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標題: 熱活化過硫酸鹽程序自由基氧化劑生成之探討
An investigation of radical oxidant generated in thermally activated persulfate process
作者: 蘇信瑋
Su, Hsin-Wei
關鍵字: In situ chemical oxidation;現址化學氧化法;Chemical probe;Persulfate;activation;kinetics;化學探針;過硫酸鹽;熱活化;反應動力
出版社: 環境工程學系所
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土壤及地下水之現地化學氧化法整治技術為復育污染土壤和地下水之可行方法之ㄧ。過硫酸鈉(Na2S2O8)具氧化還原電位2.01 V,為近年來較新應用於現地化學氧化整治法之氧化劑,經由熱活化過硫酸鹽(persulfate, PS)可產生硫酸根自由基強氧化劑(SO4-‧)(Eo = 2.4 V)。此外,於鹼性環境下硫酸根自由基可與氫氧根離子進行自由基轉換反應,生成氫氧根自由基(HO‧),不同自由基物種之存在(硫酸根自由基或氫氧根自由基)可取決於pH值條件,由於硫酸根或氫氧根自由基之存在對不同污染物之反應性不盡相同,處理成效亦有所差異,因此對於熱活化過硫酸鹽反應於不同pH條件下,SO4-‧或HO‧之生成鑑定為本研究之探討目標。由於自由基氧化劑之反應性極強、生命週期短暫,因此不易分離鑑定。本研究以化學探針(chemical probe)方法,採間接方式鑑定活化過硫酸鹽自由基氧化劑之生成。基於SO4-‧及HO‧對不同化學探針之反應速率差異,於實驗中,則採用第三丁醇(tert-butyl alcohol)、硝基苯(nitrobenzene)和酚(phenol)作為化學探針。
過硫酸鹽與化學探針之反應動力實驗結果顯示,由於第三丁醇之降解可直接與過硫酸鹽反應,因此不適用於化學探針,然而硝基苯及酚之降解,則主要是與熱活化過硫酸鹽所產生之自由基氧化劑反應所造成,因而可適用作為化學探針。過硫酸鹽與化學探針之反應系統中,過硫酸鹽濃度之反應級數接近1,而硝基苯和酚之反應則近似為0階反應。自由基氧化劑之生成鑑定實驗結果顯示,硝基苯之降解於pH = 2、4和7時其降解反應速率較pH = 9和12慢;當pH = 9時,硝基苯降解之反應速率常數較pH = 2增加13.8%,而當pH = 12時,硝基苯降解之反應速率常數則增加388%。由於硝基苯與HO‧之反應速率較SO4-‧快,因此推測當pH = 9,HO‧有增加之趨勢,當pH = 12時,HO‧為主要之自由基氧化劑。此外,於pH = 2、4和7之條件下,酚降解之反應速率皆較硝基苯快,因酚與SO4-‧和HO‧之反應速率常數皆大於109 M-1s-1,因此可以證實於酸性和中性條件下,SO4-‧為主要之自由基物種。

In situ chemical oxidation (ISCO) is an alternative to remediate soil and groundwater. Sodium peruslfate (Na2S2O8), a strong oxidant with a redox potential of 2.01 V, is recently used for ISCO. It has been postulated that persulfate anion can be thermally activated to produce a powerful oxidant known as the sulfate radical (SO4-‧), which can potentially destroy organic compounds. Under alkaline condition, the sulfate radical can proceed radical interconversion reaction with hydroxyl ions to generate the hydroxyl radical (HO‧). As sulfate and hydroxyl radicals are possibly simultaneously present or either one can prevail over the other during the activated persulfate process depending on solution conditions (especially pH), SO4-‧ and HO‧present different reactivities towards organic contaminants. Therefore, the objective of this research focuses on identifying the sulfate and hydroxyl radicals produced from persulfate activation under different pH conditions.
It is difficult to measure or identify SO4-‧ and HO‧ because short half-lives of two radicals. The chemical probe technique was attempted for identifying the radical produced in the thermal persulfate activation system. Due to the differences of their reaction rates between SO4-‧ and HO‧, tert-butyl alcohol (TBA), nitrobenzene (NB) and phenol were selected as chemical probes.
Experimental results revealed that TBA can be degraded with the sulfate radical, but also with persulfate anion. Therefore, TBA may not be a suitable chemical probe. However, NB and phenol were demonstrated to react only with radical oxidants and application as chemical probes. Furthermore, the reaction orders with respect to persulfate and chemical probe (NB and phenol) are nearly 1 and 0, respectively.
The results of radical identification experiments revealed that the degradation rate of NB at pH = 2, 4 and 7 is much slower than those at pH = 9 and 12. For example, the degradation rates at pH = 9 and 12 were increased by 13.8% and 388%, respectively, comparing to that at pH = 2. Because the reaction rate constant between NB and HO‧ is higher than that between NB and SO4-‧, it can be deduced that the concentration of HO‧ increased when pH was increased for pH = 9 and HO‧ would be the major radical oxidant. On the other hand, it was observed that the degradation rate of phenol are faster than that of NB under pH = 2, 4 and 7. The reaction rates between phenol and SO4-‧/HO‧ have been reported at near diffusion rates (109 M-1s-1). When comparing reactions of SO4-‧/HO‧ towards NB and phenol, it can be conducted that under neutral and acidic conditions, SO4-‧ is the major radical oxidant species.
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