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研究生:朱筱梵
研究生(外文):Siao-fan Jhu
論文名稱:以核磁共振測擴散的技術研究1-丁基-3-甲基咪唑六氟磷酸鹽在一些共溶劑中的離子狀態
論文名稱(外文):Studies of the Ionic States of 1-Butyl-3-methylimidazolium Hexafluorophosphate in Selected Co-solvents by NMR Diffusivity Techniques
指導教授:孫亦文
指導教授(外文):I -Wen Sun
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學系碩博士班
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2008
畢業學年度:96
語文別:中文
論文頁數:77
中文關鍵詞:擴散係數離子液體
外文關鍵詞:diffusion coefficientionic liquid
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假設i ) 離子液體中不同的離子狀態,在平衡時彼此的交換速率太快,以致於無法以核磁共振的實驗來各個區別。以及 ii) 量測到的擴散速率,可視為所有可能的狀態化合物擴散速率的總和平均。溶劑與陰離子擴散係數比值─Ds/D-,或者與陽離子擴散比值─Ds/D+,在任一特定離子液體/共溶劑內提供了下述兩點物理意義:即一、相對於自由離子,離子液體中實際的陰離子聚合度(ASS-)大於陽離子聚合度(ASS+),二、ASS- 隨共溶劑比率增大而下降程度也是大於ASS+。本篇以離子液體BMIPF6在共溶劑AN莫耳分率為0.2,室溫300K時,其ASS-由3.64降至2.05,ASS+由2.71降至1.57,可以證明上述兩點。其他共溶劑(DMF、DMSO、PC)陰陽離子聚合度以及聚合度下降幅度,不若AN大,但也都符合上述兩點。
本實驗證明室溫下帶負電簇合物的形成在AN中最大,當x=0.2時ASS- = 3.64,其次DMF( 2.45)、DMSO(1.83),最小PC (1.80)。同樣地帶正電簇合物的形成順序為AN (2.71)、DMF (1.76)、DMSO (1.66)、PC (1.43)。而由ASS- / ASS+ = HAP,可得知PC的HAP為四種溶劑中最低,也就是自由陽離子多於自由陰離子的程度,以PC最大。亦可得知含C=O的共溶劑與BMIPF6作用力優於含C≡N,因前者有較小的ASS值。
Assuming that i) various ionic states in ionic liquids (IL) are in equilibrium with exchange rates too high to be distinguished by NMR experiments and ii) the overall response of measured diffusivity is viewed as the sum of weighted responses of diffusivity of all possible components. Then, the ratio of solvent diffusivity to anion diffusivity, Ds/D- or to cation diffusivity, Ds/D+, in a specified IL/co-solvent suggests two physical meaning: i) compared to free-ion, the relative association degrees of anion-containing components (ASS-) were larger than the relative association degrees of cation-containing components (ASS+); ii) the decrease for ASS- were more than for ASS+ with the increase of molar fraction of co-solvent. It was found that when 1-butyl-3- methylimidazolium hexafluorophosphate (BMI-PF6) was mixed with acetonitrile (AN) in a the molar fraction (X) of 0.2 at 300K, the ASS- was from 3.64 to 2.05 and ASS+ was from 2.71 to 1.57. These results were in consistent with the above observations. And when mixed with other co-solvents, such as DMF, DMSO, and PC, it also showed the same results with smaller degrees of association for both ions.
This study has proven that anion-association components were formed more easily in AN than in other co-solvents. It was found that with X = 0.2 in respective co-solvent of AN, DMF, DMSO and PC, the ASS- was 3.64, 2.45, 1.83, and 1.80; whileas it was 2.71, 1.76, 1.66, and 1.43, respective. It was found that the above four co-solvents resulted in more free cations than anions. Especially, it was more obvious when PC was as the co-solvent. And with PC as the co-solvent , the HAP (i.e. ASS- / ASS+ ) is the smallest (1.27). This study also showed that co-solvent containing the moiety of C=O showed better interactions with BMI-PF6 than that containing the moiety of C≡N.
中文摘要..................................................Ⅰ
Abstract..................................................Ⅱ
誌謝......................................................Ⅲ
目錄......................................................Ⅴ
圖目錄....................................................Ⅶ
表目錄....................................................Ⅸ
第一章 序論..............................................1
1-1 離子液體的簡介.......................................1
1-2 離子液體的發展.......................................1
1-3 研究主題.............................................3
第二章 理論背景..........................................5
2-1 核磁共振(Nuclear Magnetic Resonance, NMR)............5
2-2 核磁共振的歷史背景...................................5
2-3 核磁共振的基本原理...................................7
2-4 吸收機制............................................11
2-5 遮蔽效應與化學位移..................................11
2-6 核磁共振的弛緩機制..................................12
2-7 擴散係數............................................15
第三章 實驗方法.........................................18
3-1 藥品................................................18
3-2 離子液體的合成方法..................................18
3-3 樣品配製............................................20
3-4 實驗裝置及儀器......................................21
3-5 實驗原理及方法......................................21
第四章 結果與討論.......................................25
4-1 擴散係數導出超陰離子(hyper anion)群聚...............25
4-2 BMIPF6與四種溶劑的系統擴散係數......................42
4-3 與文獻�岸騆�........................................56
4-3-1 離子性 (ionicity)............................56
4-3-2 導電度 (conductivity)........................63
4-3-3 黏度.........................................65
4-4 化學位移............................................66
4-5 弛緩時間............................................70
第五章 結論.............................................74
參考文獻.................................................76
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