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Kinetic isotope effect for the reaction of H atoms with GeH4 and GeD4

✍ Scribed by Neville L. Arthur; Ian A. Cooper; Luke A. Miles

Publisher: John Wiley and Sons
Year: 1997
Tongue: English
Weight: 128 KB
Volume: 29
Category: Article
ISSN: 0538-8066
DOI: 10.1002/(sici)1097-4601(1997)29:4<237::aid-kin1>3.0.co;2-v

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✦ Synopsis

Rate constants for H atom attack on GeH 4 and GeD 4 have been measured in pulsed photolysis experiments in which H atoms were produced by the mercury-sensitized photolysis of H 2 and monitored by Lyman-␣ absorption. The values obtained for GeD 4 in the temperature range 293 -550 K may be represented by the expression

Combination of the rate constants for GeH 4 measured in this work with those previously determined in this laboratory gives, for the temperature range 293 -455 K,

The kinetic isotope effect indicated by these expressions is given by k H /k D ϭ (0.90 Ϯ 0.12) exp[(235 Ϯ 48)/ T] which yields k H /k D ϭ 2.0 Ϯ 0.4 at 300 K. This is the first determination of the kinetic isotope effect for radical attack on a Ge 9 H bond.

The present results for the reaction of H atoms with GeH 4 have been combined with previously reported data, and the best value for the rate constant over the temperature range 210 -473 K is recommended to be k H ϭ (1.18 Ϯ 0.08) ϫ 10 Ϫ10 exp[(Ϫ 981 Ϯ 22)/ T]

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