&IGURE. -3.6. 0. 50 Ïg. / 1. 0-7 g-1 cm. 3. 100 150 200. T/K. 250. 2 Tesla. 300 350 400. -3.4. -3.2. -3.0. -2.8. -2.6. -2.4. 4EMPERATURE. GOLD. &IGURE ...
WWWGOLDBULLETINORG
!REVIEWONFULMINATING GOLD+NALLGOLD 'EORG3TEINHAUSER *~RGEN%VERS 3TEFANIE*AKOB 4HOMAS-+LAPyTKE 'ILBERT/EHLINGER
!TOMINSTITUTDERdSTERREICHISCHEN5NIVERSITiTEN 6IENNA5NIVERSITYOF4ECHNOLOGY 3TADIONALLEE 6IENNA !USTRIA $EPARTMENTOF#HEMISTRYAND"IOCHEMISTRY ,UDWIG -AXIMILIANS5NIVERSITYOF-UNICH "UTENANDTSTR $ -UNICH 'ERMANY
#ORRESPONDINGAUTHOR % MAILADDRESSGEORGSTEINHAUSER ATIACAT
!BSTRACT %XPENSIVEANDEXPLOSIVE4HEREACTIONOFAMMONIA ANDGOLD))) COMPOUNDSLEADSTOEXPLOSIVEPRODUCTS KNOWNAS±FULMINATINGGOLD²'OLDSCIENTISTSSHOULD BEAWAREOFTHEPOTENTIALHAZARDSINVOLVEDINTHE REACTIONOFTHESESTARTINGMATERIALS(EREIN A HISTORICANDSCIENTI½CREVIEWONTHISFASCINATING SUBSTANCEISPRESENTED&ULMINATINGGOLDHASBEEN KNOWNSINCEMEDIEVALTIMES BUTCANNOTBEFULLY CHARACTERIZEDDUETOITSPOLYMERICAND HETEROGENEOUSCHARACTER-AGNETICMEASUREMENTS CON½RMPREVIOUS%8!&3ANALYSESTHATTHEGOLDATOMS HAVEASQUAREPLANARCOORDINATIONENVIRONMENT !U. MOIETIESTHATAREPARTYCONNECTEDANDFORMA DIMENSIONALNETWORK 4HEEXPLOSIVEPROPERTIES ANDRESULTINGSAFETYINSTRUCTIONSAREDISCUSSEDIN DETAILASWELL
N
THISPAPER WEREVIEWTHEHISTORYASFARAS SIGNI½CANT THECHEMISTRYANDHAZARDSOFFULMINATINGGOLD ±&ULMINATING GOLD² GENERALLY TERMS THE EXPLOSIVE REACTION PRODUCTSOFGOLD))) COMPOUNDSSUCHASHALOGENIDES OXIDES AND HYDROXIDES WITH AMMONIA )N THIS PAPER WE FOCUS ON FULMINATINGGOLDPRODUCEDFROMGOLD))) CHLORIDEORHYDROGEN TETRACHLOROAURATE))) 4HIS TYPE OF FULMINATING GOLD IS ALSO TERMED ±#HLORIDKNALLGOLD² IN LITERATURE 4HE EXPRESSION ±FULMINATING²MIGHTBECONFUSINGANDSHOULDNOTBEMISTAKEN FORTHEENERGETICFULMINATEANION#./¯
4HE(ISTORYOFTHE½RSTHIGHEXPLOSIVE 4HEEARLYWORK 3INCEFULMINATINGGOLDISSYNTHESIZEDBYUSINGREADILYAVAILABLE CHEMICALS¯GOLD))) CHLORIDEANDAMMONIA¯ANDLEADSTOAN UNEXPECTEDLYEXPLOSIVESUBSTANCE ITISNOSURPRISETHATITHAS BEEN KNOWN TO ALCHEMISTS SINCE MEDIEVAL TIMES ALCHEMIST SYMBOL 4HE'ERMANALCHEMIST3EBALD3CHWAERTZER½RST MENTIONSFULMINATINGGOLDAURUMFULMINANS INLITERATUREIN HIS #HRYSOPOEIA 3CHWAERTZERIANA IN ! REPRINT OF THIS MONOGRAPHDATESBACKTO;=4RANSLATED -ANUSCRIPTS ONTHE4RUE0REPARATIONOFTHE0HILOSOPHER´S3TONE )TISSTILL AVAILABLEINSOME'ERMANLIBRARIESSEE&IGURE
+EYWORDS AURUM FULMINANS EXPLOSIVES GOLD NITROGEN BOND SAFETY ALCHEMISTS
'OLD"ULLETIN6OLUME.O
WWWGOLDBULLETINORG
&IGURE
2EPRINTOFTHEORIGINALMANUSCRIPTOF3EBALD3CHWAERTZER´SRECIPEFORTHESYNTHESISOFFULMINATINGGOLD
'OLD"ULLETIN6OLUME.O
WWWGOLDBULLETINORG
5NPROFESSIONALLYTRANSLATED 3CHWAERTZERWRITES
4HEPHILOSOPHYOFPREPARINGTHE!URUM&ULMINANS ANDHOWTOBRINGITTOHIGHESTPURITY 9OUMAYWISHTOPUT,OTS;APPROXXG=OF ;GOLD= INTOAVIALANDTOADD,OTSOF!QUAFORT;CONCENTRATED NITRIC ACID= WHICH HAS A CONSIDERABLE CONCENTRATION ANDGENTLYWARMITIN ;ABATHOF=ASHESORSANDTHEN TAKE APPROXIMATELY ,OTS OF 3ALMIAC ;AMMONIUM CHLORIDE=ANDSLOWLYTHROWITINTOTHEBEAKERDOTHAT UNTILYOUCANSEETHATTHEWATERDOESNOTWANTTOETCH ANYFURTHERTHENNATUREHASITSRIGHT0ONDUS 4HENTAKE #YPRIC6ITRIOL ;PROBABLYAMIXTUREOF&E3/À (/AND#U3/À(/=ASMUCHASYOUCANGETFOROR 0FENNIG DISSOLVEITINCOMMONWATER ½LTERITOFFSOTHAT ITISCLEARANDNOLONGERTURBIDHEREWITHPRECIPITATE THE ANDEDULCORATETHELIME;PRECIPITATE =WITHWARM WATERSOYOUWILLGETTHE INMUCHNICERFORMTHAN WHENITHADBEENGOINGTHROUGH 3PHERAM3ATURNI;LEAD SPHERES=;¨=YOUWILLNOTICEASIGNI½CANTLOSSOF ITALSO TAKES THREEFOLD EFFORTS ;¨= 4HIS IS THE TRUE PHILOSOPHIC PURI½CATION7HENITISDRIEDDISSOLVEITIN!QUAFORTAND 3ALMIAC THIS LIME ASSTATEDABOVE 9OU MAY WISH TO EVAPORATE THE !QUAFORT TO DRYNESS IN ASHESANDITWILLTAKEYOUHALFADAYTODOTHISWORK 4HENPOURFRESHWATERONTOITANDDISSOLVEITANOTHER TIMEEVAPORATEITTODRYNESSTHENDISSOLVEITATHIRD TIME9OUMUSTPAYATTENTIONTHATYOUDONOTEVAPORATE ITCOMPLETELYBUTONLYHALFOFITSOTHE -ATERIAWILLBE OILY THEN TAKE IT FROM THE ½REPLACE AND LET IT COOL DOWN 4HEN PRECIPITATE THE WITH /L 4ARTAR ;/IL OF 4ARTAR CONCENTRATED POTASSIUM CARBONATE SOLUTION= ;¨= 9OU HAVE TO BE CAREFUL WHEN PRECIPITATING WITH THAT ;/ILOF4ARTAR=OTHERWISEITMIGHTSTARTTOSTRIKE;EXPLODE= ORITMIGHTCAUSEHEAVYFOAMINGANDOVER¾OW !SSOONASEVERYTHINGISNOLONGEREFFERVESCENTANDTHE ISPRECIPITATEDYOUNEEDTOEDULCORATEITTOLETTHE SALTESCAPEWHENTHISIS½NISHEDYOUWILL½NDABEAUTIFUL PURPLE COLORED!URUM&ULMINANS 4HIS WORK CAN BE ½NISHED WITHIN DAYS SO THAT THE COMPLETEWORKDOESNOTTAKELONGERTHANDAYSTHEN THEPHILOSOPHICPREPARATION!URI&ULMINISDONE 3ATDICTUM
)T WAS *OHANN +UNCKEL VON ,yWENSTERN WHO FOUNDTHECORRECTEXPLANATIONFORTHEFORMATIONOFFULMINATING GOLDUPONTHEADDITIONOFPOTASSIUMCARBONATETOTHEGOLD))) SOLUTIONACCORDINGTOTHEORIGINALRECIPE3INCE3CHWAERTZER USEDAMMONIUMCHLORIDEFORTHEPRODUCTIONOFAQUAREGIA THESOLUTIONOFHYDROGENTETRACHLOROAURATE))) STILLCONTAINED A SIGNI½CANT AMOUNT OF AMMONIUM IONS WHICH READILY SET AMMONIA FREE WHEN TREATED WITH A BASE LIKE CONCENTRATED POTASSIUMCARBONATESOLUTION
'OLD"ULLETIN6OLUME.O
(OWEVER FULMINATING GOLD IS NOT ONLY ONE OF THE ½RST KNOWN ±COMPOUNDS² OF GOLD BUT IT IS THE ½RST HIGH EXPLOSIVE KNOWN TO MANKIND AND EVEN OLDER THAN FAMOUS HISTORIC EXPLOSIVES LIKE MERCURY)) FULMINATE +NALLQUECKSILBER ;= )NTERESTINGLY THEALCHEMISTSOFTHETHANDTHCENTURY BELIEVEDTHATTHESHOCKWAVEOFEXPLODINGFULMINATINGGOLD AIMSDOWNWARDSONLY;=4HISMYTHWAS±BUSTED²BY4HOMAS 7ILLIS;=INASIMPLEEXPERIMENT(EHEATEDASMALLAMOUNT OFFULMINATINGGOLDONASPOONANDCOVEREDITWITHACOIN 5PON EXPLOSION THE COIN ¾EW TO THE RAFTERS 2OBERT (OOKE PERFORMEDSIMILAREXPERIMENTSANDREFORMULATEDTHEANCIENT IDEASOFCOMBUSTIONONACCOUNTOFHISOBSERVATIONS *OHANN2UDOLF'LAUBER OBSERVEDTHEPURPLE FUMES OF EXPLODING FULMINATING GOLD AND USED INCREDIBLE AMOUNTS OF THIS SUBSTANCE FOR THE GOLD PLATING OF OBJECTS -UCH LATER TWO LESS HAZARDOUS TECHNICAL APPLICATIONS ARE DOCUMENTEDINPATENTLITERATURE0HOTOGRAPHYONTHEBASISOF FULMINATINGGOLDANDSILVERCOMPOUNDSASTHELIGHT SENSITIVE SUBSTANCES ;= AND THERAPEUTIC USES OF GOLD SUCCINIMIDE WHICHCANBEPREPAREDFROMSUCCINIMIDEANDGOLDCOMPOUNDS SUCHASFULMINATINGGOLD;= 0ROBABLYALMOSTEVERYCHEMISTOFTHETHCENTURYONCE WORKED ON FULMINATING GOLD SINCE ITS CONSTITUTION WAS STILL UNKNOWN )N THE COURSE OF THESE INVESTIGATIONS PROBABLY MANYEXPLOSIONSOCCURRED/NESEVEREINCIDENTOF*yNS*AKOB "ERZELIUS IN IS DOCUMENTED ;= (E WAS INJURED BY AN EXPLOSIONINTHECOURSEOFHANDLINGMORETHANGRAMS OF FULMINATINGGOLD3OMEGLASSSHARDSOFTHEBEAKERPERFORATED HISLEFTHANDANDINJUREDHISEYES!SACONSEQUENCEOFHIS INJURIESHEHADTOSTAYFORMONTHSINADARKENEDROOMUNTILHE COULD½NALLYSEEAGAIN ALTHOUGHACERTAINOPACITYOFHISRIGHT EYE REMAINED FOR YEARS (IS WOUNDED HAND HEALED TOO LEAVINGPURPLE COLOREDSCARS 4HEWORKOF3CHEELE ,AVOISIERAND$UMAS 5NTIL THE TH CENTURY MANY SCIENTISTS STILL BELIEVED THAT FULMINATINGGOLDCANBEPRODUCEDBYTHEREACTIONOFMILKOF LIME AND GOLD))) CHLORIDE OR OTHER CHEMICAL REACTIONS "Y ANALYZINGFULMINATINGGOLD #ARL7ILHELM3CHEELEFOUNDTHE EVIDENCETHATAMMONIAISTHEONLYRESPONSIBLEREAGENTFORITS FORMATION (E ALSO PROVED THAT THE GAS THAT IS GENERATED UPONITSEXPLOSION ISMOSTLY DINITROGEN;=)NA½RSTATTEMPT TODE½NEACHEMICAL±FORMULA²FORFULMINATINGGOLD !NTOINE ,AVOISIERCONCLUDEDFROM3CHEELE´SWORKTHATITWASAN±OXIDE D´ORAMMONIACAL²;= *EAN"APTISTE$UMASAPPLIEDSYSTEMATICCHEMICALANALYSIS TO GAIN FURTHER INSIGHT INTO THE FULMINATING GOLD ;= (E FOUNDTHATITCONSISTSNOTONLYOFGOLDANDNITROGENBUTALSO HYDROGEN AND CHLORINE (E GROUND THE SUBSTANCE WITH COPPER)) OXIDESOTHATITCOULDBEHEATEDANDDECOMPOSED WITHOUT EXPLOSION &ROM THE DECOMPOSITION PRODUCTS HE CALCULATEDTHEELEMENTALRATIOS(ECONCLUDEDTHATFULMINATING GOLD WAS A SALT WITH AMMONIUM AS THE CATION AND A GOLD NITROGENCOMPOUND±AZOTURED´OR² ASTHEANION
WWWGOLDBULLETINORG
4HEWORKOF2ASCHIG &RIEDRICH 2ASCHIG FOUND THAT FULMINATING GOLD WAS NOT ONE HOMOGENEOUSCOMPOUNDBUTAMIXTUREOFMORETHANONE COMPOUND ;= $ESPITE THE FACT THAT FULMINATING GOLD CONTAINSACERTAINAMOUNTOFOXYGEN HESUGGESTEDAMIXTURE OF(. !U¯.(AND(. !U¯#LANDCONCLUDEDTHATTHEGOLD NITROGEN BONDS OF THOSE AMIDO AND IMIDO LIGANDS ARE RESPONSIBLEFORTHEEXPLOSIVECHARACTER!LTHOUGHSUCHGOLD NITROGEN BONDS OFTEN CAN BE FOUND IN EXPLOSIVE GOLD COMPOUNDS EGTHEEXTREMELYEXPLOSIVETETRAAZIDOAURATES))) LIKE .(;!U. = ;= NUMEROUS EXAMPLES OF NON EXPLOSIVE COMPOUNDS CONTAINING !U¯. BONDS ARE KNOWN EG THE AMIDE ;#( !U.(= AND ;#( !U.#( = ;= ;!U.( =./ ;= ;!U#L.(= ;= ;!U"R.( = ;= 2ASCHIG´SASSUMPTIONWASTHEREFORETOOGENERALBUTAGOOD BASISFORFURTHERSTUDIES (OWEVER SOMEHUNDREDYEARSLATER (ANS .ORBERT!DAMS ;=FOUNDTHAT;!U.( =./ LEADSTOTHEFORMATIONOFA VERYEXPLOSIVECOMPOUND WHENTREATEDWITHSODIUMAMIDE INLIQUIDAMMONIAUNDERWATER FREECONDITIONS)NA'UINIER POWDERDIFFRACTOGRAM HECOULDIDENTIFYAMMONIUMNITRATE ASABY PRODUCTOFTHISREACTION;=!DAMSCONCLUDESTHAT THISINDICATESTHEPRIMARYFORMATIONOFAMIDOLIGANDS&ROM THIS OBSERVATION IT IS LIKELY THAT SOME GOLD))) AMIDES ARE EXPLOSIVES TOO(OWEVER FULMINATINGGOLDDE½NITELYDOESNOT CONSIST OF ISOLATED AMIDEIMIDE COMPOUNDS ACCORDING TO 2ASCHIG´SSUGGESTION 4HEWORKOF7EITZ %RNST7EITZ;=INVESTIGATEDTHECONSTITUTIONOFFULMINATING GOLD IN ONE OF THE MOST COMPREHENSIVE STUDIES EVER PERFORMEDONTHISTOPIC(EUSEDALLANALYTICALMETHODSTHAT
WERESTATEOFTHEARTATTHATTIMEANDGAINEDMORESCIENTI½C INFORMATION ABOUT THIS EXTRAORDINARY EXPLOSIVE SUBSTANCE 3OME OF HIS RESULTS WERE OF FUNDAMENTAL CHARACTER FOR ALL FURTHERSTUDIES.EVERTHELESS HE½NALLYERRONEOUSLYCONCLUDED THATFULMINATINGGOLDWASAMIXTURERATIOOF!U. OF ±DIAMIDO IMIDO AURICHLORIDE²#L.( !U¯.(¯!U.( #L AND !U/À.(OR!U/( À.( RESPECTIVELY (EIGNOREDTHE VERYPOORSOLUBILITYOFFULMINATINGGOLDINMOSTSOLVENTSFROM ACHEMIST´SPOINTOFVIEW ONEWOULDEXPECTACERTAINSOLUBILITY ATLEASTFORTHEISOLATED#L.( !U¯.(¯!U.( #LMOLECULE (OWEVER HE WAS CORRECT THAT FULMINATING GOLD HAS AN EXTREMELYHIGHTENDENCYOFFORMATIONINTHEAQUEOUSSYSTEM GOLD))) ¯AMMONIA¯CHLORINE 4HELATESTWORKS 3EVERALDECADESLATER 0ROFESSOR*OACHIM3TRiHLE5NIVERSITYOF 4~BINGEN 'ERMANY ANDHISCO WORKERS(ANS .ORBERT!DAMS 5LRICH'RiLEAND*OANNIS0SILITELISINCOLLABORATIONWITH0ROF (ELMUT "ERTAGNOLLI 3TUTTGART MADE ¯ TO THE AUTHORS´ KNOWLEDGE¯THELASTMAJORATTEMPTSTOSOLVETHEPROBLEMOF THECONSTITUTIONOFFULMINATINGGOLD; =4HEIRRESULTS WILLBEDISCUSSEDEXTENSIVELYINTHEFOLLOWINGSECTIONS
4HE#HEMISTRYOFFULMINATINGGOLD 'ENERALASPECTS 3OMEREACTIONSINTHESYSTEMGOLD¯AMMONIAARESUMMARIZED IN3CHEMEBELOW 4ETRAAMMINEGOLD))) NITRATE ;!U.( =./ IS THE ONLY EXCEPTION WHERE DUETOTHEEXCESSOF.( AND./¯IONS A REACTION OF AMMONIA AND HYDROGEN TETRACHLOROAURATE)))
3CHEME %"
"
%" ,"
% ,
!
route b ( ! route a Fulminating +% , gold
+% , $
% /
+ % $ -, )
$ "##%"
' * . # $ $ -%
+% ,
!% & $
/VERVIEWOFSOMEREACTIONSINTHESYSTEMGOLD¯AMMONIA PARTLYAFTER; =
'OLD"ULLETIN6OLUME.O
WWWGOLDBULLETINORG
&IGURE
A
&ULMINATINGGOLDPRODUCEDVIAROUTEA %$8ANALYSISMASS !U . #I /NOTDETECTED
&ULMINATINGGOLDPRODUCEDVIAROUTEB %$8ANALYSISMASS !U . #I /
3%-PICTURESOFFULMINATINGGOLD
DOESNOTYIELDFULMINATINGGOLD;=4HETETRAAMMINEGOLD))) IONHASBEENINTENSEOBJECTOFINVESTIGATIONWITHRESPECTTO STABILITYANDACIDDISSOCIATION;= VIBRATIONALSPECTROSCOPICAL PROPERTIES ;= AND ITS COMPROPORTIONATION WITH GOLD TO THE CORRESPONDING DIAMMINEGOLD) COMPLEX ;= 7EITZ OBSERVEDTHATTHEHYDROLYSISOF;!U.( =./ WITHTHEMILD ,EWISBASE#L¯ROUTEB LEADSTOASEEMINGLYHOMOGENEOUS SPECIES OF FULMINATING GOLD (E THEREFORE ¯ ERRONEOUSLY ¯ CONCLUDEDTHATTHISPRODUCTWASA±QUITEPURE²#L.( !U¯ .(¯!U.( #L)NDEED ROUTEBISTHEMETHODOFCHOICEIFA HOMOGENEOUS WITH RESPECT TO COLOR GRAIN SIZE AND MACROSCOPIC MORPHOLOGY AND HARDLY EXPLOSIVE PRODUCT IS DESIRED 4HE MORPHOLOGIC DIFFERENCES IN FULMINATING GOLD WHETHERPRODUCEDVIAROUTEAORBARESHOWNINTHEELECTRON MICROSCOPE PICTURES IN &IGURE %NERGY $ISPERSIVE 8 2AY %$8 ANALYTICALDATASHOULDBEREGARDEDRATHERASQUALITATIVE THANASQUANTITATIVEINFORMATION 2OUTE B FULMINATING GOLD APPEARS AS PARTLY WELDED GLOBULES WITH A SIZE OF APPROXIMATELY M IN DIAMETER WHEREASTHESAMESUBSTANCESYNTHESIZEDVIAROUTEACONSISTS OF MUCH SMALLER PARTICLES NM OF DIFFERENT SHAPES AND
'OLD"ULLETIN6OLUME.O
MORPHOLOGIES )N BOTH PICTURES CRYSTALLINE STRUCTURES ARE COMPLETELY MISSING 7E ALSO APPLIED POWDER 8 RAY POWDER DIFFRACTIONTOSEVERALBATCHESOFFULMINATINGGOLDANDFOUND THAT IT WAS AMORPHOUS ONLY ONLY ONE BROAD GLASS PEAK APPEAREDINTHEDIFFRACTOGRAMS #RYSTALLIZATIONOFFULMINATINGGOLD 4HEMOSTRELIABLEWAYOFCHARACTERIZINGACOMPOUNDISCRYSTAL STRUCTURE ANALYSIS BY 8 RAY DIFFRACTION -ANY METHODS ARE KNOWNFORTHEGROWINGOFSINGLECRYSTALSORCRYSTALLINEPOWDER PARTLYAFTER;= #RYSTALGROWTHFROMTHEGASPHASE A BYCHEMICALREACTIONS B BYTRANSPORTREACTIONS C BYSUBLIMATION #RYSTALGROWTHINAMOLTENMATERIALS #RYSTALGROWTHINSOLIDPHASE A BYRECRYSTALLIZATION B BYPOLYPHASE DIFFUSION #RYSTALGROWTHINSOLUTIONS A BYRECRYSTALLIZATION
WWWGOLDBULLETINORG
B BYDIFFUSIONANDCHEMICALREACTIONS #RYSTALGROWTHUNDERHYDROTHERMALCONDITIONS # RYSTALLIZATIONOFAMORPHOUSSUBSTANCESUNDERHIGH PRESSUREANDORHIGHTEMPERATURES !DAMS CONCLUDED THAT DUE TO ITS PHYSICAL AND CHEMICAL PROPERTIES CRYSTALLIZATION OF FULMINATING GOLD CANNOT BE ACHIEVEDBYMETHODS ANDA )NGENERAL WEAGREE WITH THIS HYPOTHESIS &ULMINATING GOLD DECOMPOSES AT APPROXIMATELY # SOMETIMES WITH EXPLOSION WITHOUT MELTING3UBLIMATIONLEADSTODECOMPOSITIONOREXPLOSIONOF FULMINATINGGOLD!MMONIUMCHLORIDECOULDBEIDENTI½EDBY 8 RAY DIFFRACTION AS ONE SUBLIMING DECOMPOSITION PRODUCT /NE TINY GREENISH YELLOW CRYSTAL COULD BE ISOLATED FROM A -ARK TUBE IN WHICH WE TRIED TO TEMPER ANDOR SUBLIME FULMINATINGGOLDWEEKAT# 7ITHASIZEOFONLYAFEW MICRONS ITWASTOOSMALLTODETERMINETHECRYSTALSTRUCTURE (OWEVER WEBELIEVETHATTHECRYSTALCONTAINSGOLDANDLIGHT ATOMSONLY BUTNOCHLORINE4HECRYSTALLOGRAPHICALCELLCOULD BEVAGUELYDETERMINEDSEE4ABLE !DAMS STATED THAT FULMINATING GOLD IS INSOLUBLE AND CANNOT BE CRYSTALLIZED FROM SOLUTIONS (OWEVER IN THIS STUDY SEVERAL SOLVENTS WERE APPLIED TO INVESTIGATE THE SOLUBILITY OF FULMINATING GOLD CARBON TETRACHLORIDE NITROBENZENE HEXAMETHYLPHOSPHORIC TRIAMIDE ACETONITRILE DIMETHYLSULFOXIDE AND DIMETHYLFORMAMIDE 4O OUR SURPRISE WEFOUNDTHAT AFTERALMOSTTWOMONTHS SMALLAMOUNTSOF FULMINATING GOLD ROUTE A DISSOLVED IN ACETONITRILE AND DIMETHYLFORMAMIDE 4HIS FACT COULD BE OBSERVED BY THE
YELLOWISH GREEN COLOR OF THE SOLUTION 4HE OTHER SOLVENTS REMAINED COLORLESS 2ECRYSTALLIZATION FROM THE SOLUTION BY SLOWEVAPORATIONORBYIN¾UENCINGTHESOLVENT´SPOLARITYINAN ETHER CHAMBER HOWEVER FAILED AS WELL %VAPORATION OF THE SOLVENTFORMSASMALLAMOUNTOFAMORPHOUSMATERIALAGAIN WHICHREADILYDISSOLVESINTHESAMESOLVENTAGAIN ! COUPLE OF EXPERIMENTS AIMING AT THE CRYSTALLIZATION OF FULMINATINGGOLDINGELSHAVEBEENPERFORMEDPREVIOUSLYAND IN THIS STUDY )N GENERAL THE SLOW DIFFUSION VELOCITY IN GELS DRASTICALLY DECREASES THE FORMATION OF SEED CRYSTALS AND ALLOWSTHECRYSTALLIZATIONOFLARGECRYSTALSOFCOMPOUNDSTHAT USUALLY FORM ½NE PRECIPITATES LIKE SILVER CHLORIDE OR CALCIUM CARBONATE¯JUSTLIKEFULMINATINGGOLD!DAMSATTEMPTEDTHE CRYSTALLIZATIONOFFULMINATINGGOLDINSODIUMSILICATE DERIVED SILICA GELS UNDER DIFFERENT CONDITIONS BY VARYING THE GEL´S DENSITY THECONCENTRATIONSOFTHESTARTINGMATERIALS THEGEL´S P( VALUE OR BY APPLICATION OF HOMOGENEOUS AND HETEROGENEOUSFORMATIONOFSEEDCRYSTALS!U/#LCRYSTALS BY DIFFERENT GEOMETRIES OF THE EXPERIMENTAL APPARATUS OR BY APPLICATIONOFLIQUIDAMMONIAUNDERHIGHPRESSURE(EALWAYS OBTAINEDAMORPHOUSPRECIPITATESORMETALLICGOLDATHIGHP( VALUES /UR EXPERIMENTS IN GELS PREPARED FROM AQUEOUS TETRAMETHOXYSILANESUSPENSIONSFAILEDASWELLANDONLYYIELDED AMORPHOUSBROWNISH YELLOWPRECIPITATES ,IKE !DAMS WE FOUND THAT CRYSTALLIZATION OF FULMINATING GOLDBYAPPLYINGGASEOUSAMMONIATOSOLUTIONSOFHYDROGEN TETRACHLOROAURATE))) FAILS )NTHISSTUDY CRYSTALLIZATIONATHIGHPRESSURESANDELEVATED
4ABLE #RYSTALLOGRAPHICAL CELL OF A SUBLIMATIONTEMPERING PRODUCT OF FULMINATING GOLD SINGLE CRYSTAL DIFFRACTOMETRY RE¾ECTIONS USED FOR CELL DETERMINATION
A`
B`
C`
A
B
G
6`
#RYSTALSYSTEM
,ATTICE
TRICLINIC
0 LATTICE
&IGURE 180
80
A
B
160 140
60
Intensity / cps
Intensity / cps
70
50 40 30
120 100 80 60 40
20
20 0
10 4
8
12
16 20 2 Theta
24
28
32
4
8
12
16
20 24 28 2 Theta
32
36
40
4WODIFFRACTOGRAMSOFFULMINATINGGOLDPRESSEDATTONSKBAR AND#A AND#B RESPECTIVELY)NA ONLYTHEBROADGLASSPEAKCANBE OBSERVED WHEREASINB THESAMEGLASSPEAKASWELLASTHEPEAKSOFTHEDECOMPOSITIONPRODUCTS!UAND.(#L ARESHOWN
'OLD"ULLETIN6OLUME.O
WWWGOLDBULLETINORG
%8!&3ANALYSES )NHIS0H$THESIS *OANNIS0SILITELISAPPLIED%8!&3%XTENDED8 2AY!BSORPTION&INE3TRUCTURE MEASUREMENTSTOGAININSIGHT TO THE STRUCTURAL CONSTITUTION OF FULMINATING GOLD ;= 4HIS METHODCANBEUSEDWITHINVARIOUSTYPESOFSUBSTANCES EVEN INAMORPHOUSANDHETEROGENEOUSMATERIALSANDLIQUIDS(E FOUNDTHATEVENINFULMINATINGGOLDPRECIPITATEDWITHONLYA SLIGHTEXCESSOFAMMONIA AGOLDATOMISNOLONGERCOORDINATED BYCHLORINEATOMSBUTEXCLUSIVELYBYNITROGENATOMSINITS½RST COORDINATIONSPHERESEE&IG 4HISISINEXACTAGREEMENTWITHTHECOORDINATIONMODEOF THE SQUARE PLANAR TETRAAMMINEGOLD))) CATION !U¯. BOND LENGTH PM ;= )N A SECOND COORDINATION SPHERE THEREAREEITHERFOURGOLDATOMSORONLYONEINADISTANCEOF PM TO THE CENTERED GOLD ATOM )N ONE POSSIBLE INTERPRETATION THE GOLD ATOMS OF BOTH SPHERES CAN BE CONNECTEDBYAN!U¯.¯!UBRIDGEANGLE OR ALTERNATIVELY
&IGURE
FULMINATING GOLD IS BUILT OF PLANAR LAYERS OF !U. MOIETIES 4HE EXISTENCE OF !U¯. BONDS HAS BEEN EVIDENCED BY VIBRATIONALSPECTROSCOPYASWELL -AGNETICMEASUREMENTS -AGNETIC SUSCEPTIBILITIES WERE DETERMINED WITH A 315)$ MAGNETOMETER-0-3 8, 1UANTUM$ESIGN)NC BETWEEN AND + WITH MAGNETIC ¾UX DENSITIES UP TO 4ESLA 3AMPLESOFABOUTMGOFFULMINATINGGOLDTYPEB WERE LOADEDINGELATINCAPSULESAND½XEDINASTRAWASTHESAMPLE HOLDER4HEDATAWERECORRECTEDFORTHESAMPLEHOLDERAND THE CORE DIAMAGNETISM 7E MEASURED THE MAGNETIC SUSCEPTIBILITIESINMAGNETIC¾UXDENSITIESOF4ESLA 4ESLA 4ESLA AND 4ESLA 4HE SAMPLE IS DIAMAGNETIC BUT SHOWS DIFFERENTSUSCEPTIBILITIESAT+ CG4 X G CM CG4 X G CM CG4 X G CM CG4 X G CM
&IGURESHOWSTHETEMPERATUREDEPENDENCYOFTHEMAGNETIC SUSCEPTIBILITY IN A MAGNETIC ¾UX DENSITY OF 4ESLA 4HE DIAMAGNETIC CHARACTER OF FULMINATING GOLD OFFERS STRUCTURAL INFORMATION &OR IONS WITH A D ELECTRON CON½GURATION DIAMAGNETISM OCCURS ONLY IN A STRICTLY SQUARE PLANAR COORDINATION ENVIRONMENT ; = ! DEVIATION FROM THIS GEOMETRYRESULTSINPARAMAGNETISMFORDCOMPOUNDS&ROM THIS FACT WE CAN CON½RM THE SQUARE PLANARITY OF THE !U. MOIETYWHICHHASALSOBEENFOUNDINPREVIOUS%8!&3ANALYSES SEEABOVEAND&IGURE
&IGURE
-2.4 2 Tesla -2.6 g / 10-7 g-1 cm3
TEMPERATURESWASATTEMPTED&ORTHISPURPOSE AMOUNTSOF APPROXMGOFFULMINATINGGOLDWERE½LLEDINBORONNITRIDE CRUCIBLES AND PRESSED IN A BELT APPARATUS AT TONS ;= 4HREE EXPERIMENTS WITH DIFFERENT TEMPERATURES WERE CONDUCTED AND # !FTER ONE HOUR THE GOLD COMPOUNDWAS½LLEDINA-ARK TUBEANDMEASUREDWITHTHE 'UINIER 8 RAY POWDER DIFFRACTOMETER )N CASE OF # THE SUBSTANCE WAS STILL AMORPHOUS !T HIGHER TEMPERATURES CHARACTERISTIC PEAKS OF AMMONIUM CHLORIDE AND CRYSTALLINE METALLIC GOLD APPEARED IN THE DIFFRACTOGRAM SEE &IG 4HEREFORE FULMINATING GOLD DECOMPOSES EVEN AT HIGH PRESSURE AND ELEVATED TEMPERATURE WITHOUT PRIOR CRYSTALLIZATION4HISMETHOD BYTHEWAY COULDBEANEFFECTIVE METHOD FOR THE PRODUCTION OF HIGHLY 8 RAY DIFFRACTING CRYSTALLINEGOLDPOWDER &ROMALLTHESEFACTSDISCUSSEDABOVE ITCANBECONCLUDED THATFULMINATINGGOLDISANAMORPHOUSMIXTUREOFPROBABLY POLYMERIC COMPOUNDS ¯ A CONDENSATION PRODUCT OF ;!U.( = ONTHEWAYTO!U ¯.4HEGOLDATOMSARELINKED VIA .( AND .( BRIDGES AS INDICATED BY VIBRATIONAL SPECTROSCOPYBY;=!DAMSSUGGESTSTHATFULMINATINGGOLD ISTHEPRODUCTOFHYDROLYSISOF ;!U .( .( =#L
-2.8 -3.0 -3.2 -3.4 -3.6 0
50
100 150 200 250 300 350 400 T/K
4HEFUNDAMENTAL SQUAREPLANAR!U. MOIETYOFFULMINATINGGOLD4HE ATOMICDISTANCESAREPMFORALL!U¯.BONDS ANDTHEANGLESARE AND RESPECTIVELY
'OLD"ULLETIN6OLUME.O
4EMPERATUREDEPENDENCYOFTHEMAGNETICSUSCEPTIBILITYOFFULMINATING GOLDMAGNETIC¾UXDENSITYOF4ESLA
WWWGOLDBULLETINORG
4ABLE !SELECTIONOFELEMENTALANALYSESEXPRESSEDASATOMICRATIOS AFTER;=
-OL.( PER!U
!TOMICRATIOINFULMINATING GOLD DATATAKENFROM;=
!TOMICRATIOINFULMINATING GOLD DATATAKENFROM;=
P(OF SOLUTION
!U
.
#L
%XPLOSIVE PROPERTIES
/
!U
.
#L
SLIGHTLYACIDIC $E¾AGRATION UPONHEATING
NEUTRAL
SLIGHTLYBASIC
BASIC
%XPLOSIONUPON IMPACT
4HERESIDUETOISASSUMEDTOBE/NEGLECTINGTHECONTENTOFHYDROGEN !NALYSISOFTHESOLUTIONSANDCONCLUSIONTOTHECOMPOSITIONOFTHEPRECIPITATE !FTERWASHINGSEVERALTIMESWITHWATER
%LECTRICALEXPERIMENTS )N OUR ATTEMPTS TO MEASURE THE ELECTRICAL RESISTIVITY OF FULMINATING GOLD IT SOON BECAME EVIDENT THAT STRONGLY REPRODUCIBLERESULTSARENOTEASILYOBTAINEDBYSIMPLEFOUR PROBE TECHNIQUESATAMBIENTPRESSURE(OWEVER FULMINATING GOLDISASUBSTANCEWITHAVERYHIGHELECTRICALRESISTIVITY4HIS APPROVES THAT AMMONIA DOES NOT REDUCE THE !U IONS TO METALLICGOLD.EVERTHELESS ADDITIONALATTEMPTSWEREMADE TOMEASURETHEELECTRICALRESISTIVITYINTHEBELTAPPARATUSWITH ONLYTWOCONTACTSATVARIABLEPRESSURESUPTOKBARUSING ROUTEBFULMINATINGGOLD (ERESOMEINDICATIONSWEREFOUND THAT THE ELECTRICAL RESISTIVITY OF FULMINATING GOLD DECREASES WITH INCREASING PRESSURE )N ORDER TO ESTABLISH THIS EFFECT QUANTITATIVELY IT IS INTENDED TO MEASURE THE RESISTANCE IN A DIAMONDANVILCELLUPTOSEVERALHUNDREDKILOBARSATAMBIENT TEMPERATURE %LEMENTALANALYSES )N THE REACTION OF GOLD))) COMPOUNDS AND AMMONIA FULMINATINGGOLDISFORMEDONLYWITHANAMMONIAEXCESSOFAT LEAST A FACTOR OF THREE IN RELATION TO !U !N EQUIMOLAR ADDITIONOFDILUTEDAMMONIASOLUTIONLEADSTOTHEFORMATION OF .(;!U#L= ;= (OWEVER THE FULMINATING GOLD SPECIES SHOW DIFFERENT ELEMENTARY ANALYSES AS A FUNCTION OF THE PRECIPITATION CONDITIONS PRIMARILY THE AMOUNT OF AMMONIA ADDED 4HESE HARDLY PREDICTABLE DIFFERENCES HAVE BEEN OBSERVEDALREADYBY7EITZAND!DAMSSEE4ABLE "ELIEVINGTHAT!DAM´SRESULTSARETHEMORERELIABLEDUETO THE USE OF MODERN ELEMENTAL ANALYTICAL FACILITIES EXTREME VALUES OF ATOMS NITROGEN AND ATOMS CHLORINE PER ATOMGOLDAREOBVIOUSFROM4ABLE )TISOBVIOUSTHATWITHINCREASINGAMOUNTSOFAMMONIAIN
'OLD"ULLETIN6OLUME.O
THE COURSE OF PRECIPITATION OR WASHING THE CONTENT OF CHLORINEINTHEPRODUCTDECREASES SODOESWASHINGWITHPURE WATER/BVIOUSLY #L¯ISTHENSUBSTITUTEDBY/(¯OR/¯ 4HE RESULTSOFANELEMENTALANALYSISVARYTHEREFOREFROMBATCHTO BATCH 2EPRODUCIBLE SYNTHESES OF FULMINATING GOLD WITH IDENTICAL ELEMENTAL ANALYTICAL VALUES ARE HARDLY POSSIBLE )N OURINVESTIGATIONS WEFOUNDTHATFULMINATINGGOLDPRODUCED VIAROUTEAISNOTEVENHOMOGENEOUSWITHINONEBATCH4WO SAMPLESALIGHTONEWITHLIGHTBROWNISH YELLOWCOLORANDA DARK BROWN COLORED ONE OF ONE PRECIPITATION BATCH WERE SUBMITTED TO ELEMENTAL ANALYSIS ( AND . DETERMINED BY A
4ABLE 3OMEELEMENTALANALYSESOFFULMINATINGGOLDMASS "OLD½GURESARE FROMTHESAMEPRECIPITATIONBATCHND NOTDETERMINED
3AMPLE 2OUTEOFPRODUCTION CODE SEE3CHEME !U
.
(
#L
A!U .(¤
A
ND
ND ND
A
ND
ND ND
A
A
DARKBROWNFRACTION
B
A
LIGHTBROWNFRACTION
B
B
ND
&ULMINATING GOLD PRODUCED VIA ROUTE B IS CHARACTERIZED BY HIGHER HOMOGENEITY FROM THE ½RST SIGHT THAN WHEN SYNTHESIZED VIA ROUTE A )NTERESTINGLY DESPITE ITS MUCH HIGHER NITROGEN CONTENT ROUTE B FULMINATINGGOLDISLESSEXPLOSIVETHANTHEROUTEAPRODUCT
WWWGOLDBULLETINORG
VARIO%,ELEMENTALANALYZER #LBYA -ETROHM4ITROPROCESSOR ANALYZER ANDSHOWEDTWOVERYDIFFERENTCOMPOSITIONS SEE 4ABLE SAMPLES A AND B 4HE GOLD CONTENT DETERMINED BY )#0 !%3 VARIES TO A LARGE EXTENT AS WELL )N SEVERALSAMPLES ITISSOHIGHTHATTHESUMOFTHECONSTITUENTS WOULDTHEORETICALLYBEFARBEYOND4HISISALSOAGOOD INDICATIONFORINHOMOGENETIESWITHINTHEBATCH $ERIVATIVESOFFULMINATINGGOLD 3EVERALORGANICAMINESHAVEBEENAPPLIEDINSTEADOFAMMONIA TO GAIN INSIGHT INTO THE CHEMISTRY OF FULMINATING GOLD BY REDUCINGTHEPOSSIBILITIESOFTHEFORMATIONOFBRIDGESVIATHE NITROGEN ATOMS ;= )NDEED THE PRODUCT OF THE REACTION OF HYDROGEN TETRACHLOROAURATE))) AND MONOMETHYLAMINE IS A SIGNI½CANTLY LESS EXPLOSIVE LIGHT BROWNISH AMORPHOUS PRECIPITATE)TISASSUMEDTHATTHEMETHYLGROUPBLOCKSONE POSSIBLE LINK ON THE NITROGEN ATOMS FOR THE FORMATION OF A THREE DIMENSIONAL NETWORK 4HE EXPLOSIVE CHARACTER OF FULMINATINGGOLDINCREASESWITHTHEDEGREEOFCROSS LINKING 7HENDIMETHYLAMINEISUSED ASECONDHYDROGENOF.(IS SUBSTITUTED BY A METHYL GROUP 4HUS THE FORMATION OF A FULMINATINGGOLD TYPEPOLYMERISIMPOSSIBLEANDTHEREACTION WITH (;!U#L= YIELDS A CRYSTALLINE PRODUCT ¯ THE ADDUCT COMPOUND!U#LÀ.(#( 4HEUSEOFPRIMARYAMINESLARGE ALKYLGROUPS EGMONO T BUTYL AMINE HINDERSTHEFORMATION OFATHREE DIMENSIONALPOLYMERASWELL4HEPRODUCTOFTHE CORRESPONDINGREACTIONWITH(;!U#L=ISTHECRYSTALLINEADDUCT COMPOUNDOFTHEABOVETYPE;= !DAMS INVESTIGATED THE REACTIONS OF BISETHYLENEDIAMINE GOLD))) CHLORIDEASAMODELSUBSTANCEFORFULMINATINGGOLD;= )NANALOGYTO;!U.( =./ ;!UEN =#LREACTSWITHBASESAND FORMS ;!UEN EN ( =#L )T CAN BE DEPROTONATED FURTHER IN A REACTION WITH SODIUM AMIDE YIELDING ;!UEN ( =#L "OTH COMPOUNDS ARE SUITABLE ANALOGS TO FULMINATING GOLD AND ;!UEN EN ( =#LISEVENSLIGHTLYEXPLOSIVEUPONHEATING 4HE ABOVE MENTIONED GOLD NITROGEN HETEROCYCLES ;#( !U.(= ;#( !U.#( = ;= ;#( !U.(= ;= AND;#( !U.(#(=;=AREMOSTLYLIGHTSENSITIVEBUTNOT EXPLOSIVE DERIVATIVES OF FULMINATING GOLD 3EVERAL PYRIDINE DERIVATIVES SHOULD BE MENTIONED AT THIS POINT AS WELL (PY;!U#L= !U#LÀPY ;!U#LPY =#LÀ(/AND;!U#LPY =;!U#L= ;= )N ANOTHER STUDY !U#LÀPY !U"RÀPY !U)ÀPY HAVE BEEN INVESTIGATED ; = 4HESE COMPOUNDS ARE LIGHT SENSITIVE SUBSTANCES4HEIODINECOMPOUNDISTHERMALLYINSTABLEAND QUICKLY DECOMPOSES ABOVE # "OTH COMPOUNDS SHOW INTERESTINGLUMINESCENCEPROPERTIES 7E INVESTIGATED THE REACTION OF ANHYDROUS !U#L AND .3I#( INABSOLUTEDIETHYLETHER4RISTRIMETHYLSILYL AMINE REACTSMUCHSLOWERTHANAMMONIAORCONVENTIONALORGANIC AMINES!FTERSEVERALHOURSOFSTIRRINGATROOMTEMPERATURE ASMALLAMOUNTOFABROWNPRECIPITATEFORMED)NVESTIGATION BY MEANS OF 8 RAY POWDER DIFFRACTION EVIDENCED A PARTIAL REDUCTION CRYSTALLINE GOLD ONLY 4HE PRECIPITATE ITSELF WAS AMORPHOUS AND NOT EXPLOSIVE IN THE ¾AME OF A "UNSENBURNER
'OLD"ULLETIN6OLUME.O
%XPERIMENTAL )N THIS STUDY WE SYNTHESIZED FULMINATING GOLD VIA ROUTEAANDB 2OUTEA FULMINATINGGOLDWASSYNTHESIZEDPRIMARILYBYTHE REACTION OF GASEOUS AMMONIA WITH AQUEOUS SOLUTIONS OF HYDROGENTETRACHLOROAURATE))) (;!U#L=À(/ 3IGMA !LDRICH 4HISSTRATEGYPROVIDEDACONTINUOUSREACTIONOF!U AND .( AVOIDING A LOCAL OVER CONCENTRATION OF AMMONIA WHICHWOULDYIELDALESSHOMOGENEOUSANDMOREEXPLOSIVE AND SENSITIVE PRODUCT 'ENERALLY A BEAKER WITH AQUEOUS HYDROGEN TETRACHLOROAURATE))) SOLUTION ;!U = MGML ANDABEAKERWITHAQUEOUSAMMONIA WEREPOSITIONED IN AN EMPTY DESICCATOR 0RECIPITATION OF FULMINATING GOLD STARTED WITHIN FEW MINUTES AND GENERALLY COMPLETED AFTER LESS THAN MINUTES !T THIS POINT THE RESIDUAL AQUEOUS SOLUTION WAS COLORLESS OR SLIGHTLY YELLOW AT MOST 4HE PRECIPITATE WAS REMOVED FROM THE SOLUTION BY ½LTRATION OR CENTRIFUGATIONANDWASHEDWITHAMINIMUMAMOUNTOFWATER $RYING WAS PERFORMED IN A DESICCATOR OVER PHOSPHORUS PENTOXIDE /NLY FOR THE DETERMINATION OF THE EXPLOSIVE PROPERTIES DROP HAMMER AND FRICTION SENSITIVITY ROUTE A FULMINATING GOLD WAS PRECIPITATED IN A DIRECT REACTION OF AQUEOUS(;!U#L=ANDAQUEOUS.(INTHEMOLARRATIOOF AND RESPECTIVELY4HECOLOROFROUTEA FULMINATINGGOLD VARIESFROMLIGHTTODARKBROWN SOMETIMESSLIGHTLYYELLOWISH GREENISHORREDDISH SOMETIMESSLIGHTLYPURPLESEE&IG 2OUTE B FULMINATING GOLD WAS SYNTHESIZED IN A TWO STEP SYNTHESIS ACCORDING TO ;= &IRSTLY THE HYDROGEN TETRACHLOROAURATE))) SOLUTION ;!U = MGML WAS SATURATED WITH AMMONIUM NITRATE AT ROOM TEMPERATURE 2ESIDUAL AMMONIUM NITRATE WAS REMOVED BY ½LTRATION !MMONIAGASINTHEFORMOFAMMONIAVAPORFROMTHEBOTTLE WITHASOLUTION WASBUBBLEDTHROUGHTHEYELLOW½LTRATE WITHASYRINGEUNTILTHESOLUTIONLOSTITSCOLORORCRYSTALLIZATION OFWHITENEEDLESOFTHEDESIRED;!U.( =./ BEGAN!FTER HOURSOFCRYSTALLIZATION THEWHITENEEDLESWERE½LTRATED ANDWASHEDWITHASMALLAMOUNTOFCOLDWATER ETHANOLAND
&IGURE
&ULMINATINGGOLDPRODUCEDVIAROUTEA
WWWGOLDBULLETINORG
&IGURE
&ULMINATINGGOLDPRODUCEDVIAROUTEB
ETHER%VENTUALLY ASECONDFRACTIONOF;!U.( =./ CANBE OBTAINEDFROMTHEMOTHERLIQUORBYBUBBLINGAMMONIAVAPOR THROUGH THE SOLUTION AGAIN 4HE YIELD AFTER AIR DRYING WAS APPROXIMATELY )N A SECOND REACTION STEP THE NEEDLES WEREDISSOLVEDINWATERCONCENTRATIONAPPROXIMATELYMG ;!U.( =./ PERML(/ 3OLIDAMMONIUMCHLORIDE FOLDMOLAREXCESSCOMPAREDTOTHETETRAAMMINECOMPLEX WAS ADDEDTOTHECLEARSOLUTION!FTERASHORTTIME PRECIPITATIONOF FULMINATINGGOLDSETIN5PONADDITIONOFAMMONIUMCHLORIDE THECOLORLESSSOLUTION½RSTTURNEDYELLOWONTHEBOTTOMOFTHE BEAKER LATERORANGEORLIGHT BROWNBYTHEFORMATIONOF½NELY DISPERSEDFULMINATINGGOLDSEE&IG
4HE(AZARDSOFFULMINATINGGOLD )T APPEARS THAT GOLD SCIENTISTS ARE NOT ALWAYS AWARE OF THE HAZARDSOFFULMINATINGGOLDANDTHEROUTESOFITSFORMATION /CCASIONALLY WARNINGS CAN BE FOUND IN LITERATURE ; = HOWEVER REPORTSONTHEPREPARATIONOFGOLDCATALYSTSBASED ON THE POTENTIALLY HAZARDOUS USE OF HYDROGEN TETRACHLOROAURATE))) ANDAMMONIUMCARBONATEORAMMONIA CANBEFOUNDMUCHMOREREGULARLY SEEEG; =)NTHIS CHAPTER THE HAZARDS SAFE TREATMENT AND DISPOSAL OF FULMINATINGGOLDASWELLASPOTENTIALALTERNATIVESTOTHEUSEOF AMMONIAARESHORTLYDISCUSSED
%XPLOSIVEPROPERTIES 7HEN INITIATED FULMINATING GOLD EXPLODES UNDER THE FORMATION OF A CHARACTERISTIC VIOLETPURPLE PLUME OF GOLD AEROSOLS &OR INITIATION EXPLOSIVES CAN GENERALLY EXHIBIT SENSITIVITYTOWARDIMPACT FRICTION ELECTRICDISCHARGE THERMAL SHOCKORHIGHTEMPERATURESANDOTHERFACTORSLIKECHANGESIN THECHEMICALENVIRONMENT3TANDARDIZEDTESTSFORTHERELIABLE ANDREPRODUCIBLEDETERMINATIONOFTHEEXPLOSIVEPROPERTIES SUCH AS THE DROP HAMMER OR FRICTION SENSITIVITY HOWEVER DEPEND ON A DE½NED COMPOUND OF HIGH PURITY BECAUSE IMPURITIES CAN IN¾UENCE THE SENSITIVITY IN A WIDE RANGE )N CASE OF FULMINATING GOLD WHICH IS NOT A HOMOGENEOUS SUBSTANCE THEDECLARATIONOFSENSITIVITYDATAMUSTTHEREFORE BEREGARDEDASDATAWITH±INFORMATIVECHARACTER²ONLY3LIGHT VARIATIONS IN THE REACTION CONDITIONS CAN IN¾UENCE THE PROPERTIES AND LEAD TO MORE SENSITIVE AND THUS HAZARDOUS PRODUCTS!SSTATEDABOVE THEOXYGENCONTENTINFULMINATING GOLD IS PROPORTIONAL THE CHLORIDE CONTENT RECIPROCALLY PROPORTIONALTOTHESENSITIVITY; =7ASHINGTHEPRECIPITATE INBOILINGWATEROR EVENWORSE ALKALINESOLUTIONS INCREASES THESENSITIVITYINAWAYTHATTHESLIGHTESTTOUCHWITHASHEETOF PAPERCANINITIATETHEDRYSUBSTANCE;= &OR THE DETERMINATION OF SENSITIVITY DATA WE APPLIED STANDARDIZEDDROPHAMMER FRICTION ANDSPARK SPRAYINGTESTS 4HEDROPHAMMERFACILITYOFTHE,-5HASVARIABLEDROPHAMMER WEIGHTS ANDKG ANDITSDROPHEIGHTCANBEADJUSTEDIN ANYORDERUPTOCM4HESAMPLEISPLACEDINASTEELCYLINDER !STEELBOLTISINSERTEDINTOTHECYLINDER WHICHISSTRUCKBYTHE FALLINGHAMMER4HEFRICTIONTESTERUSESAROUGHENEDCERAMIC PLATE AND A CERAMIC PISTIL ;= 4HE SAMPLE IS PLACED ON THE PLATE THEN THE PISTIL IS PLACED ON THE SAMPLE BY MEANS OF A LEVER4HEFORCEAPPLIEDTOTHESAMPLEISVARIEDBYSTANDARDIZED WEIGHTSTHATCANBEHUNGUPTHELEVER&ORTESTING ANELECTRIC MOTOR MOVES THE PLATE FORWARD AND BACK ! SUBSTANCE IS CLASSI½EDASFRICTIONSENSITIVE IFTHEEXPLOSIONORDECOMPOSITION CAUSEDBYFRICTIONISAUDIBLE'ENERALLY FULMINATINGGOLDISMUCH MORE SENSITIVE TOWARD FRICTION THAN TO IMPACT 4HIS IS A LESS COMMONPHENOMENONAMONGEXPLOSIVES 7E TESTED THREE SAMPLES OF FULMINATING GOLD 2OUTE A FULMINATING GOLD PRECIPITATED WITH AND EQUIVALENTS OF AMMONIAPER!U ION RESPECTIVELY ANDROUTEBFULMINATING GOLD4HERESULTSOFTHESENSITIVITYTESTSAREGIVENIN4ABLE $ECOMPOSITIONMEANSASIGNI½CANTCHANGEOFCOLORWITHOUT AUDIBLEORVISIBLEEXPLOSION
4ABLE 3ENSITIVITYDATAOFFULMINATINGGOLD
3AMPLE 2OUTEA.(!U 2OUTEA.(!U 2OUTEB
)MPACTEXPLOSION A
* *D *D
)MPACTDECOMPOSITION B
* *D *D
&RICTIONEXPLOSION C
. .C .E
%LECTRICDISCHARGE EXPLOSION DECOMPOSITION SLIGHTDECOMPOSITION
A
KGDROPHAMMERCMBKGDROPHAMMERCMCNOWEIGHTONTHELEVERDKGDROPHAMMERCMEAFORCEOFKGONTHESAMPLE
'OLD"ULLETIN6OLUME.O
WWWGOLDBULLETINORG
&IGURE
%$8ANALYSISOFTHEPLAINMATRIXMASS !U . #) /NOTDETECTED
%$8ANALYSISOFTHEFULMINATINGGOLDGLOBULESMASS !U . #) /NOTDETECTED
3%-PICTUREOFBLACK PARTLYDECOMPOSEDFULMINATINGGOLDBYTHEIMPACTOFTHEDROPHAMMER 'LOBULESOFUNDECOMPOSEDFULMINATINGGOLDCANBE FOUNDONTHESURFACE
$ECOMPOSITIONOFFULMINATINGGOLDUNDERTHEIMPACTOF THE DROP HAMMER YIELDS A THIN LUSTROUS BLACK PLATE 3%- IMAGES OF THIS METAL LIKE SUBSTANCE ARE SHOWN IN &IGURE %$8ANALYTICALVALUESCON½RMTHATTHISSUBSTANCESTILLCONTAINS GOLD NITROGENANDCHLORINEQUALITATIVEINFORMATIONONLY 4HEUPPERLIMITOFTHETHERMALSTABILITYOFFULMINATINGGOLD VARIES BETWEEN AND # )T ALWAYS EXPLODES OR DE¾AGRATESINTHE¾AMEOFA"UNSENBURNER&ULMINATINGGOLD EXPLODEDVIOLENTLYWHENSTRUCKBYAM7LASERBEAMIN THE2AMANAPPARATUS 3AFETYINSTRUCTIONS #!54)/.&ULMINATINGGOLDISANENERGETICMATERIALSHOULD BE SYNTHESIZED BY FULLY TRAINED PERSONNEL AND IN SMALL AMOUNTSONLY0ROPERPROTECTIVEMEASURESSHOULDBETAKEN 4HE FOLLOWING SAFETY INSTRUCTIONS PROVIDE A SUMMARY OF ALL NECESSARYSAFETYPRECAUTIONSTOBETAKENFORTHESAFEHANDLING OF FULMINATING GOLD AND FOR MOST READERS EVEN MORE IMPORTANT INSTRUCTIONS HOW TO AVOID THE FORMATION OF THIS EXPLOSIVE
'OLD"ULLETIN6OLUME.O
4HEGOLDENRULEFORYOURSAFETY !VOIDANYCONTACTOFAMMONIAEITHERGASEOUSORIN AQUEOUSSOLUTION TOANYGOLD))) COMPOUND )F FOR ANY REASON THIS IS NOT POSSIBLE FOLLOW THE SAFETY INSTRUCTIONS LISTED BELOW (ANDLING OF EXPLOSIVES ALWAYS INVOLVESACERTAINRISK4HEFOLLOWINGRULESWILLREDUCETHERISK TOAMINIMUM )FPOSSIBLE USESECONDARYAMINESORPRIMARYAMINESWITH ALARGEALKYLGROUPEGMONO T BUTYLAMINE INSTEADOF AMMONIATOAVOIDTHEFORMATIONOFEXPLOSIVEPRODUCTS !VOID AN EXCESS OF AMMONIA WHICH INCREASES THE PRODUCT´SSENSITIVITY INTHECOURSEOFYOURREACTION5SE ASLITTLEASPOSSIBLE )NYOURREACTIONSWITHGOLD))) COMPOUNDS BEAWARETHAT SOMECHEMICALSMAYRELEASEAMMONIA EGAMMONIUM CARBONATEORUREAATELEVATEDTEMPERATURE 7ITHOUT A MAJOR EXCESS OF AMMONIA THE ADDITION OF SIGNI½CANT AMOUNTS OF SODIUM OR POTASSIUM CYANIDE TO
WWWGOLDBULLETINORG
THESLIGHTLYBASICSSOLUTIONCANPREVENTTHEPRECIPITATION OFFULMINATINGGOLD; ="EAWAREOFTHEFORMATIONOF VERYTOXICHYDROGENCYANIDEGASFROMACIDICSOLUTIONS $ ONOTWASHTHEPRECIPITATE NEITHERWITHWATER NOREVEN WORSE WITH AMMONIA SOLUTIONS OR BASES "OTH LEADS TO THE FORMATION OF EVEN MORE SENSITIVE AND EXPLOSIVE PRODUCTS )FYOUACCIDENTALLYOBTAINAPRECIPITATEFROMAREACTIONOF GOLD))) COMPOUNDS AND AMMONIA DO NOT DRY IT BUT KEEPITMOIST/NLYTHEDRYPRODUCTISEXPLOSIVE 0RECIPITATIONINPRESENCEOFEXCESSAMOUNTSOF.( AND OR#L¯EG.(#LOR.(./ LEADSTOALESSINCASEOF #L¯ ORNOTEXPLOSIVEINCASEOF.( PRODUCT $O NOT SYNTHESIZE OR HANDLE LARGER QUANTITIES THAN MGOFFULMINATINGGOLD 5SE SAFETY EQUIPMENT WHEN HANDLING FULMINATING GOLD SUCH AS SAFETY GOGGLES FACE SHIELD LEATHER COAT EARTHENINGPERSONANDEQUIPMENT +EVLAR4-GLOVESAND WRISTPROTECTORSANDEARPLUGS)NGENERAL AVOIDTHEUSE OFGLASSORMETALEQUIPMENTEGSPATULA BECAUSEOFTHE POSSIBLE FORMATION OF SHARDS OR SHRAPNELS IN CASE OF AN EXPLOSION5SEPLASTICBEAKERSANDSPATULAINSTEAD/NLY FOR THE DRYING OF WET FRESHLY PRECIPITATED FULMINATING GOLD IN THE DESICCATOR THE USE OF A GLASS BEAKER HAS TURNED OUT AS PRACTICABLE BECAUSE FULMINATING GOLD TENDSTOADSORBONTHEBOTTOMOFAPOLYPROPYLENEBEAKER IN THE COURSE OFDRYING FROMWHEREITCANBEREMOVED ONLYBYHAZARDOUSSCRATCHING !VOID FRICTION TO THE DRY PRODUCT 2EMEMBER ITS HIGH FRICTIONSENSITIVITY!CTINACONCENTRATEDWAYANDHANDLE THEPRODUCTWITHCAREANDPRECAUTION &OR SAFE DISPOSAL OF FULMINATING GOLD DISSOLVE IT IN HYDROCHLORIC ACID CONCENTRATIONS - $ISSOLUTION MAYCONSUMESOMETIME THUSITISADVISABLETOLETTHE SUSPENSIONSTANDFORATLEASTHOURS4HEREAFTER ONLYA LITTLERESIDUEMIGHTREMAINUNDISSOLVEDONTHEBOTTOMOF THEBEAKER)TCANBEWIPEDOUTWITHAPAPERTOWELWITHOUT AHAZARD
#ONCLUSIONS
&ULMINATING GOLD IS A FASCINATING EXPLOSIVE SUBSTANCE OF HISTORICANDSCIENTI½CINTEREST(OWEVER ITISAHETEROGENEOUS MIXTURE OF POLYMERIC COMPOUNDS WITH VARIABLE PROPERTIES 4HUSITSCONSTITUTIONCANNOTBEEXPRESSEDBYASIMPLEFORMULA !DAM´STHEORYTHATFULMINATINGGOLDISTHEPRODUCTOFPARTIAL HYDROLYSISOF ;!U .( .( =#LISPROBABLYVERYCLOSETO THE TRUTH )N MAGNETIC MEASUREMENTS FULMINATING GOLD SHOWED TO BE DIAMAGNETIC 4HUS THE GOLD ATOMS ARE COORDINATEDBYFOURNITROGENATOMSINSQUAREPLANARLOW SPIN COMPLEXES 4HIS CON½RMS PREVIOUS %8!&3 ANALYSES )N ANY CASE SCIENTISTSHAVETOBEAWAREOFTHEHAZARDSINVOLVEDIN THE REACTION OF GOLD))) COMPOUNDS AND AMMONIA &ULMINATINGGOLDISUNPREDICTABLE3ATDICTUM
'OLD"ULLETIN6OLUME.O
!CKNOWLEDGEMENTS 7EWOULDLIKETOTHANK0ROF+ONSTANTIN+ARAGHIOSOFFFORHIS NUMEROUS AND ENTHUSIASTIC ATTEMPTS MEASURING OUR NON CRYSTALLINE LOOK LIKE CRYSTALS ON THE 8 RAY DIFFRACTOMETER 7E WOULD ALSO LIKE TO THANK 0ROF *OACHIM 3TRiHLE FOR PROVIDING LITERATURE AND HELPFUL COMMENTS TO THIS STUDY AND 3TEFFEN 3CHMIDTFORTHE3%-INVESTIGATIONS&INANCIALSUPPORTOFTHIS WORK BY THE ,UDWIG -AXIMILIAN 5NIVERSITY OF -UNICH ,-5 THE &ONDS DER #HEMISCHEN )NDUSTRIE &#) THE %UROPEAN 2ESEARCH/F½CE%2/ OFTHE53!RMY2ESEARCH,ABORATORY !2, UNDERCONTRACTNOS. # !. AND THE "UNDESWEHR 2ESEARCH )NSTITUTE FOR -ATERIALS %XPLOSIVES &UELSAND,UBRICANTS7)7%" UNDERCONTRACTNOS %%$8 %%$& IS GRATEFULLY ACKNOWLEDGED 'EORG 3TEINHAUSER THANKS THE !USTRIAN 3CIENCE&UND&7& FOR½NANCIALSUPPORT%RWIN3CHRyDINGER !USLANDSSTIPENDIUM PROJECTNO* .
!BOUTTHEAUTHORS 'EORG3TEINHAUSERWASBORNIN6IENNA !USTRIA IN(ERECEIVEDHISDIPLOMA INCHEMISTRYFROMTHE5NIVERSITYOF 6IENNAINANDHIS0H$IN RADIOCHEMISTRYFROMTHE6IENNA 5NIVERSITYOF4ECHNOLOGYIN(IS RESEARCHINTERESTSAREINRADIOCHEMISTRY ANDINORGANICCHEMISTRY INCLUDING INDUSTRIALANDENVIRONMENTALCHEMISTRY (EISCURRENTLYEMPLOYEDATTHE,-5 -UNICHASAN%RWIN 3CHRyDINGER &ELLOWIN THE½ELDOFENERGETICMATERIALS *~RGEN%VERSWASBORNIN$ORTMUND 'ERMANY 5NTIL HEWORKEDAS LABORATORYASSISTENTANDTHENSTUDIED CHEMISTRYATTHE&5"ERLIN(ERECEIVED HIS$IPL #HEM ANDTHE$RRER NAT BOTHFROMTHE,-5-UNICH 5NTIL HEWORKEDATTHE%4(:~RICH INTHE3OLID3TATE0HYSICS'ROUPOF '"USCHAND%+ALDIS!FTERTHE (ABILITATION ATTHE,-5-UNICH HEWAS(EISENBERG 3TIPENDIAT 0RIV $OZ AND0ROFESSOR (ISRESEARCHINTERESTSAREHIGHPRESSURE INVESTIGATIONSON:INTLCOMPOUNDSWITH ABELTAPPARATUSKBAR ANDWITHA DIAMONDANVILCELLKBAR
WWWGOLDBULLETINORG
3TEFANIE*AKOBWASBORNIN-UNICH 'ERMANY IN3HERECEIVEDHER DIPLOMAINCHEMISTRY ANDHER 0H$ FROMTHE,-5-UNICH (ERRESEARCHINTERESTSAREININORGANIC SOLIDSTATECHEMISTRY ESPECIALLY CRYSTALLOGRAPHYANDMAGNETISM3HEIS CURRENTLYEMPLOYEDATTHE,-5-UNICH 4HOMAS-+LAPyTKEWASBORNIN 'yTTINGEN 'ERMANY IN(E RECEIVEDHIS$IPL #HEM $RRER NAT AND(ABILITATION FROM THE45"ERLINANDWORKEDASA0RIVAT $OZENTATTHESAMEUNIVERSITYFROM TO!FTERTWOYEARS¯ AT'LASGOW5NIVERSITY HETOOKUP HISPRESENTPOSITIONASPROFESSOROF INORGANICCHEMISTRYAT5NIVERSITYOF -UNICHIN(ISSCIENTI½CINTERESTS INCLUDEEXPLOSIVES HIGH ENERGY DENSITY MATERIALS COMPUTATIONALCHEMISTRY AZIDECHEMISTRY ¾UORINECHEMISTRY STRONGOXIDIZERSANDNITROCHEMISTRY
7 *0OPE '" -3PETER .ITROCELLULOSE #73CHEELE #HEMISCHE!BHANDLUNGVONDER,UFTUNDDEM&EUER 5PSALA ,EIPZIG P %NCYCLOPmDIEMETHODIQUE #HIMIE VOL 0ARIS P *$UMAS !NN#HIM0HYS &2ASCHIG ,IEBIGS!NN 4-+LAPyTKE "+RUMM * #'ALVEZ 2UIZ )NORG#HEM ( .!DAMS 5'RiSSLE 7(ILLER *3TRiHLE :!NORG!LLG#HEM -7EISHAUPT *3TRiHLE :.ATURFORSCH B *3TRiHLE *'ELINEK -+yLMEL :!NORG!LLG#HEM ,(3KIBSTED !CTA#HEM3CAND ! ( .!DAMS $IPLOMATHESIS 4~BINGEN ( .!DAMS 0H$THESIS 4~BINGEN %7EITZ *USTUS,IEBIGS!NN#HEM 5'RiLE 0H$THESIS 4~BINGEN *0SILITELIS 0H$THESIS 4~BINGEN ,(3KIBSTED *"JERRUM !CTA#HEM3CAND ! --ANFAIT !*0!LIX #+APPENSTEIN )NORG#HIM!CTA ,(3KIBSTED *"JERRUM !CTA#HEM3CAND ! *%VERS (ABILITATIONTHESIS -~NCHEN +)GLHAUT 0H$THESIS -~NCHEN
'ILBERT/EHLINGERWASBORNIN3EEFELD !USTRIA IN(EISALABORATORY TECHNICIAN(ISMANIFOLDRESEARCH INTERESTSINCLUDE8 RAYINVESTIGATIONSAT AMBIENTANDATHIGHPRESSURE
#6"ANKS 266ANDER(AAR 206ANDER7AL *!M#HEM3OC 5'RiSSLE *3TRiHLE :!NORG!LLG#HEM 5'RiSSLE 7(ILLER *3TRiHLE :!NORG!LLG#HEM ( .!DAMS *3TRiHLE :!NORG!LLG#HEM ( .!DAMS 7(ILLER *3TRiHLE :!NORG!LLG#HEM 7#ONZELMANN 7(ILLER *3TRiHLE '-3HELDRICK :!NORG!LLG#HEM *!#USUMANO .ATURE *-&ISHER 'OLD"ULL
2EFERENCES
&#HEMNITIUS #HEMIKER :EITUNG - +4UNG ( 9,IN 9 7#HEN 47
3 3CHWAERTZER #HRYSOPOEIA3CHWAERTZERIANA¯-ANUSCRIPTA6ONDER
$7ANG #.
7AHRHAFFTEN"EREITUNGDES0HILOSOPHISCHEN3TEINS3AMUEL(EIL
$9IN *,IU #,I 84AN #.
(AMBURG
1&U 3+UDRIAVTSEVA (3ALTSBURG -&LYTZANI 3TEPHANOPOULOS #HEM
7"ECK *%VERS -'yBEL '/EHLINGER 4-+LAPyTKE :!NORG!LLG
#HEM /#ROLL "ASILICA#HYMICA '4AMPACH &RANKFURTA-AIN P 47ILLIS $IATRIBEDEFERMENTATIONE IN'"LASIUS (7ETSTEINEDS
/PERAOMNIA !MSTERDAM P 0%3CHOENFELDER 53
'OLD"ULLETIN6OLUME.O
%NG* 18U +##+HARAS !+$ATYE #ATAL,ETT 4"ERGMAN $ECALCEAURIFULMINATE IN/PUSCULAPHYSICAETCHYMICA VOL 5PSALA P HTTPWWWBAMDE '3TEINHAUSER 'OLD"ULL
