臺灣博碩士論文加值系統

本研究量測四個離子液體及其雙成份離子液體水溶液之比熱與電導度，主要量測系統如下：[Bmim][Cl] (1-butyl-3-methylimidazolium chloride)、[Bmim][Br] (1-butyl-3-methylimidazolium bromide)、[Bdimim][BF4] (1-butyl-2,3-dimethylimidazolium tetrafluoroborate)、[Bdimim][PF6] (1-butyl-2,3-dimethylimidazolium hexafluorophosphate)；及雙成份離子液體水溶液( [Bmim][Cl]+H2O、[Bmim][Br]+H2O、[Bdimim][BF4]+H2O、[Bdimim][PF6]+H2O)。
比熱的量測是利用示差掃描熱量計(Differential Scanning Calorimeter, DSC)，純物質量測溫度範圍為其熔點至403.2 K，雙成份系統則為(303.2–353.2) K，以溫度與濃度為變數做迴歸計算，純物質以二次方經驗式，雙成份則利用過剩比熱代入Redlich-Kister type equation；電導度的量測是利用電導度計(Conductivity Meter)，量測的溫度範圍為(293.2–353.2) K，利用其他學者所提出之模式與修正之VTF-type (Vogel-Tamman-Fulcher) equation迴歸計算。迴歸計算值與實驗值有相當良好之符合性。本研究之結果可作為熱力學與電化學應用之基礎數據的計算依據。

The molar heat capacities and electrical conductivities of four pure ionic liquids (IL) and their corresponding aqueous solutions have been studied. The investigated IL systems are 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]), 1-butyl-3-methylimidazolium bromide ([Bmim][Br]), 1-butyl-2,3-dimethylimidazolium tetrafluoroborate ([Bdimim][BF4]), and 1-butyl-2,3-dimethylimidazolium hexafluorophosphate ([Bdimim][PF6]). The molar heat capacities were measured using Differential Scanning Calorimeter (DSC), over a variety of composition ranges within the temperature range for pure ILs system was form their melting point to 403.2 K, and for the binary system was (303.2 to 353.2) K. For the pure system, the dependence of the molar heat capacity, CP, with temperature was correlated by a second order empirical equation, while for the binary systems excess molar heat capacities, CPE, were calculated using a Redlich-Kister type equation. CP and CPE data were reported as functions of temperature and composition. The electrical conductivities, , were measured over the temperature range (293.2 to 353.2) K and a complete range of composition. The experimental  data were correlated to temperature and concentration using a modified Vogel-Tamman-Fulcher type equation. The developed correlations yield satisfactory results as indicated by the average absolute deviations of 0.1 and 3.3 for CP and , respectively.

目錄
摘要 I
Abstract II
致謝 III
目錄 IV
表目錄 VII
圖目錄 IX
第1章 緒論 1
1-1 前言 1
1-2 研究動機 2
1-3 研究目的 5
第2章 DSC與電導度之理論 6
2-1 DSC簡介 6
2-2 DSC種類 6
2-3 DSC比熱量測原理 12
2-3-1 文獻回顧 12
2-3-2 比熱計算 15
2-3-3 比熱的計算模式 18
2-4 電導度量測原理 20
2-4-1 電導度之簡介 20
2-4-2 電導度之理論 21
2-4-3 電導度之迴歸模式 23
第3章 實驗 26
3-1 實驗藥品 26
3-2 實驗裝置 28
3-3 實驗步驟 30
3-3-1 比熱量測原理 30
3-3-2 樣品之製備 30
3-3-3 DSC爐子之清潔 31
3-3-4 DSC爐子之校正 32
3-3-5 比熱量測步驟 35
3-3-6 電導度量測 37
第4章 結果與討論 41
4-1 比熱之驗證 41
4-2 比熱之實驗結果與討論 41
4-2-1 純物質系統 41
4-2-2 離子液體水溶液系統 56
4-3 電導度之實驗結果與討論 74
第5章 結論 96
參考文獻 100


表目錄
Table 1 1 Literature review on the heat capacity of ionic liquids 4
Table 1 2 Literature review on the electrical conductivity of ionic liquids 4
Table 3 1 Structure and molecular weight for the ionic liquids 27
Table 3 2 Ionic liquids for this study 28
Table 3 3 Standard conductivity solution values 40
Table 4 1 Heat capacity of H2O 42
Table 4 2 Heat capacity of [Bmim][Cl] 45
Table 4 3 Heat capacity of [Bmim][Br] 48
Table 4 4 Heat capacity of [Bdimim][BF4] 51
Table 4 5 Heat capacity of [Bdimim][PF6] 53
Table 4 6 Parameters of heat capacity of ionic liquids 55
Table 4 7 Heat capacity of [Bmim][Cl] + H2O 57
Table 4 8 Heat capacity of [Bmim][Br] + H2O 61
Table 4 9 Heat capacity of [Bdimim][BF4] + H2O 66
Table 4 10 Heat capacity of [Bdimim][PF6] + H2O 70
Table 4 11 Parameters of heat capacity of aqueous solutions of ionic liquids 73
Table 4 12 Electrical conductivity of [Bmim][Cl] + H2O 75
Table 4 13 Electrical conductivity of [Bmim][Br] + H2O 80
Table 4 14 Electrical conductivity of [Bdimim][BF4] + H2O 85
Table 4 15 Electrical conductivity of [Bdimim][PF6] + H2O 89
Table 4 16 Parameters of electrical conductivity by Eq. (2 35) 93
Table 4 17 Parameters of electrical conductivity by Eq. (2 36) 94
Table 4 18 Parameters of electrical conductivity by Eq. (2 37) 95


圖目錄
Figure 2 1 Schematic of power compensated DSC 8
Figure 2 2 Schematic of heat flow DSC 10
Figure 2 3 Determination of heat capacity by classical method 13
Figure 2 4 DSC curves for heat capacity measurement 18
Figure 3 1 Schematic drawing of electric conductivity 39
Figure 4 1 Heat capacity of H2O 43
Figure 4 2 Heat capacity of [Bmim][Cl] 46
Figure 4 3 Heat capacity of [Bmim][Br] 50
Figure 4 4 Heat capacity of [Bdimim][BF4] 52
Figure 4 5 Heat capacity of [Bdimim][PF6] 54
Figure 4 6 Heat capacity of [Bmim][Cl] + H2O 58
Figure 4 7 Excess heat capacity of [Bmim][Cl] + H2O 59
Figure 4 8 Heat capacity of [Bmim][Br] + H2O 63
Figure 4 9 Excess heat capacity of [Bmim][Br] + H2O 64
Figure 4 10 Heat capacity of [Bdimim][BF4] + H2O 67
Figure 4 11 Excess heat capacity of [Bdimim][BF4] + H2O 68
Figure 4 12 Heat capacity of [Bdimim][PF6] + H2O 71
Figure 4 13 Excess heat capacity of [Bdimim][PF6] + H2O 72
Figure 4 14 Electrical conductivity of [Bmim][Cl] + H2O, lines: calculated by Eq. (2 35) 76
Figure 4 15 Electrical conductivity of [Bmim][Cl] + H2O, lines: calculated by Eq. (2 36) 77
Figure 4 16 Electrical conductivity of [Bmim][Cl] + H2O, lines: calculated by Eq. (2 37) 78
Figure 4 17 Electrical conductivity of [Bmim][Br] + H2O, lines: calculated by Eq. (2 35) 81
Figure 4 18 Electrical conductivity of [Bmim][Br] + H2O, lines: calculated by Eq. (2 36) 82
Figure 4 19 Electrical conductivity of [Bmim][Br] + H2O, lines: calculated by Eq. (2 37) 83
Figure 4 20 Electrical conductivity of [Bdimim][BF4] + H2O, lines: calculated by Eq. (2 35) 86
Figure 4 21 Electrical conductivity of [Bdimim][BF4] + H2O, lines: calculated by Eq. (2 36) 87
Figure 4 22 Electrical conductivity of [Bdimim][BF4] + H2O, lines: calculated by Eq. (2 37) 88
Figure 4 23 Electrical conductivity of [Bdimim][PF6] + H2O, lines: calculated by Eq. (2 35) 90
Figure 4 24 Electrical conductivity of [Bdimim][PF6] + H2O, lines: calculated by Eq. (2 36) 91
Figure 4 25 Electrical conductivity of [Bdimim][PF6] + H2O, lines: calculated by Eq. (2 37) 92

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