Journal of Loss Prevention in the Process Industries 15 (2002) 119127

www.elsevier.com/locate/jlp
Evaluations of kinetic parameters and critical runaway conditions
in the reaction system of hexamine-nitric acid to produce RDX in
a non-isothermal batch reactor
Kuo-Ming Luo
*
, Sheann-Huei Lin, Jih-Guang Chang, Tzung-Huei Huang
Department of Applied Chemistry, Chung Cheng Institute of Technology, National Defense University, Tashi, Taoyuan 33509, Taiwan
Abstract
In the production process of RDX from the reaction of hexamine and nitric acid, its reaction rate was evaluated and expressed
as r
A
=1.23410
6
e
5671.062
T C
NO
C
1.28
A
, where T is the reaction temperature, C
A
is the concentration of hexamine and C
NO
is the initial
concentration of added nitric acid. The critical condition of runaway reaction for the RDX production in a batch reactor is

c
=20.4374.805/[1+exp(336.7b15.65)]. Its heat transfer coefcient at critical runaway condition was also estimated and
expressed as (hS/V)
cr
=(Rq
g
AC
NO
C
n
AO
)/(Eb
2
e
1/b
f
C
). 2002 Elsevier Science Ltd. All rights reserved.
Keywords: RDX; Hexamine; Runaway reaction
1. Introduction
The explosive RDX is also known as Cyclo-trimethy-
lenetriamine, Hexogen, T4 or Cyclonite. Its nomencla-
ture is 1,3,5-trinitrohexahydro-sym-triazine or 1,3,5-trin-
itro-1,3,5-triazacyclohexane. This explosive has been
very important since World War II and has served as a
constituent of many explosive mixtures from which a
high power was required. The molecular formula of
RDX is C
3
H
6
N
6
O
6
and its chemical structure is:
RDX was used in detonators and primers, and in detonat-
ing gains or boosters it is replacing tetryl. It was used
* Corresponding author.
E-mail address: luokm@cc04.ccit.edu.tw (K.-M. Luo).
0950-4230/02/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved.
PII: S0950- 4230( 01) 00027- 4
extensively in mixtures with TNT, as so-called hexolite,
semi-liquid, fusible explosive. The mixture of TNT,
RDX and aluminium is another kind of explosive. The
plastic explosives also contained RDX.
Although the RDX has been produced and used by
many countries for a long time, its production process
is not very safe so far. Numerous thermal runaway inci-
dents and explosion catastrophes have occurred in the
past. Unfortunately, its reactive hazard has not been
clearly identied. The critical runaway temperature and
unstable criterion at its reaction process are still
unknown. The industries have to control their operating
conditions very carefully to avoid the reaction system
becoming a runaway situation. Therefore, we evaluate
its reaction kinetic parameters from known production
data of RDX in this investigation. Then, we can deter-
mine the critical runaway conditions of RDX reaction in
a non-isothermal batch reactor using the transient energy
and mass balance equations and evaluated kinetic para-
meters by numerical techniques simultaneously. Conse-
quently, this critical runaway condition can be expressed
as a function of kinetic parameters of chemical reaction,
physical properties, and ambient temperature etc. Their
required heat transfer coefcients in this critical con-
dition can also be estimated.
120 K.-M. Luo et al. / Journal of Loss Prevention in the Process Industries 15 (2002) 119127
Nomenclature
A frequency factor of Arrehenius form, (L/mole)
1.28
min
1
C
AO
initial concentration of hexamine, mole/L
C
A
reacted concentration of hexamine, mole/L
C
P
heat capacity, kJ/mole.K
C
P,m
overall heat capacity in reaction system, kJ/mole.K
E activation energy in the reaction of producing RDX, kJ/g mole.
h heat transfer coefcient, J/m
2
K s
H
o
f
heat of formation, kJ/g mole
H
o
f,o
overall heat of formation, kJ/g mole
H
o
f,p
heat of formation for product, kJ/mole
H
o
f,r
heat of formation for reactant, kJ/mole
K reaction rate constant of producing RDX, (mol/L)
1n
min
1
m
HNO
3
weight percent concentration of nitrate acid, %
M
HA
molecular weight of hexamine, g/mole
M
RDX
molecular weight of RDX, g/mole
n reaction order in the reaction of producing RDX, .
N
AO
initial mole number of hexamine, mole
N
NO
initial mole number of nitric acid, mole
N
RO
initial mole number of RDX, mole
N
RDX
mole number of RDX after reacted, mole
N
HA
mole number of hexamine after reacted, mole
N
HNO
3
mole number of nitric acid after reacted, mole
r
A
reaction rate of hexamine, mol/(L.min)
Q
d
dilution heat, kJ/mole
Q
d,o
initial dilution heat of mixture, kJ/mole
Q
d,m
average dilution heat, kJ/mole
q
g
generation heat, kJ/mole
R universal gas constant, J/g mole.K
S external surface of cooling medium of reactor, m
2
t reaction time, min.
T temperature of reaction system, K
T
a
temperature of coolant, K
W
HA
feed weight of hexamine, g
W
HNO
3
feed weight of nitric acid, g
W
RDX
product weight of RDX, g
W
T
feed weight of hexamine and nitric acid, g
V volume of reactant, liter
x
A
fractional conversion of hexamine
x
HNO
3
fractional conversion of nitric acid
Y(%) yield percentage of weight RDX per gram of hexamine,
Greek symbols
b denition in Eq. (20)
r mixed density of reactant, g/cm
3
q denition in Eq. (19)
q
o
dimensionless temperature at initial time
f denition in Eq. (21)
f
c
values of f at critical runaway condition
j denition in Eq. (22)
t denition in Eq. (23)
h denition in Eq. (24)
121 K.-M. Luo et al. / Journal of Loss Prevention in the Process Industries 15 (2002) 119127
1.1. Evaluation of reaction kinetic parameters from
batch reaction of RDX
The chemical reaction rate is very sensitive and affec-
ted by the temperature variation in an exothermic reac-
tion system. Runway reaction or thermal explosion
occurs in this exothermic hexamine-nitric acid reaction
system in its production process. If we consider this
reaction system in a batch reactor, when the total gener-
ated heat rate of reactive system exceeds removed heat
rate of the ambient cooling medium, the whole system
is very easy to accumulate energy and raise temperature.
Then, this heat increasing system becomes unbalanced
and a self-ignition reaction is triggered off. As soon as
the temperature in this batch reactor reaches the critical
point, the reactive system becomes a runaway situation
or even explosion.
The chemical reaction of hexamine and nitric acid to
produce the RDX is expressed as the following equation:
C
6
H
12
N
4
+10HNO
3

(Hexamine)
C
3
H
6
N
6
O
6
+3CH
2
(ONO
2
)
2
+NH
4
NO
3
+3H
2
O
(RDX)
(1)
This is the main reaction between the reactants of hex-
amine and nitric acid. Besides, there is another side reac-
tion between these two reactants and its reaction equ-
ation is:
C
6
H
12
N
4
16HNO
3
6CH
2
(ONO
2
)
2
4NH
4
NO
3
(2)
In a batch reactor for producing RDX, the feed
weights of the nitric acid, W
HNO
, and the hexamine, W
HA
,
are equal to 110 and 10 g, respectively. The weight per-
centage concentration of nitric acid, m
HNO
3
(%), is equal
to 98%. The average density of mixed reaction solution,
r, is equal to 1.5g/cm
3
. The reaction time and tempera-
ture were set and its production weight of RDX, W
RDX
,
was measured. Thus the yield rate of RDX, Y(%), and
the fractional conversion of hexamine, x
A
, can be esti-
mated from experimental data. The molar numbers of
hexamine and RDX which can be expressed in terms
of the fractional conversion of hexamine reaction and is
estimated from experimental data by the following corre-
lations:
N
HA
N
AO
(1x
A
) (3)
and
N
RDX
N
RO
N
AO
x
A
N
AO
x
A
(4)
where N
AO
and N
RO
are the initial mole numbers of hex-
amine and RDX, respectively. The N
HA
and N
RDX
are the
mole numbers of hexamine and RDX after the system is
reacted, respectively. Owing to the value of N
RO
equal
to zero before reaction, from Eq. (4), the fractional con-
version of hexamine, x
A
, can be expressed as a function
of production RDX as:
x
A

N
RDX
N
AO

W
RDX
/M
RDX
W
HA
/M
HA

W
RDX
/222
10/140

7
111
W
RDX
(5)
The yield of RDX, Y(%), is dened as the percentage
of molar ratio of produced RDX to initial hexamine as:
Y%
N
RDX
N
HA
100%
W
RDX
/M
RDX
W
HA
/M
HA
100%100x
A
% (6)

700
111
W
RDX
%
In a batch reactor, the produced RDX, W
RDX
, at vari-
ous reaction times, t, and reaction temperature, T, were
measured which were obtained from Dai, Yen and Chen
(1996), and are listed in Table 1. Then, we can evaluate
the values of x
A
and Y(%) using Eqs. (5) and (6), the
results are listed in the last two columns of Table 1.
The reaction rate in the hexamine-nitric acid reaction
system can be expressed as the consumption of the tran-
sient molar number variation of hexamine in a control
reactant volume as:
(r
A
)
1
V
dN
HA
dt
(7)
If using the relation of C
AO
=
N
AO
V
and substituting Eq.
(3) into Eq. (7), we can express the reaction rate in terms
of fractional conversion of hexamine reaction as:
(r
A
)
N
AO
V
dx
A
dt
C
AO
dx
A
dt
(8)
where C
AO
is the initial concentration of hexamine. From
Eq. (8) we can rearrange and correlate the reaction time
Table 1
The producing weight of RDX and evaluated percentage of yields and
the fractional conversion of hexamine at various reaction times and
temperatures
a
T, C t, min W
RDX
Y (%) x
A
25 600 13.20 83 0.83
10 360 13.10 83 0.83
0 120 13.00 82 0.82
10 45 12.95 82 0.82
20 15 12.80 81 0.81
30 10 12.75 80 0.80
35 19 12.75 80 0.80
40 5 12.50 79 0.79
50 5 11.50 73 0.73
60 5 9.97 63 0.63
a
(a) Concentration of feed nitric acid, m
HNO
3
=98%. (b) Weight ratio
of feed nitric acid to hexamine, W
HNO
3
:W
HA
=110g:10g. (c) Density of
solution, r
mix
=1.5 g/cm
3
.
122 K.-M. Luo et al. / Journal of Loss Prevention in the Process Industries 15 (2002) 119127
as a function of fractional conversion and concentration
of hexamine in a batch reactor as:
tC
AO
x
A
0
dx
A
r
A

C
A
C
AO
dC
A
r
A
(9)
From the stoichiometry of reaction of Eq. (1), the
weight ratio of nitric acid to hexamine, W
HNO
:W
HA
, is
equal to 1063:222=2.84:1. The value of experimental
weight ratio, W
HNO
:W
HA
, in batch reactor as shown in
Table 1, is equal to 11:1. Thus, it is in great excess in
the feed quantity of nitric acid. The concentration of
nitric acid in this experiment is only a minor variation,
therefore it can be assumed as constant value. Conse-
quently, the reaction rate of hexamine in the nitric acid
system can be expressed as:
r
A
kC
NO
C
n
A
(10)
where, n, k and C
NO
are the reaction order, the rate con-
stant and the initial concentration of nitric acid in this
hexamine-nitrite acid reaction system, respectively. Sub-
stituting Eq. (10) into Eq. (9) and integrating it, we can
correlate the reaction time as a function of concen-
tration as:
t
1
(n1)kC
NO
[C
1n
A
C
1n
AO
] (11)
Using the relation of C
A
=C
AO
(1x
A
), Eq. (11) can be
rewritten as
t
C
1n
AO
(n1)kC
NO
[(1x
A
)
1n
1] (12)
Express the rate constant in Arrheniuss form as
kAe
E/RT
(13)
where A, E and T are the frequency factor, the activation
energy and the reaction temperature, respectively. Com-
bining Eqs. (12) and (13) to obtain
t
(1x
A
)
1n
1

C
1n
AO
e
E/RT
C
NO
(n1)A
(14)
Taking the natural logarithm on the both sides of Eq.
(14) to obtain
n

t
(1x
A
)
1n
1

C
1n
AO
A(n1)C
NO

E
RT
(15)
Table 2 shows the formulae which are used to calculate
the values of C
AO
and C
NO
from measured experimental
data and the evaluated kinetic parameters as listed in
Table 2
Evaluation of reaction kinetic parameters for the reaction of RDX pro-
duction from the experimental data of Table 1 and Fig. 1
Reaction rate r
A

dC
A
dt
Ae

E
RTC
NO
C
n
A
Total weight of solution W=W
HA
+W
HNO
3
=10+110=120 g
Density of solution r
mix
=1.5 g/cm
3
=1500 g/L
Volume of solution V
W
r
mix

120
1500
0.08 L
Concentration of nitric acid m
HNO
3
=98%
N
NO

W
HNO
3
m
HNO
3
M
HNO
3

1100.98
63
Initial molar number of nitric
acid
1.711 mole
Initial molar number of hexamine N
AO

W
HA
M
HA

10
140
0.071 mole
Initial molar concentration of
C
NO

N
NO
V

1.711
0.08
21.388 mole/L
nitric acid
Initial molar concentration of
C
AO

0.071
0.08
0.888 mole/L
hexamine
Value of reaction order n=1.28
A
exp(15.782)
(n1)C
NO
C
n1
AO
1.234
Frequency factor of kinetic
parameters
10
6

L
mole

1.28
min
1
E=5671.0628.314=47.149
Activation energy
kJ/mole
Table 1. The calculated results of C
NO
and C
AO
are equal
to 21.388 and 0.888 mole/L, respectively. Then, we can
plot the evaluated values of n[t/(1x
A
)
1n
1] versus
1/T as shown in Fig. 1. However, the value of reaction
order n is still unknown. Thus we have to evaluate n
value by means of trial and error technique. When
n=1.28 as shown in Fig. 2, this plot can obtain the best
linear correlation which is:
123 K.-M. Luo et al. / Journal of Loss Prevention in the Process Industries 15 (2002) 119127
Fig. 1. The manufacture process of RDX in a batch reactor.
Fig. 2. The evaluation of kinetic parameters in the batch reaction
system of hexamine-nitric acid to produce the RDX using Eq. (15).
n

t
(1x
A
)
1n
1

15.782
5671.062
T
(16)
Comparing Eqs. (15) and (16), we know that
n[C
1n
AO
/AC
NO
(n1)]=15.782 and E/R=5671.062 K,
respectively. Therefore, the values of reaction kinetic
parameters n, A and E are estimated and listed in
Table 2.
2. Evaluation of critical runaway condition in
hexamine-nitric acid reaction system
In order to estimate the critical runaway condition of
hexamine-nitric acid reaction systems in a batch reactor,
we have to calculate its transient variations of tempera-
tures and fractional conversions. Thus, we require the
energy and mass balance equations to calculate both the
transient values of temperatures and fractional conver-
sions, simultaneously. The nitration process of hexamine
to product RDX in a batch reactor is shown in Fig. 1.
The inlet and outlet temperatures of the coolant medium
are T
a
and T, respectively.
The transient energy and mass balance equations for
the production of RDX in a non-isothermal batch reactor
can be expressed as follows:
The heat balance in this reactor is:
rVC
P,m
dT
dt
q
g
V(r
A
)hS(TT
a
) (17)
We can combine Eqs. (8) and (13) to obtain the rate
of fractional conversion by
dx
A
dt
Ae
E/RT
C
NO
C
n1
AO
(1x
A
)
n
(18)
Using the following dimensionless denition which
has been described by Frank-Kamenetskii (1969) and
modied by Luo, Lu and Hu (1997a, b), Luo and Chang
(1998) and Luo and Hu (1998)
q
E
RT
2
a
(TT
a
) (19)
b
RT
a
E
(20)
f
Eq
g
VAC
NO
C
n
AO
RT
2
a
hS
e

1
b (21)
j
rC
P,m
VAC
NO
C
n1
AO
hS
e

1
b (22)
t
hSt
rC
P,m
V
(23)
h
f
j

Eq
g
C
AO
RT
2
a
rC
P,m

Rq
g
C
AO
b
2
ErC
p,m
(24)
Thus, we can express Eqs. (18) and (17) in dimen-
sionless form as
dx
A
dt
jexp

q
bq+1

(1x
A
)
n
(25)
dq
dt
fexp

q
bq+1

(1x
A
)
n
q (26)
In a batch reaction system of hexamine-nitric acid to
produce the RDX, the variation of fractional conversion
of hexamine was affected by its reaction temperature.
Their relationship can be correlated by combining Eqs.
(10) and (13) to obtain the following term:
x
A
1

(r
A
)e
E/RT
AC
NO
C
n
AO

1
n
(27)
Fig. 3 shows the calculations of the fractional conver-
sion of hexamine, x
A
, versus the reaction temperature,
T, using Eq. (27) and given values of A, E, n, C
NO
and
C
AO
which are listed in Table 2. The reaction rates of
hexamine are set as parameters that are varied from 0.01
124 K.-M. Luo et al. / Journal of Loss Prevention in the Process Industries 15 (2002) 119127
Fig. 3. The relationship of fractional conversion and reaction tem-
perature at various reaction rates for the hexamine-nitric acid system
in a batch reactor.
to 100 (mole/L min) in this calculation. Each curve rep-
resents the same reaction rate of hexamine. The higher
reaction temperature leads to the higher fractional con-
version for each reaction rate prole. However, the lower
reaction rate leads to the higher fractional conversion at
a given reaction temperature.
The values of fractional conversions of hexamine are
affected by the variation of reaction temperature. At the
same time, the reaction temperatures in the hexamine-
nitric acid reaction system are also affected by the
chemical consumption of hexamine. In order to evaluate
the transient reaction temperature and fractional conver-
sion in the hexamine-nitric acid reaction system, we have
to solve Eqs. (25) and (26) simultaneously. The required
heat capacities and generation heats in the calculations
of x
A
(t) and q(t) have to be evaluated from the average
values of mixture components in the nitric acid-hexam-
ine reaction system. Table 3 shows the values of heat
capacities (C
p
), for each component in this reaction sys-
tem, heat of formation (H
0
f
) and heat of dilution (Q
d
)
which were obtained from Dai et al. (1996).
2.1. Evaluating the values of q
g
, C
P,m
and q
o
The generation heat in the hexamine-nitric acid reac-
tion system includes the heat of formation and dilution
heat of nitric acid and hexamine. The heat of formation
Table 3
Heat capacities and heat of formations in the reaction of hexamine-nitric acid system and dilution heat of hexamine and nitric acid
Property Chemical C
6
H
12
N
4
HNO
3
C
3
H
6
N
6
O
6
CH
2
(ONO
2
)
2
NH
4
NO
3
H
2
O
H
f
o
KJ/mole 136.817 173.218 71.546 199.158 365.263 285.830
C
P
KJ/mole.K 0.176 0.125 0.307 0.227 0.141 0.075
KJ/kg.K 1.256 1.989 1.382 1.926 1.759 4.187
Q
d
KJ/mole 20.083 2.931
can be determined from the stoichiometry of chemical
reaction, combining Eqs. (1) and (2), the overall reaction
for the production of RDX is
C
6
H
12
N
4
13HNO
3

1
2
RDX
9
2
CH
2
(ONO
2
) (28)

5
2
NH
4
NO
3

3
2
H
2
O
The overall heat of formation is
H
0
f,o
n
i
H
0
f,i
N
product
H
0
f,p
N
reactant
H
0
f,r

1
2
(71.546)

9
2
(199.158)
5
2
(365.263)
3
2
(285.830) (29)
136.81713(173.218)87.324 kJ/mole
The heat of dilution (Hale, 1925) for the mixture
includes the dilution of nitric acid and hexamine which
can be expressed as
Q
d,m
x
A
Q
d,HA
x
HNO
3
Q
d,HNO
3

N
HA
N
HA+N
HNO
3
Q
d,HA

H
HNO
3
N
HA
+N
HNO
3
Q
d,HNO
3

0.071
0.071+1.711
(20.083) (30)

1.711
0.07+1.711
(2.931)3.614 (kJ/mole)
Thus, we can evaluate the generation heat q
g
per mole
hexamine by adding up Eqs. (29) and (30) as
q
g
[H
0
f,0
Q
d,m
][87.3243.614] (31)
90.938 (kJ/mole)
The initial dilution heat of nitric acid and hexamine is
Q
d,0
N
HA
Q
d,HA
N
HNO
3
Q
d,HNO
3
(0.071)( (32)
20.083)(1.711)(2.931)6.441 kJ
At initial time, the heat of dilution can also be
expressed as mixing of nitric acid and hexamine as
125 K.-M. Luo et al. / Journal of Loss Prevention in the Process Industries 15 (2002) 119127
Q
d,0
(W
HA
C
p,HA
W
HNO
3
C
p,HNO
3
)(TT
a
) (33)
W
T
C
P,m
(TT
a
)
Thus, the value of (TT
a
) at initial time is
(TT
a
)
initial

Q
d,0
W
HA
C
p,HA
+W
HNO
3
C
p,HNO
3
(34)
27.841 K
If we set the values of T
a
is equal to 25C, the dimen-
sionless temperature at initial time can also be determ-
ined as
q
0

E
RT
2
a
(TT
a
)
initial

47149
8.314298.16
2
(27.841) (35)
1.776
These values of C
P,m
, q
g
and q
o
should be used in the
calculation for the critical condition.
A typical calculation in this batch reaction system for
f=0.95, b=0.053 and j=0.533 is shown in Fig. 4. The
dimensionless reaction temperature prole increases in
the beginning but decreases at the end of chemical reac-
tion. There is a maximum temperature point, i.e.
q=q
max
=2.17, at the dimensionless reaction time
t=t
max
=0.318. Another calculation shows the variation
of fractional conversion of hexamine prole increases
very fast at the starting time of reaction. It reaches
almost a constant value after the reaction time is greater
than the value of t
max
.
However, the transient temperature proles do not
always behave the same as in Fig. 4. Some of the dimen-
sionless temperature proles go to the maximum point
q
max
very quickly and sharply. The reaction temperatures
may increase very quickly to a higher degree in a reac-
tion time. Sometimes they decrease directly to a low
Fig. 4. The relationships of q and x
A
versus t for the production of
RDX in a non-isothermal batch reactor.
degree after the chemical reaction is proceeded. Fig. 5
shows the calculations of dimensionless reaction tem-
perature q versus the dimensionless reaction time t with
various values of f as parameters in a batch reactor of
hexamine-nitric acid reaction system. The values of f
for the curves of A, B and C are equal to 200, 140 and
100, respectively. These three curves of dq/dt increase
to an innite large value when the dimensionless reac-
tion time, t, reaches some conned value. These mean
that dq/dt at conned time. This phenomenon in the
reaction system is a runaway reaction. The values of f
for the curves of E, F and G are equal to 20, 5 and 1,
respectively. The situation of dq/dt never happens
for these three curves. Thus, the conditions for these
three curves belong to safe reaction. The dashed curve
D is the value of f which is equal to 60.712. This curve
is the critical curve for the reaction system either goes
to the runaway or safe reaction when the values of f are
larger or less than the value of this critical value of
60.712. We dene the value of f at this critical curve
as f
C
for a given b. When ff
C
, the reaction system
goes to the runaway situation. Otherwise, when ff
C
,
the reaction system is safe.
The transient fractional conversions of hexamine cor-
responding to each value of f is shown in Fig. 6. The
values of x
A
increases to unity very quickly when the
values of j are relatively higher. When the values of j
are relatively lower, the values of x
A
grew gently to
unity. For a given value of b, the value of f at the critical
condition of runaway reaction, f
C
, can be obtained by
means of trial and error iterations. When the value of b
is changed, the value of f
C
is also changed. Fig. 7 shows
the variations of f
C
are varied along the increasing of
b. We can express f
C
as a function of b by means of
mathematical curve tting in this calculated f
C
b data
and obtain the following equation as:
Fig. 5. The affection of f value on the q trajectories along the vari-
ation of t for the production of RDX in a non-isothermal batch reactor.
126 K.-M. Luo et al. / Journal of Loss Prevention in the Process Industries 15 (2002) 119127
Fig. 6. The affection of j value on the X
a
trajectories along the vari-
ation of t for the production of RDX in a non-isothermal batch reactor.
Fig. 7. The relationship of f
c
and b at the critical runaway condition
for the production of RDX in a non-isothermal batch reactor.
f
C
20.437
4.805
1+exp(336.7b15.65)
(36)
From this equation, we can evaluate the value of f
C
at the runaway condition for various values of b. Thus,
when the value of f in a hexamine-nitric acid batch reac-
tion system is determined, we can evaluate whether a
reaction system is runaway or safe by the following cri-
teria:
ff
C
reaction system goes to runaway.
f=f
C
critical runaway.
ff
C
reaction system is safe.
By combining Eqs. (28) and (21), the critical value
of heat transfer coefcient in a control volume can be
expressed as

hS
V

cr

Rq
g
AC
NO
C
n
AO
Eb
2
e
1/b
f
C
(37)
Fig. 8 shows the required critical values of heat trans-
fer per unit volume of batch reactor in the hexamine-
nitric acid batch reaction system. The calculated curve
of (hS/V)
cr
using Eq. (37) is the watershed of safety and
runaway situation. Below this curve, the reaction
belongs to runaway region. Another region above this
critical curve belongs to safe reaction region.
3. Conclusion
In the reaction of hexamine-nitric acid system to pro-
duce RDX in a batch reactor, its reaction rate is
r
A
1.23410
6
e
5671.062
T C
NO
C
1.28
A
The batch reaction system of RDX production being
either runaway or safe can be evaluated from the values
of f. This system is safe when the values of f is less
than f
C
. On the contrary, this system is runaway if the
values of f are larger than f
C
. The values of f
C
at the
critical runaway condition in a batch reaction of RDX
is a function of b and expressed as:
f
C
20.4374.805/[1exp(336.7b15.65)]
For a reactor design of RDX production, the values
of heat transfer are important for its safety. Its required
heat transfer per unit volume of reactor at critical con-
dition is determined by the term:

hS
V

cr

Rq
g
AC
NO
C
n
AO
b
2
Ee
1/b
f
C
Fig. 8. The critical required heat transfer coefcient per unit volume
reactor for the production of RDX.
127 K.-M. Luo et al. / Journal of Loss Prevention in the Process Industries 15 (2002) 119127
For safe production of RDX, the values of (hS/V) must
be greater than the values of (hS/V)
cr
.
Acknowledgements
The authors gratefully acknowledge the support of the
National Science Council of the Republic of China under
grant NSC 89-2214-E014-001.
References
Dai, R. Z., Yen, S. E., & Chen, Y. K. (1996). The production tech-
nology and design of explosives. Weapon Industrial Pub. Co in Chi-
nese.
Frank-Kamenetskii, D. A. (1969). Diffusion and heat transfer in
chemical kinetics (2nd ed.) (J. P. Appleton, Trans.). New York:
Plenum Press.
Hale, G. C. (1925). J. Am. Chem. Soc., 47(11), 27542763.
Luo, K.-M., Lu, K.-T., & Hu, K.-H. (1997a). J. Loss Prev. Process
Ind., 3, 141150.
Luo, K. M., Lu, K. T., & Hu, K. H. (1997b). J. Loss Prev. Process
Ind., 10 (3), 141150.
Luo, K. M., & Chang, J. G. J. (1998). Loss Prev. Process Ind., 11,
8187.
Luo, K. M., & Hu, K. H. (1998). J. Loss Prev. Process Ind., 11,
413421.