Supercritical solutions

Rapid expansion from supercritical solutions (RESS)... 

Crystallization Solutes may be crystallized from supercritical fluids by temperature and/or pressure changes, and by the PCA process described above. In the rapid expansion from supercritical solution (BESS) process, a SCR containing a dissolved solute is expanded through a nozzle or orifice in less than 1 ms to form small particles or fibers. A variety of inorganic crystals have been formed naturally and synthetically in SCR water. 

Hubert, P., Vitzthum, O., Separation of caffeine from supercritical solutions,... 

Murray, J. S., P. Lane, T. Brinck, and P. Politzer. 1993b. Relationships Between Computed Molecular Properties and Solute/Solvent Interactions in Supercritical Solutions. J. Phys. Chem. 97, 5144. 

RESS [Rapid Expansion of Supercritical Solutions] A process for depositing a film of solid material on a surface. The substance is dissolved in supercritical carbon dioxide. When the pressure is suddenly reduced, the fluid reverts to the gaseous state and the solute is deposited on the walls of the vessel. Used for size-reduction, coating, and microencapsulation. First described in 1879. Developed in 1983 by R. D. Smith at the Battelle Pacific Northwest Laboratory. 

Steve Howdle s short article Supercritical solutions in Chemistry in Britain, August 2000, p. 23, is a good introduction to the topic. 

For the underlying science of supercritical fluids, try Steve Howdle s short article Supercritical solutions in Chemistry in Britain, August 2000, p. 23, which represents a useful introduction to the topic. For more applications of such fluids, try the short review article Some applications of supercritical fluid extraction , by D. P. Ndiomu and C. F. Simpson in Analytica ChimicaActa, 1988,213,237. The article is somewhat dated now but readable. A look at the contents list of The Journal of Supercritical Fluids will be more up-to-date go to http //www.umecheme. maine.edu/jsf. 

A number of techniques are based on supercritical fluid technology. Three are of particular pharmaceutical interest, namely the supercritical antisolvent (SAS) system, the rapid expansion of supercritical solution (RESS) method, and the gas antisolvent (GAS) technique [126]. 

Supercritical solutions are characterized by very low solvent densities. As a result, they possess the interesting feature that solubility is determined more by solute-solute than solute-solvent interactions. Thus we were able to express the solubilities of naphthalene and a series of indole derivatives in four different supercritical solvents (C2H4, C2H6, C02 and the highly polar CHF3) in the same functional format, only the numerical coefficients varying from one to another.57 Solute-solvent interactions do occur,58 but solubility can be represented quite... 

This industrial process remains essentially unchanged from the 1950s [25], Here, a free-radical initiator is added to the ethylene monomer at supercritical conditions (276 MPa and 200-300 °C). The polyethylene remains in the supercritical solution until the pressure is lowered to around 5 MPa, whereupon it precipitates. A range of other monomers can be copolymerized, including carbon monoxide to give polyketones, as shown in Scheme 10.19 [26],... 

The further optimization and development concerning stability and selectivity of the organometallic catalyst in these kinds of media and the application of isolation methodologies similar to CESS (catalysis and extraction using supercritical solutions [43]) together with the physical and chemical advantages of supercritical fluids can lead to high potential catalyst matrices that fulfil the requirements of industrial processes both for bulk and fine chemicals. 

CESS Catalysis and extraction using supercritical solutions... 

Rapid expansion of supercritical solutions containing dissolved dmg, and... 

Journal of Applied Polymer Science 11, No.7, 15th Aug.2000, p. 1478-87 MORPHOLOGIES OF BLENDS OF ISOTACTIC POLYPROPYLENE AND ETHYLENE COPOLYMER BY RAPID EXPANSION OF SUPERCRITICAL SOLUTION AND ISOBARIC CRYSTALLIZATION FROM SUPERCRITICAL SOLUTION... 

By rapid expansion of supercritical propane solution (RESS), and isobaric crystallisation (ICSS), isotactic polypropylene and ethylene-butylene copolymers were precipitated from the supercritical solution. The RESS process produced microfibres with a trace of microparticles, while the ICSS process produced microcellular products. Improvement in thermal stability was achieved by first synthesising a thermoplastic vulcanisate from polypropylene and ethylene-propylene-diene terpolymer from a supercritical propane solution, followed by RESS. 28 refs. 

In practice, fiee-radical polymerization of ethylene and other small olefins is usually carried out at very high pressures (because the rate varies approximately as P ) with a solvent such as isobutane, which forms a supercritical solution at reaction conditions. 

The electron will be solvated in a region where the solvent molecules are appropriately arranged. There must be a cluster of electrons of a size of 4-5 to support the formation of the solvated electron from the results of Gangwer et al., [23], Baxendale [24,25], and Kenney-Wallace and Jonah [16]. This behavior does not depend on the specific alcohol or alkane and even occurs in supercritical solutions, as has been shown in experiments done using mixtures of supercritical ethane-methanol mixtures [19]. Experiments have also shown that the thermodynamically lowest state might not be reached. For example, the experiments of Baxendale that measured the conductivity of the solvated electron in alcohol-alkane mixtures showed that when there was a sufficient concentration of alcohols to form dimers, there was a sharp decrease in the mobility of the electron [24,25]. This result showed that the electron was at least partially solvated. However, the conductivity was not as low as one would expect for the fully solvated electron, and the fully solvated electron was never formed on their time scale (many microseconds), a time scale that was sufficiently long for the electron-alcohol entity to encounter sufficient alcohols to fully solvate the electron. Similarly, the experiments of Weinstein and Firestone, in mixed polar solvents, showed that the electron that was observed depended on the initial mixture and would not relax to form the most fully solvated electron [26]. 

Supercritical solutions also provide a large and interesting collection of phenomena that can be probed using these techniques. The greater fluctuations in these solvents may increase the rate of solvation because of the larger number of possible states that can exist. 

Supercritical solutions can be regarded as dense solvating gasses or low-viscous low-density liquids. The most well-known and probably most interesting candidate is based on carbon dioxide. Supercritical carbon dioxide can be regarded as an organic solvent. Various concepts have been developed using supercritical flu-... 

The Chinese scientists [123] have reported the preparation of nanoscale RDX (-50 nm) and nanoscale HMX (=70 nm) by an impinging method [124]. Researchers from China have also reported preparation and characterization of n-NTO and their data indicate that it decomposes at a lower temperature and at the same time, it is less sensitive to impact compared with m-NTO. This property of n-NTO is likely to be of tremendous significance for insensitive munitions [125]. The preparation of n-RDX particles with a mean size (=110-120 rim) but narrow distribution has also been reported by a novel method known as rapid expansion of supercritical solution (RESS) [126]. 

Conformal coatings. Deposition of a thin film that nniformly coats all exposed parts of a three-dimensional strnctnre is known as conformal film growth. Conformality is a common requirement for dielectric films. Penetration and uniform coverage of all topography and interstices are vital and depend upon low viscosity, as well as low surface and interfacial energies. Fluoropolymer in supercritical solution might provide die required characteristics. 

Trichlorodifluoroethane (HCFC-122) is a co-spin agent, which lowers the cloud-point pressure. The cloud-point pressure means the pressure at which a single phase liquid solution begins to phase separate. At temperatures above the critical point, there cannot be any liquid phase present and therefore a single phase, supercritical solution phase separates into a polymer-rich/spin fluid-rich, two-phase gaseous dispersion. 

Supercritical fluid chromatography provides increased speed and resolution, relative to liquid chromatography, because of increased diffusion coefficients of solutes in supercritical fluids. (However, speed and resolution are slower than those of gas chromatography.) Unlike gases, supercritical fluids can dissolve nonvolatile solutes. When the pressure on the supercritical solution is released, the solvent turns to gas. leaving the solute in the gas phase for easy detection. Carbon dioxide is the supercritical fluid of choice for chromatography because it is compatible with flame ionization and ultraviolet detectors, it has a low critical temperature. and it is nontoxic. 

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