Kinetic Studies of the Reactions of Alkyl and Silyl Hydrides Page: 84
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84
were carried out at an average temperature of 294 K and the weighted mean rate constant
of (5.07 ± 0.51) x 10"15 cm3 molecule"1 s"1 was obtained (la error limit). Table 19
summarizes the rate constant measurements. This reaction has been studied by a number
of workers124 125,126,127 and k6 2 derived in this research is comparable with the recommended
reference result of k62 = (6.09 ± 0.61) x 10"15 cm3 molecule"1 s"1 at 294 K,128 thus
confirming the reliability of the setup and the rate constants measured. Rate constants for
the reactions of OH with silane (6.3), and mono-(6.4), di-(6.5), tri-(6.6), and
tetramethylsilanes (6.7) were determined at room temperature.
OH + SiH4 -> products (6.3)
OH + Si(CH3)H3 -> products (6.4)
OH + Si(CH3)2H2- products (6.5)
OH + Si(CH3)3H - products (6.6)
OH + Si(CH3)4 - products (6.7)
Under the experimental conditions used, the pseudo-first-order decay of OH was
observed, so that
^fl=(k,[Si(CH3)KH4.,]+k,i(f)[OH]=k|Jsl[OH) (68)
where kpSl is the exponential decay constant for the loss of OH, obtained from nonlinear
least-square fits to the fluorescence signals. kdiff represents the loss of OH radicals from
the reaction zone to the walls of the reactor or other slow processes with photolysis
fragments, and ka(a = 6.3 - 6.7) was derived from the slope of a linear plot of kpS, against
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Yuan, Jessie (Jessie Win-Jae). Kinetic Studies of the Reactions of Alkyl and Silyl Hydrides, dissertation, August 1996; Denton, Texas. (https://digital.library.unt.edu/ark:/67531/metadc277864/m1/95/: accessed July 18, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; .