n-----280 v/c (3)

for Duralumin rings. With identical rates of expansion, the number of fragments for Duralu-
min rings is approximately 30% greater than for aluminum rings. This corresponds to the
effect of the limiting deformation, entering into relationship (i), on the breakup of the
ring. The values of sinh c, for these materials, from the results of a static tests, also
differ by 30%. The effect of the thickness of the ring on the number of fragments is in-
significant and lies within the limits of the scatter of the experimental data.
The principal parameters affecting the velocity of the ring are its thickness and the
relative radius of the charge. The velocity rises with an increase in the charge and with a
decrease in the thickness of the ring. In the coordinates in (~v/Rc), in R, characterizing
the dependence of the impulse of the ring on the value of the charge (Fig. 3, notation analo-
gous to Fig. 2), we obtain for aluminum rings

5v/Rc-~--O.06 Rz4, (4)

for Duralumin rings

6v!Rc ~O.O4Pd '~. (5)

The velocity of the flight of aluminum rings is somewhat greater than for Duralumin.
From (3) and (5), for Duralumin we have

n6/R = 1~R2~. (6)

Table 2 gives a series of experiments with rings having a height of I0 mm, a radius of 40
mm, and a thickness of 2, 4, 8, i0 mm. The charge, with a height of !0 mm, was varied within
the limits of 0.12-0.71. Plotting the given values in the coordinates In(n6/R), in R, we
obtain satisfactory agreement with formula (6). In Fig. 4 [O) R = 20 mm; A) R = 40 mm], the
straight line corresponds'to formula (6).

LITERATURE CITED
i. E. A. Koshelev, V. M. Kuznetsov, et al., Zh. Prikl. Mekh. Tekh, Fiz., No. 2 (1971).
2. V. M~ Kuznetsov, Fiz. Goreniya Vzryva, 2, No. 4 (1973).

MASS-SPECTROSCOPIC INVESTIGATION OF THE KINETICS OF THE HIGH-

TEMPERATURE DECOMPOSITION OF ~MMONIUM PERCHLORATE (APC)

O. P. Korobeinichev, A. G. Tereshchenko,
and G. I. Anisiforov

For an understanding of the mechanism and for the construction of a model of the process
and catalysis of the combustion of ammonium perchlorate and mixed systems based on it, we
need a knowledge of the kinetics of the thermal decomposition of these systems and their
components in the region of high temperatures, close to the temperatures at the combustion
surface. There exist very few data in the literature [1-3] on the kinetics of the high-
temperature decomposition of ammonium perchlorateand these data are contradictory. Arecently
developed method [4, 5] for studying the thermal decomposition of condensed systems, using a
time-of-flight mass spectrometer, has been found effective with the investigation of ammonium
perchlorate.

Institute of Catalysis, Siberian Division, Academy of Sciences of the USSR, Novosibirsk.

Translated from Fizika Goreniya i Vzryva, Vol. 12, No. 4, pp. 633-636, July-August, 1976.
Original article submitted September I0, 1974.

This material is protected b y copyright registered in the name o f Plenum Publishing Corporation, 227 West 1 7th Street, N e w York, 2~. Y.
10011. 1Vo part o f this publication may be reproduced, stored in a retrieval system, or transmitted, in any f o r m or by any means, electronic,
mechanical, photocopying, microfilming, recording or otherwise, w i t h o u t written permission o f the publisher. A copy o f this article is
available f r o m the publisher f o r $ 7.50.

577
 L

\ \ "-,2

, ,,4
- I

o d.4 ' ojs &.- I, z s 4'4 I,$s : :O F-

T
Fig. 1 Fig. 2

Fig. i. Dependence of the rate of decomposition of

ammonium perchlorate (250-400 p) d~/dt (sec -I) on
at 466~ (I), 457 (2), 449 (3), and 434~ (4) and of
ammonium perchlorate (5 p) at 450~ (5).
Fig. 2. Arrhenius dependence of the rate (sec -I) of
the decomposition of ammonium perchlorate (250-400 p)
on the temperature: i) data of [2]; 2) with ~ = 0.i;
3) data of [i]; 4) with ~ = 0.5.

Method of Experiment

The investigations were made under isothermal conditions at 1 atm in a kinetic unit,
using a time-of-flight mass spectrometer and a flow-through reactor of the type of a Lossing
reactor [5, 6]. A two-stage method was used for withdrawing samples: gas from the high-
pressure chamber (i atm) was fed through a primary orifice into the low-pressure chamber (15
mm Hg) and then through a secondary orifice into the ion source of the mass spectrometer. A
weighed portion of the substance (from a few to tens of milligrams) was put into a solid
aluminum block (weight 2 g), whose temperature was measured with a thin Chromel-Copel thermo-
couple.
In the system described, the heating time of the sample was 1-1.5 min. To study rapid
reactions of the decomposition of ammonium perchlorate, a heating system was used in which
the sample (3-10 mg) was placed between two titanium plates, heated by an electric current.
The temperature of the sample was measured with a ribbon-type Chromel-Copel thermocouple
(thickness i0 p) installed between the plates. A thermoc0uP! @ was also used as the pickup
of a thermoregulator of the EPR type, for maintaining the temperature of the sample constant
with an accuracy to 1 ~ The time required for the temperature of the sample to reach steady-
state conditions in this case was ~ 5 sec.

To eliminate sublimation, the sample was put into an "envelope" consisting of a thin
layer of metal foil. The rate of decomposition was measured by the method of [4, 5]. The
experiments were made mainly with ammonium perchlorate having a degree of dispersion of 250-
400 p.

Results of Experiment

There is given below the ratio of intensities of the peaks in the mass spectrum of the
decomposition of ammonium perchlorate at 460~ which was found to be practically constant
during the course of an experiment.
m/sec 2B ao 32 3G 44 70

.,:# o2+ Hci+ ci#

Intensities 0,3 0,73 0,74 0,82 0.83 1

Figure I [~ is the degree of decomposition of ammonium perchlorate, determined from the

578
 ~ r-uMGag

Fig. 3. Arrhenius dependence

of the maximal rate of the
reaction (Wmax) on the temper-
ature (El > El, ~ < i) pre-
dicted by the two-stage
scheme.
z~ ,

yield of HCI: a = (HCI)/(HCI~)] gives the results of an analysis of the experimental data.
It can be seen that the form of the kinetic curves depends on the temperature and the degree
of dispersion of ammonium perchlorate. For ammonium perchlorate with a degree of dispersion
of 250-400 ~ at 400-430~ the rate of decomposition falls monotonically with a rise in a
(effective order of reaction 0.5-1), while, with t _ ~ 460~ the rate of decomposition passes
through a maximum. For ammonium perchlorate with a degree of dispersion of ~5 ~, da/dt falls
rapidly with a = 0-0.5; then the rate of fall slows. The inital rate of decomposition at
450~ for finely dispersed ammonium perchlorate exceeds by 5 times the rate of decomposition
of coarsely dispersed ammonium perchlorate; with a ~ 0.5, the effect of the degree of dis-
persion becomes insignificant.

Figure 2, in Arrhenius coordinates, gives the results of experiments on the temperature

dependence of the initial velocities (a = 0.i) and the decomposition rates. The same figure
gives the data of [i], obtained under isothermal conditions with 260-380~ using a weight
method (ammonium perchlorate 50-100 ~) in a quartz crucible, and the data of [2], obtained
using nonisothermal methods at 340-430~ in the aluminum crucible. The absolute values of
the rate constants, obtained in the present work at 390~ are in considerably better agree-
ment with the results of Manelis et al. [i] than with the results of Goncharov et al. [2].
In the temperature range 400-470~ the activation energy of the decomposition rate with
= 0.i is ~40 kcal/mole.

With an increase in the depth of the decomposition a from 0.i to 0.5, the activation
energy rises and with a = 0.5, attains ~63 kcal/mole. The above-described laws can be
understood if the following scheme is adopted for the decomposition of ammonium perchlorate,
including two consecutive stages:

Asol ~ , ~ -~ ( I - - ~) BsolT ~Cgas;

h,,Eo

H e r e C_^_ i s t h e f i n a l g a s e o u s p r o d u c t ; A s o l , Bso 1 a r e t h e s t a r t i n g and i n t e r m e d i a t e con-

densed products, h a v i n g e x a c t l y t h e same c h e m i c a l c o m p o s i t i o n , but a different structure
(and, consequently, a different reactivity); Bso 1 i s t h e " r e s i d u e , " forming with the "low-
temperature" (200~ d e c o m p o s i t i o n o f ammonium p e r e h l o r a t e , w h i c h , d e p e n d i n g on t h e d e g r e e
of dispersion and the structure of the starting product, can make up a different fraction of
it i -- B. Obviously, the purer the original product and the larger its crystals, the lower
the value of B. The first stage has a lower activation energy than the second. This ex-
plains also the formation of a "residue" with "low-temperature" decomposition.

An analysis of this scheme (with 8<< i) shows that, in the region of low temperatures
(kl<< kl), the maximal decompositon rate is the initial rate (da/dt)~=o = + kiB. In the
region of high temperatures (k2 >>k~), da/dt as a function of a passes through a maximum;
here the initial rate is equal to k ~ , and the maximal rate is k~, i.e., it is i/8 times
greater than the initial rate. If the dependence of maximal rate on the temperature is
plotted in Arrhenius coordinates, there is obtained the following unusual situation, shown
schematically on Fig. 3. In the region of low and high temperatures, the activation energies
are equal to the activation energy of the first stage Ez (the pre-exponents differ by I/B
times); in the intermediate region, there is a considerable rise in the activation energy.
In the general case, the dependence da/dt on a can be found from the following equations,
found from a solution of the kinetic equations, which describe the scheme adopted from the
above for the decomposition of ammonium perchlorate:

579
 da/dt = ~k~z -~- k~k2 (1 -- [3)/(k2 -- k,). z (1 -- Zh~/k'--t );
a------(k~--k,~) / (k2--kl) 9 ( z - - l ) -~kl (1--~) / (k2--kl) . Zh~/k'--l ) ;
z=(A)/(Ao),

where A is the concentration of the starting product; Ao is the initial concentration. Thus,
the adopted scheme is in agreement with the observed experimental data. We note that with
a study of the kinetics of the decomposition of ammonium perchlorate, it must be shown that
the material of the crucible has no catalytic effect on the decomposition of ammonium
perchlorate. The presen t experiments have shown, for example, that the rate of decomposition
of ammonium perchlorate in crucibles made of Duralumin at 400~ exceeds by 20 times the
rate of decomposition of ammonium perchlorate located in envelopes made of metal foil.

LITERATURE CITED
I. G. B. Manelis, A. V. Proshchin, et al., Fiz. Goreniya Vzryva, 4, No. 3 (1968).
2. E. P. Goncharov, A. G. Merzhanov, and A. S. Shteinberg, in: Proceedings of the Third All-
Union Symposium on Combustion and Explosion [in Russian], Izd. Nauka, Moscow (1973).
3. A. G. Merzhanov, A. S. Shteinberg, and E. P. Goncharov, Fiz. Goreniya Vzryva, 9, No. 2
(1973).
4. O. P. Korobeinichev and G. I. Anisiforov, in: Fifth All-Union Meeting on Thermal Analysis,
Abstracts of Papers [in Russian], Izd. Nauka, Moscow (1973).
5. O. P. Korobeinichev, G. I. Anisiforov, and A. V. Shkarin, Fiz. Goreniya Vzryva, 9, No. 1
(1973).
6. O. P. Korobeinichev, G. I. Anisiforov, and A. G. Tereshchenko (Tereschenko), AIAA J., 5,
628 (1975).

EXACT CALCULATION OF DIFFUSION WITH THE FLOW OF A MULTI-

COMPONENT GAS

I. G. Druker and L. Ya. Treer

With hypersonic velocities of flight in the atmosphere of the earth or of other planets,
due to the high temperatures arising at points of stagnation of the gas, the latter, thanks
to physicochemical reactions of the type of dissociation, ionization, the formation of
radicals, as well as to chemical interaction between its components and the surface of the
solids around which the flow takes place, or with blowing for cooling the substances, be-
comes multicomponent. In various cases, the number of components can be rather large [i,
2]. Under these circumstances, in regions of the flow where there is a considerable influ-
ence of viscous effects (including, above all, the boundary layer), the phenomenon of multi-
component diffusion, which mainly determines the transfer of mass and energy, becomes
important.
The system of equations describing the flow of a viscous multicomponent gas, in partic-
ular, the system of equations of the boundary layer, contains relationships connecting the
diffusion flows with the concentrations of the components [3]

0o~ = (I/Pr M 2) ~-~-t~gL=6x6x (~ = 1. . . . , ,% (1)

where ~ is the flow of the component ~; % = p~/p~q~; M is the molecular weight of the

Institute of Theoretical and Applied Mechanics, Siberian Division, Academy of Sciences

of the USSR, Novosibirsk. Translated from Fizika Goreniya i Vzryva, Vol. 12, No. 4, pp.
636-639, July-August, 1976. Original article submitted June 16, 1975.

This material is protected b y copyright registered in the n a m e o f Plenum Publishing Corporation, 227 West 1 7th Street, N e w York, N. Y.
1001 I. N o part o f this publication may be reproduced, s t o r e d in a retrieval system, or transmitted, in any f o r m or by any means, electronic,
mechanical, p h o t o c o p y i n g , microfilming, recording or otherwise, w i t h o u t written permission o f the publisher. A c o p y o f this arffcle is
available f r o m the publisher f o r $7.50.

580