由於步進式時間解析吸收光譜法可以同時偵測多個物種的濃度隨時間之變化，因此我們利用雷射光解/時間解析-傅立葉轉換紅外吸收光譜法進行Cl + CH4反應的動力學研究。在我們的實驗結果中，證實有HCl、CH3Cl 及振動激態的CH4(2=1或4=1，表為CH4*)的生成，其中後者是其他動力學研究所從未觀測到的。我們利用CH4*之Q branch隨時間之消長，經由Facsimile 程式適解CH4* 的生成速率與消失速率，分別研究其對CH4濃度、Cl2濃度與Ar或O2濃度之變化。
我們得到hot CH4* 的生成速率常數為1.07 ×10-13 cm3 molecules-1 s-1，。Cl2對CH4*的緩弛速率常數為4.36 ×10-15 cm3 molecules s-1，Ar對CH4*的緩弛速率常數為2.20 × 10-15 cm3 molecules s-1，O2對CH4*的緩弛速率常數為1.79 ×10-14 cm3 molecules s-1。

We use a new technuque(laser photolysis/time-resolved Fourier transform absorption spectroscopy) to do the kinetic study of Cl + CH4 reaction.
We observe the products of HCl , CH3Cl and CH4 in excited states(CH4*). In the previous reports of this reaction,no one observe this products of CH4*.
In our experiments,we get the formation rate coefficient of CH4* :1.07 × 10-13 cm3 molecules-1 s-1 ;the quenching rate coefficient of Cl2 : 4.36 × 10-15 cm3 molecules s-1 ;the quenching rate coefficient of Ar:2.20 × 10-15 cm3 molecules s-1
;the quenching rate coefficient of O2 :1.79 × 10-14 cm3 molecules s-1

中文摘要………………………………………………………………….i
目錄……………………………………………………………………..ii
圖目錄………………………………………………………….…iv
表目錄………………………………………………………………..vi
第一章、緒論……………………………………………………………1
第二章、實驗原理……………………………………………….…..8
2-1 傅立葉轉換紅外光譜儀….…………………………...……..8
2-1-1 傅立葉轉換紅外光譜儀主要基本構造.....….……..9
2-1-2 傅立葉轉換紅外光譜儀的優點………………………..17
2-2 時間解析-傅立葉轉換紅外光譜法…....…………………….19
2-2-1 各種時間解析-傅立葉轉換光譜法之簡介.….……….19
2-2-2 步進式掃描……………………………………….……25
2-2-3 步進式掃描吸收光譜法………………………………29
第三章、實驗裝置與技術..........…………………………………..…32
3-1 實驗裝置...............…...................... .......………………...…32
3-1-1 White cell......................................….................………37
3-2 實驗步驟...............….............................……………...………43
3-3 數據處理...............…..................... ....…...……………...……47
第四章、結果與討論…………………………………………………..50
4-1 CH4濃度對Cl + CH4反應速率的影響....................................53
4-2 Cl2濃度對Cl + CH4反應速率的影響......................................54
4-3 壓力對Cl + CH4反應速率的影響...........................................55
第五章、結論…………………..............………………………………..69
第六章、參考文獻……..................………..……………………………70
附錄A…………………………………………………………………..72附錄B…………………………………………………………………..79

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