Kinetic Studies of the Reactions of Alkyl and Silyl Hydrides Page: 86
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86
several reactant concentrations (a minimum of four, on average, five). Figure 19 illustrates
one such plot for k6 5 at 295 K. The measured values of k63 to k67 at room temperature are
summarized in Tables 20 through 24, respectively. Variations in the flash energy by a
factor of two, the variation of the pressure by a factor of three, and the variation of [H20]
by a factor of two yielded no dependence of the derived rate constants on these
parameters. This indicates that side reactions, if any, have a negligible effect on the
measured rate constants under the conditions used.
Only one room temperature measurement of reaction (6.7) has been reported
previously. In addition, one study of reaction (6.3) was conducted over several
temperatures. Recently, Atkinson113 investigated the kinetics of a series of organosilicon
compounds with OH, N03, and 03 at 297 K by photolysis / gas chromatography with
flame ionization detection, and reported a value of (1.0 ± 0.3) x 10"12 cm3 molecule"1 s"1 for
the rate constant of OH + Si(CH3)4, k6 7. This rate constant is in good agreement with the
value of (1.09 ± 0.05) x 10"12 cm3 molecule"1 s"1 obtained in this study (where the error is
lo and refers to the precision only). With consideration of the instrumental accuracy,
which consists of the propagation errors from the pressure gauge, the flow meters, and the
thermocouple, the potential systematic error then added to the precision error gives a total
error limit of about 10%. Therefore, the weighted mean k67 can be rewritten to be (1.09 ±
0.11) x 10"12 cm3 molecule'1 s"1. The same error limits apply to the other rate constants
measured in this study. Reaction (6.3) was studied by Atkinson and Pitts110 using
photolysis / resonance fluorescence over a temperature range of 297 - 438 K. They
reported a room temperature rate measurement of the H abstraction rate of (1.26 ± 0 .2) x
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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/m1/97/: accessed July 18, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; .