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研究生: 洪紹琪
Hung, Shao-Chi
論文名稱: 添加苯及二氯甲烷於EMICl/AlCl3融鹽之效應:一篇電腦模擬
The effects of adding benzene and dichloromethane in EMICl/AlCl3 molten salt: a computational study
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: 2004
畢業學年度: 92
語文別: 中文
論文頁數: 68
中文關鍵詞: 動態模擬融鹽離子液體擴散導電
外文關鍵詞: dynamic simulation, molten salt, ionic liquid, conductivity, diffusion
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  • 摘要

    本篇以分子模擬的方法,研究溶劑的種類及其添加量對於EMICl/AlCl3融鹽之導電性質之影響。模擬之條件參考Hussey(3、9)等之實驗參數及採用Stassen修正過之AMBER力場。

    模擬結果顯示不添加溶劑時,以AlCl3莫耳分率為0.51時之陰、陽離子擴散速率最快,導電度也最高。當莫耳分率更高時,以HF/6-31G(d)為基底計算之結合能顯示溶液中過量的AlCl3會與AlCl4-互相吸引,使得離子移動速率變慢。逐步添加苯時反而會使得陰、陽離子之擴散速率加快,但苯的重量百分比超過35時,反而會促使離子集結,以致導電度下降。固定溶劑之重量百分比為35,但以二氯甲烷取代苯時,EMI+離子周圍之AlCl4-離子數與總配位數(包含溶劑與AlCl4-離子)增加,這可能是因為苯的體積較大,當它排擠掉原先配位之AlCl4-離子後,有時無法在EMI+周圍找到足夠的空間排列所致。

    Abstract

    Molecular dynamics simulation has been used to study the influence of solvent type and its amount on the conducting behavior of 1-methyl-
    3-ethylimidazolium chloride ( EMICl )/AlCl3 system. Simulations were conducted to mimic the experiment of Hussey et al. The AMBER force field adapted by Stassen et al. was used.
    It is shown that in the absence of solvent the EMI+ and AlCl4- ions have the fastest diffusion rate at AlCl3 mole fraction of 0.51, giving the highest conductivity. As more AlCl3 is added, a HF/6-31G(d) based ab initio calculation shows that the excees AlCl3 and AlCl4- attract with each other to impede the diffusion. The addition of benzene leads to an increase of the diffusion rate for both EMI+ and AlCl4- ions. However as the weight percentage of benzene is greater than 35, ion aggregation occurs which reduce the conductivity. At a fixed solvent wt % of 35, but benzene is replaced by dichloromethane, it is found that the number of AlCl4- ions around EMI+ increases, so is the overall coordination number, including solvent and AlCl4- ions. This is attributed to the size of benzene, which might prevents it from finding enough space near EMI+ ion as the original coordinated AlCl4- ions have been squeezed out.

    本文目錄 中文摘要 ……………………………………………………………Ⅰ 英文摘要 ……………………………………………………………Ⅱ 本文目錄 ……………………………………………………………Ⅲ 圖目錄 ………………………………………………………………Ⅳ 表目錄 ………………………………………………………………Ⅴ 第一章緒論 …………………………………………………………1 第二章分子動力模擬 ………………………………………………8 2-1 模擬系統 ………………………………………………………8 2-2 模擬方法 ………………………………………………………8 2-3 力場 …………………………………………………………12 2-4 數據計算 ……………………………………………………12 第三章結果與討論 …………………………………………………17 3-1 擴散係數 ……………………………………………………17 3-2 徑向分佈函數…………………………………………………27 3-3 EMI+與AlCl4-離子之集結 ………………………………… 52 3-4 模擬導電度值之修正…………………………………………59 第四章結論 …………………………………………………………66

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