Analytical Application of Ion-Exchange Polymer Modified Electrodes

• Main Authors: Chen Huen Ling, 陳慧苓
• Other Authors: Sun I-Wen
• Format: Others
• Language: zh-TW
• Published: 2001
• Online Access: http://ndltd.ncl.edu.tw/handle/12473603883635267101

碩士 === 國立成功大學 === 化學系 === 89 === Abstract In this study, an ion-exchanged polymer modified electrode was used to determine organic compounds in aqueous solution.The main content can be discussed in three parts.The first part, a Nafion film coated glassy carbon electrode(NFGCE) were employed for the determination of apomorphine in aqueous solution; the second part, a Tosflex film coated glassy carbon electrode(TFGCE) were employed for the determination of dithiophosphoric acid O,O-diethyl ester in aqueous solution; the third part, five oxidants and reductants were discussed with the influence of different pH values, different electrolytes and different electrodes. The first part, a sensitive voltammetric method is developed for the dtermination of apomorphine using a Nafion film modified glassy carbon electrode. In this method, apomorphine is first accumulated into the electrode. The redox peaks at around +0.2V(vs. Ag/AgCl) corresponding to a two-electron oxidation/reduction of apomorphine were used for detection with square-wave voltammetry. The effects of experimental parameters, such as, pH, accumulation potential, accumulation time, and square-wave voltammetric parameters were studied. Using this method, with a accumulation time of 3 min, a linear calibration curve for apomorphine was obtained up to 4×10-7M in pH6.0 buffer solution with a detection limit of 3×10-9M. The second part, a sensitive voltammetric method is developed for the dtermination dithiophosphoric acid O,O-diethyl ester of using a Tosflex film modified glassy carbon electrode. Dithiophosphoric acid O,O-diethyl ester can be preconcentrated at +0.8V with a accumulation time of 3 min and reduced at —0.7V for 3 seconds. Using this method, dithiophosphoric acid O,O-diethyl ester can be accumulated into the Tosflex film modified electrode and used for detection with square-wave voltammetry. A linear calibration curve for dithiophosphoric acid O,O-diethyl ester was obtained up to 400ppb in pH5.65 KCl solution with a detection limit of 0.01ppb. The third part, five oxidants and reductants, KMnO4、K2Cr2O7、KIO3、Na2SO3、Ascorbic acid(AA), were discussed with the influence of different pH values, different electrolytes and different electrodes. Compared with GCE, anion of oxidant and reductant can be prevented from getting in Nafion film in the NFGCE, and the interference current were not produced. 第一章 緒論 1 1-1 Apomorphine 1 1-1-1 前言 1 1-1-2 分析物之簡介 2 1-1-3 文獻回顧 2 1-1-4 研究目的 4 1-2 Dithiophosphoric acid O,O-diethyl ester 5 1-2-1 前言 5 1-2-2 分析物之簡介 6 1-2-3 文獻回顧 7 1-2-4 研究目的 9 1-3 氧化劑與還原劑 10 第二章 原理 11 2-1 電化學測定方法 11 2-1-1 循環伏安法(cyclic voltammogram, CV)[29]： 11 2-1-2 剝除伏安法(stripping voltammogram, SV) 12 2-1-3 剝除伏安法的剝除方式 14 2-1-4 剝除伏安法的種類 18 2-2 化學修飾電極 22 2-2-1 化學修飾電極的製備方法 22 2-2-2 聚合物修飾電極的種類 24 第三章 實驗部分 29 3-1 儀器與電極裝置 29 3-1-1 Apomorphine 29 3-1-2 Dithiophosphoric acid O,O-diethyl ester 29 3-1-3 相同儀器部分 29 3-2 藥品與溶液 30 3-2-1 藥品 30 3-2-2 藥品配製 31 3-3 電極製備 33 3-3-1 電極前處理步驟 33 3-3-2 Nafion膜塗覆玻璃碳電極的製作 34 3-3-3 Tosflex膜塗覆玻璃碳電極的製作 34 第四章 Apomorphine於Nafion膜塗覆玻璃碳電極上的偵測 35 4-1 APM於不同電極上的電化學行為 35 4-2 電解質溶液的選擇 37 4-3 pH值對APM分析訊號的影響 37 4-4 偵測方法 41 4-5 攪拌速率對APM分析訊號的影響 41 4-6方波伏安法參數對APM分析訊號的影響 42 4-7沉積電位對APM分析訊號的影響 45 4-8 沉積時間對APM分析訊號之影響 46 4-9 檢量線 46 4-10干擾物質的探討 48 4-11 電極之再生 48 第五章 Dithiophosphoric acid O,O-diethyl ester於Tosflex膜塗覆玻璃碳電極上的偵測 52 5-1 DEDTP於不同電極上的電化學行為 52 5-2 DEDTP之反應機構 54 5-3 掃描速率對DEDTP分析訊號的影響 56 5-4 偵測方法 59 5-5 氯化鉀濃度對DEDTP分析訊號的影響 59 5-6 pH值對DEDTP分析訊號的影響 60 5-7 方波剝除伏安法參數對DEDTP分析訊號的影響 63 5-8 沉積電位對DEDTP分析訊號的影響 65 5-9 攪拌速率對DEDTP分析訊號的影響 67 5-10 沉積時間對DEDTP分析訊號的影響 67 5-11 檢量線 71 5-12 干擾物質的探討 73 5-12 真實樣品 73 5-13 電極之再生 73 第六章 氧化劑與還原劑於玻璃碳電極及Nafion膜塗覆玻璃碳電極上的偵測 78 6-1 0.1M NaNO3溶液 78 6-1-1 1×10-3 M KMnO4 79 6-1-2 1×10-3 M K2Cr2O7 79 6-1-3 1×10-3 M KIO3 80 6-1-4 1×10-3 M Na2SO3 80 6-1-5 1×10-4 M Ascorbic acid 81 6-2 0.1M KCl 81 第七章 結論 97 參考文獻 100