Defence Technology 15 (2019) 51e57

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Defence Technology
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Crystal lattice free volume and thermal decomposition of nitramines

Svatopluk Zeman a, *, Ning Liu b, Ahmed K. Hussein a
a
Institute of Energetic Materials, Faculty of Chemical Technology, University of Pardubice, CZ-532 10, Pardubice, Czech Republic (Czechia)
b
Xi'an Modern Chemistry Research Institute, Xi'an, Shaanxi, 710065, China

a r t i c l e i n f o a b s t r a c t

Article history: The linear, directly proportional, equations between the Arrhenius parameters (Ea and log A) of the
Received 22 February 2018 thermal decomposition and the crystal lattice free space per molecule, DV, of 22 nitramines are
Received in revised form described. It is shown that, because of a significant limitation by the molecular structural characteristics
22 April 2018
of such compounds, they are divided into a number of partial relationships. These partial relationships
Accepted 27 April 2018
Available online 30 April 2018
divide the nitramines into a group of substances relating to dimethyl nitramine and a sub-group related
to ε
HNIW. These directly proportional equations mean that an increase in the DV values is related to an
increase in the thermal stability of the corresponding nitramines. A comparison with similar published
Keywords:
Crystal lattice
dependencies for the impact and friction sensitivities, on the one hand, and with the relationship be-
Thermal decomposition tween the Ea values and the sum of the negative and positive extremes of molecular surface electrostatic
Initiation reactivity potentials, on the other, confirms the well-known fact that intermolecular interaction in the nitramines
Nitramines studied plays a decisive role in the thermal reactivity of such compounds. The crystal lattice free space
manifests itself here perhaps only in the solid state thermal decomposition of RDX, HMX and DINGU. This
study again confirms a level of disorder in the distribution of the forces in the crystal lattice of the
“common” quality of ε
HNIW, compared with its “reduced sensitivity (RS)” or pure analogues.
© 2018 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction
Sensitivity of energetic materials (EMs) is intimately connected
with their chemical reactivity and/or that of their components (see
for example Refs [1,2] and quotations therein). Such reactivity de-
pends on the molecular structure, the intermolecular interactions
and the material state of the particular EM and also on their
possible admixtures. The selection of nitramines chosen for the
work described in this paper as energetic materials are, in their
molecular structures, relatively simple polynitro compounds, for
which the mechanism of the primary homolysis of their molecules
is well understood [3e7](see Scheme 1).
Aza atoms form part of the molecular skeletons of nitramines,
and their electron configuration is thus connected with the
conformation of such molecules. However, in spite of the fact that
they are “inner” atoms of the skeleton, their effect on the inter-
molecular potential will be lower than that of the atoms in the nitro
groups attached to them. The oxygen atoms of the nitro groups, by
* Corresponding author.
E-mail addresses: svatopluk.zeman@upce.cz, svatopluk.zeman@pevyt.sk
(S. Zeman).
Peer review under responsibility of China Ordnance Society
their dipole-dipole interactions, are in contact with the oxygen and
nitrogen atoms of the nitro groups in neighbouring nitramine
molecules in the crystal [8e11], which is the decisive factor gov-
erning the crystal structure of nitramines.
Taking account of these facts, and from a physical organic
chemistry point of view, the initiation reactivity, including initia-
tion of detonation, has been extensively studied for individual
organic energetic materials (EMs). Techniques such as the NMR
chemical shifts of the key atoms in the reaction centres
[1,2,5,12e17] and the modified Evans-Polaniy-Semenov relation-
ship are widely used not only for individual energetic materials
[1,2,5,12,18,19] but also for emulsion [20] and plastic bonded ex-
plosives [21]and mixtures with peroxides [22,23]. In addition, the
crystalline aspects of impact and friction sensitivities have been
studied using the heats of fusion for such compounds [1,12,24e26].
However, intensive use of quantum chemical methods in the study
of EMs in general is head and shoulders above the mentioned
chemical approach, as well as in the study of their initiation reac-
tivity [1,27e35] but with a tendency to make a general conclusion
for several EMs with different molecular structures. However,
Politzer and Murray have shown that the correlations found here
[30] are restricted to specific classes(i.e. nitroaromatics, nitro-
heterocyclics and nitramines) which is perfectly in line with

https://doi.org/10.1016/j.dt.2018.04.012
2214-9147/© 2018 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
52 S. Zeman et al. / Defence Technology 15 (2019) 51e57

Scheme 1. Structural formulas of the nitramines studied.

findings from approaches based on physical organic chemistry
principles (see Refs. [1,5,12,14,15,17,25]).
The already mentioned dipole-dipole interactions are connected
with the non-binding inter-atomic distances between oxygen
atoms inside and outside all of the nitro groups in these poly-nitro
compounds. These are shorter than those corresponding to the
intermolecular contact radii for oxygen in carbonyl or nitro groups
[36e40]; this distance is especially short inside the most reactive
nitro groups [40e42]. These facts led to the research of the free
spaces in crystal lattices of EMs and of their influence on EMs'
impact sensitivity [32e34] but originally without taking into ac-
count the very important molecular-structural similarity
[2,32e35]. This deficiency has already been remedied by recent
studies of the influence of the free spaces in crystal lattices on the
impact [41] and friction [42] sensitivities of nitramines. In both
these cases it seems that it is not the free volume in the crystal
lattice, but intermolecular interaction which plays a decisive role in
initiation reactivity under mechanical impulses.
Thermal decomposition of energetic materials has also been
extensively studied X [1,4,6,7,43]. In the area of EM testing it is
 S. Zeman et al. / Defence Technology 15 (2019) 51e57 53

sometimes not entirely clear in which physical state the given Refs. [51,55,58,60,63]) and some output from thermo-gravimetry
substance decomposes; facts reported in paper [44] suggest a need (TG) of EMs which have been evaluated by means of the modified
to study the pre-decomposition states of thermal decomposition Kissinger-Akahira-Sunose (KAS) isoconversional method
and the beginning phase of the heat initiation of nitramine crystals. [61,65,66]. The formulas of the nitramines studied are shown in the
Nevertheless, it is not without interest to determine the relation- chart below:
ship between the free volumes in crystal lattices and the Arrhenius
parameters of the thermal decomposition of the nitramines. This is 2.2. Results of calculations for crystal lattice free volume of
the subject of this paper. nitramine explosives

All compounds were optimised at computational level of B3LYP/

2. Data sources
6e311 þ g (d,p) by using the Gaussian 09 software. The crystal
volume [V(0.003)] was calculated by using the Multiwfn 3.3.9
2.1. Arrhenius parameters of thermal decomposition
software. The effective volume per molecule (Veff) was calculated
as: Veff ¼ M=d, where M is molecular mass, d is crystal density.
The thermoanalytical data used for the study of individual
The intrinsic gas phase molecular volume (Vint) was calculated by
nitramines were taken from the published literature and are
the 0.003 au surface according to Ref. 34, Vint ¼ V(0.003). Therefore,
grouped in Table 1 for both the Arrhenius parameters of the
the free space per molecule (DV) is:
monomolecular decomposition. The majority of the data was ob-
tained by the Russian isothermal manometric (RMM) method, DV ¼ Veff
Vint ¼ Veff
Vð0:003Þ (1)
making use of Bourdon's glass compensation manometer [4,7,45].
These data are known to correspond to the primary non- Results of these calculations are summarised in Table 2, together
autocatalysed stage of thermal decomposition of the energetic with crystal densities of the nitramines studied.
materials [1,4,7,45,46,48,52,53]. In the case of thermal decompo-
sition in the condensed state, only the results of some thermoa- 2. Results and discussion
nalytical methods are directly comparable with the results of RMM,
especially those from differential scanning calorimetry (DSC, e.g. Simple relationships of the activation energies, Ea, and the

Table 1
A list of the nitramines studied, showing the Arrhenius parameters (Ea in kJ$mol
1 and log A in s
1) of their low-temperature monomolecular thermal decomposition.

Data No. Chemical name Code designation Arrhenius parameters

Method of evaluation Temp. region/K State of decomp. Ea log A Ref.

1.1 2-Nitro-2-azapropane DMNA IR 298 Solid 192.5 14.2 [49]

1.2 DMNA NMR 360b Liquid 159.8 14.7 [47]
2.1 1,4-Dinitro-1,4-diazabutane EDNA Manometric 393e418 Solid 186.2 18.0 [49]
3.1 2,4-Dinitro-2,4-diazapentane OCPX Manometric 453e503 Liquid 169.6 13.5 [48]
4.1 2,5-Dinitro-2,5-diazahexane DMEDNA Manometric 483e513 Solution 173.8 14.2 [48]
5.1 2,4,6-Trinitro-2,4,6-triazaheptane ORDX Manometric 453e503 Liquid 178.4 14.9 [48]
6.1 1,3-Dinitro-1,3-diazetidine TETROGENa Calc. 450b 153.1 14.1c [50]
7.1 1,3,3-Trinitroazetidine TNAZ DSC 400e510 Liquid 161.6 15.7 [51]
8.1 1,3-Dinitroimidazolidine CPX Manometric 423e473 Liquid 149.4 13.5 [52]
8.2 CPX Manometric 383e403 Solid 197.8 18.7 [53]
9.1 1,4-Dinitropiperazine DNDC Manometric 489e507 Solid 198.4 17.3 [52]
10.1 1,3,5-Trinitro-1,3,5-triazinane RDX Manometric 486e572 Liquid 198.9 18.5 [54]
10.2 RDX DSC 486e525 Liquid 197.1 18.3 [55]
10.3 RDX Manometric 423e470 Solid 213.5 18.6 [47]
10.4 RDX Manometric 423e470 Solid 217.6 19.1 [56]
15
11.1 1,3,5-Trinitro-1,3,5-triazepane HOMO N NMR 490b Solid 207.1 18.6 [15]
12.1 3,5,7-Trinitro-1-oxa-3,5,7-triazocane TNOTZ Manometric 463e498 Liquid 190.1 16.4 [57]
13.1 3,4,6-Trinitrohexahydro-2H-imidazo[4,5-d][1,3]oxazole TNIO Manometric 408e428 Solid 203.9 18.2 [58]
13.2 TNIO Manometric 440e468 Liquid 166.4 15.2 [58]
14.1 b-1, 3, 5, 7-Tetranitro-1, 3, 5, 7-tetrazocane b-HMX Manometric 544e587 Solid 220.5 19.5 [54]
14.2 b-HMX DSC 544e558 Solid 214.6 18.8 [59]
14.3 b-HMX MS 534e549 Solid 209.0 17.8 [60]
Data No. Chemical name Code designation Arrhenius parameters
Method of evaluation Temp. region/K State of decomp. Ea log A Ref.

15.1 cis-1,3,4,6-Tetranitrooctahydro-imidazo-[4,5-d]imidazole BCHMX Manometric 453e473 Solid 210.2 18.0 [58]

16.1 trans-1,4,5,8-Tetranitrodecahydro-pyrazino[2,3-b]pyrazine TNAD DSC 477e507 Solid 210.0 18.9 [61]
17.1 1,3,5,7,9-Pentanitro-1,3,5,7,9-pentaazacyclodecane DECAGENa 15
N NMR 520b Solid 213.5 18.6 [15]
18.1 4,10-Dinitro-2,6,8,12-tetraoxa-4,10-diazaisowurtzitane TEX Manometric 483e498 Solid 196.8 15.4 [62]
19.1 4,8,10,12-Tetranitro-2,6-dioxa-4,8,10,12-tetraazaisowurtzitane a
Aurora 5 Manometric 463e483 Solid 188.4 16.7 [65]
19.2 b
Aurora 5 Manometric 423e463 Solid 188.8 16.8 [65]
20.1 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane ε
HNIW TGA 433e453 Solid 172.0 13.8 [63]
20.2 ε
HNIW DSC 483e533 Solid 176.0 15.1 [64]
20.3 ε
HNIW Manometric 443e473 Solid 216.9 19.8 [65]
20.4 ε
HNIW Iso-TGA 446e484 Solid 223.4 20.5 [66]
20.5 g
HNIW Iso-TGA 445e467 Solid 196.0 17.7 [67]
21.1 1,4-Dinitrotetrahydroimidazo[4,5-d]imidazole-2,5-(1H,3H)-dione DINGU Manometric 458e473 Solid 203.0 18.5 [58]
22.1 1-(Methylnitramino)-2,4,6-trinitrobenzene TETRYL Manometric 403e438 Liquid 156.9 14.5 [68]
a
a substance which has not yet been synthesised.
b
the estimated values.
54 S. Zeman et al. / Defence Technology 15 (2019) 51e57

Table 2
A survey of the molecular mass, M, crystal densities, d, effective volume, Veff, crystal volume, V(0.003) and free space per molecule, DV.

Compound Molecular weight M/  10
24/g Crystal density/(g.cm
3) Veff/(Å3) V(0.003)/(Å3) DV/(Å3)

No. Codedesignation

1 DMNA 90.1 149.67 1.36 110.0 81.72 28.33

2 EDNA 150.1 249.34 1.71 145.9 119.69 26.21
3 OCPX 164.1 272.59 1.50 181.73 135.88 45.85
4 DMEDNA 178.1 295.85 1.45 204.03 153.19 50.84
5 ORDX 238.2 395.68 1.66 238.36 189.56 48.80
6 TETROGEN 148.1 246.01 1.81 135.92 110.67 25.25
7 TNAZ 192.1 319.10 1.86 171.56 139.26 32.30 (37)
8 CPX 162.1 269.27 1.65 163.19 126.03 37.16
9 DNDC 176.1 292.52 1.63 179.46 142.23 37.23
10 RDX 222.1 368.94 1.81 203.83 161.97 41.86 (46)
11 HOMO 236.1 392.19 1.77 221.58 178.06 43.52
12 TNOTZ 252.1 418.77 1.80 232.65 187.42 45.23
13 TNIO 250.1 415.45 1.78a 233.4 178.14 55.26
14 HMX 296.2 492.03 1.91 257.61 214.79 42.82 (49)
15 BCHMX 294.2 488.70 1.92 254.53 206.06 48.47
16 TNAD 322.2 535.22 1.84 290.88 237.96 52.92
17 DECAGEN 370.2 614.95 1.89a 325.37 269.20 56.17
18 TEX 262.2 435.55 1.99 218.87 179.33 39.54
19 AURORA 5 350.2 581.73 2.01 289.42 235.16 54.26
20 ε-HNIW 438.2 727.91 2.04 356.82 290.84 65.98
21 DINGU 232.1 385.55 1.99 193.74 162.34 31.40
22 TETRYL 287.1 476.91 1.73 275.67 210.47 65.20

Note:The DV values listed in parentheses are taken from Ref. [34].

The crystal density values for Decagen and TNIO were calculated.

crystal lattice free volume values, DV, of the nitramines studied are
reproduced in Fig. 1. Due to molecular-structural similarity and the
various states of thermal decomposition (solid or liquid state, pre-
melting or dissolution in products, etc.), the relationship obtained is
not unambiguous (this is also the case for impact and friction
sensitivities [41,42]). Nitramines in Fig. 1 appear as if divided into
two groups, one derived from dimethyl nitramine (DMNA) and one
related to 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-
hexaazaisowurtzitane (HNIW). Fig. 1 is very strongly reminiscent
of a similar relationship between the Ea values and the sum of the
negative and positive extremes of molecular surface electrostatic
potentials, VS,S, of the nitramines studied [2,44], but with this dif-
ference - that the straight lines A and B create in the referenced case
only one line which corresponds there to nitramines, decomposed
in the solid state [2,44]. On the basis of comparing also with results
of paper [21] the straight lines C and D in Fig. 1 associate nitramines
in which it is not entirely clear in what physical state they were
found (micro-regions in their crystals) during the initial phase of
their thermal decomposition (similar to the case in Ref. [21]) and
line E corresponds to crowded molecules decomposed in the liquid
state.
How it is possible that the DV values also correlate with data for

Fig. 1. Molecular-structural analysis of the relationship between activation energies of thermal decomposition, and the crystal lattice free volumes, DV.
 S. Zeman et al. / Defence Technology 15 (2019) 51e57
thermal decomposition in the liquid state? This decomposition can
proceed in the bulk of the crystal, on its surface and/or on defects in
the crystalline lattice. The reaction occurring on defects has the
same activation energy as in the liquid phase (or close to it) [69].
However, decomposition of solid compounds proceeds very often
through the liquid phase, formed as a result of the melting of im-
purities, the decomposition products, or their eutectic mixture with
the original substance [7]. Reaction in the bulk of the crystal re-
quires the formation of a cavity with a volume exceeding the
activation volume, so that the leaving group does not feel the forces
of interatomic attraction [69]. In the second case, the crystal lattice
free volume might play a certain role in decomposition. Already,
interrelations between the DV values and sensitivities to impact
[41] and friction [42] have been reported, where the intermolecular
interactions should play a decisive role in such initiation activities.
In the case of Fig. 1, the crystal lattice free volume might have some
influence on the thermal decomposition of DINGU, RDX and HMX
in the solid state (straight line A); for the other nitramines inter-
molecular interaction should be the dominating factor, similar to
the already mentioned comparison with analogous relationships
between the Ea values and a sum of the negative and positive ex-
tremes of molecular surface electrostatic potentials, VS,S [2,44]. The
warping and subsequent collapse of the crystalline lattice during
melting leads to the removal of the resistance against the formation
of the activated complex in the molecular crystals and thus to a
reduction in the activation energy, but the principal intermolecular
interaction should be preserved.
Concerning the pre-exponent of the Arrhenius equation, a semi-
logarithmic relationship exists with the DV values (Fig. 2) in the
sense that the nitramines under study are divided again into two
basic groups as in the case of Fig. 1: data around the straight lines F,
G and H have a relationship with the HNIW data and those around
the straight lines I, J and K with the DMNA data. The pre-
exponential factor is also known as a frequency factor, and in the
transition state theory is connected with the internal structure, the
rotational and vibrational behaviour of reactants and the activation
complex (if the activated complex has freer rotation than the
reactant, the first-order pre-exponential factor is high [70]). It has
Fig. 2. Semi-logarithmic relationship of the pre-exponent of the Arrhenius equation for thermal decomposition of nitramines, and the crystal lattice free volume, DV.
55
thus a relationship with the degrees of freedom of the given
molecule (mobility of the molecule in the crystal lattice). When
molecular complexity increases, activation entropy is increasingly
more negative and the logA value declines [71]. This means that an
increase in molecular complexity corresponds here to a decrease in
the crystal lattice free volume.
In both Figs. 1 and 2 two different positions are visible for the
HNIW data; points on the intersections of the straight lines B and C
in Fig. 1 and lines F, G, and H in Fig. 2 correspond to measurements
by Russian authors in isothermal conditions (see data 20.3 and 20.4
in Table 1 [65,66]). Data for g-HNIW have been derived using the
same method [67]. The HNIW points on the straight lines E and K
were obtained using the non-isothermal TGA and DSC techniques.
Reasons for these differences have already been discussed in our
recent papers [2,21,41,42,44]: the correlation of the g
HNIW data
with the straight lines C and K clearly shows that this polymorphic
modification substitutes for a liquid phase of HNIW [21]. In the case
of ε-HNIW it might be related to complications in its ε
g poly-
morph transitions [21,44,67,72] (mainly cracking of the HNIW
crystals [21,44]), its level of purity, sublimation during measure-
ment and flaws in the crystal lattice (the difference between
“normal” and “reduced sensitivity” quality of ε-HNIW
[2,21,41e44,73]). In defective crystals (“normal” quality of ε-HNIW)
or crystals with impurities (NATO STANAG-4566 tolerates these up
to 3% by wt.) conditions exist for a decomposition reaction in bulk
to which Arrhenius parameters generally correspond as for thermal
decomposition in the liquid phase [69,74].
3. Conclusion
The relationship between the Arrhenius parameters (Ea and log
A) of the thermal decomposition, and the crystal lattice free space
per molecule, DV, of 22 nitramines is described by linear, directly
proportional equations. These are divided into a number of partial
relationships caused by a significant limitation of the molecular
structural characteristics of such compounds. These partial re-
lationships divide the nitramines into a group of substances
relating to dimethyl nitramine and a sub-group related to
56 S. Zeman et al. / Defence Technology 15 (2019) 51e57
ε
2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane. The
relationship mentioned in the case of the Ea values is very remi-
niscent of a similar relationship between them and the sum of the
negative and positive extremes of molecular surface electrostatic
potentials, VS,S, of the nitramines studied [2,44]. Taking into ac-
count the findings from a study of the relationships of the DV values
to the impact [41] and friction [42] sensitivities, this would tend to
confirm the well-known fact that intermolecular interaction in the
nitramines under study plays a decisive role in the thermal reac-
tivity of these compounds. The crystal lattice free space manifests
itself here perhaps only in the solid state thermal decomposition of
1,3,5-trinitro-1,3,5-triazinane, 1,3,5,7-tetranitro-1,3,5,7-tetrazocane
and 1,4-dinitrotetrahydroimidazo[4,5-d]imidazole-2,5-(1H,3H)-
dione. A directly proportional relationship between the Arrhenius
parameters and the DV values means that an increase in the latter is
related to a rise of thermal stability of the corresponding nitr-
amines. Similarly, as in our recent studies about initiation reactivity
of nitramines [2,21,41e44,73], the ε
modification of 2,4,6,8,10,12-
hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane of the “normal”
quality (impact sensitivity 2e4 J) is an exception which gives the
impression of disorderliness in the distribution of the actions of
force in its crystal lattice (and/or content of impurities in it) in
comparison with its “reduced sensitivity” (RS-ε
HNIW) or pure
analogue variants.
Acknowledgements
The work described in this paper received partial financial
support from the Students Grant Projects No. SGSFCHT_2016002 of
the Faculty of Chemical Technology at the University of Pardubice.
Other financial support came from the Chinese State Administra-
tion of Foreign Experts Affairs, which funded the six month train-
eeship of Dr. LIU Ning in the Institute of Energetic Materials at the
University of Pardubice in 2016.
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