807

ACTIVATION ENERGY OF GAS REACTIONS WITH SOLID CARBON

87
THE ACTIVATION ENERGY OF GAS REACTIONS WITH SOLID CARBON
By P. A. T E S N E R
Introduction
Reactions of many gaseous substances with
carbon are of great importance and have been
intensively investigated. They include reactions
of carbon combustion and gasification, i.e.,
carbon reactions with oxygen, steam and carbon
dioxide in which solid carbon is converted to
gaseous products. Of great significance also are
reactions of hydrocarbon thermal decomposition
which, conversely, led to the formation of carbon
from gaseous molecules.
Based on the analysis of extensive experimental material, this paper shows that the
activation energy of reactions between gases
and solid carbon does not remain constant, but
decreases regularly with rising temperature.

Experimental Procedure
A number of facts associated with the process
of carbon formation in the thermal decomposition of hydrocarbons have led us to the conclusion that the activation energy of these processes
does not remain constant, but decreases with
rising temperature. This concept has proved to
be valid not only for reactions of carbon formation by thermal decomposition of hydrocarbons,
but also for reactions of carbon combustion and
gasification.
In the case of activation energy variation
with temperature, determination of the activation energy from the data on the temperature
dependence of the reaction rate constant produces erroneous results. Because, in the case
under review, we assumed temperature dependence of the activation energy, we did not undertake its determination from the temperature
dependence of the reaction rate constant, i.e.,
from the slope of a straight line in coordinates
In K, lIT. The activation energy was determined from the molecular kinetic equation of the
absolute reaction rate:

v = No exp ( - - E / R T ) ,

(1)

where
v = reaction rate, moleeules/cm2sec
No = number of collisions of molecules with
the surface, molecules/cm%ec
E = activation energy, cal/mole.

The activation energy for each temperature

was found from Equation (1), using the experimental values of the reaction rate per cm2 of
reacting surface. The number of collisions, No,
was obtained from equations of the molecular
kinetic theory.

Nowhere:
p =
m =
K =
T =

(2)

gas pressure dyne/cm 2

mass of molecule, g
Boltzmann constant, erg/C
absolute temperature, K

THERMAL DECOMPOSITION OF HYDROCARBONS

Carbon formation in the thermal decomposition of hydrocarbons obeys simple kinetic rules.
The reaction is first-order with respect to hydrocarbon, and represents, in our opinion, a molecular process of direct interaction of hydrocarbon
molecules at the carbon surface 1, 2 which does
not require any preliminary stage occurring
within the hydrocarbon volume.
Table 1 presents the results of measurements
to determine the rate of carbon formation,
carried out at the VNIIGAS, as well as the
results of activation energy calculations for
temperatures ranging from 800 to 1350C.
A comparison of activation energies at temperatures of 800 to 900 and 1260 to 1350C
indicates a decrease in the activation energy of
over 20,000 eal/mole.
Figure 1 depicts graphically the temperature
dependence of the activation energy for methane,
benzene and acetylene. Although the results of
activation energy measurements shown in
Figure 1 are somewhat short of providing a precise idea of the dependence E = f ( T ) because
of the small number of points, they do demonstrate convincingly, a drastic drop in the activation energy of the thermal decomposition of
hydrocarbons.
I n this ease, temperature variation of the
activation energy appears to be almost linear.
However, it is difficult to assume the existence
of a certain critical temperature above which
the activation energy becomes zero. It is more

FORMATION, COMBUSTION, EXPLOSION AND DETONATION OF SOLIDS

808

TA:BLE 1. RATE AND ACTIVATION ]~N~I~G"Z OF THE REACTION OF CA~BON lq'ORMATrON

BY THErMAl, DECOMPOSITION OF HYDnOCAI~BONS
'

Hydrocarbon

Temperature

oK

Mean
Concentration of
Hydrocarbon

Activation Energy (cal/mole)

Number of
Collisions

e--E/RT

Rate of Growth

(Eq. (1))
(Eq.
(1))

mole %

m ole/cm-2/sec -1

Methane
Methane
Benzene
Benzene
Benzene

1176
1250
1073
1148
973

100
100
100
100
12.5

19.4
18.8
9.27
8.92
1.22

X
X
X
X
X

1022
10 ~2
102:
10 2~
102~

Methane
Acetylene
Acetylene
Benzene
Methane

973 100
926
5.0
1373
4.0
1398
8.7
1623
7.4

21.4
8.5
5.66
7.05
12.3

X
X
X
X
X

102"0
10 ~1
10 ~1 340
1021 3180
1021 809

sec-I

0.052
0.39
0.74
46

According to
Arrhenius

Authors

mole/cm-2 sec-x

2.78
2.15
0.139
0.896
1.12
2.28 X 10- n

X
X
X
X
X

1.07
8.95
2.77
6.96
6.10

X
X
X
X
X

0.38 X 10 -12
2.53 X 10-12

10 -1 51200~
Tesner and
10-9 49300178000
Echei10-8
s t o v a 2, 3
10-7
10 -11 48500
} Tesner and
Rafalkes 1
10-12 53300
10 -11 42300
Measure10 -5 28600
m e n t s of
10 - s 26700
VNIIGAS
10-5 31400

"\o

20
\\\\
\
%
k

0
500

/000

"'/500
2000 K
Temporature ,

" 2_-_-_

2500

3000

FIG. 1. A c t i v a t i o n e n e r g y of r e a c t i o n s of c a r b o n f o r m a t i o n b y t h e r m a l d e c o m p o s i t i o n of h y d r o carbons. Curves:/--reaction

CH~ = C + 2H2 , 2 - - r e a c t i o n CsHs = 6C + 3H~ , 3 - - r e a c t i o n C~H2 = 2C +
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 ?

809

ACTIVATION ENERGY OF GAS REACTIONS WITH SOLID CARBON

p r o b a b l e t h a t a t sufficiently high t e m p e r a t u r e s
t h e a c t i v a t i o n energy approaches zero a s y m p totically, as shown b y the dashed lines of Figure 1.
CARBON

COMBUSTION AND

GASIFICATION

I n all previous investigations of c a r b o n comb u s t i o n a n d gasification, w i t h o u t exception, t h e

a c t i v a t i o n energy was assumed to be c o n s t a n t
over the t e m p e r a t u r e range of interest. I n view
of the fact t h a t a rapid fall-off of the a c t i v a t i o n
energy w i t h t e m p e r a t u r e is observed for these
reactions, this a s s u m p t i o n leads to erroneous
results, which explains t h e extensive range of
a c t i v a t i o n energies o b t a i n e d b y different authors.
U n f o r t u n a t e l y , despite t h e t r e m e n d o u s n u m b e r
of papers on c a r b o n c o m b u s t i o n a n d gasification, v e r y few of t h e m c o n t a i n d a t a on the
absolute reaction rate as related to u n i t reacting
surface. T h e results o b t a i n e d in these works
were applied b y us in the calculation of the
a c t i v a t i o n energy from E q u a t i o n (1) as was done

a b o v e for carbon f o r m a t i o n reactions in the

t h e r m a l decomposition of hydrocarbons.
Reaction C + 02 A p a r t from Snegireva's
m e a s u r e m e n t s 5 the results of only three works ~, 7, s
could be used for calculating the a c t i v a t i o n
energy of this reaction.
I n the calculations for v a c u u m experiments, G. 7
it was assumed t h a t gas molecules h i t t i n g the
surface h a d a n a m b i e n t t e m p e r a t u r e which was
t a k e n to be T = 300K. T h e results are given
in T a b l e 2 a n d Figure 2. I t can be seen t h a t ,
j u s t as for reactions of h y d r o c a r b o n decomposition on t h e surface, t h e a c t i v a t i o n energy of the
reaction C + O2 drops drastically with rising
t e m p e r a t u r e , a n d a t a t e m p e r a t u r e of a b o u t
1300K is only a few t h o u s a n d cal/mole, whereas
a t 800 to 900K the a c t i v a t i o n energy is of the
order of 40,000 cal/mole.
E x p e r i m e n t a l points for t e m p e r a t u r e s exceeding 1300K show a f u r t h e r drop in the a c t i v a t i o n
energy a t these t e m p e r a t u r e s , a l t h o u g h the drop

T A B L E 2. RATE AND ACTIVATION ENERGY OF THE REACTION C q- 02

Run

Tem- Pressure of O5
perature
mm Hg

Number of
Collisions

723
773
823
873
[170
[178
L194
[228
[160
[390
[520
[960
~)050
[150
[280
[280
[340
[455
t905
t925
t975
.)125
.)245
.)265
.)465
.)475

285
6.55
285
6.32
163
3.54
15
0.31
760
13.8
160
2.9
160
2.86
19
0.33
2 . 6 X 10-3 9.36
3.4 X 10-3 12.25
2.7 X 10-3 9.70
2 . 1 X 10
7.56
1.9 X 10-~ 6.85
27 10-~ 97.0
27 X 10-8 97.0
380 X 10-~ 1370
0.83 X 10-~ 2.98
0.83 X 10-~ 2.98
1.86 X 10_8 6.5
0.48 X 10-~ 1.73
1.66 X 10-5 5.98
D.66X 10-5 2.38
1.3 X 10-5 4.68
1.66 X 10-5 5.98
3.96 X 10-~ 3.46
1.66 X 10-~ 5.98

e--EIRT

Activation Energy
(cal/mole)
Authors

(Eq.(1))
According to
(Eq.(1))
Arrhenius

oK

257
243
253
256
A
B
B
P
172
199
227
265
273
93
94
95
97
98
105
110
118
107
112
117
114
116

Rate of Consumption of O5

X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X

mole/cra-2sec-1
1022 0.15 X
1022 0.58 X
1022 1.84 X
1022 0.37 X
1022 1.3 X
1022 7.1 X
1022 1.3 X
1025 1.3 X
1017 0.5 X
1017 1.28 X
1017 0.33 X
1017 6.7 X
1017 15.5 X
1017 1.87 X
1017 5.0 X
1017
54 X
1017 0.25 X
1017 0.27 X
1017 0.53 X
1017 0.85 X
1017 1.3 X
1017 3.3 X
1017 6.6 X
1017 8.9 X
1017 24.6 X
1017 3.1 X

10-12 0. 138 X 10-11

10-12 0. 553 X 10-11
10-12 3.14 X 10-11
10-15 7.22 X 10-11
10-4
5.72 X 10-4
10-~
1.49 X 10-3
10-~
2.73 X 10-3
10-4
2.34 X 10-2
10-s
3 . 0 X 10-3
10-8
6 . 9 X 10-3
10-8
2 . 2 X 10-3
10_8 5.35 X 10-2
10-8
13.7 X 10-2
10-s
1 . 2 X 10-3
10-s
3 . 2 X 10-3
10_8
2 . 5 X 10-3
10-s
5 . 2 X 10-3
10-8
5 . 9 X 10-3
10-s
0.5 X 10-2
10_8 2.86 X 10-2
10-8
1.35 X 10-2
10_8 0.85 X 10-i
10-8
8.6 X 10-2
10-s
9.05 X 10-2
10_8
43 X 10-2
10-s
31.8 X 10-2

39200]

4oooo~
39600 /
40500j
17300 /
15100~104000

13900|
9100J

3480]
2980120000-3000
3660J
1750
1190

Measurement s
of V N I I G A S
K l i b a n o v a , Z.,
and F r a n k Kamenetsky,
D. s

Meyer, L. 8

40201
3450]
3580120000-25000
3150 /
3080l
318~

213~
2580 /
1380!70O00
1470~
1440]
505 /
686)

Martin, H.,
and Meyer,
L. 7

810

FORMATION, COMBUSTION, EXPLOSION AND DETONATION OF SOLIDS

is considerably slower than that in the temperature range of 800 to 1300K. The activation
energy approaches zero asymptotically and at
temperatures exceeding 2300 to 2400K it is
below 1000 cal/mole. I t should be noted that
from the paper by Martin and Meyer, who
obtained results relating to temperatures above
1300K, we used only the results for the lowest
oxygen pressures, because in high pressure
experiments the effect of diffusion inhibition of
the reaction is quite pronounced. Therefore, it is
possible that the data of Figure 2 regarding
temperatures above 1300K are in error because
of diffusion. The diffusion inhibition diminishes
the reaction rate and brings about (in calculations based on Equation (1)) an apparent increase
in the activation energy. I t is possible, therefore,
that the activation energies obtained are somewhat high and that, consequently, the activation
energy actually tends to vanish more rapidly
than suggested by Figure 2.
Reaction C + C02. In calculating the activa-

tion energy of this reaction we applied the

results of the following two works: the already
cited work 7 on carbon filament gasification in a
vacuum, and a comparatively recent work of
Bastick 9 who studied the interaction of carbon
dioxide with coke and simultaneously measured
the actual reaction surface.
The results of activation energy calculations
based on these works are illustrated in Table 3
and Figure 2. As is shown by the curve, the
activation energy of the reaction C 3- CO.a as
well as that of the other reactions investigated
drops (curve 2)drastically with temperature.
At 2200K it equals 7000 cal/mole, whereas at
1200K it is 60,000 cal/mole. Of course, one
should make the reservation that the sharply
declining section of the curve has no experimental
points and is drawn tentatively.
I t should be noted that, as in the case of hightemperature methane decomposition, the activation energy of the reaction C 3- C02 is sig

70
0

O~
\\\

30

\\

20
\\

500

~00

_ 1500

2~

Temperatuhe, "K

2500

JOOg

FIG. 2. Activation energy of reactions of carbon combustion and gasification

Curves:/--reaction C 3- 02 \
2--reaction C 3- CO2J E from Eq. (1)
/--reaction C 3- 02
H--reaction C -4- CO:f E from the data of Khitrin 1
~--mcasurements of VNIIGAS
O--Martin, Meyer 7
O--Klibanova and Frank-Kamenetsky s
~--Bastick 9
~--Meyer 6

811

ACTIVATION ENERGY OF GAS REACTIONS WITH SOLID CARBON

T A B L E 3. R A T E AND ACTIVATION E N E R G Y OF THE REACTION C -~ C 0 2

Temperature

Activation Energy
(cal/mole)
Pressure of C02

Number of
Collisions

Rate of Consumption of C02

e--EIRT

Authors

:Eq. (I)
Eq. (1)

27
45
62
67
70

1073
1273
1323
229C
223G
234G
261C
266C

mole/em-2/sec-I

mm Hg

760
760
760
2.66 X
3.68 X
1.3 X
0.24 X
0.24 X

10-a
10-s
10-a
10-a
10-a

according
to
Arrhenius

12.3
11.3
11.0
8.15
11.25
3.98
7.34
7.34

X
X
X
X
X
X
X
X

1022
1022
1022
1017
1017
1017
1016
1016

0.021 X 10-11
1.15 X 10-n
3.11 X 10-11
O. 108 X 10-6
O. 192 X 10-s
O.239 X 10-s
0 . 7 7 X 10-6
O. 586 X 10-~

nifieantly lower than the reaction heat which is

41,200 eal/mole.
The curves I and II of Figure 2 reflect the
temperature dependence of the activation energy
for the reactions C + C02 and C + C02 on the
basis of Khitrin's data/ Equation (1) could not
be used to calculate the activation energy from
these data as they refer to the so-called reaction
gas-exchange coefficient. This value takes into
account the reaction rate in the pores of the substance per 1 cm 2 of its external surface and is not
helpful in estimating the true reaction rate per
unit reacting surface.
Because of this, the calculation was made by
extrapolating the curve representing the temperature dependence of the reaction gas-exchange coefficient to its maximum value where
the activation energy of the process should be
zero. Figure 2 shows that the activation energies
found in this manner, as well as the values obtained from Equation (1), decrease with increasing temperature.
Of course, there is a considerable discrepancy
between these curves and those obtained from
Equation (1). It would be natural to attribute
this to the fact that the gas-exchange coefficient
of the reaction is not a chemical reaction constant and depends markedly on the depth to
which the reaction extends into the pores of the
substance. Because this depth diminishes with
rising temperature, this leads to an apparent
drop in the temperature coefficient of the reaction
rate and hence in the temperature coefficient of
the activation energy.
Discussion

The observed decrease with temperature of the

activation energy of reactions involving the

0.103 X 10-11 59000 53000

0.613 X 10-1 60000
Bastick, M. '~
1.705 X 10-1 59400 54700
0 . 8 X 10-4
56501
1.03 X 10-4
5530/
3.59 X 10-4
4760~ 90000}Martin, H.,
63.0 X 10-4
and Meyer,
2780 I
L . 11
48.0 X 10-4
2330/

interaction of solid carbon with oxygen, carbon

dioxide and hydrocarbons seems to be of sufficiently general significance and should be observed in any other reactions involving solid
carbon. It is believed that a variation in the
activation energy with temperature should be
observed in other reactions, too.
We attribute the decrease in the activation
energy with temperature to the increase in the
activity of the carbon surface with temperature.
The higher the temperature, the higher the
activity, i.e., the higher the energy state of
active surface atoms of carbon, the lower may
be the kinetic energy of the gaseous molecules
hitting the surface and causing the reaction. At
a sufficiently high temperature, the energy of the
surface atoms becomes so significant that they
are capable of reacting with gas molecules with a
lower energy than the heat of the endothermic
reaction which is proceeding. Even strongly
endothermie reactions (e.g., C + C02) may
occur at near-zero activation energies provided
the temperature is high enough. This does not,
however, constitute a violation of thermodynamic laws, for we do not take into account
the energy of the active reacting surface atoms.
At sufficiently high temperatures, the activation energy becomes so low that each or almost
each collision of a gas molecule with the carbon
surface causes a reaction. This means that the
majority of surface carbon atoms possess an
activity similar to that of free radicals.
It appears to us that a further study of this
problem may be of fundamental interest for the
understanding of the mechanism of chemical
surface processes and, in particular, the mechanism of catalytic processes.
It is especially interesting that in the case

812

FORMATION, COMBUSTION, EXPLOSION AND DETONATION OF SOLIDS

under consideration we are able to watch the

temperature variation of activity.In this connection, attention should be focused on the fact that
the investigated concept of the activity of the
carbon surface is meaningful only with respect
to a specific reaction. Indeed, the activation
energy, which may be regarded as a yardstick
for the activity of the carbon surface, is different
for different reactions, the temperature being
equal. For instance, for the reaction C + 02, the
activation energy is 5000 cal/lnole at 1300K,
and for the reaction C + C0., the same activation energy is attained at 2300K. It is evident,
however, that in all the cases discussed the
activation energy has the same form of temperature dependence, i.e., evidently, the same law
of thermal activation of the surface.
The regular nature of the decrease in the
activation energy with temperature explains
the diversity of the experimental activation
energy values obtained by different authors for
reactions which involve solid carbon. As an
illustration, we might quote the value of the
activation energy of the carbon formation
process in the thermal decomposition of benzene.2
A calculation based on the slope of a straight
line in Arrhenius coordinates yielded 138 keal/
mole whereas the value obtained from Equation
(1) is about 40 kcal/mole. The results obtaineds
for the combustion of carbon are similar. With
the concept of the constancy of the activation
energy for a temperature range of 16, these
authors obtained a value of 104,000 cal/mole,
whereas a calculation with Equation (1) produced
a value of 15,100 cal/mole for 905C and 13,900
cal/mole for 921C.
It should be noted, however, that the experimental results of Klibanova and Frank-Kamenetsky s do not cause any doubt and are the only
published data on the reaction rate in the region
of a rapid decrease in the activation energy and,
consequently, of an exceedingly rapid change in
the reaction rate. These data were obtained by
the original investigation method used by the
authors which made it possible to measure the
instantaneous rate of a rapid reaction at the
instant of initiation. It is thought that a more
extensive application of this method, in conjunction with the Meyer method, will allow a reliable
measurement of the rate of these rapid reactions
over a wide temperature range.
It should also be emphasized that ~he results
obtained by no means contradict the highly
productive idea of Arrhenius, that the reaction

involves only molecules having some excess

energy. We have only shown that the widely
applied practice of determining the activation
energy from the slope of a straight line in Arrhenius coordinates, i.e., assuming the constancy
of the activation energy over the given temperature range, may cause significant errors.
The available experimental data on the type
of function E = f(T) are not conclusive, of
course, and further experimental work is needed.

Conclusions
In chemical interaction of gaseous substances
with solid carbon the activation energy of the
process decreases with rising temperature, and
at a certain temperature reaches zero or a value
of the order of several thousand cal/mole which
is characteristic of the activation energy of
radical reactions.
The observed reduction in the activation
energy with temperature is attributed to the
increase in the activity of the surface carbon atoms
with rising temperature. Further investigation is
required to establish the mechanism of this
thermal activation.
In studying surface or heterogeneous chemical
processes, the activation energy obtained from
the absolute reaction-rate equation is a criterion
of the activity of the solid surface with respect
to the process under consideration.
REFERENCES
1. TESNER, P. A., AND RAFAnKES,I. S.: Doklady
Acad. Sci. U. S. S. R., 87, 821 (1952); and
VNIIGAS Proceedings, p. 3. Gostoptehisdat, Moscow, 1953.
2. TESNER, P. A,: Seventh Symposium (International) on Combustion, p. 546, Butterworth
and Company, Ltd., London, 1959.
3. TESNER, P. A., AND ECHEISTOVA,A . I.:
Doklady Acad. Sci. U. S. S. R., 87, 1029
(1952).
4. JONES, G. W., KENNEDY, R. E., SPOLAN, I.,
AND SCOTT, G. S.: Bureau of Mines Report of
Investigation, 4695, May, 1950.
5. SNEGEREVA, W. D.: VNIIGAS Proceedings,
p. 74. Gostoptehisdat, Moscow, N 6 (14)
1959.
6. MEYEn, L.: Z. Phys. Chem., 17, 385 (1932).
7. MARTIN, H., AND MEYER, L. : Z. Electrochem.,
41, 136 (1935).
8. KLIBANOVA, Z., ANn FRANK-KAMENETSKII, ]). :
Acta Physicochimica U. S. S. R., 18, 387
(1943).
9. BASTICK, M. : Bull. Soc. Chem. France, No. 7,
916 (1957).

813

ACTIVATION ENERGY OF GAS REACTIONS WITH SOLID CARBON

10. KHITRIN, L. N.: Physic of Combustion and

Explosion, Moscow University Press, Moscow, 1957; ~nd Sixth Symposium (International) on Combustion, p. 565. Reinhold
Publishing Corporation, New York, 1956.
]--)ISCUSSIONBY R. ~-I. ESSENttIGtt
Commentary is hampered by nonaccess to the
complete papers by Golovina, Khaustovich and
Tesner, however, the following points would seem
to be relevant.
In the abstract the authors conclude that the
limiting of the reaction of carbon with C Q at
high temperatures is due to reduced effective
surface by formation of the surface oxide complex. In my opinion, this is most unlikely and in
any event is unnecessary to explain the observed
effects. This may be deduced from the mathematical analysis of the system.
Use of the Davis and Hottel ~ cup data to
interpret the Tu, Davis and Hottel ~ sphere data
indicates that, at the air velocities used by
Golovina and Khaustovich, the thickness of the
diffusion boundary layer is reduced to a value
that is too low to affect the reaction rate significantly. This is confirmed by the independence
of reaction rate with ambient velocity observed
experimentally by the authors.
The Langmuir adsorption isotherm, which
takes into account coverage by the surface oxide
complex, may now be applied. For an oxygen
partial pressure p, the reaction rate/unit area
R may be written:

R -

klk2p
kl p -~- ks

(1)

in which kx and k~ are the velocity or rate constants for adsorption and desorption, respectively. Adsorption requires true activation
energy E~, desorption requires true activation
energy E2.
The influence of internal reaction modifies the
relation by requiring the use of the square roots
of the rate constants; the form of the equation,
however, is unchanged.
With changing temperature this Equation (1)
has two limiting conditions:

(i)

T < T~, k2 << kl p

so
R = k2 = A2 exp ( - - E 2 / R T )
(ii)

T > T~, k.2 >> hi p

(2)

SO
R = k i p = A l p exp ( - E I / R T )

(3)

in which T~ is a critical temperature at which

condition (i) changes to condition (ii); in practice, Tc is a temperature band inside which
there is a transition from Equation (2) to Equation (3), requiring the use of the full Equation
(1)2
The data given by thc authors indicate that
Tc for the carbon/CO.o reaction is about 1400C;
for the carbon/O~ system Tc has been identified
as 2000 4- 200C.
Equations (2) and (3) predict:
(i)

Zero-order reaction wrt

p

(ii)

at

T<Tc

First-order reaction wrt

p

at

T>

To.

The authors report zero-order reaction at T

< Tc (1400C) for the C/C0.2 reaction; and
dependence on P at T > T~ for the same reaction.
The Langmuir equation would, therefore, seem
to apply, so that we have the following rate control mechanisms:
(i) T < Tc (low temp); the solid surface is
almost completely saturated by the oxide complex, and decomposition of this complex (desorption) is the rate-controlling factor of the
reaction as a zero-order reaction wrt unit area
of surface. (This is the mechanism attributed
by the authors to the high temperature region.)
(ii) T > Tc (high temp); the solid surface is
almost clear of the oxide complex, and desorption
occurs almost instantaneously after adsorption.
The rate control is then the rate of adsorption.
This is calculable in part from Kinetic Theory.
For a rate of bombardment Z and oxygen
partial pressure p, the rate of adsorption is Zp
exp ( - E x / R T ) , E1 being the activation energy
of adsorption. E~ is low, possibly being in the
range 1000 to 5000 cal (cf. 4000 cal found by
Blyholder and Eyring a for the C/O~. reaction).
E~ has not yet been calculated from first principles.
Qualitatively, the equations given account
quite satisfactorily for the shapes of the reported
curves. Quantitative check may also show
agreement.
The equations derived above are also relevant
to the change of activation energy found by

814

FORMATION, COMBUSTION, EXPLOSION AND DETONATION OF SOLIDS

Tesner and attributed to a change in activity of

the carbon surface.
The change from Equation (2) controlling to
Equation (3) controlling involves a drop in
activation energy of roughly 40,000 cal to
4000 cal3, 4. ~ (a factor of 10).
This does not rule out a probable change in
surface activity as a perturbing factor, but it
accounts quite satisfactorily for all of the major
changes observed experimentally, without recourse to any special assumptions on activity
that are not yet required by independent experiment.
ADDITIONAL REFERENCES
1. DAVIS, H., AND HOTTEL, H. C.: I/EC 26, 889

(1934).
2. Wu, C. M., DAvis, AND HOTTEL: I/EC 26, 749

(1934).
3. BLYHOLDER, G. D., AND EYRING, H.: U.S.A.F.

Office of Scientific Research Technical Note

Report O.A. No. XX, August, 1956.

4. ESSENHIGH, R. H., AND PERRY, M. C.: Inst. Fuel

Conf. Science in Use of Coal, p. D1 (Sheffield,
April, 1958).
5. ESSENHIGH, R. I-I.: J. Fuel Soc., 6, 15 (1955)
(Sheffield University).
AUTHOR'S REPLY

We believe that the change in surface activity

is a major factor which accounts for all experimentally observed changes in reactions with solid
carbon.
The change in the energy of activation can be
indeed formally explained by superposition of two
reactions with different energies of activation,
but it requires the postulation of two different
mechanisms for each reaction.
Dr. R. H. Essenhigh offers such a mechanism
for the reaction C + 02 .And what can be proposed
for the reactions C -t- C~Hm and others? And what
can be the reason for the change of the mechanism
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
The objective of this study is to determine the
particle size distribution of metal oxides resulting from the combustion of solid rocket propellants and its effect upon the thrust of rocket
motors.
It is found experimentally that the delivered
specific impulse of metalized solid propellants
begins to fall significantly below the calculated
value as the percentage of metal is increased. A
portion of this difference between delivered and
calculated specific impulse is usually assigned to
nozzle inefficiency and the remainder to combustion inefficiency. The delivered specific impulse
is then expressed as a percentage of the calculated
value.

Recently, it has become of interest to increase

the combustion efficiency of solid propellants,
even though some are currently operating at the
95 per cent efficiency level. The question then
arises as to whether the inefficiency is to be

found mainly in the nozzle, in the combustion

process, or somewhere else. There is, of course,
also the possibility that the inefficiency found
experimentally is a combination of several factors,
none of which are particularly significant themselves. It would seem that the first step toward
improvement is to discover just what the cause
of the inefficiency really is.
One plausible cause for reduced specific impulse
is that the particles or droplets of condensed
oxide do not achieve velocity equilibrium with
the gases during their transit time through the
nozzle. This effect was studied by several authors,
including Gilbert, Davis and Altman,1 and most
recently Kliegel.~ These correlations predict
widely differing results, but all have as a common
parameter the particle or droplet diameter. None
of these authors offered any evidence as to what
the size might be.
An alternate reason for the loss in specific
impulse is combustion inefficiency, here defined
as the nonachievement of chemical equilibrium