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研究生： 鄭國志
Cheng, Kuo-Chih
論文名稱： 藉由液態核磁共振的技術來探討不同溶劑在室溫熔鹽所造成分子動力行為
Molecular dynamics of BMI-PF6 in various solutions by 19F-NMR relaxation and 1H-NMR diffusion
指導教授： 王小萍
Wang, Shiao-Ping
學位類別： 碩士
Master
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2006
畢業學年度： 94
語文別： 中文
論文頁數： 74
中文關鍵詞： 室溫融鹽 、擴散係數
外文關鍵詞： diffusion coefficient, ionic liquid
相關次數： 點閱：121  下載：1 
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    • 　　1-butyl-3-methylimidazolium hexafluorophosphate (BMI-PF6) 是目前較熱門且較多人研究的離子液體，因其具有較特殊的物化性質。於此即利用NMR的實驗技巧來了解BMI-PF6與有機溶劑（如：Acetontrile (AN)，Propylene Carbonate (PC)，N,N-dimethylformamide, (DMF)，Methyl Sulfoxide (DMSO) 之間的作用情形，方便廣泛的做運用。且發現到有機溶劑與陰離子的作用情況為：PC > DMSO > DMF > AN。且其離子強度可利用溶劑與BMI+的擴散係數比來定量出在此混合溶液的解離程度。

    　　 於含AN的混合溶液內，預測其具較小的介電常數導致在本實驗的溫度及濃度的條件下，其會以contact ion pairs形式存在，而DMF雖和AN具有相似的介電常數，但發現其會與離子液體有較強的作用，相對地，在PC中則具有較大的介電常數，以致於其多會以solvent-separated ion pairs形式存在。

    　　1-butyl-3-methylimidazolium hexafluorophosphate (BMI-PF6) is one of the most popular and investigated classes of room temperature ionic liquid. The nature of interaction between BMI-PF6 and solvents has been investigated by analyzing NMR diffusion coefficient of (1) BMI containing species and (2) aprotic organic solvents (AOS), including Acetontrile (AN), Propylene Carbonate (PC), N,N-dimethylformamide (DMF), Methyl Sulfoxide (DMSO). It has been found the self-diffusing ions are associated to different extents, depending on AOS-anion interactions in the order: PC > DMSO > DMF > AN. The strengths of ionicity, quantified in terms of “degree of dissociation,” which are evaluated by proposed “the method of ratio of diffusion coefficient.” The association capabilities, dissociation of bridged ion-pairs, are in the reverse order of the above-mentioned AOS-PF6 interaction trend.

    　　The AN solvent, as predicted by its small dielectric constant, results in complete paired ( vanishing dissociation ) IL in the range of experimental temperature and concentration. DMF has similar magnitudes of  to that of AN, but can interact better with IL, revealed by a larger degree of dissociation of IL in DMF. PC has slightly larger value of dielectric constant than DMSO, but considerably stronger interaction with PF6 than DMSO. This can explain the much better dissociation of IL found experimentally in PC than in DMSO.

    表目錄…………………………………………………　iii 圖目錄…………………………………………………　iv 第一章　序論…………………………………………　1 第二章　理論背景……………………………………　3 　　　　　2-1 離子液體……………………………　3 　　　　　　2-1-1 離子液體的簡介………………　3 　　　　　　2-1-2 離子液體的定義………………　5 　　　　　　2-1-3 離子液體的性質………………　7 　　　　　2-2 核磁共振……………………………　12 　　　　　　2-2-1 核磁共振的歷史背景…………　12 　　　　　　2-2-2 核磁共振的基本原理…………　14 　　　　　　2-2-3 吸收機制………………………　18 　　　　　　2-2-4 遮蔽與化學位移………………　19 　　　　　　2-2-5 核磁共振的遲緩機制…………　20 　　　　　　2-2-6 擴散係數………………………　23 第三章　實驗過程……………………………………　26 　　　　　3-1 藥品…………………………………　26 　　　　　3-2 離子液體的合成方法………………　26 　　　　　　3-2-1 BMIC的製備……………………　26 　　　　　　3-2-2 BMI-PF6的合成方法……………　28 　　　　　3-3 藥品配置……………………………　28 　　　　　3-4 實驗裝置與儀器……………………　29 　　　　　3-5 實驗原理與方法……………………　29 　　　　　　3-5-1 擴散係數的測量方法…………　29 　　　　　　3-5-2 遲緩時間的測量………………　31 　　　　　　3-5-3 黏度與密度的測量方法………　32 第四章　結果與討論…………………………………　36 　　　　　4-1 化學位移的影響……………………　36 　　　　　　4-1-1 具芳香環的非質子酸有機溶劑　38 　　　　　　4-1-2 具極性的非質子酸有機溶劑…　44 　　　　　4-2 擴散係數的影響……………………　47 　　　　　4-3 遲緩時間的影響……………………　55 　　　　　4-4 黏度與密度的影響…………………　61 第五章　結論…………………………………………　67

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