Kinetic Studies of the Reactions of Alkyl and Silyl Hydrides Page: 4
ix, 125 leaves : ill.View a full description of this dissertation.
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4
by Rogers.9
Instead of measuring k, and k_, independently, Benson and co-workers1011 have
used the very low pressure reactor (VLPR) technique which is a variation of very low
pressure pyrolysis12 (VLPP) to measure the equilibrium constants for the following
reactions directly:
CH4 + CI * HC1 + CH3 (1.2)
c-C3H6 + CI * HC1 + c-C3H5 (1.3)
If the equilibrium constant is measured at a single temperature, the R-H bond energy can
be determined by the "third-law" method (for details see chapter 3). This method
determines AH from the calculated AG from the equilibrium constant and a separately
derived AS, then the bond energy of R-H is obtained as before. In a simple VLPR
experiment, molecules of gas reactants are allowed to flow into a Knudsen cell reactor
(typically pressure 0.1 - 10 mtorr), and the reaction mixture is analyzed by molecular-
beam mass spectrometric detection which is designed to eliminate complicated secondary
reactions of radicals on the walls of the mass spectrometry chamber. The same technique
was applied by Choe and Choo13 to determine the rate and equilibrium constants of Br
with trimethylsilane and to estimate the Si-H bond strength in (CH3)3SiH.
Association / Dissociation Equilibria. Study of the association / dissociation equilibria,
e.g.
R-R'*R + R' (1.4)
R * olefin + H or CH3 (1.5)
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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/m1/15/: accessed July 18, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; .