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研究生: 詹宗翰
Tsung-Han Chang
論文名稱: 266 nm 雷射光解一氯二溴甲烷之放射光譜研究
Emission spectrum of 266 nm photolysis of bromodichloromethane
指導教授: 張伯琛
Bor-Chen Chang
口試委員:
學位類別: 碩士
Master
系所名稱: 理學院 - 化學學系
Department of Chemistry
畢業學年度: 95
語文別: 中文
論文頁數: 86
中文關鍵詞: 一氯二溴甲烷光解放射光譜研究
外文關鍵詞: 266 nm, photolysis, emission spectrum
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  • 光解一氯二溴甲烷分子(CHBr2Cl)後所產生的溴原子,是破壞大氣層中臭氧層的主要來源之一,而由長於真空紫外光波長(>200 nm)造成的光解反應之相關研究是相當有限的,因此對此一光解反應的反應機制還未有定論。本研究以266 nm為光解光源,分別於「超音速自由噴射裝置」(supersonic free jet)以及「流動式樣品槽」(flow cell)中進行一氯二溴甲烷的光解反應,搭配具高靈敏度之增強式偶合電荷裝置偵測器,成功取得光解後之放射光譜。所得物種包括CH (A2Δ)、CH (B2Σ-)、CH (C2Σ+)、Br2 (X1Σg+)、激發態Br原子以及由兩個CH碰撞產生之C2。其中實驗數據顯示CH為三個光子過程之產物,激發態Br原子為兩個光子過程之產物以及Br2為一個光子過程之產物。參考其他實驗數據與文獻資料,可以推論出一氯二溴甲烷在266 nm的光解機構,並可和溴仿(CHBr3)的光解機構比較,顯示這兩個溴化合物其光解產物雖然類似,但其反應機構有明顯的差異。


    Atmospheric bromine atoms come from the photolysis of dibromochloromethane (CHBr2Cl) is one importance source of the ozone depletion. The studies of the photolysis of CHBr2Cl at long ultraviolet wavelengths (>200 nm) are very limited, and the reaction mechanism is still unclear. The photolysis reaction of CHClBr2 at 266 nm was observed in a supersonic free jet expansion as well as in a slow flow cell. Nascent emission spectra were successfully acquired with an intensified charge-coupled device (ICCD) detector. In the emission spectra, several species include the CH (A2Δ), CH (B2Σ-), CH (C2Σ+), Br2 (X1Σg+), excited Br atom and the collisional product C2 were observed. The power-dependence experiments indicate that CH, excited Br atom and Br2 are likely the products of a three-photon process, a one-photon process and a two-photon process, respectively. Based upon our results and other related references, the reaction mechanisms of the 266 nm photolysis of CHClBr2 are elucidated. Moreover, in comparison with the photolysis of bromoform (CHBr3), in spite of the similar products of this photolysis, their reaction mechanisms are distinctively different.

    摘要 (中文) Ⅰ 摘要 (英文) Ⅱ 謝誌 Ⅲ 目錄 Ⅳ 表目錄 Ⅵ 圖目錄 Ⅶ 第一章 序論 1-1 研究方向及目標 1 1-2 一氯二溴甲烷的相關研究 6 第二章 實驗 2-1 光譜技術簡介 9 2-2 自由基產生技術 11 2-3 超音速自由噴射分子束裝置 12 2-4 增強式電荷偶合裝置偵測器(ICCD Detector) 18 2-5 超音速自由噴射裝置下光解一氯二溴甲烷 22 2-6 流動式樣品槽下光解一氯二溴甲烷 25 2-7 光解後之放光收集 26 2-8 染料雷射與石榴石雷射(Nd:YAG Laser)同步實驗 30 第三章 光解CHBr2Cl之放射光譜與機構探討 3-1 超音速自由噴射裝置下光解CHBr2Cl 31 3-2 流動式樣品槽內光解CHBr2Cl 34 3-3 光解反應可能之中間產物的觀測 37 3-4 光解反應機構的探討及推測 42 第四章 結論 47 參考文獻 85

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