Thermodynamics molecular

Prausnitz, J. M., "Molecular Thermodynamics of Fluid-Phase Equilibria," Prentice-Hall, Englewood Cliffs, N.J. (1969)... 

PRAUSNITZ J.M. MOLECULAR THERMODYNAMICS OF FLUID PHASE EQUILIBRIA, PRENTICE-HALL. ENGLEWOOD CLIFFS. N.J.I19691. 

Lee L L 1988 Molecular Thermodynamics of Nonideal Fluids (Boston ButtenA/orths)... 

McQuarrie, D. A. Simon, J. D., 1999. Molecular Thermodynamics. University Science Books, Sausalito, CA. 

J. W. Whalen, Molecular Thermodynamic.s A Statistical Approach John Wiley Sons,... 

Gas AntisolventRecrystallizations. A limitation to the RESS process can be the low solubihty in the supercritical fluid. This is especially evident in polymer—supercritical fluid systems. In a novel process, sometimes termed gas antisolvent (GAS), a compressed fluid such as CO2 can be rapidly added to a solution of a crystalline soHd dissolved in an organic solvent (114). Carbon dioxide and most organic solvents exhibit full miscibility, whereas in this case the soHd solutes had limited solubihty in CO2. Thus, CO2 acts as an antisolvent to precipitate soHd crystals. Using C02 s adjustable solvent strength, the particle size and size distribution of final crystals may be finely controlled. Examples of GAS studies include the formation of monodisperse particles (<1 fiva) of a difficult-to-comminute explosive (114) recrystallization of -carotene and acetaminophen (86) salt nucleation and growth in supercritical water (115) and a study of the molecular thermodynamics of the GAS crystallization process (21). 

The kinetic theory attempts to describe the individual molecules energies and interactions statistical thermodynamics attempts to fundamentally develop the equation of state from considerations of groupings of molecules. These approaches are complementary in many ways (3,123,124). A weU-referenced text covering molecular thermodynamics is also available (125). 

Kamlet-Taft Linear Solvation Energy Relationships. Most recent works on LSERs are based on a powerfiil predictive model, known as the Kamlet-Taft model (257), which has provided a framework for numerous studies into specific molecular thermodynamic properties of solvent—solute systems. This model is based on an equation having three conceptually expHcit terms (258). 

Modern theoretical developments in the molecular thermodynamics of liquid-solution behavior are often based on the concept local... 

FIG. 22-20 Six classes of binary liquid-fluid phase diagrams (Frausnitz et at. Molecular Thermodynamics of Fluid-Phase Equilibria, 1986. Reptinted hy peimission ofFrentice-Hall, Inc.). 

Prausnitz, J.M., Lichtenthaler, R.N. and Gomes de Azevedo, E., Molecular Thermodynamics of Fluid-Phase Equilibria. Prentice Hall, Upper Sadie River, NJ, 1999. 

Liquid-Fluid Equilibria Nearly all binary liquid-fluid phase diagrams can be conveniently placed in one of six classes (Prausnitz, Licntenthaler, and de Azevedo, Molecular Thermodynamics of Fluid Phase Blquilibria, 3d ed., Prentice-Hall, Upper Saddle River, N.J., 1998). Two-phase regions are represented by an area and three-phase regions by a line. In class I, the two components are completely miscible, and a single critical mixture curve connects their criticsu points. Other classes may include intersections between three phase lines and critical curves. For a ternary wstem, the slopes of the tie lines (distribution coefficients) and the size of the two-phase region can vary significantly with pressure as well as temperature due to the compressibility of the solvent. 

In part II of the present report the nature and molecular characteristics of asphaltene and wax deposits from petroleum crudes are discussed. The field experiences with asphaltene and wax deposition and their related problems are discussed in part III. In order to predict the phenomena of asphaltene deposition one has to consider the use of the molecular thermodynamics of fluid phase equilibria and the theory of colloidal suspensions. In part IV of this report predictive approaches of the behavior of reservoir fluids and asphaltene depositions are reviewed from a fundamental point of view. This includes correlation and prediction of the effects of temperature, pressure, composition and flow characteristics of the miscible gas and crude on (i) Onset of asphaltene deposition (ii) Mechanism of asphaltene flocculation. The in situ precipitation and flocculation of asphaltene is expected to be quite different from the controlled laboratory experiments. This is primarily due to the multiphase flow through the reservoir porous media, streaming potential effects in pipes and conduits, and the interactions of the precipitates and the other in situ material presnet. In part V of the present report the conclusions are stated and the requirements for the development of successful predictive models for the asphaltene deposition and flocculation are discussed. 

Dixon, J. and Johnston, K. (1991) Molecular thermodynamics of solubilities in gas antisolvent crystallization. AIChE Journal, 37 (10), 1441-1449. 

To tackle these problems successfully, new concepts will be required for developing systematic modeling techniques that can describe parts of the chemical supply chain at different levels of abstraction. A specific example is the integration of molecular thermodynamics in process simulation computations. This would fulfill the objective of predicting the properties of new chemical products when designing a new manufacturing plant. However, such computations remain unachievable at the present time and probably will remain so for the next decade. The challenge is how to abstract the details and description of a complex system into a reduced dimensional space. 

Prausnitz, J.M. Lichtenthaler, R.N. Azevedo, E.G. "Molecular Thermodynamics of Fluid Phase Equilibria" Prentice-Hall Englewood Cliffs, NJ, 1985 pp. 306-16. 

K. K. Irikura, D. J. Frurip, Eds. Computational Thermochemistry Prediction and Estimation of Molecular Thermodynamics. ACS Symposium Series 677 American Chemical Society Washington, DC, 1998. 

L. Lee, Molecular Thermodynamics of Nonideal Fluids, Bntterworth, Boston, 1988. 1. N. Israelachvili, Intermolecular and Surfaces Forces, Academic Press, London, 1992 Watanabe, A. M. Brodsky, andW. P. Reinhardt,/. Phys. Chem. 95 (1991) 4593. 

A. Reisman, Phase Equilibria, Basic Principles, Applications, and Experimental Techniques, Academic Press, New York, 1970 H. E. Stanley, Introduction to Phase Transitions and Critical Phenomena, Oxford University Press, New York, 1971 J. R. Cunningham and D. K. Jones, eds.. Experimental Results for Phase Equilibria and Pure Component Properties, American Institute of Chemical Engineers, New York, 1991 S. Malanowski, Modelling Phase Equilibria Thermodynamic Background and Practical Tools, Wiley, New York, 1992 J. M. Prausnitz, R. N. Lichtenthaler, and E. G. de Azevedo, Molecular Thermodynamics of Eluid-Phase Equilibria, Prentice-Hall, Upper Saddle River, NJ, 1999. 

Prausnitz J. M., Lichtenhaler R. N., and De Azvedo E. G. (1986). Molecular Thermodynamics of Fluid Phase Equilibria. New York Prentice-Hall. 

R. Dickerson (1969) Molecular Thermodynamics, p. 452, W. A. Benjamin, New York. (This is a remarkably lucid treatment of thermodynamics.)... 

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