X-Ray Diffraction Patterns for the Identification of Crystalline Constituents of Explosives ALBERT \1. SOLD-ITE
4ND
RICH 1RD 51. NOYES, California Institute of Technology, Pasadena, C a l q .
R
ents which could be separated easily from each other; however, the authors feel that the technique will frequently be valuable for the identification of simple mixtures. All the data were obtained from the forms of these compounds commonly occurring in the explosives under investigation and no attempt \vas made to study other polymorphic modfications.
E C E N T studies a t the California Institute of Technology have demonstrated that x-ray diffraction photographs are of considerable aid in the rapid identification of many of the crystalline constituents in explosives of unknoLvn composition. During the course of these studies photographs have been taken of powdered samples of several substances that are sometimes present in explosives, and the data have been used as aids in the identification of constituents in unknown samples. 3Iany of the results duplicated those that had already been reported in the literature, but no previous p o d c r diffraction data have been reported for eighteen of the substances that the authors have studied. The results of nieasurements on theseeighteensubstancesare presented in this article in a forni similar to that used by Hailalvalt and coworkers ( 1 ) for the presantation of x-ray powder data to be used for analytical purposes. Most of the explosives examined by this technique either contained only one crystalline constituent or else contained constitu-
EXPERIXIENTAL PROCEDURE
The samples m r r ground to a suit,ablestate of subdivision in an agate mortar. For most of the photographs the pulverized samples were mounted on Pyres fibers n i t h the aid of a little vaseline; samples of the more volatile substances were mounted in thinwalled Pyres capillaries. These procedures were found to be adequate for the quantitative identification of the substances concerned. Possible departures from complete randomness of orientation would doubtless cause some modifications in the relative intensities reported in the tables. X-ray photographs of the samples were made either in a cylindrical evacuated camera with a radius of 7.21 em. or in a cylindrical nonevacuated camera with a radius of 5.00 em. I n the latter instance the samples w r e rotated during exposure. All exposures were made with copper Iia: radiation Table 1. Names arid Formulas of Eighteen Crystalline Organic which wak filtered by nickel foil and collimated Constituents of Explosives by a system of two slits which were 0.014 inch in Pattern Tvidth. The photographs xere measured and the 10 Cheniical Saiiie Trade S a m e interplanar spacings were calculated by the usual I’entaerythritol tetrariitrnte PETS 1 methods. 2 3 4 5
t
2,4-Dinirrotoluene 2,4,6-Triiiiirotoluene Picric acid Guanidine picrate Ethylene dinitriiiniiie
DXT TXT
EDTA (haleite)
i
Xitroguanidine
8
2,?,j,5-TetramethyIol cyclopentanone tetraiiitrate
Fivonite
Dihydroxyethyl nitraiiiine dinitrate Hexogen (hexahydro-l,3,5-trinitro-a-triazine)
DISA
Octahydro-l,3,5,7-tetranitro-stetrazine
HMX
9 10
11
The names and formulas of the eighteen substances for which new data m r e obtained are presented in Table I. EXPERIMENTAL DATQ
The interplanar spacings calculated from the x-ray diffraction lines observed for each substance are presented in Table 11. The approximate intensity of each line relative to the other lines on the same film was estimated visually and is recorded in Table I1 by means of an appropriate designation:
Cycloni re,
RDX
vs s
m f vf
Very strong Strong Medium Faint Yery faint
,
ACKNOWLEDGMENT 12
Octahydro-l-acetyl-3,5,i-trinitro-Q D X , S E X s-tetrazine
CH? XOl-S
/’
‘\
4 L \
sot-s
S-COCHa ‘CH,
/
The authors wish to acknowledge their indebtedness to Henri A. Levy and Robert B. Corey, under whose direction this work was carried out, for their interest and advice.
K-XO2
\CHi 13
or,B-Diethylcarbanilide
LITERATURE CITED
Ethyl centralite (carbamite i
(1) Hanawalt, J. D., Rinn, H. W., and Yrevel, L.
K.. IND, ENG.CHEX.,A x . 4 ~ .ED.,10, 457-513 (1938).
14 15 16 17 18
Diphenylamine N-Nitrosodiphenylaniine 2-Kitrodiphenylamine 2,4‘-Dinitrodiphenylamlne 4,4’-Dinitrodiphenylawine
COXTRIBUTIOS from the Gates and Crellin Laboratories of Chemistry, California Institute of Technology, KO. 1053. This paper is based in whole or in pert o n work done for the Office of Scientific Research and Development under Contracts OERfsr-702 and OEMsr-881 with the California Institute of Technology.
442
’
JULY 1947
443
Table 11. Powder Diffraction Data for Eighteen Crystalline Organic Constituents of Explosives Spacing
Intensity
Spacing
kX
Intensity
k X
Pentaerythritol tetranitrate 6.64 m5.44 vf m4.67 3.83 YE 3.54 8 3.31 m 3.15 m 2.95 mm2.82
Spacing k .Y
Intensity
Spacing kX
Intensity
1.
2.70
2.
m-
m m
2.60 2.35 2.27 2.21 2.05 1.81 1.78 1.7Q 1 53
vf -
m m
f4f+
vf vi
2,4-Dinitrotoluene 9.88 6.54 5.96 5.54 4.98 4.71 4.41 4.15 3.98 3.84 3.67 3.57 3.32 3.22 2.98 2.77 2.17 2.06
+
7.84 7.04 6.79 6.10 5.54 4.87 4.58 4.31 4.03 3.92 3.79 3.69 3 41 3.37 3.27 3.11 3.02 2.80 2.75
a
vvf mm vi
f-
f+ m
f
mVS
vs
f f
vf vf
2,2,5,5-TetramethyIol cyclopentanone tetranitrate vf vf 2 67 2 61 f vf vi (broad) 2 54 vf (very broad) 2 46 2 34 m va 2 29 2 20 m-t 2 15 f+ f 2 10 f+ 2 02 vs 1 95 vf 1 91 f 1 85 f 1 80 in 1 75 m1 62 a1 56 f 1 08 f
+ +
3.
6.99 6.40 5.99 5.62 5.43 5 15 4.99 4 65 4.26 4.11 4.00 3.84 3.70 3.52 3 43 3 32 3 26 3.14
.
2,4,6-Trinitrotoluene 3.04 3.00 2.92 2.86 f 2.78 Y \.f 2.73 s2 67 f - (broad) 2.59 S 2.52 f2 43 vf 2 36 vva 2 30 2.22 rn ,doublet) 2.18 ni 2 13 n1 \Tf 2.04 111 1.94 vf 1.88
8.
e+ 8-
+
++
++
f m+
vf -
S 6 -
ni vvf m + (broad) 111
111
+
\-f -
?+
2 2 2 2 55 2 48 2 40 ..
+ v,-f 111
111
I+
3
v vf
rf
9. Dihydroxyethyl nitramine dinitrate 71 f+ m11 97 20 90 78 m+ vf 66 m 57 9 47 f 09 01 88 74 mm 64
7 6 4 4 3 3 3 3 3 3
-
ff vf m-
~
4. 9.53 5 47 4.78 4.60 4.46 4 . 17 4.06 3.86 3.73 3.55 3 48 3.40 3.32 11 ,3 00 2 8; 2.80 2 67 2 57 2 50 2 39 2 31 2.20 2 04 1 89
3
6. i 4 3 3 3 2 2 2 2 2 2 2 2 2 2 2 1 1 1 1 1
39 57 67 39 08 96 80 67 56 52 37 28 26 19 13 03 98 84 79 60 53
Picric acid f
+ f111
f+
vi
f+
5. Guanidine picrate 9 37 f 4.68 f + (broad) vvf 4 23 4.12 rf 3.69 vf 3.16 VVS 2.65 af 2.56 vf 2 36 vf (broad) 2.26 f 2 15 vf 2.03 vvf 1.97 vvf (broad) 1 ,.59 v r f (hroadj
S
m+ in Ill
f f f in in fin f (broad) f
+
vvf \Tf \-vi vrf
Ethylene dinitramine
m+ 3-
(broad)
+
\-f (broad) 111 111
f (broad)
v vf vf incompletely vi'('reao1ved)
vf f vvf vvf v vf
f ff
"I
vvf vf vf vf 10.
6 5 5 .5 4 4 4 4 3 3
3
rvf
5 Ill
I .
2 08 2 03 1 78 1 72
+
f
f-
2.33 ' 'I
7. Nitroguanidine 5 00 4 39 4.15 3.59 3 47 3 23 3.04 2 93 2 86 2.65 2.60 2.49 2.39 2.31 2.24 2.17 2.13 2.08 2.05 2.00 1.90 1.85 1.79 1.74 1.68 1.65 1.62 1 53 1.26
?
(broad)
Ill
+
f+
rvf
In 7
+
73 72 34 10
95 35 17 02 91 76 50 30 04 93 86 76
3 3 2 2 2 2 69 2 56 2 51 2 43 2 36 2 28 2 22 2 13
in I11 111
-
1-f
x-vf rf rf
vf
in
m fS
S
vf
-
vi
vf
vi (broad) vrf f vvf f f (very broad) 1-f (very broad)
6 04 5 52 4 85 431 4 05 3 86 3' 40 3 26 3 02 2 79 2 68 2 53 2 41 2 25 2 18 2 12 2 08 2 00 1 90 I 86
(Continued on page 444)
-
S VS
f
\-f S-
f m f mf+ vi (broad) vf (broad) f1I.
-
mfin -
vf
S
VS
(broad)
in -
+
x-f in -
f-
ff vf f-
vf f f f (broad)
f
vf
m
T-I+
(broad)
i
f vf
rf
vf vvf
vi
vrf Ti vvf v r f (broad) vf vi (broad) vvf vvf
Octahydro-1,3,5,7-tetranitro-s-tetrazine
m m f (broad)
vf f-
Hexogen 2.08 2.02 1.96 1 86 1.79 1.76 1.72 1.64 1.56 1.52 1.4e l.'di 1 12 1.39 1 35 1 32 1.30 1.27 1.25 1.21 1.18 1 15 1.12
80 70 66 61 57 54 52 46 42 39 34 30 26 20 17 16 10
+
08 06 01
vf vf
-
vi vf -
'
vi
vf vf vvf
+-
vi -
vf
-
vvi f (broad) fvvf fvvf vf vf rf
++
VOLUME
444
12. 6 9.i
S-
2.22 2.10 2.03 1 .98 1.92 1.84 1 8% 1.76
nl
1.72
111 111
1
fi 62
S i-
ii 08
vvf -
4.74 4 44 4 01 3.71 3 . J4 3.44 3.30 3.18 3.02 2.92 2.73 2.63 2.34 2.46 2.41 2.33 2.20
\.S I,,
+
Vb
f-
Ill
Ill
+
f f vi+ f f f f 4
f\-Tf
7 06
-
R . 10 4.62
f+
vi+ vf f f fff-
I .79 1 .33 1 48 1.44 1.41 1.38 1.35 1 31 1 28
?.20 .3 67 3 43 2.99 2 87 2.30 2.12 2 02 1 93
T-vf rf a\-f vf vvf +
..+ (t)roa(l) F+
f ibroadl ffvrf (hr,M
