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1961 - Symposium (International) On Combustion - The Activation Energy of Gas - Tesner PDF
1961 - Symposium (International) On Combustion - The Activation Energy of Gas - Tesner PDF
87
THE ACTIVATION ENERGY OF GAS REACTIONS WITH SOLID CARBON
By P. A. T E S N E R
Introduction The activation energy for each temperature
Reactions of many gaseous substances with was found from Equation (1), using the experi-
carbon are of great importance and have been mental values of the reaction rate per cm2 of
intensively investigated. They include reactions reacting surface. The number of collisions, No,
of carbon combustion and gasification, i.e., was obtained from equations of the molecular
carbon reactions with oxygen, steam and carbon kinetic theory.
dioxide in which solid carbon is converted to
gaseous products. Of great significance also are No- P (2)
reactions of hydrocarbon thermal decomposition
which, conversely, led to the formation of carbon where:
from gaseous molecules. p = gas pressure dyne/cm 2
Based on the analysis of extensive experi- m = mass of molecule, g
mental material, this paper shows that the K = Boltzmann constant, erg/C
activation energy of reactions between gases T = absolute temperature, K
and solid carbon does not remain constant, but
decreases regularly with rising temperature. THERMAL DECOMPOSITION OF HYDROCARBONS
Activation En-
' Mean ergy (cal/mole)
Tem- Con-
centra- Number of e--E/RT
Hydrocarbon per- Rate of Growth Authors
ature tion of Collisions (Eq. (1)) Accord-
Hydro- (Eq. ing to
carbon (1)) Arrhen-
ius
"\o
20
\\\\
\
%
k
\
O - - m e a s u r e m e n t s of V N I I G A S
O - - T e s n e r , E c h e i s t o v a 2, 3
O--Tesner, Rafalkes 1
{ D - - J o n e s et a I ?
ACTIVATION ENERGY OF GAS REACTIONS WITH SOLID CARBON 809
Activation Energy
(cal/mole)
Run Tem- Pressure of O5 Number of Rate of Con- e--EIRT
per- Authors
N ature mm Hg Collisions sumption of O5 (Eq.(1))
According to
(Eq.(1)) Arrhenius
oK mole/cra-2sec-1
257 723 285 6.55 X 1022 0.15 X 10-12 0. 138 X 10-11 39200]
243 773 285 6.32 X 1022 0.58 X 10-12 0. 553 X 10-11 4oooo~ Measurement s
253 823 163 3.54 X 1022 1.84 X 10-12 3.14 X 10-11 39600 / of V N I I G A S
256 873 15 0.31 X 1022 0.37 X 10-15 7.22 X 10-11 40500j
A [170 760 13.8 X 1022 1.3 X 10-4 5.72 X 10-4 17300 / K l i b a n o v a , Z.,
B [178 160 2.9 X 1022 7.1 X 10-~ 1.49 X 10-3 15100~104000 and F r a n k -
B L194 160 2.86 X 1022 1.3 X 10-~ 2.73 X 10-3 13900| Kamenetsky,
P [228 19 0.33 X 1025 1.3 X 10-4 2.34 X 10-2 9100J D. s
172 [160 2 . 6 X 10-3 9.36 X 1017 0.5 X 10-s 3 . 0 X 10-3 3480]
199 [390 3.4 X 10-3 12.25 X 1017 1.28 X 10-8 6 . 9 X 10-3 2980120000-3000
227 [520 2.7 X 10-3 9.70 X 1017 0.33 X 10-8 2 . 2 X 10-3 3660J Meyer, L. 8
265 [960 2 . 1 X 10 7.56 X 1017 6.7 X 10_8 5.35 X 10-2 1750
273 ~)050 1.9 X 10-~ 6.85 X 1017 15.5 X 10-8 13.7 X 10-2 1190
93 [150 27 10-~ 97.0 X 1017 1.87 X 10-s 1 . 2 X 10-3 40201
94 [280 27 X 10-8 97.0 X 1017 5.0 X 10-s 3 . 2 X 10-3 3450]
95 [280 380 X 10-~ 1370 X 1017 54 X 10_8 2 . 5 X 10-3 3580120000-25000
97 [340 0.83 X 10-~ 2.98 X 1017 0.25 X 10-s 5 . 2 X 10-3 3150 /
98 [455 0.83 X 10-~ 2.98 X 1017 0.27 X 10-8 5 . 9 X 10-3 3080l
105 t905 1.86 X 10_8 6.5 X 1017 0.53 X 10-s 0.5 X 10-2 318~ Martin, H.,
110 t925 0.48 X 10-~ 1.73 X 1017 0.85 X 10_8 2.86 X 10-2 213~ and Meyer,
118 t975 1.66 X 10-5 5.98 X 1017 1.3 X 10-8 1.35 X 10-2 2580 / L. 7
107 .)125 D.66X 10-5 2.38 X 1017 3.3 X 10_8 0.85 X 10-i 1380!70O00
112 .)245 1.3 X 10-5 4.68 X 1017 6.6 X 10-8 8.6 X 10-2 1470~
117 .)265 1.66 X 10-5 5.98 X 1017 8.9 X 10-s 9.05 X 10-2 1440]
114 .)465 3.96 X 10-~ 3.46 X 1017 24.6 X 10_8 43 X 10-2 505 /
116 .)475 1.66 X 10-~ 5.98 X 1017 3.1 X 10-s 31.8 X 10-2 686)
810 FORMATION, COMBUSTION, EXPLOSION AND DETONATION OF SOLIDS
is considerably slower than that in the tempera- tion energy of this reaction we applied the
ture range of 800 to 1300K. The activation results of the following two works: the already
energy approaches zero asymptotically and at cited work 7 on carbon filament gasification in a
temperatures exceeding 2300 to 2400K it is vacuum, and a comparatively recent work of
below 1000 cal/mole. I t should be noted that Bastick 9 who studied the interaction of carbon
from the paper by Martin and Meyer, who dioxide with coke and simultaneously measured
obtained results relating to temperatures above the actual reaction surface.
1300K, we used only the results for the lowest
The results of activation energy calculations
oxygen pressures, because in high pressure
based on these works are illustrated in Table 3
experiments the effect of diffusion inhibition of
and Figure 2. As is shown by the curve, the
the reaction is quite pronounced. Therefore, it is
activation energy of the reaction C 3- CO.a as
possible that the data of Figure 2 regarding
temperatures above 1300K are in error because well as that of the other reactions investigated
of diffusion. The diffusion inhibition diminishes drops (curve 2)drastically with temperature.
the reaction rate and brings about (in calcula- At 2200K it equals 7000 cal/mole, whereas at
tions based on Equation (1)) an apparent increase 1200K it is 60,000 cal/mole. Of course, one
in the activation energy. I t is possible, therefore, should make the reservation that the sharply
that the activation energies obtained are some- declining section of the curve has no experimental
what high and that, consequently, the activation points and is drawn tentatively.
energy actually tends to vanish more rapidly I t should be noted that, as in the case of high-
than suggested by Figure 2. temperature methane decomposition, the activa-
Reaction C + C02. In calculating the activa- tion energy of the reaction C 3- C02 is sig
70
2
0 O~
\\\
i \
\
\\
30
%
20
\\
Activation Energy
(cal/mole)
Tem- Number of Rate of Con- e--EIRT
per- Pressure of C02 Collisions sumption of C02 :Eq. (I) Authors
ature according
Eq. (1) to
Arrhenius
K mm Hg mole/em-2/sec-I
1073 760 12.3 X 1022 0.021 X 10-11 0.103 X 10-11 59000 53000
1273 760 11.3 X 1022 1.15 X 10-n 0.613 X 10-1 60000 Bastick, M. '~
1323 760 11.0 X 1022 3.11 X 10-11 1.705 X 10-1 59400 54700
27 229C 2.66 X 10-a 8.15 X 1017 O. 108 X 10-6 0 . 8 X 10-4 56501
45 223G 3.68 X 10-s 11.25 X 1017 O. 192 X 10-s 1.03 X 10-4 5530/
62 234G 1.3 X 10-a 3.98 X 1017 O.239 X 10-s 3.59 X 10-4 4760~ 90000}Martin, H.,
67 261C 0.24 X 10-a 7.34 X 1016 0 . 7 7 X 10-6 63.0 X 10-4 2780 I and Meyer,
70 266C 0.24 X 10-a 7.34 X 1016 O. 586 X 10-~ 48.0 X 10-4 2330/ L . 11
nifieantly lower than the reaction heat which is interaction of solid carbon with oxygen, carbon
41,200 eal/mole. dioxide and hydrocarbons seems to be of suffi-
The curves I and II of Figure 2 reflect the ciently general significance and should be ob-
temperature dependence of the activation energy served in any other reactions involving solid
for the reactions C + C02 and C + C02 on the carbon. It is believed that a variation in the
basis of Khitrin's data/ Equation (1) could not activation energy with temperature should be
be used to calculate the activation energy from observed in other reactions, too.
these data as they refer to the so-called reaction We attribute the decrease in the activation
gas-exchange coefficient. This value takes into energy with temperature to the increase in the
account the reaction rate in the pores of the sub- activity of the carbon surface with temperature.
stance per 1 cm 2 of its external surface and is not The higher the temperature, the higher the
helpful in estimating the true reaction rate per activity, i.e., the higher the energy state of
unit reacting surface. active surface atoms of carbon, the lower may
Because of this, the calculation was made by be the kinetic energy of the gaseous molecules
extrapolating the curve representing the tem- hitting the surface and causing the reaction. At
perature dependence of the reaction gas-ex- a sufficiently high temperature, the energy of the
change coefficient to its maximum value where surface atoms becomes so significant that they
the activation energy of the process should be are capable of reacting with gas molecules with a
zero. Figure 2 shows that the activation energies lower energy than the heat of the endothermic
found in this manner, as well as the values ob- reaction which is proceeding. Even strongly
tained from Equation (1), decrease with increas- endothermie reactions (e.g., C + C02) may
ing temperature. occur at near-zero activation energies provided
Of course, there is a considerable discrepancy the temperature is high enough. This does not,
between these curves and those obtained from however, constitute a violation of thermo-
Equation (1). It would be natural to attribute dynamic laws, for we do not take into account
this to the fact that the gas-exchange coefficient the energy of the active reacting surface atoms.
of the reaction is not a chemical reaction con- At sufficiently high temperatures, the activa-
stant and depends markedly on the depth to tion energy becomes so low that each or almost
which the reaction extends into the pores of the each collision of a gas molecule with the carbon
substance. Because this depth diminishes with surface causes a reaction. This means that the
rising temperature, this leads to an apparent majority of surface carbon atoms possess an
drop in the temperature coefficient of the reaction activity similar to that of free radicals.
rate and hence in the temperature coefficient of It appears to us that a further study of this
the activation energy. problem may be of fundamental interest for the
understanding of the mechanism of chemical
Discussion
surface processes and, in particular, the mech-
The observed decrease with temperature of the anism of catalytic processes.
activation energy of reactions involving the It is especially interesting that in the case
812 FORMATION, COMBUSTION, EXPLOSION AND DETONATION OF SOLIDS
under consideration we are able to watch the involves only molecules having some excess
temperature variation of activity.In this connec- energy. We have only shown that the widely
tion, attention should be focused on the fact that applied practice of determining the activation
the investigated concept of the activity of the energy from the slope of a straight line in Arrhe-
carbon surface is meaningful only with respect nius coordinates, i.e., assuming the constancy
to a specific reaction. Indeed, the activation of the activation energy over the given tempera-
energy, which may be regarded as a yardstick ture range, may cause significant errors.
for the activity of the carbon surface, is different The available experimental data on the type
for different reactions, the temperature being of function E = f(T) are not conclusive, of
equal. For instance, for the reaction C + 02, the course, and further experimental work is needed.
activation energy is 5000 cal/lnole at 1300K,
and for the reaction C + C0., the same activa- Conclusions
tion energy is attained at 2300K. It is evident, In chemical interaction of gaseous substances
however, that in all the cases discussed the with solid carbon the activation energy of the
activation energy has the same form of tempera- process decreases with rising temperature, and
ture dependence, i.e., evidently, the same law at a certain temperature reaches zero or a value
of thermal activation of the surface. of the order of several thousand cal/mole which
The regular nature of the decrease in the is characteristic of the activation energy of
activation energy with temperature explains radical reactions.
the diversity of the experimental activation The observed reduction in the activation
energy values obtained by different authors for energy with temperature is attributed to the
reactions which involve solid carbon. As an increase in the activity of the surface carbon atoms
illustration, we might quote the value of the with rising temperature. Further investigation is
activation energy of the carbon formation required to establish the mechanism of this
process in the thermal decomposition of benzene.2 thermal activation.
A calculation based on the slope of a straight In studying surface or heterogeneous chemical
line in Arrhenius coordinates yielded 138 keal/ processes, the activation energy obtained from
mole whereas the value obtained from Equation the absolute reaction-rate equation is a criterion
(1) is about 40 kcal/mole. The results obtaineds of the activity of the solid surface with respect
for the combustion of carbon are similar. With to the process under consideration.
the concept of the constancy of the activation
energy for a temperature range of 16, these REFERENCES
authors obtained a value of 104,000 cal/mole, 1. TESNER, P. A., AND RAFAnKES,I. S.: Doklady
whereas a calculation with Equation (1) produced Acad. Sci. U. S. S. R., 87, 821 (1952); and
a value of 15,100 cal/mole for 905C and 13,900 VNIIGAS Proceedings, p. 3. Gostop-
cal/mole for 921C. tehisdat, Moscow, 1953.
It should be noted, however, that the experi- 2. TESNER, P. A,: Seventh Symposium (Inter-
mental results of Klibanova and Frank-Kamenet- national) on Combustion, p. 546, Butterworth
and Company, Ltd., London, 1959.
sky s do not cause any doubt and are the only
3. TESNER, P. A., AND ECHEISTOVA,A . I.:
published data on the reaction rate in the region Doklady Acad. Sci. U. S. S. R., 87, 1029
of a rapid decrease in the activation energy and, (1952).
consequently, of an exceedingly rapid change in 4. JONES, G. W., KENNEDY, R. E., SPOLAN, I.,
the reaction rate. These data were obtained by AND SCOTT, G. S.: Bureau of Mines Report of
the original investigation method used by the Investigation, 4695, May, 1950.
authors which made it possible to measure the 5. SNEGEREVA, W. D.: VNIIGAS Proceedings,
instantaneous rate of a rapid reaction at the p. 74. Gostoptehisdat, Moscow, N 6 (14)
instant of initiation. It is thought that a more 1959.
6. MEYEn, L.: Z. Phys. Chem., 17, 385 (1932).
extensive application of this method, in conjunc-
7. MARTIN, H., AND MEYER, L. : Z. Electrochem.,
tion with the Meyer method, will allow a reliable
41, 136 (1935).
measurement of the rate of these rapid reactions 8. KLIBANOVA, Z., ANn FRANK-KAMENETSKII, ]). :
over a wide temperature range. Acta Physicochimica U. S. S. R., 18, 387
It should also be emphasized that ~he results (1943).
obtained by no means contradict the highly 9. BASTICK, M. : Bull. Soc. Chem. France, No. 7,
productive idea of Arrhenius, that the reaction 916 (1957).
ACTIVATION ENERGY OF GAS REACTIONS WITH SOLID CARBON 813
Tesner and attributed to a change in activity of 4. ESSENHIGH, R. H., AND PERRY, M. C.: Inst. Fuel
the carbon surface. Conf. Science in Use of Coal, p. D1 (Sheffield,
The change from Equation (2) controlling to April, 1958).
Equation (3) controlling involves a drop in 5. ESSENHIGH, R. I-I.: J. Fuel Soc., 6, 15 (1955)
activation energy of roughly 40,000 cal to (Sheffield University).
4000 cal3, 4. ~ (a factor of 10).
This does not rule out a probable change in AUTHOR'S REPLY
surface activity as a perturbing factor, but it
We believe that the change in surface activity
accounts quite satisfactorily for all of the major
is a major factor which accounts for all experi-
changes observed experimentally, without re-
mentally observed changes in reactions with solid
course to any special assumptions on activity
carbon.
that are not yet required by independent experi- The change in the energy of activation can be
ment. indeed formally explained by superposition of two
ADDITIONAL REFERENCES reactions with different energies of activation,
1. DAVIS, H., AND HOTTEL, H. C.: I/EC 26, 889 but it requires the postulation of two different
(1934). mechanisms for each reaction.
2. Wu, C. M., DAvis, AND HOTTEL: I/EC 26, 749 Dr. R. H. Essenhigh offers such a mechanism
(1934). for the reaction C + 02 .And what can be proposed
3. BLYHOLDER, G. D., AND EYRING, H.: U.S.A.F. for the reactions C -t- C~Hm and others? And what
Office of Scientific Research Technical Note can be the reason for the change of the mechanism
Report O.A. No. XX, August, 1956. of reaction, if not a change in surface activity?
88
PARTICLE SIZE OF CONDENSED OXIDES FROM COMBUSTION OF
METALIZED SOLID PROPELLANTS
By BILLINGS BROWN AND K E N N E T H P. McARTY
Introduction found mainly in the nozzle, in the combustion
process, or somewhere else. There is, of course,
The objective of this study is to determine the
also the possibility that the inefficiency found
particle size distribution of metal oxides result-
experimentally is a combination of several factors,
ing from the combustion of solid rocket pro-
none of which are particularly significant them-
pellants and its effect upon the thrust of rocket
selves. It would seem that the first step toward
motors.
improvement is to discover just what the cause
It is found experimentally that the delivered
of the inefficiency really is.
specific impulse of metalized solid propellants
One plausible cause for reduced specific impulse
begins to fall significantly below the calculated
is that the particles or droplets of condensed
value as the percentage of metal is increased. A
oxide do not achieve velocity equilibrium with
portion of this difference between delivered and the gases during their transit time through the
calculated specific impulse is usually assigned to nozzle. This effect was studied by several authors,
nozzle inefficiency and the remainder to combus- including Gilbert, Davis and Altman,1 and most
tion inefficiency. The delivered specific impulse recently Kliegel.~ These correlations predict
is then expressed as a percentage of the calculated widely differing results, but all have as a common
value. parameter the particle or droplet diameter. None
Recently, it has become of interest to increase of these authors offered any evidence as to what
the combustion efficiency of solid propellants, the size might be.
even though some are currently operating at the An alternate reason for the loss in specific
95 per cent efficiency level. The question then impulse is combustion inefficiency, here defined
arises as to whether the inefficiency is to be as the nonachievement of chemical equilibrium