利用雷射光解—雷射誘發螢光技術研究CN + NCO → NCN + CO之動力學

Abstract

摘要 本研究利用雷射光解(laser photolysis) /雷射誘發螢光(laser-induced fluorescence)技術配合電腦模擬程式Facsimile在254，273，298，353 K及123 – 566 Torr之He中測量CN + NCO→ NCN + CO反應之速率常數值。結果顯示此反應之速率常數值在此壓力範圍內不隨壓力改變，但有負溫度效應，其速率常數可表示為:

k = (1.61 ± 1.16) × 10-11 exp[(342 ± 45)╱T] cm3 molecule－1 s－1

實驗之結果可配合理論計算，來驗證此一反應路徑之各個中間物和過渡態，並檢驗速率常數之正確性。

Abstract

Absolute rate constants for the reaction CN + NCO → NCN + CO were determined at 254，273，298，and 353 K in 123 to 566 torr of He by means of the laser photolysis / laser induced fluorescence technique coupled with computer simulations。 We found that the rate constants are pressure – independent and temperature-dependent。The rate constant can be expressed by :

k = (1.61 ± 1.16) × 10-11 exp[(342 ± 45)╱T] cm3 molecule－1 s－1

Our results will compared with the results of a quantum mechanical calculation on the intermediates and transition states in the reaction paths，and a RRKM calculation of the rate constants of individual reaction path。