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Hot atom reactions involving multivalent and univalent species. Progress report, February 1980-January 1981 [electronic resource].

Published:
College Station, Tex. : Texas A & M University, 1981.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy.
Physical Description:
Pages: 65 : digital, PDF file
Additional Creators:
Texas A & M University and United States. Department of Energy. Office of Scientific and Technical Information
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Summary:
Major progress was made in the study of recoil /sup 31/Si reactions. The most significant discovery is that monomeric /sup 31/SiF/sub 2/ adds to two molecules of C/sub 2/H/sub 4/ to give 1,1-difluorosilacyclopentane as a final product. When radical scavengers were added, the yield of this product was not altered. When 1,3-butadiene was added to the above recoil /sup 31/Si system to compete with C/sub 2/H/sub 4/ for the available /sup 31/SiF/sub 2/, a nearly complementary relationship was found between 1,1-difluorosilacyclopent-3-ene-/sup 31/Si, the butadiene product, and 1,1-difluorosilacyclopentane-/sup 31/Si. Quantitatively, it was deduced that butadiene is about ten times more reactive than C/sub 2/H/sub 4/ for the trapping of /sup 31/SiF/sub 2/. When Ne was added as a moderator to the 5:1 C/sub 2/H/sub 4/:butadiene competition system, the two product ratio shifts from 1:2 in favor of butadiene to 10:1 in favor of C/sub 2/H/sub 4/. This indicates that it is the lower energy /sup 31/SiF/sub 2/ species which is captured by C/sub 2/H/sub 4/, while it is favorable for the more energetic /sup 31/SiF/sub 2/ to be captured by butadiene. In the systems reacting recoil /sup 31/Si atoms with C/sub 2/H/sub 4/ in the presence of PF/sub 3/, four unidentified products with yields less than that of 1,1-difluorosilacyclopentane were also observed. Two of them were also formed when either PH/sub 3/ or (CH/sub 3/)/sub 3/P were used as the /sup 31/Si precursor. This means that they are likely to be direct /sup 31/Si atom reaction products. When recoil /sup 31/Si atoms reacted with C/sub 2/H/sub 4/ in the presence of (CH/sub 3/)/sub 3/P, the main product was identified as /sup 31/SiH(CH/sub 3/)/sub 2/CH = CH/sub 2/. This might mean the formation of dimethylsilene, /sup 31/Si(CH/sub 3/)/sub 2/, and the addition of it to CH/sub 2/ = CH/sub 2/ to give the product. In addition, catalytic C-F hydrogenolysis of CH/sub 2/ = CHF, CH/sub 3/CH/sub 2/F, CHF = CHF, CH/sub 2/ = CF/sub 2/, CH/sub 3/CHF/sub 2/, and CH/sub 3/CF/sub 3/ were studied at temperatures ranging from 75/sup 0/ to 400/sup 0/C. The apparent activation energies and the A factors have been evaluated.
Report Numbers:
E 1.99:doe/er/03898-52
doe/er/03898-52
Subject(s):
Other Subject(s):
Note:
Published through SciTech Connect.
01/01/1981.
"doe/er/03898-52"
Tang, Y.N.
Funding Information:
AS05-76ER03898
View MARC record | catkey: 14761382