Irreversible absorption

FIGURE 13.24 Enhancement factor as a function of Hatta number. Chemical absorption, irreversible reactions. 

With disk diameters above 5.25 in., all parameters, eg, water absorption and thermal expansion, become more critical which aggravates the expansion or warp of disks. If in the future disk rotation speeds have to be increased significantly to boost data transfer rates, higher demands will be placed on warp (tilt angle) and modulus to avoid creeping (ie, irreversible elongation in radial direction). A survey of the requirement profile for the substrate material of optical disks is given in Table 5 (182,186,187,189). 

Irreversible processes are mainly appHed for the separation of heavy stable isotopes, where the separation factors of the more reversible methods, eg, distillation, absorption, or chemical exchange, are so low that the diffusion separation methods become economically more attractive. Although appHcation of these processes is presented in terms of isotope separation, the results are equally vaUd for the description of separation processes for any ideal mixture of very similar constituents such as close-cut petroleum fractions, members of a homologous series of organic compounds, isomeric chemical compounds, or biological materials. 

The gas-phase rate coefficient fcc is not affecded by the fact that a chemic reaction is taking place in the liquid phase. If the liquid-phase chemical reaction is extremely fast and irreversible, the rate of absorption may be governed completely by the resistance to diffusion in the gas phase. In this case the absorption rate may be estimated by knowing only the gas-phase rate coefficient fcc of else the height of one gas-phase transfer unit Hq =... 

If the liqmd-phase reaction is extremely fast and irreversible, the rate of absorption may in some cases be completely governed by the gas-phase resistance. For practical design purposes one may assume (for example) that this gas-phase mass-transfer limited condition will exist when the ratio yj/y is less than 0.05 everywhere in the apparatus. 

Gas-Film Coefficient Since the gas film is not affected by the liquid-phase reaction, one of the many available correlations for physic absorption may be apphcable. The coefficient also may be found directly after elimination of the hquid-film coefficient by employing a solution that reacts instantaneously and irreversibly with the dissolved gas, thus cancehng out any backpressure. Examples of such systems are SO2 in NaOH and NH3 in H2SO4. 

Since the optical transitions near the HOMO-LUMO gap are symmetry-forbidden for electric dipole transitions, and their absorption strengths are consequently very low, study of the absorption edge in Ceo is difficult from both an experimental and theoretical standpoint. To add to this difficulty, Ceo is strongly photosensitive, so that unless measurements arc made under low light intensities, photo-induced chemical reactions take place, in some cases giving rise to irreversible structural changes and polymerization of the... 

There is another type of condition that results from exposure to high humidity. The alteration in electrical properties caused by moisture absorption in nylon and phenolics is reversible. When the moisture content is decreased, the properties of the materials recover to close to the original values. In some instances the exposure to moisture and electrical fields can cause irreversible damage that can lead to failure. 

Now if any irreversible changes occur in the system itself during the execution of the cycle, the principle of dissipation of energy shows that the available energy will be diminished in virtue of these, and since the available energy of the system must be the same after as it was before the execution of the cycle, because the state of the system is unaltered, it follows that some available energy must have been absorbed from outside in connection with the absorption of heat hence (A ) and therefore also... 

Among the causes producing irreversibility w7e may instance the forces depending on friction in solids, viscosity of liquids imperfect elasticity of solids inequalities of temperature (leading to heat conduction) set up by stresses in solids and fluids generation of heat by electric currents diffusion chemical and radio-active changes and absorption of radiant energy. 

Again for the case of the sparingly soluble gas whose absorption is accompanied by a simultaneous irreversible first-order reaction, Lightfoot (L5, L6) made the following assumptions ... 

We wish to show that no points to the leftbb of 2 on the isotherm 62 are accessible from point 1 via any adiabatic path, reversible or irreversible. Suppose we assume that some adiabatic path does exist between 1 and 2. We represent this path as a dotted curve in Figure 2.11a. We then consider the cycle I —>2 —> 1 — 1. The net heat associated with this cycle would be that arising from the last step 1 — 1, since the other two steps are defined to be adiabatic. We have defined the direction 1 — 1 to correspond to an absorption of heat, which we will call qy. From the first law, the net work vv done in the cycle, is given by w = —q, since AU for the cycle is zero. Thus, for this process, iv is negative (and therefore performed by the system), since qy is positive, having been absorbed from the reservoir. The net effect of this cycle, then, is to completely convert heat absorbed at a high temperature reservoir into work. This is a phenomenon forbidden by the Kelvin-Planck statement of the Second Law. Hence, points to the left of 2 cannot be reached from point 1 by way of any adiabatic path. 

In many applications of mass transfer the solute reacts with the medium as in the case, for example, of the absorption of carbon dioxide in an alkaline solution. The mass transfer rate then decreases in the direction of diffusion as a result of the reaction. Considering the unidirectional molecular diffusion of a component A through a distance Sy over area A. then, neglecting the effects of bulk flow, a material balance for an irreversible reaction of order n gives ... 

The overall reaction between CO2 and GMA was assumed to consist of two elementary reactions such as a reversible reaction of GMA and catalyst to form an intermediate and an irreversible reaction of this intermediate and carbon dioxide to form five-membered cyclic carbonate. Absorption data for CO2 in the solution at 101.3 N/m were interpreted to obtain pseudo-first-order reaction rate constant, which was used to obtain the elementary reaction rate constants. The effects of the solubility parameter of solvent on lc2/k and IC3 were explained using the solvent polarity. 

The reversible oxygenation of Fe(DMG)2 (B)2 in aqueous dioxane solution, as monitored by reversible changes in the visible absorption spectrum and manometric oxygen evolution, has been reported (55), but in a more recent study 54) it was not possible to confirm the earlier findings. However it was established that there was a slow irreversible... 

Figure 3.2. Sequence of PM-RAIR spectra taken on a sputtered Co(0001) surface. The starting conditions were lOOmbar of CO at 298 K 200mbar of H2 was then added and the temperature increased stepwise to 490 K. It can be seen that the absorption signal due to CO attached to defect sites is removed in an irreversible process. The lowest curve was obtained at room temperature and under vacuum conditions and the hydrogen desorbs from the Co, while the CO and hydrocarbons remain. (After Beitel et al. 1997.)...

Chromatographic methods (essentially using ion-exchange resins) are especially useful for separating heparin from other glycosaminoglycans, for further analytical and structural characterization. However, it should be realized that recovery of heparin from resins is seldom quantitative,42 probably because of irreversible absorption of heparin fractions in the... 

Another important type of physical chemical interaction that may alter absorption is that of drug binding or adsorption onto the surface of another material. As with complexation and micellarization, adsorption will reduce the effective concentration gradient between gut fluids and the bloodstream, which is the driving force for passive absorption. While adsorption frequently reduces the rate of absorption, the interaction is often readily reversible and will not affect the extent of absorption. A major exception is adsorption onto charcoal, which in many cases appears to be irreversible, at least during the time of residence within the GIT. As a result, charcoal often reduces the extent of drug absorption. Indeed, this fact... 

Separation in absorption is sometimes enhanced by adding a component to the liquid that reacts with the solute. The discussion regarding absorption has so far been restricted to physical absorption. In chemical absorption, chemical reactions are used to enhance absorption. Both irreversible and reversible reactions can be used. An example of an irreversible reaction is the removal of S02... 

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