硫酸根自由基(sulfate radical, SO4-)具有較高的還原電位，常用於降解汙染物，稱為硫酸根自由基高級氧化程序(sulfate-radical-based advanced oxidation processes, SR-AOPs)。此方法中常以紫外光照射過硫酸鈉(sodium persulfate, Na2S2O8)產生硫酸根自由基，且根據前人文獻，當過硫酸根高於特定濃度時，會競爭硫酸根自由基使分解汙染物的效率降低，因此決定硫酸根自由基與過硫酸根之反應速率常數至關重要，但在過往文獻未有一致的結果。故吾人以瞬態吸收光譜法偵測不同濃度過硫酸鈉水溶液經266 nm脈衝雷射光解後，產生於455 nm之硫酸根自由基差異吸收度時間側寫。硫酸根自由基消逝途徑主要透過自身再結合(Rrecom)及與過硫酸根的雙分子(Rbi)反應，二者的反應速率常數分別以krecom及kbi表示。吾人以硫酸根自由基再結合反應積分速率定律式獲得krecom約為(8.8 - 10.8) × 10^8 M-1 s-1，並計算於實驗條件下的Rrecom/Rbi = 75 - 170，二者結果顯示硫酸根自由基消逝途徑以其自身再結合反應為主。但若僅藉由積分速率定律式及Rrecom/Rbi的分析將無法正確地描述其差異吸收度時間側寫，故吾人以非線性動力學方法模擬不同過硫酸鈉初始濃度對其差異吸收度時間側寫之影響，以kbi = 1.0 × 10^4 M-1 s-1模擬結果和實驗較吻合。過往研究中曾提出甲醇與硫酸根自由基之反應速率常數，但為較早期的結果，且較少對於該反應之動力學同位素效應(kinetic isotope effects, KIE)進行探討，故吾人以上述瞬態吸收光譜法研究15 - 55°C之過硫酸鈉和(氘代)甲醇混合水溶液經光解後，產生之硫酸根自由基與(氘代)甲醇之準一級反應速率常數(kMeOH)，而結果顯示kMeOH與溫度無關。此外，若將甲醇羥基的氫置換為氘時，平均kMeOH幾乎不變；而將甲醇碳上的氫置換為氘時，平均kMeOH下降，其KIE約為2，顯示硫酸根自由基與甲醇反應涉及α碳上的氫而非羥基的氫。

Sulfate radical (SO4-) possesses a high reduction potential and has been widely used in the sulfate-radical-based advanced oxidation processes (SR-AOPs) for degrading pollutants. Generally, SO4- is generated by the ultraviolet photolysis of sodium persulfate (Na2S2O8). In principle, the increase in the [S2O82-] can enhance the efficiency of contaminant degradation. However, exceeding a specific concentration of S2O82- can lead to a decrease in contaminant degradation efficiency due to competitive reactions of S2O82- + SO4-. Therefore, the reaction rate constant of SO4- + S2O82- is crucial for understanding the contributions of this competitive reaction. In this study, UV-Vis transient absorption spectroscopy was used to probe the kinetics of SO4- at 455 nm upon pulsed 266 nm excitation of S2O82- solutions at different initial concentrations. Generally, SO4- decay was dominated by the recombination reaction of SO4- (Rrecom) and bimolecular reaction with S2O82- (Rbi), with the reaction rate coefficients krecom and kbi, respectively. krecom was determined to be approximately (8.8 - 10.8) × 10^8 M-1 s-1 by the integrated rate law of recombination reactions, and the corresponding ratio Rrecom/Rbi was 75-170, indicating that the recombination reaction majorly dominated the decay of SO4-. However, the result of kinetics are not sufficient to illustrate the decay of SO4-. Therefore, non-linear kinetics simulations were performed to simulate the temporal profiles of SO4-, and the simulation results with kbi = 1.0 × 10^4 M-1 s-1 agreed with the experimental data. In addition, the reaction rate coefficients between methanol (CH3OH) and SO4- has been reported decades ago, and the kinetic isotope effects (KIE) of this reaction has not been greatly investigated. The transient absorption spectroscopy was used to investigate the pseudo-first-order reaction rate coefficients (kMeOH) between SO4- and CH3OH isotopologues in 15 - 55°C. The results showed that kMeOH is independent of temperature. Additionally, replacing the hydrogen in hydroxyl group with deuterium did not alter to averaged kMeOH; replacing the hydrogen in α carbon with deuterium caused a decrease in the average kMeOH, with a KIE of approximately 2. This indicates that the reaction between SO4- and CH3OH involves the α hydrogen abstraction rather than the hydroxyl group.

摘要
Abstract
目錄
第一章 緒論..........................................................1
1.1氣溶膠於大氣反應之重要性............................................2
1.1.1氣溶膠的來源與組成...............................................2
1.1.2濕氣溶膠於大氣中提供的反應環境....................................2
1.2大氣中硫化物之反應.................................................3
1.2.1硫循環..........................................................3
1.2.2大氣中二氧化硫之相關反應..........................................3
1.2.3硫酸根自由基之相關反應............................................4
1.3硫酸根自由基高級氧化程序............................................5
1.4大氣中甲醇之來源與反應..............................................7
1.5動力學同位素效應...................................................7
1.5.1一級動力學同位素效應.............................................8
1.5.2二級動力學同位素效應............................................10
1.6研究動機.........................................................10
參考文獻............................................................20
第二章 光譜技術原理、實驗系統與樣品溶液製備............................29
2.1 穩態紫外/可見吸收光譜法...........................................29
2.1.1穩態紫外/可見吸收光譜法原理......................................29
2.2瞬態吸收光譜法....................................................30
2.2.1實驗系統架設....................................................30
2.2.2雷射光解系統....................................................31
2.2.3樣品推進系統....................................................31
2.2.4溫度控制系統....................................................31
2.2.5實驗步驟.......................................................32
2.2.6實驗系統儀器參數設定............................................32
2.3樣品溶液製備......................................................32
2.3.1過硫酸鈉水溶液..................................................33
2.3.2甲醇水溶液.....................................................33
2.3.3過硫酸鈉/(氘代)甲醇 = 50/40 mM之混合水溶液.......................33
參考文獻............................................................42
第三章 以MATLAB軟體進行非線性動力學模擬...............................43
3.1 MATLAB軟體......................................................43
3.2 MATLAB於化學動力學上的應用.......................................43
3.3常微分方程式之程式庫..............................................44
3.4運算流程.........................................................45
3.4.1 Formula.......................................................45
3.4.2 Simulation....................................................46
參考文獻............................................................48
第四章 結果與討論....................................................49
4.1過硫酸鈉與甲醇混合水溶液之穩態紫外吸收光譜..........................49
4.2硫酸根自由基差異吸收度時間側寫與動力學分析..........................50
4.2.1瞬態吸收系統於時間初期的干擾訊號.................................50
4.2.2過硫酸鈉濃度對硫酸根自由基時間側寫之影響..........................50
4.2.3以非線性動力學方法數值模擬過硫酸鈉水溶液初始濃度對硫酸根自由基濃度時間側寫之影響..........................................................52
4.2.4過硫酸鈉受雷射激發之光解量估計...................................53
4.3滿足準一級反應之(氘代)甲醇的濃度用於與過硫酸鈉反應...................54
4.4硫酸根自由基與(氘代)甲醇反應之動力學分析............................56
4.5硫酸根自由基與(氘代)甲醇反應速率常數受動力學同位素效應之影響..........56
參考文獻............................................................74
第五章 結論.........................................................76
附錄................................................................77
附錄一 Formula檔....................................................77
附錄二 Simulation檔.................................................79

第一章 緒論
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第二章 光譜技術原理、實驗系統與樣品溶液製備
[1] Halstead, J. A. Teaching the Spin Selection Rule: An Inductive Approach. J. Chem. Educ. 2013, 90, 70-75.
[2] Xie, J.; Zare, R. N. Selection Rules for the Photoionization of Diatomic Molecules. J. Chem. Phys. 1990, 93, 3033-3038.
[3] Signorell, R.; Merkt, F. General Symmetry Selection Rules for the Photoionization of Polyatomic Molecules. Mol. Phys. 1997, 92, 793-804.
[4] Mayerhöfer, T. G.; Pahlow, S.; Popp, J. The Bouguer-Beer-Lambert Law: Shining Light on the Obscure. ChemPhysChem 2020, 21, 2029-2046.
[5] Truscott, T. G. Pulse Radiolysis and Flash Photolysis. In Photobiology: The Science and Its Applications, Riklis, E. Ed.; Springer US, 1991; pp 237-247.
[6] 黃品淳，以紫外/可見光吸收光譜法、拉曼光譜法及瞬態吸收光譜法探討甲二醇與硫酸根自由基之反應產物與動力學，國立清華大學，2023。
[7] USB4000 Fiber Optic Spectrometer: Installation and Operation Manual; 2008.
[8] Harvey, D. Modern Analytical Chemistry; McGraw-Hill, 2000.

第三章 以MATLAB軟體進行非線性動力學模擬
[1] 呂承宗，以紫外可見吸收光譜法搭配數值方法探討甲二醇與亞硝酸鹽混合水溶液之光解反應機構及反應動力學，國立清華大學，2022。
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[3] Cheney, E.; Kincaid, D. Numerical Mathematics and Computing; Cengage Learning, 2007.

第四章 結果與討論
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[11] Jiang, P.-Y.; Katsumura, Y.; Nagaishi, R.; Domae, M.; Ishikawa, K.; Ishigure, K.; Yoshida, Y. Pulse Radiolysis Study of Concentrated Sulfuric Acid Solutions. Formation Mechanism, Yield and Reactivity of Sulfate Radicals. J. Chem. Soc., Faraday Trans. 1992, 88, 1653-1658.
[12] Herrmann, H. On the Photolysis of Simple Anions and Neutral Molecules as Sources of O−/OH, SOX− and Cl in Aqueous Solution. Phys. Chem. Chem. Phys. 2007, 9, 3935-3964.
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[14] Chitose, N.; Katsumura, Y.; Domae, M.; Zuo, Z.; Murakami, T. Radiolysis of Aqueous Solutions with Pulsed Helium Ion Beams—2. Yield of SO4− Formed by Scavenging Hydrated Electron as a Function of S2O82− Concentration. Radiat. Phys. Chem. 1999, 54, 385-391.