大氣中的雲滴可能同時存在亞硝酸根及甲二醇。當亞硝酸根光解後將產生氫氧自由基及一氧化氮自由基並可能與甲二醇反應，然而目前並未有相關文獻詳細探討雲滴或水溶液中同時含有氫氧自由基、一氧化氮自由基及甲二醇之反應動力學。於本研究中，吾人係以原處(in situ)及即時(on time)之穩態紫外/可見吸收光譜法探討甲二醇/亞硝酸鈉混合水溶液受365 nm發光二極體激發後，亞硝酸根受光激發產生之氫氧自由基及一氧化氮自由基與甲二醇之反應機制和動力學。以365 nm激發樣品後，吾人觀察到300−390 nm屬於亞硝酸根受光解消逝之吸收譜帶，及在250−275 nm時間前期屬於水合甲醛自由基(hydrated formyl radical, CH(OH)2)及時間後期包含二氧化碳自由基陰離子(carbon dioxide radical anion, CO2- )及NOCO2-之生成吸收譜帶。結合鄭巧彌同學之拉曼光譜實驗結果、趙源鈞同學之理論計算結果及吾人數值模擬建構亞硝酸根光解後與甲二醇反應之反應機構及動力學資訊，所模擬上述各物種濃度之時間側寫與實驗一致。其中CH(OH)2+NO -> HCOOH + HNO為一重要但未被提出過的反應路徑，其反應速率常數為 ，以及長生命期(半生期約為333 秒)的中間產物水合甲醛自由基(CH(OH)2)。和以往僅能透過偵測最終產物間接推測反應機構的方法相比，例如層析法，吾人於本研究以原處及即時的光譜技術，將有助於更完整建立光化學反應機構及相關動力學。而吾人於本研究中成功建立甲二醇/亞硝酸鈉混合水溶液之光反應機制及各步速率常數，將有助於了解若兩者同時存在於水溶液或雲滴中所扮演的角色。

The nitrite (NO2- ) and methanediol (CH2(OH)2) could exist simultaneously in the cloud droplet or aqueous aerosols. Under ultraviolet irradiation, short-lived radicals, e.g., hydroxyl radical (OH) and nitric oxide (NO), via the photolysis of nitrite, could react with methanediol. Nevertheless, there have been no detailed researches on the reaction kinetics between hydroxyl radical, nitric oxide, and methanediol in cloud droplet or aqueous solution. In this work, the reaction mechanism and kinetics of nitrite aqueous solution containing varied amounts of methanediol upon continuous exposure was studied by steady-state UV/Vis spectroscopy. Upon the continuous irradiation of the mixture containing sodium nitrite and methanediol with 365 nm light from a LED, a decay band at 300−390 nm could be attributed to the photolysis of nitrite, and the formation band at 250−275 nm could be attributed to long-lived hydrated formyl radical(CH(OH)2) in the early period and carbon dioxide anion(CO2-) and NOCO2- in the later period, respectively. Based on the Raman spectra from Cheng, theoretical calculation results from Jhao, and numerical analyses in my work, the mechanism and the corresponding kinetic properties of photolysis reaction of nitrite aqueous solution containing methanediol has been thoroughly discussed. The simulated concentrations of aforementioned species were consistent with our experimental results. Furthermore, we also proposed an unrevealed reaction pathway,CH(OH)2+NO -> HCOOH + HNO , with a bimolecular reaction coefficient of 1.0x10^2 M-1s-1 . In addition, hydrated formyl radical was proposed to be a long-lived intermediate, with the half-life of ca. 300 sec. Compared with the conventional methods by detecting the reaction end products, e.g., chromatography, we used UV/Vis spectroscopy to in situ and on time monitor the photochemical reactions, benefitting the establishment of reaction mechanism and kinetics. Furthermore, understanding the reaction mechanism and the related reaction rate coefficients of the photolysis reaction of nitrite aqueous solution containing methanediol helps us understand the roles of nitrite and methanediol simultaneously existing in aqueous solution or in cloud droplet.

第一章 緒論 1
1.1 雲滴對於大氣之重要性 1
1.1.1 雲滴來源及組成 1
1.1.2 雲滴提供之反應環境 1
1.2 大氣中亞硝酸根之重要性 2
1.2.1 亞硝酸根之來源 2
1.2.2 亞硝酸根之光解反應及後續相關反應 2
1.2.3 氫氧自由基與一氧化氮自由基之重要性及氧化反應 4
1.3 大氣中甲二醇之重要性 5
1.3.1 甲二醇之來源 5
1.3.2 甲二醇之聚合反應 6
1.3.3 甲二醇之氧化反應 6
1.4 研究動機 7
第二章 光譜技術原理、實驗系統及樣品溶液製備 24
2.1 穩態紫外/可見光吸收光譜法 24
2.1.1 紫外/可見光吸收光譜法原理 24
2.1.2 實驗系統架設 27
2.1.3 發光二極體激發系統 28
2.1.4 實驗步驟 28
2.2 離子層析法 28
2.2.2 薄膜抑制器 29
2.2.3 實驗步驟 30
2.3 儀器參數設定 31
2.3.1 紫外/可見吸收光譜 31
2.3.2 離子層析儀 31
2.4 樣品溶液製備 32
2.4.1 甲二醇水溶液 32
2.4.2 亞硝酸鈉水溶液 33
2.4.3 甲二醇/亞硝酸鈉混合水溶液 33
2.4.4 甲醇/亞硝酸鈉混合水溶液 33
2.4.5 甲酸鈉/亞硝酸鈉混合水溶液 34
2.4.6 鹽酸水溶液 34
2.4.7 氫氧化鈉水溶液 34
2.4.8 pH=7之甲酸鈉水溶液 34
2.4.9 pH=7之亞硝酸鈉水溶液 34
2.4.10 pH=7之草酸根水溶液 35
2.4.11 液態氮/酒精混合溶液 35
2.4.12 一氧化二氮水溶液 35
第三章 以MATLAB軟體建構動力學模擬與分析 46
3.1 MATLAB軟體簡介與其於化學動力學上的應用 46
3.2 常微分方程式之函式庫 47
3.2.1 ode45函式庫 47
3.2.2 ode15s函式庫 48
3.3 運算流程 48
3.3.1 Formula 49
3.3.2 Simulation 50
第四章 結果與討論 55
4.1 各樣品光解前之穩態紫外/可見光吸收光譜 55
4.2 亞硝酸鈉水溶液之光解反應 56
4.3 甲二醇/亞硝酸鈉混合水溶液之光解反應 57
4.3.1 反應機構 57
4.3.2 以離子層析法確認光解甲二醇/亞硝酸鈉混合水溶液之各物種濃度 59
4.3.3 以紫外/可見吸收光譜法探討甲二醇/亞硝酸鈉混合水溶液之光解反應 60
4.3.3.1 時間前期於255 nm之未知物種 61
4.3.3.2 時間後期於255 nm之未知物種 63
4.3.3.3激發光強度對於樣品光解反應之影響 64
4.4 動力學分析 64
4.4.1 亞硝酸根水溶液之光解速率 65
4.4.2 模擬甲二醇/亞硝酸鈉66.7 mM/99.3 mM混合水溶液光解反應 66
4.4.3 各物種時間側寫與模擬結果之比較 67
4.4.3.1 亞硝酸根時間側寫 67
4.4.3.2 水合甲醛自由基時間側寫 67
4.4.3.3 與二氧化碳自由基陰離子時間側寫 68
第五章 結論 101
附錄一 3.3.1節使用之Formula檔 A-1
附錄二 3.3.2節使用之Simulation檔 A-2
附錄三 4.4節使用之Formula檔 A-3
附錄四 4.4節使用之Simulation檔 A-6

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第二章
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第四章
[1] Chu, L.; Anastasio, C. Temperature and Wavelength Dependence of Nitrite Photolysis in Frozen and Aqueous Solutions. Environ. Sci. Technol. 2007, 41, 3626-3632.
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