The risk of mixing dilute hydrogen peroxide and acetone solutions

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RESEARCH ARTICLEThe risk of mixing dilutehydrogen pacetone soThe present study documents the enmixing diluteH2O2 and acetone so hehas been shown to be potentially 2 wexplosive peroxides. Mixing conc idshock and friction sensitive explo diasearch of the chemical literature ppinformation that addressed the p s wacetone solutions. The conclusion ingthan 3%H2O2 and 7% acetone, th nt athe presence of an acid catalyst, hu roTATP is relatively insoluble in wa levH2O2 solutions, thus any acetone catthe aqueous cleaning solution.Hydrogen peroxide mixed withorganic solvents is known to form dan-it is insoluble in water and is highlysensitive to friction, shock and tem-perature. It is called a primary explo-equal parts of acetonewith 10%H2O2.He found that TATP crystals were inso-luble in water, acids and alkalis buthly con-7. Theypingthetures ofs. Theby thentainingblastingtion ory. Milasducts of2 2 ne withJimmie CChemistRhode IUSA (Tefax: 401e-mail: jJoseph BChemistRhode required. One approach is introduc-tion of dilute aqueous hydrogen per-oxide (H2O2). A concern is that in ascrubber used to remove acetone fromprocess air, the combination of H2O2and acetone could form explosive per-oxides. To evaluate this concern, thesereagents were combined in acidicandwithout acid. They found that solu-tions of acetone and hydrogen peroxidein the presence of acid would predomi-nately form the trimer TATP. In theabsence of acid, 2,2-dihydroperoxypro-pane was formed and slowly convertedto [dioxybis(1-methylethylidene)]bis-hydroperoxide. Sauer and Edwards4Steven A. Wilson is affiliated with theEastman Chemical Company, King-sport, TN 37662, USA.James L. Smith is affiliated with theChemistry Department, University ofRhode Island, Kingston, RI 02881,1871-5532/$36.00 Division of Chemical Health and Safety of the American Chemical Society 27doi:10.101that other peroxide molecules can alsobe formed, including diacetone diper-oxide (DADP). Figure 1 provides themolecular structures and physicalproperties of TATP, DADP and otherperoxide products that are formedaccording to the literature.The potential for forming explosiveperoxides when mixing dilute solu-tions of H2O2 and acetone has notbeen documented. Industrial scrub-bers are routinely used in chemicalplants. Periodic cleaning to removebio-sludge buildup inside the scrubberas acetone. Shanley and Grepreparedareviewarticleontheand chemical properties of higcentratedH2O2 solutions in 194provideda ternarydiagrammapdetonable compositions of mixacetonewaterH2O2 solutionexplosive power was measuredinspection of lead pipes co10 mL mixtures initiated bycaps. There was no identificaisolation of TATP in this studandGolubovic3 studied the prothe reaction of H O and aceto. Oxley is affiliated with thery Department, University ofsland, Kingston, RI 02881,l.: 401 874 2103;874 2103; is affiliated with thery Department, University ofsland, Kingston, RI 02881,gerous peroxides. Hydrogen peroxide sive due to its ease of detonation. Note, readily soluble in organic solvents suchenspan2physicalBy [TD$FIRSTNAME]Jimmie C. [TD$FIRSTNAME.E] [TD$SURNAME]Oxley [TD$SURNAME.E], [TD$FIRSTNAME]Joseph [TD$FIRSTNAME.E] [TD$SURNAME]Brady [TD$SURNAME.E],[TD$FIRSTNAME]Steven A. [TD$FIRSTNAME.E] [TD$SURNAME]Wilson [TD$SURNAME.E], [TD$FIRSTNAME]James L. [TD$FIRSTNAME.E] [TD$SURNAME]Smith [TD$SURNAME.E]INTRODUCTION6/j.jchas.2011.07.010eroxide anlutionsresults of a literature search and experimlutions. The use of diluteH2O2 to clean chazardous due to the reaction of H2Oentrated H2O2 and acetone with an acsives triacetone triperoxide (TATP) andwas unable to identify any directly aotential formation of explosive peroxideof these experiments is that when mixe solutions are unlikely to form significandreds of parts per million of organic peter, it is soluble at roughly the 15 ppmperoxides that are formed without acidand acetone is an especially hazardouscombination that can form variousexplosive peroxides when mixed athigh concentration while using an acidcatalyst.1,319 The primary explosivetriacetone triperoxide (TATP) is anoteworthy reaction product, becausedtal work to assess the risks ofmical vessels is common, but itith organic solvents to formcatalyst is known to form thecetone diperoxide (DADP). Alicable research or technicalhen mixing dilute H2O2 anddilute solutions, such as lessmounts of TATP or DADP. Inxides can be formed. Althoughel and higher for acetone andalyst should remain soluble inmedia and alkaline media, and in thepresence of steel coupons containingwelding materials.Prior to experimental work, a com-prehensive literature search was con-ducted. Wolffenstein first reported theformationofTATPin1885whenmixing1Elsevier Inc. All rights reserved.[(Figure_1)TD$FIG]H OOOOs-hpro6-8hyl. = # 1,2,4xidOOHOOOO 1,1'-(1-methylethylidene)bi(2,2-DihydroperoxyCAS# 2614-73,3,6,6-tetramethyl-1(Diacetone Diperostudied the formation of 2,2-dihydro-peroxypropane at various pH values.The work provided reaction kineticsparameters, but there was no mentionof TATP or DADP. They later studiedthe formation of higher adducts, butonly proposed that TATP is formed bya reaction between acetone and [dioxy-bis(1-methylethylidene)]bis-hydroper-oxide.5 Evans et al.6 described, in aforensic science case study, how easilyTATP is formed by mixing acetone, 6%H2O2 and concentrated sulfuric acid. Areview by Mackenzie7 addressed thehandling and use of H2O2, and stressedsafety precautions necessary at variousstrengths. There was no mention ofTATP, but he did warn against thebuildup of gases, including oxygen, asH2O2 degraded. In addition, therewerewarnings that after the reaction oneshouldbecautiousduringprocess steps,such as distillation, that would concen-trateanyunstableperoxidecompounds.A 1991 review byMackenzie8 providedCAS# 1073-91M.P. = 133 - 135 Vapor Pressure (298 K) =Figure 1. Re28HO OH +OHOOOOydroperoxidepane) [dioxybis(1-methyletM.PCAS,5-tetroxanee, DADP)safety considerations for processdesigns that use H2O2 and organic che-micals. It highlighted various risks,including the dangers from decomposi-tion of H2O2, as well as a variety ofproduction hazards. U.S. patent5,003,1099 describes a process ofdestroying acetone peroxides formedduring phenol synthesis by heating,decreasing pH, and adding a coppercompound. The work implies that thechemical destruction of acetone perox-ides would require conditions difficultto achieve during industrial processing.In1999,Bellamy10 foundthatonecouldchemicallydestroyTATPby refluxing inethanol containing tin(II) chloride.They also report that TATP is almostas powerful as trinitrotoluene (TNT),but is extremely sensitive to frictionand impact sensitivity tests. TATPis quite soluble in chloroform(42.7 wt%), toluene (28.6 wt%), acet-one (17.2 wt%), and hexane(14.4 wt%). Jiang et al.11 described the-2C (17) 17.7 Pa (17)3,3,6,6,9,9-hexamethy(Triacetone TrCAS# 1M.P. = Vapor Pressure (action Products of Hydrogen Peroxide andJournal of ChemO OOHOOOidene)]bis-hydroperoxide34C (3)471-09-6preparation of tetrameric acetone per-oxide (CAS #74515-93-8). They claimthat SnCl45H2O or SnCl22H2O couldact asacatalyst to forma tetramer.Theirresults indicate that no reaction takesplace when treating acetone with 30%H2O2 and no catalyst, but when0.5 mmol of catalyst was added, a>19% yield of tetrameric acetone per-oxidewasformed. In2002,Oxleyetal.12studied thedecompositionof TATPandconcluded that the predominantdecomposition product in the gas phaseismethylacetate. Inacondensed-phase,or within proton-donating solvents,TATP breaks down predominately intoacetone and water. Widmer et al.13developedanLC/MSmethodtoreplaceGC/MS methods, stating TATPdegrades GC columns. This paper alsoobserved that TATP has two structuralisomers, both stable at room tempera-ture. Their method was sensitive to10 ng per 100 mL (or 0.1 ppm).Schulte-Ladbeck et al.14 developed al-1,2,4,5,7,8-hexoxonaneiperoxide, TATP)7088-37-894 C (17)298K) = 7.8 Pa (17)Acetone.ical Health & Safety, March/April 2012with an average linear velocity of117 cm/sec. The inlet was held at170 8C in the splitless mode for0.50 minutes at 2.37 psi before theinlet purged at 40.0 mL/minute. Themakeup gas to the mECD was UHPnitrogen run in the constant flowmodeat a rate of 30 mL/minute and thedetector was held at 280 8C. The ovenwas initially held at 40 8C for 2 min-utes, ramped at 20 8C/minute to150 8C and held for 1 minute, followedby a 0.50 minutes post run at 250 8C.The presence and quantity of TATPwas determined bymatching the reten-kamp et al. (Figure 3).Solubility of TATP in Acetone andAqueous Acetone SolutionsThe solubilities of TATP and DADP inpure acetone were measured as151 mg/mL (0.191 mg/mg) and43 mg/mL (0.0548 mg/mg) respec-tively. TATP was found to have a solu-bility of 200 mg/mL (0.298 mg/mg) inchloroform. These values were deter-mined by adding solvent drop wise tothe solid peroxide while stirring in around-bottom flask. Qualitative solu-bility tests in aqueous acetone and[(Figure_2)TD$FIG]TATentrrveEXPERIMENTALGeneral Experimental Set-UpA mix was defined as a combinationof hydrogen peroxide (initially50 wt%) and acetone (initially 100%)added to water to give hydrogen per-oxide concentrations that varied from30 wt% to 12 wt% to 3 wt% and theacetone concentrations of 50 wt% or7 wt%. Catalysts included various con-centrations of sulfuric acid, aqueoussodium hydroxide (50 wt%) or metalcoupons. The ability of the mix toform TATP was judged by gas chroma-tography (GC) analysis equipped witheither a mass selective detector (MSD)or an electron capture detector (ECD).If, after 48 hours, white solid precipi-tate was observed, the solids were col-lected, dried and analyzed by GC/MSto confirm their identity. If, after48 hours, no solid had formed, thesolutions were left for an additional 3to 6 days and extracted with chloro-form or dichloromethane, and theorganic extract was analyzed by gaschromatography.trace analysis method for TATP. Themethod uses liquid chromatography toseparate the analytes followed by post-column UV irradiation and derivativi-zation-based fluorescence detection.Denekamp et al.15 further describedthe two structural isomers of TATPand explained that a high transitionenergy step was the cause of the twoconformations being stable at roomtemperature. In 2004, Oxley et al.16developed procedures for training dogsto detect TATP. The work highlightsthat loss of TATP from surfaces is dueto its high rate of sublimation. In 2009,Oxley et al.17 studied the vapor densityof TATP. This work determines vaporpressures of both DADP and TATP(17.7 and 7.8 Pa at 25 8C). Dubnickovaet al.18 studied the decomposition ofTATP and determined that it is not anenthalpy-based explosion, but rather,an entropic burst in which four gasmolecules are created from one TATPmolecule. Eyler19 explored the solventeffects on the thermal decomposition ofTATP (1351708 C) and found that theratewaspositively influencedbysolventpolarity.Journal of Chemical Health & Safety, MarchAn Agilent 6890 gas chromatographcoupled with an Agilent 5973i Massselective detector (GC/MS), and anAgilent 6890 gas chromatographcoupled with a micro-electron capturedetector (GC/mECD), were employedto separate, identify andquantify TATP.The GC/MS was fitted with a 6-meterAgilent DB-5MS capillary columnwitha nominal diameter of 250 mm and filmthickness of 0.25 mm. The carrier gaswas UHP helium at an initial flow rateof 2.5 mL/min and an average linearvelocity 129 cm/sec. The inlet was runwith a 5:1 split at 170 8Cat a pressure of1.09 psi. The oven was held at 50 8C for2 minutes, ramped to 190 8C at 20 8Cper minute and the transfer line to theMSDwas held at 275 8C.To ensure thatall materials had passed through thecolumn, a 1 minute post run at 280 8Cwith a flow rate of 8 mL/minute wasused.The GC/mECD was fitted with a 6-meter Restek RTX-200 capillary col-umn with a nominal diameter of530 mm and a film thickness of1.50 mm. The carrier gas was UHPhelium at a rate of 15.8 mL/minuteCalibration Curve for 017500035000020100ConcPeak AreaFigure 2. Calibration Cu/April 2012tion times and mass spectra of samplesto authentic standard solutions. A cali-bration curve for TATP was developedby dissolving a known amount ofauthentic TATP in dichloromethaneand preparing concentrations thatbracketed the amounts that wereexpected during an analytical run. Atypical set of concentrations for ananalytical run on the GC/MS was100, 200, 300, 400 and 500 mg/L ofTATP. A typical set of concentrationsfor an analytical run on the GC/mECDwas 0.5, 1, 2.5, 5, 10, 25, and 50 mg/L.A linear dependence was determinedby measuring the peak height or inte-grating the area under the character-istic peak for TATP and plotting thearea or height versus concentration(Figure 2).It should be noted that TATP chro-matograms exhibit two peaks, one foreach conformational isomer. Underthe GC conditions used in Figure 3,the isomeric peaks eluted 0.9 min-utes apart. When each peak was exam-ined by GC/MS, the mass spectra wereidentical, confirming that the twopeaks are isomers as reported byDene-15P in DichloromethaneR2 = 0.9987504030ation TATP (mg/L)for TATP by GC/mECD.29were combined, rinsed twice with10 mL of deionized water, dried overmagnesium sulfate and that solutionwas analyzed by GC/MS (Tables 2and 3).Mixing with Welded Steel CouponsThree types of steel coupons were eval-uated to determine the catalytic effectsassociated with formation of TATP.The three types were a coupon withouta weld, a coupon with a dirty weld,and a coupon with a clean weld. Asingle coupon of each type was placedin the six acetone/hydrogen peroxidemixtures. The reaction vessels weresealed and left at room temperaturesfor approximately 100 hours. An ali-quot was removed and analyzed byGC/MS as described above. Only the50%/30% and 50%/12% mixtures of[(Figure_3)TD$FIG]Figure 3. Chromatograms of Authentic TATP Standard Solutions. From Top toBottom: 50, 25, 10, 5, 2.5, 1 mg/L TATP Standard Solutions.aqueous hydrogen peroxide are sum-marized in Table 1. Solubility wasdetermined by visual inspection.Mixing under Acidic ConditionsSolutions for the acidic media condi-tions were prepared as follows; thewater necessary for dilution wasplaced in an Erlenmeyer flask, andthe flask was immersed in an ice bath.Hydrogen peroxide (0.10 mol) andthen acetone (0.10 mol) were addedto the chilled water in proportionssuch that the final concentration ofthe mixture mimicked the combina-tion of 30%, 12%, or 3% (w/w) hydro-gen peroxide with 50% or 7% (w/w)Table 1. Solubility of TATP in Various SoluTATP (mg) H2O Amount (kg) Aceton24.7 1.800025.6 1.600024.5 1.0000 1025.3 0.9999 1051 2.0001 1025.4 1.0001 1524.2 1.0000 1525.2 0.2504 7924.8 1.0002 2050.2 0.9999 1375.8 1.9999 1025.6 1.0316 9725 0.473725.2 0.400024.8 0.500030acetone. Each of the six possible com-binations was prepared in triplicateand either 0, 1 or 5 drops of concen-trated sulfuric acid was added to eachof the samples. The average mass ofone drop of concentrated sulfuric acidwas found to be 50 mg.The flasks were sealed with Parafilmand left at room temperature for 2 to 7days. If a precipitate formed after 2days, it was removed by filtration,washed with water, dissolved in acet-onitrile, and analyzed by GC/MS. If noprecipitate was observed after 7 days, a10 mL aliquot of the aqueous solutionwas extracted twice with 10 mL ofdichloromethane, the organic extractstions.e (ppm) H2O2 (g) H2O2 (wt%) Dis000 72 h0 72 h0 72 h9 72 h0 72 h0 96 h5 96 h9 96 h0.585 0.12% 96 h24 12% 24 h30 12% 96 hJournal of Chemhydrogen peroxide/acetone indicatedthe presence of TATP by GC/MS.Table 4 shows the configurations thatwere examined and the concentrationof TATP observed in these solutions.Alkaline ConditionsThe most concentrated mixture inves-tigated in the presence of acid was re-investigated in the presence of base(50% acetone/30% hydrogen perox-ide). In a 125 mL Erlenmeyer flask,water, hydrogen peroxide and acetonewere combined so that acetone was50 wt% and hydrogen peroxide was30 wt%. Drops of sodium hydroxidesolution, 0, 1, 2, or 10, were added.solved Not dissolved TATP (ppm)100 hours 13.7100 hours 16100 hours 24.5100 hours 25.3ours 25.5ours 25.4ours 24.2ours 101ours 24.8ours 50.2ours 37.9ours 24.8ours 52.8ours 63ours 49.6ical Health & Safety, March/April 2012peroxide solutions (12% and 3%). The7% acetone solutions were combinedwith the hydrogen peroxide solutionssuch that the mixture contained0.1 mol of each reactant, theoreticallyyielding 0.033 mol TATP. The 0.04%acetone solutions were combined withhydrogen peroxide such that eachmix-ture contained 0.01 mol of each reac-tant, theoretically yielding 0.0033 molTATP. After acetone and hydrogenperoxide were combined, one drop ofsulfuric acid (18 M, 13 M, 5 M, or0.1 M) was added, and the mixtureswere sealed and left at room tempera-ture for 75 hours. The mixtures fromthe 12% and 7% acetone wereextracted with 20 mL dichloro-methane twice. The organic extractssium sulfate (Table 5).Table 2. Mixes Prepared to Test TATP Formation Under Acidic Conditions.Acetone (%) H2O2 (%) H2SO4 (d.)TATP ppt in 48 hours 50 30 550 12 550 30 150 12 1TATP in solution after 7 days 50 3 550 3 150 30 050 12 07 30 57 12 57 3 57 30 17 12 17 3 1No TATP after 7 days 50 3 0777Each solution was prepared in dupli-cate. The flasks were sealed and leftundisturbed at room temperature for 8days. The mixtures were twiceextracted as described above and theextracts were analyzed for TATP byGC/mECD. The concentration of theNaOH solution was determined byrecording the mass necessary to fill a2 mL volumetric flask and repeatedthree times. The density was found tobe 1.522 g/mL. By comparing thisvalue to literature values, the solutionwas found to be 48.58% NaOH bymass. The mass of a drop of the NaOHwas determined to be 38 mg by record-Table 3. TATP Found in Solutions WithoutAcetone Peroxide Acid(drop7% 30% 57% 30% 17% 12% 550% 3% 550% 12% 07% 12% 17% 3% 57% 3% 150% 3% 150% 3% 07% 30% 07% 12% 07% 3% 0Journal of Chemical Health & Safety, Marching the mass of 10 individual drops andtaking the average. After 8 days, GCmECD analysis of the organic extractsof the alkaline solutions showed nodetectable TATP had been generated,while two control solutions (acetone,hydrogen peroxide, no NaOH) werefound to contain TATP in excess of50 mg/L.Examination of Dilute Acids in Acetone/30 012 03 0Peroxide MixtureTo determine if more dilute solutionsof acetone in hydrogen peroxide couldform TATP, solutions of acetone (7%and 0.04%) were mixed with hydrogenPrecipitate after 7 Days.s)Mass %AcetoneMass %Peroxide6.2% 3.6%6.2% 3.6%5.2% 3.1%4.7% 2.7%14.6% 8.5%5.2% 3.1%3.0% 1.7%3.0% 1.7%4.6% 2.7%4.7% 2.7%6.1% 3.6%5.2% 3.0%3.0% 1.7%/April 2012RESULTS AND DISCUSSIONSolubility of TATP in WaterTATP is practically insoluble in water,but is soluble in acetone. Solubilityvalues of dilute aqueous solutions ofacetone have not been published. Inthis study, 25 mg of TATPwas added tovarious aqueous solutions of acetoneMass %ReactantsMass TATP insolution (mg)9.8% 10,0829.8% 6,2248.3% 5,9687.4% 5,91423.1% 5,3228.3% 4,3624.7% 4,1364.7% 3,7207.3% 3,3437.4% Not found9.8% Not found8.3% Not found4.7% Not foundwere combined and rinsed with10 mL of water to remove any residualacid or acetone and dried over magne-sium sulfate. The mixtures from the0.04% acetone solutions had a totalvolume of approximately 1,560 mLand were extracted twice with 50 mLdichloromethane and rinsed once with20 mL water and dried over magne-31SteWeTable 4. TATP Found in Solutions withAcetone,Initial conc.HP, Initialconc.50% 30%50% 30%50% 30%50% 12%50% 12%50% 12%50% 3%50% 3%50% 3%and visually inspected to determine ifthe solid dissolved. Table 1 is a compi-lation of the results. The TATP solubi-lity in neat water was determined to bebelow 15 mg/L while solubility in a0.1% acetone solution exceeded25 mg/L for TATP. TATP solubilityin the two H2O2 solutions screenedwas found to be greater than 50 mg/L. The slight solubility of TATP inwater is slightly increased by the inclu-sion of acetone and H2O2.Table 5. TATP Found in Solutions PrepareInitialAcetoneInitialH2O2AcidConc.7% 12% 18 M7% 12% 18 M7% 12% 13 M7% 12% 5 M7% 3% 18 M7% 3% 18 M7% 3% 13 M7% 3% 5 M7% 3% 0.1 M0.04% 3% 18 M0.04% 3% 13 M0.04% 3% 5 M0.04% 3% 0.1 M7% 12% 50% 12% 7% 30%7% 30%7% 30%7% 12%7% 12%7% 12%7% 3%7% 3%7% 3%Weld type: C = cleaned weld, D = dirty weld, N32el Coupons.eldtypeMass %AcetoneMass %PeroxidC 25.3% 14.9%D 25.2% 15.0%N 25.3% 14.8%C 14.6% 8.5%D 14.6% 8.6%N 14.4% 8.4%C 4.7% 2.7%D 4.6% 2.7%N 4.7% 2.7%Influence of Concentration and AcidCatalyst on TATP FormationThis experiment was conducted todetermine if TATP would be formedat concentrations that might beencountered in an industrial process.Table 2 lists the results of this experi-ment. Note that the concentrations ofH2O2 were initially 30%, 12%, and 3%,while the concentrations of acetonewere initially 50% and 7%. The higherconcentrations were included to pro-d with Dilute Acid.Mass TATP(mg)pH MasAcet4,993 2.41 5.272669 2.64 5.212,803 2.65 5.221,632 2.86 5.21279 2.86 2.96170 2.63 2.97154 2.76 3.13103 2.98 2.960 3.11 2.990 0.040 0.040 0.040 0.04 3.84 1.24 3.44 C 6.1% 3.6%D 6.2% 3.6%N 6.2% 3.6%C 5.2% 3.0%D 5.2% 3.1%N 5.2% 3.1%C 3.0% 1.7%D 3.0% 1.7%N 3.0% 1.7%= no weld.Journal of ChemMass %ReactantsMass TATP(mg)40.2% 22,63640.2% 26,53640.1% 23,77023.1% 4,94723.1% 4,15322.8% 4,4817.4% 07.3% 07.4% 0vide levels known to make TATP withthe purpose of verifying the experi-mental methods of observing or mea-suring TATP. Solid TATP was seen inthe highest concentrations with 50%acetone and 30% or 12% H2O2, withthe sulfuric acid catalyst, and smallamounts of precipitate were observedin the 50% acetone, 30% H2O2 mix-ture. After 7 days, the remaining solu-tions were extracted and analyzed byGC/mECD. TATP was detected in alls %oneMass %H2O2Mass %Reactants% 3.06% 8.33%% 3.10% 8.32%% 3.07% 8.29%% 3.09% 8.30%% 1.74% 4.70%% 1.73% 4.70%% 1.74% 4.87%% 1.73% 4.68%% 1.73% 4.72%% 0.02% 0.06%% 0.02% 0.06%% 0.02% 0.06%% 0.02% 0.06%9.8% 09.8% 09.8% 08.3% 08.3% 08.3% 04.7% 04.7% 04.7% 0ical Health & Safety, March/April 2012solutions in which sulfuric acid cata-lyst had been added. Note that for thesolutions with no acid, TATP was seenan acid catalyst appears to be a keyAlkaline ConditionsThe literature concerning the forma-tion of TATP focuses on the use of acidcatalysts and there is no mention onthe effects of alkalinity. To evaluatethese conditions, test solutions weretions screened here. The cyclic dimer,DADP, was not found in any of thehundreds of ppm) which could accu-mulate. This study shows that the sim-ple mixing of dilute solutions ofhydrogen peroxide and acetone doesnot appear to accumulate TATP in16. Oxley, J. C.; Smith, J. L.; Moran, J.;Nelson, K.; Utley, W. E. Proc. SPIE,ingredient for making TATP in dilutesolutions.Influence of 304L Stainless Steel andWelds on TATP FormationTo evaluate if stainless steel surfaces orstainless steel welds might catalyze theformation of TATP, coupons wereobtained to serve as examples of the304L stainless steel metal commonlyused to build an industrial scrubber.Coupons were also obtained whichrepresented clean and dirty welds on304L stainless steel to evaluate theinfluence of weld seams. The solutionsfrom the above experiments, with noacid catalyst present (Table 2), were re-evaluated using the metal coupons aspotential catalyst materials. The resultsare shown in Table 4. TATP wasdetected only in the 50% acetoneand 30%H2O2 solution at nearly iden-tical concentrations to those withoutthe coupons. This experiment suggeststhat 304L stainless steel does not cat-alytically influence the formation ofTATP.Influence of Acidity on TATP FormationThe formation of TATP is an acid cat-alyzed reaction, but the amount of acidrequired to generate the peroxide hasnot been published. Solution acidity isan important consideration for estab-lishing a safe boundary for the use ofH2O2 in the presence of acetone. H2O2solutions are often sold and storedunder acidic conditions for increasedstability. Table 5 contains the results ofan evaluation of the influence of acid-ity. No TATP was detected at any acidlevel for the 0.04% acetone solutions.There was also no TATP detected forthe 7% acetone and 3% H2O2 with0.1 M acid solution added. Theseresults highlight the need for sufficientacid concentration in forming TATP.Journal of Chemical Health & Safety, Marchconfigurations, leading one to con-clude that the formation of DADPnecessitates a relatively high concen-tration of acid catalyst. Acid catalyzedmixtures of acetone and hydrogen per-oxide are capable of producing hazar-dous amounts organic peroxides (i.e.,prepared with three different concen-trations of NaOH. No TATP wasdetected in these experiments, indicat-ing that the formation of TATP is notbase catalyzed and, furthermore, thatthe presence of trace amounts ofNaOH inhibits the formation of TATP.CONCLUSIONSOxidation of acetone with hydrogenperoxide produces TATP. While thisreaction is relatively gentle, the pro-duct, TATP, is highly sensitive to shockand friction that results in explosivedecomposition. Situations whereTATP accumulates are highly hazar-dous. This study was initiated to assessthe possibility that TATP accumulationcould result from cleaning processesfor industrial scrubbers which usedilute hydrogen peroxide and acetone.Hydrogen peroxide solutions aremildly acidic and even solutions con-taining only a few percent of acetoneand hydrogen peroxide can formTATP. Without additional catalyticactivity, the formation of small quan-tities of TATP in dilute H2O2 and acet-one in aqueous solutions are likely toremain soluble in the reaction media.The presence of 304L stainless steeldid not catalyze the formation ofTATP. The presence of trace amountsof sodium hydroxide in solutions thatnormally form TATP inhibits the for-mation of TATP in all the configura-/April 2012vol. 5403. 2004, .17. Oxley, J. C.; Smith, J. L.; Luo,W.; Brady,J. Prop. Exp. Pyro. 2009, 34(6), 539.18. Dubnickova, F.; et al. J. Am. Chem.Soc. 2005, 127, 1146.19. Eyler, G. N. J. Phys. Org. Chem. 2006,19(11), 776.hazardous amounts. The solubility ofTATP in pure water is about 15 ppmand somewhat higher when acetoneand peroxide are present. The smallamount of TATP produced withoutacid catalysis is likely to remain solublein the aqueous cleaning solution.REFERENCES1. Wolffenstein, R. Ber. Dtsch. Chem.Ges. 1885, 28(1459), 2265.2. Shanley, E. S.; Greenspan, R. P. Ind.Eng. Chem. 1947, 39, 1536.3. Milas, N. A.; Golubovic, A. J. Am.Chem. Soc. 1959, 81, 6461.4. Sauer, M. C. V.; Edwards, J. S. J. Phys.Chem. 1971, 75(19), 3004.5. Sauer, M. C. V.; Edwards, J. S. J. Phys.Chem. 1972, 76(9), 1283.6. Evans, H. K. ; Tulleners, F. A. J.;Sanchez, B. L.; Rasmussen, C. A. J.Forensic Sci. 1981, 31(3), 1119.7. Mackenzie, J. Chem. Eng. 1990, 97(6),84.8. Mackenzie, J. Plant Oper. Prog. 1991,10(3), 164.9. Constantini M. Destruction of AcetonePeroxides. US Patent 5,003,109(Rhone-Poulenc Chimie), 1989.10. Bellamy, A. J. J. Forensic Sci. 1999,44(3), 603.11. Jiang, H.; Chu, G.; Gong, H.; Qiao, Q.J. Chem. Res. 1999, 28, 288.12. Oxley, J. C.; Smith, J. L.; Chen, H. Prop.Exp. Pyro. 2002, 27(4), 209.13. Widmer, L.; Watson, S.; Schlatter, K.;Crowson, A. Analyst, 2002, 127, 1627.14. Schulte-Ladbeck, R.; Kolla, P.; Karst, U.Trace analysis of peroxide-based explo-sives. Anal. Chem. 2003, 75, 731735.15. Denekamp, C.; et al. Org. Lett. 2005,7(12), 2461.only in the 50% acetone and 30%H2O2 solution; thus, the presence of33The risk of mixing dilute hydrogen peroxide and acetone solutionsIntroductionExperimentalGeneral Experimental Set-UpSolubility of TATP in Acetone and Aqueous Acetone SolutionsMixing under Acidic ConditionsMixing with Welded Steel CouponsAlkaline ConditionsExamination of Dilute Acids in Acetone/Peroxide MixtureResults and discussionSolubility of TATP in WaterInfluence of Concentration and Acid Catalyst on TATP FormationInfluence of 304L Stainless Steel and Welds on TATP FormationInfluence of Acidity on TATP FormationAlkaline ConditionsConclusions


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