Reaction rates of the hydrated electron with N2O in high temperature water and potential surface of the N2O− anion
作者:Kenji Takahashi、Shintaro Ohgami、Yasushi Koyama、Sadashi Sawamura、Timothy W. Marin、David M. Bartels、Charles D. Jonah
DOI:10.1016/j.cplett.2003.11.050
日期:2004.1
The reaction rate of hydrated electrons, (e−)aq, with N2O can be fitted with an Arrhenius-type temperature dependence up to 300 °C with an activation energy of 15.5 kJ/mol. At higher temperatures, the rate constant decreases to give a local minimum at 380 °C. Ab initio calculations of the N2O− anion suggest a possible dissociation path of N2O− in water. The calculated free energies for electron transfer
水合电子的反应速率,(E - )水溶液,用N 2 O可以被装配有阿仑尼乌斯型温度依赖性高达300℃下用15.5千焦/摩尔的活化能。在较高温度下,速率常数会降低,从而在380°C时达到局部最小值。从头的N计算2 ö -阴离子暗示N的可能解离路径2 ö -水。电子转移所计算的自由能建议向(e - )水溶液用N反应2 ö应该落在马库斯抛物线的“正常”的一部分,并且由于这个原因,反应不扩散的限制。