臺灣博碩士論文加值系統

本篇論文的主要目的，在於利用傅立業轉換紅外線光譜儀，來偵測一些具有立體障礙醇類的自結合現象。利用醇類在稀薄溶液中OH基的吸收光譜，可以分別求出單體與雙體的面積。這些光譜中單雙體面積重疊的部分，則利用高斯—勞倫茲混合分佈校正曲線予以分離。再根據濃度變化的數據，依照我們新推導出的兩個公式，分別求出單體吸收係數、雙體吸收係數以及平衡常數。最後再根據平衡常數隨溫度變化的關係，利用van't Hoff理論作圖，可以求得各個系統的標準結合熵(�寒o)和標準結合焓(�巽o)。
研究主要分為兩個系統。第一個系統為探討2,2-二甲基-3-乙基-3-戊醇溶解於四氯化碳、二硫化碳、四氯乙烯、正辛烷等溶劑中的氫鍵自結合現象。第二個系統則為探討3-乙基-2-甲基-3-戊醇溶解於四氯化碳、二硫化碳、四氯乙烯、正辛烷等溶劑中的氫鍵自結合現象。我們可由這些探討更加瞭解氫鍵的性質。

The monomer-dimer self-association of some alcohols with bulky side chains has been studied using FTIR spectroscopy. The spectral band of the OH fundamental stretching for a monomer and that for a dimer were resolved and their respective integrated absorbances were calculated. The dilution shift data of OH proton were measured and employed to determine the molar absorptivity of the monomer band, the dimer band and the dimerization constant. The standard enthalpy and entropy of dimerization were determined via a van't Hoff plot from the temperature variation of the dimerization constant.
This study includes two systems. The first deals with the self- association of 2,2-dimethyl-3-ethyl-3-propanol through hydrogen bonding in carbon tetrachloride, carbon disulfide, tetrachloroethylene and n-octane. The second deals with the self-association of 3-ethyl-2- methyl-3-propanol through hydrogen bonding in carbon tetrachloride, carbon disulfide, tetrachloroethylene and n-octane. We can understand the character of hydrogen bonding through this discussion.

目 錄
中文摘要 i
英文摘要 ii
誌謝 iii
目錄 iv
圖目錄 vii
表目錄 xix
第一章 緒論
1.1 氫鍵簡介 1
1.1.1 氫鍵的物理性質 2
1.1.2關於氫鍵的振動光譜 6
1.1.3影響氫鍵平衡的三種主要因素 7
1.1.4探討氫鍵自結合的常見模式 8
1.2 FTIR簡介 9
1.2.1 FTIR儀器 12
1.2.2光譜解說 14
1.3 IR與NMR光譜法的氫鍵測量比較 19
1.4 參考文獻 22


第二章 理論 25
2.1 公式推導 25
2.2 新方法的優點及適用對象 32
2.3 參考文獻 34

第三章 以FTIR探討2,2-二甲基-3-乙基-3-戊醇與3-乙基-2-甲基-3-戊醇在四氯化碳、二硫化碳四氯乙烯及正辛烷等溶液中的氫鍵自結合現 35
3.12,2-二甲基-3-乙基-3-戊醇與3-乙基-2-甲基-3-戊醇簡介 35
3.2 實驗 37
3.2.1 儀器設備 37
3.2.2 藥品 38
3.2.3 實驗步驟 38
3.3 結果 40
3.3A 2,2-二甲基-3-乙基-3-戊醇溶於CCl4溶液 40
3.3B 2,2-二甲基-3-乙基-3-戊醇溶於CS2溶液 56
3.3C 2,2-二甲基-3-乙基-3-戊醇溶於正辛烷溶液 71
3.3D 2,2-二甲基-3-乙基-3-戊醇溶於C2Cl4溶液 86
3.3E 3-乙基-2-甲基-3-戊醇溶於C2Cl4溶液 101
3.3F 3-乙基-2-甲基-3-戊醇溶於CCl4溶液 116
3.3G 3-乙基-2-甲基-3-戊醇溶於CS2溶液 131
3.3H 3-乙基-2-甲基-3-戊醇溶於正辛烷溶液 146
3.4 討論 157
3.5 參考文獻 163

第四章 結論 165

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