Reaction kinetics and isotope effect of water formation by the surface reaction of solid H2O2 with H atoms at low temperatures

被引:32
|
作者
Oba, Yasuhiro
Osaka, Kazuya
Watanabe, Naoki
Chigai, Takeshi
Kouchi, Akira
机构
[1] N19W8, Kita-ku, Sapporo Hokkaido
基金
日本学术振兴会;
关键词
EFFECTIVE RATE CONSTANTS; GAS-GRAIN CHEMISTRY; HYDROGEN-PEROXIDE; ATMOSPHERIC CHEMISTRY; AMORPHOUS ICE; H2O-CO ICE; AB-INITIO; CO; METHANOL; H2CO;
D O I
10.1039/c3fd00112a
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We performed laboratory experiments on the formation of water and its isotopologues by surface reactions of hydrogen peroxide (H2O2) with hydrogen (H) atoms and their deuterated counterparts (D2O2, D) at 10-30 K. High-purity H2O2 (>95%) was prepared in situ by the codeposition of molecular oxygen and H atoms at relatively high temperatures (45-50 K). We determined that the high-purity H2O2 solid reacts with both H and deuterium (D) atoms at 10-30 K despite the large activation barriers (similar to 2000 K). Moreover, the reaction rate for H atoms is approximately 45 times faster than that for D atoms at 15 K. Thus, the observed large isotope effect indicates that these reactions occurred through quantum tunneling. We propose that the observed HDO/H2O ratio in molecular clouds might be a good tool for the estimation of the atomic D/H ratio in those environments.
引用
收藏
页码:185 / 204
页数:20
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