TECHNOLOGY

Shock Sensitivity of Explosives Clarified

Why some explosives are more sen- excitation, that probability is re-
sitive to shock than others with sim- mote. Nitroaromatic explosives
ilar structures may depend on the The summation of many such ex-
CH3
stability of carbon-carbon bonds in citations and radiationless transitions 1
02N. 2 0 2 N . s\j4Q,
the aromatic rings and on hydro- is an Auger spectrum showing the
Cr"°
gen bonding. These apparent rela-
tionships resulted from studies by a
team of scientists at Sandia Nation-
al Laboratory, using x-ray excited
number of transitions at different
energy levels. The shapes of the
spectra of the various molecules re-
veal subtle but unmistakable differ-
V N0 2
1 V N0 2
TNT
TNB
Auger electron spectroscopy (XAES) ences in the molecular bonds local
to probe the electronic structures of to the carbon sites. N0 2 N0 2

Q*
nitroaromatic explosives. For example, the spectra for TNB
The research team's leader, chem- and TNT confirm theoretical pre- 02N- ^ VNO2
ist J. William Rogers Jr., notes that dictions that adding nitro groups
the studies involved benzene and weakens the benzene ring's carbon N0 2 N0 2
five explosives built on the ben- bonds. The reason, Rogers says, is HNS
zene ring: trinitrobenzene (TNB), that nitro groups are strong elec-
trinitrotoluene (TNT), monoamino- tron withdrawers. The carbon- NHL NH2
trinitrobenzene (MATB), diamino- carbon bond is formed by the shar- 1 c
0 2 NU N 02N^/ ^ N 0
trinitrobenzene (DATB), and tri- ing of electrons between two adja- VAY °2 2

aminotrinitrobenzene (TATB).
Although the five compounds
have a lot in common, their shock
initiation thresholds—the shock
pressure required to cause detona-
tion 50% of the time—vary widely.
The threshold is 17 kilobars for TNB,
21 for TNT, 30 for MATB, 46 for
DATB, and 75 for TATB.
To learn the reasons for the dif-
ferences, Rogers and his Sandia col-
leagues—chemists Henry C. Peebles,
Robert R. Rye, and J. Stephen
Binkley and physicist Jack E. Hous-
ton—used XAES to measure effects
of substituent groups on bond
strengths, and then compared their
results with theoretical calculations
of molecular electronic properties.
The technique allows scientists to
look specifically at the energy lev-
els involving carbon-carbon bonds,
Rogers explains. In XAES, an x-ray
photon removes a tightly bound
inner-shell electron from an atom.
The excited atom responds with an
Auger transition, wherein an elec-
tron from an outer orbital moves to
the vacated deep electron site.
There's a good reason for using
x-rays, rather than a beam of elec-
trons, to excite the atoms, Rogers
says. The electron beam is so ener-
getic that it can cause an explosive
to detonate. With the "softer" x-ray
cent carbon atoms. When some of
those electrons are partially pulled
away to participate in the carbon-
nitro bond, the carbon-carbon bond
is weakened, thus easier to break,
and thus more sensitive to shock.
Rogers notes that other work has
identified a related effect in the ex-
plosive hexanitrostilbene (HNS),
which resembles two TNT molecules
joined with a carbon-carbon double
bond (but which has a higher initi-
ation threshold than TNT). Because
the carbon-carbon double bond is
so close to some of the nitro groups
on the rings, two of the three nitro
groups on each ring are twisted out
of the plane. As a result, these nitro
groups can't participate in resonance
electron withdrawal and thus can't
weaken the carbon-carbon bonds in
the rings.
Adding amino groups to the ben-
zene ring decreases shock sen-
sitivity. There appear to be two rea-
sons, Rogers explains. First, amino
groups are net electron donors. The
bond-strengthening effect of the
amino electron donation compen-
sates for the nitro group electron
withdrawal.
More important, however, add-
ing amino groups redistributes the
charge, causing the molecule to be-
come polarized, with the amino
VN0 2
{X f ^ N H 2
N0 2
MATB DATB
NH,
1
02N ^ ^ N 0 2
H2N^\^^NH 2
N0 2
TATB
groups slightly positive and the ni-
tro groups slightly negative. That
leads to the formation of a strong
hydrogen bonding network. TATB,
for instance, consists of planar sheets
of molecules, with the nitro groups
on one ring connected to the amino
group on another through strong
hydrogen bonds.
In the "special case" of TNT, the
single methyl group is a weak in-
ductive electron donor. There is also
a small degree of intermolecular hy-
drogen bonding, absent in TNB.
From their findings, the Sandia
scientists infer that adding amino
groups raises the initiation thresh-
old because the resulting networks
of hydrogen bonds absorb energy
from a shock front and reduce the
amount that goes to the ring itself.
Ward Worthy, Chicago
August 10, 1987 C&EN 25