濕氣膠能提供水相反應環境並表現出與氣相環境不同之反應性。而亞硝酸根為濕氣膠的組成鹽類之一，且其光解後會產生氫氧(OH) 與一氧化氮(NO) 自由基及後續生成之一系列NxOy 物種。此外，於濕氣溶膠中亦可能存在一元醇(例如甲醇) 及偕二醇(例如甲醛水合產生之甲二醇) 等醇類。若兩者同時存於濕氣膠時，所涉及與OH 自由基以及後續NxOy 物種的反應性差異尚未被討論。因此吾人將以步進式時間解析紅外光譜儀觀測含有不同濃度甲醇或甲二醇之亞硝酸鈉混合水溶液受355 nm 脈衝雷射激發後的時間解析紅外差異吸收光譜，並藉由觀測亞硝酸根光解後產生的三氧化二氮生成量與消逝速率以瞭解甲醇和甲二醇之反應性差異。吾人發現加入不同濃度甲醇或甲二醇並不影響三氧化二氮生成，且由於氫氧自由基和亞硝酸根的一系列反應可生成三氧化二氮，故推測甲醇和甲二醇上之Hα 對於氫氧自由基並無反應性差異，亦即甲二醇上之兩羥基官能基無提升Hα 對於氫氧自由基的反應性。此外，加入甲醇後會延緩三氧化二氮消逝，與含有甲二醇之樣品不同，推測甲二醇上之兩羥基官能基可在甲醛與水的快速平衡中作為水的儲存槽並提供與水類似的反應環境，參與水解溶劑化反應。此研究可提供在研究偕二醇反應時，應考慮其可能表現出與一元醇不同之反應性，以及研究與甲醛相關反應時，應考慮其水合與非水合間之反應性差異。

Aqueous aerosol provides an aqua-based environment for chemical reactions. Nitrite (NO2-) is one in the constituent in aqueous aerosol, and it could generate hydroxyl (OH) and nitric oxide (NO) radicals and a series of subsequent NxOy species upon photolysis. Generally, the aqueous aerosol also contains alcohols such as monobasic alcohols, e.g., methanol (CH3OH), and geminal diols, e.g., methanediol (CH2(OH)2), which was produced by hydration of formaldehyde (CH2O). While nitrite and CH3OH/CH2(OH)2 are present in the aqueous aerosol, the differences in the reactivity of CH3OH or CH2(OH)2 with OH radicals and subsequent NxOy species have not been sufficiently studied. In this work, a step-scan Fourier transfer interferometer was employed to probe the time-resolved infrared difference absorption spectra of the NaNO2 solution containing different concentrations of CH3OH or CH2(OH)2 upon 355 nm pulsed excitation. By measuring the generation and decay rates of dinitrogen trioxide (N2O3) after photolysis of NO2– for comparing the reactivity differences in CH3OH and CH2(OH)2, we found that the presence of different concentrations of CH3OH or CH2(OH)2 cause similar amounts of transient N2O3. As N2O3 can be generated from a series of reactions between OH radicals and NO2–, the similar population of N2O3 suggested that there is no significant difference in the reactivity of CH3OH and CH2(OH)2 with OH; that is, the two hydroxyl functional groups on CH2(OH)2 can not enhance the reactivity of Hα with OH radical. In addition, the presence of CH3OH retarded the decay of N2O3 more than CH2(OH)2. The mono-hydroxyl group on CH3OH does not behave like the hydroxyl group of water, whereas the two hydroxyl groups at CH2(OH)2 can be treated as the water reservoir, via the quick equilibrium between H2O and CH2O, for the hydrolytic solvation reaction of N2O3. In this study, the reactivities of geminal diols could be different from those of monobasic alcohols in different chemical reactions, e.g., Hα abstract and hydration. Besides, the difference in reaction kinetics involving hydration should be thoroughly taken into account when studying formaldehyde-related reactions.

第一章緒論. . . . . . . . . . . . . . 1
1.1 氣溶膠之性質及在大氣中的重要性. . . . . . . . . . . . . . . . . . . . . . 1
1.1.1 氣溶膠的來源、種類與組成. . . . . . . . . . . . . . . . . . . . . . 2
1.1.2 濕氣膠提供之反應環境. . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2 環境中NO –
2 的來源及重要性. . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2.1 NO –
2 於水相的光解反應. . . . . . . . . . . . . . . . . . . . . . . . 3
1.2.2 與OH 和NO 自由基相關之反應及重要性. . . . . . . . . . . . . . 5
1.3 CH2(OH)2 於大氣中的來源. . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.3.1 CH2(OH)2 之聚合反應. . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.3.2 CH2(OH)2 與OH 自由基反應的重要性. . . . . . . . . . . . . . . . 7
1.4 大氣中CH3OH 的來源及其與OH 自由基反應的重要性. . . . . . . . . . . 8
1.5 研究動機. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
第二章光譜技術原理、實驗系統架設及樣品溶液配製30
2.1 光譜技術原理. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.1.1 吸收光譜法. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.1.2 紫外/可見光吸收光譜法. . . . . . . . . . . . . . . . . . . . . . . . 30
2.1.3 傅立葉轉換紅外光譜法. . . . . . . . . . . . . . . . . . . . . . . . . 31
2.1.3.1 麥克森干涉儀. . . . . . . . . . . . . . . . . . . . . . . . . 32
2.1.3.2 單色光與多色光干涉. . . . . . . . . . . . . . . . . . . . . 32
2.1.3.3 傅立葉轉換. . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.1.3.4 截斷函數與削足函數. . . . . . . . . . . . . . . . . . . . . 34
2.1.3.5 相位誤差與相位校正. . . . . . . . . . . . . . . . . . . . . 36
2.1.3.6 連續式掃描模式. . . . . . . . . . . . . . . . . . . . . . . 37
2.1.4 衰減全反射傅立葉轉換紅外光譜法. . . . . . . . . . . . . . . . . . 38
2.1.5 步進式掃描時間解析傅立葉轉換紅外光譜法. . . . . . . . . . . . . 39
2.1.5.1 工作原理. . . . . . . . . . . . . . . . . . . . . . . . . . . 39
2.1.5.2 跳點取樣. . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2.1.5.3 AC/DC 耦合數據擷取處理. . . . . . . . . . . . . . . . . . 41
2.2 實驗系統架設. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
2.2.1 穩態光譜儀. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
2.2.1.1 穩態紫外/可見光吸收光譜儀. . . . . . . . . . . . . . . . 42
2.2.1.2 衰減全反射式傅立葉轉換紅外光譜儀. . . . . . . . . . . 43
2.2.2 時間解析紅外差異吸收光譜之實驗系統架設. . . . . . . . . . . . . 43
2.2.2.1 雷射激發系統. . . . . . . . . . . . . . . . . . . . . . . . . 43
2.2.2.2 樣品槽. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2.2.2.3 樣品推進系統. . . . . . . . . . . . . . . . . . . . . . . . . 44
2.2.2.4 步進式掃描時間解析傅立葉轉換紅外光譜儀. . . . . . . 44
2.2.2.5 數據擷取系統. . . . . . . . . . . . . . . . . . . . . . . . . 45
2.3 儀器參數設定. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
2.3.1 穩態紫外/可見光吸收光譜. . . . . . . . . . . . . . . . . . . . . . . 45
2.3.2 衰減全反射式傅立葉轉換紅外光譜. . . . . . . . . . . . . . . . . . 46
2.3.3 步進式掃描時間解析傅立葉轉換紅外光譜. . . . . . . . . . . . . . 47
2.4 樣品溶液配製. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
2.4.1 NaNO2 水溶液. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
2.4.2 (CH2O)n 水溶液. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
2.4.3 NaNO2/(CH2O)n 之混合水溶液. . . . . . . . . . . . . . . . . . . . . 49
2.4.4 NaNO2/CH3OH 之混合水溶液. . . . . . . . . . . . . . . . . . . . . 51
第三章理論計算75
3.1 計算方法、基底函數和溶劑效應. . . . . . . . . . . . . . . . . . . . . . . . 75
3.2 相關分子的最佳化結構與預測非簡諧振動波數. . . . . . . . . . . . . . . . 75
第四章實驗結果與討論80
4.1 穩態紫外/可見與紅外光吸收光譜. . . . . . . . . . . . . . . . . . . . . . . 80
4.2 時間解析紅外差異吸收光譜. . . . . . . . . . . . . . . . . . . . . . . . . . 81
4.2.1 NaNO2 水溶液之光解反應. . . . . . . . . . . . . . . . . . . . . . . 81
4.2.2 添加不同濃度CH3OH 或(CH2O)n 之NaNO2 水溶液的光解反應. . 83
4.3 動力學分析. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
第五章結論. . . . . . . . . . . . . . . . . . . 101
附錄. . . . . . . . . . . . . . . . . . . A1

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