Decomposition of a Multi-Peroxidic Compound:
Triacetone Triperoxide (TATP)

It would appear word is catching on in professional circles about the highly versatile and easily improvised acetone peroxide. Consider this recent journal article from Propellants, Explosives, Pyrotechnics. I am sure many will find some enjoyment from a professionally produced tidbit where so few exist especially when this article gives a modern method of AP (henceforth TATP) synthesis! I am especially eager to get my hands on references 17 and 18, although they probably say much the same. If anyone would like to get those be my guest as I am unsure when next I will be getting by the library. We at least now have a definitive name to call this stuff, TATP. There are many graphics and charts that go along with this showing detailed decomposition mechanisms and pathways for both TATP and DATP which only members of the FTP will get if they download the original. See the file "JOPEP vol 27 iss 4 decomp of acetone peroxide.pdf" on the FTP.
They were nice enough even to include NMR spectra data. I have been planning to run some tests myself once I next get access to the 1 GHz research grade NMR (and a finer use of a $30 million machine there never could be :) ), so it's nice to know what to look for.

Summary
The thermal decomposition of triacetone triperoxide (TATP)
was investigated over the temperature range 151 to 230_C and
found to be first order out to a high degree of conversion. Arrhenius
parameters were calculated: activation energy, 151 kJ/mol
and pre-exponential factor, 3.75_1013 s_1. Under all conditions
the principle decomposition products were acetone (about 2 mole
per mole TATP in the gas-phase and 2.5 �} 2.6 mole per mole in
condensed-phase) and carbon dioxide. Minor products included
some ascribed to reactions of methyl radical: ethane, methanol,
2-butanone, ethyl acetate; these increased at high temperature.
Methyl acetate and acetic acid were also formed in the decomposition
of neat TATP; the former was more evident in the gasphase
decompositions (151 _C and 230_C) and the latter in the
condensed-phase decompositions (151 _C). The decomposition of
TATP in condensed-phase or in hydrogen-donating solvents
enhanced acetone production, suppressed CO2 production, and
slightly increased the rate constant (a factor of 2 �} 3). All
observations were interpreted in terms of decomposition pathways
initiated by O_O homolysis.

1 Introduction
Peroxides have awide commercial use as bleaching agents
and polymerization catalysts(1).Due to the weakO_Obond
peroxides undergo facile thermal decomposition to produce
radicals. Many peroxides are shock sensitive and their
overall decompositions are exothermic so that special
handling precautions must be taken(2,3). Depending on the
molecular stoichiometry of the peroxide, its decomposition
may be explosive. Most peroxides, such as the commonly
used dibenzoyl peroxide or di-t-butyl peroxide, contain too
much carbon to be true explosives; but they have been rated
as having TNTequivalence of 25% and 30%, respectively(4).
On the other hand, the stoichiometry of hydrogen peroxide
is perfect to allow it to act as an explosive; albeit, it does so
only in concentrations exceeding those at which it is
commonly available(5). This study examines the decomposition
behavior of multi-peroxidic triacetone triperoxide
(TATP) and compares it with that of diacetone diperoxide
(DADP), both of which exhibit explosive behavior. In
recent yearsTATP has been used as an improvised explosive
because its precursor chemicals are readily obtained and its
synthesis is straightforward. However, it is frequently
prepared in admixture with diacetone diperoxide
(DADP), and this mixture readily undergoes accidental
initiation(6).
The alkyl cyclic diperoxides have been the subject of
mechanistic studies since the 1970�s(7,8). Concerted decomposition
has been considered because luminescence at
435 nm was observed in the thermolysis of gaseous DADP
which could indicate a concerted electrocyclic reaction
yielding acetone in an excited singlet state(9), but stepwise
decomposition is usually postulated. RecentAM1 molecular
orbital calculations on DADP(10) indicated that C_O
scission (Figure 1, route 3) is only slightly more energetic
than that of O_O, but O_O homolysis (Figure 1, route 2) is
the generally accepted mechanism. Following initial O_O
homolysis, both C_O and C_C bond scission have been
suggested as routes to products (Figure 1 route 2 a and b).
There have been several studies on series of diperoxides.
McCullough et al. found that the yield of ketone from cyclic
diperoxides (R2COO)2 decreased as the stability of the
radical fragment R. increased, thus, making radical reactions
more important. Diacetone diperoxide decomposed
to acetone (_68%), acetic acid, carbon dioxide and ethane;
and since the thermolysis was performed in benzene,
toluene and biphenyl were also observed(8). Cafferata et al.
reported that the decompositions of various diperoxides in a
variety of solvents were first-order to about50%decomposition(
11-13). Since the rate constants were generally independent
of initial concentration and solvent effects, they
concluded the first decomposition step was O_O bond
homolysis. Plotting _H versus _S showed that five diperoxides
fit an isokinetic relationship, but DADP did not(11).
Furthermore, at elevated temperatures DADP decomposition
exhibited linear dependence on the initial concentration
of DADP suggesting induced decomposition(12). In
addition, the decomposition rate of DADP exhibited a
degree of solvent dependence not observed with the other
cyclic diperoxides(13). This latter observation was interpreted
as adduct formation between the peroxide and the
solvent. This is important with DADP due to its relatively
low steric hinderance. Decomposition products of DADP
have been reported as acetone in the gas-phase decomposition(
9) and acetone, methyl isopropyl ether, and oxygen
in benzene solution(12).
The decomposition of few cyclic triperoxides have been
studied: tricyclohexylidene triperoxide(14), diethyl ketone
cyclic triperoxide(15) and TATP in solution(16). The decomposition
of TATP in toluene was found to be first-order and
independent of initial TATP concentration out to 78%
conversion. The authors concluded the decomposition
included no second-order processes which would induce
decomposition; however, they did note that toluene would
be a good trap for radicals(16). This study examines the
decomposition of neat TATP as the first step to assessing the
hazards associated with explosive peroxides.

2 Experimental Section
2.1 Sample Preparation
Preparation of TATP followed the method of Milas with
modifications as follows: a 100 mL round bottom flask was
charged at room temperature with 5 mL of acetone and
5 mL of 35% hydrogen peroxide(17,18). The flask was
immersed in a dry ice bath; and when the mixture reached
-20_C, 3 mL of sulfuric acid was added dropwise taking
care to maintain the temperature below -10 _C. Addition of
acid typically took 30 minutes; to hurry the process was to
invite a violent event which in one case cracked a shatterproof
shield and the Corning stirrer/hot plate top. The
reaction was considered complete when further addition of
acid did not evoke violent bubbling. This usually required
the entire 3 mL of acid. After the acid had been added, and
while the mixture was still cold, 20 mL of methylene
chloride were added. The resulting solution was transferred
to a separatory funnel and allowed to warm to room
temperature. The remaining H2SO4 was removed by
washing three times with distilled water. TATP was
separated from the methylene chloride by allowing the
solvent to evaporate as the solution sat in the hood
overnight. The isolated TATP was re-crystallized in methanol,
resulting in 0.649 g (13% yield) of white crystals with
melting point of 95 �} 96_C. Poor yield may be a result of high
volatility; we observed that TATP sublimes at the rate of
about 0.9% per hour.
1H-NMR(400 MHz, CDCl3) _ 1.43 (s); 13C-NMR
(100 MHz, CDCl3) _ 21.4 (CH3), 107.5 (ring C).
GC/MS using Finnigan TSQ 700 triple-stage: CI (methane):
223 (M_1). EI 222 (P); 117 {HOO[C(CH3)2]2};
101{HO[C(CH3)2]2}; 75 [HOOC(CH3)2]; 59 [HOC(CH3)2];
43 [CH(CH3)2].

2.2 Thermal Analysis
A TA Instruments Model 2910 Differential Scanning
Calorimeter (DSC) was operated under nitrogen flow and
calibrated against indium (m.p. 156.60 _C, _Hf 28.5 J/g).
The TATP samples (0.1 to 0.4 mg) were sealed in capillary
tubes (1.5 mm O.D., 0.28 mm wall thickness, and 8 mm
length) which were held in aluminum cradles(19). Thermo-
grams of the samples were recorded from 40_C to 500_C,
generally at a ramp rate of 20_C/min. The exothermic peak
maximum temperature was used to indicate the relative
stability of samples. For isothermal kinetics studies, samples
(0.1 �} 0.6 mg) were sealed in glass capillary tubes of various
sizes. Primarily tubes of dimensions 2 mm I.D._50 mm
(150 _L volume) were used, but in some experiments the
surface area and volume of the tube were purposely varied �}
5 mm_50 mm (1 mL) and 1 mm_50 mm (25 _L). In one
set of experiments 3 mg TATP samples were sealed in 25 _L
ampoules to ensure reaction occurred in the condensed
phase. Generally samples were sealed under air, but we
found no difference in the product distribution whether
samples were sealed under vacuum rather than air.
Thermolyses at 150_C were conducted in an oven
(_/_1_C), while those at higher temperatures were
performed in a molten metal bath.

2.3 Gas Chromatography/Electron Capture Detector
(GC/ECD)
After thermolysis the sample tubeswere rinsedwith acetone
and volumes were adjusted to 10 mL. To assess TATP remaining,
a 1 _L aliquot of solution was injected via a Hewlett
Packard (HP) 6890 auto-sampler into an HP 5890 series
II GC with DB-5MS megabore column (6 m_0.53 mm)
and ECD detector. Helium was used as carrier gas, and
nitrogen as anode purge gas for the detector. The injector
temperature was 165_C; the detector temperature, 300_C;
the oven was programmed to run at an initial temperature of
50_C for two minutes, then ramped at 20 _C/min to a final
temperature of 280_C where it was held 3.5 minutes.
2.4 Analysis of Gaseous Decomposition Products
Complete thermolysis of TATP left no visible residue.
Decomposition gases were analyzed by gas chromatography/
mass spectrometry (GC/MS). An HP 5890 GC, equipped
with model 5971 electron impact mass selective
detector, was run in scan mode (mass range 12 to 200)
with a threshold of 150 and a sampling of 2 (3.5 scans/s).
Helium was used as the carrier gas, and theGCcolumnwas a
PoraPLOT Q (0.25 mm diameter_25 mm length) purchased
from Chrompack. The injector temperature was
100_C; the detector temperature, 190_C; the oven was
programmed to sit for 5 minutes at _80 _C, then ramped at
15_C/min to a final temperature of 190_C where it was held
10 minutes(20). The sealed samples were injected into the
GC by placing them in a Nalgene (I.D. 1/8 inch and O.D.
3/16 inch) sample loop in line with the carrier gas to the
injector. The sample loop was purged with helium. The
decomposition gases were introduced to the system by
bending the flexible Nalgene loop, thus, breaking the
capillary tube. Decomposition gases were identified by
comparing their GC retention times and mass spectra to
authentic samples. When authentic samples were not
available, sample spectra were compared with the NIST
MS library for a tentative assignment.

3 Results
The thermolysis of neat TATP was generally performed in
_160 _L ampoules over the temperature range 150 to
225_C. These thermolyses were first-order out to about90%
conversion at least at temperatures above 160_C. Generally
first-order plots were constructed with seven to eight data
points with a R2 fit better than 0.99. Even at 150_C TATP
samples appeared to be gaseous. To ensure that condensedphase
kinetics were examined, the reaction tubes were
reduced to 25 _L and the sample size increased to 3 mg.
Thermolyses were also performed in the presence of agents
which would
(a) produce methyl radicals (di-t-butyl peroxide);
(b) trap radical (di-t-butyl cresol); and
(c) donate hydrogen (isopropanol and 1,4-cyclohexadiene).
Table 1 shows the resulting rate constants. DSC was used
for initial screening of the TATP samples. Although
the melting point was relatively sharp, centered at 98_C
(109 J/g), the exotherm (215 _C, 3400 J/g, 800 cal/g)
was extremely broad ranging about 80_C at a scan rate of
20_C/min. For this reason the variable heating rate ASTM
DSC method could not be used to assess activation
parameters for TATP(21). In fact, at heating rates below
10_C/min, the exotherm appeared to consist of several
partially overlapping peaks, indicating the decomposition
included multiple reaction steps.
TATP decomposition products were identified and
quantified by GC/MS at two temperatures and two degrees
of conversion. At 230_C thermolysis was run in air and in
vacuum; no significant difference in the products was noted.
Acetone and carbon dioxide were the main products; these
were identified and quantified by comparison to the
authentic compounds. Other species were present as less
than 6%of the total ion current (TIC). Most were identified
by matching against a computer library (Table 2).

4 Discussion
Across a 75_C temperature range the gas-phase decomposition
of TATP was first-order out to a high degree of
conversion, indicating induced decomposition was not
important. The Arrhenius plot was linear over the entire
temperature range (Figure 2) suggesting the same ratedetermining
step was operative over the entire range. At
151_C the decomposition of TATP was not accelerated by
the presence of di-t-butyl peroxide, but thermolysis in the
condensed phase or in 2-propanol slightly increased the rate
of decomposition (Table 1). Figure 2 plots the rate constants
determined in this study of neat TATP along with those
obtained by another laboratory for the thermolysis of TATP
in toluene and acetone(16). That data fit reasonably well with
ours indicating that the decomposition pathway is essentially
the same regardless whether TATP is in toluene
solution or in the gaseous state. This result differs from the
decomposition of DADP where in solution the decomposition
of DADP is significantly accelerated (Figure 3).
Though the decomposition of gaseous DADP is much
slower than that of TATP, the decomposition of DADP
in solution is similar to that of TATP (Figure 3)(12,13).
The activation energies for the decomposition of gaseous
DADP (163 kJ/mol)(9) and TATP (153 kJ/mol) are quite
similar to each other and in line with O_O bond cleavage
energy.
Sanderson and Story compared the decomposition of
dicyclohexylidene diperoxide and tricyclohexylidene triper-
oxide and observed a difference in the way their decompositions
were affected by the solvent(14). The diperoxide
decomposition showed a linear dependence on solvent
polarity, while the triperoxide showed linear dependence
with the cohesive energy density of the solvent (i.e. the
energy necessary to form a solvent cavity as the reactant
goes from initial to transition state). It was concluded that
the transition state of the diperoxide was sensitive to the
solvent, while in the triperoxide, the initial state was more
sensitive. DADP has been shown to be somewhat unique
among the diperoxides because its low steric hinderance
makes interaction with solvent possible. TATP is much less
sensitive to the presence of toluene than is DADP. Such
solvent interactions may not be possible for the largerTATP.
However, TATP is sensitive to hydrogen-donating solvents.
Hydrogen donation was indicated in the thermolysis of
TATP in 1,4-cyclohexadiene because large amounts of
benzene were formed. This cannot be explained by methyl
radical scavenging since no increase in methyl radical
derived products was observed.
TATP product distributions were dependent on experimental
conditions (Table 2). Thermolysis of TATP gave
principally acetone and CO2. These products were quantified
against standard calibration curves (Table 2). Complete
decomposition ofTATPcould theoretically give three moles
of acetone, and oxygen:
C9H18O6_3 OC(CH3)2_1.5 O2
Although oxygen was not observed under the thermolysis
conditions, at 151_C in the melt phase and in hydrogendonating
solvents (2-propanol and 1,4-cyclohexadiene)
up to 2.6 moles of acetone formed per mole TATP. Under
these conditions, CO2 production was suppressed, and
decomposition rate constants were enhanced by factors
of 2 to 3.
The decomposition of TATP over the temperature range
230_C�} 151_C yielded a single Arrhenius plot with decompositions
first-order to a high degree of conversion. These
observations suggest a single rate-determining step over the
entire temperature range. Homolysis of an O_O bond is in
line with the observed activation energy. Following O_O
homolysis, both C_O and C_C bond cleavage have been
considered for cyclic diperoxides. For TATP a second O_O
bond homolysis might also be postulated. This would
produce dioxirane and the diradical [A] (Figure 4 route 3).
The diradical [A] would then decompose as shown in
Figure 1, explaining the similarity of the decomposition
products of DADP and TATP. The problem with this
pathway is that the diradical [A] should also form some
DADP; and even though DADP decomposes much more
slowly than TATP, no DADP was observed in any of the
TATP thermolyses.
Under the experimental conditions, C_C scission producing
methyl radical was a minor decomposition path for the
[B] diradical.We identified certain products as arising from
methyl radical reactions [ethane (methyl coupling); methanol
(methyl_OH), 2-butanone (methyl_acetone), ethyl
acetate (methyl_methyl acetate)] under most reaction
conditions, more abundant at 230_C than 151_C, more
abundant in gas phase than condensed (151 _C), and
extremely minor in hydrogen-donating solvents (Table 2).
At 230_C CO2, which can be thought of as a byproduct of
methyl radical formation, was at the highest value found in
this study. To determine whether carbon dioxide was a late
breakdown product in the gas-phase reaction, its distribution
was determined during the decomposition cycle. At
151_C the acetone/TATP ratio matched that of the fraction
decomposed (20%), but carbon dioxide was slightly high
(Table 2). At 230_C the fraction ofCO2 /TATP and acetone/
TATP ratios matched the fraction of TATP decomposed
(38%) to within experimental error. Thus, carbon dioxide is
mainly formed in the primary decomposition rather than in
the breakdown of some other product.
Postulating C_O bond homolysis in diradical [B] would
account for the major decomposition product acetone, at
least two moles/mole TATP. However, the mechanism
should also account for the formation of minor products
methyl acetate and acetic acid. Both species were almost
non-existent in the thermolysis of TATP in hydrogendonating
solvents, but in each case their gas-phase formation
was greater at 151_C than at 230_C. These two observations
might suggest these minor products arise from a common
source, such as the CH3COO. radical. However, not all
aspects of their formation were parallel. Furthermore, acetic
acid formation was not enhanced in hydrogen-donating
solvents. Because CH3COORformation is uniformly
enhanced at low temperature we postulate that its formation
involves an internal re-arrangement or in-cage radical
reaction. McCullough et al. did not observe methyl acetate
in the thermolysis of DADP but did detect the corresponding
ester in the decomposition of dibenzyl diperoxide(8).
They considered four routes to the ester:
a) in-cage radical recombination of RCOO. with R.
b) induced decomposition of the diperoxide by R.
c) in-cage induced decomposition of the peroxide intermediate
[A] by R.
d) alkyl migration in the intermediate biradical followed
by a second O_O bond fission.
They selected route c based on two observations.Amixture
of two diperoxides failed to produce significant RCOOR_
(ruling out route a). The thermolysis of the cyclic diperoxide
of benzyl phenyl ketone produced mainly benzyl benzoate,
small amounts of phenyl benzoate (should be sole product if
route a) and no phenyl phenyl acetate (should be formed to
some extent if route d) nor benzyl phenyl acetate(8).
We cannot postulate that methyl acetate was formed by
any of the pathways proposed by McCullough(8) because we
do not believe the diradical [A] forms under our experimental
conditions. If any of the four proposed reactions
occurred starting with diradical [B], diradical [A] would
form in addition to methyl acetate. Therefore, wemust look
for an alternative route to methyl acetate. We envision
diradical [B] to decompose such that the end carbon groups
form acetone while the remaining atoms [(CH3)2CO4]
produce dimethyl dioxirane and oxygen. Dioxiranes undergo
unimolecular conversion to the corresponding ester(22),
and this would account for the formation of methyl acetate.
Dimethyl dioxirane is a reasonable intermediate; in fact,
under some conditions it even forms diacetone diperoxide(
23). Although dioxirane has not been proposed as an
intermediate in the decomposition ofDADP, the energetics
may make it more likely when considering cyclic triperoxides.
In contrast with methyl acetate, acetic acid formation
was significantly greater in the condensed-phase (151 _C)
thermolysis compared to the gas-phase reaction. McCullough
et al. observed acetic acid in the thermolysis of
DADP but were unable to explain its formation(8). It is
somewhat puzzling that acetic acid production was enhanced
in the condensed-phase decomposition of TATP
and depressed when hydrogen-donating solvents were
present. In most other respects, the two types of reaction
conditions yielded similar results: increased acetone formation
(2.5 �} 2.6 mol/mol); lack of methyl-radical-produced
products; low quantities of methyl acetate; slightly elevated
decomposition rates (2 to 3 fold). We speculate that when
diradical [B] loses the two end groups forming acetone,
under conditions where the intermediate can be stabilized,
dioxirane is not formed. In the presence of stabilizing
species, such as a hydrogen-donating solvent or another
molecule ofTATP, oxygen is captured as water, and the third
(CH3)2Cgroup is often transformed to acetone. (It should be
noted that unlike with the reported DADP thermolyses(12),
oxygen was not observed in our experiments. Any oxygen
produced was apparently consumed in oxidative processes.
Attempts to show that singlet oxygen was involved in the
decomposition of diperoxides were not successful(24).) The
large amount of acetone produced when TATP was heated
in 2-propanol (over 7 moles per mole TATP) undoubtedly
arises from the oxidation of 2-propanol. McCullough
reported a similar result for DADP(8).

5 Conclusions
The products and activation energies for TATP decomposition
are similar to those of DADP. Over a large
temperature range (230 �} 150_C), TATP decomposition is
initiated by O_O bond homolysis. Acetone was the major
decomposition product; carbon dioxide,methyl acetate, and
acetic acid were also observed as well as minor species
thought to result from methyl radical reaction. However, we
do not believe the decomposition of TATP proceeds
through the same intermediate diradical as DADP because
no DADP was observed in partially decomposed TATP.
Furthermore, neat TATP decomposed significantly faster
than DADP. Had DADP formed, it should have been
sufficiently long-lived for observation. FollowingO_Obond
homolysis rapid C_O scission yields two molecules of
acetone. The fate of the remaining atoms depends on the
reaction conditions. Gas phase favors the formation of
dimethyl dioxirane; high temperature favors its decomposition
to carbon dioxide; lower temperature favors production
of methyl acetate. Condensed-phase or reaction in a
hydrogen donating solvent favors the formation of a third
molecule of acetone rather than dioxirane.

6 References
(1) J. Kroschwitz (ed.), Kirk-Othmer Concise Encyclopedia of
Chemical Technology∫, 4th ed., －Organic Peroxides� Wiley,
New York, Chichester, 1999, pp. 1472 �} 1483.
(2) S. M. Kaye (ed.), Encyclopedia of Explosives and Related
Items∫, PATR2700 Vol. 8, U.S. Army ArmamentResearch &
Development Command, Dover, NJ 1978, p. 203.
(3) D. N-S Hon, Take care when using organic peroxides in the
laboratory∫, Pulp & Paper Canada 86(6), 129 �} 131 (1985).
(4) T. Yoshida, K. Muraaga, T. Matsunaga, and M. Tamura,
Evaluation of Explosive Properties of Organic Peroxides
with a Modified Mk IIII Ballistic Mortar∫, J. Hazardous
Materials 12, 27 �} 41 (1985).
(5) T. Urbanski, Chemistry and Technology of Explosives∫
Vol. 3, Pergamon Press, Oxford, 1967, pp. 299 �} 305.
(6) D. J. Reutter, E. D. Bender, and R. L. Rudolph, Analysis of
an Unusual Explosive: Methods Used and Conclusions
Drawn from Two Cases∫, International Symposium Analysis
& Detection of Explosives, U.S. Dept. Justice, FBI, Quantico
(VA), March 1983, pp. 149 �} 158.
S. Zitrin, S. Kraus, and B. Glattstein, Identification of Two
Rare Explosives∫, International Symposium Analysis &
Detection of Explosives, U.S. Dept. Justice, FBI, Quantico
(VA), March 1983, pp. 137 �} 141. H. K. Evans, A. J. Tulleners,
B. L. Sanches, and C. A. Rasmussen, An Unusual Explosive,
Triacetone Triperoxide∫, J. Forensic Sci. 31(3), 1119 �} 1125
(1986).
G. M. White, An Explosive Drug Case∫, J. Forensic Science,
37(2), 652 �} 656 (1992).
A. J. Bellamy, Triacetone Triperoxide: Its Chemical Destruction∫,
J. Forensic Sci. 44(3), 603 �} 608 (1999).
E. Shannon, The Explosives: Who Built Reid�s Shoes?∫,
Time, Feb. 25, 50 (2002).
(7) H. A. Brune, K. Wulz, and W. Hetz, ber den Substituenten-
Einfluss auf die konformative Beweglichkeit zyklischer
Peroxide∫, Tetrahedron 27, 3629 �} 3644 (1971).
(8) K. J. McCullough, A. R. Morgan, D. C. Nonhebel, and P. L.
Pauson, Ketone-derived Peroxides. Part II. Synthetic
Methods∫, J. Chem. Res. Synopses (M), 629 �} 650 (1980).
K. J. McCullough, A. R. Morgan, D. C. Nonhebel, and P. L.
Pauson, Ketone-Derived Peroxides. Part III. Decomposition
of Cyclic Diperoxydes Derived from Dialkyl Ketones∫, J.
Chem. Res. Synopses (M), 651 �} 676 (1980).
(9) L. F. R. Cafferata, J. D. Lombardo, Kinetics and Mechanism
of the Thermal Decomposition Reaction of Acetone Cyclic
Diperoxide in the Gas Phase∫, Int. J. Chem. Kinet. 26, 503 �}
509 (1994).
(10) S. G. Hong, Y. H. Li, AM1 Study of Thermolysis of Acetone
Cyclic Diperoxide∫, J. Mol. Struct. (Theochem) 363, 339 �} 342
(1996).
(11) L. F. R. Cafferata, G. N. Eyler, E. L. Svartman, A. I. Can izo,
and E. J. Borkowski, Mechanism of the Thermal Decomposition
of the Activation Parameters of the Unimolecular
Reactions∫, J. Org. Chem. 55, 1058 �} 1061 (1990).
(12) L. F. R. Cafferata, G. N. Eyler, and M. V. MirIfico Kinetics
and Mechanism of Acetone Cyclic Diperoxide (3,3,6,6-
Tetramethyl-1,2,4,5-tetroxane) Thermal Decomposition in
Benzene Solution∫, J. Org. Chem. 49, 2107 �} 2111 (1984).
(13) L. F. R. Cafferata, G. N. Eyler, E. L. Svartman, A. I. Can izo,
and E. Alvarez, Solvent Effect in the Thermal Decomposition
Reactions of Cyclic Ketone Diperoxides∫, J. Org.
Chem. 56, 411 �} 414 (1991).
(14) J. R. Sanderson, P. R. Story, Macrocyclic Synthesis. The
Thermal Decomposition of Dicyclohexylidene Diperoxide
and Tricyclohexylidene Triperoxide∫, J. Org. Chem. 39, 3463
(1974).
(15) G. N. Eyler, A. I. Can izo, E. E. Alvarez, and F. R. Cafferata,
Solvent Effects on the Thermal Decomposition of Diethyl
Ketone Cyclic Triperoxide∫, An. Assoc. Qui￢m. Argent. 82(3),
175 �} 181 (1994).
(16) G. N. Eyler, C. M. Mateo, E. E. Alvarez, A. I. Can izo,
Thermal Decomposition Reactions of Acetone Triperoxide
in Toluene Solution∫, J. Org. Chem. 65, 2319 �} 2321 (2000).
(17) N. Milas, A. Golubovic, Studies in Organic Peroxides.
XXIV. Preparation, Separation and Identification of Peroxides
Derived from Diethyl Ketone and Hydrogen Peroxide∫,
J. Am. Chem. Soc. 81, 3361 �} 3364 (1959).
(18) G. N. Eyler, A. I. Can izo, E. E. Alvarez, L. F. R. Cafferata,
Improved Procedure for the Preparation of Diethyl Ketone
Triperoxide and Kinetics of its Thermal Decomposition
Reaction in Solution∫, Tetrahedron Lett. 34(11), 1745 �} 1746
(1993).
(19) L. F. Whiting, M. S. Labean, S. S. Eadie, Evaluation of a
Capillary Tube Sample Container for Differential Scanning
Calorimetry∫, Thermochem. Acta 136, 231 �} 245 (1988).
(20) W. Zheng, X. X. Dong, E. Rogers, J. C. Oxley, and J. L.
Smith, Improvements in Determination of Decomposition
Gases from 1,3,3-Trinitroazetidine (TNAZ) and 5-Nitro-2,4,-
dihydro-3H-1,2,4-triazol-3-one (NTO) using Capillary Gas
Chromatography/Mass Spectrometry∫, J. Chromat. Sci. 35,
478 �} 482 (1997).
(21) Standard Test Method for Arrhenius Kinetic Constants for
Thermally Unstable Materials, The American Society for
Testing and Materials (ASTM) Committee E-27, Designation:
E 698 �} 79, reapproved 1993.
(22) R. W. Murray, Dioxiranes∫, Chem. Rev. 89, 1187 �} 1201
(1989).
(23) L. Cassidei, M. Fiorentino, R. Mello, O. Sciacovelli, and R.
Curci, J. Org. Chem. 52(4), 699 �} 700 (1987).
(24) J. R. Sanderson, P. R. Story, Singlet Oxygen Scavenger
Method for the Determination of Ketone Peroxide Kinetics∫,
J. Org. Chem. 39(21), 31 �} 3185 (1974).
Acknowledgement
We thank the FAATechnical Center for funding this research.
(Received September 26, 2001; Ms 2001/018)

Interesting.

Their method of production was a bit strange though.

"Addition of acid typically took 30 minutes; to hurry the process was to invite a violent event which in one case cracked a shatterproof
shield and the Corning stirrer/hot plate top"

WTF? Steam explosion, or detonation? Either way, I've never heard of anyone on this forum, or elsewhere having this problem.

"The reaction was considered complete when further addition of acid did not evoke violent bubbling"

Surely that "violent bubbling" is local overheating of the solution? Despite the dry-ice cooling, IMHO the addition rate of acid is too high.

5ml acetone, 5ml 35% H2O2 and 3ml H2SO4 (conc not specified, but I bet it's in the 90's) seems like they have way too much catalyst. So despite an addition rate 3ml over 30 mins, it's too fast because of the relative volume of the other reactants.

No neutralisation, despite the very high acidity of the finished solution and crystals.

Why methylene chloride was added after acid addition was complete I don't know. If it was to aid in drying, it would have made more sense to add it after washing.

They probably know what they're doing, they've got the big expensive toys afterall, I just find aspects of their method strange.

I wonder how many people here actually use the 35% varity of H2O2? That could be one reason why their reaction is so vigerous. If you read through the article they mention the different effects solvents have on TATP vs. DADP. The use of methylene chloride may in fact be a means to selectively isolate only TATP while leaving out DADP. I have little doubt that their sample is quite pure, if it was not their NMR and GC/MS analysis would have been off and they would likely have commented.

There use of such low temperatures really underscores the importance of not allowing any DADP to form. Reference 6, wihch is actually several references of forensics journals, really drills home the importance of how dangerous DADP really is. This is also the likely culpret why many members report their AP is either really safe, or completly unsafe. Different methods of synthesis lead to differing amounts of DADP which can drasticially increase sensitivity.

Again I must point the use of sulfuric acid as the catalyst of choice. All of the professional literature uses it, while the improvised literature uses HCl. I wonder what the difference really is? While HCl does seem to work fine, this reaction presented here is seemingly desperate to complete the reaction in as short an amount of time as possible. It could be that the vast amount of such a strong acid as sulfuric is all quite important in the reaction, as if doing it slower somehow promotes a different reaction. I am sure the key to these questions lies in the original literature from which this procedure is derived.

Why are you so very interested in references 17 and 18? I've read 17, and it appears that diethyl ketone peroxides aren't notably explosive. There is a large series of these "Studies in Organic Peroxides" articles (ref 17), and in others (such as ones on peroxides of acetone and methyl ethyl ketone) the authors explicitly note the explosive nature of the substances under study. They don't make any such warnings in the diethyl ketone article.

One interesting thing about "Studies in Organic Peroxides" article on acetone peroxides is that the authors prepared it at 0 to -5 degrees Celsius and obtained TATP in about 90% purity; the remaining 10% was, I believe, mostly the dimeric form. When they combined 50% H2O2 and acetone and allowed the mixture to stand at room temperature, they obtained

.......OOH..
.......|......
CH3-C-CH3
.......|......
.......OOH..

The authors of this older article didn't use as much sulfuric acid as the authors of the one Megalomania just posted.

I am disinclined to believe that H2SO4 vs. HCl really makes much difference. I would guess that everybody who wants to study these peroxides looks at the existing literature, says "everybody else used H2SO4," and then uses H2SO4 as well. I think chemists are shy of changing things that they know work. Consider how many lab procedures specify benzene as a solvent when the far less dangerous toluene would work nearly as well.

My guess as to why the authors of this newer article obtained such a pure substance was because they ran it at such a low temperature, and perhaps also because they extracted it with DCM.

Regarding the extremely vigorous reaction they experienced on adding the acid, I think the basement chemists may actually be wiser than the professionals here. Would you pre-mix acetone and H2O2 and then drip conc. H2SO4 into it? I sure wouldn't. I would mix the H2O2 and H2SO4, so that the heat of dilution is expended without any acetone around to add to the danger, chill the acid/H2O2 mix and the acetone, and mix them all together once cold.

I am willing to retract my statements about H2SO4 and the procedures used if evidence to the contrary appears, of course <img border="0" title="" alt="[Wink]" src="wink.gif" />

As far as the acidity of final product goes, I think it's prudent to wash TATP of acid just so it won't be absorbing water (if you used H2SO4) or corroding things. It's probably fine to wash it with bicarbonate solution. I would be wary, though, of washing it with stronger bases. Peroxides are unstable in alkaline conditions. Mix 10 g 30% H2O2 and 2 g H2SO4. Now mix 10 g 30% H2O2 and 2 g NaOH. I know, I should compare moles to moles, but the point stands. It's the *alkaline* peroxide that will soon be fizzing itself to death. Acid does no harm. TATP isn't nitrocellulose.

I may perform some experiments in the near future - cautiously! - to see if there is noticeable sensitization or decomposition of organic peroxides (probably HMTD) under stronger alkaline conditions. I know this won't definitively answer questions about acetone peroxides and pH, but I don't have the patience to prepare and analyze TATP for chromatographic purity.

edit: fixed ASCII art so bonds line up

<small>[ February 12, 2003, 02:13 AM: Message edited by: Polverone ]</small>

I found 50% h202 and acetone to be very hot reaction, just the addition of acetone causes it to create enough heat to almost stop me from touching the sides of the container, the addition of acid will instantly form crystals, but you can alread tell what type. Simmiler results when creaking MEKP except that it has a tendincy to have micro explosions...

Anyway i though that they created there AP at such low temps so that very little dimer would form, as you know it forms at higher temps.

As Polverone said, the chemists tend to imitate the ancestors. Hence the use of H2SO4. On the other hand the HCl is unstable, and before usig it you have to titrate it, if you want to know the EXACT quantity. Not talking about the purity problems. And apparently if a mineral acid is needed for a reaction, H2SO4 is the choise in all the books.

</font><blockquote><font size="1" face="Verdana, Arial, Helvetica">quote:</font><hr /><font size="2" face="Verdana, Arial, Helvetica"> I wonder how many people here actually use the 35% varity of H2O2? </font><hr /></blockquote><font size="2" face="Verdana, Arial, Helvetica">I got 35% at a hydroponics store, using HCl the temp is fairly easy to keep below 5*C but I guess that's not cold enough for the fancy types. I haven't tried it with H2SO4 yet, but I just got some high quality H2SO4 (i.e. not drain opener!) and I'll test them out.

I'd be interested in seeing the results of your alkaline peroxide tests Polverone.

That is a shitload of acid they used, I guess they were in a hurry, hence blasting their hotplate! <img border="0" title="" alt="[Eek!]" src="eek.gif" /> :p

My bad, I obviously didn't read it thoroughly enough.

I still don't understand their desire to complete the reaction in as rapid a fashion as possible. Possibly more of the dimmer is formed if the reaction is "left" to complete like we amateurs do. But I don't see why if the temperature is kept low.

I too would be interested in your results, Polverone.

Sorry to be a nuisance guys, but I'm having a mental block. Can someone please help with balancing/fixing up these reactions? I've had a lengthy search, and racked my brains, but to no avail :( .

Trimeric AP

CH₃COCH₃_(l) + H₂O₂_(aq) >-(in the presenceof H⁺)-> C₉H₁₈O₆_(s) + H₂O_(l)

Dimeric AP

CH₃COCH₃_(l) + H₂O₂_(aq) >-(in the presence of H⁺)-> C₆H₁₂O₄_(s) + H₂O_(l)

Thanks.

Edit: Scrub that, finally worked it out after a couple of hours :rolleyes: . Sorry to be of any inconvenience. Finding below.

Trimeric AP

3 CH₃COCH₃_(l) + 3 H₂O₂_(aq) >-(in the presenceof H⁺)-> C₉H₁₈O₆_(s) + 3 H₂O_(l)

Dimeric AP

2 CH₃COCH₃_(l) + 2 H₂O₂_(aq) >-(in the presence of H⁺)-> C₆H₁₂O₄_(s) + 2 H₂O_(l)

<small>[ March 03, 2003, 11:55 PM: Message edited by: 0EZ0 ]</small>

I don't think the formation of TATP or DADP is a metathesis reaction like that. If you check my website on the acetone peroxide page, you will see a graphic outlining the formation of explosive peroxides. There are many complex side reactions that occur along with the primary product, TATP. The formula you have given is a good approximation of the net reaction though.

Mega, I was wondering about why it was so difficult to work out the reaction. Using the ratios that everyone has desribed for AP(typically 1 part pure H₂O₂ to 6 parts Acetone by volume), It was impossible to balance the equation :confused: . What you say about multiple side reactions makes sense. Thanks for the info. I will have a good read of the page on your site. I'm trying to learn as much info as I can on various reactions at the moment, but got stuck with TATP and DADP.

Thanks again :) .

i am using 60% H2O2 in volume ratio of 1:6 with acetone, just adding the minimum amount, drop by drop the acid into the solution, and keep them cool, i got abundant crystals of AP :D as i am not a chemist, sometimes i had idiot question :confused: why the reaction just stop in maximum result of tricycloacetoneperoxide, is it possible maybe to make them formed tetra, penta, or hexacycloperoxyacetone someday? :D and hope they are more stable and stronger than TCAP, sorry for this idiot imagination :D

</font><blockquote><font size="1" face="Verdana, Arial, Helvetica">quote:</font><hr /><font size="2" face="Verdana, Arial, Helvetica">Mega, I was wondering about why it was so difficult to work out the reaction. Using the ratios that everyone has desribed for AP(typically 1 part pure H2O2 to 6 parts Acetone by volume), It was impossible to balance the equation.</font><hr /></blockquote><font size="2" face="Verdana, Arial, Helvetica">Reaction procedures almost never use the exact stoichiometric ratios as alot of thermodynamic and kinetic effects are not accounted for in an equation.
For example, you will use more hydrogenperoxide than necessary, because of it's inherent instability.
Nitration reactions with mixed acid usually have an excess of sulfuric acid to absorb the water produced by the reaction and thus preventing dilution of the nitric acid.

You won't be learning very much about organic chemistry or the progress of a reaction by balancing equations. Although it's always a nice exercise ofcourse :) .

Aster, I've seen a PDF circulating around this forum about the preparation of tetrameric acetone peroxide with the use of SnCl₂ or SnCl₄.

<small>[ March 05, 2003, 04:48 PM: Message edited by: vulture ]</small>

</font><blockquote><font size="1" face="Verdana, Arial, Helvetica">quote:</font><hr /><font size="2" face="Verdana, Arial, Helvetica"> Reaction procedures almost never use the exact stoichiometric ratios as alot of thermodynamic and kinetic effects are not accounted for in an equation.
For example, you will use more hydrogenperoxide than necessary, because of it's inherent instability.
Nitration reactions with mixed acid usually have an excess of sulfuric acid to absorb the water produced by the reaction and thus preventing dilution of the nitric acid.

You won't be learning very much about organic chemistry or the progress of a reaction by balancing equations. Although it's always a nice exercise ofcourse .
</font><hr /></blockquote><font size="2" face="Verdana, Arial, Helvetica">Vulture, there are as you say alot of thing to take into account with the chemistry behind the reactions. Balancing the AP reaction was just a tidbit that was getting to me. So i thought investigation could prove a learning experience. I'm only just starting to take a proper interest in the chemistry areas. So bare with me if a make a few mistakes. I've still got a lot of learning to do. So any guidance is appreciated :) .

The other reason I was focusing on particularly balancing the AP reaction was to try and economise to get a good yield using less materials. In this case, a balanced reaction is a good starting point, then one can also take into account reactant decomposition, volatisation, dilution, purity etc. I even tested some new ratios I came up with to see how different reactant ratios performed and what kind of crystal structure was produced with AP. The adjusted ratios grew crystals out of the liquid and climbed up the beaker to about twice the volume of the liquid. But the crystals produced were quite coarse though it was not what i was looking for. For the traditional ratios the amount of crystalline AP was less because there was too much excess of acetone, thus dissolving a marginal amount of crystals. Concluding, I found that not so much Acetone is needed. So with less acetone also less acid to keep the reaction time the same as with traditional ratios, while still getting a similiar yield.

Little experiments like this just help me to get a visual grasp on things. As learning from books isn't always a good substitute for actual experience.

Well, back to the books again.

<small>[ March 05, 2003, 08:43 PM: Message edited by: 0EZ0 ]</small>

</font><blockquote><font size="1" face="Verdana, Arial, Helvetica">quote:</font><hr /><font size="2" face="Verdana, Arial, Helvetica"> I am disinclined to believe that H2SO4 vs. HCl really makes much difference. I would guess that everybody who wants to study these peroxides looks at the existing literature, says "everybody else used H2SO4," and then uses H2SO4 as well. </font><hr /></blockquote><font size="2" face="Verdana, Arial, Helvetica">Actually some experiments indicate that the purity of the final product depends on the catalyst used. Allegedly HCl is supposed to result in TATP (TriAcetone TriPeroxide) of higher purity than when using H2SO4 as catalyst. The use of H2SO4 as catalyst results in an increased formation of the dimeric form, DADP.

The following is a quote from the article "Triacetone Triperoxide: Its Chemical Destruction" in Journal of Forensic Sciences (1999, 44 (3), pp. 603 - 608):

The purity of a TATP sample was found to be dependant upon the acid used to catalyze the condenzation, HCl giving a much purer product than H2SO4 as judged by TLC, GC, FTIR and DSC. The TATP from a H2SO4 catalyzed reaction is usually contaminated (TLC, GC, FTIR) with diacetone diperoxide (DADP, II).

However, if this is due to the fact that sulfuric acid might heat the solution more than hydrochloric acid would (as suggested by CragHack in the thread "AP catalysts - Archive File") I do not know. The author does not go into very much detail about the synthesis but focuses mainly on the possible ways of destroying TATP.

Anyway it's a very nice article about TATP. It also gives Rf values for TATP and DADP when doing a TLC analysis on 60 F254 silica gel plates from Merck: Rf=0.57 for TATP and Rf=0.66 for DADP (using ethyl acetate as solvent). That might come in handy when doing your optimizations :)
Also, even a saturated solution (~28 wt%) of TATP in toluene cannot be detonated, even when using a no. 8 blasting cap. Might be a bit difficult to recrystalize the TATP though, as toluene is not that volatile (boils at 110.6C according to Merck Index). And then again, that rather expensive toluene can be used for other more entertaining purposes :D

OEZO, if you want to find the BEST ratio for academic reasons, why not make a batch of the stuff, and let it go to completion over say 24 hours. Then separate out the crystals (whatever they are) and split the filtered clear liquid left into two batches.

Since it is already acidified, to one batch add more peroxide, to the other add more acetone, and watch if one creates more crystals. If so that reagent was lacking in the original formula quantities.

-----------------------------------------
However I will say that the fine academics is not all that valuable to the ones on this forum making the stuff. They want something that is relatively safe, easy to make quickly, and has a good bang factor. If a few % loss is involved that is of little concern in small production.

If its dim-eric+trim-eric, that doesn't matter much either if one has physically tested whatever-it-is for sensitivity, and storage.

I had hoped to get something practical from the journal article, but it began at a temp no one would subject AP to, (150 - 250 C) my god, that's abuse to anything explosive except maybe melt-able explosives like TNT.

The article is probably very good for theoreticians, but for experimenters I believe this forum is a superior authority than any I have seen yet. As for his ability to detonate some in the hood, that does not say much for his experience. Many novices make the stuff and I have not heard of a runaway explosion yet.

The dumping of 35% peroxide into the proper amount of acetone gets warm, not hot. The one who used 50% peroxide says that gets hot. There are two calibration points as to what % one ought use.

When a liter of 35% peroxide was mixed with the usual volume of acetone, (check the optimizing-apan post for quantities used there) it got up to about 40C, and when cooled down to about 5 C the slug of HCL was thrown in all at once, and it warmed up to about 10 C and clouds of white crystals formed until it became a slush.

If it was a mixture of di and tri ap, then so be it. That mixture or substance, whatever it is, when washed neutralized, dried, and tested for friction is not overly sensitive. When dried with warm air till half of it had sublimed, it was only slightly more friction sensitive, not enough to cause accidents.

About the neutralization, I am not so sure that is needed. Peroxide is shipped with a small fraction of a percent phosphoric acid in it for STABILITY purposes. The ph of store 3% peroxide is about 6.

AP stored in water with ph about 6 seems to evolve less bubbles for the 48 hours after creation, than when pure water or ph 8 water is used. Baking soda washing is practically neutral for it is a powerful buffer, being used in the body's blood system for ph control.

(It is an excellent powder to throw on skin that has been exposed to either acid or base spills for it neutralizes both. Put some on a finger with sodium hydroxide on it and it looses its slippery feel instantly. It takes much water washing to do the same. Moral if working with acids and bases keep a jug of strong baking soda water handy. It can turn a major disaster into a WOW, that was close. A pound box of soda in a gallon of water seems good, even for eye splashes).

Whatever people are making when they do AP, it explodes with all the violence anyone could ask for. It withstands slow compacting with pressures approaching 1000 psi with no reaction to that. Doing that in milliseconds would probably heat entrapped air to the ignition point and bang.

It stands rather abusive rubbing with steel on steel, and fairly hard abuse with heat insulating surfaces like dry wood. What it would not stand for is mortar and pestle grinding, even gently, at which small amounts crackled giving ample warning that you were courting disaster.

As one non professional poster put it, mortar pestle grinding was pissing it off and it was giving you the canine-like growling to let you know bad things were coming next if it didn't stop. He tried that with a bb size lump. Try that with a spoon full and the first crackle may be carried to you by all of the AP moving at mach 7 or so.

I tend to agree that the professionals probably use sulfuric because that is in the prior literature. Using anything different would have tainted their results enough for some hot shot competitor to claim that rendered them of little value.

For all I know there may be a particular acid, phosphoric, acetic, etc that is even better than HCL, but what the hell, HCL is danged good as it is, and makes gobs of something useful, and does it fast enough.

The theorists will likely be about a decade behind the tinkerers. Fedorof waded through acetone peroxides in the 1960's and not much more has been done on them since, apparently. He must have scared hell out of all professionals.

Hopefully some theoretical document will eventually give us some practical guidelines, but that's not likely, as AP is gaining the "terrorist agent" label. Soon it will be considered that nobody but a terrorist would make the stuff, and viola, if you got ap you are a certified terrorist, just not yet bloomed out. Barney, call the TV cameras and see the terrorist we captured before he got anything done...

I have noticed that some arab like people are being arrested in European nations for having trace amounts of ap around their digs. It is hard to make without getting some just about everywhere. Keep that in mind if experimenting with it for it is easy to test for, (although it is reported drug dogs cannot detect it...take that with a grain of salt, it may be a trap for those who believe it),

If you attracted fuzz attention doing something else, they might proceed to do a publicity show on you if they tested and found traces. If you are in a nation which has pissed off the world, and is hyper on terrorists, experimenting with chemicals that go bang is a hazardous occupation.

Those nations are looking for terrorists, and finding none, are making up some, from non terrorists who do anything out of the ordinary choir boy stuff. They gotta keep the people hyper sensitive so they won't notice all the crime going on in those governments.

Farting brisantly can get you reported to the local block "watcher" in some retirement communities, and god help you if you lit it and the tattler saw fire also, or smelled poison gas kind of smells.

IF you experiment with it, try not to contaminate the whole house, and store the stuff in an all plastic (plastic cap also) half liter pop bottle (no metal at all to arouse metal detectors, take any metalized label off also) filled above the ap with water, and buried somewhere, rather than keep it close around your hood.

I have not found any posts anywhere yet on whether it's better to leave the cap slightly loose to exhaust any gas, or to make it tight so the vapor pressure of AP is reached and it stops subliming.

If it gives off co2 the water will absorb a lot of that, but it may reach bursting pressures eventually. Half liter pop bottles burst at about 150 psi or so. Filled with water no noise but if half full of gas, a poof if shallow buried. Blame it on a groundhog farting. It will NOT detonate when soaking wet unless you hit it with a primer cap blast, and even then it's not all that impressive I hear.

One could let any AP evolved gas accumulate in another bottle under water and test it to see if its co2 or oxygen, or hydrogen.

Some bubbling was noticed by some posters elsewhere for about two days after creation. That varied and some batches did bubble a little over 24 hours, and their whole mass of crystals tended to barely float in water, while other batches did not float and sank, with no bubbles. Yet both kinds appeared identical when dried and tested for quality. One poster adjusted his storage water to ph 6 and said the bubbling seemed to stop and the crystals then sank. Being experimenters, they merely mentioned the facts with no idea why or what. Those were all using the hcl method best I recall, so I'll call their stuff hcl AP.

Hello all,

I use SnCl4 all the time now to make Tetrameric AP and it works just fine! No acid at all (yes, I know SnCl4 is a Ph acidic), just stating you do NOT need either H2SO4 or HCL. I was going to try AlCl3 or FeCl3, but have never gotton around to it. Later........

Would AlCl3 work? I can do tests if you wish, however i am not sure how one would distinguish the tri from the tetra.

I am wondering what would be the exact reaction involving the acid catalyst ? The fact is we keep using acids, from HCl to citric acid (we've discussed that many times). I would be interested in knowing the etaps with catalysts like SnCl4, the reactions surely is quite different and may be more efficient easier, etc...

If anyone knows...

How do you use your catalyst Alchemist? just stir powder in your mix ?

I know I am dredging up an old and long thread, but this information/article is directly on topic with the title of the thread. The search engine is a wondrous thing ;) It might be old news to some, but I found it kind of interesting. I've tried to decipher the original post by Mega, but it's a bit above my scientific understanding. For all I know this just boils down Megas post for us dumb 'cuntry folk. :D


I found this article on the New Scientist (http://www.newscientist.com/home.ns), one of my favorite sites to browse.


Terrorist explosive blows up without flames (http://www.newscientist.com/article.ns?id=dn6925)

10:55 31 January 2005
Exclusive from New Scientist Print Edition
Jenny Hogan

"An explosive sometimes used by terrorists does not burn when it detonates. Instead, its molecules simply fall apart. The chemist who has discovered this is so concerned by its implications that he has decided to abandon this line of research.

Triacetone triperoxide (TATP) has been used by suicide bombers in Israel and was chosen as a detonator in 2001 by the thwarted "shoe bomber" Richard Reid. Now calculations by Ehud Keinan from the Technion-Israel Institute of Technology in Haifa show that most of its explosive force comes from a rapid release of gas rather than a burst of energy.

In conventional high explosives such as TNT, each molecule contains both a fuel component and an oxidising component. When the explosive detonates, the fuel part is oxidised and as this combustion reaction spreads it releases large amounts of heat almost instantaneously.

TATP molecules are made up of fragments that could react in a similar way. But Keinan says that videos showing samples of TATP being detonated show that it can do so without producing any flame.

Oxygen and ozone

His team's calculations indicate why. Explosions are driven by the reaction that takes the least energy to start. In this case it is not oxidation but disintegration. The TATP molecule sheds acetone units, setting free the oxygen atoms that bound them together to form the gases oxygen and ozone. It also releases just enough energy to spread the reaction to the next molecule.

One molecule of TATP produces four of gas, giving TATP its explosive power. Just a few hundred grams of the material will produce hundreds of litres of gas in a fraction of a second.

"It's different to conventional explosives," agrees Jimmie Oxley, a chemist at the University of Rhode Island in Kingston, US, who has studied TATP and worked with Keinan on other projects. But it is not unique. The decomposition of azide, for example, which produces nitrogen gas but little heat, is used to fill airbags for cars.

TATP turns out to be the most extreme example so far, and it may be possible to design molecules that behave as an even more powerful explosive. But the idea does not appeal to Keinan. "I don't want to continue this kind of research," he says. Instead, he plans to work with security agencies to develop a device that can detect TATP.

Journal reference: Journal of the American Chemical Society (DOI: 10.1021/ja0464903)"

Well since you brought up the thread I guess I�ll attach a couple files relating to the chemical destruction of AP and it�s decomposition in toluene. The files are already on the ftp but I though I would attach them anyway, as they might be of help to some.

I'm sure those scientist know what they are doing too. But their report of cracking the flask was probably just one of those clumsy guys dropping a flask or something. I can't tell you how many skinny nerdy kids are at my school that break shit all the time. Some people just don't know how to work with there hands. I use 35% H202 all the time, and I cool down all my reactants below 0 degrees Celsius before I begin. I can add H2SO4 all at once every time and not have to worry about a run away type reaction. However, as I stated before my reactants are extremely cold when I mix them. Also, when I add my acid all at once it always forms DADP so I generally don't do this. I've noticed that the exothermic reaction is much more violent when making HTMD.

What alternates to acetone could be used to make a 'disintegrating' molecule more powerful? We know about the ketones, what else is there? Could metallic ions be attached instead?

The disintegrating reaction is probably apt for many peroxides in general. Unfortunately the same mechanism that gives these compounds their explosive power also likely contributes to their extreme sensitivity and instability. Anything more powerful would probably be nearly impossible to isolate, and would be quite dangerous to form in the first place. However, there might be an island of stability with certain structures. That is probably why he won't do any more research.

I wonder, can TACP be called an explosive at all then since it does not explode? This is more of a legal question since if the substance is not "explosive" per se then you may have an argument in court of you get pinched using it. Let us challenge the BATF's recent appointment of TATP to The List!

That silly jew abandoned an entire line of research because of the implications of his work? He isn't even making explosives, he is only characterizing them. That would be like Einstein getting out of physics because he found out atoms are split by neutrons. A more plausable story is he will no longer PUBLICALLY disclose the results of his research, instead doing it under classified military contract for the development of jew weapons.

Sorry but IMO he (that jew) is an idiot. Does he tell us AP releases acetone and ozone during detonation, but it is no explosive because nothing is oxidized? I bet my ass the end products are CO2, CO, H2O, H2 according to OB. Will DDNP detonate froming DNP + nitrogen? TATNB will form TNB + nitrogen? Anything with the peroxi- or azo-group would be a non-explosive in Ehud's terms.

It is true that the stressed bonds in these groups promote explosive decomposition, but what happens next is a standard CHNO explosive decomposition towards the end products (OK forget the N for peroxides).

I think the reason these guys are all having so much fun is that they didn't come here and read how to make this stuff properly, so they screwed it up.

They probably tried to do it from first principles, and a crap-book, and hence they blew some beakers apart.

Either that, or they want to try to convince everyone that AP is worse than nukes??!?

...but no researchers ever have a hidden agenda like that, so they?

Shit yeah!
Take AP off The List baby!!!
HEH, HEH, HEH.

That theory of 'breaking up' instead of exploding does sound rather plausible when taken in light of the article Mega wrote up.
In it it states that the products of decomposition typically include acetone and other stuff like that.
So thank you MightyQuinn!
So we have distinct reason to believe that triacetone triperoxide (cyclic) perhaps may fail to meet many a country's definition of an "explosive".
I feel that all country's should make it be publicly known exactly what definition they make use of to classify a substance as such.

You know what bugs me?
It's that many countries ban all purchase or sale or possession of explosives without a valid license. And they then let people buy pure nitromethane from a shop.
WTF?
They know it can be made to explode with a suitable detonator, you don't even need a sensitizer.
Dumb fucks!
Could you imagine if every person and industry or company that used nitromethane for anything suddenly required a permit to use it as a solvent.
Or if every farmer needed one to be able to use ammonium nitrate for fertilizer.
There might just be a small outcry.
Yay.

Could the low yield experienced by the journal writers perhaps be due to the fact that (unless I read it wrong) they didn't wait very long be fore performing the extractions.
Yes I know that they used H2SO4 (probably >~90%) but still, I'm sure that not all the AP was formed in that short time.
Also, does anybody else have the feeling that, when dreaming up AP with conc. H2SO4, they lost some of their product towards the end of the acid addition.
Perhaps the bubbling encountered was due to either AP decomp. or H2O2 decomposing into O2?

Due to the recent London bombings I have been reflecting on acetone peroxide for a bit. I re-reviewed this article and I have a question... Since it seems the decomposition product of AP is 3 moles of acetone per mole of AP, would it not be feasable to add something to AP in order to combust all that acetone? Certainly many already admix their AP with other materials. Perhaps using neat AP is not the best way to go. The Encyclopedia of Explosives states AP has a detonation temperature over 5000 degrees, so I would think some of the acetone would combust. Still it would make for a more effective detonation if an additional oxident could be added to react with the acetone, and perhaps something to raise the detonation temperature as well.

Due to the recent London bombings I have been reflecting on acetone peroxide for a bit. I re-reviewed this article and I have a question... Since it seems the decomposition product of AP is 3 moles of acetone per mole of AP, would it not be feasable to add something to AP in order to combust all that acetone? Certainly many already admix their AP with other materials. Perhaps using neat AP is not the best way to go. The Encyclopedia of Explosives states AP has a detonation temperature over 5000 degrees, so I would think some of the acetone would combust. Still it would make for a more effective detonation if an additional oxident could be added to react with the acetone, and perhaps something to raise the detonation temperature as well.

Interesting... I didn't know that decomposing AP yielded acetone...

That's another thing to add to my list of things that help explain why a mixture of 25% AP and 75% KNO3 seems to be more powerful than the same amount of pure AP.

NOTE: Power refers to raw power (i.e. loudness, crater size, distance it will throw a nearby object), VoD is actually lowered, so stick to pure AP for detonators, mixtures with KNO3 are suited only to salutes and low-hygroscopicness (is that a word?) booster charges, where KNO3 is much less hygroscopic than AN, although also a lot less powerful

My previous theory was that although the KNO3 doesn't itself detonate, it supplies extra oxygen allowing the AP to detonate fully.

I mucked around with different ratios to arrive at a 25/75 mixture as my salute-on-steroids composition. Later I did an oxygen balance calculation on the AP/KNO3 mixture, and IIRC it turned out that 25% AP to 75% KNO3 was roughly the right ratio as far as oxygen balance was concerned.

NOTE 2: 25% AP to 75% KNO3 is still flame sensitive, and very much so...



Back to the topic now, wouldn't the acetone formed in AP decomposition simply evaporate off as it formed? I mean, if you leave AP to decompose, even inside a sealed container (don't try the latter at home, kids...), it doesn't form any visible amount of liquid in there...

Interesting... I didn't know that decomposing AP yielded acetone...

That's another thing to add to my list of things that help explain why a mixture of 25% AP and 75% KNO3 seems to be more powerful than the same amount of pure AP.

NOTE: Power refers to raw power (i.e. loudness, crater size, distance it will throw a nearby object), VoD is actually lowered, so stick to pure AP for detonators, mixtures with KNO3 are suited only to salutes and low-hygroscopicness (is that a word?) booster charges, where KNO3 is much less hygroscopic than AN, although also a lot less powerful

My previous theory was that although the KNO3 doesn't itself detonate, it supplies extra oxygen allowing the AP to detonate fully.

I mucked around with different ratios to arrive at a 25/75 mixture as my salute-on-steroids composition. Later I did an oxygen balance calculation on the AP/KNO3 mixture, and IIRC it turned out that 25% AP to 75% KNO3 was roughly the right ratio as far as oxygen balance was concerned.

NOTE 2: 25% AP to 75% KNO3 is still flame sensitive, and very much so...



Back to the topic now, wouldn't the acetone formed in AP decomposition simply evaporate off as it formed? I mean, if you leave AP to decompose, even inside a sealed container (don't try the latter at home, kids...), it doesn't form any visible amount of liquid in there...

It does not form acetone when it decomposes, the formation of acetone and ozone happens when it is detonated. AP does not form the usual combustion products of CO2 and water one would expect from an explosive, rather the molecule reconfigures into 3 molecules of acetone and one of ozone. This reaction happens supersonicially and as the products take up more space than the original you get and explosive shockwave.

Now then, since the product gasses are mostly acetone, itself a flammable material, it should be possible to combust that acetone. This would lead to more volume of gas, hence a bigger crater. Indeed I would not expect an increase it detonation velocity.

It does not form acetone when it decomposes, the formation of acetone and ozone happens when it is detonated. AP does not form the usual combustion products of CO2 and water one would expect from an explosive, rather the molecule reconfigures into 3 molecules of acetone and one of ozone. This reaction happens supersonicially and as the products take up more space than the original you get and explosive shockwave.

Now then, since the product gasses are mostly acetone, itself a flammable material, it should be possible to combust that acetone. This would lead to more volume of gas, hence a bigger crater. Indeed I would not expect an increase it detonation velocity.

Thats crap. I highly dought the decomposition of AP into acetone and ozone is even exothermic.. it'd be a pretty keeewwwll explosive :rolleyes: . Theres no way in hell ozone is going to be an end product of this explosion but lets just pretend it does, how long do you think its going to last in admixture with acetone during a detonation, how hot is it again?

I think people should step back and think a bit.

Thats crap. I highly dought the decomposition of AP into acetone and ozone is even exothermic.. it'd be a pretty keeewwwll explosive :rolleyes: . Theres no way in hell ozone is going to be an end product of this explosion but lets just pretend it does, how long do you think its going to last in admixture with acetone during a detonation, how hot is it again?

I think people should step back and think a bit.

That's what I thought, I too doubt with an explosion temperature that high that the most if not all of the decomp products will not combust. But, I will defer to the scientist with the multi-million dollar lab... It is possible that they detonated such a small amount that there is insufficient local heating to combust the acetone.

I should add that I am in error about the explosion temperature! I quoted the figure shortly after I closed the file in question, but the number that stuck in my head was the detonation velocity NOT the detonation temperature. Repeat, the detonation temperature is NOT 5000 degrees. In fact I could not find reference to the detonation temperature, or any thermodynamic data at all... I know it is around here somewhere :(

That's what I thought, I too doubt with an explosion temperature that high that the most if not all of the decomp products will not combust. But, I will defer to the scientist with the multi-million dollar lab... It is possible that they detonated such a small amount that there is insufficient local heating to combust the acetone.

I should add that I am in error about the explosion temperature! I quoted the figure shortly after I closed the file in question, but the number that stuck in my head was the detonation velocity NOT the detonation temperature. Repeat, the detonation temperature is NOT 5000 degrees. In fact I could not find reference to the detonation temperature, or any thermodynamic data at all... I know it is around here somewhere :(

Wasn't the AP heated and *slowly* decomposed in a solvent? IIRC they used an apparatus similar (identical?) to the one used to detect the maximum exotherm of energetic materials, which is *not* the detonation point.

Maybe that misunderstanding comes from an article stating that *initially* the molecule is shattered into Acetone + O3. At the high temp (again I doubt the 5000 K) they will react normally towards equilibrium like all hot detonation gasses.

Jut THINK people: A fuel plus oxygen (ozone even!) in molecular admixture, at 10+ times the ignition temp......

BTW is acetone even stable above 1000K?

Wasn't the AP heated and *slowly* decomposed in a solvent? IIRC they used an apparatus similar (identical?) to the one used to detect the maximum exotherm of energetic materials, which is *not* the detonation point.

Maybe that misunderstanding comes from an article stating that *initially* the molecule is shattered into Acetone + O3. At the high temp (again I doubt the 5000 K) they will react normally towards equilibrium like all hot detonation gasses.

Jut THINK people: A fuel plus oxygen (ozone even!) in molecular admixture, at 10+ times the ignition temp......

BTW is acetone even stable above 1000K?

No acetone isn't stabile at high temperatures. IIRC it decompose at wire heated up to 700 degrees Celsius as laboratory procedure for making ketene and acetic acid anhydride (plus methane of course). I believe that old industrial process was the same until Monsanto procedure for acetic acid. So I don't think that acetone is stabile at 1000K.

No acetone isn't stabile at high temperatures. IIRC it decompose at wire heated up to 700 degrees Celsius as laboratory procedure for making ketene and acetic acid anhydride (plus methane of course). I believe that old industrial process was the same until Monsanto procedure for acetic acid. So I don't think that acetone is stabile at 1000K.

It is possible that they detonated such a small amount that there is insufficient local heating to combust the acetone.

The thermolysis of neat TATP was generally performed in
_160 _L ampoules over the temperature range 150 to
225_C. These thermolyses were first-order out to about90%
conversion at least at temperatures above 160_C. Generally
first-order plots were constructed with seven to eight data
points with a R2 fit better than 0.99. Even at 150_C TATP
samples appeared to be gaseous. To ensure that condensedphase
kinetics were examined, the reaction tubes were
reduced to 25 _L and the sample size increased to 3 mg.

It doesn't appear that they detonated anything as Boomer said. After all if they did the products simply could not exist together, ozone reacts with nearly everything combustable at room temp and at the extreme pressure suddenly generated by the formation of 4 moles of gas by one mole of solid it will react quite quickly with that acetone, and the remaining acetone will also begin to decompose in the high temperatures following the combustion....
It does explain why AP has such a unique smell after it is detonated. If someone isolated the compounds remaining after a detonation, then a much clear picture of the detonation process of AP could be gained.

Boomer started a little buzz in my head with his question. Combustion or explosion or whatever it is oxidation process for which radical process is postulated. This could explain why MEK gives more fragile product with H2O2 compared with acetone since partial decomposition of of MEK can give ethyl radical and ethylene as end product of those few steps making that step more exotermic compared with breaking up acetone to methyl radical and methane - both process of course yields ketene but that is common point that won't influence energy status. Please comments - aplause or tomatoes?