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研究生： 蘇建源
Su, Jian-yuan
論文名稱： 以核磁共振技術和分子動力模擬探討乙氰和苯甲氰在1-羥乙基-3-甲基咪唑四氟硼酸鹽中的物理狀態
Studies on the physical states of acetonitrile and benzonitrile in 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate by NMR techniques and molecular dynamics simulations
指導教授： 施良垣
Shy, Liang-Yuan
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： 2009
畢業學年度： 97
語文別： 中文
論文頁數： 181
中文關鍵詞： 黏度 、導電度 、擴散係數 、離子液體 、Benzonitrile 、Acetonitrile 、HEMIMBF4 、核磁共振 、分子動力模擬
外文關鍵詞： viscosity, conductivity, diffusion coefficient, acetonitrile, benzonitrile, ionic liquid, HEMIMBF4, nuclear magnetic resonance, molecular dynamics simulations
相關次數： 點閱：120  下載：4 
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    • 本篇以核磁共振的方法，觀察1-羥乙基-3-甲基咪唑四氟硼酸鹽
    (簡稱HEMIMBF4)分別加入稀釋劑 Acetonitrile (AN) 與 Benzonitrile (BN) 後，稀釋劑含量及溫度的改變，對於化學位移、擴散係數及遲緩時間(1H、19F) 之影響。本篇同時也測量混合液之黏度、密度與比導電度等巨觀性質，並佐以分子動力模擬以期對於離子的擴散與導電有更深入的瞭解。

    結果顯示，HEMIM+之H2、H10、H5 與H4原子的化學位移偏差之大小為H10 ＞H2 ＞H5 ～ H4。這顯示H10 (羥基之氫原子)與BF4－及稀釋劑的氫鍵作用力較H2(五圓環上兩個氮之間的氫原子)者強。此結果與分子模擬所得的電荷密度相符合。此外，由NOESY 光譜得知純HEMIMBF4主要是以大離子團進行運動。當稀釋劑之含量增加時，大離子團逐漸被拆開，而以小離子團的形式出現，此結果可由分子動力模擬得到印證。
    BF4－ 離子的擴散係數大於HEMIM+ 離子者，且XAN為0.8時之陽離子擴散係數較0.7者大許多，這是因為HEMIM+ 離子周圍配位之AN分子數急遽增加所致。

    當稀釋劑含量增加時，溶液黏度也隨之下降，遲緩時間上升，離子之擴散速率及比導電度均隨之遞增。這些現象可由分子動力模擬所得的配位數、自由離子比率與離子群之平均離子數獲得解釋。

    在相同的溫度及稀釋劑莫耳分率下，BN與HEMIM+的作用力較AN者強。含BN系統離子之Stokes-Einstein半徑較AN者小，故其擴散係數與導電度均較AN系統者大。此結果可由陽離子周圍稀釋劑個數、平均自由離子機率、稀釋劑之莫耳體積及混合液之黏度獲得解釋。

    根據分子動力模擬之結果，本篇繪出以HEMIM+離子為中心的周圍環境示意圖，這些圖對於實驗的微觀解釋有實質的幫助。

    Nuclear magnetic resonance techniques have been applied to investigate the influences of diluent type, diluent content and temperature on the chemical shift, diffusion coefficient and the relaxation time for
    1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate (HEMIMBF4).The macroscopic properties, like viscosity, density and conductivity of the mixture were measured.

    To understand further the details of ionic diffusion and conductivity, molecular dynamics simulations were also conducted.

    It’s known from the experiment that the 1H chemical shift difference has the order：H10＞H2＞H5～H4, which indicates that the hydroethyl hydrogen atom of HEMIM+ ion forms a stronger hydrogen bond with BF4－ ion and diluent molecules than any other hydrogen atoms. The result is in accord with the partial charge obstained from the simulations.

    The NOESY spectra shows that most of the ions in pure HEMIMBF4 aggregate to form large clusters, the size of which diminishes with the increase of diluent content, which is further confirmed by the simulations.

    In general, the diffusion coefficient of BF4－ ion is greater than that of HEMIM+ ion. The diffusion rate of HEMIM+ at a acetonitrile (AN) molar fraction (XAN) of 0.8 is far greater than that at 0.7, owing to the rapid increase of coordinating acetonitrile molecules around HEMIM+ ion.

    As the diluent content increases, the viscosity of solution decreases, but the relaxation time, diffusion rate and specific conductivity increases. These phenomena can be interpreted with the coordination number, free ion fraction and ionic cluster size that are obtainable from the simulations.

    At constant temperature and diluent concentration, benzonitrile molecule has stronger interaction with HEMIM+ than AN. For HEMIMBF4 / BN system, the Stokes-Einstein radius is smaller than that of AN containing system, which leads to the high diffusion rate and conductivity.
    The origin can be traced back to the differences in the coordination number, free ion fraction, diluent size and solution viscosity.

    Based on this work, the surroundings around the HEMIM+ ion is now clear, which is believed to be helpful for the microscopic explanation of experimental observations.

    目 錄 合格書...............................................................................................................I 中文摘要..........................................................................................................II 英文摘要.........................................................................................................IV 誌謝.................................................................................................................VI 目 錄............................................................................................................VII 圖目錄...............................................................................................................X 表目錄...........................................................................................................XIV 第一章 緒論......................................................................................................1 1－1 離子液體的簡介......................................................................................1 1－2 離子液體的發展......................................................................................2 1－3 離子液體的性質......................................................................................4 1－4 研究動機..................................................................................................7 第二章 理論背景..............................................................................................9 2－1 核磁共振( Nuclear Magnetic Resonance, NMR )...................................9 2－2 核磁共振的歷史背景..............................................................................9 2－3 核磁共振的基本原理............................................................................12 2－4 吸收的機制............................................................................................15 2－5 遮蔽效應與化學位移............................................................................16 2－6 核磁共振的弛緩機制............................................................................17 2－7 擴散係數................................................................................................20 2－8 密度................................................................................................22 2－9 黏度................................................................................................22 2－10 導電度..................................................................................................23 第三章 實驗方法............................................................................................24 3－1 離子液體的合成方法............................................................................24 3－2 樣品配製................................................................................................26 3－3 實驗裝置及儀器....................................................................................27 3－4 實驗方法及原理....................................................................................28 第四章 電腦模擬............................................................................................34 4－1 分子動力模擬 (Molecular Dynamics Simulation)...............................34 4－2 模擬系統................................................................................................35 4－3 力場........................................................................................................36 4－4 相關數據計算........................................................................................41 第五章 結果與討論......................................................................................45 5－1 化學位移................................................................................................45 5－2 二維光譜................................................................................................54 5－3 遲緩時間................................................................................................62 5－4 擴散係數................................................................................................69 5－5 導電度....................................................................................................77 5－6　密度與黏度..........................................................................................85 第六章 分子動力模擬..................................................................................95 6－1 擴散係數與比導電度之模擬................................................................95 6－2 徑向分佈函數(原子)、配位數與自由離子機率之探討....................112 6－3 徑向分佈函數(質心)、配位數與配位機率之探討............................143 6－4 離子群的分析.......................................................................................165 第七章 結 論.............................................................................................173 附錄.................................................................................................................176 參考文獻.........................................................................................................179 圖目錄 圖1-1 N-methyl-pyridinium chloride 之結構式...........................................2 圖1-2 EMIPF6 與 EMIBF4 之結構式........................................................4 圖1-3 離子液體中常見的陰、陽離子..........................................................5 圖1-4 利用不同的陰陽離子所設計的離子液體..........................................6 圖1-5 HEMIMBF4之結構式.........................................................................7 圖1-6 稀釋劑之結構式..................................................................................8 圖2-1 Larmor equation ω＝γ(B0－σ) 右手定則...................................10 圖2-2 原子核在一外加磁場下所產生的磁矩.............................................12 圖2-3 在I=1/2的原子核在外加磁場 B0 的能階分佈圖..........................14 圖2-4 在外加磁場中能階差的關係圖.........................................................14 圖2-5 溫度 60 ℃時，密度隨取代基不同之變化情形.............................22 圖3-1 [HEMIM＋][Cl－] 的合成反應式.....................................................24 圖3-2 減壓蒸餾裝置圖..................................................................................25 圖3-3 [HEMIM＋][BF4－] 的合成反應式..................................................25 圖3-4 樣品配製示意圖..................................................................................27 圖3-5 PGSE method中所用的脈衝回聲序列...........................................29 圖3-6 用向量的方式表示 spin-echo 的實驗過程.......................................29 圖3-7 在 inversion recovery 的實驗方法中所用的脈衝序列.......................................30 圖3-8 以向量的方式來表示測量 T1 的實驗過程.......................................30 圖3-9 奧斯瓦黏度計裝置..............................................................................33 圖3-10 導電度計圖..........................................................................................33 圖4-1 融鹽及稀釋劑之結構式......................................................................38 圖5-1 HEMIMBF4 的示意圖........................................................................45 圖5-2 BN分子與HEMIM+ 離子之π-π作用力........................................47 圖5-3 HEMIMBF4 /AN系統中，陽離子之H2、H4、H5與H10的化學位移變化圖...............................................................................................49 圖5-4 HEMIMBF4 /BN系統中，陽離子之H2、H4、H5與H10的化學位移變化圖...............................................................................................50 圖5-5 HEMIMBF4 /AN、BN系統中，陽離子之H2與H10的化學位移變化圖.......................................................................................................51 圖5-6 HEMIMBF4 /AN、BN系統中，BF4－之F原子的化學位移變化圖.......................................................................................................53 圖5-7 純HEMIMBF4 之NOESY光譜............................................55 圖5-8 HEMIMBF4 / AN (XAN = 0.8)之NOESY光譜............................................56 圖5-9 HEMIMBF4 / BN (XBN = 0.25)之NOESY光譜...............................57 圖5-10 純HEMIMBF4 之 HOESY光譜圖...................................................59 圖5-11 HEMIMBF4 /AN (XAN =0.8)之HOESY光譜圖................................60 圖5-12 HEMIMBF4 / BN (XBN=0.25)之HOESY光譜圖..............................61 圖5-13 HEMIMBF4 /AN系統中，陽離子之H2、H4、H5與H10的遲緩時間.........................................................................................65 圖5-14 HEMIMBF4 /BN系統中，陽離子之H2、H4、H5與H10的遲緩時間.........................................................................................66 圖5-15 HEMIMBF4 / AN、BN系統中，陽離子之H2與H10的遲緩時間 ...........................................................................................67 圖5-16 HEMIMBF4 / AN、BN系統中，陰離子之F的遲緩時間................68 圖5-17 純HEMIMBF4 陰、陽離子之擴散係數與溫度之關係圖................72 圖5-18 HEMIMBF4 /AN 系統之陰、陽離子和稀釋劑之擴散係數與濃度之關係圖............................................................................................... 73 圖5-19 純HEMIMBF4 系統中，加入稀釋劑後的示意圖............................74 圖5-20 溫度300 K時，HEMIMBF4 /BN 系統之陰、陽離子和稀釋劑 之擴散係數與濃度之關係圖................................................................75 圖5-21 溫度300 K，稀釋劑之莫耳分率為0.2時，陰、陽離子之擴散係 數比較圖................................................................................................76 圖5-22 HEMIMBF4 AN系統中，AN莫耳分率的改變對於溶液比導電度 的影響....................................................................................................79 圖5-23 HEMIMBF4 /BN系統中，BN莫耳分率的改變對於溶液比導電 度的影響................................................................................................80 圖5-24 溫度300 K時，稀釋劑之莫耳分率為0.2時之比導電度圖.....................................81 圖5-25 HEMIMBF4 /AN系統之比導電度用阿瑞尼斯方程式作圖................82 圖5-26 HEMIMBF4 /BN系統之比導電度用阿瑞尼斯方程式作圖................83 圖5-27 溫度300 K時，比導電度之活化能與稀釋劑濃度之關係圖................84 圖5-28 HEMIMBF4 /AN系統之密度與溫度之關係圖....................................86 圖5-29 HEMIMBF4 /BN系統之密度與溫度之關係圖....................................87 圖5-30 純HEMIMBF4與稀釋劑之莫耳分率為0.2時之溶液密度與溫度 之關係圖................................................................................................88 圖5-31 HEMIMBF4 /AN 系統之溶液黏度與溫度的關係圖..........................90 圖5-32 HEMIMBF4 /BN 系統之溶液黏度與溫度的關係圖...........................91 圖5-33 純HEMIMBF4 與稀釋劑莫耳分率分別為0.2時之黏度與溫度的關係圖................................................................................................92 圖5-34 稀釋劑之莫耳分率為0.2時，1/D HEMIM+ 對 η/T 之作圖 ................................................................................................................93 圖5-35 稀釋劑之莫耳分率為0.2時，1/DBF4－ 對 η/T 之作圖..............94 圖6-1 純HEMIMBF4系統之HEMIM +與BF4－離子均方位移圖...........96 圖6-2 純HEMIMBF4系統之總體均方位移圖.............................................98 圖6-3 AN之莫耳分率為0.2時之均方位移圖............................................101 圖6-4 AN莫耳分率之改變對於擴散係數之影響.......................................103 圖6-5 BN之莫耳分率為0.2時之均方位移圖............................................104 圖6-6 BN莫耳分率之改變對於擴散係數之影響.......................................106 圖6-7 稀釋劑種類之改變對於HEMIM+與BF4－離子之擴散係數模擬 值之影響..............................................................................................107 圖6-8 含AN系統之總體均方位移圖..........................................................108 圖6-9 含BN系統之總體均方位移圖..........................................................109 圖6-10 稀釋劑種類之改變對於模擬比導電度之影響..................................111 圖6-11 純HEMIMBF4系統之H2與H10對BF4－之F之徑向分佈函數圖 ..............................................................................................................117 圖6-12 HEMIMBF4 /AN系統之H2對BF4－之F之徑向分佈函數圖.................................................118 圖6-13 HEMIMBF4 /AN系統之H10對BF4－之F之徑向分佈函數圖.................................................119 圖6-14 HEMIMBF4 /AN系統之H2對AN之N之徑向分佈函數圖.................................................120 圖6-15 HEMIMBF4/AN系統之H10對AN之N之徑向分佈函數圖.................................................121 圖6-16 HEMIMBF4 /AN系統之H2周圍之F原子配位數圖.................................................122 圖6-17 HEMIMBF4 /AN系統之H10周圍之F原子配位數圖.................................................123 圖6-18 HEMIMBF4 /AN系統之H2周圍之N原子配位數圖.................................................124 圖6-19 HEMIMBF4 /AN系統之H10周圍之N原子配位數圖.................................................125 圖6-20 HEMIMBF4 /AN系統之H2、H10周圍之F原子配位數比較圖.................................................127 圖6-21 HEMIMBF4 /AN系統之H2、H10周圍之N原子配位數比較圖.................................................128 圖6-22 含AN系統之平均自由離子機率圖.................................................129 圖6-23 HEMIMBF4 /BN系統之H2對BF4－之F之徑向分佈函數圖.................................................130 圖6-24 HEMIMBF4 /BN系統之H10對BF4－之F之徑向分佈函數圖.................................................131 圖6-25 HEMIMBF4 /BN系統之H2對BN之N之徑向分佈函數圖.................................................132 圖6-26 HEMIMBF4 /BN系統之H10對BN之N之徑向分佈函數圖.................................................133 圖6-27 HEMIMBF4 /BN系統之H2周圍之F原子配位數圖.................................................134 圖6-28 HEMIMBF4 /BN系統之H10周圍之F原子配位數圖.................................................135 圖6-29 HEMIMBF4 /BN系統之H2周圍之N原子配位數圖.................................................136 圖6-30 HEMIMBF4 /BN系統之H10周圍之N原子配位數圖.................................................137 圖6-31 HEMIMBF4 /BN系統之H2、H10周圍之F原子配位數比較圖.................................................139 圖6-32 HEMIMBF4 /BN系統之H2、H10周圍之N原子配位數比較圖.................................................140 圖6-33 含BN系統之平均自由離子機率圖.................................................141 圖6-34 HEMIMBF4 /AN系統之HEMIM+ 周圍BF4－ 離子之徑向分佈函數.........................................................................................................147 圖6-35 HEMIMBF4 /AN系統之HEMIM+周圍BF4－離子之配位數圖..............................................148 圖6-36 HEMIMBF4 /AN系統之HEMIM+周圍之BF4－離子之配位機率圖 .............................................................................................................149 圖6-37 HEMIMBF4 /AN系統之HEMIM+周圍AN分子之徑向分佈函數圖 .............................................................................................................150 圖6-38 HEMIMBF4 /AN系統之HEMIM+周圍之AN分子之配位數圖...151 圖6-39 HEMIMBF4 /AN系統之HEMIM+周圍之AN分子之配位機率圖 .............................................................................................................152 圖6-40 純HEMIMBF4系統之HEMIM+ 周圍環境示意圖.......................154 圖6-41 AN莫耳分率為0.2之HEMIM+ 周圍環境示意圖.........................154 圖6-42 AN莫耳分率為0.7之HEMIM+ 周圍環境示意圖.........................155 圖6-43 AN莫耳分率為0.8之HEMIM+ 周圍環境示意圖.........................155 圖6-44 HEMIMBF4 /BN系統之HEMIM+周圍BF4－離子之徑向分佈函數 圖.........................................................................................................156 圖6-45 HEMIMBF4 /BN系統之HEMIM+周圍之BF4－離子之配位數圖 .............................................................................................................157 圖6-46 HEMIMBF4 /BN系統之HEMIM+周圍之BF4－離子之配位機率圖 .............................................................................................................158 圖6-47 HEMIMBF4 /BN系統之HEMIM+周圍BN分子之徑向分佈函數圖 .............................................................................................................159 圖6-48 HEMIMBF4 /BN系統之HEMIM+周圍之BN分子之配位數圖...160 圖6-49 HEMIMBF4 /BN系統之HEMIM+周圍之BN分子之配位機率圖 .............................................................................................................161 圖6-50 BN莫耳分率為0.1之HEMIM+ 周圍環境示意圖.........................163 圖6-51 BN莫耳分率為0.2之HEMIM+ 周圍環境示意圖.........................163 圖6-52 含AN系統之離子群組成圖............................................................169 圖6-53 含BN系統之離子群組成圖............................................................170 圖6-54 含AN系統之小離子群組成圖........................................................171 圖6-55 含BN系統之小離子群組成圖........................................................172 附圖A-1 AN之莫耳分率為0.7時之均方位移圖........................................176 附圖A-2 AN之莫耳分率為0.8時之均方位移圖........................................177 附圖A-3 BN之莫耳分率為0.1時之均方位移圖........................................178 表目錄 表4-1 稀釋劑的物理性質.............................................................................35 表4-2 模擬條件.............................................................................................36 表4-3 PCFF位能函數表...............................................................................37 表4-4 HEMIMBF4原子部分電荷................................................................39 表4-5 分子群組之設定..................................................................................40 表5-1 含AN系統之XAN為0.7與0.8之陽離子周圍AN分子數及平均自 由離子機率...........................................................................................71 表5-2 溫度300 K，稀釋劑之莫耳分率為0.2時之比較............................71 表6-1 純HEMIMBF4系統之均方位移圖之虛線斜率、截距與相關係 數..........................................................................................................97 表6-2 純HEMIMBF4系統之擴散係數值...................................................97 表6-3 純HEMIMBF4總體均方位移圖之虛線斜率、截距與相關係數............................................................................................................99 表6-4 純HEMIMBF4系統之總體擴散係數Dcoll與比導電度σ...........99 表6-5 含AN系統之均方位移圖之虛線斜率、截距與相關係數.........102 表6-6 含AN系統之擴散係數值...............................................................102 表6-7 BN系統均方位移圖之虛線斜率、截距與相關係數....................105 表6-8 BN系統之擴散係數值....................................................................105 表6-9 含AN與BN系統之總體均方位移圖之虛線斜率、截距與相關係數..............................................................................................................110 表6-10 含AN與BN系統之總體擴散係數模擬值Dcoll與比導電度值σ .........................................................................................................................110 表6-11 HEMIMBF4 /AN系統之H2與H10周圍之配位數.......................126 表6-12 含AN系統之自由離子機率...........................................................129 表6-13 含BN系統之HEMIM+ 之H2與H10周圍之配位數表.............138 表6-14 含BN系統之自由離子機率............................................................141 表6-15 稀釋劑莫耳分率為0.2之HEMIM+ 之H2與H10周圍之配位數表 .........................................................................................................................142 表6-16 稀釋劑莫耳分率為0.2之自由離子機率表....................................142 表6-17 含AN系統之HEMIM+ 周圍之配位數表....................................153 表6-18 含BN系統之HEMIM+ 周圍之配位數表....................................162 表6-19 稀釋劑莫耳分率為0.2之HEMIM+周圍之配位數表...................164 表6-20 稀釋劑莫耳分率為0.2之HEMIM+周圍之最大配位數表...................164 表6-21 各種離子群之比率...........................................................................167 表6-22 小離子群之分析表...........................................................................168

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