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Pyrolysis of Monosilane
M. A. Ring, M. J. Puentes, and H. E. O'Neal
Contribution f r o m the Department of Chemistry, San Diego State College,
San Diego, California 92115. Received February 12, 1970
Abstract: The pyrolysis of silane-silane-d4 mixtures and silane-d4 in the presence of hydrogen has been examined.
The results from these experiments and those reported by Purnell and Walsh' strongly suggest that silane decomH ; 2SiH3 +
poses by the followingroute: %HI-. SiH3 H ; H f SiH4- H Z SiH3; SiH3 f SiH4-t Si&
SizH6. With this result, the activation energy obtained by Purnell and Walsh can be used to demonstrate that
D2980(SiH3-SiH3)
and Dzsao(SiH3-H)are of the order of 81 and 94 kcal mol-', respectively. Results from the
pyrolysis of methylsilane-methylsilane-d3mixtures suggest that in addition to the reactions present in the silane
decomposition, steps forming methylsilene and hydrogen are also important in the pyrolysis of methylsilane.
+
e
e
SM4+SiHz Hz
SiHz SiH4
%He
SiH2 &He
SisHs
+
+
(1)
(2)
(3)
+
+
(4)
(5)
(6)
(7)
Results
The pyrolysis of equimolar silane-silane-& mixtures
was examined in a static system a n d in a circulating
flow system with low-temperature (- 130") trapping
(3) J. J . Kohanek, P. Estacio, and M . A. Ring, Inorg. Chem., 8 , 2516
(1969).
(4) J. H. Meal and M. K. Wilson, J . Chem. Phys., 24, 385 (1956);
M. A. Ring and D. M . Ritter, J . Amer. Chem. Soc., 83, 802 (1961).
( 5 ) M. A. Ring, G. D. Beverly, F. H. Koeqter, and R . P. Hollandsworth, Inorg. Chem., 8 , 2033 (1969).
Pyrolysis of Monosilane
4846
Table I. The Per Cent Composition of the Disilane and Hydrogen Fractions from the Decomposition of Equimolar SiH4-SiD4Mktures
x
decomposition
Mode
-% disilanes
S ~ Z D BHSizDa H z S ~ Z H3Si2D3
D~
DzSizH4 DSizH5 SizHs
I
Flow pyrolysis
4
17
12
17
0
Static pyrolysis
2
5
12
27
15
Photolysisn
-3
12
17
17
0
Dischargea,
-3
10
5
21
0
Dis~harge~,~
-3
9
20
13
14
a Reference 5.
I,High pressure (0.30 atrn).
Low pressure (0.014 atm).
Table 11. Results of the Pyrolysis of SiDd-Hz Mixtures
Total
presTime, Temp, sure, Ratio % composition of hydrogen
min
"C
mm HZ/SiDd
DZ
HD
HZ
135
10
5
380
380
310
383
279
230
1.20
2.43
3.32
41
12
0.7
43
43
2.8
16
45
96.5
515
510
10
15
decomposition
4
4
DZ
HD
Hz
28
32
21
16
51
52
~~~
1 92:16
32
5
37
44
25
31
46
22
29
44
28
20
24
18
20
41
34
54
53
36
SiD4
SiD,
D2
SiDz SiDa +SipDs
(8)
(9)
from mechanism B6
+
+ SiD,
+
+H
+ * + SiD3
+
+ SLD,
% composition of hydrogen
8
6
6
10
9
12
13
hydrogensHD
HP
Dz
D
SiD4+DP
D
Hz +HD
H
SiD4
HD
SiD,
SiD4 +D
16
26
8
---%
(10)
(11)
(12)
(13)
(14)
SiH, -t SiH2
(15)
Reaction 14 provides a path for mixed silane production, while reaction 15 is a process by which both mixed
silanes and disilanes can be formed. Reaction 14
should be operative in both the flow and static pyrolyses, while reaction 15 should be very important in the
static pyrolysis but relatively unimportant in the flow
pyrolysis. The latter follows from the fact that disilane
products in the flow system were removed by trapping
soon after their formation.
C. Justification for Reactions 14 and 15. Reaction
14 should be as fast and probably faster than reaction 6
(6) For mechanism B we have calculated a chain length of 10" (see
Appendix), so that essentially all of the disilane i s formed in step 6
(=step 13).
-- 10 k c d mol-', while
(7) Alo
All and Ela 5 h a , since AH:oo
A H l l " N 0 kcal mo1-I.
4847
(formation of Siz&
H), since one would estimate that
EI4 5 Ea and A14 2 A6. It should be pointed out that
reaction 14 is not essential to the explanation of our
data.
Reaction 15 is a secondary reaction. Inclusion into
the overall mechanism suggests that disilane decomposition into silene and silane is fast relative to the
overall silane decomposition. The reverse of reaction
15 must also be extremely fast (see ref 12).
There are at present no reliable kinetic data on the
pyrolysis of polysilanes, but our qualitative studies
on the pyrolysis of disilane and trisilane8 show that
disilane is thermally more stable than t r i ~ i l a n e . ~The
inference, by extrapolation then, is that silane should be
more stable than disilane. Certainly by analogy with
the hydrocarbons, such a stability sequence (SiH4
> Si2& > Si3& in stability) is intuitively reasonable.
A rough calculation from the data of Tebben and
Ring* gave a rate of disilane decomposition an order of
magnitude larger than the decomposition rate for silane
observed by Purnell and Walsh.
Another qualitative result is pertinent to this point.
In the flow pyrolysis of Siz& in the presence of excess
CH3SiH3,lo the products observed were SiD4 and
CH3SiH2SiD2H,' , 1 2 with only trace quantities of Dz
and no HD. At the end of this pyrolysis, silane-d4
product pressures in the flow pyrolysis chamber were
about the same as those of the disilane. Thus, from the
small yields of D2 and lack of H D formation it would
appear that the product silane-d4 was relatively stable
compared to disilane-d6.
D. Disilane Product Formation. With a long chain
length operative in mechanism B,6 the disilane must be
formed in step 6. We propose that the activated complex for step 6 is
H3Si
SiH,
-+
4848
55.9
1-51-
+ 17.1
+
Chain length
92.16
/ August
101+56/B[SiH41"*
1016.0-94/8
g 1013.0(3 X 10-3)1/2
- 1011.5
(21) Note that reactions 4 and 7 must also be in their falloff regions if
the inert gas effect observed by Purnell and Walsh is correct. This only
serves to compound the A factor problem, since it would tend t o lower
A i more than A T .
12, 1970