Modifying Nitrate Ester Sensitivity Properties Using Explosive Isomers

Article abstract of DOI:10.1021/acs.cgd.9b01062

Understanding explosive sensitivity is key to the safe handling and development of new explosives. Macro- and microscale studies have concluded that multiple physical and chemical factors affect sensitivity, both intermolecular and intramolecular. Stereoisomers are molecular pairs with the same bond connectivity but differing spatial arrangement of those bonds, and in certain cases can exhibit vastly different chemical and physical properties. Herein we report the synthesis of stereoisomers of erythritol tetranitrate (ETN) and the reported stereoisomers mannitol hexanitrate (MHN) and sorbitol hexanitrate (SHN). Isomers of ETN and MHN had altered physical properties such as melting point, state of matter, and crystal structure. These different physical properties caused changes in the impact sensitivity of the isomers. The melting point of the explosive was determined to be a key factor in the impact sensitivity measurements, altering the physical state of the explosive at room temperature or by potentially facilitating access to the more sensitive liquid state of the explosive.

Full text of DOI:10.1021/acs.cgd.9b01062

Subscriber access provided by UNIV OF DURHAM
Article
Modifying Nitrate Ester Sensitivity Properties using Explosive Isomers
Nicholas Lease, Lisa M. Kay, Geoffrey W. Brown, David E
Chavez, Phil Leonard, David Robbins, and Virginia W. Manner
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.9b01062 • Publication Date (Web): 26 Sep 2019
Downloaded from pubs.acs.org on September 29, 2019
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a service to the research community to expedite the dissemination
of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in
full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully
peer reviewed, but should not be considered the official version of record. They are citable by the
Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,
the “Just Accepted” Web site may not include all articles that will be published in the journal. After
a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web
site and published as an ASAP article. Note that technical editing may introduce minor changes
to the manuscript text and/or graphics which could affect content, and all legal disclaimers and
ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or
consequences arising from the use of information contained in these “Just Accepted” manuscripts.
is published by the American Chemical Society. 1155 Sixteenth Street N.W.,
Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 21
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
Modifying Nitrate Ester Sensitivity Properties using
Explosive Isomers
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Nicholas Lease,[a] Lisa M. Kay,[a] Geoffrey W. Brown,[a] David E. Chavez,[a] Philip W. Leonard,[a]
David Robbins,[b] and Virginia W. Manner*[a]
[a] High Explosives Science & Technology, Los Alamos National Laboratory,
Los Alamos, NM, 87545
[b] Detonation Science & Technology, Los Alamos National Laboratory,
Los Alamos, NM, 87545
Keywords: Explosive, ETN, SHN, MHN, Sensitivity, Impact, Diastereomers, Sorbitol
Hexanitrate, Mannitol Hexanitrate, Erythritol Tetranitrate
Abstract: Understanding explosive handling sensitivity is key to the safe handling and
development of new explosives. Macro and microscale studies have concluded that
multiple physical and chemical factors affect sensitivity, both intermolecular and
intramolecular. Stereoisomers are molecular pairs with the same bond connectivity but
differing spatial arrangement of those bonds, and in certain cases can exhibit vastly
ACS Paragon Plus Environment
1

Crystal Growth & Design
Page 2 of 21
1
2
3
4
5
6
7
8
9
different chemical and physical properties. Herein we report the synthesis of
stereoisomers of erythritol tetranitrate (ETN) and the reported stereoisomers mannitol
hexanitrate (MHN) and sorbitol hexanitrate (SHN). Isomers of ETN and MHN had
altered physical properties such as melting point, state of matter, and crystal structure.
These different physical properties caused changes in the impact sensitivity of the
isomers. The melting point of the explosive was determined to be a key factor in the
impact sensitivity measurements, altering the physical state of the explosive at room
temperature or by potentially facilitating access to the more sensitive liquid state of the
explosive.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Introduction:
The term “explosive sensitivity” refers to the threshold levels at which an explosive is
expected to react toward destructive stimuli with defined probability. Understanding
this sensitivity is key to the safe handling of explosives, and studies have shown that
various factors can play a role in this property. Energetic functional groups often dictate
classes of sensitivity more than other effects. However, sensitivity can be influenced by
structural effects, such as hydrogen bonding1-6 and crystal structure.7 Other factors that influence
sensitivity include physical effects such as temperature,8 particle size,9,10 bubble collapse,10,11,12
and the physical state of the explosive.13-15 Previously, we have investigated the various factors
that play a role in sensitivity.16 However, changing functional groups in explosive molecules
modifies multiple properties of the materials, which complicates interpretation of results.17 In
ACS Paragon Plus Environment
2

Page 3 of 21
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
order to investigate the importance of the molecular packing environment of explosive
molecules while minimizing changes to chemical properties, we have been
investigating stereoisomers of common nitrate ester explosives.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Stereoisomers refer to isomeric molecules which have the same chemical formulas and bond
constitution but have differing spatial geometry, resulting in variations in steric effects and
crystal structure. Stereoisomers include enantiomers and diastereomers, and can have differential
physical properties despite the molecules being constitutionally identical. Specifically,
enantiomeric molecules are mirror images of each other, and contain chiral centers that are non-
superimposable. Enantiomers can have very similar physical properties to one another but can
differ from their racemic mixture (50:50 mixture of enantiomers). Diastereomers contain
multiple non-superimposable chiral centers, and typically exhibit significantly different chemical
and physical properties from one another. In application, stereoisomers sometimes have
drastically different chemical behavior, for example in the field of medicine. Diastereomers and
enantiomeric pairs are known to interact differently in some biological situations, including
binding to proteins, absorption into cells, or having radically different pharmaceutical
characteristics.18-23 In the field of explosives, isomers have been characterized in numerous
unrelated studies, generally as constitutional isomers with differing bond connectivity.24-27
Baran and Sabatini recently reported the first systematic study on explosive nitrate ester
stereoisomers, demonstrating the effects of stereochemistry on physical and explosive properties
of strained cyclobutane molecules.28 With the large amount of research on the importance of
isomer effects in biological and chemical applications, and the growing number of isomers that
have been characterized in the field of explosive chemistry, it is surprising that there are so few
reports investigating the differences in handling sensitivity between explosive isomers.
ACS Paragon Plus Environment
3

Crystal Growth & Design
Page 4 of 21
1
2
3
4
5
6
7
8
9
Nitrate esters are a common class of explosive molecules that are well-known for their
straightforward synthesis procedures from the corresponding sugar molecules. Common nitrate
ester explosives include pentaerythritol tetranitrate (PETN), erythritol tetranitrate (ETN) and
mannitol hexanitrate (MHN), which have recently received attention in the literature due to their
potential use as homemade explosives.29,30,31 For example, recent reports have studied possible
factors that can affect ETN stability, including particle size32 and physical state.33 However,
diastereomers of ETN have not been synthesized or investigated. Herein we report the first
syntheses of ETN diastereomers, L-ETN and D-ETN, as well as sensitivity characterization on
the reported diastereomers, MHN and SHN (sorbitol hexanitrate), in order to investigate the
differences in sensitivity between these conformational isomers. This is the first study to
investigate a series of explosive diastereomers in order to determine how differences in crystal
structure and physical properties such as melting point influence handling sensitivity properties.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Experimental:
Materials and Methods: Acetic acid, acetic anhydride, nitric acid (70%) and sulfuric
acid (fuming) were purchased from Sigma Aldrich and Amresco and were used as received.
L-Threitol, D-Threitol, mannitol and sorbitol were purchased from Sigma Aldrich and used as
received. Deuterated solvents (acetonitrile d3, chloroform d) were purchased from Acros
1
chemical and used as received. H-NMR and 31C-NMR were recorded on a 400-MHz Bruker
spectrometer. NMR signals were referenced using residual solvent signals. Mannitol hexanitrate
and sorbitol hexanitrate were prepared according to literature procedures.29,30 Samples were
prepared on a 2 gram scale.
ACS Paragon Plus Environment
4

Page 5 of 21
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
Synthesis of Materials: Caution: Erythritol tetranitrate isomers, mannitol hexanitrate and
sorbitol hexanitrate are very sensitive explosives and should only be handled in approved
explosives facilities.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
L-ETN Synthesis: Acetic Acid (17.2 mL) and acetic anhydride (17.2 mL) were added
to a 100 mL round bottom flask and the solution was cooled to 0°C. Fuming nitric acid
(8.8 mL) was added dropwise to the cooled solution. Upon full addition, the solution
stirred at 0°C for one hour. L-threitol (2.0 g, 16.3 mmol) was then added slowly to the
stirring solution. Upon complete addition of L-threitol the solution stirred at 0°C for 2
hours. Next the solution was warmed to room temperature and stirred for an additional
2 hours. The solution was then poured into ice water upon which an oil became visible.
This water solution was extracted with dichloromethane (3x). The combined organic
layer is then washed with water, an aqueous sodium bicarbonate solution (5x) and
water again (2x). The organic layer was then dried on magnesium sulfate and the
1
solvent was removed leaving a colorless oil. Yield: 3.4 g (69%). H-NMR (400 MHz,
CDCl3) δ 4.67 (dd, J = 5.58, 13.38 Hz, 2H, CH), 4.91 (dd, J = 3.3, 13.2 Hz, 2H, CH), 5.58 (h,
J = 3.8 Hz, 2H, CH). 13C-NMR (100 MHz, CDCl3) δ 67.8, 74.6.
D-ETN Synthesis: Acetic Acid (17.2 mL) and acetic anhydride (17.2 mL) were added
to a 100 mL round bottom flask. The solution was cooled to 0°C. Fuming nitric acid (8.8
mL) was added dropwise to the cooled solution. Upon full addition the solution stirred
at 0°C for one hour. D-threitol (2.0 g, 16.3 mmol) was then added slowly to the stirring
ACS Paragon Plus Environment
5

Crystal Growth & Design
Page 6 of 21
1
2
3
4
5
6
7
8
9
solution. Upon complete addition of D-threitol the solution stirred at 0°C for 2 hours.
Next the solution was warmed to room temperature and stirred for an additional 2
hours. The solution was then poured into ice water upon which an oil became visible.
This water solution was extracted with dichloromethane (3x). The combined organic
layer is then washed with water, an aqueous sodium bicarbonate solution (5x) and
water again (2x). The organic layer was then dried on magnesium sulfate and the
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
solvent was removed leaving a colorless oil. Yield: 3.4 g (69%). H-NMR (400 MHz,
CDCl3) δ 4.67 (dd, J = 5.58, 13.38 Hz, 2H, CH), 4.91 (dd, J = 3.3, 13.2 Hz, 2H, CH), 5.58 (h,
J = 3.8 Hz, 2H, CH). 13C-NMR (100 MHz, CDCl3) δ 67.8, 74.6.
50:50 Mixture of L-ETN and D-ETN: Acetic Acid (17.2 mL) and acetic anhydride (17.2
mL) were added to a 100 mL round bottom flask. The solution was cooled to 0°C.
Fuming nitric acid (8.8 mL) was added dropwise to the cooled solution. Upon full
addition the solution stirred at 0°C for one hour. D-threitol (1.0 g, 8.15 mmol) and L-
threitol (1.0 g, 8.15 mmol) were then added slowly to the stirring solution. Upon
complete addition of D-threitol the solution stirred at 0°C for 2 hours. Next the solution
was warmed to room temperature and stirred for an additional 2 hours. The solution
was then poured into ice water upon which an oil became visible. This water solution
was extracted with dichloromethane (3x). The combined organic layer is then washed
with water, an aqueous sodium bicarbonate solution (5x) and water again (2x). The
organic layer was then dried on magnesium sulfate and the solvent was removed leaving a
ACS Paragon Plus Environment
6

Page 7 of 21
Crystal Growth & Design
1
2
3
4
1
colorless oil. Yield: 3.4 g (69%). H-NMR (400 MHz, CDCl3) δ 4.67 (dd, J = 5.58, 13.38 Hz,
5
6
13
2H, CH), 4.91 (dd, J = 3.3, 13.2 Hz, 2H, CH), 5.58 (h, J = 3.8 Hz, 2H, CH). C-NMR (100
7
8
9
MHz, CDCl3) δ 67.8, 74.6.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Impact Testing: Impact testing was performed using ERL Type 12 drop hammer equipment
using a 2.5 kilogram weight, a 0.8 kilogram striker, and sound detection equipment. For each
run, 40 mg of material was used either with grit paper or directly on the smooth (bare) anvil and
was impacted using the drop weight from various heights. A Go was defined as a 120 average
decibel level from two sound detectors. The parameter reported is the DH50, which is defined as
the height from which 50% of the drops are expected to be Go’s. The DH50 values were
calculated using the Neyer D-Optimal method. The DH50 value is collected in cm (shown in the
Supporting Information) and converted to Joules. Higher DH50 values corresponds to lower
sensitivity to initiation.
For solid samples the striker was placed gently on top of the sample. For liquid samples, a ~1
mm gap was imposed between the striker and the anvil (the striker was held loosely in place with
magnets) to prevent dispersion of the liquid between the anvil and striker. In this configuration,
the top surface of the liquid was in contact with the striker. Impact testing at elevated
temperatures was performed using a hollow aluminum collar around the anvil that was heated
and cooled using ethylene glycol in a circulating bath. Temperatures of the anvil were confirmed
using a thermocouple attached to the center of the anvil before drops were conducted. Strikers
were heated in a furnace to the appropriate temperature prior to use. During the molten ETN test
some bubbles were observed during the melting process and unable to be removed. No bubbles
were observed with L-, D-ETN or SHN. One striker was used per test before returning to the
ACS Paragon Plus Environment
7

Crystal Growth & Design
Page 8 of 21
1
2
3
4
5
6
oven to ensure the temperature of the striker remained within the range of the impact test
temperature.
7
8
9
Samples of L-ETN and SHN were analyzed by NMR spectroscopy after heating to the
temperature of the impact tests, and no decomposition or changes were observed.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Thermal Testing: Thermal testing was carried out with a TA Instruments Q2000
differential scanning calorimeter with attached cooling accessory. Samples were held in
crimped aluminum pans and run at 10 C per minute with ultrapure nitrogen flowing
through the cell. The instrument was calibrated with sapphire and indium.
Results and Discussion
ETN and its diastereomers, L-ETN and D-ETN, are shown in Scheme 1. It is
important to note that ETN is a diastereomer to both L-ETN and D-ETN (and therefore
should exhibit significant differences in properties to L- and D-ETN). However, L-ETN
and D-ETN are enantiomers to each other and should display almost identical
properties. L-erythritol tetranitrate (L-ETN) and D-erythritol tetranitrate (D-ETN) were
prepared using a mixed acid synthesis: the precursor, L-threitol or D-threitol, was
mixed with nitric and acetic acid in the presence of acetic anhydride. Though ETN is
isolated as a white powder, both L-ETN and D-ETN were obtained as clear oils. NMR
spectroscopy of L-ETN and D-ETN showed signals identical to each other, and slightly
ACS Paragon Plus Environment
8

Page 9 of 21
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
shifted compared to ETN in both the proton and carbon spectra (see Supporting
Information). Attempts to crystallize both L-ETN and D-ETN at temperatures down to -
80 C were unsuccessful.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ONO2
ONO2
ONO2
O2NO
O2NO
O2NO
ONO2
ONO2
ONO2
ONO2
ONO2
ONO2
ETN
L-ETN
D-ETN
Scheme 1. Erythritol tetranitrate (ETN), L-erythritol tetranitrate (L-ETN) and D-
erythritol tetranitrate (D-ETN). L-ETN and D-ETN are enantiomers (mirror images) of
each other, but both are diastereomers to ETN.
Thermal studies of L- and D-ETN with differential scanning calorimetry (DSC)
showed similar onset decomposition temperatures, 154.3°C and 154.7°C respectively
(ETN decomposition temperature, 163.4°C). Because these materials could not be
crystallized, no melting point was observed. There was evidence of a glass transition
near -50°C for both materials.
Impact tests are a key tool used to screen for explosive handling sensitivity, though it
is important to test under standardized conditions in order to obtain consistent results.
Recently we have reported impact tests of ETN in its molten state, indicating that ETN is more
sensitive as a liquid than when in its powder form.33 Impact testing at elevated temperatures to
study molten ETN was carried out using a hollow aluminum collar surrounding the anvil used
for sensitivity measurements. The collar was plumbed to a liquid thermal controller for heating
ACS Paragon Plus Environment
9

Crystal Growth & Design
Page 10 of 21
1
2
3
4
5
6
7
8
9
and cooling. ETN was heated to 65°C on the bare anvil until fully liquid, and impact tests were
performed, giving a DH50 value of 0.24 ± 0.15 J. In contrast, the DH50 value for solid ETN is 3.6
± 0.83 J (Table 1). Chemical analysis of the ETN showed no difference between starting material
and material that had been heated to 65°C and re-solidified. We concluded that the difference in
sensitivity between solid and molten ETN were not chemical effects but most likely due to the
change in phase.15,33
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Because L-ETN and D-ETN are both oils, impact testing was performed on a bare anvil
instead of the standardized method with grit paper typically used with solid materials. Impact
tests were performed at room temperature, resulting in DH50 values of 0.74 ± 0.05 J for L-ETN
and 0.74 ± 0.10 J for D-ETN, a marked increase in sensitivity when compared to ETN powder on
a bare anvil at room temperature (Table 1). The results are closer to what was observed with
molten ETN at 65°C, with the molten ETN being slightly more sensitive. The differences
observed between solid ETN versus L-ETN, D-ETN, and molten ETN at room temperature are
not unexpected. Studies have shown that liquid explosives tend to be more sensitive than solids
due to hot spots created by bubble collapse, and potentially due to increases in density or shear
forces in the liquids.11,12 To control for the effects of elevated temperature, impact sensitivity
testing was also performed on L-ETN at 65°C, giving DH50 values of 0.56 ± 0.29 – 1.2 ± 0.07 J,
which are within error of what was observed for molten ETN. These results have led us to
conclude that the difference in impact sensitivity between ETN and the liquid ETN isomers (L-
ETN and D-ETN) is likely due to physical effects exhibited by the liquid explosives.
Friction sensitivity was measured for both ETN and L-ETN, giving 38.1 ± 12.0 N for ETN and
> 360 N for L-ETN. The large observed differences are not surprising, given that friction
measurements on liquid samples typically exhibit lower sensitivities compared to solid
ACS Paragon Plus Environment
10

Page 11 of 21
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
samples.34 A direct comparison between molten ETN and L-ETN could not be performed, as
we currently do not have a reliable method to heat a sample of ETN on the friction
apparatus.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Table 1. Drop-weight impact test results for ETN, L-ETN, D-ETN, D/L-ETN
Material
Impact DH50
Impact DH50
(J),a bare, RT b bare, temp control b
Impact DH50 (J),a
Friction DH50 (N)
DSC (°C) melt
/ decomp onset
(conditions) (J),a grit, RT
ETN
1.3 ± 0.24 s
3.6 ± 0.83 s
2.9 ± 0.07 s
(65°Ccool)
4.4 ± 1.0 (55°C) s
4.9 ± 0.98 (55°C) s
38.1 ± 12.0 s
62.5 / 163.4
0.24 ± 0.15 (65°C) l
0.24 ± N/A (65°C) l
L-ETN
0.74 ± 0.05 l
0.56 ± 0.29 (65°C) l ˃360 l
No melt /
154.28
0.74 ± 0.05 l
0.74 ± 0.10 l
1.2 ± 0.07 (65°C) l
D-ETN
D/L-ETN
PETN
No melt /
154.75
0.56 ± 0.24 l
5.0 ± 1.05 s
No melt /
158.22
2.5 ± 0.22 s
6.1 ± 0.54 (55°C) s
6.7 ± 1.27 (65°C) s
63.1 ± 10.8 s
141.4 / 165.4
a
b
Impact heights are given in cm in the Supporting Information.
In some cases, repeat
measurements were performed with multiple samples and/or different anvils (see Supporting
Information).
Direct comparison of L-ETN or D-ETN to solid ETN was not possible, since these
materials do not crystalize even at low temperatures. In another attempt to crystalize the product,
a sample of 50:50 L-ETN and D-ETN was prepared (D/L-ETN). NMR spectroscopy of the
sample was identical to the pure diastereomers. The isolated product was an oil, as observed with
L-ETN and D-ETN. All attempts to crystalize the product were also unsuccessful and it showed
ACS Paragon Plus Environment
11

Crystal Growth & Design
Page 12 of 21
1
2
3
4
5
6
the same glass transition near -50°C. Impact tests of the mixture were performed at room
temperature, resulting in a DH50 value of 0.56 ± 0.24 J.
7
8
9
Due to the difference in explosive sensitivity of ETN and its diastereomers, we chose to
look at another pair of explosive diastereomers, MHN and SHN (Scheme 2). Both MHN and
SHN have been reported in the literature, and are both solids at room temperature.29,30 These
complexes were synthesized following literature reports and obtained as white solids. MHN was
isolated as a stable white powder with no decomposition observed over weeks. SHN was isolated
as a flaky white solid, and was observed to decompose after prolonged time at room temperature.
Upon decomposition the SHN sample turns to a yellow/green oil.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ONO2ONO2
ONO2ONO2
ONO2
ONO2
O2NO
O2NO
ONO2ONO2
MHN
ONO2ONO2
SHN
Scheme 2. Mannitol hexanitrate (MHN) and sorbitol hexanitrate (SHN).
Impact testing of MHN and SHN was conducted using both grit paper and the bare anvil.
Impact data was collected using grit paper at room temperature, giving DH50 values of 2.0 ± 0.17
– 2.2 ± 0.24 J and 0.49 ± 0.12 – 0.64 ± 0.15 J, respectively (Table 2). This significant difference
(~1.6 J) in impact sensitivity between MHN and SHN was not expected after the small
differences observed between molten ETN and its diastereomers (L-ETN and D-ETN). Impact
tests were also performed on MHN and SHN using a bare anvil, with DH50 values of 3.6 ± 0.59
and 3.1 ± 0.47 J, respectively. Though SHN was more sensitive than MHN on the bare anvil,
only a 0.5 J difference was observed in this case. It is important to note that morphology
differences were not controlled for in these impact tests. However, in previous studies with ETN
impact tests, changes in morphology did not influence sensitivity properties.32 The observed
ACS Paragon Plus Environment
12

Page 13 of 21
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
impact sensitivities of these nitrate esters (SHN, MHN, ETN, L/D-ETN) are not unexpected, as
they are very similar to other sensitive nitrate ester explosives such as nitroglycerin, butanetriol
trinitrate, and trimethylolethane trinitrate (TMETN).7,35,36 The highly electrophilic nature of the
molecules and the reactivity of the O–N bond in secondary nitrate esters when in close proximity
to each other can be expected to result in more reactive (and sometimes less stable)
energetics.37,38
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
MHN and SHN exhibited similar friction sensitivities, at 37 – 38 N (Table 2). Notably, these
values are also similar to ETN (Table 1). All three materials have high friction sensitivities
compared with PETN (63.1 ± 10.8, Table 2), as might be predicted based on the high
impact sensitivities. The friction values obtained for MHN, ETN, and SHN do not follow the
same general trend as observed with impact, but we and others have found that friction
sensitivity does not always correlate with impact sensitivity or molecular structure.39
Table 2. Drop-weight impact test results for MHN and SHN.
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Material
(conditions)
Impact DH50
(J),a grit, RT b
Impact DH50 (J), a Impact DH50 (J), a
bare, RT
Friction DH50 (N), DSC (°C) melt /
decomp onset
bare, temp control b
MHN
SHN
2.2 ± 0.24 s
2.0 ± 0.17 s
3.6 ± 0.59 s
38.1 ± 12.0 s
36.9 ± 19.7 s
63.1 ± 10.8 s
110.7 / 143.7
55.5 / 145.2
141.4 / 165.4
0.64 ± 0.15 s
0.49 ± 0.12 s
3.1 ± 0.47 s
5.0 ± 1.0 s
0.37 ± 0.24 (59°C) l
PETN
2.50 ± 0.22 s
6.1 ± 0.54 (55°C) s
6.7 ± 1.27 (65°C) s
ACS Paragon Plus Environment
13

Crystal Growth & Design
Page 14 of 21
1
2
3
4
a
b
Impact heights are given in cm in the Supporting Information.
In some cases, repeat
5
6
7
8
measurements were performed with multiple samples or different anvils (see Supporting
Information).
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Crystal structures have recently been published for MHN30 and SHN,29 and we have
examined these in order to determine if differences in crystal structure would correlate with the
sensitivity of the materials. Table 3 gives a summary of crystal structure properties of MHN and
SHN relative to ETN.7,32 The crystal structures for SHN and MHN are superficially similar to
each other as well as ETN, with similar nitro group angles and nitro-nitro intermolecular
interactions, as described previously29,30,32 and summarized in Table 3. Though MHN has a
slightly higher measured density than SHN, the density and crystallographic data were collected
at lower temperature. MHN and ETN have similar intermolecular O---N distances, but SHN
distances are slightly longer, which may could possibly correlate with less steric hindrance
between molecules. Qualitatively, crystal structure differences between MHN and SHN are fairly
subtle. Both structures have similar amounts of visual steric hindrance when viewed along the a,
b, and c axes (Figure 1). If anything, SHN exhibits slightly less steric hindrance (in the b axis)
than MHN, suggesting SHN should be less sensitive,40,41 which is the opposite of the observed
impact data results.
Table 3. Intermolecular contacts, bonds and angles, and other crystallographic information
for MHN,30 SHN,29 and ETN.32
Bonds and Angles
O---O (Å) a
MHN
2.810, 2.835
SHN
2.864, 2.878
ETN
2.772, 2.884
O---N (Å) a
2.898, 2.979
3.006, 3.089
2.804, 2.875
ACS Paragon Plus Environment
14

Page 15 of 21
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
C–C–C (°)
C–O–N (°)
O–C–C (°)
Oterm–N–Oterm
113.3(2)-114.4(2)
111.03(13)–116.31(13)
113.22(14)–115.86(16)
103.42(12)–112.02(14)
130.1(2)-131.1(2)
114.10(12)−114.16(12)
113.04(9)−114.54(8)
102.37(11)−104.38(9)
129.30(11)−130.35(11)
112.6(2)-115.7(2)
102.6(2)-112.2(2)
129.9(2)-131.6(2)
110.7(2)-118.5(2)
Obridge–N–Oterm
111.4(2)-118.3(2)
111.33(9)−118.59(9)
ρcalc (g cm−3) [temp (K)]
1.894 [100]
1.868 [298]
1.851 [140]; 1.773 [298]
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Crystal System / Space
Group
Orthorhombic / P212121
Monoclinic / P21
Monoclinic / P21/c
a Two shortest intermolecular contacts are shown.
Figure 1. Crystal structures for MHN30 and SHN,29 as viewed along the a, b, and c axes.
In order to examine why the increase in sensitivity of SHN relative to MHN was
observed, especially in the presence of grit paper, further testing was performed. Several groups
have investigated thermal decomposition properties of nitrate esters like MHN and SHN.42,43,44
Differential scanning calorimetry of MHN and SHN showed similar decomposition temperature
onsets of 143.7°C and 145.2°C respectively. However the DSC data did show a significant
difference in the melting point of MHN versus SHN: 110.7°C and 55.5°C, respectively. During
ACS Paragon Plus Environment
15

Crystal Growth & Design
Page 16 of 21
1
2
3
4
5
6
7
8
9
impact testing in the presence of sandpaper, grit-on-grit interactions are expected to facilitate
localized frictional heating of the explosive sample.10,15 Due to the substantially lower melting
point of SHN relative to MHN, it is possible that localized areas of the SHN sample could melt
in the presence of frictional heating on the timescale of the impact testing. Impact tests of
molten SHN were conducted to determine if liquid phase SHN on a bare anvil had comparable
impact sensitivities to SHN on grit paper at room temperature. SHN was heated to 59°C on a
bare anvil using a heated aluminum collar. The sample was allowed to equilibrate to the
temperature of the anvil for 5 minutes and no bubbles were observed when the SHN sample
melted. The impact sensitivity for molten SHN is 0.37 ± 0.24 J, similar to the impact sensitivity
of SHN at room temperature conducted with grit paper (Table 2). The role of the grit paper in
the increased sensitivity of SHN could potentially be attributed to the facilitation of SHN from
the solid phase to the liquid phase through frictional heating. However, it is possible that SHN
could melt during impact testing in the absence of grit as well, so further experiments are needed
to determine the differences in ignition mechanisms on grit vs. bare anvils. Once SHN is in the
liquid phase, it could have increased sensitivity relative to the solid due to the potential for
multiple mechanisms of initiation, including sheer forces, viscous flow,10 and adiabatic gas
bubble compression45,46 in the explosive.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Conclusions
Herein we have reported the synthesis of stereoisomers of known explosives ETN and MHN.
While constitutionally identical, these stereoisomers show differences in crystal structure and
physical properties (physical state and melting point). ETN diastereomers (D- and L-ETN) are
liquids at room temperature, exhibiting only a transition to an amorphous solid at lower
ACS Paragon Plus Environment
16

Page 17 of 21
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
temperatures. Impact testing of the room temperature liquids revealed higher sensitivities than
standard solid ETN at room temperature, and similar impact sensitivities to molten ETN. Though
SHN is a solid at room temperature like its isomer MHN, it exhibits a significantly reduced
melting point relative to MHN. SHN was more sensitive than MHN especially in the presence of
grit paper, indicating that the lower melting point could potentially allow it to access the liquid
state on the timescale of the impact test. Energetic reaction of liquid SHN could then depend on
multiple phenomena that combine to provide enough heat for ignition somewhere in the sample,
such as shear forces and bubble collapse. This study emphasizes the importance of melting point
as it can affect the physical state of the explosive, solid or liquid, at room temperature during
measurements and explosive operations. Manipulating melting points in isomeric materials may
be a way of accessing more/less sensitive handling sensitivity.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Supporting Information
For additional reference materials including NMR spectra, impact and friction sensitivity data,
and thermal data please refer to the supporting material.
Acknowledgements
This work was supported by the US Department of Energy through the Los Alamos
National Laboratory. Los Alamos National Laboratory is operated by Triad National
Security, LLC, for the National Nuclear Security Administration of U.S. Department of
Energy (Contract No. 89233218CNA000001). The authors would like to acknowledge
ACS Paragon Plus Environment
17

Crystal Growth & Design
Page 18 of 21
1
2
3
4
5
6
7
8
9
Matt Holmes for helpful discussions, and Jacqueline M. Veauthier, Brent A. Faulkner,
Thuy-Ai D. Nguyen, and Robert J. Houlton for use of the aluminium collar for
temperature-controlled impact measurements, supported by the Laboratory Directed
Research and Development program of Los Alamos National Laboratory under
20180369ER. LA-UR-19-27150
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
References
1
2
(a) Cady, H.H.; Larson, A.C. The Crystal Structure of 1,3,5-Triamino-2,4,6-Trinitrobenzene. Acta Crystallogr.
1965, 18, 485–496. (b) Kolb, J.R.; Rizzo, H.F. Growth of 1,3,5-Triamino-2,4,6-Trinitrobenzene (TATB) I.
Anisotropic Thermal Expansion. Propellants, Explos. Pyrotech., 1979, 4, 10–16.
(a) Ma, Y.; Zhang, A.; Zhang, C.; Jiang, D.; Zhu, Y.; Zhang, C. Crystal Packing of Low-Sensitivity and High-Energy
Explosives. Cryst. Growth Des., 2014, 14, 4703–4713. (b) Bennion, J.C.; McBain, A.; Son S.F.; Matzger, A.J.
Design and Synthesis of a Series of Nitrogen-Rich Energetic Cocrystals of 5,5'-Dinitro-2H,2H'-3,3'-bi-1,2,4-
Triazole (DNBT). Cryst. Growth Des. 2015, 15, 2545–2549.
3
4
Zhurova, E.A.; Stash, A.I.; Tsirelson, V.G.; Zhurov, V.V.; Bartashevich, E.V.; Potemkin, V.A.; Pinkerton, A.A.
Atoms-in-Molecules Study of Intra- and Intermolecular Bonding in the Pentaerythritol Tetranitrate Crystal. J.
Am. Chem. Soc., 2006, 128, 14728–14734.
(a) Rice, B.M.; Larentzos, J.P.; Byrd, E.F.C.; Weingarten, N.S. Parameterizing Complex Reactive Force Fields
Using Multiple Objective Evolutionary Strategies (MOES): Part 2: Transferability of ReaxFF Models to C-H-N-O
Energetic Materials. J. Chem. Theory Comput. 2015, 11, 392–405. (b) Yau, A.D.; Byrd, E.F.C.; Rice, B.M. An
Investigation of KS-DFT Electron Densities used in Atoms-in-Molecules Studies of Energetic Molecules. J.
Phys.Chem. A, 2009, 113, 6166–6171.
5
6
Chellappa, R.S.; Dattelbaum, D.M.; Coe, J.D.; Velisavljevic, N.; Stevens, L.L.; Liu, Z. Intermolecular Stabilization
of 3,3'-Diamino-4,4'-Azoxyfurazan (DAAF) Compressed to 20 GPa. J. Phys. Chem. A, 2014, 118, 5969–5982.
(a) Dippold, A.A.; Klapӧtke, T.M. A Study of Dinitro-bis-1,2,4-Triazole-1,1'-diol and Derivatives: Design of High-
Performance Insensitive Energetic Materials by the Introduction of N-Oxides. J. Am. Chem. Soc., 2013, 135,
9931–9938. (b) Evers, J.; Gobel, M.; Krumm, B.; Martin, F.; Medvedyev, S.; Oehlinger, G.; Steemann, F.X.;
Troyan, I.; Klapӧtke, T.M.; Eremets, M.I. Molecular Structure of Hydrazoic Acid with Hydroen-Bonded
Tetramers in Nearly Planar Layers. J. Am. Chem. Soc., 2011, 133, 12100–12105. (c) Klapӧtke, T.M. Sabate,
C.M. Bistetrazoles: Nitrogen-Rich, High-Performing, Insensitive Energetic Compounds. Chem.Mater. 2008, 20,
3629–3637.
7
8
Manner, V.W.; Cawkwell, M.J.; Kober, E.M.; Myers, T.W.; Brown, G.W.; Tian, H.; Snyder, C.J.; Perriot, R.;
Preston, D.N. Examining the Chemical and Structural Properties that Influence the Sensitivity of Energetic
Nitrate Esters. Chemical Science. 2018, 9, 3649 – 3663.
Rae, P.J.; Baca, E.V.; Cartelli, A.R.; Holmes, M.D.; Kuiper, T.A. The Increased Shock Sensitivity of PBX 9502 at
High Temperature. Journal of Physics: Conference Series 500, 2014, 052036.
ACS Paragon Plus Environment
18

Page 19 of 21
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
Matyas, R.; Pachman, J. Primary Explsoives.; Springer; London, 2013.
10 Balzer, J.E.; Field, J.E.; Gifford, M.J.; Proud, W.G.; Walley, S.M. High-Speed Photographic Study of the Drop-
Weight Impact Response of Ultrafine and Conventional PETN and RDX. Combustion and Flame, 2002, 130,
298–306.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
11 Bourne, N.K.; Field, J.E. Bubble Collapse and the Initiation of Explosion. Proc. R. Soc. Lond. A, 1991, 435, 423–
435.
12 Field, J.E.; Swallowe, G.M.; Heavens, S.N. Ignition Mechanisms of Explosives During Mechanical Deformation.
Proc. R. Soc. Lond. A, 1982, 382, 231–244.
13 Preston, D. N.; Brown, G. W.; Tappan, B. C.; Oschwald, D.; Schoonover, M. “Drop weight impact
measurements of HE sensitivity: modified detection methods,” J. Phys.: Conf. Ser. 2014, 500, 182033.
14 Denisaev, A.A.; Korsunskii, B.L.; Pepekin, V.I.; Matyushin, Y.N. Impact Sensitivity of Liquid Explosives.
Combust. Explos. Shock Waves, 2010, 46, 74–80.
15 Bowden, F.P.; Yoffe, A.D. Initiation and Growth of Explosion in Liquids and Solids, The University Press,
Cambridge, ch. 3, 1952.
16 Manner, V.W.; Myers, T.W.; Cawkwell, M.J.; Kober, E.M.; Brown, G.W.; Tian, H.; Snyder, C.J.; Preston, D.N.
Understanding and Manipulating the Sensitivity of Nitrate Ester Explosives. AIP Conference Proceedings 1979,
2018, p. 150027.
17 Manner, V. W.; Cawkwell, M. J.; Brown, G. W.; Yeager, J. D.; Kay, L.; Shorty, M.; Leonard, P.; Tappan, B. C.;
Veauthier, J. M. “Examining the Effects of Crystal Structure and Bonding on Explosive Impact Sensitivity,” In
Proceedings of the 16th International Detonation Symposium; Cambridge, MD, 2018; in press.
18 Katzung, B.G.; Masters, S.B.; Trever, A.J. Basic and Clinical Pharmacology. 11th ed; Tata Mcgraw- Hill: Noida,
UP, India, 2009.
19 L.L. Brunton, K.L. Parker, D.K. Blumenthal, and I.L.O. Buxton, Goodman and Gilman's Manual of Pharmacology
and Therapeutics. 12th ed. New York: The Mac Graw Hill Company; 2011.
20 Baltes, E.; Coupez, R.; Giezek, H.; Voss, G.; Meyerhoff, C.; Strolin-Benedetti, M. Absorption and Disposition of
Levocetirizine, the Eutomer of Cetirizine, Administered Alone or as Cetirizine to Healthy Volunteers. Fundam.
Clin. Pharmacol. 2001, 15, 269–277.
21 Cheng, H.; Rogers, J.D.; Demetriades, J.L.; Holand, S.D.; Seibold, J.R.; Deputy, E. Pharmacokinetics and
Bioinversion of Ibuprofen Enantiomers in Humans. Pharma Res. 1994, 11, 824–830.
22 Murphy, P.J.; Nickander, R.C.; Bellamy, G.M.; Kurtz., W.L. Effect of 1-Propoxyphene on Plasma Levels and
Analgesic Activity of D-Propoxyphene in the Rat. J Pharmacol Exp Ther. 1976, 199, 415–422.
23 Vargesson, N. Thalidomide-Induced Teratogenesis: History and Mechanisms. Birth Defects Res C Embryo
Today. 2015. 105, 140-156
24 Klapötke., T.M.; Stierstorfer, J. Azidoformamidinium and 5-Aminotetrazolium Dinitramide-Two Highly
Energetic Isomers with a Balanced Oxygen Content. Dalton Trans., 2009, 643–653.
25 Shlomovich, A.; Pechersky, T.; Cohen, A.; Yan, Q.L.; Kosa, M.; Petrutik, N.;Tal, N.; Aizikovich, A.; Gozin, M.
Energetic Isomers of 1,2,4,5-Tetrazine-Bis-1,2,4-Triazoles with Low Toxicity. Dalton Trans., 2017, 46, 5994–
6002.
26 Ling, Y.; Ren, X.; Lai, W.; Luo, J. 4,4,8,8-Tetranitroadamantane-2,6-diyl Dinitrate: A High-Density Energetic
Material. Eur. J. Org. Chem. 2015, 1541–1547.
27 Zhai, L.; Fugiang, B.; Luo, Y.; Wang, N.; Zhang, J.; Wang, B. New Strategy for Enhancing Energetic Properties by
Regulating Trifuroxan Configuration: 3,4-Bis(3-nitrofuroxan-4-yl)furoxan. Scientific Reports. 9, 2019,
Article number: 4321.
ACS Paragon Plus Environment
19

Crystal Growth & Design
Page 20 of 21
1
2
3
4
5
6
7
8
28 Barton, L. M.; Edwards, J. T.; Johnson, E. C.; Bukowski, E. J.; Sausa, R. C.; Byrd, E. F. C.; Orlicki, J. A.; Sabatini, J.
J.; Baran, P. S. "Impact of Stereo- and Regiochemistry on Energetic Materials," J. Am. Chem. Soc, 2019, 141,
12531-12535.
29 Gribanov, S.; Topchiy, M.A.; Fedyanin, I.V.; Asachenko, A.F.; Nechaev, M.S.; Pleshakov, D.V. Reexamination of
an Energetic Nitrate Ester SHN. Propellants, Explos. Pyrotech. 2017, 42, 1014 – 1019.
30 Hartel, M.A.C.; Klapӧtke, T.M.; Stierstorfer, J.; Zehetner, L. Vapor Pressure of Linear Nitrate Esters
Determined by Transpiration Method in Combination with VO-GC/MS. Propellants, Explos. Pyrotech. 2019,
44, 484 – 492.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
31 Stark, K.A.S.; Alvino, J.F.; Kirkbride, K.P.; Sumby, C.J.; Metha, G.F.; Lenehan, C.E.; Fitzgerald, M.; Wall, C.;
Mitchell, M.; Prior, C. Crystal Structure, Sensitiveness and Theoretical Explosive Performance of Xylitol
Pentanitrate (XPN). Propellants, Explos. Pyrotech. 2019, 44, 541 – 549.
32 Manner, V.W.; Tappan, B.C.; Scott, B.L.; Preston, D.N.; Brown, G.W. Crystal Structure, Packing Analysis, and
Structural-Sensitivity Correlations of Erythritol Tetranitrate. Crystal Growth & Design, 2014, 14, 6154–6160.
33 Lease, N.; Kay, L.; Chavez, D.E.; Robbins, D.; Manner, V.W. Increased Handling Sensitivity of Molten Erythritol
Tetranitrate (ETN). J. Hazard. Mater. 2019, 367, 546 – 549.
34 Sandstrom, M.M.; Brown, G.W.; Preston, D.N.; Pollard, C.J.; Warner, K.F.; Sorensen, D.N.; Remmers, D.L.;
Phillips, J.J.; Shelley, T.J.; Reyes, J.A.; Hsu P.C.; Reynolds, J.G. Variation of Methods in Small-Scale Safety and
Thermal Testing of Improvised Explosives. Propellants, Explos. Pyrotech. 2015, 40, 109–126.
35 Chavez, D. E.; Hiskey, M. A.; Naud, D. L.; Parrish, D. Synthesis of an Energetic Nitrate Ester, Angew. Chem. Int.
Ed. 2008, 47, 8307 – 8309.
36 T. Urbanski, “Chemistry and Technology of Explosives”, Pergamon Press: New York 1965, Vol. 2.
37 Hiskey, M.A.; Brower, K.R.; Oxley, J.C. Thermal Decomposition of Nitrate Esters. J. Phys. Chem. 1991. 95,
3955-3960.
38 Hiskey, M. A.; Hatch, M. J.; Oxley, J. C. Nitrato Amine Nitrates: Nitrate Ester Explosives with Reduced Impact
Sensitivity, Propellants, Explos. Pyrotech. 1991, 16, 40 – 42.
39 Klapotke, T. M.; Krumm, B.; Steeman, F. X.; Umland, K.-D. Bis(1,3-dinitratoprop-2-yl) Nitramine, a New
Sensitive Explosive Combining a Nitrate Ester with a Nitramine, Z. Anorg. Allg. Chem. 2010, 636, 2343–2346.
40 Zhang, C.; Jiao, F.; Li, H. Crystal Engineering for Creating Low Sensitivity and Highly Energetic Materials. Cryst.
Growth Des. 2018, 18, 5713–5726.
41 Myers, T.W.; Snyder, C.J.; Manner, V.W. Reduction of Mechanical Sensitivity in Alkyl Nitrate Explosives
through Efficient Crystal Packing. Crystal Growth & Design 2017, 17, 3204–3209.
42 Dong, J.; Yan, Q.L.; Liu, P.J.; Hei, W.; Qi, X.F.; Zeman, S. The Correlations Among Detonation Velocity, Heat of
Combustion, Thermal Stability and Decomposition Kinetics of Nitric Esters. J. Therm. Anal. Calorim. 2018, 131,
1391 – 1403.
43 Yan, Q.L.; Kunzel, M.; Zeman, S.; Svoboda, R.; Bartoskova, M. The Effect of Molecular Structure on Thermal
Stability, Decomposition Kinetics and Reaction Models of Nitric Esters. Thermochimica Acta. 2013, 566, 137 –
148.
44 Oxley, J.C.; Smith, J.L.; Brady IV, J.E.; Brown, A.C. Characterization and Analysis of Tetranitrate Esters.
Propellants, Explos. Pyrotech. 2012, 37, 24 – 39.
45 Chaudhri, M.M.; and Field, J.E. The Role of Rapidly Compressed Gas Pockets in the Initiation of Condensed
Explosives. Proc. R. Soc. Lond. A, 1974, 340, 113-128.
46 Starkenberg, J. “Ignition of Solid High Explosive by the Rapid Compression of an Adjacent Gas Layer,” Proc.
Seventh Symposium (International) on Detonation, Naval Surface Weapons Center: Dahlgren, 1981, pp 3-16.
ACS Paragon Plus Environment
20

Page 21 of 21
Crystal Growth & Design
1
2
3
4
5
6
TOC Graphic
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Erythritol tetranitrate
(ETN)
L-erythritol tetranitrate
(L-ETN)
Solid
Liquid
Isomers of explosives allow us to manipulate phase
and melting points, influencing handling sensitivity
ACS Paragon Plus Environment
21