1992
DOI: 10.1021/j100204a043
|View full text |Cite
|
Sign up to set email alerts
|

Rate constant for the tunneling reaction hydrogen + deuterium atom .fwdarw. hydrogen atom + hydrogen deuteride in the solid deuterium-hydrogen mixture at 4 K

Abstract: Amounts of D and H atoms, produced by y-radiolysis of D2-n-H2( 1 mol %) mixtures, were measured at 4.2 or 1.9 K by ESR. The amounts of D atoms decay upon storage of the irradiated sample at 4.2 K up to 114 h, while those of H atoms are nearly constant. The results were interpreted in terms of competition of a tunneling reaction n-H2 + D -H + HD with combination reactions of D and H atoms. Similar decay behaviors of D and H atoms were also observed in D2-pH2(1 mol 96) mixtures at 4.2 K and D2-n-Hz( 1 mol %) mix… Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
2
2
1

Citation Types

2
8
0

Year Published

1993
1993
2006
2006

Publication Types

Select...
7
2

Relationship

3
6

Authors

Journals

citations
Cited by 17 publications
(10 citation statements)
references
References 3 publications
2
8
0
Order By: Relevance
“…This result suggests the partial contribution of the tunneling in the abstraction reaction. The present results exceed by about two orders of magnitude the gas-phase values and are rather close to the isotope effects of the abstraction reactions of H and D in the solid H 2 , D 2 , and HD at ∼4 K where the importance of the tunneling in the abstraction reaction was well established. …”
Section: Resultssupporting
confidence: 77%
See 1 more Smart Citation
“…This result suggests the partial contribution of the tunneling in the abstraction reaction. The present results exceed by about two orders of magnitude the gas-phase values and are rather close to the isotope effects of the abstraction reactions of H and D in the solid H 2 , D 2 , and HD at ∼4 K where the importance of the tunneling in the abstraction reaction was well established. …”
Section: Resultssupporting
confidence: 77%
“…The tunneling abstraction reactions by H and D in hydrogen molecules (H 2 , HD, D 2 , and their mixtures) have been investigated experimentally in the solid state at very low temperature. However, no report has been published on the reaction in liquid helium.…”
Section: Introductionmentioning
confidence: 99%
“…Figure shows ESR spectra of γ-irradiated solid (a) p-H 2 −D 2 (11 mol %), (b) p-H 2 −HD (11 mol %), and (c) pure p-H 2 at 4.2 K. A narrow and sharp singlet signal at g = 2.002 is observed in (a) and (b), but not in (c). Resolution of the singlet signal in Figure (a) and (b) is remarkably improved compared with that observed in ref , because of the absence of a heat spike and the ESR signal of D atoms (which have already disappeared by the tunneling reaction D + H 2 → DH + H in this study). Figure shows microwave power saturation behaviors of the ESR intensities of the narrow singlet signal in p-H 2 −D 2 (11 mol %), the H atom signal, and the H 2 - signal in pure p-H 2 at 4.2 K. , The ESR intensity of the singlet signal saturates at very low microwave power as compared with that of the H atoms and H 2 - anions.…”
Section: Resultssupporting
confidence: 41%
“…Miyazaki et al 9 reported that the rate constant for reaction ͑2͒ measured in ␥-ray-irradiated solid D 2 -H 2 ͑ H 2 = 0.01͒ is smaller than these theoretical results by a factor of 10 4 -10 5 at 4.2 K. The discrepancy is ascribed to their invalid assumption that the reaction follows homogenous reaction kinetics. Since they irradiated the solid for ϳ1 h and started ESR measurement ϳ30 min after the irradiation, reaction ͑2͒ of D atoms at the nearest neighbor of H 2 molecules, which corresponds to the fast process in our study, should have already finished before they started ESR measurement.…”
Section: B Reaction Without Diffusion Below 6 Kmentioning
confidence: 89%