Forensic Science International 228 (2013) 170–173

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Forensic Science International

journal homepage: www.elsevier.com/locate/forsciint

Study of TATP: Method for determination of residual acids in TATP

Robert Matyáš a,*, Jaromı́ra Chýlková b
a
Faculty of Chemical Technology, University of Pardubice, Institute of Energetic Materials, Studentska 95, Pardubice, Czech Republic
b
Faculty of Chemical Technology, University of Pardubice, Department of Environmental and Chemical Engineering, Studentska 95, 532 10 Pardubice, Czech Republic

A R T I C L E I N F O A B S T R A C T

Article history: Triacetone triperoxide (3,3,6,6,9,9-hexamethyl-1,2,4,5,7,8-hexoxonane, TATP) is nowadays one of the

Received 1 February 2012 most commonly used improvised explosives. It is prepared by the action of hydrogen peroxide on
Received in revised form 5 November 2012 acetone in an acidic environment. Easily available mineral acids – hydrochloric, sulfuric, nitric and
Accepted 7 January 2013
perchloric – are the most often recommended on the extremist web pages dealing with improvised
Available online 28 March 2013
production of explosives. The various TATP producers’ choice of acid mainly depends on the author’s
experiences and the local availability of the acid. A knowledge of the kind of acid used for TATP
Keywords:
production can help in detecting the person who has made the TATP, or who has committed a criminal
TATP
act using TATP. Therefore, a capillary isotachophoretic method was developed for determination of
Triacetone triperoxide
3,3,6,6,9,9-Hexamethyl-1,2,4,5,7,8- residual anions (originating from the acid used during TATP synthesis) in the resulting TATP crystals. This
hexoxonane analytical method has proved to be reliable; the acid used for TATP synthesis was correctly identified in
Residual acid all samples analyzed.
Catalyst ß 2013 Elsevier Ireland Ltd. All rights reserved.
Isotachophoresis

1. Introduction
Triacetone triperoxide (3,3,6,6,9,9-hexamethyl-1,2,4,5,7,8-hex-
oxonane, TATP) is currently one of the most synthesized and
misused improvised explosives. One of the first published abuses
of this compound was reported by Zitrin, Kraus and Glattstein in
Israel [1]. These authors reported TATP as an unusual and rare
explosive used for terrorist activity at that time. Unfortunately,
some 30 years later, TATP has become one of the most common
improvised explosives used by young chemists, criminals and
terrorists throughout the world [2–4]. Probably the most well-
known abusive use of TATP was by Richard Reid who used it as a
primary explosive in his shoe bomb in the attempted bombing of a
US airliner in December 2001 [4]. The reason why TATP is used so
much is its simple synthesis procedure; knowledge of the synthesis
is widespread and available via internet; ingredients for synthesis
are easily available in the chemical trade networks or do-it-
yourself markets without any restrictions on the sale of such
substances [5].
In improvised conditions, TATP is always prepared by reaction
of acetone with hydrogen peroxide in an acidic environment. The
various acids published on web pages for preparing TATP as an
improvised explosive depend on the particular author of the
procedure and his experiences, and on local availability of the acid.
The acid used has not only an impact on product composition
[6–8] but also on the properties of the TATP synthesized [9]. A
small amount of the acid used as a catalyst during TATP
preparation remains in the crude TATP even though thorough
washing of the TATP crystals is carried out after preparation. As we
reported in our previous studies, the residues of acid have a strong
impact on TATP’s properties (thermal stability [10]; transforma-
tion of TATP to 3,3,6,6-tetramethyl-1,2,4,5-tetraoxane (known
under the acronym DADP) [11,12]; stability of TATP in solutions
[13]). The residual acid can be quantified by titration. Unfortu-
nately, the published analytical procedure can only determine the
level of acidity (H+ ions) and not the specific anions [10].
The aim of this work was to utilize capillary isotachophoresis
for determining the kind of residual anions in crude TATP, thereby
determining the acid used in TATP preparation. This method can be
utilized for forensic analysis of TATP, because TATP is usually not
purified by re-crystallization in improvised conditions and the acid
remains in the crude TATP. A knowledge of the acid used for TATP
production can contribute to discovery of who has produced the
explosive or who has used it for criminal purposes.
2. Materials and methods
Caution: TATP is a primary explosive sensitive to impact, friction, electric discharge
and flame even when wet. The synthesis and handling of TATP are dangerous operations
that require standard safety precautions for handling primary explosives!!!

2.1. TATP synthesis

* Tel.: +420 466038018. Triacetone triperoxide was synthesized by procedures that are published in
E-mail address: robert.matyas@upce.cz (R. Matyáš). various modifications on web pages dealing with improvised explosives. It was

0379-0738/$ – see front matter ß 2013 Elsevier Ireland Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.forsciint.2013.01.007
 R. Matyáš, J. Chýlková / Forensic Science International 228 (2013) 170–173 171

prepared by the standard route from acetone and hydrogen peroxide catalyzed
using four different acids – 37% hydrochloric acid; 31% sulfuric acid; 65% nitric acid;
and 70% perchloric acid. Altogether six batches of TATP were prepared using each
acid mentioned (giving in total 24 batches). The molar ratio of acid to acetone was
always 0.25. The synthesis details have already been published in our previous
work (weights were one-tenth of original procedure) [14]. None of the TATP
samples was purified by re-crystallization.
2.2. Preparation of solutions for analysis
For preparing the aqueous solutions containing residual acidity, extraction of
highly concentrated toluene solutions of TATP with water was used. Desiccation
of toluene solutions leads to formation of a crystalline crust of TATP, which
therefore represents a certain risk when handling toluene TATP solutions. The
crust is highly sensitive to various external mechanical impulses, and thus it is
essential to prevent desiccation of such solutions. Laboratory glass equipment
which has been in contact with TATP solutions must be thoroughly washed with
ethanol or acetone immediately after use. The washings, together with any
toluene TATP-containing residues from the extraction analysis, should be
collected in a special container. However, should desiccation occur and the solid
TATP crust be formed, it should be washed away immediately. Collected TATP-
containing residues can be safely disposed of by incineration in an open
container at a suitable place where people and the neighborhood are not
exposed to any explosion or fire risk. This procedure has been examined and
published by Bellamy [15]. Only people experienced in working with TATP or
explosives in general should be allowed to handle TATP (such as weighing,
extraction, laboratory equipment washing, incineration of residues, etc.).
Undesirable explosion risk is minimized as long as all safety precautions are
respected. We have successfully prepared and analyzed more than a 100 TATP
samples.
About 1–1.5 g of TATP (precisely weighed) was dissolved in 10 ml toluene and
then extracted with 10 ml distilled water (precisely measured using a pipette).
Extraction time is about 15 min. Then the mixture was poured into a separating
funnel with a well greased stopcock. Good lubrication is very important for
elimination of any TATP ignition risk from excessive friction inside the stopcock
during turning. The aqueous extract was then separated and analyzed by
isotachophoresis.
by standards. It is a reliable and selective method for analyzing
mixtures. Isotachophoretic analysis also allows quantification of
ionic substances present, using the length of the zones.
For determining the following anions – Cl , NO3 , SO42 and
ClO4 – it is necessary to choose a suitable electrolytic system
consisting of a leading electrolyte, the anions of which must
have a mobility that is higher than that of any of the sample
anionic species, and a terminating electrolyte, the anions of
which must have a mobility that is lower than all sample anions.
The cations of the leading electrolyte should also have a
buffering capacity at the pH at which the analyses will be
performed. For this project, two electrolytic systems were used.
The one for determining nitrates, sulfates and perchlorates
consisted of 10 mM hydrochloric acid and 1,3-bis[tris(hydrox-
ymethyl)methylamino]propane and histidine as the counter
ions with pH 5.8. The terminating ions were acetates. The other
operational system, for determining chlorides, consisted of
10 mM nitrates and Cd2+ ions as the counter ions. The
terminating ions were citrates.
Isotachopherograms of the test mixtures of the anions
studied are given in Fig. 1. From these figures it can be seen
that the zones are well separated and identification of anions
is assured. The dependences of zone lengths of a particular
anion on its concentration are linear and were statistically
evaluated by linear regression using the program ADSTAT
(Trilobite s.r.o., Pardubice 1995). The statistical results found
(limit of quantification and limit of detection) are summarized
in Table 1.

2.3. Isotachophoresis

Chemicals: All chemicals used for isotachophoresis analysis were of analytical

reagent grade. Hydrochloric acid, acetic acid, citric acid, sodium perchlorate,
sodium sulfate, sodium nitrate, sodium chloride and cadmium nitrate were from
Lachema (Brno, Czech Republic). D,L Histidine and 1,3-bis[tris-(hydroxymethyl)-
methylamino]propane were obtained from Sigma (St. Louis, USA), hydroxyethyl
cellulose 4000 (HEC) from Serva (Heidelberg, Germany). Standard solutions were
prepared from de-ionized and redistilled water.
Instruments and parameters for isotachophoretic analysis: Capillary isotachophor-
esis experiments were performed in an Isotachophoretic Analyser (Villa Labeco,
Spišská Nová Ves, Slovakia) equipped with a column coupling system consisting of
two polytetrafluorethylene capillaries. The first, pre-separation, capillary
(130 mm  0.8 mm I.D.) was connected to the analytical capillary
(180 mm  0.3 mm I.D) via the bifurcation block which enables determining the
macro-components and micro-components of the samples. Both columns
contained a conductivity detector. Sample volume was 35 ml. The driving current
for the pre-separation capillary was 250 mA. For determining the SO42 , ClO4 and
NO3 anions the electrolyte systems consisted of a leading electrolyte (LE) – 10 mM
Cl , 20 mM His+, 5 mM 1,3-bis[tris(hydroxymethyl)methylamino]propane, 1%
hydroxyethyl cellulose (HEC), pH 5.8 and a terminating electrolyte (TE) – 10 mM
acetic acid. Determining chloride anions was carried out using 5 mM Cd(NO3)2 and
1% HEC – LE, and 10 mM citric acid – TE.

2.4. Experimental approach, verification of results

Experiments were performed using blind scenarios. All samples of TATP

were prepared, and the subsequent water extraction carried out, by the
synthesist. The water solutions of anions were then passed to the analyst
without revealing any information about the synthesis method. In this way the
analyst was always ignorant of any expected results. This was the approach
used in order to verify the reliability of the method for determining the type of
acid.

3. Results and discussion
Capillary isotachophoresis is a separation method very suitable
for determining the presence of ionic substances. Identification of
ionic species is based on the position of zones. The positions of the
unknown zones are compared with the positions of zones occupied
Fig. 1. Isotachopherogram of the separation of model mixture of nitrates,
perchlorates, sulfates and chlorides. Nitrates, perchlorates and sulfates were
analyzed in the operational system at pH 5.8, with 10 mM HCl and 1,3-
bis[tris(hydroxymethyl)methylamino]propane and histidine as the counter ions
(left isotachopherogram). The terminating ions were acetates. Chlorides were
analyzed in the operational system with 10 mM nitrates and cadmium as the
counter ions (right isotachopherogram). The terminating ions were citrates.
172 R. Matyáš, J. Chýlková / Forensic Science International 228 (2013) 170–173

The isotachopherograms of the real samples of aqueous

Fig. 2. Isotachophoreograms of the real samples. Chlorides (a) were analyzed in the
operational system with 10 mM nitrates and cadmium as the counter ions. The
terminating ions were citrates. Sulfates (b), nitrates (c) and perchlorates (d) were
analyzed in the operational system at pH 5.8, with 10 mM HCl and 1,3-
bis[tris(hydroxymethyl)methylamino]propane and histidine as the counter ions.
The terminating ions were acetates.
extracts (from TATP toluene solutions) are presented in Fig. 2.
Identification by comparing the position of the standard zones
with the position of the unknown ions is unambiguous because
the samples analyzed contained only one anion in significant
concentrations.
Isotachophoretic analysis allows also quantification of ionic
substances using the length of the zones. Results of the
quantitative analysis of residual anions in extracts from TATP
are presented in Table 2. The table summarizes the results of the
analysis of six batches of TATP from each acid examined. The order
of magnitude of concentration of residual anions in the TATP
crystals is 10 3 mol l 1. This concentration is high and therefore
the results obtained can be considered as precise. Isotachophoretic
analysis can also be used to analyze lower concentrations –
between 10 4 and 10–5 mol l 1. Due to the high sensitivity of this
method the small concentration of other anions (originating from
impurities) can be also detected. Such anions originate from the
low-purity chemicals often used for TATP preparation in impro-
vised conditions. Therefore the results of such analysis have to be
evaluated carefully. For example, if a very low concentration of
SO42 is detected (originating perhaps from impurities) using the
electrolytic system for NO3 , SO42 and ClO4 , the detection of Cl
anions using the other electrolytic system is also worth carrying
out before final evaluation.
The reliability of the method is high – we tested 24 samples (six
samples from each acid) and the acid was unequivocally
determined in all cases. Apart from the results presented in this
paper we also measured 80 other samples with the same results.
The analyst always correctly determined which acid had been used
for the TATP preparation.
Some other analytical method could be also promising for
acid determination in water extracts (e.g. capillary electropho-
resis or ion chromatography). However these methods are not
available in our laboratories, so this is a field for other
researchers.

Table 1
4 1 3 1
Evaluation of model samples of anions studied in a range of concentration from 2  10 mol l to 1  10 mol l by linear regression using the program ADSTAT (Trilobite
s.r.o., Pardubice 1995).
1
Anion Slope (cm/mmol l ) Intercept (cm) Correlation Limit of quantification Limit of detection
coefficient (mmol l 1) (mmol l 1)

SO42 5.58  3.08  10 2 0.79  10 2

 1.91  10 6
0.99988 0.02 8.5  10 3
NO3 1.43  2.99  10 3 3.33  10 4
 1.85  10 7
0.99998 0.07 2.3  10 2
Cl 1.7  4.2  10 8 9.99  10 4
 2.61  10 8
1 0.06 1
ClO4 1.45  1.69  10 3 6.7  10 3
 1.05  10 4
0.99999 0.07 2.15  10 2

Table 2
Concentration of residual anions in water extract for TATP prepared from hydrochloric, sulfuric, nitric and perchloric acids.

Number of batch 1 2 3 4 5 6

TATP from HCl

Weight of TATP (g) 1.287 1.390 1.250 1.569 1.105 1.195
Concentration of Cl (mmol l 1) 1.82 2.48 2.48 2.30 1.32 1.48
TATP from H2SO4
Weight of TATP (g) 1.480 1.337 1.235 1.276 1.145 1.442
Concentration of SO42 (mmol l 1) 1.58 1.08 1.25 1.36 1.09 1.30
TATP from HNO3
Weight of TATP (g) 1.232 1.040 1.327 1.346 1.342 1.330
Concentration of NO3 (mmol l 1) 1.86 1.17 1.77 1.85 0.92 1.21
TATP from HClO4
Weight of TATP (g) 1.421 1.228 1.195 0.854 0.924 1.213
Concentration of ClO4 (mmol l 1) 1.90 2.00 1.32 0.94 1.05 1.36
 R. Matyáš, J. Chýlková / Forensic Science International 228 (2013) 170–173
4. Conclusions
Various acids are used by young chemists, criminals or
terrorists for improvised preparation of TATP. The most common-
ly used are all widely available – hydrochloric acid, sulfuric acid,
nitric acid and perchloric acid. These acids are the most often
mentioned on web pages aimed at improvised synthesis of
explosives. The acid chosen mainly depends on the person’s
experience and on local availability of the acid. A knowledge of the
acid that has been used for TATP preparation can help criminal
investigators in discovering the identity of TATP producers or
those responsible for criminal acts using TATP. Therefore an
isotachophoretic method for determining the acid used in TATP
preparation has been developed, and the method for determining
mixtures of anionic species presented here is suitable for routine
analysis. The acid used for synthesizing TATP was correctly
identified in all samples analyzed. Sufficient sensitivity, reliabili-
ty, ease of use and low running costs are important attributes of
this method.
Acknowledgements
This work was carried out as a part of the Ministry of Interior of
the Czech Republic Project No. VG 20102014032 and the Ministry
of Education, Youth and Sports of the Czech Republic Project No.
MSM 0021627501.
173
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