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High-pressure solution behavior such as density and phase behavior is a critical fundamental property for the design and optimization of various chemical processes, such as distillation and extraction in the production and purification of oils, polymers, and other natural materials. In this Ph. D. study, solution behavior data are experimentally determined and equation of state (EoS) modeled for n-hexadecane, n-octadecane, n-eicosane, methylcyclohexane, ethylcyclohexane, cis-1,2-dimethylcyclohexane, cis-1,4-dimethylcyclohexane, trans-1,4-dimethylcyclohexane, o-xylene, m-xylene, p-xylene, and 2-methylnaphthalene at temperatures to 525 K and pressures to 275 MPa. A variable-volume view cell coupled with a linear variable differential transformer is used for the high-pressure determination. The reported density data are less than 0.4% of available literature data, which is within the estimated accumulated experimental uncertainty, 0.75%. Special attention is paid to the effect of architectural differences on the resultant high-pressure solution behavior. The reported data of low molecular weight hydrocarbons are modeled with Peng-Robinson (PR) equation of state (EoS), high-temperature high-pressure volume-translated cubic (HTHP VT-cubic) EoS, and perturbed-chain statistical fluid theory (PC-SAFT) EoS. The three pure-component parameters in PC-SAFT EoS can be either obtained from literature or from a group contribution (GC) method. Generally, PR EoS gives the worst predictions and HTHP VT-cubic EoS provides modest improvements over the PR EoS, but both of the equations underpredict the densities at high pressures. On the other hand, PC-SAFT EoS, with parameters from the literature or from a GC method, gives the improved density predictions with respect to PR EoS and HTHP VT-cubic EoS, although an overprediction of densities is found at high pressures. Model calculations also highlight the capability of these equations to account for the different densities observed for the hydrocarbon isomers. However, none of the EoS investigated in this study can fully account for the effect of isomeric structural differences on the high-pressure densities. For a better prediction of densities at high pressures, a new set of PC-SAFT pure-component parameters are obtained from a fit of the experimental density data obtained in this study and the mean absolution percent deviation is within 0.4%. The experimental technique and PC-SAFT EoS modeling method are extended to a star polymer-propane mixture. Star polymers with a fixed number of arms have a globular structure that does not promote chain entanglements. Star polymers can be synthesized with a large number of functional groups that can be readily modified to adjust their physical properties for specific applications in the areas of catalysis, coatings, lubrication, and drug delivery. In this study, a star polymer with a divinylbenzene core and statistically random methacrylate copolymer arms is synthesized with reversible addition-fragmentation-transfer method and fractionated with supercritical carbon dioxide and propane to obtain fractions with low molecular weight polydispersity. The phase behavior and density behavior are experimentally determined in supercritical propane for fractionated star polymers and the corresponding linear copolymer arms at temperatures to 423 K and pressures to 210 MPa. Experimental data are presented on the impact of the molecular weight, the backbone composition of the lauryl and methylmethacrylate repeat units in the copolymer arms, and the DVB core on the polymer-propane solution behavior. The star polymer is significantly more soluble due to its unique structure compared with the solubility of the linear copolymer arms in propane. The resultant phase behavior for the two homopolymers and the copolymers in propane are modeled using the PC-SAFT and copolymer PC-SAFT EoS, which give reasonable predictions for both phase behavior and density behavior. Model calculations are not presented for the phase behavior of the star polymers in propane since the PC-SAFT approach is not applicable for star polymer structures.
A comprehensive handbook comprising two volumes, High Pressure Phase Transformations classifies and systemizes data on phase transformations of 2,263 elements and compounds under high pressure (at least 0.1 GPa). Each compound has a separate paragraph and bibliography that includes information on the behavior of the material under normal pressure. A critical analysis is made of experimental data on melting, first- and second-order phase transitions, crystal stuctures and phase diagrams, and data on new materials and compounds synthesized under high pressure are presented and discussed.
This volume presents reports from the 1997 conference, held in Maastricht, Netherlands. The papers, covering a broad range of topics from the estimation of physical properties to the design and performance of contacting trays, demonstrate the high rate of advance in technology.
Masters Theses in the Pure and Applied Sciences was first conceived, published, and disseminated by the Center for Information and Numerical Data Analysis and Synthesis (CINDAS) * at Purdue University in 1 957, starting its coverage of theses with the academic year 1955. Beginning with Volume 13, the printing and dissemination phases of the activity were transferred to University Microfilms/Xerox of Ann Arbor, Michigan, with the thought that such an arrangement would be more beneficial to the academic and general scientific and technical community. After five years of this joint undertaking we had concluded that it was in the interest of all con cerned if the printing and distribution of the volumes were handled by an interna tional publishing house to assure improved service and broader dissemination. Hence, starting with Volume 18, Masters Theses in the Pure and Applied Sciences has been disseminated on a worldwide basis by Plenum Publishing Cor poration of New York, and in the same year the coverage was broadened to include Canadian universities. All back issues can also be ordered from Plenum. We have reported in Volume 32 (thesis year 1987) a total of 12,483 theses titles from 22 Canadian and 176 United States universities. We are sure that this broader base for these titles reported will greatly enhance the value of this important annual reference work. While Volume 32 reports theses submitted in 1987, on occasion, certain univer sities do report theses submitted in previous years but not reported at the time.
Understanding the phase behavior of the various fluids present in a petroleum reservoir is essential for achieving optimal design and cost-effective operations in a petroleum processing plant. Taking advantage of the authors' experience in petroleum processing under challenging conditions, Phase Behavior of Petroleum Reservoir Fluids introdu
Phase Behavior provides the reader with the tools needed to solve problems requiring a description of phase behavior and specific pressure/volume/temperature (PVT) properties.