THE JOURNAL OF

PHYSICAL CHEMISTRY
Registered in U.S. Patent Oflice @ Copyright, 1967, by the American Chemical Society

VOLUME 71, NUMBER 8 JULY 14, 1967

On the Products Formed in the Combustion of Explosives.

Freeze-out of the Water-Gas Reaction

by Richard R. Bernecker and Louis C. Smith

Universi& of California, Los Alamos Scientific Laboratory, Loa Alamos, New Mexico 87644
(Received March 9, 1967)

RDX, HMX, PETN, TNT, and composition B were burned under helium in a closed bomb
a t initial pressures of from 1 to 120 atm and the combustion products were analyzed. At
low initial pressures (below 10 atm), burning was erratic and it appears that the products
were formed in part, a t least, a t a relatively low temperature. The products formed a t
high pressures consisted primarily of Nz and the species involved in the water-gas reaction,
except in the case of TNT, where significant amounts of carbon were formed. The high-
pressure data are interpreted in terms of a mechanism which involves the freezing out
of the water-gas equilibrium in the rapidly cooling combustion products. This freeze-out
process is discussed analytically and certain numerical results obtained with a high-speed
computer also are presented. Simple procedures for estimating freeze-out temperatures
and final product compositions, valid over a wide range of conditions, are given and are
used to estimate cooling rates in these and certain related experiments.

Introduction It was found that many of the data obtained at higher

One method used to compare the decomposition
mechanisms of explosives under various conditions is
to compare the compositions of the gaseous products
produced. For example, in this manner Robertson
and Yoff e concluded that for nitroglycerin, pentaeryth-
ri to1 tetranitrate (PETK) , and cyclotrime t hylene-
trinitramine (RDX) decomposition under impact
conditions occurs by a very similar mechanism to that
operative in thermal decomposition.
The purpose of our work was to determine the prod-
ucts formed when several common explosives are burned
a t moderate pressures in an inert atmosphere (helium).
pressures could be interpreted in terms of the kinetics
and equilibrium of the water-gas reaction and the rate
of cooling of the combustion products. At low pres-
sures, ignition and/or burning became erratic and the
composition of the combustion products changed
significantly.
Experimental Section
The samples (-1 g) were burned in a 240-ml Parr
high-pressure oxygen bomb (Model 1104) equipped with
(1) A. J. B,Robertson and A. D. Yoffe, Nature, 161, 806 (1948).

2381
2382
a heavy, stainless steel sample cup and sample support
cage.2 An electrically heated Pt wire was used to
ignite the samples. The explosives were of standard
ordnance manufacture and quality. The powdered
samples were obtained from stock used as standards
for the drop-weight impact test at Los Alamos. The
high-density samples were prepared by pressing the
explosive (HE) in a mold to the desired density and
then machining the pressed pellets to the desired cy-
lindrical shape (0.200-in. diameter X 0.900-in. length).
The platinum ignition wire was 18 mils in diameter
and was wound in the shape of a helix. For the
powders, the helix was l/s-in. in diameter and was
partially buried in the powdered HE; for the pressed
charges, the diameter of the helix was just large enough
to allow the cylindrical charge to be slipped inside.
The powdered samples were placed directly in the
sample cup, while the pressed cylinders were suspended
just above the bottom of the cup by the Pt helix.
After the bomb was assembled, it was evacuated,
filled with helium, and connected to a low-voltage,
high-amperage ignition system powered by several
6-v batteries. Since the ignition circuit was not a con-
stant-resistance network, the start of burning could be
observed by a sudden drop in current. Current was
applied to the sample only long enough to initiate
burning.
The gases were sampled by allowing the bomb prod-
ucts to expand into an evacuated 10-ml high-pressure
bomb. The contents of the 10-ml bomb were ex-
panded, in turn, into several 1-1. glass bulbs for analy-
sis. The gas samples were analyzed on a Consoli-
dated Electrodynamics Corp. RIodel 21-103 mass
spectrometer. Analysis by mass spectrometry is
expected to give routinely good results for CO, C02,
Nz, H2, N20, S O , and CH4, but less accurate results
for some of the other products. NO2 does not produce
a parent peak in our mass spectrometer, but is readily
detected by its color. Xone was seen in any of the
sample bulbs. Water, a major product, is very dif-
ficult to determine quantitatively in a routine mass
spectral analysis. Water was found in the analyses,
but the amount detected depended upon the condi-
tions of the experiment and the method of sampling
(liquid water was frequently present in the bomb when
it was opened). Similar difficulties are encountered
with S H a , HCK, and HzCO; however, in our experi-
ments these were present in minor amounts and repre-
sent a relatively small source of error. For these
reasons we have presented the analytical data for many
of the samples in two ways. In the first method, used
for all the samples, the analyses are reported on a
water-free basis. That is, the mole per cent of each
The Journal of Physical Chemistry
RICHARD A N D LOUISC. SMITH
R. BERNECKER
gas other than water was computed as though no water
were present.
For those explosives expected to produce only vola-
tile products, a second set of data mas obtained by
adding sufficient water to the water-free data to give
the proper O/C or, in a few cases, O/N ratio. Justi-
fication for this procedure is that in most such cases
it does produce an excellent material balance, in-
cluding the correct value for the independent H/C
(or H/N) ratio.
Results
Cyclotrimethylenetrinitramine ( R D X ) and P-Cyclo-
tetramethylenetetranitramine ( P - H M X ) . The gaseous
products from the burning of R D X were studied at
various pressures and HE densities, while the products
from 0-HMX were obtained only on the powdered ma-
terial at several pressures. Table I contains the ex-
perimentally determined (water-free) compositions
and the corresponding material balances and also
the compositions and material balances obtained after
correcting the data for water, as already described.
For samples in which >99% decomposition occurred,
the calculated material balances match the molecu-
lar formula quite well. Infrared analyses of the few
milligrams of material left in the sample holder in
the high-pressure runs indicated that it was pure
starting material for the R D X experiments and a mix-
ture of the HMX polymorphs for the HMX experi-
ments.
The effect of explosive density on gas composition
was briefly investigated for RDX. Powdered samples
burned a t 359, 640, and 1740 psi and a pressed sample
(1.62 g/cc) burned at 646 psi show nearly identical
gas compositions. Two pressed charges (1.755 g/cc,
96.5% of crystal density) burned at approximately
1780 psi show slightly different compositions.
At lower pressures, combustion of the samples is less
complete and the composition of the product gases
changes noticeably. This is consistent with the ob-
servations of Andreev and P l y a ~ u n o v ,who
~ reported
that at pressures of a few atmospheres intermediate
products of combustion (such as the nitrogen oxides)
tend to be formed, whereas at high pressures only the
products of complete conversion are found. Their
data for the combustion of RDX under 1 atm of Nz
also are given in Table I. A comparison of the data
from our low-pressure runs with their data shows reason-
able agreement, the main discrepancy being in the
amount of Nz found. This is reflected in their material
(2) Described in Spec. No. 1100, Parr Instrument Go., Moline, Ill.
(3) K. K. Andreev and hl. S. Plyasunov, Z h . Vses. Khim. Obsh-
chestza im. D . I . Mendeleeta, 8, 586 (1963).
PRODUCTS FORMED I N THE COMBUSTION O F EXPLOSIVES
balance for Nz and may represent an analytical dif-
ficulty causcd by the large amount of Nz initially pres-
ent in their experiments.
The HMX data confirm the trend observed with
RDX, but here we have, in addition, two cases of very
incomplete combustion, accompanied by drastic changes
in composition. Evidently either ignition or burning
becomes erratic at sufficiently low pressure under the
conditions of our experiments and it is quite possible
that these composition changes are the accidental
result of a mixed burning-thermal decomposition proc-
ess rather than :L direct effect of pressure per se.
Evidence supporting this interpretation is contained in
the data of Robertson4 (Table I), which show the
thermal decomposition gases obtained from molten
H M X during a 2-min reaction at 280. Large amounts
of NO and NzO are common in both experiments; how-
ever, the presence of equally large amounts of HCN in
our sample, but not in Robertsons, shows that the two
results are not strictly comparable.
Pentaerythritol Tetranitrate ( P E T N ) . Data on the
combustion products of P E T N have not been re-
ported in the literature and hence a more thorough
study of the effect of pressure was undertaken on
powdered samples. The gas compositions and ma-
terial balances are shown in Table I for a pressure
range of 19-724 psi. Higher pressures were not studied,
since the differences between the 375 and 724 psi data
indicated constant compositions, as already noted
for R D X and HMX. The data of Table I include
both the water-free and corrected compositions. These
corrected data show that at high pressures Nz,CO,
COZ,Hz,and HzOare the final products.
At low pressures we again find incomplete combus-
tion of the sample, accompanied by a marked change
in gas composition. Data on the thermal decom-
position products of P E T N at 210, obtained by
Robertson5 and given in the table, again suggest the
possibility of a mixed burning-thermal decomposi-
tion process for our low-pressure experiments, al-
though we do not find the large amounts of N 2 0 and
NO2 reported by him.
2,4,6-Trinitrotoluene ( T N T ) . The burning char-
acteristics of T N T differ from those of the three ex-
plosives already discussed, in part because of its lower
melting point (81). Attempts to burn pressed T N T
met with failure. Even though the Pt helix in which
the cylindrical charge was placed covered 90% of the
length of the charge, the T N T would merely melt
where the wire contacted it and the sample would
slide through the wire without igniting.
Powdered T N T samples could be burned; however,
from the ignition characteristics and examination of
2383
some recovered samples, it appeared that substantial
melting occurred before the sample ignited. In one
unsuccessful run in which ignition did not occur, the
upper part of the sample had melted and was fused onto
the platinum wire, while the lower part of the sample
was in its initial state.
The data in Table I show the gas compositions from
the burning of T N T over the pressure range of 21-
1811 psi. The high-pressure combustion experi-
ments show essentially constant compositions and poor
material balances, especially for carbon. The latter
is to be expected, as a fluffy deposit of carbon was
found in the bomb. We have, therefore, reported
these results on the basis 0 = 6 rather than C = 7.
A low-pressure (21-psi) combustion run was made to
compare our results with those reported by Andreev and
Plyasunov13 whose data are shown for comparison.
The agreement is good, although the Russians have
a slightly poorer nitrogen balance. This 21-psi run
gave only a partial burn (<50% decomposition of
TNT) and thus the material balances are not expected
to be good. It is evident from the material balances
that there are serious shortages in carbon and hy-
drogen-more serious at the lower pressures than a t the
higher pressures. It seems clear that the decomposi-
tion produces nonvolatile products other than carbon
under these conditions.
Composition B-3 (60% RDX :40% T N T ) . Compo-
sition B-3 is prepared by cooling a slurry of R D X in
molten T N T and it thus represents an intimate mix-
ture of these two materials. The data given in Table
I were obtained on the loose powder and on pressed
pellets prepared from the powder. Excellent material
balances are obtained from the corrected gas analysis
data, which suggests that equilibrium between the
products of the two components has been reached in
the flame. There is no variation in composition over
the 350-1800-psi pressure region or in going from the
bulk explosive to charges pressed to 98% of the theo-
retical maximum density. Decomposition of the
samples was nearly complete, although trace amounts
of carbon black and other colored material were found
in the sample cup after burning.
Discussion
In the higher pressure runs with RDX, HMX,
PETN, and composition B, the combustion products
consist primarily of Nz and the species involved in the
water-gas reaction given as eq 1.
(4) A. J. B. Robertson, Trans. Faraday Soc., 45, 85 (1949).
(5) A. J. B. Robertson, J. SOC.Chem. Ind. (London), 67,221 (1948).
Volume 71, Number 8 July 1967
2384 RICHARD AND LOUISC. SMITH
R. BERNECKER

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The Journd of Physical ChemiutTy

PRODUCTS OF EXPLOSIVES
IN THE COMBUSTION
FORMED 2385

Volume 71, Number 8 July 1967

2386 RICHARD AND LOUISC. SMITH
R. BERNECKER

Table I1 : K for High-pressure Runs

Approx initial
bomb press..
psi Pellets
RDX
Powder
- HMX
powder
PETN
powder
-Corhposition
Pellets
B
Powder

1780 3.86, 4 . 0 3 4.62 4.89 3.71

724 4.15
645 4.56 4.49 3.76, 3.91 3.87
37 0 4.62 4.32 3.98 3.86 3.68
160 4.29
Average values -
4.59 f 0.26 4.14 f 0.39 3.80f0.10
(RDX and HMX powder)
&95y0 confidence limits.

ture a t which reaction effectively ceases in the rapidly

It is to be expected, therefore, that the kinetics and
equilibrium of this reaction will play a decisive role
in determining the composition of the product gases.
The values computed for the quantity K = ~ O X ~ , O /type, however, the cooling rates cannot be calculated
x ~ ~ ~ where , xi are the mole fractions in the com-
x H ~ the
bustion products, are given in the last column of Table
I. It is evident that incomplete combustion of the
sample leads to high values of K and, indeed, with the
exception of the 39-psi sample, a reasonably good
linear relationship between K and the per cent de-
composition can be obtained from the P E T N data.
Somewhat less obvious is that the formation of N 2 0 is
accompanied by slightly high values of K even though
combustion of the sample is nearly complete. In-
complete combustion and formation of NZO were ob-
served only in experiments carried out a t low pressures. temperature T depends on time in the cooling gases.
Evidently, under these conditions processes may occur
which lead to atypical product compositions.
The remaining values of K, obtained at initial
pressures of 160 psi or higher, are collected in Table 11.
The composition B-3 values fall within quite a small
range and scarcely suggest any dependence of K on
either pressure or the degree of consolidation of the
sample. P E T N and HMX were burned only as loose
powders, but again no dependence of K on P is sug-
gested by these results. For RDX, the two values
obtained with pressed charges at the highest pressure
appear to be significantly lower than the remaining
cooling combustion products.
As has been shown by Behrens, the process involved
here can, in principle, be analyzed in terms of the ki-
netics of the water-gas reaction and the rate of cooling
of the combustion products. In experiments of this
from the initial conditions; all we can hope to do is to
use the analysis to estimate the cooling rates and then
inquire whether the values so obtained are reasonable
in terms of the processes believed to be occurring in
the bomb. The approach used in the analysis given
here is quite different from that used by Behrens.
The quantity of interest is (uvlxy) - K , where u =
[CO], v = [HzO],x = [C02],y = [Hz],and K is the
equilibrium value of uv/xy. K depends on time t
through the relations K = K ( T ) and T = T(t), the
latter of which expresses the manner in which the
Throughout the discussion we will assume that T(t)
can be adequately approximated over the range of
interest by a linear function.
We further assume that the water-gas reaction can
be represented in the kinetic form implied by eq 1 ;
that is, that it is a simple reversible reaction, second
order in both directions. It is then easy to show
that, for constant T, the dependence of uv/xy on t
is given by
d uv
dtxy
-- =
d uv
-(-
dt xy - K ) = -h~~p(t
-K) (2)

four values.
If K is equated to the equilibrium constant K , the
temperatures corresponding to the values shown in
Table I1 range from about 1750 to 2100K.6 These
temperatures are much lower than the adiabatic flame
temperatures and presumably represent the tempera-
(6) K as a function of T was obtained from F. D. Rossini, et al.,
Selected Values of Physical and Thermodynamic Properties of
Hydrocarbons and Related Compounds, A. P. I. Research Project
44, Carnegie Press, Pittsburgh, Pa., 1953, p 748.
(7) H. Behrens, Z. Phyaik. Chem. (Leipzig), 195, 24 (1950). See
also 9.S.Penner, Chemistry Problems in Jet Propulsion, Pergamon
Press, New York, N . Y., 1957, Chapter 23.

The Journal of Phvsical Chemistry

 FORMED
PRODUCTS OF EXPLOSIVES
IN THE COMBUSTION 2387

where p (uv/xy) (x y) u+ + +v will be assumed
constant during the "freeze-out" process. The total
differential with respect to time is d/dt = (a/&)
(dT/dt) (d/dT) and, therefore, the time dependence
of (uv/zy) - K is given by the integral of the equation
d(y - K) = -kw1fi(g dtfi
- K ) - dTdK
dt xy
This equation cannot be integrated in a form useful
for our purposes. We can, however, use it to obtain
a method of estimating freeze-out temperatures via
the following argument.
For the case we are interested in here, dT/dt < 0,
and, over a limited temperature range, we can assume
-dK/dt E constant > 0. If initially (uv/zy) - K =O,
then (dldt) [(uvlxy) - K ] 2 0 for all t , and (uv/xy) -
K is a positive, nondecreasing, continuous function of
t for all t > 0. It follows that (uvlxy) - K can re-
main small only if
(except., possibly, for momentary fluctuations) or, from
(3) and our assumptions on K(t), if
- K)
k-d3(: g dt constant
Now, k-1 decreases as t increases, and eq 5 thus defines
the rate at which (uv/xy) - K must increase if (4)is
to hold. In particular, by differentiating eq 5 we ob-
tain
Here we have introduced the relaxation time r = - dt/d
In [(uvlxy) - K ] from eq 2 and an Arrhenius expres-
+ sion for the dependence of k-1 on T , L-1 = Ae- E / R T
It is clear that eq 5 may fail (and undoubtedly does)
long before (d/dt) [(uvlzy) - K ] attains its maximum
value. The point we are interested in here, however,
is that eq 5 cannot be true when the inequality expressed
(3)
in eq 6 is satisfied. That is, eq 6 is a sufficient (but not
necessary) condition for (uv/xy) - K t o increase
rapidly, or, in other words, for freeze-out to occur.
Shock tube studies of the macroscopic kinetics of the
reaction 1 have been made by RiIatthews*in a tempera-
ture and pressure range close to that of interest here.
Neither A nor E was determined with great precision,
but from a least-squares fit of his data Matthews
summarized his results for kl in the form
kl = 3.6 X 1011e --59,40O/RT 1. sec-~
Matthews' measurements were made in the tempera-
ture range 2180-2580"K1 whereas we are interested
(4) primarily in the rate of the reverse reaction a t tempera-
tures around 1800K. From IC-, = Ll/K we have
= En, - AH
and
A ki
(5) log - = log K
Ak-1
+-AH
2.3RT
where AH is the heat of reaction. At 1800"K, AH =
6.5 kcal/mole and K = 3.8@and hence
Using this result in eq 6 with T = 1800"K, we obtain

or, using (5) again

7 > 12013 (7)
dK d In k-@
--
dt dt
+ k-@A(y
dt xy
- K) 20
In other words, freeze-out occurs as soon as the relaxa-
tion time exceeds the time required for the temperature
to decrease by about 100-150". This is essentially
However, this condition cannot be satisfied for arbi- the result Behrens obtained numerically.
trarily small values of k-$, for the maximum possible An alternative form of eq 6 convenient for more ac-
value for (d/dt)[(uv/xy) - K ] is, from (3), -dK/dt. curate calculations is
Therefore, eq 5 surely can no longer be true when
E/2.3R
- 1 -dKdlnk-@ " - - - K > - -dK < log a + 2 log T - log (E/R)
(8)
k-ip dt dt - dt (uvxy ) dt
where a = @ A / B and B = -dT/dt. The iteration
or when
on T converges very rapidly.
1 dt - While eq 7 and 8, used with equal signs, are con-
7 = - > -
k-,p d In k-lp venient rules of thumb for estimating freeze-out tem-

-dt/dT = RT"ldt! (6) (8) J. C. Matthews, "A Shock Tube Study of the Reaction Between
d l n k-lp/dT E dT H2 and COO," Dissertation, Washington University, 1965.

Volume 7 1 , Number 8 July 1967

2388 R. BERNECKER
RICHARD AND LOUISC. SMITH

Table 111: Comparison of K ( T r ) with Computed Values of (uv/zy)r

-E 62,400----
Tr
(eq 8) K ( Tr) (UV/ZY) f

1 x 103 1880 4.21 4.03 2230 5.44 5.22 2560 6.28 6.11
3 x 103 1750 3.69 3.50 2060 4.88 4.70 2380 5.86 5.67
1 x 104 1620 3.14 2.96 1910 4.33 4.15 2200 5.35 5.17
3 x 104 1510 2.67 2.54 1790 3.85 3.68 2060 4.88 4.72
1 x 105 1410 2.25 2.13 1670 3.35 3.20 1930 4.41 4.23
3 x 105 1330 1.92 1.81 1570 2.93 2.81 1820 3.97 3.81
1 x 106 1250 1.61 1.52 1480 2.54 2.43 1710 3.52 3.38
3 x 106 1180 1.34 1.28 1400 2.21 2.12 1620 3.14 3.02
1 x 10' 1120 1.13 1.07 1330 1.92 1.82 1540 2.80 2.66
3 x 10' 1070 0.970 0.905 1270 1.68 1.59 1460 2.46 2.37
1 x 108 1010 0.786 0.751 1200 1.42 1.36 1390 2.16 2.08
3 x 108 970 0.673 0.633 1150 1.24 1.18 1330 1.92 1.85
1 x 109 920 0.543 0.523 1100 1.07 1.01 1270 1.68 1.62
3 x 108 890 0.471 0.439 1060 0.938 0.878 1220 1.49 1.43
1 x 10'0 850 0.383 0.360 1010 0.786 0.750 1170 1.31 1.25

peratures, they give no information concerning the
final value of uv/xy, which is, of course, the quantity
ultimately determined in the experiments. There-
fore, eq 3 in the equivalent form (eq 9) was integrated
numerically on a computer for a range of values of
01 and E and using the least-squares polynomial fit
of Rossini's data to express the dependence of K on T
K = 7.9395 x - 4.8006 x I O - 6 ~ 2 +
10-427
8.1576 X 10-9T3 - 4.2506 X 10-12T4 +
9.3176 X 10-"T6 - 7.4736 X 10-20T6
The results of the calculations are given in Table 111,
together with the freeze-out temperatures obtained
from eq 8 and the corresponding values of K.
Two methods of estimating the final value of uv/xy
for a given 01 and E can be obtained from these results.
First, the computer results can be summarized in the
convenient form
This reproduces the computer results to within 15%
for the entire range of 01's and E's given in the table and
is good to better than 10% in all but a few cases.
Alternatively, one can calculate the freeze-out tem-
perature Tf from eq 8 and use the corresponding value
of K as the estimate of (uv/zy)r. The error in the esti-
mate obtained in this way will be less than 7%. All the
deviations are positive, however [K(Tt) > (uv/zy)fl,
and the error can be reduced considerably (to less than
3%) if 0.955 K(Tf) is used instead of K(Tf). This is
remarkable in view of the wide range of parameters
represented in Table 111.
It remains to discuss the data of Table I1 in terms of
the process believed to be occurring in the bomb, which,
for our high-pressure runs, can be described as follows.
The l-g sample of explosive, contained in or suspended
just above the sample cup, burns in a time of the order
of a few tenths of a s e ~ o n d . The
~ volume of gas
evolved, at the adiabatic flame temperature and a
total pressure of 100 atm, is about 100 cc. The hot
combustion products are propelled through the support
cage into the cold helium. In the initial stages of their
motion, they do not mix with the helium and hence
remain hot. At some point, a rapid, turbulent mixing
occurs, accompanied by high cooling rates and freeze-
out of the water-gas equilibrium.
To estimate the cooling rate, we must first assign a
value to 8. For a run in which the initial pressure of
helium is 100 atm, the final pressure, if no heat is lost
to the walls or metal parts of the bomb, will be about
400 atm. If we take 200 atm as the average pressure
and 1900K as the approximate freeze-out tempera-
ture and assume that the products have mixed with an
equal volume of helium at the time freeze-out occurs,
then g 1.4. For E = 52,900 cal/mole, a value of 4
for (uu/xy)f corresponds, from eq 10, to an CY of 8.9 X
lo3. If A = 1.5 X 1010, then B = / ~ A / c= Y 2.4 X
lo6deg/sec. Tf (from eq 8) is 1900K.
This result is not very sensitive to errors in A and E
(9) Estimated from burning rate data given by A. P. Glaskova and
I. A. Tereshkin, Russ. J. Phys. Chem., 3 5 , 795 (1961).

The Journal of Physical Chemietry

PRODUCTS
FORMED OF EXPLOSIVES
IN THE COMBUSTION 2389

within the range permitted by Matthews data. From Thus, the cooling rates for these three experiments
his data we calculate a 95% confidence limit for E of can be summarized (Table V). We view those results
*21,100 cal/mole.1 However, the 95% confidence as being qualitatively consistent.
limit of log kl a t the midpoint (in 1/T) of his measure-
ments is only It0.08. Thus, unless there is a large
systematic error in his rate measurements, errors Table V
in E must be accompanied by compensating errors in
Estimated
A . In Table IV are shown the values of A / a and Tf cooling
computed from eq 10 and 8 for (uv/zy)f = 4 and with Heat Estimated Tr, rate,
transfer turbulence O K deg/sec

Muraour and At walls Moderate 1400 -loa

Aunis
Table IV: Effect of Variations in A and E,
Omellas, et a2. At walls Very high 1670 104-106
Log k-l at 2383K = 5.34
Bernecker and B y mixing Moderate 1900 -lo6
Smith
A, A/a,
l./mole E, 1. deg/ Tr, 0 H. Behrens, 2.Physik. Chem. (Leipzig), 195, 24 (1950).
sec cal/mole mole sec OK

5.8 X lo8 37 ,300 0.6 X lo6 1600

2.8 x 109 44,800 1.3 X lo8 1780
1.5 X 10lo 52,900 1.7 X lo6 1900
1.1 x 10 62 ,400 1.1 x 106 1920
4.2 X 10 68,500 0.4 X lo6 1870
values of A and E so chosen that log k-l(2383K) =
5.34. If the extreme values, which represent choices
near the edge of the confidence band of the least-
squares fit, are omitted, the variations in A l a and Tf
are, for our purposes, relatively minor.
The value lo6 deg/sec for the cooling rate is sur-
prisingly high, yet it appears reasonably consistent
with the cooling rates estimated for related experiments.
For example, in the experiments of Rluraour and
Aunis, which were the subject of Behrens discussion,
the samples were burned in a long, narrow, evacuated
bomb and cooling necessarily occurred a t the walls
in the turbulent combustion products. That process
would be expected to be considerably slower than the
cooling by mixing that we believe occurs in our ex-
periments and, from Muraour and Aunis pressure-
time measurements, Behrens estimated that the cooling
rate in their experiments was about loadeg/sec.
Ornellas, Carpenter, and Gum1* detonated PETN
charges in an evacuated spherical bomb some 20-cm
i.d. They calculated that, because of shock reflections
at the walls, the temperature of the expanded detona-
tion products from their unconfined charge was, ini-
tially, well above the freeze-out temperature. Thus,
freeze-out must have occurred in this experiment also
as a result of heat transfer to the walls from the highly
turbulent combustion products. The observed value
of K is 3.02, which, if E = 52,900, corresponds to an
a of 8.3 X lo4 and a T t of 1670K. With A = 1.5
X 1O1O and /3 = 0.26, we have B = 5 X lo4 deg/sec.
It should be noted that the term cooling by mixing
is an oversimplification of the process as we picture it,
particularly in its terminal stages. Once the hot gas
begins to undergo turbulent mixing with the helium,
cooling by conduction and diffusion will become im-
portant a t the boundary between the hot and cold gas.
We have already noted that the data of Table I1
suggest that K = (uv/zy)t is independent of P over
the range investigated. This implies that a and hence
A / a is independent of P. Since /3 decreases with P , B
does also. That is a reasonable consequence of the
model. As the initial pressure of helium decreases,
the proportion of helium in the final gas mixture also
decreases and the average temperature of the [cold
gas increases. Thus, cooling the combustion products
to a temperature below the freeze-out temperature re-
quires more complete mixing in the latter stages of the
low-pressure runs and the average cooling rate will be
correspondingly slower.
If the model is correct, K would be expected to
increase with the burning rate of the explosive because
of the higher initial velocity of the hot combustion
products. The order K (RDX or HMX) > K
(PETN) > K (compositioq B) from the data of Table
I1 is consistent with the probable relative burning rates
of these explosives, although burning rate data on
composition B have not been reported in the literature
(data on RDX and P E T N are given in ref 9).
(10) J. C . Matthews (see ref 8, p 133) gives =t23,900 cal/mole for the
90% confidence limit of E / R , hut it appears he omitted a factor
l / ( n - 2) (n = number of measurements = 15) in calculating the
variance.
(11) H. Muraour and G . Aunis, Z. Ges. Schiess- u. Sprengsto#w.,
35, 127 (1940).
(12) D. L. Ornellas, J. H. Carpenter, and S. R. Gunn, Rea. Sci.
Instr., 37, 907 (1966).

Volume 7 1 , Number 8 Julv 1967

2390 M. M. KOSANI~,
Z. D. DRAGANI~, AND 11.T. N E N A D O V I ~

Thus, while the mixing-cooling process in our experi-
ments cannot be sufficiently well defined to provide a
quantitative test of the details of the analysis, the
procedure described does lead to a qualitatively con-
sistent interpretation of these and other related experi-
ments. The technique would appear to be applicable
to other reactions and other systems as well and should
lead to quantitatively useful results under more favor-
able circumstances.
Finally, it is obvious that the product composition
cannot be used to distinguish between different modes
of decomposition in those cases in which the products
are formed above the freeze-out temperature. At
sufficiently low pressures, the products of burning may
be formed below t,hat temperature and under these
conditions they may be characteristic of that mode of
decomposition.
Acknowledgments. The authors gratefully acknowl-
edge the assistance of Dr. Howard H. Cady, who per-
formed the numerical integrations on the Los Alamos
computers. This work was performed under the aus-
pices of the U. S. Atomic Energy Commission.

Competition Studies of the Hydroxyl Radical Reactions in Some T-Ray

Irradiated Aqueous Solutions at Different pH Values

by Z. D. Draganii, M. M. KosaniC, and M. T. Nenadovii

Boris Kidrid Institute of Nuclear Sciences, VinEa, Yugoslavia (Received July 6 , 1966)

Competition studies of OH radical reactions were performed on the following oxygenated

+ +
aqueous systems: C2H50H HzC204, CH30H H2C204, C2H50H KBr, and CH80H + +
KBr. The corresponding rate constant ratios were measured a t pH 6-7, 2.7, and 1.3.
The cross-check confirmed the correctness of the reaction schemes used and the relative
rate constants measured. From these data the ratio k0H+ethanol/k0H+methanol was derived.
Assuming kOH+&hanol = 1.06 X log M-' sec-', the following absolute rate constants were
calculated for OH radical reactions with different forms of oxalic acid: 0.6 X lo7, 3.5 X
lo7, and <lo7 M-' sec-' for C2042-, HC204-, and HzC204 forms, respectively. The pH
effect on the rate constant of the OH radical reaction with bromide ions was also con-
- : X lo9,4.0 X lo9, and 0.6 X
firmed. The following values were derived for ~ o H . ~ B ~ 5.8
lo9 M-' sec-I a t pH 1.3, 2.7, and -6, respectively. The intercepts of competition dia-
grams gave primary hydroxyl radical yields in good agreement with the value previously
obtained for the aqueous oxalic acid-oxygen system a t the pH values studied.

Introduction c20d2- + OH +OH- + COZ + COO- (3)

Oxalic acid was used as the OH radical scavenger in Kralji6 and Trumbore4 measured at pH the rate
determining the PH effect on the Primary Products of constant for reaction 3. The rate constants of reac-
water
H&@4 + OH +H2O + coz + COOH (1) (1) I. G.Draganib, J . Chim. Phys., 56, 18 (1959).

HC204- + OH +OH- + CO2 + COOH (2)

(2) Z. D. Draganib, I. G. Draganib, and M. M. KosaniE, J . Phys.
Chem., 6 8 , 2085 (1964).

The Journal of Physical Chemistry