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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.
Nowhere:
p =
m =
K =
T =
(2)
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
808
Hydrocarbon
Temperature
oK
Mean
Concentration of
Hydrocarbon
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
809
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
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
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
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-
70
0
O~
\\\
30
\\
20
\\
500
~00
_ 1500
2~
Temperatuhe, "K
2500
JOOg
811
Temperature
Activation Energy
(cal/mole)
Pressure of C02
Number of
Collisions
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-~
812
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
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)
so
R = k2 = A2 exp ( - - E 2 / R T )
(ii)
(2)
SO
R = k i p = A l p exp ( - E I / R T )
(3)
(ii)
at
T<Tc
at
T>
To.
814
(1934).
2. Wu, C. M., DAvis, AND HOTTEL: I/EC 26, 749
(1934).
3. BLYHOLDER, G. D., AND EYRING, H.: U.S.A.F.
88