臺灣博碩士論文加值系統

芳香醇類和我們日常生活中息息相關，例如它們常被加在香料、香水、合成精油、化妝品及工業溶劑中。在本研究中我們將測量兩種芳香醇類在異丙醇溶液中的一些物理性質。
在常壓下，我們測量三成份系統：異丙醇+苯甲醇+2-苯乙醇在溫度308.15 K以及雙成份系統異丙醇+苯甲醇、異丙醇+2-苯乙醇、苯甲醇+2-苯乙醇在溫度298.15 K、308.15 K、318.15 K下的密度、黏度、折射率與表面張力。密度是以震盪管式密度計測量，黏度是以Ubbelholde毛細管黏度計測量，折射率是以數位式Abbe型測量儀測量，表面張力則是以Wilhelmy-plate方式測量。雙成分的過剩體積、黏度偏差、折射率偏差以及表面張力偏差是以Redlich-Kister方程式來關聯，並且利用McAllister三分子模型和四分子模型來關聯雙成分的運動黏度。三成份系統則利用Jasinski and Malanowski 方程式、Cibulka 方程式、Singh 方程式、Pintos方程式, Calvo方程式和其他衍生出來的方程式來做數據關聯。

The flavor alcohols are vitally intererelated to our daily lives. The flavor alcohols are the essential compounds contained in flavoring, perfumery, artifical essences, cosmetics, and industrial solvents. In this study, we measured the physical properties of two kinds of flavor alcohols in the isopropanol solution.
Densities, viscosities, refractive indexes and surface tensions of the ternary system isopropanol + benzyl alcohol + 2-phenylethanol at T = 308.15 K and the binary systems isopropanol + benzyl alcohol, isopropanol + 2-phenylethanol and benzyl alcohol + 2-phenylethanol at T = (298.15, 308.15, 318.15) K and atmospheric pressure over the whole composition range. Densities were determined using a vibrating-tube density meter. Viscosities were measured with an automatic Ubbelholde capillary viscometer. Refractive indices were measured using a digital Abbe-type refractometer.Surface tensions were determined by the Wilhelmy-plate method. Excess molar volume VE, deviations in the viscosity Δη, deviations in the refractive indexes ΔxnD, Δ nD, and ΔR, deviations in the surface tensions Δxσ and Δσ for the binary mixtures were correlated with the liquid composition using the Redlich-Kister equation. The kinematic viscosity of binary data were correlated using McAllister Three-Body and Four-Body-Interaction models. For the ternary data, several polynomial equations have been tested to minimize the set of parameters for adequate correlation. The Jasinski and Malanowski equation, Cibulka equation, Singh equation, Pintos equation, Calvo equation, and other extender equations were individually used to correlate ternary data.

中文摘要．．．．．． ．．．．．．．．．．．．．．．I
英文摘要．．．．．．．．． ．．．．．．．．．．．．II
目錄．．．．．．．．．．．．．． ．．．．．．．．．III
表目錄．．．．．．．．．．．．．．．．．．．．．．．V
圖目錄．．．．．．．．．．．．．．．．．．．．．．．XII
符號表．．．．．．．．．．．．．．．．．．．．．．．XXIII
主文
第一章 緒論．．．．．．．．．．．．．．1
第二章 理論與回顧．．．．．．．．．．．．．．．．．．．．． 3
2.1 密度基本原理與回顧．．．．．．．．．．．．．．．3
2.1-1密度測量之儀器．．．．．．．．．．．．．．．．．7
2.2 液體黏度之基本原理．．．．．．．．．．．．．．．12
2.2-1黏度測量之儀器．．．．．．．．．．．．．．．．．21
2-3 液體折射率之基本原理．．．．．．．．．．．．．．32
2.3-1折射率測量之儀器．．．．．．．．．．．．．．．．40
2.4 液體表面張力之基本原理．．．．．．．．．．．．．43
2.4-1表面張力測量之儀器．．．．．．．．．．．．．．．46
第三章 實驗部份．．．．．．．．．．．．．．．．．．．．． 52
3.1 實驗設備．．．．．．．．．．．．．．．．．．．52
3.2 實驗藥品來源、純度與實驗條件．．．．．．．．．69
3.3 測量前準備．．．．．．．．．．．．．．．．．．72
3.4 實驗步驟．．．．．．．．．．． ．．．．76
第四章 結果與討論
4.1 雙成分的實驗數據之迴
歸．．．．．．．．．．．． 86
4.1-1 密度實驗值ρ及過剩體積VE的討論．．．．．．． 87
4.1-2 黏度實驗值η及黏度偏差Δη的討論．．．．．．．89
4.1-3 折射率nD和莫爾折射R與折射率偏差ΔxnD
、Δ nD與莫爾折射偏差ΔR的討論．．．． ．90
4.1-4 表面張力實驗值σ與表面張力偏差Δxσ與Δ σ
的討論．．．．．．．．．．．94
4.2 雙成分的運動(kinematic)黏度數據及迴歸．．99
4.3 三成份的過剩性質及數據之廻歸．．．．．．．103
第五章 結論．．．．．．．．．．．．．．．．．．．．．．112
參考文獻．．．．．．．．．．．．．．．．．．．．．．．．．． 290

參考文獻
(1)賴耿陽，實用香料化學，復漢出版社，民國八十七年。

(2)Vargaftik, N. B. Tables on the Thermophysical Propperties of Liquids and Gases.Hemisphere Publishing. New York, 1975.

(3)Meyer, E. F.; Wanger, R. E. Cohesive Energies in Polar Organic
Liquids. J. Phys. Chem. 1976, 70, 3162-3168.

(4) Weast, R. C. Handbook of Chemistry and Physics. CRC Press. Inc.
Ohio. 1976.

(5) Reid, R. C.; Prausnitz, J. M.; Sherwood, T. K. The Properties of
Gases and Liquids. McGraw-Hill. New York, 1977.

(6) Rackett, H. G. Equation of State for Saturated Liquids. J. Chem.
Eng. Data 1970, 15, 514-517.

(7) Yamada, T.; Gunn, R. C. Saturated Liquid Molar Volumes. Rackett
Equation. J. Chem. Eng. Data 1973, 18, 234-236.

(8) Krevelen, V.; Hoftyzer, D. W. Properties of Polymers. Correlation
with Chemical Structure. Elsevier Scientific: Amsterdam. 1972, 4,
41-65.

(9) Elbro, H. S.; Fredenslund, A.; Rasmussen, P. Group Contribution
Method for the Prediction of Liquid Densities as a Function of
Temperature for Solvents, Oligomers, and Polymers. Ind. Eng.
Chem. Res. 1991, 30, 2576-2582.

(10) 賴雅韻，官能基貢獻方法應用於有機化合物液體密度之預測，
碩士論文，靜宜大學應用化學研究所，民國七十八年。

(11) 江漢全，儀器分析：黏度測量儀器，東大圖書公司，民國九十年。

(12) Bauer, N.; Lewin, S. Z. Physical Methods of Organic Chemistry. A.
Weissberger., Ed. Interscience. New York, 1959, 3,131-75.

(13) Gibson, R. E. The System Sodium Sulphate-Water: I. The Densities
and Specific Volumes of Aqueous Solutions of Sodium Sulphate
Between 25 and 40°, and the Fictive Volumes of Sodium Sulphate in
Solution. J. Phys. Chem. 1927, 31, 496-510.

(14) Pesce, B.; Hoelemann, P. Z . Elektrochem. 1934, 40, 1

(15) Gibson, R. E.; Loreffler, O. H. Pressure-Volume-Temperature
Relations in Solutions. II. The Energy-Volume Coefficients of
Aniline, Nitrobenzene, Bromobenzene and Chlorobenzene. J. Am.
Chem. Soc. 1939, 61, 2515-2521.

(16) 彭一航，模擬汽油與含氧化合物添加劑的熱力學性質，碩士論
文，靜宜大學應用化學研究所，民國九十一年。
(17) 陳慧玟，摻合辛烷值提升劑在汽油碳氫化合物中的混和性質，碩
士論文，靜宜大學應用化學研究所，民國九十四年。
(18) 許先志，利用基團貢獻方法預測純益體黏度，碩士論文，靜宜
大學應用化學研究所，民國八十六年。

(19) Lucas, K. Chem. Ing. Tech. 1981, 53, 959.

(20) Andrade, E. M. da C. Phil. Mag. 1934, 17, 497 & 698.

(21) Vogel, H.; Weiss A. Ber. Bunsenges. Phys. Chem. 1981, 85, 539.

(22) Goletz, E.; Tassios, D. Ind. Eng. Chem. Process Design. Develop.
1977, 16, 75.

(23) Cohen, M. H.; Turnbull, D. Molecular Transport in Liquids and
Glasses. J. Chem. Phys. 1959, 31, 1164-1169.

(24) Glasstone, S.; Laidler, K. J.; Eyring, H. The Theory of Rate
Processes. McGraw-Hill. New York, 1941.

(25) 陳美如，液體混合物黏度的計算，碩士論文，台灣大學化學工
程研究所，民國八十年。
(26) Macedo, P. B.; Litovitz,T. A. On the Relative Roles of Free Volume
and Activation Energy in the Viscosity of Liquids. J. Chem. Phys.
1965, 42, 245-256.

(27) Grunberg, L.; Nissan, A. H. Mixture Law for Viscosity. Nature.
1949, 164, 779-780.

(28) Wei, I. C.;Rowley, R. L. A Local Composition Model for
Multicomponent Liquid Mixture Shear Viscosity. Chem. Eng.
Sci. 1985, 40, 401-408.

(29) Poling, B.E.; Prausnitz, J. M.; O´Connell J. P. The Properties of
Gases And Liquids. McGraw-Hill. 2001, 8, 17.

(30) Vogel,H.; Weiss,A. Ber. Bunsenges. Phys. Chem. 1982, 86, 193.

(31) Teja, A. S.; Rice, P. Generalized Corresponding States Method
for the Viscosities of Liquid Mixtures. Ind. Eng. Chem. Fundam.
1981, 20, 77-81.

(32) Pikkarainen, L. Densities and Viscosities of Binary Solvent Mixture
of N-Methylacetamide with Aliphatic Alcohols. J. Chem. Eng. Data
1983, 28, 381-383.

(33) Cao, W. A. Fredenslund and P. Rasmussen, Statistical
Thermodynamic Model for Viscosity of Pure Liquids and Liquid
Mixtures. Ind. Eng. Chem. Res. 1992, 31, 2603-2619.

(34) Wu, D. T. Prediction of Viscosities of Liquid Mixtures by a Group
Contribution Method. Fluid. Phase. Equilib. 1986, 30, 149-156.

(35) Chevallier, J. L.; Petrino, P. J.; Gaston-Bonhomme,Y. Estimation
Mothod for the Kinematic Viscosity of A Liquid-Phase Mixtures.
Chem. Eng. Sci. 1988, 43, 1303-1309.

(36) Liu, H. Q.;Wang, W. C.; Chang,C. H. Model with
Temperature-Independent Parameters for the Viscosities of Liquid
Mixtures. Ind. Eng. Chem. Res. 1991, 30, 1617-1624.

(37) McAllister, R. A. The Viscosity of Liquid Mixtures. AIChE J. 1960,
6, 427-431.

(38) Heric, E. L. On the Viscosity of Ternary Mixtures. J. Chem. Eng.
Data 1966, 11, 66-68.

(39) Irving, J. B. Viscosities of Binary Liquid Mixtures：A survey of
Mixture Equations. Natl. Eng. Lab. Rept. 1977, 630.

(40) Katti, P. K.; Chaudhri,M. M. Viscosities of Binary Mixtures of
Benzyl Acetate with Dioxane, Aniline, and m-Cresol. J. Chem. Eng.
Data 1964, 9, 442-443.

(41) Hwang, M. J.;Whiting,W. B. A Corresponding States Treatment
for the Viscosity of Polar Fluids. Ind. Eng. Chem. Res. 1987, 26,
1758-1766.

(42) 劉健運，硝基甲烷與醇類液體混合物密度及黏度的測量，碩士
論文，靜宜大學應用化學研究所，民國八十八年。

(43) 李樹田，塑膠e學苑 psdn.pidc.org.tw，塑膠物語：黏度計簡介。

(44) Ma, R. F.; Shi, L.; Duan Y.Y.; Han, L. Z.; Liu, N.X. Saturated
Liquid Viscosity of Cyclopentane and Isopentane. J. Chem. Eng.
Data 2003, 48, 1418-1421.

(45) 丹東市百特儀器有限公司 www.bettersize.com/index.asp，基本理
論，沉降法粒度测試技術及應用。
(46) 周澤川編著，化工儀器，東大圖書公司，民國八十七年。

(47) 邱承美編著，陶金華校訂，儀器分析原理(修訂版)，科文出版
社，民國七十六年。
(48)葉和明編著，基礎化工，東大圖書公司，民國七十九年。

(49) Riddick, A.; Bunger, W. B.; Sakano, T. K. Organic Solvents,
Physical Properties and Method of Purification. Wiley Interscience:
New York, 1986, 4.

(50) Ruostesuo, P.; Mattila, T. Thermodynamic Properties of Binary
Mixtures Containing Sulfur Amide. 2. Excess Molar Volumes of 1,4-
Dioxane + N,N-Dimethymethanesulfinamide and 1,4-dioxane +
N-methylmethanesulfinamide. J. Chem. Eng. Data 1987, 32,
241-243.

(51) Mohammad M. H. Bhuiyan, Kazuhiro Tamura,* and Toshiro Yamada. Excess Molar Enthalpies for Ethanol + 2-Propanol + Methyl tert-Butyl Ether and 1-Propanol + 2-Propanol + Methyl tert-Butyl Ether at the Temperature of 298.15 K. J. Chem. Eng. Data 2001, 46, 1499-1503

(52) Tamura, K.; Saito, M.; Yamada, T. Ternary Excess Molar Enthalpies
for Methanol or Ethanol + 1-Propanol + 2-Propanol at the Temperature 298.15 K. J. Chem. Eng. Data 1999, 44, 626-
630.

(53) Contreras S., M. Densities and Viscosities of Binary Mixtures of 1,4-Dioxane with 1-Propanol and 2-Propanol at (25, 30, 35, and 40) ℃. J. Chem. Eng. Data 2001, 46(5), 1149-1152.
(54) Amalendu Pal* and Gurcharan Dass Excess Molar Volumes and Viscosities for Binary Liquid Mixtures of 2-Propoxyethanol and of 2-Isopropoxyethanol with Methanol, 1-Propanol, 2-Propanol, and 1-Pentanol at 298.15 K. J. Chem. Eng. Data 2000, 45, 693-698

(55) Rodriguez, A.; Canosa, J.; Dominguez, A.; Tojo, J. Dynamic viscosities of diethyl carbonate with linear and secondary alcohols at several temperatures. J. Chem. Eng. Data 2004, 49, 157-162.

(56) Gangfeng Ouyang,* Zhongqi Huang, Jiamin Ou, Wenqian Wu, and Beisheng Kang. Excess Molar Volumes and Surface Tensions of Xylene with 2-Propanol or 2-Methyl-2-propanol at 298.15 K. J. Chem. Eng. Data 2003, 48, 195-197.

(57) Saeid Azizian* and Nowrouz Bashavard. Surface Tension of Dilute Solutions of Linear Alcohols in Benzyl Alcohol. J. Chem. Eng. Data 2005, 50(4), 1303-1307.

(58) Lange’s Handbook of Chemistry, 13th ed.; Dean, J. A., Lange, N.
A., Eds.; McGraw-Hill Inc.: New York, 1985.

(59) Doz, M. B. G.; Solimo, H. N. Excess Molar Volume and Excess
Viscosity of Benzyl Alcohol + 4-Hidroxy-4-Methyl-2-Pentanone
and Water + 4-Hidroxy-4-Methyl-2-Pentanone Binary Systems
at 298.15 K. Phys. Chem. Liq. 1995, 29, 79-86.

(60) Saeid Azizian* and Nowrouz Bashavard. Equilibrium Surface Tensions of Benzyl Alcohol + Ethylene Glycol Mixtures. J. Chem. Eng. Data 2005, 50(2), 709-712.

(61) Sorkau, V. W. Zur Kenntnis de U¬ berganges von der geordneten
zur Turbulenzstro¨mung in Kapillarro¨hren. I. Phys. Z. 1914, 15,
768-772.

(62) TRC Databases for Chemistry and Engineering-SOURCE Database,
Version 1998-2. B-1880, 1965. Thermodynamic Research Center: Texas A&M University System, College Station, TX,1998.

(63) Glinski, J.; Chavepeyer, G.; Pletten, J.-K. Surface Properties of
Dilute Aqueous Solutions of Cyclohexyl and Benzyl Alchols and
Amines. New J. Chem. 1995, 19, 1165.

(64)Pandharinath S. Nikam* and Sanjeevan J. Densities and Viscosities of Binary Mixtures of N,N-Dimethylformamide with Benzyl Alcohol and Acetophenone at (298.15, 303.15, 308.15, and 313.15) K. J. Chem. Eng. Data 2003, 48, 1291-1295.

(65) Redlich, O.; Kister, A. T. Thermodynamics of Nonelectrolyte
Solutions. Algebraic Representation of Thermodynamic Properties
and the Classification of Solutions. Ind. Eng. Chem. 1948, 40,
345-348.

(66) Treszczanowicz, A. J.; Kiyohara, O.; Benson, G. C. Excess volume
for n-Alkanols + n-Alkanes Ⅳ. Binary Mixture of Decane-1-ol +
n-Pentane, + n-Hexane, + n-Octane, + n-Decane, and +
n-Hexadecane. J. Chem. Thermodyn 1981, 13, 253-260.

(67) Brocos,P.; Pineiro, A.; Bravo, R.;Amigo, A. Refractive Indices, Molar Volumes and Molar Refractions of Binary Liquid Mixtures: Concepts and Correlations. Phys. Chem. Chem. Phy . 2003, 5, 550–557

(68) Pilar Brocos, AÄ ngel Pin˜ eiro, Ramo´n Bravo, and Alfredo Amigo*. Thermodynamics of Mixtures Involving Some Linear or Cyclic Ketones and Cyclic Ethers. 1. Systems Containing Tetrahydrofuran. J. Chem. Eng. Data 2002, 47, 351-358.

(69)Jasinski,B;Malanowski, S. Chem.Eng.Sci. 1970, 25.913-920.

(70)Cibulka, I. Collect. Czech. Chem. Commun.1982, 47. 1414-1419.

(71)Singh,P.P.;Nigam, R.K.;Sharma,S.P.;Aggarwal,S. Fluid. Phase.Equil. 1984, 18.333-344.

(72)Pintos,M.;Amigo,A.;Bravo,R.;Calvo,E. J Chem. Thermodyn. 1994,26.803-807.

(73)Calvo,E.;Cadtro,I.;Pintos,M.;Amigo,A.;Bravo,R.J.Chem.Thermodyn.1995,27.1221-1226.

(74)Mascato,E.;Mosteiro,L,;Pineiro,M.M,;Garci’a,J.;Iglesias,T.P.;Legido,J.L.Thermodynamic Properties of Mixing for (1-alkanol + a n-Alkane + a Cyclic Alkane) at T = 298.15 K.I.(n-Hexane + Cyclohexane + 1-Butanol). J Chem. Thermodyn.2001,33.269-286.