Gas-like diffusion

Supercritical fluids (SCFs) offer several advantages as reaction media for catalytic reactions. These advantages include the ability to manipulate the reaction environment through simple changes in pressure to enhance solubility of reactants and products, to eliminate interphase transport limitations, and to integrate reaction and separation unit operations. Benefits derived from the SCF phase Fischer-Tropsch synthesis (SCF-FTS) involve the gas-like diffusivities and liquid-like solubilities, which together combine the desirable features of the gas- and liquid-phase FT synthesis routes. 

Supercritical fluids possess characteristics that make them interesting for use as polymerization media. A supercritical fluid exists at temperatures and pressures above its critical values. In the supercritical state, the fluid exhibits physical and transport properties intermediate between the gaseous and liquid state. This is illustrated in Table 2. SCFs have liquid-like densities, but gas-like diffusivities. These intermediate properties can provide advantages over liquid-based processes. In particular, the higher diffusivities of SCFs reduce mass transfer limitations in diffusion-controlled processes. Additionally, lower energy is required for processing the supercritical fluid because its viscosity is lower than that of most liquids, and because the need to vaporize large quantities of liquid is avoided. 

Supercritical fluids have long been known for their abilities to dissolve organic contaminants. Their ability to display a wide range of solvent characteristics and the ability to tune solubility with small changes in temperature and pressure were identified early on in our search for alternative cleaning methods. The gas-like diffusivity and low surfece tension combined with liquid-like densities were important... 

Under supercritical conditions, a gas, such as carbon dioxide, possesses liquid-like density and solubility, and gas-like diffusivity and viscosity, along with zero surface tension. Thus, supercritical fluids work extremely well as a processing media for a wide variety of chemical, biological, and polymer extractions. This solvent power of supercritical fluid has been known since 1879. Nevertheless, its application was not considered until recently when the sharp increases in energy cost, environmental regulations, and performance demands on materials have caused industry to consider alternative... 

Saim and Subramaniam [38] and Ginosar and Subramaniam [39] also found that the in situ extraction of the coke compounds by near-critical or supercritical reaction mixtures prevents pore plugging that otherwise occurs at subcritical (gas-like) conditions. Although the coke laydown decreased at supercritical (liquid-like) conditions, the isomerization rates were lower and deactivation rates were higher due to pore diffusion limitations in the liquid-like reaction mixtures. It was therefore concluded that near-critical reaction mixtures provide an optimum combination of solvent and transport properties that is better than either subcritical (gas-like) or dense supercritical (liquid-like) mixtures for maximizing the isomerization rates and for minimizing catalyst deactivation rates. These findings indicate that catalytic reactions which require liquid-like reaction media for coke extraction and heat removal, yet gas-like diffusivities for enhanced reaction rates, can benefit from the use of near-critical reaction media. 

The solvent characteristics of supercritical fluids have been extensively investigated over the past two decades (2). Supercritical fluids have increased solvent strength versus gases due to their liquid-like densities. The pressure and temperature within the supercritical region can be adjusted to regulate the density and therefore the solvent strength of a supercritical fluid. In addition to the liquid-like density, supercritical fluids exhibit gas-like diffusivity and viscosity. 

CO2 has many properties that make it an interesting solvent it is abundant, inexpensive, nontoxic, and nonflammable. It has been proposed as a green alternative to traditional organic solvents because it is not regulated as a volatile organic chemical (VOC) or restricted in food or pharmaceutical applications. CO2 attains the supercritical state at near-ambient temperature (Tc = 31°C) and a relatively moderate pressure Pc = 73 bar). Supercritical CO2, like all supercritical fluids, offers many mass transfer advantages over conventional organic solvents due to its gas-like diffusivity, low viscosity, and surface tension. 

Reactions. Supercritical fluids are attractive as media for chemical reactions. Solvent properties such as solvent strength, viscosity, diffusivity, and dielectric constant may be adjusted over the continuum of gas-like to Hquid-like densities by varying pressure and temperature. Subsequently, these changes can be used to affect reaction conditions. A review encompassing the majority of studies and apphcations of reactions in supercritical fluids is available (96). 

As the density of a gas increases, free rotation of the molecules is gradually transformed into rotational diffusion of the molecular orientation. After unfreezing , rotational motion in molecular crystals also transforms into rotational diffusion. Although a phenomenological description of rotational diffusion with the Debye theory [1] is universal, the gas-like and solid-like mechanisms are different in essence. In a dense gas the change of molecular orientation results from a sequence of short free rotations interrupted by collisions [2], In contrast, reorientation in solids results from jumps between various directions defined by a crystal structure, and in these orientational sites libration occurs during intervals between jumps. We consider these mechanisms to be competing models of molecular rotation in liquids. The only way to discriminate between them is to compare the theory with experiment, which is mainly spectroscopic. 

The development of CO2 fixation reactions in supercritical CO2 attracts increasing attention due to its gas-like low viscosities and high diffusivities and its liquid-like solubilizing power. Matsuda et al. attempted to carry out the con-... 

The enzyme catalysed epoxidation of alpha-olefins like 1-octene with oxygen to the optically active epoxide provides an interesting example of a four-phase system (de Bont et al., 1983). The hold-up of the organic phase may be 2-4 % and the presence of biosurface active agents leads to the creation of a large liquid-liquid interfacial area the liquid droplet size becomes smaller than the gas-liquid diffusion film thickness. 

Heterogeneous uptake on surfaces has also been documented for various free radicals (DeMore et al., 1994). Table 3 shows values of the gas/surface reaction probabilities (y) of the species assumed to undergo loss to aerosol surface in the model. Only the species where a reaction probability has been measured at a reasonable boundary layer temperature (i.e. >273 K) and on a suitable surface for the marine boundary layer (NaCl(s) or liquid water) have been included. Unless stated otherwise, values for uptake onto NaCl(s), the most likely aerosol surface in the MBL (Gras and Ayers, 1983), have been used. Where reaction probabilities are unavailable mass accommodation coefficients (a) have been used instead. The experimental values of the reaction probability are expected to be smaller than or equal to the mass accommodation coefficients because a is just the probability that a molecule is taken up on the particle surface, while y takes into account the uptake, the gas phase diffusion and the reaction with other species in the particle (Ravishankara, 1997). 

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