Pressure dependence viscosity effect

The pressure dependence of effective viscosity obviously depends upon the value of the momentum accommodation coefficient. Momentum accommodation data are relatively rare, but some representative data are given in Table 1. Note that all values are relatively close to unity. Because of this observation, momentum accommodation coefficients are normally assumed to be unity in applications... 

There is one important caveat to consider before one starts to interpret activation volumes in temis of changes of structure and solvation during the reaction the pressure dependence of the rate coefficient may also be caused by transport or dynamic effects, as solvent viscosity, diffiision coefficients and relaxation times may also change with pressure [2]. Examples will be given in subsequent sections. 

The drop in pressure when a stream of gas or liquid flows over a surface can be estimated from the given approximate formula if viscosity effects are ignored. The example calculation reveals that, with the sorts of gas flows common in a concentric-tube nebulizer, the liquid (the sample solution) at the end of the innermost tube is subjected to a partial vacuum of about 0.3 atm. This vacuum causes the liquid to lift out of the capillary, where it meets the flowing gas stream and is broken into an aerosol. For cross-flow nebulizers, the vacuum created depends critically on the alignment of the gas and liquid flows but, as a maximum, it can be estimated from the given formula. 

The effects of temperature and pressure on fluidized-bed systems cannot be considered independently of particle size. Whether temperature and pressure have an effect (and indeed, even the direction of that effect) on a system, depends strongly on particle size. In addition, the type of interaction between gas and solids, i.e., whether the interaction is due to momentum or drag, determines if gas viscosity has an effect upon the system. As will be shown, gas viscosity is not important in systems in which momentum is important, but is important in systems dominated by drag. 

Since the activation energy for ionic recombination is mainly due to viscosity we use the activation energy for viscous flow (10kJ.mol l). AH ] and 3 were determined from conductance as 44.2kJ.mol and 11,4kJ.mol From the data presented in Table III it is clear that the temperature dependence of the slope is very satisfactorily described by A% +l/2(AHd-AH3). Another, and rather critical, test for the applicability of eq. 14b is the effect of pressure since the slope of eq. 14b is largely pressure independent so that we ask here for a compensation of rather large effects. From Table III we Indeed see an excellent accordance between the experimental value and the pressure-dependence calculated from the activation volume of viscous flow (+20.3 ctPmol ), AVd (-57.3 cnAnol" ) and (-13.9 cnAnol ) the difference between the small experimental and calculated values is entirely with the uncertainties of compressibility - corrections and experimental errors. 

Distributed Parameter Models Both non-Newtonian and shear-thinning properties of polymeric melts in particular, as well as the nonisothermal nature of the flow, significantly affect the melt extmsion process. Moreover, the non-Newtonian and nonisothermal effects interact and reinforce each other. We analyzed the non-Newtonian effect in the simple case of unidirectional parallel plate flow in Example 3.6 where Fig.E 3.6c plots flow rate versus the pressure gradient, illustrating the effect of the shear-dependent viscosity on flow rate using a Power Law model fluid. These curves are equivalent to screw characteristic curves with the cross-channel flow neglected. The Newtonian straight lines are replaced with S-shaped curves. 

The conclusion that changes in solvent viscosity are responsible for the observed pressure and temperature effects is further corroborated by the same dependence of the product ratio 13c 16. Irrespective whether the viscosity is calculated from the pressure or temperature experiments, a plot of the product ratio vs. viscosity affords two straight lines with slopes that are identical within experimental error (Figure... 

Supercritical viscosity lies in between the viscosity of liquids and gases. For this reason, supercritical fluids exhibit more favourable hydrodynamic properties than do liquids. Also, the low surface tension of SFs allows them to readily penetrate porous solids and packed beds. The viscosity of SFs, like that of conventional fluids, is temperature-dependent however, while pressure has little effect on the viscosity of fluids, it exerts a strong influence on that of SFs. As a result, increased pressures lead to increased supercritical viscosity and hence to diminished solute diffusivity and hindered transport phenomena, but also, most often, to increased solubility through decreased density. 

Secondary pressure effects are almost always neglected in liquid chromatography, because the pressure dependence of the density (i.e., the compressibility) and the viscosity of liquids are relatively small. Typical values are 1x10 atm for the former and 1x10 atm for the latter. The pressme dependence of the liquid density tends to increase the retention volumes, compared to those expected with a noncompressible fluid under the same conditions [23,24], The pressxire dependence of the viscosity results in an increase of the retention time beyond the value that would be observed under the same conditions, with a solvent having a constant viscosity [23]. We discuss these effects in Section 5.3.I.2. 

The effect of osmotic pressure in macromolecular ultraflltra-tlon has not been analyzed in detail although many similarities between this process and reverse osmosis may be drawn. An excellent review of reverse osmosis research has been given by Gill et al. (1971). It is generally found, however, that the simple linear osmotic pressure-concentration relationship used in reverse osmosis studies cannot be applied to ultrafiltration where the concentration dependency of macromolecular solutions is more complex. It is also reasonable to assume that variable viscosity effects may be more pronounced In macromolecular ultra-filtration as opposed to reverse osmosis. Similarly, because of the relatively low diffuslvlty of macromolecules conqiared to typical reverse osmosis solutes (by a factor of 100), concentration polarization effects are more severe in ultrafiltration. 

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