摘要……….…………………………………………….I
目錄……………………………………………………III
圖目錄…………………………………………………IX
表目錄………………………………………………..XV
符號說明…………………………………………….XVI
第一章 緒論
1-1 本研究之動機與主旨……………………………………..1
1-2 影響催化活性之因素……………………………………..2
1-3 締合常數…………………………………………………..2
1-3-1 以導電度方程式求締合常數………………………………….…2
1-3-1.1 Fuoss-Kraus equation (FK)…………………………………………………2
1-3-1.2 Shedlovsky equation (SE)…………………………………………………..3
1-3-1.3 Fuoss-Shedlovsky equation (FS)……………………………………………3
1-3-1.4 Pitts equation (PE)…………………………………………………………..4
1-3-1.5 Fuoss-Onsager-Skinner equation (FOS)…………………………………….5
1-3-1.6 Fuoss-Hsia equation (FH)…………………………………………………...6
1-3-1.7 Fuoss-Hsia-Fuoss-Pitts-Justice equation (FHFPJ)………………………….6
1-3-1.8 Fuoss equation (FE)…………………………………………………………7
1-3-1.9 Lee-Wheaton equation (LW)………………………………………………..8
1-3-1.10 modification of Debye-Huckel-Onsager equation (DHO)………………….8
1-3-2 以非導電度法求締合常數……………………………………….8
1-3-3無限稀釋溶液莫爾導電度( )與離子對締合常數( )之文獻值
比較與討論……………………………………………………10
1-3-3.1 四丁基銨氯鹽( )之( )與( )之文獻值比較………………….10
1-3-3.2 四丁基銨溴鹽( )之( )與( )之文獻值比較………………….11
1-3-3.3 四丁基銨碘鹽( )之( ) 與( )之文獻值比較………………….13
1-3-3.4 四丁基銨過氯酸鹽( )之( )與( )之文獻值比較………….17
1-3-3.5 四丁基銨四酚硼鹽( )之( )與( )之文獻值比較………….18
1-3-3.6 四丁基銨四丁基硼鹽( )之( )與( )之文獻值比較……….19
1-3-3.7 四丁基銨硝酸鹽( )之( )與( )之文獻值比較……………...20
1-3-3.8 四丁基銨苦味酸鹽( )之( )與( )之文獻比較..20
1-3-3.9 討論………..………………………………………………………………20
1-4 四丁基銨鹽之飽和溶解度………………………………21
1-4-1 四丁基銨鹽飽和溶解度之文獻整理…………………………...21
1-4-2 四丁基銨鹽飽和溶解度之文獻值比較與討論………………...23
1-4-2.1 四丁基銨鹽在單一溶劑中之 ………………………………………….23
1-4-2.2 四丁基銨鹽在混合溶劑中之 ………………………………………….24
1-4-2.3 討論………………………………………………………………………..25
1-5 四丁基銨鹽之活性係數………………………………..25
1-5-1 活性係數之計算方法…………………………………………...25
1-5-1.1 Debye-Huckel limiting law…………………………………………………..25
1-5-1.2 Pitzer equation……………………………………………………………….26
1-5-2 四丁基銨鹽活性係數之文獻整理……………………………...26
1-6 四丁基銨鹽之分佈係數與萃取常數…………………..27
1-6-1 四丁基銨鹽之分佈係數………………………………………...27
1-6-1.1 四丁基銨鹽分佈係數之文獻整理………………………………………..27
1-6-1.2 四丁基銨鹽分佈係數(KP)之文獻值比較………………………………...28
1-6-2 四丁基銨鹽之萃取常數………………………………………...28
1-6-2.1 四丁基銨鹽萃取常數之文獻整理………………………………………..29
1-6-2.2 四丁基銨鹽在有機溶劑/水之萃取常數(KE)之文獻值比較……………..30
1-6-2.3 討論………………………………………………………………………..32
1-7 四丁基銨鹽之離子半徑………………………………..32
1-7-1 Stokes radii( )…………………………………………………...32
1-7-1.1 四丁基銨鹽Stokes radii之文獻整理……………………………………..33
1-7-1.2 四丁基銨鹽Stokes radii之文獻值比較…………………………………..33
1-7-2 solvated radii ( )………………………………………………...35
1-7-2.1 四丁基銨鹽solvated radii之文獻整理……………………………………36
1-7-2.2 四丁基銨鹽solvated radii之文獻值比較…………………………………37
1-7-3 crystallographic radius……………………………………………39
1-7-4 討論……………………………………………………………...39
1-8 本研究之方法與步驟…………………………………..39
第二章 理論…………………………………...……...41
2-1 溶劑性質間之關係……………………………………....41
2-2 粒子間之作用……………………………………………48
2-2-1 離子-溶劑間之作用……………………………………………..48
2-2-1.1 Born model………………………………………………………………...48
2-2-1.2 Ion-dipole model…………………………………………………………...48
2-2-1.3 Ion-induced model…………………………………………………………49
2-2-2 極性與極性分子間之作用……………………………………...49
2-2-2.1 Dipole-dipole model……………………………………………………….49
2-2-2.2 Dipole- induced dipole model……………………………………………..50
2-3 溶劑性質與季銨鹽陰離子結構對該鹽溶解度CS之影響
…………………………………………………….……..51
2-4 Debye-Huckel Onsager導電度方程式...…………………52
2-4-1 Electrophoretic retarding force, ………………………………52
2-4-2 Relaxation retarding force, …………………………………...53
2-4-3 離子在溶劑中所受之總力, …………….……..…………..54
2-4-4 Debye-Huckel-Onsager Equation………………………………...55
2-5 締合常數KA與莫耳導電度 之關係式.………………..57
2-6 、KA與 之實驗求法…………………………….…...61
2-6-1 初值之求法…………………………………………………..61
2-6-2 及KA之實驗求法…..…………..……………………….……62
2-6-3 之求法……………..…………..……………………….……62
2-7 溶劑性質與催化劑結構對締合常數KA之影響………..63
2-8 溶劑性質與催化劑結構對分佈係數KP之影響………...64
第三章 實驗部分…………………………..………....66
3-1 實驗與分析之藥品………………………………………66
3-2 實驗裝置及分析儀器……………………………………67
3-2-1 實驗裝置………………………………………………………...67
3-2-1.1 溶解度……………………………………………………………………..67
3-2-1.2 締合常數及分佈係數……………………………………………………..67
3-2-2 離心裝置………………………………………………………...68
3-2-3 導電度計………………………………………………………...68
3-3 導電度之分析……………………………………………68
3-3-1 導電度計之分析條件…………………………………………...68
3-3-2 導電度計之校正………………………………………………...69
3-3-3 之校正曲線……………………………………………….69
3-3-4 樣品分析………………………………………………………...69
3-4實驗項目………………………………………………….70
3-4-1 溶劑性質對四丁基銨鹽飽和溶解度Cs之影響………………..70
3-4-2 四丁基銨鹽結構對其飽和溶解度Cs之影響…………………..70
3-4-3 溶劑性質對四丁基銨鹽之極限離子導電度 及離子對締合常數KA之影響……………………………………………………70
3-4-4 四丁基銨鹽結構對其極限離子導電度 及其離子對締合常數KA之影響……………………………………………………….71
3-4-5 溶劑性質對四丁基銨鹽分佈係數之影響……………………...71
3-4-6 四丁基銨鹽結構對其分佈係數之影響………………………...72
3-5實驗操作步驟…………………………………………….72
3-5-1 溶解度測定……………………………………………………...72
3-5-2 締合常數實驗…………………………………………………...73
3-5-3 分佈係數實驗…………………………………………………...73
第四章 結果與討論…………………………………..75
4-1 四丁基銨鹽之飽和溶解度 (CS)………………………...75
4-1-1 四丁基銨鹽陰離子對其飽和溶解度CS之影響………………..75
4-1-2 溶劑性質對四丁基銨鹽飽和溶解度之影響…………………..76
4-2 四丁基銨鹽之極限導電度 與締合常數KA………….77
4-2-1 四丁基銨鹽陰離子結構對其締合常數KA之影響……………..77
4-2-2 溶劑性質對四丁基銨鹽極限導電度 與締合常數KA之影響
…………………………………………………………………..77
4-2-2.1 溶劑性質對四丁基銨鹽極限導電度 之影響……………………….77
4-2-2.2 溶劑性質對四丁基銨鹽締合常數KA之影響…………………………….78
4-3 四丁基銨鹽之活性係數…………………………………78
4-4 四丁基銨鹽之分佈係數…………………………………79
4-4-1 溶劑性質對四丁基銨鹽分佈係數之影響……………………..79
4-4-2 濃度對四丁基銨鹽分佈之影響………………………………..80
第五章 結論……………………………………….123
參考文獻……………………………………………..126
參 考 文 獻
[1]王天財、黃定加與葉茂榮，“芐基氯之相轉移催化取代作用與溶劑對在兩相分佈之影響”，國立成功大學化工所七十九年博士論文.
[2]R. M. Fuoss and C. A. Kraus, “Properties of Electrolytic Solutions. IV. The Conductance Minimum and the Formation of Triple Ions Due to the Action of Colomb Forces”, J. Am. Chem. Soc., Vol.55, p.2387~2399, 1957.
[3]R. M. Fuoss and T. Shedlovsky, “Extrapolation of Conductance Data for Weak Electrolytes”, J. Am. Chem. Soc., Vol.71, p.1496~1498, 1949.
[4]E. Pitter, “An extension of the theory of the conductivity and viscosity of electrolyte solutions”, Proc. Roy. Soc. A, Vol.217, p.43~70, 1953.
[5]R. M. Fuoss, L. Onsager and J. F. Skinner, “The Conductance of Symmetrical Electrolytes. V. The Conductance Equation”, J. Phys. Chem., Vol.69, p.2571~2594, 1965.
[6]C. H. Springer, J. F. Coetzee and R. L. Kay, “Transference Number Measurements in Acetonitrile as Solvent”, J. Phys. Chem. Vol.73, No.3, 1969.
[7]R. M. Fuoss and K. L. Hsia, “Associayion of 1-1 salts in water”, Proc. Nat. Acad. Sci. U. S. A., Vol.57, p.1550~1557, 1967.
[8]J. C. Justic, “An Interpretation for the distance parameter of the Fuoss-Onsager conductance equation in the case of ionic association”, Electrochimica Acta., Vol.16, p.701~712, 1971.
[9]R. M. Fuoss, “Conductance-Concentration Function for the Paired Ion Model”, J. Phys. Chem., Vol.82, No.22, p.2427~2440, 1978.
[10]B. Das and D. K. Hazra,“Studies on the Viscosities, Conductances, and Adiabatic Compressibilities in 2-Methoxyethanol”, Bull. Chem. Soc. Jpn., Vol.65, No. 12, p.3470~3476, 1992.
[11]W. H. Lee and R. J. Wheaton, “Conductance of Symmetrical, Unsymmetrical and Mixed Electrolytes”, J. Chem. Soc., Faraday Trans. II, Vol.74, p.1456~1482, 1978.
[12]W. H. Lee and R. J. Wheaton, “Conductance of Symmetrical, Unsymmetrical and Mixed Electrolytes”, J. Chem. Soc., Faraday Trans. II, Vol.75, p.1128~1145,1979.
[13]J. O. Bockris and A. K. N. Reddy, “Modern Electrochemistry”, Plenum Publishing Company Ltd, 1977.
[14]S. Asai, H. Nakamura and Y. Furuichi, “The Distribution and Dissociation Equilibria of Phase-Transfer Catalyst Tricapryl -methylammonium Chloride and its Aqueous-Phase Mass”, J. Chem. Eng. Jap.,Vol.24, No.5, p.653~658, 1991.
[15]H. S. Wu, T. R. Fang and S. S. Meng, “Equilibrium and Extraction of Quaternary Salts in an Organic Solvent/Water System”, J. Chin. Inst. Chem. Engrs., Vol.29, No.2, p.99~108, 1998.
[16]S. Kusakabe, M. Shinoda and K. Kusafuka, “Ion Association of Tetrabutylammonium Halides in 1,1- and 1,2-dichloroethane and 4-methyl-2-pentanone”, Bull. Chem. Soc. Jpn., Vol.62, p.333~335, 1989.
[17]S. Kusakabe and Miwa Arai, “Solvent Extraction of Several Anions with Tetrabutylammonium Ion into 1,2-dichloroethane and Hydration of Anions in the Organic Phase”, Bull. Chem. Soc. Jpn., Vol.69, p.581~588, 1996.
[18]郭啟忠, “季銨鹽之溶解度及其在有機相-水相系統中之締合與分佈”, 國立中央大學化工碩士論文, 1996.
[19]S. Asai, H. Nakamura, M. Tanabe and K. Sakamoto, “Distribution and Dissociation Equilibria of Phase-Transfer Catalysts, Tetrabutylammonium Salts”, Ind. Eng. Chem. Res.,Vol.32, p.1438~1441, 1993.
[20]J. Barthel, M. Krell, L. Iberl and F. Feuerlein, “Conductance of 1-1 Electrolytes in Methanol Solutions from -45℃ to +25℃”, J. Electroanal. Chem., Vol.214, p.285~505, 1986.
[21]B. S. Krumgalz, “Ionic association in aqueous solution of salts with tetraalkylammonium ions”, Vol.73,74, p.133~145, 1997.
[22]M. R. Islam, I Ahmad and A. A. Ansari, “Applicability of Fuoss’s Conductance Equation to Dilute Electrolytic Solutions in Aqueous, Nonaqueous, and Aquo-Organic Mixture”, J. Electrochem. Soc., Vol.136, No.5, p.1303~1308,1989.
[23]A. A. Ansari and M. R. Islam, “Conductimetric studies of ionic association of tetraalkylammonium halides in iso-propanol+water mixture at 25℃. Part II.”, Can. J. Chem., Vol.66, p.1720~1727, 1987.
[24]R. M. Fuoss and C. A. Kraus, “Ionic Association. II. Several Salts in Dioxane-Water Mixtures”, J. Am. Chem. Soc., Vol.79, p.3304~3310, 1957
[25]E. Iwamoto, K. Ito and Y. Yamamoto, “Solute-Solvent Interactions in Ion-Pair Extraction of Tetraalkylammonium Iodides. 1. A New Approach to the Extraction Constant”, J. Phys. Chem., Vol.85, p.894~901, 1981.
[26]K. Ito, E. Iwamoto and Y.Yamamoto, “Solute-Solvent Interactions in Ion Pair Extraction of Tetraalkylammonium Iodides. II. The Effect of Hydration of Iodide in Organic Solvents on the Extraction Constant”, Bull. Chem. Soc. Jpn., Vol.55, p.2143~2146, 1982
[27]N. Papadopoulos and G. Ritzoulis, “The Conductance of Tetrabutylammonium Iodide in Toluene-Acetonitrile Mixture at 15, 25, and 35℃”, J. Sol. Chem., Vol.16, No.1, p.31~37, 1987.
[28]V. K. Syal, P. Bisht and P. C. Ranowt, “Conductance and viscosity measurements of some electrolytes in binary solvent mixtures of dimethylsulphoxide and dioxane at 25℃”, Collect. Czech. Chem. Commun.,Vol.56, p.1813~1832, 1991.
[29]D. E. Arrington and E. Griswold, “A Conductance Study of Quaternary Ammonium Halides”, J. Phys. Chem., Vol.74, No.1, p.123~128, 1970.
[30]D. S. Gill and J S. Cheema, “Conductance Measurements of some Electrolytes in N,N-Dimethylformamide and in Binary Mixture ofN,N-Dimethylformamide Containing Some Organic Bases and Acetonitrile”, Electrochimica Acta., Vol.6, p.775~758, 1982.
[31]P. G. Sears, E. D. Wilhoit and L. R. Dawson, “Conductance of some Quaternary ammonium Bromides and Iodides in dimethylformamide at 25℃”, J. Phys. Chem., Vol.59, p.373~375, 1955.
[32]D. S. Gill and A. N. Sharma, “Acetone+N,N-Dimethylformamide Solvent System”, J. Chem. Soc., Faraday Trans. 1.,Vol 78, p.465 ~474, 1982.
[33]A. K. Srlvastava and A. R. Desal, “Conductance Behavior of Some Potassium and Tetraalkylammonium Salfs in Solfolane+Water”, J. Chem. Eng. Data., Vol.37, p.322~327, No.3, 1992.
[34]M. Ue, “Mobility and Association of Lithium and Quaterm Ammonium Salts in Propylene Carbonate and -Butyrolactone.”, J. Electrochem. Soc., Vol.141, No.12, 1994.
[35]B. D. Gill, M. S. Chauhan and M. B. Sekhri, “Conductance and Viscosity Measurements of Tetrabutylammonium Tetraphenylboride in Non-aqueous Solvents at 25℃”, J. Chem. Soc., Faraday Trans., Vol.1, p.3461~3466, 1981.
[36]D. S. Gill and M. B. Sekhri, “New Approach to the Evaluation of Single-ion Conductances in Pure and Mixed Non-aqueous Solvents”, J. Chem., Faradary Trans. 1.,Vol.78, p.119~125, 1982.
[37]J. F. Coetzee and G. P. Cunningham, “Physical and Inorganic Chemistry”, J. Am. Chem. Soc., Vol.87, No.12, p.2529~2534,1965
[38]D. J. Mead, R. M. Fuoss and C. A. Kraus, “Properties of electrolytic solutions, XIX. Conductance of mixed electrolytes in ethylene chloride. Tetrabutyl- and tetraamethyl-ammonium picrates”, Chem. Rev., Vol.17, p.594~606, 1935.
[39]W. E. Thompson and C. A. Kraus, “Properties of electrolytic solutions. XXVII. The conductance of several quaternary ammonium salts in ethylene chloride at 25℃”, J. Am. Chem., Vol.69, p.1016~1020, 1947.
[40]H. Kakayama, “Solid-Liquid and Liquid-Liquid Phase Equilibria in the Symmetrical Tetreelkylammonium Halide-Water System”, Bull. Chem. Soc. Jpn., Vol.54, p.3717~3722, 1981.
[41]H. Talukder and K. K. Kundu, “Transfer Energetics of tetraalkylammonium Ions in Aquo-Organic System and the Solvent Effect on Hydrophobic Hydration”, J. Phys. Chem., Vol.96, p.970~975, 1992.
[42]H. Nakayama, H. Kuwata, N. Yamamoto, Y. Akagi and H. Matsui, “Solubilities and Dissolution States of a Series of Symmetrical Tetraalkylammonium Salts in water”, Bull. Chem. Soc. Jpn., Vol.62, p.985~992, 1989.
[43]J. Steigman and J. Dobrow, “The Interaction of antagonistic and Cooperative Electrolytes in Water at 25℃. A Hypothesis Concerning Anion-Exchange Resins”, J. Phys. Chem., Vol.72, No.10, p.3432~3436, 1968.
[44]F. Franks and D. L. Clarke, “Solubilities of alkyammonium Iodides”, J. Phys. Chem., Vol. 71, No.4, p.1155~1156,1966.
[45]G. M. Goldberg and A. A. Vernon, “The solubility of Quaternary Ammonium Salts in Methanol-Benzene Mixture. The Anomalous Behavior of Tetraethylammonium Iodide ”, J. Am. Chem. Soc., Vol.73, p.2845~2846, 1951.
[46]高志宏, “鹵化四丁基銨之合成動力學、溶解、萃取及精製研究”, 國立中央大學化工碩士論文,2000.
[47]K. S. Pitzer, “Thermodynamics of Electrolytes. 1. Theoretical Basis and General Equations”, J. Phys. Chem., Vol.77, No.2, p.268~277, 1972.
[48]S. Lindenbaum and G. E. Boyd, “Osmotic and Activity Coefficients for the Symmetrical Tetraalkyl Ammonium Halides in Aqueous Solution at 25℃”, J. Phys. Chem., Vol.68, No.4, p.911~917, 1964.
[49]W. Y. Wen, S. Saito and C. M. Lee, “Activity and Osmotic Coefficients of Four Symmetrical Tetraalkylammonium Fluorides in Aqueous Solutions at 25℃”, J. Phys. Chem., Vol.70, No.4, p.1244~1248, 1966.
[50]S. Motomizu, “Relative extractabilities of cations and anions in the extraction constants from chemical structure”, Bunseki Kagaku, Vol.33, p.31~36, 1984.
[51]S. Motomizu, S. Hanada and K. Toei, “Liquid-Liquid distribution behavior of quaternary ammonium salts”, Bunseki Kagaku, Vol.32, p.648~653, 1983.
[52]E. V. Dehmlow and S. S. Dehmlow, “Phase Transfer Catalysis”, VCH Publishers, Inc., New York, NY(USA),1993.
[53]E. Iwamoto, H. Ohmorl and Y. Yamamoto, “Solute-Solvent Interactions in Ion-Pair Extraction of Tetraalkylammonium Iodides. 3. The Role of Relative Permittivity and Solubility Parameter in Nitrobenzene-Tetrachloromethane Mixtures at 25℃”, J. Phys. Chem., Vol.87, p.1776~1782, 1983.
[54]Y. Takeda and Y. Matsumoto, “Thermodynamic study on solvent Extraction of 18-crown-6-alkali Metal Ion Complexes and tetraalkylammonium Ions with Picrate Anions into Benzene”, Bull. Chem. Soc. Jpn., Vol.60, p.2313~2317, 1987.
[55]R. A. Robinson and R. H. Stokes, “Electrolyte solutions”, London butter worths, 1959.
[56]B. S. Krumgalz, “Dimensions of Tetra-alkyl(aryl)onium Ions”, J. Chem. Soc., Faraday Trans. 1., Vol.78, p.437~449, 1982.
[57]D. S. Gill, “New Approach for the Evaluation of Single-ion Conductances in Pure and Mixed Non-aqueous Solvents”, J. Chem. Soc., Faraday Trans. 1., Vol.77, p.751~758, 1981.
[58]P. K. Muhuri and D. K. Hazra, “Electrical Conductances for some Tetraalkylammonium Bromides, Lithium Tetrafluoroborate and Tetrabutylammonium tetrabutylborate in Propylene Carbonate at 25℃”, J. Chem. Soc. Faraday Trans., Vol. 87, No.21, p.3511~ 3513, 1991.
[59]D. S. Gill, “Evaluation of Solvated radii of ions in non-aqueous solvents”, Electrochimica Acta., Vol.24, p.701~703, 1979.
[60]L. Pauling, “The Nature of The Chemical Bond”, Cornell university press. Ithaca, New York, 1969.
[61]劉叔杰, “丙烯基氯之相轉移催化水解以合成丙烯醇/丙烯醚之研究” 國立中央大學化工碩士論文, 1993.
[62]J. Brandrup, E. H. Immergut, E. A. Grulke and D. R. Bloch, “Polymer Handbook4th”, A wiley-interscience publication, 1999.
[63]L. A. Prausnitz, “Molecular Thermodynamics of Fluid-Phase Equilibria”, Prentice Hall, Englewood cliffs New Jersey..
[64]M. W. Hauna, B. E. Dickersor and W. C. Gardiner, “Molecular Thermodynamics”, 歐亞書局, 1969
[65]H. J. Noggle, “Physical Chemistry”, Scott, Foresma, Company Co., New York, 1989.
[66]K. J. Laider and J. H. Meiser, “Physical Chemistry”, 歐亞書局,1989.
[67]J. A. Riddick and W. B. Banger, “Thechniques of Chemistry Volume II Organic Solvents”,1970.