臺灣博碩士論文加值系統

本研究探討溫度、碘離子濃度、氧化劑與懸浮物對於碘光度測氧法的干擾影響。碘光度法所測得的訊號來自於兩碘物種的混合光譜(如I2 和 I3-)，故兩物種的平衡狀態是決定準確度的重要因素。實驗中必須利用高濃度的碘離子醃劑來確保[I_3^- ]/[I_2 ]比例的恆定。除此之外，溫度是值得注意的問題，溫度的提升會使得碘分子的吸收訊號下降，但卻會使得三碘錯離子的吸光值增加。以溶氧值約250μM的淡水樣品為例，每上升1℃會造成溶氧值高估0.40%。所以溫度改變不只影響了碘物種的平衡，同時也改變了碘物種的光譜。為了解決這一問題，研究中利用恆溫裝置改裝了分光光度計，使測量過程中的溫度變動可以維持在0.5℃內。此外，自然環境中廣泛存在著碘酸根、過氧化氫與亞硝酸根等氧化物，這些物質都會影響溶氧的測量。幸運的是利用反加試劑扣除法即可快速有效解決碘酸根的干擾；過氧化氫的干擾則可以透過添加鉬酸鹽來催化反應後才可扣除。至於亞硝酸根部分則建議添加疊氮化鈉來遮蔽其干擾。懸浮物干擾方面，因採樣過程中樣品無法過濾，容易受到懸浮物的影響，建議測完溶氧後原瓶添加硫代硫酸鈉，褪色後再次測量即可扣除水中的懸浮物干擾。綜合以上發現，碘離子試劑濃度、溫度、氧化劑與懸浮物皆會干擾碘光度測氧法的測量，唯有控制好以上干擾因素才有助於再提升溶氧測定的準確性與精密性。

This study investigates effects of temperature, iodide concentration, oxidants and suspended solid on the colorimetric determination of oxygen in natural waters. Since the measurement involves the mixture of two iodine species (i.e. I2 and I3-), the equilibrium between them becomes a crucial factor to the precision of the method. A high concentration of iodide in the pickling reagent was found essential to ensure a stable [I_3^- ]/[I_2 ] ratio. Besides, it was also found that elevated temperature can cause a lower signal of molecular iodine, but increase the absorbance of triiodide ion. An over-all increment of 0.4% per 1 ℃ has been observed for a freshwater sample having oxygen concentration of ca. 250 μM. Therefore, temperature deviation can not only change the equilibrium constant but also alter the spectra of both iodine species. To solve this problem, the spectrophotometer has been modified using a thermostat unit which ensures the temperature difference between samples be kept within 0.5 ℃. Iodate, hydrogen peroxide, nitrite which are known to exist in natural environment all interfere the oxygen measurement. A quick reverse pickling procedure can be used to identify the iodate interference. Addition of sodium azide is always suggested to remove overestimate from nitrite. Since the sampling for oxygen usually excludes filtration therefore suspended solid in a sample can be another source of error. Re-measurement of the absorbance of the same sample after adding sodium thiosulfate reagent to remove the iodine color is considered the most effective way to correct for the interference from turbid water.

口試委員會審定書 #
誌謝 i
中文摘要 ii
ABSTRACT iii
目錄 iv
圖目錄 viii
表目錄 x
Chapter 1 簡介 1
1.1 溶氧的測定演進 1
1.2 溫可樂滴定法的原理與優缺點 3
1.3 希巴辣光度測氧法原理操作與優缺點 5
1.4 Labasque的等吸光點訴求及其優缺點 7
1.5 黃天福教授的氧化物干擾論 9
1.6 表觀耗氧量之考量 12
1.7 懸浮物問題 13
1.8 本研究的動機與期待成果 14
Chapter 2 碘物種光譜與溫度進階討論 15
2.1 氧濃度、碘酸根濃度與碘離子濃度 15
2.1.1 氧濃度的計算 15
2.1.2 碘酸根濃度的計算 16
2.1.3 參數設定 17
2.1.4 結果與討論 18
2.2 碘酸根添加實驗 24
2.2.1 藥品與儀器 24
2.2.2 實驗步驟 24
2.2.3 經驗K的計算 25
2.2.4 結果討論 25
2.3 平衡常數與溫度間之理論推演 26
2.4 分子碘光譜與溫度的關係 29
2.4.1 藥品與儀器 29
2.4.2 碘分子溶液配置 29
2.4.3 碘分子溶液光譜實驗步驟 30
2.4.4 碘分子溶液光譜實驗結果與討論 30
2.5 混合光譜與溫度的關係 32
2.5.1 藥品與儀器 32
2.5.2 三碘錯離子溶液配置與計算 32
2.5.3 混合碘光譜實驗步驟 33
2.5.4 混合碘光譜溶液光譜實驗結果與討論 33
2.6 混合碘光譜與碘離子的影響 35
2.6.1 藥品與儀器 35
2.6.2 實驗步驟 36
2.6.3 實驗結果與討論 36
2.7 混合碘光譜與離子強度的關係 39
2.7.1 藥品與儀器 39
2.7.2 實驗步驟 39
2.7.3 結果討論 40
2.8 等吸光點討論 41
2.9 海淡水樣品在不同波長受溫度的影響 42
2.9.1 藥品與儀器 42
2.9.2 實驗步驟 42
2.9.3 結果討論 43
2.10 實際操作過程中溫度的變化與影響 45
2.10.1 藥品與儀器 45
2.10.2 實驗步驟 45
2.10.3 實驗結果 45
2.11 分光光度計恆溫光槽之設計 46
Chapter 3 氧化物之干擾 48
3.1 自然界可能存在的氧化物干擾特性 48
3.2 正加試劑添加法與反加試劑添加法 48
3.2.1 原理 48
3.2.2 藥品與儀器 49
3.2.3 實驗步驟 49
3.2.4 各種添加法穩定度研究結果與討論 50
3.3 碘酸根干擾與去除討論 54
3.3.1 原理 54
3.3.2 結果與討論 54
3.4 過氧化氫干擾與去除討論 56
3.4.1 原理 56
3.4.2 結果與討論 56
3.5 亞硝酸根干擾與去除討論 59
3.5.1 原理 59
3.5.2 結果與討論 60
3.6 對氧化物干擾之建議 63
Chapter 4 懸浮物的問題 64
4.1 懸浮物與碘光度法 64
4.2 原瓶漂白扣除法 65
4.2.1 原理 65
4.2.2 實驗步驟 65
4.2.3 結果與討論 65
4.3 穿透率探針扣除法 67
4.3.1 原理 68
4.3.2 實驗結果 68
4.4 對懸浮物干擾的建議 71
Chapter 5 結論 72
參考文獻 74

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