本文選題：吡啶基離子液體 + 密度��； 參考：《遼寧大學(xué)》2017年碩士論文

【摘要】：離子液體憑借自身獨(dú)特的優(yōu)良性能,諸如飽和蒸氣壓低,液態(tài)溫度范圍寬以及功能可設(shè)計(jì)性等,不僅在化學(xué)化工研究領(lǐng)域是環(huán)境友好的綠色溶劑、高效催化劑和萃取劑,而且在醫(yī)學(xué)領(lǐng)域中藥物增溶方面也有廣泛的的用途,此外,作為電解質(zhì)在電池體系中的應(yīng)用也有所突破�？梢�,離子液體作為一種潛在的新興產(chǎn)業(yè),已經(jīng)在人們與日俱增的需求和日新月異的生產(chǎn)中顯示出了卓越的潛在價(jià)值,旨在綠色發(fā)展、可再生能源的難題上迎接新的機(jī)遇和更大的挑戰(zhàn)。本文采用中和法設(shè)計(jì)并合成兩類吡啶基離子液體:N-烷基吡啶醋酸型離子液體[CnPy][OAc](n=2-6)和N-烷基吡啶三氟乙酸型離子液體[CnPy][TFA](n=2-6),共十種離子液體,以核磁共振氫譜(1H NMR)、差示量熱掃描(DSC)對其進(jìn)行表征。由于這兩類離子液體中陰離子CH3COO-和CF3COO-與極性溶劑水易形成氫鍵且利用常規(guī)方法難以除去,因此在本文的熱力學(xué)性質(zhì)測定中,均采用標(biāo)準(zhǔn)加入法(SAM)來消除雜質(zhì)水的干擾,線性擬合之后經(jīng)過外推得到純離子液體的各項(xiàng)性質(zhì)數(shù)據(jù)。在(293.15-343.15)±0.1 K溫度范圍內(nèi),每隔5 K測定了不同含水量的這兩類離子液體的密度、表面張力和折光率。在此實(shí)驗(yàn)數(shù)據(jù)基礎(chǔ)上,利用半經(jīng)驗(yàn)方法估算了這兩類離子液體的體積性質(zhì)和表面性質(zhì)。首先,計(jì)算了離子液體的分子體積并考察了分子體積隨溫度和烷基鏈中碳原子數(shù)的變化情況;根據(jù)Glasser理論得到標(biāo)準(zhǔn)熵(298)和晶格能的數(shù)值,并分析了標(biāo)準(zhǔn)熵隨烷基鏈中碳原子數(shù)的線性變化情況,得到了每個亞甲基對標(biāo)準(zhǔn)熵的貢獻(xiàn)值;通過比較離子液體與無機(jī)熔融鹽的晶格能的大小,解釋了離子液體被稱為室溫熔融鹽的原因;此外,計(jì)算了離子液體的表面熵和表面能,發(fā)現(xiàn)離子液體的表面能相較無機(jī)熔融鹽是很小的,解釋了離子液體在室溫仍能保持液體狀態(tài)的原因。以Kabo和Rebelo的經(jīng)驗(yàn)方程分別計(jì)算了離子液體的汽化焓并分析了導(dǎo)致結(jié)果存在差異的可能性。利用摩爾表面Gibbs自由能的概念對傳統(tǒng)的E?tv?s方程進(jìn)行改進(jìn),在所得的修正E?tv?s方程中,其斜率和截距都有明確的含義,分別代表摩爾表面熵和摩爾表面焓。結(jié)合摩爾表面Gibbs自由能和折光率對這兩類離子液體的表面張力進(jìn)行估算,結(jié)果與相應(yīng)的實(shí)驗(yàn)值吻合。根據(jù)空隙理論計(jì)算所得的兩類離子液體的熱膨脹系數(shù),在數(shù)量級上與相應(yīng)的實(shí)驗(yàn)值一致。經(jīng)過對空隙理論的延伸,本文提出空隙摩爾表面Gibbs自由能的概念,通過推導(dǎo)發(fā)現(xiàn)其值是一個與離子液體的種類無關(guān)的常量。最后,利用液體的溶解性參數(shù)這一新標(biāo)度對兩類離子液體的極性進(jìn)行了估算,用極性大小判斷其親、疏水性,結(jié)果與我們的日常經(jīng)驗(yàn)判斷相一致。
[Abstract]:Ionic liquids are not only environmentally friendly green solvents, efficient catalysts and extractants, but also have excellent properties such as low saturated vapor, wide range of liquid temperature and functional designability. In addition, the application of electrolyte in battery system is also breakthrough. It can be seen that ionic liquids, as a potential emerging industry, have shown remarkable potential value in increasing demand and rapid production, aiming at green development. Renewable energy challenges to meet new opportunities and greater challenges. In this paper, two kinds of pyridyl ionic liquids, [CnPy] [OAC] (CnPy) and [CnPy] [TFA] [CnPy] [TFA], have been designed and synthesized by neutralization method. It was characterized by 1H NMR and differential scanning calorimetry (DSCS). Since the anions CH3COO- and CF3COO- in these two kinds of ionic liquids are easy to form hydrogen bonds with polar solvent water and are difficult to be removed by conventional methods, the standard addition method (SAM) is used to eliminate the interference of impurity water in the determination of thermodynamic properties of these two kinds of ionic liquids. After linear fitting, the properties of pure ionic liquids were extrapolated. In the temperature range of 293.15-343.15) 鹵0.1 K, the density, surface tension and refractive index of the two kinds of ionic liquids with different water content were measured every 5 K. Based on the experimental data, the volume and surface properties of the two kinds of ionic liquids were estimated by semi-empirical method. Firstly, the molecular volume of ionic liquids is calculated and the variation of molecular volume with temperature and the number of carbon atoms in alkyl chain is investigated. The linear variation of standard entropy with the number of carbon atoms in alkyl chain is analyzed, the contribution of each methylene to standard entropy is obtained, and the lattice energy of ionic liquid and inorganic molten salt is compared. The reason why ionic liquids are called room temperature molten salts is explained. In addition, the surface entropy and surface energy of ionic liquids are calculated. It is found that the surface energy of ionic liquids is smaller than that of inorganic molten salts. The reason why ionic liquids can remain liquid at room temperature is explained. The enthalpy of vaporization of ionic liquids was calculated by the empirical equations of Kabo and Rebelo and the possibility of difference in the results was analyzed. By using the concept of Gibbs free energy of molar surface, the traditional Etvsof equation is improved. The slope and intercept have clear meanings in the modified Etotvs equation, which represent the molar surface entropy and the molar surface enthalpy, respectively. The surface tension of these two kinds of ionic liquids is estimated by combining the Gibbs free energy and refractive index of the two kinds of ionic liquids, and the results are in agreement with the corresponding experimental values. The thermal expansion coefficients of the two kinds of ionic liquids calculated according to the void theory are in agreement with the corresponding experimental values in the order of magnitude. Through the extension of the void theory, the concept of Gibbs free energy on the void molar surface is proposed in this paper. It is found that its value is a constant independent of the species of ionic liquids. Finally, the polarity of two kinds of ionic liquids is estimated by using the new scale of solubility parameter of liquid. The hydrophobicity and hydrophobicity of the two kinds of ionic liquids are judged by the size of polarity. The results are in agreement with our daily experience.
【學(xué)位授予單位】：遼寧大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O645.1

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