the eyesandrespiratory passages.Vaporconcentrationsof 500-1000 parts permillion(ppm) by volume are
dangeroustolife atexposuresfor0.5 to 1 hour.
The maximumpermissibleexposureweightedover8hours is0.1 ppm.At this level brominecanstill be detectedby
itsodour.A concentrationof 10 ppmcan hardlybe toleratedformore thana few moments.
Bromine,apowerful oxidizingagent,iscapable of causing combustiblestoignite oncontact.Itis Extremely
HazardousSubstances.
Chemical Reactions
Bromine isa veryreactive elementcharacterizedbyastrong oxidizing capability.Itformsawide range of bromine
containingcompoundson reactionwithnumerousinorganicandorganicsubstrates.A limited,but
typical,illustrationof suchreactionsfollows.
Inorganic Bromine Compounds
Bromine readilyoxidizesmetallicand non-metallicelementsas indicatedbythe followingequations:
3Br2 + 2Fe 2FeBr3
6Br2 + P4 4PBr3
3Br2 + S +4H2O 6HBr + H2SO4
Br2 + H2 2HBr
Reactionof bromine withwaterresultsinthe formationof anaqueous solutionof hydrobromicandhypobromous
acids.The latterisrelatively stable onlyinsolution,anddecomposesunderthe influence of heat, lightorcopper
catalysistoproduce hydrobromicacidand oxygen.
Br2 + H2O HBr + HOBr
Reactionsof bromine andammoniaoccurreadily,anddependingupon temperature andpressure,produce
nitrogenandhydrogenbromide, bromamines,andammoniumbromide.The ammoniumbromide formsas aresult
of the reactionbetweenhydrogenbromide andexcessammonia present.
Withstrong alkalisatlowtemperaturesinaqueoussolutions,bromine reactstoproduce bromide andhypobromite
salts.
Br2 + 2 NaOH NaBr + NaOBr + H2O
At elevatedtemperatures,the hypobromite undergoesanoxidationreduction reactiontoproduce bromate and
bromide salts.
3 NaOBrNaBrO3 + 2NaBr
The balancedsummationof these tworeactionequationsyields:

2. 3 Br2 + 6 NaOH 5 NaBr + NaBrO3 + 3 H2O
Some typical oxidation-reductionreactionsof bromine withinorganiccompoundsunderalkalineoracidic
conditionsare illustratedinthe followingreactions:
Br2 + H3PO3 + 3NaOH NaH2PO4 + 2NaBr + 2 H2O
Br2 + 2KI 2KBr + I2
Br2 + NaNO2 + H2O NaNO3 + 2HBr
2Br2 + FeSO4+8 NaOH Na2FeO4+ Na2SO4 + 4NaBr + 4H2O
Br2 + 2FeSO4 + H2SO4 Fe2(SO4)3+ 2HBr
Procedures for the Safe Handling of Bromine
Extreme care must be exercisedinthe storage,handling,shippingand use of bromine.Vaporsare asevere skin,
eye andmucousmembrane irritant.Contactwithliquidbromine cancause severe burns.The readilyidentifiable
colorand pungentodorgivesimmediatewarningof bromine’spresence.Ataconcentrationof onlyone part per
million (ppm),bromine iseasilydetectableandevenlesseramountscancause eye irritation.The OSHA Permissible
Exposure Limit(PEL) forbromine is0.1 ppm.
Safetyisthe personal responsibilityof everyone workingwithor aroundbromine.Supervisorypersonnelmust
knowand enforce the recommendedsafe handlingpracticesoutlinedinthismanual.Every employeeandcontract
employeeis tobe safetytrainedatthe time of employmentandup-datedonsafetyproceduresmonthly.
Personal Safety Precaution --Recommendations
1. Wear AmericanNational StandardsInstitute (ANSI) approved chemical safetygogglesatall times.Whenhandling
Br2 use a full face shieldovereyewear.Eyewashfountainsshouldbe locatedin areaswhere bromine ishandled,
usedor stored.If bromine liquidor vaporcontacts the eyes,theymustbe irrigatedimmediatelywith large amounts
of runningwater.Eye washstationsare preferable for irrigation.If one isnotavailable,ahose,drinkingfountain,or
otherwatersource witha liberal,gentle flowmaybe utilized.The eyelidsshouldbe heldapartduringirrigationto
ensure contactof waterwithall accessible tissuesof the eyesandlids.Eyesshould be washedcontinuouslyfora
minimumof 30 minutes.If possible, continue flushingthe eyeswhiletransportingthe employeetoa physician.
2. When indangerof contact withliquidbromine,wearanapproved chemical resistantsuit.Inanenclosedarea,
wearcleanclothing, protective glovesandeye andface protection.Neverwearclothes thatsmell of bromine.
Wash contaminatedclothingandequipment beforereuse.
3. Wear leatheror othernon-wovenANSIapprovedsteel-toedshoes. Protectiverubberbootsshouldbe wornover
shoesforextraprotection. Discardshoesthathave beenincontact withliquidbromine.
4. For skincontact, the affectedareashouldbe floodedimmediately withlarge amountsof waterfroma safety
showeror othersource of flowingwater.All contaminatedclothing,includingshoes,should be removedasquickly
as possible while the victimisunderthe shower.Washingshouldbe continuedforaminimumof 30 minutes.
The victimshouldreceive medical attentionassoonaspossible. (Extendedwashtimesof twohoursor more have
provenbeneficial.)
5. To insure adequate personnel protection,periodicallyinspectand repairall protectiveclothingandequipment.
6. To avoidbromine ingestion:
a) Alwayswashface,handsandarms before eating.

3. b) Neverplace bromine contaminatedarticlesinthe mouth.
c) Don’tsiphonor blowoutcloggedlinesornozzlesbymouth.
7. To avoidinhalationof bromine:
a) Stayupwindwhenloading,unloadingandtransporting bromine.
b) Have NIOSHapprovedrespiratorsandself-containedbreathingapparatusavailable.
c) Whenhandlingbromine inanenclosedareawearprotective clothingandrespiratoryequipment.
d) Adhere toyour plant regulationsregardingrespiratory equipmentforbromine handling.
8. Bromine isso painful tothe eyes,nose andthroatthat it gives ample warningof itspresence inacutely
hazardousconcentrations.
If overexposure doesoccur,the victimshouldbe immediatelyremovedfromthe contaminatedareatofreshair.
The victimshould be placedina comfortable position.Usually,thatwill be asitting orpartlyrecliningposition.The
exposedindividualshouldavoid exertion.If vomitingoccurs,turnthe patientonhisside to avoid choking.Keepthe
patientwarm.If the patientdoesnotrecover quicklyoriscoughingand showingsignsof respiratorydistress,
properlytrainedpersonnelshouldadministeroxygen.If respiration hasceased,artificialrespirationshouldbe
administered.The victim shouldreceive medical attentionassoonaspossible.
Personal Protective , Clothing and Equipment , Respiratory Equipment
1. For escape only,provide eithera5-minute airbottle withhood,a mouthpiece respiratorwithacid cartridge,ora
full face or half mask respiratorwithchemical cartridges.Refermanufacturerinstructions.
2. For work inan enclosedora poorlyventilatedarea,NIOSH approvedpressure demandself-containedbreathing
apparatusor pressure hose and maskswithegressbottle are used.
3. All respiratoryequipmentmustbe carefullymaintainedandstored inaccordance withmanufacturer’s
instructions.
Clothing
The protective clothingshownisthe recommendedminimum protectionthatshouldbe wornwhere bromineis
handled.
 Coveralls&Jacket
 PVC
 Face Shield
 Polycarbonate
 Goggles
 Chemical SplashResistant
 Boots
 PVCBlendBoots
 Gloves
 100% Nitrile rubbergloves
Safety Practices in the Work Area
GENERAL INSTRUCTIONS
1. Read and followall directionsandwarninglabelscarefully.

4. 2. Informall personnel of the potentialhazardsof contactwith bromine andtrainthemin appropriate first-aid
procedures.
3. Store andhandle bromine overdrippansdrainedbya sumpthat is ventedtoa scrubbersystem.
4. Bromine handlingareasshouldbe clearlymarkedandrestrictedto qualified,trainedpersonnel only.
5. Maintainuncontaminatedequipment,floorsandworkareas.As routine maintenance,periodicallyscrubfloors.
6. Immediatelycontainandcleanupall bromine spills.
a) Wear approvedrespiratoryequipmentandprotective clothing.
b) Carefullyrelease anhydrousammoniavaportoneutralize bromine vapoursinthe air.Ammonia(16to 25% by
volume) canforman explosive mixture withair.
c) Poursoda ash solutionorhyposolutiononthe liquid bromine toneutralize.
d) Using coldwater,washneutralizedbromine toasump for disposal.
e) Opendoorsand windowstoventilate.
7. Avoidcontact of bromine withstrongreducingagents,strongalkalis, metals,wood,paperproducts,fabric,
grease andoil or other combustiblematerials.
VENTILATION
1. Restrictbromine vaporconcentrationinthe workarea to lessthan 0.1 ppmwithadequate exhausthoods,
ventilationsystemsand scrubbers. Analyseairforpropercontrol.
2. Transferor repackage bromine onlyinacontrolled,closed environment.
3. Exhaustventilatingsystemsmustbe usedinenclosedareaswhere bromine ishandled.
CONTAINERS AND STORAGE
1. Empty shippingcontainerscompletely.
2. Neverputwaterin steel bromine cylindersexceptasinstructedin the cylinderdecontaminationprocedures.
3. Do notreturnusedor recycledbromine orotherbromine containingliquidstoChemical drumsorcylinders.
Thiscan leadtoseriouscorrosionof the drumsand cylindersandresultineventualfailure.
4. Store bromine inadry, well-ventilatedarea,protectedfrommoistureandexcessiveheatorcold.
5. Store onlyinstandardcontainers,neverinthose thatresemble food orbeverage packaging.
6. Checkall equipmentusedforbromine handlingorprocessingfor deteriorationandleakyvalvesandcouplings.
7. Protect bromine-handlingequipmentfromstrongalkalis,reducing agents,othermetals,wood,fabric,paper,
grease andoils.
FIRE PRECAUTIONS
1. Alwaysweara self-containedbreathingapparatusaroundbromine or bromine-containingcompoundsinafire.
2. Bromine doesnotburn,but it isa strong oxidizerandwill react violentlywith aluminium,titanium, mercury,
sodiumandpotassium.

5. 3. Wood, paperproducts,fabric,petroleumproducts,plasticsandother organicsmayspontaneouslycombustin
the presence of liquid bromine,whichisapowerful oxidizer.
4. Dry bromates(productsof sodiumhydroxide neutralizationof bromine) are powerful oxidantsandare shock
sensitive. Theymustbe handledwithextreme care.
HOW TO RECOGNIZE BROMINE OVEREXPOSURE
Because bromine ishighlyirritatingtothe eyes,nose andmucous membranes,overexposureisunlikelytooccur.
However,if overexposure occurs,symptomsinclude:excessive tearing,rednessandirritationof the eyes,throat,
and nose,severe skinburnsand,withprolonged, unprotectedexposure,respiratorydamage andrespiratoryarrest.
FIRST AID FOR BROMINE EXPOSURE
1. Immediate medical assistance isrequiredif bromine is swallowed,inhaledorhascontactedthe eyesor skin.
2. If bromine hasbeeningested,donotgive anythingbymouth.Seek medical attentionimmediately.Donotinduce
vomiting.
3. If bromine hasbeeninhaled,move the exposedpersontoawell ventilated area.Seekmedical attention
immediately.The victim shouldbe placedinacomfortable sittingorpartlyrecliningposition.
The exposedindividual shouldavoidexertion.If vomiting occurs,turnthe patientonhisside toavoidchoking.Keep
the patientwarm.If the patientiscoughingandshowingsignsof respiratorydistress,properlytrainedpersonnel
shouldadministeroxygen.
4. For skincontact, the affectedareamustbe floodedimmediately withlarge amountsof cleanwaterfroma safety
showeror otherappropriate source of flowingwater.Seekmedical attentionimmediately.
All contaminatedclothing,includingshoes,shouldbe removedasquicklyaspossiblewhile the victimisunderthe
shower. Washingshouldbe continuedforaminimumof 30 minutes. If possible,continuetowashthe affectedarea
duringtransportto medical facilities.(Extendedwashtimesof twohoursormore have provenbeneficial.)
5. If bromine liquidorvaporcontacts the eyes,theymustbe irrigated immediatelywithlarge amountsof running
water.Eye wash stations are preferable forirrigation.If one isnotavailable,ahose,drinking fountain,orwater
source witha liberal,gentleflow maybe utilized.
The eyelidsmustbe heldapartduringirrigationtoensure contactof waterwithall accessible tissuesof the eyes
and lids.Eyesshould be washedcontinuouslyforaminimumof 30 minutes.If possible, continue flushingthe eyes
while transportingthe employeetoa physician.
In all casesof bromine injury,obtainimmediatemedical attention. Provide emergencypersonnel withinformation
aboutall materialsused bythe personandprovide appropriate informationaboutbromine and firstaid
procedures.
TOXICOLOGY
Bromine isa verystrongoxidant.Itis extremelytoxicandmayprove fatal if inhaledorswallowed.Severe burns
may resultfromskincontact, and contact withthe eyesmaycause blindness.Bromine is extremelydestructive to
tissue of the mucousmembranesandupper respiratorytract.Bromine exposure mayresultinspasm, inflammation
and edemaof the larynx andbronchi,chemical pneumonitisandpulmonary edema.Low concentrationsof bromine
vapor cause irritation, tearingandinflammationof the eyes.Athigherconcentrationsblepharospasm and
photophobiadevelopanda splashinthe eyescauses severe burnsand/orblindness.Softtissue burnsmaybe deep
and very slowtoheal.
Storage

6. Store drums,emptyor full,uprightandinside,inacool (above -7oC/ 20oF),dry,place.Exposingdrumstoheat will
cause dangerous pressure todevelop.Severe corrosionoccursif the drumsare exposedtomoisture.
Do not expose toroughhandling.Neverreturnbromine to these drums,due tothe potentialforcontaminationand
corrosion.
Whenstoredoverextendedperiods,periodicallyinspectdrums,bungs andgaskets.