Thermochemistry and Reaction Mechanisms of

Nitromethane Ignition
C. Melius

To cite this version:

C. Melius. Thermochemistry and Reaction Mechanisms of Nitromethane Ignition. Journal de Physique
IV Colloque, 1995, 05 (C4), pp.C4-535-C4-548. �10.1051/jp4:1995443�. �jpa-00253749�

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 JOURNAL DE PHYSIQUE IV
Colloque C4, supplCment au Journal de Physique ID,Volume 5, mai 1995

Thermochemistry and Reaction Mechanisms of Nitromethane Ignition

C.F. Melius
Combustion Research Facility, Sandia National Laboratories, Livemore, CA 94551-0969,U.S.A.

Abstract: The thermochemistry and reaction mechanisms of nitromethane initiation are

modeled using detailed chemical kinetics. Initial conditions correspond to gaseous
nitromethane at atmospheric and liquid-like densities and initial temperatures between
1100 and 2000 K. Global reactions as well as elementary reactions are identified for each
of the two stages of ignition. The chemical steps to convert the nitro group to N2 involve a
complex set of elementary reactions. The time-dependence of the ignition steps (ignition
delay times) as a function of temperature and pressure is used to determine effective
activation energies and pressure dependencies to ignition. The ignition delay times range
from several nanoseconds to tens of microseconds. At atmospheric conditions, the delay
times for both ignition stages are in excellent agreement with observed experimental data.
At the high densities, the ignition times at these elevated temperatures appear to be
dominated by the same reaction mechanism that occurs for atmospheric gaseous
nitromethane initiation. This is to be contrasted with lower temperature, condensed-
phase ignition studies where it appears that solvent-assisted reactions dominate.

1. INTRODUCTION

The ability to identify the chemical reactions involved in the initiation of energetic materials is
challenging due to the extremely short time scales involved as well as the high temperatures and
pressures that are generated. Furthermore, the chemical intermediates of ignition are highly
reactive. The chemistry of nitro compounds, such as nitramines and nitroaromatics, is further
complicated by the fact that they may undergo two-stage ignition. We therefore have investigated
the initiation of nitromethane as a prototype of an energetic material containing the nitro moiety.
The ignition of nitromethane has been studied both experimentally 11-9 ] and computationally
[1,10-15 1. In particular, the ignition delay time of gas-phase ignition of nitromethane has been
studied by Guirguis et al. [I] in which they were able to observe two stages of ignition. Several
groups have modeled the ignition process using detailed chemical kinetics [1,9], including previous
work by us [13,14]. The modeling was able to treat the first-stage ignition reasonably well, but
the second-stage ignition delay times were off by several orders of magnitude. Recent work by
Lin and coworkers [16-181 have improved our understanding of the elementary reactions involving
the NO, HNO, NO2, and HCN species. This has enabled us to generate an improved detailed
reaction mechanism for nitromethane. We use this improved mechanism to study the initiation of
gaseous nitromethane at atmospheric conditions as well as at densities corresponding to that of

*Work supported by the U. S. Department of Energy.

Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jp4:1995443
C4-536 JOURNAL DE PHYSIQUE IV

liquid nitromethane. We present the thermodynamics and reaction pathways of the ignition steps.
We then use the ignition delay times to determine effective activation energies and pressure
dependencies.

2. METHOD

The study of ignition in a uniformly heated system, such as in a shock tube, allows us to study the
combustion chemistry of energetic materials in a environment that can provide the initial
decomposition and initiation reaction mechanisms. The energetic material can be treated as a
homogeneous gas mixture in a closed system, in which we follow the time-dependent evolution of
the chemical species. For instance, we can treat an adiabatic system with constant pressure or
volume, or we can follow the chemistry under shock detonation conditions. We use the SENKIN
program [19], which includes sensitivity analysis, for the integration of the energy and mass
conservation equations.

In this section, we study the chemistry of gaseous nitromethane initiation. The ignition of
nitromethane is treated as being under constant volume. The governing equations are [14,19]

-=
dYk V ik
~k (k = 1, ..., K).
dt
and
K
dT
cv- = - V C ek &k ~ k ,
dt k= 1

In the above equations, T is the temperature, Yk the mass fraction of the kth species, Wk is the
molecular weight of the kth species, t is time, v = V/m is the specific volume, ek is the internal
energy of the kth species, c , is the constant volume heat capacity of the mixture, and & is the
molar rate of production of the kth species. The chemical reaction mechanism included 48 species
and 312 elementary reactions. The thermochemical dynamic properties and chemical production
rates are evaluated using the Chemkin package [19]. The 48 species and their heats of formation
are presented in Table I.

Table I. The chemical species used in the detailed chemical kinetic modeling of nitromethane.
Also given are the heats of formation at 298 K (AH&*), where energies are given in kcal-mol-1.

CH3N02 CH30NO
NO NO2
HNO HONO
N20 H
H2 0
02 OH
H20 H02
N N2
NH NH2
NH3 NNH
HNNO HNOH
H2NO N2H2
CO co2
HCO CH2O
CH3O CH20H
Table I. (Cont.)
31 CH30H CH3
33 CH4 CN
35 HCN HzCN
37 CH3NH HCNO
39 HOCN HNCO
41 NCO NCN
43 CH3NO H2CN02
45 H2CNO CH3NHO
47 H2CNOH CH2N02H

3. RESULTS

In Figs. 1 and 2, we present the temperature and species profiles as a function of time for the
initiation of 100 per cent gaseous CH3N02 at 7.25 atmospheres and 1131 K. These conditions are
representative of the experimental conditions of Guirguis et al. [I]. The initiation undergoes two
ignition stages, at 13.3 psec and 25.8 pet, respectively. The final temperature is 3598 K.

The chemistry can be subdivided by time into several stages: (I) a preliminary stage of slow
decomposition followed by (11) a first-stage ignition that undergoes a rapid temperature rise
followed by (III) an intermediate stage in which the temperature remains on a plateau followed by
(IV) a second-stage ignition where the temperature again rises rapidly to form the final products.
The reaction mechanism flow diagrams for the first-stage ignition (11), the intermediate stage (111),
and the second-stage ignition (IV) are shown in Figs. 3-5. These reaction pathways show the
dominating elementary reactions occurring in each of these stages, with thick arrows being the
major pathways while thin arrows are the minor pathways. We have separately shown the
reaction chemistry for the carbon atom and the nitrogen atom of nitromethane. The carban atom
must be oxidized, to form CO and, to a lesser extent, C02 (note that there is not enough oxygen in
nitromethane to oxidize the carbon to C02 and the hydrogen to H2O). Meanwhile, the nitrogen,
which is in an oxidized state as part of the nitro group moiety, must be reduced to N2. The reaction
flow diagram for the preliminary decomposition stage (I) is similar to that of the first-stage ignition
(11) and thus is not shown. The major difference is that the preliminary stage (I) occurs at the low
end of the temperature range, giving rise to slower rates and resulting in a greater variety of minor
intermediate species being formed.

In Figs. 6-8, we show the enthalpies and free energies of possible species corresponding to the
composition ClH3N102. This represents the composition of nitromethane and includes tautomers
of nitromethane as well as various product species. Besides the AH at 300K (see Table I for
individual species heats of formation), we present the AG's at 300K and 2000K.

Fig. 1 showed the time profile for nitromethane initiation at 7.25 atmospheres and 1131 K,
indicating two rapid temperature rises at 13.6 psec and 26.1 psec, designated 71 and 72
respectively. In Table 11, we present these ignition delay times, 71 and 72, for various initial
temperatures and pressures. These results are used to determine activation energies of ignition,
defined by the relation In ('Ta/7b) = (AEI R) (1/T, - 1ITb). The resulting AE's for the first-stage
and second-stage ignitions are presented in Table 111. In a similar manner, we can define pressure
dependencies to the ignition delay time by the relation In (za/7b) n In (Pa / Pb), which corresponds
to T being proportional to P". The resulting pressure exponents are given in Table IV.
(3-538 JOURNAL DE PHYSIQUE IV

4000'

Nitromethane Ignition
3000,
E
V

E'
7
+,

!
al
2000

E"
8'
1000.
I
Temperature

0'
1 4

0 10 20 30

Time (microsec)

Fig. 1. Temperature vs. time profile for ignition of nitromethane. Initial conditions are 1131 K and
7.25 atm.

Species Concentration
1.o

CH3N02
........... NO
0.8 -.-.-.-, H2
........... H20
N2
-.-,-,-,
C CO
.P 0.6 ........... CH20
+,
0
E
........... CH4
-
'C

al
0
HCN

0.4'

...... ,,&.,f: ............

- .. -.---* ..........---.-.
/ s - ' - - - 2 -

.mL-,-,-,-

0.2. ......'........*.
. - . e m -
,
: r

0.0
0 10 20 30

Time (microsec)

Fig. 2. Species vs. time profile for ignition of nitromethane. Intial conditions are 1131 K and 7.25
atm.
 Nitromethane First Stage Ignition Chemistry
Carbon Mechanism
CbONO
+M
+H + NO
+ CH3
+M + CH3 + NOp
CH3N02- C H 3 x CH30 HCO CO

+H
CH4 CH30H CH20H

Nitrogen Mechanism

CH3N02+
+M
NO
+ HCO
+M
+ HNO
HNO -+ 0 -
+M
Nz

Fig. 3. Reaction mechanism flow diagrams for the first stage-ignition of nitromethane. Thick arrows
indicate major pathways. Dominant collision partners for bimolecular reactions are indicated next to
arrows. Unimolecular decomposition reactions are indicated by the third-body notation +M. The
chemistry of carbon- and nitrogen-containing species are presented separately.

Nitromethane Intermediate Stage Chemistry

Carbon Mechanism

+M

CH4
+H
*CH3 ----t H2CN - +M
HCN

=
+ OH
CH30H CH,OH d C H 2 0 4 HCO 4 CO
+H +H +M
+CO,
+ OH

NO -
Nitrogen Mechanis rr
+ CH3
HCN

Fig. 4. Reaction mechanism flow diagrams for the intermediate stage (between first- and second-
stage) ignition of nitromethane. See Fig. 3 for further caption descriptions.
 JOURNAL DE PHYSIQUE IV

Nitromethane Second Stage Ignition Chemistry

Carbon Mechanism

HCN
4
+ NCO

Nitrogen Mechanism from HCN Nitrogen Mechanism from NO

HNO

NNH
NCO HNO

Fig. 5. Reaction mechanism flow diagrams for the second-stage ignition of nitromethane. See Fig. 3
for further caption descriptions.

Heats of Formation for Nitromethane

and Its Tautomers at 300K

HCNO
+ H20
-15.0

HNCO
+ H20
-86.4

HOCN
9 H
,
-106.2\H

Fig. 6. Heats of formation, AH'S, at 300 K for nitromethane and its tautomers and other
stoichiometric products. Enthalpies are in kcal-mol-1.
 Gibbs Free Energy for Nitromethane
and Its Tautomers at 300K

CYO
-13.7 + HNO
HO -0 -8.7
H,CN
'
H
' HCNO
-29.4
+ '420

HNCO
-71.O CO + H 2 0
H0 'C=N +H20
-81-0 + : ~ 2 + : ~ 2
HO' H
' -87.4
-903 H C02 + NH3
-98 2
-100

Fig. 7. Free energies, AG's, at 300 K for nitromethane and its tautomers and other stoichiometric
products. Free energies are in kcal-mol- l .

Gibbs Free Energy for Nitromethane

and Its Tautomers at 2000K

64.6
H\
HO/'*\OH
30.5
HCNO CYO
+ H20 + HNO

9/H
HOCN, HNCO
H + H20
-45.4

Fig. 8. Free energies, AG's, at 2000 K for nitromethane and its tautomers and other stoichiometric
products. Free energies are in kcal-mol-1.
C4-542 JOURNAL DE PHYSIQUE IV

Table 11. Ignition delay times for gaseous nitromethane for different initial temperatures and
pressures.

T (K) P (Atm) 71 z2 72- 71

Table 111. Activation energies of ignition (defined by In ( z, / zb ) = AE / R ( 1/T, - I&)).

Ignition delay times are taken from Table 11. Energies in kcal-mol-1.

Constant Pressure T(K) P (Atm) AEl BE2

1230 5.25 33.2 7.6

1230 7.25 35.6 5.1

1230 1574.4 45.4 44.9

1230 1852.8 45.7 45.3

Constant Volume T(K) P (Atm) AE 1 AE2

1230 5.25 35.7 11.0

1230 1574.4 45.9 45.6

1950 2644.8 34.8 21.3

Table IV. Pressure dependence of ignition delay times for gaseous nitromethane. Pressure
dependence is defined by T = Pn or In ( T~/ q,) = n Zn ( Pa / Pb ). Ignition delay times are taken
from Table II.

Low Pressure T (K) n~ n2

1131 -0.36 -0.99

1331 -0.85 - 1.52

Low to High T (K) n1 n2

1131 -0.22 -0.37

1331 -0.35 -0.82

High Pressure T (K) n1 n2

1131 -0.09 -0.15

1331 -0.19 -0.32

4. DICUSSION

4 .1 Chemical Reactions

Several points regarding the nitromethane thermochemistry can be observed from Figs. 6-8. First,
from the AH'S presented in Fig. 6, it is seen that indeed nitromethane is an unstable tautomer of
C1H3N102,lying -90 kcal-mol-1 above the most stable form, C(0)OHNHz. In fact, C(0)OHNH2
is more stable than the major products of detonation, CO, H20, N2, and H2 (see Fig. 2).
Furthermore, as can be seen in Fig. 6, the lowest bond-breaking moiety for CH3N02 is the
breaking of the C-N bond to form CH3 + N02. which is endothermic by nearly 59 kcal-mo1.-1 Thus,
from an enthalpy view point, CH3N02 would appear to be a reasonable energetic material.

However, while one tends to think of the thermochemistry of the reactions in terms of enthalpies
(e.g., heats of reaction), it is the free energy of the system that drives the reaction. Dividing the
ClH3N102 molecular species into two or more species lowers the free energy, particularly at
higher temperatures. As one can see from Fig. 8, at 2000K, the AG of CH3 + NO2 is more stable
than that of CH3N02 itself. And the breakup of CH3NO2 into its small product molecules, CO,
H20, N2, and Hz, forming three molecules from one reactant molecule is extremely exothermic.
Thus, it is necessary to have more than the thermostability to bond breaking to make an
insensitive energetic material. As we shall see, it is necessary to have a reaction pathway which
prevents direct conversion of the energetic material to products.

The overall reaction chemistry converting nitromethane to products is

with minor contributions of the following reactions

C4-544 JOURNAL DE PHYSIQUE I V

Contributions of R2-R4 relative to reaction R1 are given in parentheses. The heats of reaction
AHRxnare given in kcal-mol-1.

As stated above, the chemistry can be subdivided by time into several stages: (I) a preliminary
stage of slow decomposition followed by (11) a first-stage ignition that undergoes a rapid
temperature rise followed by (111) an intermediate stage in which the temperature remains on a
plateau followed by (IV) a second-stage ignition where the temperature again rises rapidly
forming the final products. This temporal division of chemical reactions, as indicated in Fig. 2, is
consistent with the temporal division of the temperature into a preliminary, first-stage ignition,
intermediate region, and second-stage ignition, as indicated in Fig. 1. The reaction chemistry
during the preliminary stage (I) is

9 CH3N02 + 5 CH2O + 518 HNO + 714 CO + 3518NO + 512 H2 + 3 H20 + 314 N20
+ HCN + CH4 + NO2 + 114 C02 + N2 + 318 HONO A H R x ~= -10, (R5)

the reaction during the first-stage ignition (11) is

the reaction during the intermediate-stage ignition (111) between the first- and second-stage
ignitions is

while the reaction during the second-stage ignition (IV) is

In order to relate the heats of reaction, A H R ~of~ the

, individual reactions to each other, we have
normalized the A H R for ~ ~each of the reactions to the CH3N02 molecule. Thus, the AHR~,,'Sare
normalized per CH3N02 (R5 and R6) or NO (R7 and R8) molecule.

The global reactions for each stage in the nitromethane initiation can be further subdivided into
subglobal reactions which begin to indicate the reaction mechanism of each stage. While this
reaction subdivision is not unique, we have attempted to define those subglobal reactions which
represent simple combinations of elementary reactions, as indicated in Figs. 3-5. In addition to
the subglobal reaction, we also indicate the relative contribution of each reaction to the net
reactions presented above. We also give the absolute heat of reaction, AHRxn, for each of the
subglobal reactions.

The preliminary stage (I) global reaction R5 is composed of the subglobal reactions

CH3N02 + CH2O + HNO (4) A H R=~ +~13 (R5a)

CH3N02 + CO + NO + 3/2 H2 (1) AHRX~= +12 (R5b)
2 CH3N02 + CH4 + CO +. H2+ NO + NO2 (1) AHRX~= +19 (R5c)
2CH3N02+HNO+HCN+CH20+2H20+2N0 (1) AHRX~= -58 (R5d)
2 HNO + N20 + H z 0 (314) A H R=~ -85
~
NO2 + HNO + HONO + NO ( I ) A H R=~ -28
~ (R50
CO+2HNO+CO:!+N2+H20 (3/8) AHRxn = -173. (R5g)

The first-stage global reaction R6 is composed of the subglobal reactions

The intermediate-stage global reaction R7 is composed of the subglobal reactions

CH4+ NO + HCN + H20 + 112 H2

H2+ NO + H20 + N2
CO + H20 *
C02+ H2

The second-stage global reaction R8 is composed of the subglobal reactions

The net result of the preliminary (I) and first-stage ignition (11) reactions steps is the conversion
of the NO2 moiety to NO. During the preliminary stage (I), the decomposition of CH3N02 is only
slightly exothermic. In fact, the dominant decomposition reaction R5a is endothermic. Subsequent
reactions involving the HNO species provide the exothermic heat release. The first-stage ignition
(11) chemistry is slightly more exothermic. However, the major exothermic heat release of
initiation arises during the second-stage ignition chemistry.

The net result of the intermediate (111) and second-stage ignition (IV) reactions is the conversion
of NO to N2. The NO to N2 conversion does not occur readily and requires the presence of
hydrogen and HCN. The formation of HCN occurs primarily during the intermediate stage (111).
This stage (111), which removes the CHq, is also exothermic but slow. The rapid reaction rates of
the second-stage ignition are a result of the high temperatures.

While the net reaction is conversion of CH3N02 to CO, H20, N2, and H2, the overall chemical
process of ignition is complicated. Many steps are required to form the final exothermic products.
The chemistry can be divided into two major efforts, (1) conversion of the NO2 moiety to NO and
(2) conversion of the NO moiety to N2. This process is generic to all nitro-containing energetic
materials, including nitrate esters and nitramines [14]. The result is two separated ignition
stages, denoted the first or primary stage and the secondary stage.

The primary-stage ignition is conversion of the NO2 to NO. This can be written stoichiometrically
as CH3N02 + CO + NO + 3/2 H2. Note that this reaction is itself endothermic (see reaction
R6a). On the other hand, three and a half molecules are formed for each nitromethane molecule, so
the entropy of this reaction if favorable, leading to a favorable free energy of reaction as the
temperature increases. In order to gain heat release, some of the NO must be reduced. In the
preliminary stage (I), N20 is formed via the HNO intermediate. During the first-stage ignition
(11), the temperature rise is sufficient to allow thermal decomposition of the N2O to form N2. The
relative importance of CH4 and CH30H has changed from our previous investigation 1141, with
CH4 now playing the more significant role. The relative importance of CH4 to CH30H is extremely
sensitive to the pressure dependence used for various elementary rate constants. In both cases,
these species serve to create a temporary heat source (see reaction R6b). The formation of CH4
occurs earlier in the reaction mechanism (arising from CH3) than does formation of CH30H
(arising from CH3O as indicated in ref. 14).

One can see from Fig. 3 that even the oxidation of the carbon of nitromethane to CO is a multistep
process. The major pathway has the CH3N02 breaking the C-N bond to form CH3 + NO2 which
recombines to form CH30NO which breaks the 0-N bond to form CH3O + NO. The NO then
abstracts the H from CH30 to form CH20 + HNO. Subsequent abstraction of hydrogen atoms
C4-546 JOURNAL DE PHYSIQUE IV

from CH2O lead to CO. As one can see from Figs. 6-8, this series of reactions is itself
endothermic. Thus, the initial set of reactions do not produce significant heat release. This
complex set of reactions plays an important role in keeping the nitro compounds from
spontaneously decomposing. The heat release from any exothermic reactions is converted into net
endothermic reactions. These series of elementary reactions are necessary to move the oxygen
atom from the nitrogen atom to the carbon atom, which cannot occur until the C-N bond is first
broken.

The secondary stage ignition is the reduction of NO to N2. This occurs by first reducing one of the
nitrogen atoms to a reduced state in HCN. This reduced nitrogen is then oxidized with another
oxidized nitrogen of NO to form the formally neutral N2. The formation of the reduced state of
nitrogen, HCN, occurs during the intermediate stage (111). This step is necessary because the NO
molecule is very stable, even at the intermediate temperatures.

As noted above, the large free energy release of the reaction is enhanced by the net increase in the
entropy of the reaction. The majority of this entropy increase occurs during the preliminary and
first-stage ignition, where the decomposition of each nitromethane molecule leads to between two
and three new molecules. Thus, while the exothermicity of the preliminary and first stages of the
reaction are small compared to that of the intermediate and second stages, the increase in entropy
plays an important role in driving the initiation process, allowing the initial reactions to proceed.

4.2 Ignition Delay Times

As discussed in the above section on the reaction mechanism, the nitromethane molecule cannot
"spontaneously" decompose to form exothermic products but rather must undergo a series of
intermediate steps, many of which are endothermic. These reactions lead to finite ignition delay
times, both for the primary and secondary stages. We can analyze these ignition delay times, 71
and Q, in terms of energies of activation, AE1 and AE2, and pressure dependencies nl and n2, as
defined above and in Tables 11-IV. The AE's and ni's are define as derivatives of the ignition delay
times xi's with respect to temperature and pressure, respectively, and thus, have meaning only in
the near region of the temperature and pressure specified. We have calculated the ignition delay
times for atmospheric pressures as well as a high pressure range corresponding to a nitromethane
density of that of liquid nitromethane. The pressure values presented in Tables 11-IV are an
idealized gas effective pressure with the real gas pressure being much higher. For the constant
volume calculations, it is better to view the calculations as constant density calculations.

The atmospheric conditions match the experimental data of Guirguis et al. [I]. The ignition delay
times are in quite good agreement with the experimental data. The 7.25 atm, 1131 K conditions,
for which the experimental was able to separate the two ignition stages, yielded a .ti and a T2 of
13.3 and 25.8 psec, which are in remarkable agreement with the experimental data of -12 and -25
psec respectively. These results give us confidence that the elementary reactions for modeling
nitromethane are accurate. This represents an improvement over the reaction mechanism used
previously [14], which had a reasonable first-stage ignition but a much delayed second stage
ignition. The ignition delay times range from microseconds at the low pressure to hundreds of
nanoseconds in the high density regime. At the high temperatures and densities, the 71.'~approach
the nanosecond time scale.

The effective activation energies of ignition are presented in Table 111. The resulting AE's indicate
that the first-stage ignition has an activation energy AE1 of -33-36 kcal-mol-1 at atmospheric
pressures, consistent with the experimental data [I]. At high densities, the AE1 is larger, -46
kcal-mo1,-1 though at elevated temperatures (1950 K), the AEl is -35 kcal-mo1.-1 These large
activation energies are dominated by the initial C-N bond breaking process, which has a bond
dissociation energy of 59 kcal-mo1.-l The second-stage ignition delay times, ~ ' sshow , a wide
variation in activation energies. This occurs because the ~ 2 ' sdecrease significantly faster than the
71's with increasing temperature and pressure. Ultimately, the q ' s approach the 71's and are
dominated by the 21 times at high densities. However, the difference between the two stages, 22 -
71, is still several nanoseconds (see Table 11).

The effective pressure dependencies of ignition (at constant temperature) are presented in Table
IV. The resulting nits exhibit varied behavior. At low temperature and pressure, the first-stage nl
pressure dependence is between zeroth order (nl = 0) and first order (n2 = I), corresponding to
effective unimolecular and bimolecular behavior. The secondary stage nz pressure dependence at
the low temperature and pressure is first order and greater. At high pressures, both the nl and n2
pressure dependencies approach zeroth order, indicating the dominance of the first-stage ignition
delay time and the high effective activation energy representative of C-N bond breaking. It is
difficult to relate these pressure dependencies to shock induced experiments where temperature
changes occur simultaneously with pressure changes.

The comparison of our high density results with the experimental ignition delay times at kilobar
pressures and low temperatures indicate some significant differences. As an example, we use the
experimental ignition delay times measured by Lee et al. [3] for 10 and 50 kbar and 400-600 K.
Their z's range from 10 - 100 seconds and have an effective activation energy of -16 kcal-mo1.-1
While this activation energy is significantly lower than what we calculate for the higher
temperature (1 100-1300K) conditions (-45 kcal-mol-I), our pre-exponential rate constants are
much larger. Defining the rate constant k as the inverse of the ignition delay time, the effective
high temperature rate constant is k - 1.4 1014 exp(-45.4RT) while the effective low temperature
rate constant (at 10 kbar) is 2.7 108 ;xp(-15.7/R~). That is, our ignition delay times are between
200 nsec - 4 psec while their extrapolated 7's are still longer than 100 psec. On the other hand,
our 7's in the 400-600K range would be longer than theirs. This suggests a switch in mechanism in
which at the lower temperatures, the reaction mechanism is "condensed phaseu-like, involving
proton transfer and hydrolysis reactions, while at high temperatures above 1000 K, the reaction
mechanism is "gas phasew-like,involving radical species. We have investigated the inclusion of
bimolecular as well as solvent-assisted proton transfer and hydrolysis reactions in our mechanism
to mimic the condensed phase reaction process. The results are encouraging. The small pre-
exponential rate constants for such reactions (possessing severe entropy constraints) make such
reactions important in the 400-600 K temperature range while they have essentially no effect in
the 1100-1900 K range. Considerable work remains in order to elucidate the actual elementary
reactions for the low temperature, condensed-phase regime.

5. CONCLUSIONS

We have calculated the initiation process for nitromethane using detailed chemical kinetics. The
starting conditions were gaseous nitromethane at atmospheric pressures as well as elevated
pressures corresponding to liquid density and temperature above 1000 K. The results indicate that
the chemical reaction mechanism requires multiple steps, in which many of the initial steps are
endothermic. This complex chemical mechanism prevents the energetic nitro-compound from
releasing its stored chemical energy immediately as a shock wave passes by. Ignition delay times
indicate relatively high activation energies and low pressure dependencies, indicative of initial
bond-breaking of the C-N bond. The agreement between our ignition delay times and the
experimentaldata of Guirguis et al. [I] is encouraging for the modeling of other nitro-containing
energetic material. These systems will have similar NO, HNO, N20, and HCN chemistry,
particularly for the second-stage ignition. These results indicate that a different mechanism is
occurring at elevated temperatures (> 1000 K) compared to lower temperatures.

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