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研究生:陳一銘
研究生(外文):E-Ming Cheng
論文名稱:以電化學及層析等技術探討一品松之蛻化命脈
論文名稱(外文):Theoretical fate studies of O-ethyl O-4-nitrophenyl phenylphosphonothioate (EPN) by electrochemical method and chromatographic techniques.
指導教授:鄭政峰鄭政峰引用關係
指導教授(外文):Jen-Fon Jen
學位類別:碩士
校院名稱:國立中興大學
系所名稱:化學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2001
畢業學年度:89
語文別:中文
論文頁數:128
中文關鍵詞:一品松電化學蛻化命脈
外文關鍵詞:EPNECfate study
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在本篇研究當中,主要是利用電化學方法及高效能液相層析技術來探討有機磷農藥一品松(O-ethyl O-4-nitrophenyl phenylphosphonothioate)在進行氧化或還原反應時蛻化的情形。在電化學方法當中,首先利用循環伏安法(Cyclic Voltammetry method)掃描,發現一品松在+600毫伏特電壓下及-800毫伏特電壓下分別可進行氧化及還原反應。在經由反應槽當中施以定電位反應之後,其氧化及還原反應之產物及殘餘量經由高效能液相層析儀(HPLC)結合紫外-可見光系統偵測、分離並收集而進一步鑑定。透過鑑定之結果建立其反應機構。
本篇研究亦對於蛻化過程當中的動力學進行探討。在氧化及還原的反應過程當中皆為一級反應,其反應速率常數分別為0.0017min-1及0.05968min-1,一品松在鹼性環境下亦會進行鹼分解反應並反應速率隨著pH值增加而上升,在pH值等於10、11、12時,其反應速率常數分別為0.00116, 0.00405, 0.0117 min-1。
由實驗結果顯示、經由電化學方法結合液相層析技術可成功地偵測並推導有機磷農藥一品松在氧化及還原反應當中之蛻化命脈及產物。以達到追蹤其在環境中可能發生之毒性變化之目的。

Degradation of O-ethyl O-4-nitrophenyl phenylphosphonothioate (EPN) was investigated with electrochemical reaction and chromatographic determination. EPN was oxidized and reduced electrochemically with the potential of +600mV and —800mV, respectively. Both the oxidation and reduction products as well as the reactant were analyzed by HPLC-UV and identified by related analytical techniques.
After series studies, a scheme for possible degradation pathway was thus built-up.
The degradation reactions were also studied kinetically. Experiment results indicate that the degradation of EPN was followed the apparent first-order reaction. The rate constants for electrochemical degradation were 0.0017min-1 for oxidation and 0.05968min-1 for reduction. The rate constants increase with the basicity of solution. There was no significance degradation occurred under the pH value below 9.0 without electrochemical reaction. The rate constants were 0.00116, 0.00405, 0.0117 min-1, for pH 10, 11, 12, respectively.

摘要‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧Ⅰ
目錄‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧Ⅱ
圖次‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧Ⅴ
表次‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧Ⅶ
簡語表‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧Ⅷ
第一章 緒論‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ 1
一、研究動機‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ 1
二、電化學分析方法之簡介‧‧‧‧‧‧‧‧‧‧‧‧‧‧ ‧3
A. 循環伏特安培法‧‧‧‧‧‧‧‧‧‧‧ ‧‧‧‧‧‧‧ 4
B. 定電位電化學反應‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧4
三、有機污染物概述‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧5
A.有機污染物簡介‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧5
B.農藥簡介‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧6
C.污染物在環境中的作用及變化‧‧‧‧‧‧‧‧‧‧‧‧‧9
D.有機污染物的蛻化行為‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧20
E.如何減少有機污染物對環境的衝擊‧‧‧‧‧‧‧‧‧23
四、一品松‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧25
第二章 實驗方法‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧28
一、實驗藥品、器材、儀器設備‧‧‧‧‧‧‧‧‧‧‧28
A.藥品‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧28
B.器材‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧29
C.儀器設備‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧30
二、藥品配制‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧31
三、儀器操作條件‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧33
A.高效能液相層析儀(HPLC)系統‧‧‧‧‧‧‧‧‧33
B.電化學分析儀 (Electrochemical analyzer)系統 34
第三章 實驗過程‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧35
一、液相層析分析方法的建立‧‧‧‧‧‧‧‧‧‧‧‧35
A.UV偵測波長的選擇‧‧‧‧‧‧‧‧‧‧‧‧‧‧35
B.層析管柱的選擇‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧35
C.動相的選擇‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧35
D.層析方法再現性測試‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧35
二、一品松在鹼環境下分解速率的探討‧‧‧‧‧‧‧36
三、電化學分析方法的建立‧‧‧‧‧‧‧‧‧‧‧‧‧36
A.循環伏特安培圖的掃描‧‧‧‧‧‧‧‧‧‧‧‧36
B.定電位電化學反應方法的建立‧‧‧‧‧‧‧‧‧38
四、分析物蛻化反應途徑(Reaction pathway)的探討‧38
A.定電位電化學反應途徑‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧38
B.日光照射反應途徑‧‧‧‧‧‧‧‧‧‧‧‧‧‧39
C.光化學反應器照光反應途徑‧‧‧‧‧‧‧‧‧‧39
五、產物鑑定方法的建立‧‧‧‧‧‧‧‧‧‧‧‧‧40
A.LC-MS分離鑑定‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧40
B.GC-MS分離鑑定‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧40
C.直接以質譜儀鑑定結構‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧41
D.以HPLC分離及純化‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧41
六、產物反應機制的建立‧‧‧‧‧‧‧‧‧‧‧‧‧41
七、EPN及p-nitrophenol校正曲線的建立‧‧‧‧‧‧‧‧‧42
八、定電位電化學反應動力學上反應速率的探討‧‧‧‧‧‧43
A.定電位電化學反應方法再現性測試‧‧‧‧‧‧‧‧‧‧‧44
B.水中溶氧對反應速率的影響‧‧‧‧‧‧‧‧‧‧‧‧‧‧44
C.溶液pH值對反應速率的影響‧‧‧‧‧‧‧‧‧‧‧‧‧45
D.輔助電解質濃度對反應速率的影響‧‧‧‧‧‧‧‧‧‧‧45
九、分析物及其蛻化產物的毒性分析‧‧‧‧‧‧‧‧‧‧‧45
十、蛻化反應過程的控制‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧47
第四章 EPN蛻化途徑探討‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧48
一、液相層析分析方法的建立‧‧‧‧‧‧‧‧‧‧‧‧‧48
A.UV偵測波長的選擇‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧48
B.層析管柱的使用‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧48
C.動相的選擇‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧51
D.層析方法再現性測試‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧52
二、一品松在鹼環境下分解速率的探討‧‧‧‧‧‧‧‧‧‧53
三、電化學分析方法的建立‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧53
A.循環伏特安培圖的掃瞄‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧53
B.定電位電化學反應‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧67
四、分析物蛻化反應途徑(Reaction pathway)的探討‧‧‧67
A.定電位電化學反應途徑‧‧‧‧‧‧‧‧‧‧‧‧‧‧67
B.日光照射反應途徑‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧68
C.光化學反應器照光反應途徑‧‧‧‧‧‧‧‧‧‧‧‧‧68
五、蛻化產物結構的鑑定‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧69
六、產物反應機制的建立‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧81
七、EPN及p-nitrophenol校正曲線的建立‧‧‧‧‧‧‧‧‧81
八、定電位電化學反應動力學上反應速率的探討‧‧‧‧‧‧81
A.定電位電化學反應方法再現測試‧‧‧‧‧‧‧‧‧‧‧‧92
B.水中溶氧對反應速率的影響‧‧‧‧‧‧‧‧‧‧‧‧‧93
C.溶液pH值對反應速率的影響‧‧‧‧‧‧‧‧‧‧‧‧‧‧94
D.輔助電解質濃度對於反應速率的影響‧‧‧‧‧‧‧‧‧‧95
第五章 p-nitrophenol蛻化命脈探討‧‧‧‧‧‧‧‧‧‧‧96
一、液相層析分析方法的建立‧‧‧‧‧‧‧‧‧‧‧‧‧‧96
A.UV偵測波長的選擇‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧96
B.動向的選擇‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧96
C.層析方法再現性測試‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧96
二、電化學分析方法的建立‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧98
A.循環伏特安培圖的掃瞄‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧98
B.定電位電化學反應‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧103
三、分析物蛻化反應途徑的探討‧‧‧‧‧‧‧‧‧‧‧‧‧103
四、蛻化產物結構的鑑定‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧106
五、反應機構(Reaction mechanism)的建立‧‧‧‧‧‧‧‧113
六、p-nitrophenol校正曲線的建立‧‧‧‧‧‧‧‧‧‧113
七、定電位電化學反應動力學上反應速率的探討‧‧‧‧‧‧113
A.定電位電化學反應方法再現性測試‧‧‧‧‧‧‧‧‧‧116
B.水中溶氧對反應速率的影響‧‧‧‧‧‧‧‧‧‧‧‧‧‧119
C.溶液pH值對反應速率的影響‧‧‧‧‧‧‧‧‧‧‧‧‧119
D.輔助電解質的濃度對反應速率的影響‧‧‧‧‧‧‧‧‧‧120
第六章 結論‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧121
第七章 參考文獻‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧122

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