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HowtousetheHandbook Toseek 1. Stabilitydataonsinglespecificcompounds: lookinSection1usingeitherthechemicalnameindex(Appendix4)ortheempirical molecularformulaatrightofsecondtitleline(Carbon;thenHydrogenifpresent;otherelementsfollowalphabetically)tolocatethe page.Membershipofageneralgroupisshownbya Seeother ...cross-reference.
2. Dataonpossibleviolentinteractionbetweentwoormorecompounds: determinewhichappears“morereactive”andfinditasin1 above.Thenlookdownthesubentrytitlesfortheothercompound(s)involvedwhichmaybegivenasasinglecompoundorasoneofa groupThelatterarelistedin Appendix6
3. Generaldataonaclassorgroupofcompounds,orinformationonidentityofindividualsinaknownhazardousgroup: referto theAlphabeticalSection2.Thereisaclassifiedindexin Appendix6
4. Structureassociatedwithexplosiveinstability: See EXPLOSIBILITY
5. Informationongeneraltopics: usetheindexesin Appendix6
6. Fire-relateddata: thisistabulatedin Appendix2
7. InformationonacompoundidentifiedbyitsCASRegistrynumber:thereisanumericalindexofCASnumbers vs Serialnumbers in Appendix5
Donotassumethatlackofinformationmeansthatnohazardexists.Lookfurtheratrelatedstructures,using Appendix6. Seerearendpaperfor Whatthehandbookprovides.
Readersareencouragedtosubmitdetailsofnewreactivehazardsforinclusioninlatereditions.Thereisapageyoucancopyforthis purposeattheendofbook.
Bretherick’sHandbookof
ANINDEXEDGUIDETOPUBLISHEDDATA
Bretherick’sHandbookof ReactiveChemical Hazards EighthEdition Editedby PGUrben
Assistedby MJPitt DepartmentofChemicalandBiologicalEngineering UniversityofSheffield
Elsevier Radarweg29,POBox211,1000AEAmsterdam,Netherlands TheBoulevard,LangfordLane,Kidlington,OxfordOX51GB,UnitedKingdom 50HampshireStreet,5thFloor,Cambridge,MA02139,UnitedStates
© 2017ElsevierLtd.Allrightsreserved.
Nopartofthispublicationmaybereproducedortransmittedinanyformorbyanymeans,electronicormechanical,including photocopying,recording,oranyinformationstorageandretrievalsystem,withoutpermissioninwritingfromthepublisher. Detailsonhowtoseekpermission,furtherinformationaboutthePublisher’spermissionspoliciesandourarrangementswith organizationssuchastheCopyrightClearanceCenterandtheCopyrightLicensingAgency,canbefoundatourwebsite: www.elsevier.com/permissions.
ThisbookandtheindividualcontributionscontainedinitareprotectedundercopyrightbythePublisher(otherthanasmaybe notedherein).
Notices
Knowledgeandbestpracticeinthisfieldareconstantlychanging.Asnewresearchandexperiencebroadenourunderstanding, changesinresearchmethods,professionalpractices,ormedicaltreatmentmaybecomenecessary.
Practitionersandresearchersmustalwaysrelyontheirownexperienceandknowledgeinevaluatingandusingany information,methods,compounds,orexperimentsdescribedherein.Inusingsuchinformationormethodstheyshouldbe mindfuloftheirownsafetyandthesafetyofothers,includingpartiesforwhomtheyhaveaprofessionalresponsibility.
Tothefullestextentofthelaw,neitherthePublishernortheauthors,contributors,oreditors,assumeanyliabilityforany injuryand/ordamagetopersonsorpropertyasamatterofproductsliability,negligenceorotherwise,orfromanyuseor operationofanymethods,products,instructions,orideascontainedinthematerialherein.
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ISBN:978-0-08-100971-0
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PrefacetotheEighthEdition Chemicalsafetystudiesmostlyconcentrateontoxicity.Butaccidentalpoisoningisrare,and,whenithappens,asatBhopal,the poisonwasoftenbroadcastbyaviolentreaction.Explosionand fire,thelatteralsofrequentlyprecededbylossofcontainment, aremoreoftenwhatkillandinjurechemicalworkers,evenif notasoftenastheroadstoandfromwork.
Explosionhazards,thoughwell-demonstrated,maybeforgottenoverthedecades-so,acenturyafteritsexplosivitywas shown,anexplosivecomparablewithTNTmayberegardedas justanothersolvent.
Fiftyyearsago,thelateLeslieBretherick,aworkingchemist inindustry,resolvedtoassembleacompendiumofknownviolent andexplosivereactionhazards,leavenedbyoccasionaltouchesof humour.Thishelaterorganisedbyempiricalformulae,for chemicalnomenclaturechanges,butformulaedonot.
Twenty-fiveyearssince,hissightfailing,hehandedover responsibilitytome,alsoanindustrialchemist,ablyassisted byDr.MartinPittcoveringChemicalandBiologicalEngineering material.LeslieBretherickwishedtoupholdtheinsightsofpractitioners,notthefearsofSafetyProfessionals.Evennow,heis stillresponsibleforhalfofthecontent,andoversawmy
contributionsuntilhisdeath.Nowmyselfofdecliningsight, andsomeyearsretiredthuslosingcontactwithchemicalreality, thiswillbemylastedition.Itishopedthatasuccessorcanbe found,orwillpresentthemselves.
Originally,Bretherickattemptedtocoverallaspectsofhazard byreaction,exceptexplosive,propellantandpyrotechnicformulationsintheirintendeduse,butproliferatingtheoreticalsafety publicationshavecausedustofocusmoreonthe“undoctoredincidentsthatactuallyoccurred.”
Muchoftheevidenceisanecdotalandempiricalso(re) searchersarewarnedthat,althoughareportedexplosion undoubtedlyhappened,thegivenexplanationmaynotbecorrect. Inparticular,attributiontominorcomponentsorimpuritiesis suspect,thesemaycatalysereaction,butdonotprovidemajor energies.Neithershoulditbeassumedthatalllistedcomponents ofamixcontributedtothemishap.
You,reader,remainultimatelyresponsibleforyoursafety: Search,readandthink,beforeexperimenting,toavoidpresent harmtoyourselfandothers.And,toprotectfutureothers,please reportanymishapsyoumayhave,andanyerrorsandomissions youmayfindinthiscompendium.
Section1
SPECIFICCHEMICALS1 (ElementsandCompoundsArrangedinFormulaOrder)
Section2
CLASS,GROUPANDTOPIC1155 (EntriesArrangedinAlphabeticalOrder)
APPENDIX1SourceTitleAbbreviationsused inHandbookReferences1403
APPENDIX2TabulatedFire-relatedData1409
APPENDIX3GlossaryofAbbreviationsand TechnicalTerms1427
APPENDIX4IndexofChemicalNamesand SynonymsusedinSection11431
APPENDIX5IndexofCASRegistry Numbers vs SerialNumbersinSection11477
APPENDIX6IndexofSection2Titles ClassifiedbyType1493
Introduction THISSHOULDBEREADTHROUGHCAREFULLYTOGAINFULLBENEFITFROMWHATFOLLOWS
AimsoftheHandbook Thiscompilationhasbeenpreparedandrevisedtogiveaccesstoa wideandup-to-dateselectionofdocumentedinformationto researchstudents,practisingchemists,safetyofficersandothers concernedwiththesafehandlinganduseofreactivechemicals. Thiswillallowreadyassessmentofthelikelypotentialfor reactionhazardswhichmaybeassociatedwithanexistingorproposedchemicalcompoundorreactionsystem.
Asecondary,longer-termpurposeistopresenttheinformation inawaywhichwill,asfaraspossible,bringoutthecausesof,and interrelationshipsbetween,apparentlydisconnectedfactsandincidents.Thisisdesignedtoencourageanincreasedawarenessof potentialchemicalreactivityhazardsinschool,collegeanduniversityteachinglaboratories,andtohelptodispeltherelative ignoranceofsuchmatterswhichisstillinevidenceinthis importantareaofsafetytrainingduringtheformativeyearsof technicaleducation.
Othersinvolvedinamoregeneralwaywiththestorage, handling,packing,transportanddistributionofchemicals,or emergenciesrelatedthereto,arelikelytofindinformationofrelevancetotheiractivities.
Scopeandsourcecoverage ThisHandbookincludesallinformationwhichhadbecome availabletotheEditorbyearly2014onthereactivityhazards ofindividualelementsorcompounds,eitheraloneorincombination.Appropriatesourcereferencesareincludedtogiveaccess tomoreexpansiveinformationthanthatcompressedintothenecessarilyabbreviatedtextentries.
Awidevarietyofpossiblesourcesofpublishedinformation hasbeenscannedtoensuremaximumcoverage.Primarysources havelargelybeenrestrictedtojournalsknowntofavourorspecialiseinpublicationofsafetymatters,andthetextbookseriesspecialisinginsyntheticandpreparativeprocedures.
Secondarysourceshavebeenafairlywidevarietyofboth specialisedandgeneraltextbooksandencyclopaediccollections (notablythoseofMellor,Sidgwick,PascalandBailarinthe inorganicarea,Houben-Weylintheorganicandorganometallic areas,andbothKirk-OthmerandUllmannintheindustrialarea). Section50of ChemicalAbstracts,theCASselection Chemical Hazards,Health,&Safety,the Universities’SafetyAssociation SafetyNews (nowlapsed),theCIA CISHCChemicalSafety Summary,(publicationofwhichceasedin1986after56years), andtheIChemE LossPreventionBulletin havebeenrichsources,
togetherwiththelaterrecentRSC LaboratoryHazardsBulletin and ChemicalHazardsinIndustry.Additionally,varioussafety manuals,compilations,summaries,datasheetsandcasehistories havebeenused,andfullerdetailsofthesourcesusedaresetout inAppendix1.Referencesinthetexttotextbookslistedin Appendix1arecharacterisedbyabsenceoftheauthor’sinitials afterthesurname.
DatatakenfromtheInternethasbeenincludedwhenitfulfills twoofthefollowingthreecriteria:TheEditorfindsitcredible;the sourceisauthoritative;thehazardorincidentwasnotpreviously included.
Informationontoxichazardshasbeenspecificallyexcluded becauseitisavailableelsewhereinmanywell-orderedandreadily usableforms.Howeveritshouldberememberedthatmanyofthe compoundsincludedinthisHandbookshowhighreactivityofone sortoranothertowardothermaterials,somayingeneraltermsbe expectedtobereactiveeveninbriefcontactwithanimal organismsortissue(includingyours),withpossibletoxiceffects, eitheracuteorchronic.Toxicityhas,however,beenconsidered whenachemicalreactionnotforseeablebytheaveragestudent generatesavolatilepoison – thereisnowarningthatsulfides andacidsgeneratehydrogensulfide,frequentcauseoffatality thoughthatis,butgenerationofcarbonmonoxidebyinteraction ofalkalianddriedmilkiscovered.
Noattempthasbeenmadetoincludedetailsofallflammable orcombustiblematerialscapableofburningexplosivelywhen mixedwithairandignited,norofmostincidentsrelatedtothis mostfrequentcauseofaccidents,suchinformationagainbeing availableelsewhere.However,tofocusattentiononthepotential hazardsalwaysassociatedwiththeuseofflammableandespeciallyhighlyflammablesubstances,some560gasesandliquids withflashpointsbelow25°Cand/orautoignitiontemperature below225°Chavebeenincludedinthetext,theirnamesprefixed withadagger.Thenumericalvaluesofthefirehazard-related propertiesofflashpoint,autoignitiontemperatureandexplosive (flammability)limitsinairwhereknownaregiveninthetabular Appendix2.Thoseelementsorcompoundswhichigniteon exposuretoairareincludedinthetext,butnotintheTable.
Generalarrangement Theinformationpresentedonreactivehazardsisoftwomain types,specificorgeneral,andthesetypesofinformationhavebeen arrangeddifferentlyintheirrespectiveseparateSections1and2. Specificinformationoninstabilityofindividualchemical compounds,andonhazardousinteractionsofelementsand/or
compounds,iscontainedinthemainformula-basedSection1of theHandbook.Foranexampleofanunstablecompound, see Ethylperchlorate,p.208
Foranexampleofahazardousinteractionbetween2compounds, see Nitricacid:Acetone,p.926 or2separateexamplesinvolvingthesamecompound, see Nitricacid:Acetone,or:Ethanol,pp.926,927 andoneinvolving3compounds, see Hydrogenperoxide:Nitricacid,Thiourea,p.126
Generalinformationrelatingtoclassesorgroupsofelementsorcompoundspossessingsimilarstructuralorhazardous characteristicsiscontainedin thesmalleralphabeticallybased Section2.
See ACYLNITRATES,p.1161
PYROPHORICMETALS,p.1354
Referencesinthetexttothesegeneralclassesorgroupsofmaterialsisalwaysinsmallcapitalstodifferentiatethemfromreferencestospecificchemicals,thenamesofwhicharegivenin normalromantypeface.
Someindividualmaterialsofvariablecomposition(substances)andmaterialswhichcannotconvenientlybeformulated andplacedinSection1arealsoincludedinthisgeneralsection.
See BLEACHINGPOWDER, CELLULOSENITRATE,pp.1186,1192
Boththeoreticalandpracticalhazardtopics,someindirectly relatedtothemainthemeofthisbook,arealsoincluded.
See DISPOSAL, EXPLOSIBILITY,pp.1216,1228
GASCYLINDERS, OXYGENENRICHMENT,pp.1241,1329
Severaltopicswhichbringtogetherincidentsinvolvinga commonphysicalcauseoreffectbutdifferenttypesofchemicals arenowincludedinSection2.
See CATALYTICIMPURITYINCIDENTS,p.1190 GASEVOLUTIONINCIDENTS,p.1241
Specificchemicalentries(Section1) Asingleunstablecompoundofknowncompositionisplacedinthe mainfirstsectionandislocatedonthebasisofitsempirical molecularformulaexpressedintheHillsystemusedby Chemical Abstracts (CandHifpresent,thenallotherelementsymbols alphabetically).Theuseofthisindexingbasispermitsacompound tobelocatedifitsstructurecanbedrawn,irrespectiveofwhethera validnameisknownforit.Arepresentationofthestructureof eachcompoundisgivenonthethirdboldtitlelinewhilethename ofthecompoundappearsasthefirstboldtitleline.Referencesto theinformationsourcearegiven,followedbyastatementofthe observedhazard,withanyrelevantexplanation.Cross-reference tosimilarcompounds,ofteninagroupentry,completestheentry.
See Trifluoroacetylnitrite,p.156
Wheretwoormoreelementsorcompoundsareinvolvedina reactivehazard,andanintermediateorproductofreactionisidentifiableasbeingresponsibleforthehazard,bothreactingsubstancesarenormallycross-referredtotheidentifiedproduct. Thewell-knownreactionofammoniaandiodinetogiveexplosive nitrogentriodide-ammoniaisanexampleofthistype.Thetwo entries
Ammonia:Halogens,p.980
Iodine:Ammonia,p.1016 arereferredbacktothemainentryundertheidentifiedmaterial Nitrogentriiodide-ammonia,p.1019
Noattempthasbeenmade,however,tolistallcombinationsof reactantswhichcanleadtotheformationofaparticularmainentry compound.
Inamulti-reactantsystemwherenoidentificationofan unstableproductwaspossible,oneofthereactantshadtobe selectedasprimaryreactanttoprepareandindexthemainentry, withtheothermaterial(s)assecondaryreactant(s).Nostrictly logicalbasisofchoiceforthisisobvious.
However,itemergedduringthecompilationphasethatmost twocomponentreactionhazardsystemsofthistypeinvolvea fairlyobviousoxidantmaterialasoneofthereactants.Wherethis situationwasrecognised,theoxidanthasnormallybeenselected asprimary(indexing)reactant,withtheotherassecondary reactant,followingthecolon.
See Potassiumpermanganate:Aceticacid,etc.,p.1026
Inthemarkedlyfewercaseswhereanobviousreducanthas beeninvolvedasonereactant,thatwasnormallyselectedas primaryreactant.
See Lithiumtetrahydroaluminate:3,5-Dibromocyclopentene, p.29
Intherelativelyfewcaseswhereneither(ornone)ofthereactantscanberecognisedasanoxidantorreducant,thechoicewas madewhichappearedtogivethemoreinformativemainentry text.
See Chloroform:Acetone,etc.,p.97
Wheresomehazardhasbeennotedduringthepreparationofa specificcompound,butwithoutitbeingpossibletoidentifyaspecificcause,anentryforthatcompoundstates‘Preparativehazard’, andback-referstothereactantsinvolvedinthepreparation.
See Sulfurdioxide,p.1106
Occasionally,departuresfromtheseconsiderationshavebeen madewheresuchactionappearedadvantageousinbringingouta relationshipbetweenformallyunrelatedcompoundsorhazards.In allmulti-componentcases,however,thesecondaryreactants (exceptairandwater)appearasformulaentriesback-referredto themainentrytext,sothatthelatterisaccessiblefromeither primaryorsecondaryreactants.
See Dimethylsulfoxide:Acylhalides(mainentry),p.220
Acetylchloride:Dimethylsulfoxide(backreference),p.180
Groupingofreactants Thereareadvantagestobegainedingroupingtogetherelements orcompoundsshowingsimilarstructureorreactivity,becausethis tendstobringouttherelationshipsbetweenstructureandactivity moreclearlythanseparatetreatment.Thiscoursehasbeenadopted widelyforprimaryreactantsinSection2,andforsecondaryreactantswhereoneprimaryreactanthasbeeninvolvedseparately withalargenumberofsecondarymaterials.Wherepossible,the latterhavebeencollectedtogetherunderasuitablegeneralgroup titleindicativeofthecompositionorcharacteristicsofthose materials.
See Chlorine:Hydrocarbons,p.820
Hydrogenperoxide:Metals,Metaloxides,Metalsalts,p.966 Hydrogensulfide:Oxidants,p.976
Thisarrangementmeans,however,thatsomepracticewill benecessaryontheuser’spartindecidingintowhatgroup anindividualsecondaryreactantfallsbeforethelonger-term advantagesofthegroupingsbecomeapparent.Theformalgroup titlesinSection2,classifiedinAppendix6,willbeofusein
thisconnection.However,itshouldbenotedthatsometimes informalgrouptitlesareusedwhichdonotappearinthese Appendices.
Generalgroupentries(Section2) Insomecasesliteraturereferencesrelatingtowell-definedgroups ofhazardouscompoundsortohazardtopicshavebeenfound,and thesearegiven,withacondensedversionofrelevantinformation atthebeginningofthetopicorgroupentry,underasuitablebold title,thelatterbeingarrangedinalphabeticalorderinSection2.
Crossreferencestorelatedgrouporsub-groupentriesarealso included,withagrouplistofthenamesandserial(notpage) numbersofthechemicalsappearinginSection1whichliewithin thestructuralorfunctionalscopeofthegroupentrytitle.Compoundswhicharecloselysimilarto,butnotinstrictconformity with,thegroupdefinitionareindicatedbyaprefixedasterisk.
Thegroupentriesthusserveassub-indexesforeachstructurallybasedgroupofhazardouscompounds.Conversely,each individualcompoundentryisback-referredtothegroupentry, andthencetoallitsstrictstructuralanaloguesandrelatedcongenersincludedinSection1ofthisHandbook.Notethatthese grouplistsofchemicalsarenowinalphabetical(notformula) order,andgivetheserialnumber(notpagenumber)forthe chemical.
Thesefeaturesshouldbeusefulinattemptstoestimatethestabilityorreactivityofacompoundorreactionsystemwhichdoes notappearinthisHandbook.Theeffectsonstabilityorreactivity ofchangesinthemolecularstructuretowhichthedestabilisingor reactivegroup(s)isattachedareinsomecasesdiscussedinthe groupentry.Otherwisesuchinformationmaybegainedfromcomparisonoftheinformationavailablefromtheindividualcompound entrieslistedcollectively(nowinalphabeticalorder,withserial number)inthegroupentry.
Careis,however,necessaryinextrapolatingfromthe describedpropertiesofcompoundstoothersinwhichtheuser ofthisHandbookmaybeinterested.Dueallowancemustbemade forchangesinelementalreactivityupordownthecolumnsofthe PeriodicTable,andfortheeffectsofvariationinchainlength, branchingandpointofgroup-attachmentinorganicsystems. Purityofmaterials,possiblecatalyticeffects(positiveornegative)ofimpurities,andscaleofoperationsmayallhaveadirect bearinguponaparticularreactionrate.Theseandotherrelated mattersaredealtwithinmoredetailinthefollowingIntroductory Chapter.
Nomenclature WiththedirectencouragementandassistanceofthePublishers,an attempthasbeenmadetousechemicalnameswhichconformto recentrecommendationsofIUPAC.Whilethishasnotbeenan essentialpartofthecompilation,becauseeachtitlenamehas thecorrespondingstructuralandmolecularformulaadjacent,it seemsnonethelessdesirabletominimisepossibleconfusionby adoptingtheunambiguoussystemofnomenclaturepresentedin theIUPACpublications.
WheretheIUPACnameforacompoundisverydifferentfrom apreviouslyusedrecenttrivialname,thelatterisincludedasa synonyminparentheses(andinsinglequoteswherenolonger anacceptablename).Generally,retainedtrivialnameshavenot
beenusedasmainentrytitles,buttheyhaveoftenbeenincluded intheentrytexts.Rarely,onthegroundsofbrevity,namesnotconformingstrictlytoIUPACprinciplesbutrecommendedforchemicalsusedinindustryinBS2474:1983havebeenused.The prefix mixo-,torepresentthemixturesofisomerssometimesused asindustrialmaterials,isacaseinpoint.
SomeoftherigidlysystematicnamesselectedbytheAssociationforScienceEducationfortheirnomenclaturelistin1985 fromtheIUPACpossibilities,andsomeofthesystematicindexing namesusedby ChemicalAbstracts since1972,aregivenassynonymsintheIndexofChemicalNames.Thisshouldassistthose comingintoindustryandresearchwithacommandofthose nomenclaturesystemsbutwhomaybeunfamiliarwiththecurrent varietyofnamesusedforchemicals.Theinclusion,wherepossible,oftheCASRegistryNumberforeachtitlecompoundshould nowsimplifytheclarificationofanychemicalnameorsynonym problems,byreferencetotheRegistryHandbookorotherCAS source.AnindexofCASnumbersisgiveninAppendix5.
InconnectionwiththegrouptitlesadoptedforthealphabeticallyorderedSection2,ithasbeennecessaryinsomecasesto devisegroupnames(particularlyintheinorganicfield)toindicate inaverygeneralwaythechemicalstructuresinvolvedinvarious classes,groupsorsub-groupsofcompounds.Forthispurpose,all elementshavebeenconsideredeitheras METALS or NON-METALS, andofthelatter, HALOGENS, HYDROGEN, NITROGEN, OXYGEN,and SULFUR wereselectedasspeciallyimportant.Groupnameshave thenbeencoinedfromsuitablecombinationsofthese,suchas thesimple
METALOXIDES, NON-METALSULFIDES
N-HALOGENCOMPOUNDS, NON-METALHYDRIDES
METALNON-METALLIDES, COMPLEXHYDRIDES orthemorecomplex
METALOXOHALOGENATES
AMMINECHROMIUMPEROXOCOMPLEXES
OXOSALTSOFNITROGENOUSBASES
METALOXONON-METALLATES Organicgroupentriesarefairlyconventional,suchas
HALOALKENES
NITROARLCOMPOUNDS
DIAZONIUMSALTS
Wherenecessary,suchgroupnamesareexplainedinthe appropriateSection2groupentry,ofwhichaclassifiedlisting isfoundintheAppendix6.
Crossreferencesystem Thecross-referencesystemadoptedinthisHandbookplaysa largepartinprovidingmaximumaccessto,anduseof,therather heterogeneouscollectionofinformationherein.Thesignificance ofthefivetypesofcross-referencewhichhavebeenusedisas follows.
See referstoadirectlyrelateditem.
Seealso referstoanindirectlyrelateditem.
Seeother referstolistedstrictanaloguesofthecompoundetc. Seerelated referstolistedrelatedcompounds(congeners)or groupsnotstrictlyanalogousstructurally.
Seeentry pointstoaortherelevantreferenceinSection2. CROSSREFERENCESINCAPITALSREFERTO SECTION2
Informationcontentofindividualentries Aconsciousefforthasbeenmadethroughoutthiscompilationto excludemuchfringeinformationnotdirectlyrelevanttothe involvementofchemicalreactivityinthevariousincidentsor observations,whilegivingenoughdetailtoallowthereaderto judgetherelevanceorotherwiseofthequotedreference(s)to hisorherparticularreactivityproblemsorinterests.
Itmustbestressedthatthisbookcandonomorethantoserve asaguidetomuchmoredetailedinformationavailable via the quotedreferences.Inallbutafewcasesitcannotrelievethe studentorchemistoftheirmoralandnowlegalobligationtothemselvesandtotheirco-workers,toequipthemselveswiththefullest possibleinformationfromthetechnicalliteratureresourceswhich arewidelyavailable, before attemptinganyexperimentalwork withmaterialsknown,orsuspected,tobehazardousorpotentially so.Itcouldbeimpossibleforyou after theevent.
THEABSENCEOFAMATERIALORACOMBINATION OFMATERIALSFROMTHISHANDBOOKCANNOTBE TAKENTOIMPLYTHATNOHAZARDEXISTS.LOOK THENFORANALOGOUSMATERIALSUSINGTHEGROUP ENTRYSYSTEMANDTHEINDEXESTHERETO.
Oneaspectwhich,althoughitisabsentfrommostentrytexts, isneverthelessofvitalimportance,isthatofthepotentialfor damage,injuryordeathassociatedwiththevariousmaterials andreactionsystemsdealtwithinthisHandbook.
Thoughsomeoftheincidentshaveinvolvedlittleorno damage(see CANOFBEANS,p.1189),othershaveinvolvedpersonal injuries,oftenofunexpectedseverity(see SODIUMPRESS,p.1371), andmaterialdamageisoftenimmense.Forexample,theincident givenunderPerchloricacid:Cellulosederivatives,(reference1, p.1191)involveddamageto116buildingsandalossapproaching 3Mdollarsat1947values.Thedeath-rollassociatedwithreactive chemicalhazardshasrangedfrom1or2(see Tetrafluoroethylene: Iodinepentafluoride,p.906)tosome600with2000injuredinthe incidentatOppauin1921(see Ammoniumnitrate,reference4, pp.990,991),andnowtoseveralthousand,withmorethan 100,000injured,bymethylisocyanatefumesatBhopalin1984 (reference7,p.1320).
Thissometimesvastpotentialfordestructionagainemphasisestheneedtogainthemaximumofdetailedknowledge before startingtouseanunfamiliarchemicalorreactionsystem.
ReactiveChemicalHazards Thisintroductorychapters eekstopresentanoverview ofthecomplexsubjectofreactivechemicalhazards, drawingattentiontotheunderlyingprinciplesandto somepracticalaspectsofmin imisingsuchhazards.It alsoservesinsomemeasuretocorrelatesomeofthetopic entriesinthealphabetica llyarrangedSection2ofthe Handbook.
BASICS Allchemicalreactionsimplicitlyinvolveenergychanges (energyofactivation+energyofreaction),fortheseare thedrivingforce.Themajorityofreactionsliberateenergy asheat(occasionallyaslightorsound)andaretermedexothermic.Inaminorityofreactions,thereactionenergyis absorbedintotheproducts,whenboththereactionandits productsaredescribedasendothermic.
Allreactivehazardsinvolvethereleaseofenergyin quantitiesoratratestoohightobeabsorbedbytheimmediateenvironmentofthereactingsystem,andmaterial damageresults.Thesourceoftheenergymaybeanexothermicmulti-componentreaction,ortheexothermic decompositionofasingleunstable(oftenendothermic) compound.
Allmeasurestominimisethepossibilityofoccurrence ofreactivechemicalhazardsarethereforedirectedatcontrollingtheextentandrateofreleaseofenergyinareacting system.Inanindustrialcontext,suchmeasuresarecentral tomodernchemicalengineeringpractice.Someofthe factorswhichcontributetothepossibilityofexcessive energyrelease,andappropriatemeansfortheircontrol, arenowoutlinedbriefly,withreferencestoexamplesin thetext.
KINETICFACTORS Therateofanexothermicchemicalreactiondeterminesthe rateofenergyrelease,sofactorswhichaffectreaction kineticsareimportantinrelationtopossiblereaction hazards.Theeffectsofproportionsandconcentrationsof reactantsuponreactionratearegovernedbytheLawof MassAction,andtherearemanyexampleswherechanges inproportionand/orconcentrationofreagentshave
transformedanestablisheduneventfulprocedureintoa violentincident.Forexamplesoftheeffectofincreasein proportion,
see 2-Chloronitrobenzene:AmmoniaSodium4nitrophenoxide
Fortheeffectofincreaseinconcentrationuponreaction velocity, see Dimethylsulfate:Ammonia Nitrobenzene:Alkali(reference2)
Theeffectsofcatalysts(whicheffectivelyreducethe energyofactivation),eitherintentionalorunsuspected,is alsorelevantinthiscontext.Increaseintheconcentration ofacatalyst(normallyusedat1-2%)mayhaveadramatic effectonreactionvelocity.
See Trifluoromethanesulfonicacid:Acylchlorides,etc 2-Nitroanisole:Hydrogen HYDROGENATIONCATALYSTS
Thepresenceofanunsuspectedcontaminantorcatalytic impuritymayaffectthevelocityorchangethecourseof reaction.Forseveralexamples,
see CATALYTICIMPURITYINCIDENTS
Inthesamecontext,butinoppositesense,thepresence ofinhibitors(negativecatalysts,increasingenergyofactivation)mayseriouslyinterferewiththesmoothprogressof areaction.Aninhibitormayinitiateaninductionperiod whichcanleadtoproblemsinestablishingandcontrolling adesiredreaction.Forfurtherdetailsandexamples, see INDUCTIONPERIODINCIDENTS
Undoubtedlythemostimportantfactoraffecting reactionratesisthatoftemperature.Itfollowsfromthe Arrheniusequationthattherateofreactionwillincrease exponentiallywithtemperature.Practically,itisfound thatanincreaseof10°Cinreactiontemperatureoften doublesortreblesthereactionvelocity.
Becausemostreactionsareexothermic,theywilltendto accelerateasreactionproceedsunlesstheavailablecooling capacityissufficienttopreventriseintemperature.Note thattheexponentialtemperatureeffectacceleratingthe reactionwillexceedthe(usually)lineareffectoffalling reactantconcentrationindeceleratingthereaction.When theexothermislargeandcoolingcapacityisinadequate, theresultingacceleratingreactionmayproceedtothepoint oflossofcontrol(runaway),anddecomposition,fireor explosionmayensue.
Thegreatmajorityofincidentsdescribedinthetextmay beattributedtothisprimarycauseofthermalrunawayreactions.Thescaleofthedamageproducedisrelateddirectly tothesize,andmoreparticularlytothe rate,ofenergy release.
See RUNAWAYREACTIONS
Reactionsathighpressuremaybeexceptionallyhazardousowingtotheenhancedkineticenergycontentof thesystem.
See HIGH-PRESSUREREACTIONTECHNIQUES
Althoughdetailedconsiderationofexplosionsisoutside thescopeofthisHandbook,threelevelsofintensityof explosion(i.e.ratesoffastenergyrelease)canbediscerned androughlyequatedtothematerialdamagepotential.
Deflagrationinvolvescombustionofamaterial,usually inpresenceofair.Inanormalliquidpoolfire,combustion inanopensituationwillnormallyproceedwithout explosion.Mixturesofgasesorvapourswithairwithin theexplosivelimitswhicharesubsequentlyignitedwill burnatnormalflamevelocity(afewm/s)toproducea‘soft’ explosion,withminormaterialdamage,oftenlimitedto scorchingbythemovingflamefront.Injuriestopersonnel maywellbemoresevere.
Ifthemixture(oradustcloud)isconfined,evenifonly bysurfaceirregularitiesorlocalpartialobstructions,significantpressureeffectscanoccur.Fuel-airmixturesnearto stoicheiometriccompositionandcloselyconfinedwill developpressuresofseveralbarwithinmilliseconds,and materialdamagewillbesevere.Unconfinedvapourexplosionsoflargedimensionsmayinvolvehigherflamevelocitiesandsignificantpressureeffects,asshowninthe Flixboroughdisaster.
See DUSTEXPLOSIONINCIDENTS
PRESSUREINCREASEINEXOTHERMICDECOMPOSITION
VAPOURCLOUDEXPLOSIONS
Detonationisanextremeformofexplosionwherethe propagationvelocitybecomessupersonicingaseous,liquid orsolidstates.Thetemperaturesandparticularlypressures associatedwithdetonationarehigherbyordersofmagnitudethanindeflagration.Energyreleaseoccursina fewmicrosecondsandtheresultingshatteringeffectsare characteristicofdetonation.Deflagrationmayaccelerate todetonationiftheburningmaterialandgeometryofconfinementareappropriate(endothermiccompounds,long narrowvesselsorpipelines).
See Acetylene(reference9)
ENDOTHERMICCOMPOUNDS
EXPLOSIONS
UNITPROCESSINCIDENTS
Factorsofimportanceinpreventingsuchthermal runawayreactionsaremainlyrelatedtothecontrolof reactionvelocityandtemperaturewithinsuitablelimits. Thesemayinvolvesuchconsiderationsasadequateheating andparticularlycoolingcapacityinbothliquidandvapour
phasesofareactionsystem;proportionsofreactantsand ratesofaddition(allowingforaninductionperiod);use ofsolventsasdiluentsandtoreduceviscosityofthe reactionmedium;adequateagitationandmixinginthe reactor;controlofreactionordistillationpressure;useof aninertatmosphere.
See AGITATIONINCIDENTS
Insomecasesitisimportantnottoovercoolareaction system,sothattheenergyofactivationismaintained.
See Acetylene:Halogens(reference1)
ADIABATICSYSTEMS Becauseprocessheatingisexpensive,laggingisinvariably appliedtoheatedprocessvesselstominimiseheatloss, particularlyduringlong-termhotstorage.Suchadiabatic ornear-adiabaticsystemsarepotentiallyhazardousif materialsoflimitedthermalstability,orwhichpossess self-heatingcapability,areusedinthem.Insufficientlystabilisedbulk-storedmonomerscomeintothelattercategory.
See 1,2,4,5-Tetrachlorobenzene:Sodiumhydroxide, Solvent
POLYMERISATIONINCIDENTS
SELF-HEATINGANDIGNITIONINCIDENTS
THERMALSTABILITYOFREACTIONMIXTURES
VIOLENTPOLYMERISATION
REACTIVITYVS.COMPOSITIONAND STRUCTURE Theabilitytopredictreactivityandstabilityofchemical compoundsfromtheircompositionandstructureisasyet limited,sotheabilityaccuratelytoforeseepotentialhazards duringpreparation,handlingandprocessingofchemicals andtheirmixturesisalsorestricted.Althoughsomeconsiderableprogresshasbeenmadeintheuseofcomputerprogramstopredicthazards,thebestavailableapproachfor manypracticalpurposesappearstobeaninitialappraisal basedonanalogywith,orextrapolationfrom,datafor existingcompoundsandprocesses.Thispreliminary assessmentcanbesupplementedwithcalorimetricinstrumentalexamination,thenbench-scaletestingprocedures forthermalstabilityappliedtorealisticreactionmixtures andprocessingconditions,shouldanydoubtofsafety persist.Awiderangeofequipmentandtechniquesis nowavailableforthispurpose.
See ACCELERATINGRATECALORIMETRY
ASSESSMENTOFREACTIVECHEMICALHAZARDS
COMPUTATIONOFREACTIVECHEMICALHAZARDS
DIFFERENTIALSCANNINGCALORIMETRY
DIFFERENTIALTHERMALANALYSIS
MAXIMUMREACTIONHEAT
REACTIONSAFETYCALORIMETRY
Ithaslongbeenrecognisedthatinstabilityinsingle compounds,orhighreactivityincombinationsofdifferent materials,isusuallyassociatedwithparticulargroupingsof atomsorotherfeaturesofmolecularstructure,suchashigh proportionsorlocalconcentrationsofoxygenornitrogen. Detailsofsuchfeaturesassociatedwithexplosiveinstabilityarecollectedundertheheading EXPLOSIBILITY
Anapproximateindicationoflikelyinstabilityinacompoundmaybegainedfrominspectionoftheempirical molecularformulatoestablishstoicheiometry.
See HIGH-NITROGENCOMPOUNDS
OXYGENBALANCE
Endothermiccompounds,formedastheenergy-rich productsofendothermicreactions,arethermodynamically unstableandmaybeliabletoenergeticdecompositionwith lowenergyofactivation.
See ENDOTHERMICCOMPOUNDS
REACTIONMIXTURES Sofarasreactivitybetweendifferentcompoundsisconcerned,somesubdivisioncanbemadeonthebasisofthe chemicaltypesinvolved.Oxidants(electronsinks)are undoubtedlythemostcommonchemicaltypetobe involvedinhazardousincidents,theothercomponents functioningasfuelsorotherelectronsources.Air(21% oxygen)isthemostwidelydispersedoxidant,andairreactivitymayleadtoeithershort-orlong-termhazards. Wherereactivityofacompoundisveryhigh,oxidation mayproceedsofastinairthatignitionoccurs.
See PYROPHORICMATERIALS
Slowreactionwithairmayleadtothelonger-term hazardofperoxideformation.
See AUTOXIDATION
PEROXIDATIONINCIDENTS
PEROXIDESINSOLVENTS
PEROXIDISABLECOMPOUNDS
Oxidantsmoreconcentratedthanairareofgreater hazardpotential,andtheextentofinvolvementofthe commonoxidants
Perchloricacid
Chlorine
Nitricacid
Hydrogenperoxide
Sulfuricacid
METALCHLORATES
maybejudgedfromthelargenumberofincidentsinthe textinvolvingeachofthem,aswellasother OXIDANTS
Atthepracticallevel,experimentaloxidationreactions shouldbeconductedtomaintaininthereactingsystema minimumoxygenbalanceconsistentwithotherprocessing requirements.Thismayinvolveaddingtheoxidantslowly withappropriatemixingandcoolingtotheotherreaction materialstomaintaintheminimumeffectiveconcentration
ofoxidantfortheparticularreaction.Itwillbeessentialto determinebyasuitablediagnosticprocedurethatthe desiredreactionhasbecomeestablished,topreventbuildupofunusedoxidantandapossibleapproachtotheoxygen balancepoint.
See OXYGENBALANCE
Reducants(richelectronsources)inconjunctionwith reduciblematerials(electronacceptors)featureratherless frequentlythanoxidantsinhazardousincidents.
See REDUCANTS
Interactionofpotentoxidantsandreducantsis invariablyhighlyenergeticandofhighhazardpotential.
See Dibenzoylperoxide:Lithiumtetrahydroaluminate
Hydrazine:Oxidants
REDOXREACTIONS
ROCKETPROPELLANTS
Similarconsiderationsapplytothosecompoundswhich containbothoxidisingandreducingfunctionsinthesame molecularstructure.
See REDOXCOMPOUNDS
Wateris,afterair,oneofthemostcommonreagents likelytocomeintocontactwithreactivematerials,and severalclassesofcompoundswillreactviolently,particularlywithrestrictedamountsofwater.
See WATER-REACTIVECOMPOUNDS
Mostoftheabovehasbeenwrittenwithdeliberateprocessingconditionsinmind,butitmustberememberedthat thesameconsiderationswillapply,andperhapstoagreater degree,undertheuncontrolledreactionconditionsprevailingwhenaccidentalcontactofreactivechemicals occursinstorageortransit.
Adequateplanningisthereforenecessaryinstorage arrangementstosegregateoxidantsfromfuelsandreducants,andfuelsandcombustiblematerialsfromcompressedgasesandwater-reactivecompounds.Thiswill minimisethepossibilityofaccidentalcontactandviolent reactionarisingfromfaultycontainersorhandlingoperations,andwillpreventintractableproblemsintheevent offireinthestorageareas.
See STORAGEOFCHEMICALS
Unexpectedsourcesofignitionmayleadtoignitionof flammablematerialsduringchemicalprocessingorhandlingoperations.
See FRICTIONALIGNITIONOFGASES
IGNITIONSOURCES
SELF-HEATINGANDIGNITIONINCIDENTS
STATICINITIATIONINCIDENTS
PROTECTIVEMEASURES Theneedtoprovideprotectivemeasureswillbedirectly relatedtothelevelofpotentialhazardswhichmaybe assessedfromtheproceduresoutlinedabove.Measures concernedwithreactioncontrolarefrequentlymentioned
inthefollowingtext,butdetailsoftechniquesand equipmentforpersonalprotection,thoughusuallyexcluded fromthescopeofthiswork,areobviouslyofgreat importance.
Carefulattentiontosuchdetailisnecessaryasasecond lineofdefenceagainsttheeffectsofreactivehazards.The levelofprotectionconsiderednecessarymayrangefrom
theessentialandabsoluteminimumofeffectiveeyeprotection, via thesafetyscreen,fumecupboardorenclosed reactor,uptotheultimateofaremotelycontrolledand blast-resistantisolationcell(usuallyforhigh-pressureoperations).Intheabsenceoffacilitiesappropriatetothe assessedlevelofhazard,operationsmustbedeferreduntil suchfacilitiesareavailable.
Section1 SpecificChemicals (ElementsandCompoundsarrangedinformulaorder)
EXPLANATORYNOTES Thissectiongivesdetailedinformationonthehazardouspropertiesofindividualchemicals,eitheraloneorincombination withothercompounds.Theitemsarearrangedinorderof theempiricalformula(atrightofsecondboldtitleline)which correspondstothechemicalname,orasynonymwithinparentheses,usedasthefirstlineboldtitleofeachmainentry; (nomenclatureisnowratherpromiscuoussincethesystematisershavecontrivedtogivemanymaterialstwooreventhree newnamessincethefirsteditionwaspublished,whilethe nameusedwherechemicalsarehandled,asopposedtoin lecturerooms,willbesomethingelseagain).The3part numberwithinsquarebracketsattheleftofthesecondtitleline istheCASregistrynumber,nowbeingwidelyusedtoprovide areliablebasisforestablishingequivalencebetweendiffering chemicalnamesandtradenamesforthesamechemicalcompound(butnotethatonecompound,withinthetermsofthis work,mayhavenumerousCASnumbersbyvirtueofisotopic composition,undefinedstereo-andregio-chemistryorvariant solvationlevels).Lackofcontentwithinthesquarebrackets indicatesthataregistrynumberhasnotyetbeenlocated,(or maynotexistifCASconsidersthecompoundinsufficiently characterised,whichishighlyprobableformaterialswhich explodedduringanalysis)and(ion)afterthenumberindicates thatthemainiononlyhasbeenlocated,ratherthanthespecific titlesalt.Wherepossible,analpahanumericrepresentationof thestructureofthetitlecompoundisgivenatthecentreof thethirdtitleline,otherwiseadrawnstructure.
A†prefixedtothechemicalnameindicatestheexistence oftabulatedinformationonfire-relatedpropertiesin Appendix2.The†prefixisalsoappendedtotheentry (andanysynonym)intheindexinAppendix4ofthechemicalsappearingastitlelines.Immediatelyunderthetitle linessomereferencestosourcesofgeneralsafetyrelateddata concerninguseandhandlingprecautionsforthetitlechemical aregiven.Thereferencestotheseriesof MCASafetyData Sheets aregiveninparenthesesbecausethewholeseries waswithdrawnin1980,apparentlyongroundsotherthan obsolescenceofthetechnicalcontent.Sincethesedatasheets arenolongeravailable,alternativereferencesaregivenwhere possibletotheDataSheetsavailablefromtheNationalSafety Council (NSC),Chicago;theFireProtectionAssociation (FPA),London;totheappropriatepageof’HandlingChemicalsSafely1980’ (HCS1980), publishedinHolland;or tothenew LaboratoryHazardDataSheet seriesbeingpublishedbytheRoyalSocietyofChemistry (RSC), nowinCambridge.Nonewdatasheetshavebeenincludedsince1990, sincedistinctionbetweentheproliferationofsourceswould
beinvidious,mostappeartohavebencompiledmy(mis) information(ne)scientistsattheircomputers,connectedto theworldwideweb,butnottoapractisedchemistwhois familiarwiththematerialinquestion.Fortunately,themanufacturer’sdatasheets,nowsuppliedevenbylaboratorysupply houses,aresteadilyimprovingandmeanthatreferenceto othersimilarsourcesislessneedful
Thefirstreference(s)anddatagivenunderthetitlelines refertothehazardsofthetitlematerialalone,orinthepresence ofair,unlessstatedotherwise.Whereother(secondary)chemicalsareinvolvedwiththetitlecompoundinareactive incident,thename(s)followsinromancharactersunderthe boldtitleentry.AsinpreviouseditionsofthisHandbook, wherethesesecondarychemicalsaredescribedingroupterms (e.g.Polynitroarylcompounds),referencetothealphabetical groupentriesnowinSection2maysuggestotheranalogous possibilitiesofhazards.Referencestooriginalorabstractliteraturethenfollow,andsufficientoftherelevantinformation contentisgiventoallowageneralpictureofthenatureand degreeofhazardtobeseen.
TwofeaturesrelevanttoentriesforpairsofreactivechemicalsarisefromtheworkofProf.T.Yoshidaindeveloping amethodforthecalculationofmaximumreactionheats (MRH)possibleforbinary(orternary)mixturesofchemicals, andthepublicationofhistabulatedresults.Whereavailablefor combinationsexistinginthistext,thesedataaregivenopposite thenameofthesecondarychemicalintheformMRH2.9/22. Thismeansthatthecalculatedreactionheatismaximalat 2.9kJ/ginamixturecontaining22%wtofthesecondary reactantwith78%ofthemain(boldtitle)compound.The secondfeatureistheinclusionofthesecondaryentry‘Other reactants’underwhichtheextentoftheinformationavailable inYoshida’sbookforsome240titlecompoundsisgiven.More detailontheoriginofthesefiguresisgiveninSection2under theentry MAXIMUMREACTIONHEAT.
Alltemperaturesinthetextareexpressedindegrees Celsius;pressuresinbars,mbarsorPa;volumesinm3,litres orml;andenergyasjoules,kJorMJ.Whereappropriate, attentionisdrawntocloselysimilarorrelatedmaterialsor eventsby See or Seealso cross-references.Finally,ifatitle compoundisamemberofoneofthegeneralclassesor groupsinSection2,itisrelatedtothosebya Seeother cross-reference.Ifthecompoundisnotstrictlyclassifiable,a Seerelated cross-referenceestablishesalessdirectlinkto thegroupcompoundindexlistsinSection2,suchcompounds beingprefixedinthelistsbyanasterisk.Inrelativelyfewcases, literaturereferences(orfurtherreferences)forindividual
compoundsareinthealphabeticalentriesinSection2,anda Seeentry cross-referenceleadstothatentrywiththeliterature reference.Analphabeticalindexofthechemicalnamesusedas boldtitlesinSection1,togetherwithsynonyms,isgivenin Appendix4.
Detailsofcorrectionsoftypographicalorfactualerrors,or offurtheritemsforinclusioninthetext,willbewelcomed,and apagewhichcanbephotocopiedforthispurposewillbefound atthebackofthebook.
0001Silver [7440-22-4]Ag
Acetyleniccompounds
MRHAcetylene8.70/99+
See ACETYLENICCOMPOUNDS
Aziridine
See Aziridine:Silver
Bromineazide
See Bromineazide
3-Bromopropyne
See 3-Bromopropyne:Metals
Carboxylicacids
Silverisincompatiblewithoxalicortartaricacids,sincethe silversaltsdecomposeuponheating.Silveroxalateexplodes at140°C,andsilvertartratelosescarbondioxide.
Koffolt,J.H.,privatecomm.,1965
Seeother METALOXALATES
Chlorinetrifluoride
See Chlorinetrifluoride:Metals
Copper,Ethyleneglycol
See Ethyleneglycol:Silveredcopperwire
Electrolytes,Zinc
MRH1.42/36
Iodoform
Incontactwithfinelydivided(reduced)silver,incandescenceoccurs.
Grignard,1935,Vol.3,320
Otherreactants
MRHvaluesforsevencombinations,largelywithcatalyticallysusceptiblematerials,aregiven.
Yoshida,1980,103
Ozonides
See OZONIDES
Peroxymonosulfuricacid
See Peroxymonosulfuricacid:Catalysts
Peroxyformicacid
See Peroxyformicacid:Metals
Seeother METALS
MRH5.69/100
Causesofspontaneouscombustionandotherhazardsof silver—zincbatterieswereinvestigated.
Britz,W.K. etal.,Chem.Abs.,1975, 83, 150293
Ethanol,Nitricacid
Actionofsilveronnitricacidinthepresenceofethanol mayformthereadilydetonablesilverfulminate.
Luchs,J.K., Photog.Sci.Eng.,1966, 10,334
See Nitricacid:Alcohols
Seealso SILVER-CONTAININGEXPLOSIVES
Ethylhydroperoxide
See Ethylhydroperoxide:Silver
Ethyleneoxide
See Ethyleneoxide:Reference4
Hydrogenperoxide
See Hydrogenperoxide:Metals
MRH3.72/99+
MRH1.59/99+
0002Silver—aluminiumalloy [11144-29-9]Ag—Al
Ag Al
Combustionandexplosionhazardsofthepowderedalloy usedinbatterieswerestudied.Increaseinsilvercontent leadstohighervaluesoftheignitiontemperatureand COI[1][2].
1 Popov,E.I. etal.,Chem.Abs.,1977, 87,205143
2 Popov,E.I. etal.,Chem.Abs.,1980, 94,35622
Seeother ALLOYS
Seeother SILVERCOMPOUNDS
0003Silveredcopper [37218-25-0]Ag—Cu
Ag Cu
Ethyleneglycol
See Ethyleneglycol:Silveredcopperwire Seerelated ALLOYS
0004Silver—thoriumalloy [12785-36-3](1:2)Ag—Th AgTh
See PYROPHORICALLOYS
0005Silvertetrafluoroborate [14104-20-2]AgBF4
B F F F F Ag+
Preparativehazard
Experimentaldirectionsmustbefollowedexactlyto preventviolent,spontaneousexplosionsduringpreparationofthesaltfromsilveroxideandborontrifluoride etherateinnitromethane,accordingtotheearliermethod [1].Thelatermethod[ 3]isgenerallysaferthanthat in[2].
1. Meerwein,H. etal.,Arch.Pharm.,1958, 291,541–544
2. Lemal,D.M. etal.,TetrahedronLett.,1961,776–777
3. Olah,G.A. etal.,J.Inorg.Nucl.Chem.,1960, 14, 295–296
Seeother SILVERCOMPOUNDS
0006Silvertetrafluorobromate [35967-89-6]AgBrF4
F F F F Ag+
See METALPOLYHALOHALOGENATES
Seeother SILVERCOMPOUNDS
0007Silverbromate [7783-89-3]AgBrO3 Br O OO Ag+
1 Taradoire,F., Bull.Soc.Chim.Fr.,1945, 12,94–95
2 Pascal,1960,Vol.13.1,1004
Seeother METALOXOHALOGENATES
Seeother SILVERCOMPOUNDS
0008Silverchloride [7783-90-6]AgCl Cl Ag+
Aluminium
See Aluminium:Silverchloride
Ammonia
Exposureofammoniacalsilverchloridesolutionstoairor heatproducesablackcrystallinedepositof“fulminating silver”(mainlysilvernitride),withsilverdiimideandsilver amidealsopossiblypresent[1].Attentionisdrawn[2]to thepossibleexplosionhazardofamethodofrecovering silverfromchloridebypassinganammoniacalsolution ofthechloridethroughanionexchangecolumntoseparate theAg(NH3)+ ion,priortoelutionasthenitrate[3].Itis essentialtoavoidlettingtheammoniacalsolutionstand forseveralhours,eitheraloneoronthecolumn[2].
1 Mellor,1941,Vol.3,382
2 Kauffmann,G.B., J.Chem.Educ.,1977, 54,132
3 Ranganathan,S. etal.,J.Chem.Educ.,1976, 53,347
See Silvernitride
Seeother METALHALIDES
Seeother SILVERCOMPOUNDS
0009Silverazidechloride [67880-13-1]AgClN3
Itisshocksensitivewhendry.
Frierson,W.J. etal.,J.Amer.Chem.Soc.,1943, 65,1698
Seeother METALAZIDEHALIDES
Seeother SILVERCOMPOUNDS
Otherreactants
MRHvaluesfor16combinationswithoxidizablematerials aregiven.
Yoshida,1980,133
Sulfurcompounds
MRHSulfur2.0/12
Thebromateisapowerfuloxidant,andunstablemixtures withsulfurigniteat73°C–75°C,andwithdisulfur dibromideoncontact[1].Hydrogensulfideigniteson contactwiththebromate[2].
0010Silverchlorite [7783-91-7]AgClO2
O O Ag +–
Alone,orIodoalkanes
Thesaltisimpact-sensitive,cannotbefinelyground,and explodesat105°C.Attemptstoreactsilverchloritewith
Br
iodo-methaneor-ethanecausedexplosions,immediatelyin theabsenceofsolvents,ordelayedintheirpresence.
Levi,G.R., Gazz.Chim.Ital.[2],1923, 53,40
Hydrochloricacid,orSulfur
Itexplodesincontactwithhydrochloricacidorupon rubbingwithsulfur.
Mellor,1941,Vol.2,284
Nonmetals
Finelydividedcarbon,sulfur,orredphosphorusareoxidizedviolentlybysilverchlorite.
Pascal,1960,Vol.16,264
Seeother CHLORITESALTS
Seeother SILVERCOMPOUNDS
0011Silverchlorate [7783-92-8]AgClO3
Aceticacid
Anexplosivecompoundandpowerfuloxidant.
Sorbe,1968,126
Ethyleneglycol
See Ethyleneglycol:Oxidants
Otherreactants
MRH2.68/17
MRHvaluesfor17combinations,largelywithoxidizable materials,aregiven.
Yoshida,1980,69
Seeother METALCHLORATES
Seeother SILVERCOMPOUNDS
0012Silverperchlorate [7783-93-9]AgClO4
Itmeltswithoutdecomposition,althoughtheenthalpyof theconversiontosilverchlorideandoxygenappearsto beabout 0.5kJ/g.Anexplosionwhilegrindingthesalt (whichhadnotbeenincontactwithorganicmaterials) hasbeenreported.Apowerfuloxidant.
Anon., Angew.Chem.(Nachr.),1962, 10,2
MRH2.80/22
Thesaltsolvatedwithaceticacidisimpactsensitive.
Mellor,1956,Vol.2,Suppl.1,616
See Aromaticcompounds,below
Alkynes,Mercury
Concentratedsolutionsoftheperchloratein2-pentyneor 3-hexyne(wherecomplexesareformed)explodeon contactwithmercury.
Comyns,A.E. etal.,J.Amer.Chem.Soc.,1957, 79,4324
See METALACETYLIDES
Aromaticcompounds
MRHAniline3.47/11, toluene3.51/9
Silverperchlorateformssolidcomplexeswithaniline,pyridine,toluene,benzene,andmanyotheraromatichydrocarbons[1].Asampleofthebenzenecomplexexploded violentlyuponcrushinginamortar.Theethanolcomplex alsoexplodedsimilarly,andunspecifiedperchloratesdissolvedinorganicsolventswereobservedtoexplodeaswell [2].Solutionsoftheperchlorateinbenzenearesaidtobe dangerouslyexplosive[3],butthismaybeinerrorfor thesolidbenzenecomplex.Theenergyreleasedupon decompositionofthebenzenecomplexhasbeencalculated as3.4kJ/g,some75%ofthatforTNT[4].
1. Sidgwick,1950,1234
2. Brinkley,S.R., J.Amer.Chem.Soc.,1940, 62,3524
3. Peone,J. etal.,Inorg.Synth.,1974, 15,69
4. Stull,1977,22
Carbontetrachloride,Hydrochloricacid Silverperchlorateandcarbontetrachloride,inthepresence ofalittlehydrochloricacid,producetrichloromethylperchlorate,whichexplodesat40°C.
491M,1975,368
See Trichloromethylperchlorate
1,2-Diaminoethane
Dropwiseadditionoftheaminetothesaltledtoan explosion(possiblyinitiatedbyheatliberatedbycomplex formation).
491M,1975,368
Diethylether Aftercrystallizationfromether,thematerialexplodedviolentlyuponcrushinginamortar.Ithadpreviouslybeen consideredstablesinceitmeltswithoutdecomposition[1].
Heim,F., Angew.Chem.,1957, 69,274
Dimethylsulfoxide Thecrystallinecomplexsolvatedwith2DMSOexplodes withextremeviolenceifrubbedorscratched.
Ahrland,S. etal.,Acta.Chem.Scand.A,1974, 28,825
See Dimethylsulfoxide:Metaloxosalts
Ethanol
See Aromaticcompounds,above
Otherreactants
MRH3.30/13
MRHvaluesfor20combinationswithoxidizablematerials aregiven.
Yoshida,1980,81
1,4-Oxathiane
Theperchlorateformscomplexeswith2,3,or4molsof oxathiane,whichexplodeuponheating.
Barnes,J.C. etal.,J.Chem.Soc.Pak.,1982, 4,103–113
Tetrachlorosilane,orTetrabromosilane,orTitanium tetrachloride,andDiethylether
Reactiongivesexplosivevolatileorganicperchlorates, probablyethylperchlorate.
Schmeisser,M., Angew.Chem.,1955, 67,499
See ALKYLPERCHLORATES
Tetrasulfurtetraimide
See Tetrasulfurtetraimide–silver(I)perchlorate
Seeother METALPERCHLORATES
Seeother OXIDANTS
Seeother SOLVATEDOXOSALTINCIDENTS
0013Silverfluoride
[7775-41-9]AgF
F Ag+
Calciumhydride
See Calciumhydride:Silverhalides
Nonmetals
Boronreactsexplosivelywhengroundwithsilverfluoride; siliconreactsviolently.
Mellor,1941,Vol.3,389
Titanium
Interactionat320°Cisincandescent.
Mellor,1941,Vol.7,20
Seeother METALHALIDES
Seeother SILVERCOMPOUNDS
0014Silverdifluoride [7783-95-1]AgF2
FF Ag 2+ – –
Boron,Water
Mixturesofboronandsilverdifluoridefunctionasdetonatorswhenincontactwithwater.
Tulis,A.J. etal.,Proc.7thSymp.Explos.Pyrotechnics, 1971, 3(4),1–12
Dimethylsulfoxide
See Iodinepentafluoride:Dimethylsulfoxide
Hydrocarbons,orWater
Itreactsevenmorevigorouslywithmostsubstancesthan doescobaltfluoride.
Priest,H.F. Inorg.Synth.,1950, 3,176
Seeother METALHALIDES
Seeother SILVERCOMPOUNDS
0015Silveramide [65235-79-2]AgH2N N H H Ag +
Extraordinarilyexplosivewhendry.
Brauer,1965,Vol.2,1045
See Nitrogentriiodide—silveramide
Seeother N-METALDERIVATIVES
Seeother SILVERCOMPOUNDS
0016Silver N-nitrosulfuricdiamidate []AgH2N3O4S N S N + O O O O N H H Ag + ––
Thesilversaltofthenitroamideisexplosive.
Sorbe,1968,120
SeeotherN-METALDERIVATIVES
SeeotherN—NITROCOMPOUNDS
Seeother SILVERCOMPOUNDS
0017Silverphosphinate
[]AgH2O2P P O O H H Ag +
Explosive,butlesssensitivethantheazideorfulminate.
Luchs,J.K., Photog.Sci.Eng.,1966, 10,335
Seeother METALPHOSPHINATES
Seeother SILVERCOMPOUNDS
0018Diamminesilverpermanganate
[]AgH6MnN2O4 Mn O OO O Ag + N H H H N H H H
Itmayexplodeuponimpactorshock.
Pascal,1960,Vol.16,1062
Seeother AMMINEMETALOXOSALTS
Seeother SILVERCOMPOUNDS
0019Dihydrazinesilvernitrate
[31247-72-0]AgH8N5O3 N + O O O N N H H H H N N H H H H Ag +
Thesaltexplodesat 1.5°C.
Gall,H. etal.,Z.Anorg.Chem.,1932, 206,376
Seeother AMMINEMETALOXOSALTS
Seeother SILVERCOMPOUNDS
0020Silveriodate [7783-97-3]AgIO3
Metals MRHPotassium1.50/25,sodium1.92/35
Sodium:Iodates
See Potassium:Oxidants
Otherreactants
MRHvaluesfor16combinationswithoxidizablematerials aregiven.
Yoshida,1980,194
Tellurium
Interactionisviolent.
Pascal,1960,Vol.13.2,1961
Seeother METALHALOGENATES
Seeother SILVERCOMPOUNDS
0021Silverpermanganate [7783-98-4]AgMnO4
Sulfuricacid
Themoistsaltexplodedduringdryingovertheconcentratedacidinavacuumdesiccator(presumablyowingto theformationoftracesofmanganeseheptoxidefrom reactionwithsulfuricacidvapor).
491M,1975,369
Seeother OXIDANTS
Seeother SILVERCOMPOUNDS
0022Silvernitrate [7761-88-8]AgNO3
+
HCS1980,822
Apotentoxidant,formingexplosivemixtureswithmany combustibles.
Seealso METALNITRATES
Seeother SILVERCOMPOUNDS
