臺灣博碩士論文加值系統

　　本實驗利用一連串化學方法切割己烷分子，企圖得到己烷分子內個別碳之穩定碳同位素比值，以期利用至天然氣探勘開採與作為油氣比對之指紋。
　　合成無機金屬ReH7(PPh3)2作為還原己烷之催化劑，經其催化之己烷可成功的還原為1-己烯，再利用臭氧針對其裂解為戊醛與甲醛並加入NaBH4使其還原為1-戊醇與甲醇，取少量樣品經GC-C-IRMS分離其中之甲醇並偵測其穩定碳同位素比值，即可得C1之穩定碳同位素比值；另一部分之樣品則先將甲烷去除進而收集另一產物1-戊醇，並針對其作(1)磺酸化反應與(2)去磺酸化反應後，即可成功收集得到1-戊烯，其可再經由重複的反應:臭氧裂解、NaBH4還原，依序切割下C2、C3偵測其穩定碳同位素比值，再針對醇類作(1)磺酸化反應與(2)去磺酸化反應分別得到烯類；此一系列化學反應可針對極微量(100µL)之己烷成功做切割與分析。

　　In this study, using a series of chemical reactions to cleavage terminal carbon of hexane, attempt to get the intramolecular stable carbon isotope ratio of hexane, which be applied to the fingerprint of oil gas.
　　Synthesize the catalyst ReH7(PPh3)2 to reduct hexane into 1-hexene, keep on via ozone reaction、reduction by NaBH4, here can receive methanol and then detect it by GC-C-IRMS, come here we can get the stable carbon isotope ratio of C1；another way, the other product 1-Pentanol to proceed tosylaion and de-tosylaion reaction, then obtain 1-pentene. The study can degrade 1-hexene successfully in microanalysis(about 100µL).

目 錄
摘要 i
英文摘要 ii
致謝 iii
表目錄 viii
圖目錄 ix

第一章 序論 1
一、同位素的定義及分布 1
二、同位素效應 2
三、穩定碳同位素比值分析 5
(一) 氣相層析儀-燃燒-同位素比值質譜儀 5
(二) 穩定同位素比值δ定義 8
(三) 化合物特異性同位素分析 9
1. CSIA 9
2. PSIA 10
四、穩定同位素分析在近年來的相關研究 13
(一) 環境污染 13
(二) 氣候變化 13
(三) 植物生長 14
(四) 醫學應用 14
五、研究動機 15
(一) 1999年 17
(二) 2002年 19
(三) 研究目的 20
第二章 實驗 23
一、藥品 23
二、儀器 25
三、實驗步驟 28
(一) ReH7(PPh3)2的製備 28
1.合成ReOCl3(PPh3)2 28
2. ReH7(PPh3)2的製備 29
(二) n-Hexene的製備 30
(三) 己烯的裂解 30
(四) 將戊醇反應為戊烯 34
1. 磺酸醯化反應 34
2.去磺酸醯化反應 35
(五) 己烯之微量分析 36
第三章 結果與討論 37
一、實驗之結果 37
(一) 合成ReOCl3(PPh3)2 37
(二) 合成ReH7(PPh3)2 37
(三) 己烯的生成 38
(四) 己烯之裂解反應 39
(五) 將戊醇反應為戊烯 40
二、己烷之微量分析 40
三、動力同位素探討 40
第四章 參考文獻 42
附錄 49

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