臺灣博碩士論文加值系統

本研究使用高壓震盪管密度儀分別測量寡聚物溶液在溫度介於298.15 K-348.15 K，壓力高達50 MPa的密度數據，這些混合物包含了由兩種溶劑茴香醚與苯乙酮和兩種寡聚物聚乙二醇單月桂酸酯與聚乙二醇壬基苯基醚所組成的四組雙成分系統。實驗所量取的密度數據，均可用Tait模式和一半經驗模式準確關聯。
由實驗所得之密度數據，計算出不同條件下之過剩體積。苯乙酮＋聚乙二醇壬基苯基醚系統過剩體積與組成之關係圖呈現S形狀。茴香醚＋聚乙二醇單月桂酸酯和苯乙酮＋聚乙二醇單月桂酸酯在整個組成範圍之過剩體積皆為負值。茴香醚＋聚乙二醇壬基苯基醚在所有組成範圍的過剩體積為正值。這些混合物在定溫及定壓條件下之過剩體積與組成之關係可用Redlich-Kister模式表示。
實驗所量取之雙成分PVT數據均用FOV (Flory-Orwoll-Vrij)與Schotte狀態方程式關聯，各系統之雙成分交互作用參數分別由雙成分之 PVT 數據，擬合狀態方程式訂定。

In this study, we used a high-pressure vibrating tube densimeter
to measure the densities of oligomeric solutions at temperatures from 298.15 K to 348.15 K and pressures up to 50 MPa. The investigated mixtures included four binary systems containing two solvents : anisole and acetophenone and two oligomeric materials : polyethylene glycol mono-laurate (PEGML) and polyethylene glycol mono-4-nonylphenyl ether (PEGNPE). The Tait equation and a semi-empirical model can correlate accurately the experimental density data over the entire
pressure range.

The excess volumes were calculated from the experimental density
data. It was found that the excess volumes varied with composition in
an S shape for acetophenone + PEGNPE. Over the entire composition range, the excess volumes are negative for anisole + PEGML and acetophenone + PEGML mixtures, and positive for anisole + PEGNPE. The Redlich-Kister model represented well the excess volumes varying
with composition at specific temperature and pressure.

The FOV (Flory-Orwoll-Vrij) and the Schotte equations of state
were also employed to correlate the PVT data. The binary interaction
parameter for each binary system was determined by fitting the binary
PVT data to the equations of state.

中文摘要 Ⅰ
英文摘要 Ⅱ
誌謝 Ⅲ
目錄 Ⅴ
圖表索引 Ⅶ


第一章 緒論 1

1-1 前言 1
1-2 液體密度的量測 2
1-3 應用於高分子系統的模式回顧 2
1-4 高分子溶液及其摻合物系統熱物性質量測文獻回顧 7
1-5 研究動機與範圍 9
1-6 本文各章要點 11


第二章 寡聚物混合溶液之高壓密度量測 13

2-1 液體密度量測裝置 13
2-2 實驗操作步驟 14
2-3 待測系統及量測之條件 15
2-4 密度儀校正 17
2-5 實驗結果與討論 19


第三章 數據關聯 110
3-1 Flory-Orwoll-Vrij (FOV) 狀態方程式 110
3-2 Schotte狀態方程式 111
3-3 混合律與雙成分交互作用參數 112


第四章 結論與建議 123

4-1 結論 123
4-2 建議 124


參考文獻 126
符號說明 137

Acevedo, I. L., L. Lugo, M. J. P. Comuñas, E. L. Arancibia, and J. Fernández, " Volumetric Properties of Binary Tetraethylene Glycol Dimethyl Ether + Heptane Mixtures between (278.15 and 353.15) K and up to 25 MPa," J. Chem. Eng., Vol. 48, pp. 1271-1278 (2003).
Aminabhavi, V.A., T.M. Aminabhavi, and R. H. Balundgi, "Evaluation of Excess Parameters from Densities and of Binary Mixtures of Ethanol with Anisole, N,N-Dimethylformamide, Carbon Terachloride, and Acetophenone from 298.15 to 313.15 K," Ind. Eng. Chem. Res., Vol. 29, pp.2106-2111(1990).
Aucouturier, C., G. Roux-Desgranges, and A. H. Roux, "Excess Molar Volumes and Excess Molar Heat Capacities of (Polyethylene Glycols + Water) at Temperatures between T = 278 K and T = 328 K, " J. Chem. Thermodyn., Vol. 31, pp. 289-300 (1999).
Aurora, C., S. M. Cancho, R. G. Rubio, and A. C. Colin, "Equation of State of Hydrogen-Bonded Polymer Solutions: Poly(4-hydroxystyrene) + Ethanol and + Tetrahydrofuran," J. Phys. Chem., Vol. 99, pp. 10261 -10266 (1995).
Barker, J. A., "Lattice Theories of the Liquid State," in International Encyclopedia of Physical Chemistry and Chemical Physics, Topic 10, Pergamon, New York, 1963.
Bessières, D., H. Saint-Guirons, and J.-L. Daridon, "Volumetric Behavior of Decane + Carbon Dioxide at High Pressures. Measurement and Calculation, " J. Chem. Eng. Date, Vol. 46, pp. 1136-1139 (2001).
Colin, A. C., S. M. Cancho, R. G. Rubio, and A. Compostizo, "Equation of State of Hydrogen-Bonded Polymer Solutions. Poly(propylene glycol)＋n-Hexane and Poly(propylene glycol)＋Ethanol," Macromolecules, Vol. 30, pp. 3389-3394 (1997).
Colin, A. C., R. G. Rubio, and A. Compostizo, "Equation of State of a Blend of Water-Soluble Polymers: Poly(propylene glycol) + Poly(ethylene glycol)," J. Chem. Eng. Data, Vol. 41, pp. 7407-7414 (2000).
Comuñas, M. J. P., A. Baylaucq, C. Boned, and J. Fernández," PρT Measurements of Polyethylene Glycol Dimethylethers between 278.15 and 328.15 K at Pressures to 12 MPa," Int. J. Thermophys., Vol. 4, pp. 831-851 (2000).
Comuñas, M. J. P., A. Baylaucq, C. Boned, and J. Fernández," Volumetric Properties of Monoethylene Glycol Dimethyl Ether and Diethylene Glycol Dimethyl Ether up to 60 MPa," J. Chem. Eng., Vol. 48, pp. 1044-1049 (2003).
Dean, J. A., Lange’s Handbook of Chemistry, 14th ed., McGraw-Hill,
Inc., New York, 1992.

Dominik, A., S. Jain, and W. G. Chapman, "New Equation of State for Polymer Solutions Based on the Statistical Associating Fluid Theory (SAFT)-Dimer Equation for Hard-Chain Molecules, " Ind. Eng. Chem. Res., Vol. 46, pp. 5766-5774 (2007).
Eliassi, A., M. Rahbari-Sisakht, and M. Taghizadeh , "Densities and Viscosities of Binary Mixtures of Poly(ethylene glycol) and Poly(propylene glycol) in Water and Ethanol in the 293.15-338.15 K Temperature Range," J. Chem. Eng. Data, Vol. 48, pp. 1221-1224 (2003).
Fandiño, O., A. S. Pensado, L. Lugo, M. J. P. Comuñas, and J. Fernández, " Compressed Liquid Densities of Squalane and Pentaerythritol Tetra(2-ethylhexanoate), " J. Chem. Eng. Data, Vol. 50, pp. 939-946 (2005).
Fernandez, J., O. Fandino, J. Garcıa, M. J. P. Comunas, and E. R. Lopez, " PρT Measurements and Equation of State (EoS) Predictions of Ester Lubricants up to 45 MPa," Ind. Eng. Chem. Res., Vol. 45, pp. 1172-1182 (2006).
Flory , P. J., R. A. Orwoll, and A. Vrij, "Statistical Thermodynamics of Chain Molecule Liquids. I. An Equation of State for Normal Paraffin Hydrocarbons," J. Amer. Chem. Soc., Vol. 86, pp. 3507-3514 (1964).
Garg, S. K., Banipal, T. S. and Ahluwalia, J. C. "Densities, Molar Volumes, Cubic Expansion Coefficients, and Isothermal Compressibilities of 1-Alkanols from 323.15 to 373.15 K and at Pressures up to 10 MPa," J. Chem. Eng. Data, Vol. 38, pp. 227-230 (1993).
Geyer, H., P. Ulbig, M. Görnert, and A. Susanto, "Measurement of Densities and Excess Molar Volumes for (1,2-Propanediol, or 1,2-Butanediol + Water) at the Temperatures (288.15, 298.15, and 308.15) K and at the Pressures (0.1, 20, 40, and 60) MPa, " J. Chem. Thermodyn., Vol. 33, pp. 987-997 (2001).

Ghonasgi, D., and W. G. Chapman, "A New Equation of State for Chain Molecules, " J. Chem. Phys., Vol. 100, pp. 6633-6639 (1994).

Goharshadi, E. K., and A. R. Berenji, " Prediction of Thermodynamic Properties of Polymeric Liquids Using a New Equation of State, " Polymer, Vol. 47, pp. 4726-4733 (2006).

Goharshadi, E. K., and F. Moosavi, "Prediction of Thermodynamic Properties of Some Hydrofluoroether Refrigerants Nsing a New Equation of State, "
Fluid Phase Equilib., Vol. 238, pp. 112–119 (2005).

Gomes, J., N. Henderson, and M. Rocha, "Modelling the Vapor-Liquid Equilibrium of Polymer Solutions Using a Cubic Equation of State," Macromolecular Theory and Simulations, Vol. 10, pp. 816-826 (2001) .

Gross, J., and G. Sadowski, " Perturbed-Chain SAFT: An Equation of State Based on a Perturbation Theory for Chain Molecules, " Ind. Eng. Chem., Res., Vol. 40, pp. 1244-1260 (2001).
Haar, L., J. S. Gallagher, and G. S. Kell, NBS/NRC Steam Tables: Thermodynamic and Transport Properties and Computer Programs for Vapor and Liquid States of Water in SI Units, Hemisphere, New York, 1984.
Harmony, S. C., D. C. Bonner, and H. R. Heichelheim, "Calculation of Phase Equilibria for Ethylene/Low Density Polyethylene Mixtures," AIChE J., Vol. 23, pp. 758-764 (1977).
Huang, S. H., and M. Radosz, "Equation of State for Small, Large, Polydisperse, and Associating Molecules," Ind. Eng. Chem. Res., Vol. 29, pp. 2284-2294 (1990).
Huh, J. Y. and Y. C. Bae, " Vapor-Liquid Equilibria of Polymer Solutions by Group-Contribution Method : Applicability of Modified Double Lattice Model," Macromol. Chem. Phys., Vol. 202, pp. 1466-1471 (2001).
Jeon, K. S., K. Char, D. J. Walsh, and E. Kim, "Thermodynamics of Mixing Estimated by Equation-of-State Parameters in Miscible Blends of Polystyrene and Tetramethylbisphenol-A Polycarbonate, " Polymer, Vol. 41, pp. 2839-2845 (2000).
Kinart, C. M., W. J. Kinart, A. Ćwilińska, and M. Klimczak,"Excess Molar Volumes of the Binary Mixtures of Polyethylene Glycol 300 with Ethoxyethanols at Various Temperatures," J. Chem. Thermodyn., Vol. 38 , pp. 1017-1024 (2006).
Kirinčič, S. and C. Klofutar, "A Volumetric Study of Aqueous Solutions of Poly(ethylene glycol)s at 298.15 K, " Fluid Phase Equilib., Vol. 149, pp. 233-247(1998).
Kuus, M., H. Kirss, E. Siimer, and L. Kudryavtseva, "Excess Enthalpies for the Systems o-Xylene + Cyclohexanol + Phenol and o-Xylene + Cyclohexanol + 1,3-Butanediol at 318.15 K, " J. Chem. Eng. Data, Vol. 43, pp. 351-353 (1998).
Lagourette, B., C. Boned, H. Saint-Guirons, P. Xans, and H. Zhou, " Densimeter Calibration Method Versus Temperature and Pressure," Meas. Sci. Technol., Vol. 3, pp. 699-703 (1992).
Lee, M. J., K. L. Ho, and H. M. Lin, "Pressure-Volume-Temperature Properties for Binary Oligomeric Solutions of Poly(ethylene glycol) and Poly(ethylene glycol methyl ether) with Acetophenone up to 50 MPa," J. Chem. Eng. Data, Vol. 51, pp. 1115-1121 (2006).
Lee, M. J., T. S. Hsu, and H. M. Lin, "Pressure-Volume-Temperature Properties for 1-Octanol +Acetophenone, Poly(propylene glycol) + 1-Octanol + Acetophenone, and Poly(ethylene glycol) + Poly(ethylene glycol methyl ether) +Anisole," J. Chem. Eng. Data, Vol. 49, pp. 1052-1058 (2004).
Lee, M. J., C. K. Lo, and H. M. Lin, "PVT Measurements for Mixtures of Poly(ethylene glycol methyl ether) with Poly(ethylene glycol) from 298 K to 338 K and Pressures up to 30 MPa," J. Chem. Eng. Data, Vol. 43, pp. 1076-1081 (1998).
Lee, M. J., C. K. Lo, and H. M. Lin, "PVT Measurements for Mixtures of 1-Octanol with Oligomeric Poly(ethylene glycol) from 298 K to 338 K and Pressures up to 30 MPa," J. Chem. Eng. Data, Vol. 44, pp. 1379-1385 (1999).
Lee, M. J., C. McCabe, and P. T. Cummings, "Square-Well Chain Molecules : A Semi-Empirical Equation of State and Monte Carlo Simulation Data," Fluid Phase Equilib., Vol. 221, pp. 63-72 (2004).
Lee, M. J., Y. C. Tuan, and H. M. Lin, "Pressure, Volume, and Temperature for Mixtures of Poly(ethylene glycol methyl ether)-350 + Anisole and Poly(propylene glycol)-200 + Anisole from 298 K to 338 K and Pressures up to 50 MPa," J. Chem. Eng. Data, Vol. 45, pp. 1100-1104 (2000).
Lee, M. J., Y. C. Tuan, and H. M. Lin, "Pressure-Volume-Temperature Properties for Binary and Ternary Polymer Solutions of Poly(ethylene glycol), Poly(propylene glycol), and Poly(ethylene glycol methyl ether) with Anisole," Polymer, Vol. 44, pp. 3891-3900 (2003).
Lin, H. M., J. T. Chen, and M. J. Lee, "A Cubic Perturbed Hard-Chain Equation of State," Fluid Phase Equilib., Vol.126, pp.29-52 (1996).
Lin, H. M., T. S. Hsu, and M. J. Lee, "Pressure-Volume-Temperature Properties for Binary Polymer Solutions of Poly(propylene glycol)with 1-Octanol and Acetophenone," Macromolecules, Vol. 34, pp. 6297-6303 (2001).
Mekhilef, N., "Viscoelastic and Pressure-Volume-Temperature Properties of Poly(vinylidene fluoride) and Poly(vinyldene fluoride) - Hexafluoropropylene Copolymers," J. Appl. Polym. Sci., Vol. 80, pp. 230-241 (2000).
Muller, E. A., and K. E. Gubbins, "Molecular-Based Equations of State for Association Fluids: A Review of SAFT and Related Approaches," Ind. Eng. Chem. Res., Vol. 40, pp. 2193-2211 (2001).
Murugesan, T., and M. Perumalsamy, "Densities and Viscosities of Polyethylene Glycol 2000 + Salt + Water Systems from (298.15 to 318.15) K," Ind. Eng. Chem. Data, Vol. 50, pp. 1290-1293 (2005).
Orbey, H., C. P. Bokis, and C. C. Chen, "Polymer-Solvent Vapor-Liquid Equilibrium: Equations of State Versus Activity Coefficient Models," Ind. Eng. Chem. Res., Vol. 37, pp. 1567-1573 (1998).
Orbey, H., and S. I. Sandler, "Comparison of Huron-Vidal Type Mixing Rules of Mixtures of Compounds with Large Size Differences, and a New Mixing Rule," Fluid Phase Equilib., Vol. 132, pp. 1-14 (1997).
Ottani, S., D. Vitalini, F. Comelli, and C. Castellari, "Densities, Viscosities, and Refractive Indices of New Mixtures of Poly(ethylene glycols) + Dialkyl Carbonates at 313.15 K," J. Chem. Eng. Data, Vol. 49, pp. 148-154 (2004).
Ougizawa, T., G. T. Dee, and D. J. Walsh,"Pressure-Volume-Temperature Properties and Equation of State in Polymer Blends : Characteristic Parameters in Polystyrene /Poly(vinyl methyl ether) Mixtures," Macromolecules, Vol. 24, pp. 3834-3837 (1991).
Pečar, D., and V. Doleček, " Isothermal Compressibilities and Isobaric Expansibilities of Pentane, Hexane, Heptane and Their Binary and Ternary Mixtures from Density Measurements, " Fluid Phase Equilib., Vol. 211, pp. 109-127 (2003).
Pečar, D., and V. Valter Doleček, " Volumetric Properties of Ethanol-Water Mixtures under High Temperatures and Pressures, " Fluid Phase Equilib., Vol. 230, pp. 36-44 (2005).
Peng, D. Y., and D. B. Robinson, "A New Two-Constant Equation of State," Ind. Eng. Chem. Fundam., Vol. 15, pp. 59-64 (1976).
Piñeiro, M. M., D. Bessières, J. M. Gacio, H. Saint-Guirons, and J. L. Legido, " Determination of High-Pressure Liquid Density for n-Perfluorohexane and n-Perfluorononane," Fluid Phase Equilib., Vol. 220, pp. 127-136 (2004).
Prigogine, I., N. Trappeniers, and V. Mathot, "On the Application of the Cell Method to r-Mer Liquids," J. Chem. Phys., Vol. 21, pp.559-560 (1953a).
Prigogine, I., N. Trappeniers, and V. Mathot, "Statistical Thermodynamics of r-Mer and r-Mer Solutions," Disc. Faraday Soc., Vol. 15, pp. 93-107 (1953b).
Riddick, J. A., Bunger, W. B., and Sakano, T. K. Techniques of
Chemistry, Organic Solvents. Physical Properties and Methods of
Purifications, Vol. II, John Wiley & Sons, New York, 1986.
Rodgers, P. A., "Pressure-Volume-Temperature Relationships for Polymeric Liquids: A Review of Equations of State and Their Characteristic Parameters for 56 Polymers," J. Appl. Polym. Sci., Vol. 48, pp. 1061-1080 (1993).
Sako, T., A. H. Wu, and J. M. Prausnitz, "A Cubic Equation of State for High-Pressure Phase Equilibria of Mixtures Containing Polymers and Volatile Fluids," J. Appl. Polym. Sci., Vol. 38, pp. 1839-1858 (1989).
Sanchez, I. C., and R. H. Lacombe, "An Elementary Molecular Theory of Classical Fluids. Pure Fluids," J. Phys. Chem., Vol. 80, pp. 2352-2362 (1976).
Saraiva, A., G. M. Kontogeorgis, V. I. Harismiadis, A. Fredenslund, and D. P. Tassios, "Application of the van der Waals Equation of State to Polymers. 4. Correlation and Prediction of Lower Critical Solution Temperatures for Polymer Solutions," Fluid Phase Equilib., Vol. 115, pp. 73-93 (1996).
Schotte, W., "Vapor-Liquid Equilibrium Calculations for Polymer Solutions," Ind. Eng. Chem. Process Des. Dev., Vol. 21, pp. 289-296 (1982).
Simha, R., and T. Somcynsky, "On the Statistical Thermodynamics of Spherical and Chain Molecule Fluids," Macromolecules, Vol. 2, pp. 342-350 (1969).
Soave, G., "Equilibrium Constants from a Modified Redlich-Kwong Equation of State," Chem. Eng. Sci., Vol. 27, pp. 1197-1203 (1972).
Song, Y., S. M. Lambert, and J. M. Prausnitz, "Perturbed Hard-Sphere -Chain Equation of State for Normal Fluids and Polymers," Ind. Eng. Chem. Res., Vol. 33, pp. 1047-1057 (1994).
Steele, W. V., R. D. Chirico, S. E. Knipmeyer, and A. Nguyen, "Vapor Pressure of Acetophenone, ( )-1,2-Butanediol, ( )-1,3-Butanediol, Diethylene Glycol Monopropyl Ether, 1,3-Dimethyladamantane, 2-Ethoxyethyl Acetate, Ethyl Octyl Sulfide, and Pentyl Acetate, "J. Chem. Eng. Data, Vol. 41, pp. 1255-1268 (1996).
Tekac, V., I. Cibulka, and R. Holub, "PVT Properties of Liquids and Liquid Mixtures: A Review of the Experimental Methods and the Literature Data," Fluid Phase Equilib., Vol. 19, pp. 33-149 (1985).
Tochigi, K., T. Matsumoto, K. Kurihara, and K. Ochi, "Estimation of PVT for Polymers and Solvent Activities in Polymer Solutions Using Simplified Parameter for the Sako-Wu-Prausnitz Equation of State," Ind. Eng. Chem. Res., Vol. 41, pp. 1094-1097 (2002).
"TRC Thermodynamic Tables, Non-Hydrocarbons," Thermodynamics Research Center, The Texas A&M University System: College Station, TX , 1993.
Troncoso, J., D. Bessières, C. A. Cerdeiriña, E. Carballo, and L. Romaní, " Automated Measuring Device of ( p, ρ, T ) Data Application to the 1-Hexanol + n-Hexane System," Fluid Phase Equilib., Vol. 208, pp. 141-154 (2003).
Turri, S., M. Scicchitano, C. Tonelli, and G. Gianotti, "Concentrated Solutions of Perfluoropolyoxyalkylene Oligomers - II: Viscosity and Density in Polar Solvents," European Polymer J., Vol. 31, pp. 1235-1242 (1995).
Ulbig, P., M. Bubolz, C. Kornek, and S. Schulz, "Excess Volumes of Binary Mixtures Containing Diisopropyl Ethanol + 1-Butanol or Diisoproyl Ether + Diethyl Ketone and Ethanol + Heptane at High Pressures, " J. Chem. Eng. Data, Vol. 42, pp. 449-452 (1997).
Vargaftik, N. B., Tables on the Thermodynamical Properties of Liquids and Gases, 2nd ed., Hemisphere, Washington, DC, 1975.
Watson, G., C. K. Zéberg-Mikkelsen, A. Baylaucq, and C. Boned, " High-Pressure Density Measurements for the Binary System Ethanol + Heptane," J. Chem. Eng., Vol. 51, pp. 112-118 (2006).
Wong, D. S. H., H. Orbey, and S. I. Sandler, "Equation of State Mixing Rule for Nonideal Mixtures Using Available Activity Coefficient Model Parameters and that Allows Extrapolation over Large Ranges of Temperature and Pressure," Ind. Eng. Chem. Res., Vol. 31, pp. 2033-2039 (1992).
Zafarani-Moattar, M. T., and S. Sarmad, "Volumetric and Ultrasonic Studies of the Poly(ethylene glycol) Methacrylate 360 + Alcohol Systems at 298.15 K," J. Chem. Eng. Data, Vol. 51, pp. 968-971 (2006).
Zéberg-Mikkelsen, C. K., L. Lugo, and J. Fernández, " Density Measurements under Pressure for the Binary System (Ethanol + Methylcyclohexane)," J. Chem. Thermodyn., Vol. 37, pp. 1294-1304 (2005).
Zéberg-Mikkelsen, C. K., L. Lugo, J. García and, J. Fernández, " Volumetric Properties under Pressure for the binary System Ethanol + Toluene, " Fluid Phase Equilib., Vol. 235, pp. 139-151 (2005).
Zoller, P., and H. H. Hoehn, "Pressure - Volume - Temperature Properties of Blends of Poly(2,6-dimethyl-1,4-phenylene ether) with Polystyrene," J. Polymer Sci. Polymer Phys., Vol. 20, pp. 1385-1397 (1982).
張基昇，"液化煤典型成份及高分子物質的熱力性質研究"，博士論文，國立臺灣工業技術學院化工研究所，臺北 (1997)。
羅建國，"高分子攙合物與高分子溶液的高壓密度研究"，碩士論文，國立臺灣工業技術學院化工研究所，臺北 (1997)。
古翠如，"高壓下聚乙二醇辛基苯基醚高分子溶液的PVT性質研究"，碩士論文，國立臺灣科技大學化工研究所，臺北 (2004)。
鍾雅芳，"高壓下聚乙二醇醚寡聚物溶液的PVT性質研究"，碩士論文，國立臺灣科技大學化工研究所，臺北 (2005)。
呂建豐，"高壓下聚乙二醇單月桂酸酯寡聚物溶液的PVT性質研究"，碩士論文，國立臺灣科技大學化工研究所，臺北 (2006)。