低揮發性化合物亨利常數量測方法之研究｜國立中央大學博碩士論文系統

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研究生：	陳俊成 Chun-Cheng Chen
論文名稱：	低揮發性化合物亨利常數量測方法之研究 A method to measure Henry’s law constants of low volatile compounds
指導教授：	李俊福 Jiunn-Fwu Lee
口試委員:
學位類別：	碩士 Master
系所名稱：	工學院 - 環境工程研究所 Graduate Institute of Environmental Engineering
畢業學年度：	93
語文別：	中文
論文頁數：	128
中文關鍵詞：	揮發、亨利常數、表面損失揮發模式、擾流、風速
外文關鍵詞：	surface depletion rate-limiting model, volatilization, liquid stirring, wind speed, Henry’s law constant
相關次數：	點閱：14 下載：0
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本研究主要內容在於建立新的量測方法，用以估算低揮發性化合物之亨利常數值。傳統上測量低揮發性化合物之亨利常數值常使用氣提法或者是密閉系統法，然而在使用上述方法估算亨利常數時，會有化合物吸附、平衡時間過長和實驗設備要求高等問題存在。為了克服上述問題，本研究以半密閉系統之模廠，在不同擾流條件下，測量低揮發性有機化合物揮發速率常數，最後利用表面損失揮發模式(surface depletion rate-limiting, SDRL)，在氣相參數β已知與擾流常數α假設為一的情形下，求得低揮發性化合物之亨利常數值。藉由文獻值與以模式預測獲得到之亨利常數值來驗證本研究發展之方法所求得亨利常數的準確性。
由實驗結果顯示，所選擇有機化合物均能利用一階反應方程式求得揮發速率常數值，所計算之亨利常數值亦都在文獻值的範圍內，且相對於傳統密閉系統來說，本研究所使用的時間較短且容易控制，不過所使用的化合物亨利常數值愈高，高擾流條件的效率愈差。至於本研究求得之結果與蒸氣壓/水溶解度、官能基與鍵結貢獻模式等預測模式推估之值有所差距的原因，應是本研究選用低水溶解度與化學結構式複雜的化合物所導致。與傳統二層膜理論計算之亨利常數值相比較，表面損失揮發模式所求得的亨利常數值相對較低，其原因可能在於質量傳送假設與參考化合物不同所造成。由各模式相互比較之後，以本研究之表面損失揮發模式計算的亨利常數值較具準確性。

The lack of accurate Henry''s law constants (H) is one of the major problems on determining fates of organic compounds in the environment. Methods of experimentally determine H can be roughly divided into kinetic and static thermodynamic measurement. It takes more than half month for the traditional static methods to experimentally determining the Henry’s law constants of low volatility organic compounds. Thus, a new approach in this study has been developed to measure the H of low volatility organic compounds（dimensionless < 10-4）.
According to the traditional concepts, the volatilization rate constants of low H compounds in aqueous solution have a good correlation with their H values. Thus, the H values of low H compounds （dimensionless < 10-4） were considerably obtained from the kinetic method based on the loss rate of a substance from water. In our previous investigation, the surface depletion rate-limiting model (SDRL) for calculating volatilization rates of low H compounds under gas and liquid turbulence was developed. As a result, the H values of the low H compounds under the gas and liquid turbulence were estimated with the SDRL model. The obtained H values were compared with other approaches including traditional two film theory, vapor pressure /aqueous solubility, bond contribution method and group contribution method.
As the H values obtained form the above-mentioned method was compared the literature values, SDRL model shows more accuracy than the other method. It can be concluded that the presented approach is a good way on determining the H values for the low H compounds.

目錄
目次                                                                       頁次
目錄	                                                                  I
圖目錄	                                                                  VI
表目錄	                                                                  VIII
第一章  前言	                                                         1
1-1 研究緣起	                                                         1
1-2 研究目的	                                                         4
第二章  文獻回顧	                                                         5
2-1 基本理論介紹	                                                         5
2-1-1 勞特定律	                                                         5
2-1-2 亨利定律	                                                         6
2-1-3 二層膜理論	                                                         8
2-1-4 氣體動力學觀念                                                       10
2-1-5表面損失揮發模式                                                      11
2-1-6 Arrhenius 活化能方程式                                               12
2-1-7 增溶作用	                                                         13
2-1-8 UNIFAC模式	                                                         13
2-2亨利常數之測量	                                                         15
2-2-1直接測量兩項濃度值                                                    15
2-2-2 密閉系統	                                                         16
2-2-3測量農藥亨利常數值                                                    17
2-2-4 氣提法測量亨利常數	                                                18
2-3 模式預測亨利常數值	                                                20
2-3-1 水溶解度與蒸氣壓模式	                                                20
2-3-2 以活性係數推估亨利常數值	                                       21
2-3-3 官能基/鍵結貢獻模式	                                                22
2-3-4 分子關連模式	                                                         24
2-3-5 線性溶解能量關係	                                                26
2-3-6 類神經網路估算亨利常數的方法	                                       27
2-4 影響亨利常數因子	                                                27
2-4-1 溫度	                                                         28
2-4-2 大分子有機物與界面活性劑	                                       29
2-4-3 鹽類	                                                         31
2-4-4 共同溶劑效應	                                                         32
2-5 影響揮發速率之因素	                                                32
2-5-1 液相體積	                                                         32
2-5-2 氣、液相擾流	                                                         33
第三章 實驗材料、設備與方法	                                                36
3-1 研究架構	                                                         36
3-2 實驗材料	                                                         38
3-2-1 有機化合物	                                                         38
3-2-2 其他有機溶劑	                                                         43
3-3 實驗設備	                                                         44
3-4 實驗方法	                                                         47
3-4-1 有機化合物揮發速率之量測	                                       47
3-4-2 液相擾流強度之控制	                                                49
3-4-3 氣相擾動之控制	                                                50
3-4-4 溫度控制	                                                         51
3-4-5 反應槽尺寸	                                                         51
3-4-6 反應時間	                                                         51
3-4-7 取樣時間	                                                         51
3-4-8 萃取溶劑	                                                         54
3-4-9 水揮發修正	                                                         54
3-5 以實驗方式計算亨利常數方法	                                       56
3-5-1 計算KOL值	                                                         56
3-5-2 利用表面損失揮發模式計算亨利常數值	                              57
3-5-3 利用二層膜理論計算亨利常數值	                                       58
第四章 結果與討論	                                                         61
4-1 實驗條件與化合物揮發特性之探討	                                       61
4-1-1 取樣時間	                                                         61
4-1-2 化合物質量傳送係數之選擇	                                       64
4-1-3 揮發速率與擾流之關係	                                                68
4-2 表面損失揮發模式所得結果	                                       73
4-2-1 不同液相擾流強度下之亨利常數值	                                       73
4-2-2 不同氣相擾流下之亨利常數值	                                       75
4-2-3 氣相與液相擾流下之亨利常數值	                                       78
4-2-4 表面損失揮發模式與文獻值差異	                                       79
4-3 以其他方式計算亨利常數值	                                       85
4-3-1 蒸氣壓/水溶解度	                                                86
4-3-2 鍵結與官能基貢獻模式	                                                88
4-3-3傳統二層膜理論	                                                92
4-4 各種不同模式之比較	                                                95
4-4-1 各評估模式對文獻值之相關係數圖	                                       95
4-4-2 各評估模式對文獻值之差距百分比	                                       99
4-5 各種模式優缺點分析	                                                103
4-5-1 發展方式與傳統測量亨利常數值方法比較	                              103
4-5-2 靜態與動態方式求得亨利常數值比較	                              104
4-5-3 二層膜理論與表面損失揮發模式比較	                              105
4-5-4 各模式優缺點比較	                                                106
第五章 結論與建議	                                                         107
5-1 結論	                                                                  107
5-2 建議	                                                                  108
參考文獻	                                                                  109
圖目錄
目次                                                                       頁次
圖2-1 二層膜理論所假設之揮發過程	                                        8
圖2-2 測有機氯農藥亨利常數之實驗設備圖	                              18
圖2-4 氣提方法測量亨利常數之實驗設備圖	                              19
圖3-1 研究架構圖	                                                         37
圖3-2 實驗模廠設計圖	                                                45
圖3-3 實驗流程圖	                                                         55
圖4-1 氯苯胺總採樣時數8小時濃度變化圖	                              62
圖4-2 氯苯胺總採樣時數48小時濃度變化圖	                              62
圖4-3 安沙番於相同擾流條件下揮發速率常數對濕度作圖	                     67
圖4-4 DDE轉速對質量傳送係數圖	                                       69
圖4-5 DDE風速對質量傳送係數圖	                                       69
圖4-6 安沙番轉速對質量傳送係數圖	                                       70
圖4-7 安沙番風速對質量傳送係數圖	                                       70
圖4-8 氯苯胺轉速對質量傳送係數圖	                                       71
圖4-9 氯苯胺風速對質量傳送係數圖	                                       71
圖4-10 表面損失揮發模式與文獻之亨利常數對數比較	                     96
圖4-11二層膜理論與文獻之亨利常數對數比較	                              96
圖4-12 蒸氣壓/水溶解度與文獻之亨利常數對數比較	                     97
圖4-13 鍵結貢獻模式與文獻之亨利常數對數比較	                              97
圖4-14 官能基貢獻模式與文獻之亨利常數對數比較	                              98
表目錄
目次                                                                      頁次
表2-1 在25℃之鍵結貢獻值	                                                23
表3-1 有機化合物之物理化學特性	                                       38
表3-2 有機化合物之分子結構式	                                       39
表3-3 各化合物之偵測儀器與條件	                                       48
表3-4 標的化合物在液相擾流中之實驗參數表	                              49
表3-5 標的化合物在氣相擾流中之實驗參數表	                              50
表3-6 各化合物之實驗時間	                                                52
表3-7 各化合物理論之實驗時間	                                       53
表3-8 在不同擾流條件下之氣相擾流因子β	                          58
表3-9 參考化合物苯在各種環境條件下之質傳係數	                              59
表3-10 水在不同風速下之氣相質傳係數	                                       60
表4-1 各化合物在各種氣相擾流條件下之質量傳送係數	                     65
表4-2 各化合物在各種液相擾流條件下之質量傳送係數	                     66
表4-3 各化合物於不同液相擾流之亨利常數對數值	                              74
表4-4 各化合物於不同氣相擾流之亨利常數對數值	                              76
表4-5 各化合物於同時和單獨氣相與液相擾流之亨利常數對數值                    78
表4-6 計算之亨利常數值與文獻值比較	                                       80
表4-7 化合物在液相擾流下之平均差距百分比	                              83
表4-8 化合物在氣相擾流下之平均差距百分比	                              84
表4-9 各化合物由蒸氣壓/水溶解度所得之亨利常數比較	                     87
表4-10 官能基貢獻模式係數表                                              	   89
表4-11 化合物由官能基與鍵結模式所得亨利常數比較                          	   91
表4-12 化合物二層膜理論與文獻之亨利常數比較	                              93
表4-13 各模式對文獻值之差距百分比	                            	  100
表4-14各模式優缺點比較	                            	           106

                                

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