Vapor desorption

The water vapor desorption can be measured as shown in the scheme in Figure 1.85.1 and be calculated by... 

Figure 16 Simulated temperature profiles along a reactor with and without "desorptive" cooling at various times for the oxidation of CO on a Pt catalyst with water vapor desorption from 3A zeolite in a fixed bed comprising equal proportions of catalyst and adsorbent. The solid curves give the simple regenerative behavior and the dotted curves describe the desorptively cooled case. Initial reactor temperature is 125°C, initial adsorbent loading 0.12 kg/kg, inlet CO-concentration 0.2 mol/l, gas loading 6000 h-1.

Figure 5 summarizes the low pressure end of water vapor adsorption isotherms obtained on quartz A. Bound water loss, above the surface condition resulting from 400° C. outgassing in vacuum, is indicated by displacement of the adsorption origin to reflect total water content (bound water plus adsorbed water) as a function of water vapor relative pressure. Vapor desorption curves show that... 

The analysis of the evolution and/or destruction of hydrocarbons during the incineration of MSW and hazardous waste involves heat transfer, mass transfer, and reaction kinetics. The key phenomena include the flashing of liquid hydrocarbons the vaporization, desorption, and stripping of hydrocarbons the pyrolysis and charring of hydrocarbons and the oxidation of char. To a certain extent these processes occur in parallel (steps 2, 3,4, and 5) and are common to most thermal treatment processes. 

Precision of Five Replicate Determinations of Phenol by Vapor Desorption-Ion Mobility Spectrometry... 

In the past several years, a number of new ionization methods in mass spectrometry have been introduced. These new techniques have extended mass spectrometric analysis to a wide variety of labile (thermally unstable), highly polar, and higher molecular weight materials. Field ionization (FI) and field desorption (FD) are two of the pioneering techniques in this list of alternative ionization methods. FI-MS, which was introduced for organic molecules in 1954, was the first soft ionization method. (Soft ionization refers to processes that produce high relative abundances of molecular, or quasimolecular, ions.) FD-MS, which was invented in 1969, was the first desorption/ionization method. (Desorption/ionization refers to processes in which die vaporization/ desorption, and ionization steps occur essentially simultaneously.)... 

By exposing PEDOT-PSS/PVP and PVP nanofibers to the solvents, these solvents produced opposite electrical responses in the PEDOT-PSS/PVP and PVP nanofibers. In the case of alcohol vapor sensing, the resistances of PEDOT-PSS/PVP and PVP nanofibers decreased and became constant upon certain saturation, but resistance was increased during alcohol vapor desorption by air. Such decrease may be associated with the dielectric constant of alcohols (Table 1.5]. 

The thin films can equilibrate and desorb vapors within a few seconds to minutes, often at room temperature, while the bulk materials need substantial heating (ca. 200-300°C) to remove the absorbed vapors (the last ppm desorption steps of water from polar zeolite films at r.t. can take 30-50 min). Thus the sensor response occurs at a satisfactory time scale. The kinetics of vapor desorption from the zeolite layers are strongly dependent on the adsorbate/zeolite combination, thus providing an additional capability for molecular recognition. 

Fig. XVI-7. Dielectric isotherms of water vapor at 15°C adsorbed on a-FeiOa (solid points indicate desorption). A complete monolayer was present at P/P = 0.1, and by P/P = 0.8 several layers of adsorbed water were present. (From Ref. 110.)...

Laser desorption is commonly used for pyrolysis/mass spectrometry, in which small samples are heated very rapidly to high temperatures to vaporize them before they are ionized. In this application of lasers, very small samples are used, and the intention is not simply to vaporize intact molecules but also to cause characteristic degradation. 

Laser desorption to produce ions for mass spectrometric analysis is discussed in Chapter 2. As heating devices, lasers are convenient when much energy is needed in a very small space. A typical laser power is 10 ° W/cm. When applied to a solid, the power of a typical laser beam — a few tens of micrometers in diameter — can lead to very strong localized heating that is sufficient to vaporize the solid (ablation). Some of the factors controlling heating with lasers and laser ablation are covered in Figure 17.2. 

Some solid materials are very intractable to analysis by standard methods and cannot be easily vaporized or dissolved in common solvents. Glass, bone, dried paint, and archaeological samples are common examples. These materials would now be examined by laser ablation, a technique that produces an aerosol of particulate matter. The laser can be used in its defocused mode for surface profiling or in its focused mode for depth profiling. Interestingly, lasers can be used to vaporize even thermally labile materials through use of the matrix-assisted laser desorption ionization (MALDI) method variant. 

The above direct process does not produce a high yield of ions, but it does form many molecules in the vapor phase. The yield of ions can be greatly increased by applying a second ionization method (e.g., electarn ionization) to the vaporized molecules. Therefore, laser desorption is often used in conjunction with a second ionization step, such as electron ionization, chemical ionization, or even a second laser ionization pulse. 

Ionization can be improved in many cases by placing the sample in a matrix formed from sinapic acid, nicotinic acid, or other materials. This variant of laser desorption is known as matrix-assisted laser desorption ionization (MALDI). The vaporized acids transfer protons to sample molecules (M) to produce protonated ions [M + H]+. 

The process of field ionization presupposes that the substance under investigation has been volatilized by heat, so some molecules of vapor settle onto the tips held at high potential. In such circumstances, thermally labile substances still cannot be examined, even though the ionization process itself is mild. To get around this difficulty, a solution of the substance under investigation can be placed on the wire and the solvent allowed to evaporate. When an electric potential is applied, positive or negative ions are produced, but no heating is necessary to volatilize the substance. This technique is called field desorption (FD) ionization. 

The ablated vapors constitute an aerosol that can be examined using a secondary ionization source. Thus, passing the aerosol into a plasma torch provides an excellent means of ionization, and by such methods isotope patterns or ratios are readily measurable from otherwise intractable materials such as bone or ceramics. If the sample examined is dissolved as a solid solution in a matrix, the rapid expansion of the matrix, often an organic acid, covolatilizes the entrained sample. Proton transfer from the matrix occurs to give protonated molecular ions of the sample. Normally thermally unstable, polar biomolecules such as proteins give good yields of protonated ions. This is the basis of matrix-assisted laser desorption ionization (MALDI). 

Thermal desorption. The vaporization of ionic or neutral species from the condensed state by the input of thermal energy. The energy input mechanism must be specified. 

This principle is illustrated in Figure 10 (45). Water adsorption at low pressures is markedly reduced on a poly(vinyhdene chloride)-based activated carbon after removal of surface oxygenated groups by degassing at 1000°C. Following this treatment, water adsorption is dominated by capillary condensation in mesopores, and the si2e of the adsorption-desorption hysteresis loop increases, because the pore volume previously occupied by water at the lower pressures now remains empty until the water pressure reaches pressures 0.3 to 0.4 times the vapor pressure) at which capillary condensation can occur. 

Fig. 10. Adsorption ( , O)"desorption (A, A) isotherms of water vapor on poly(vinylidene chloride) (PVDC) carbon before (filled symbols) and after...

The desorptive process may be analyzed before boiling. The key assumption is that the vapor and adsorbed phases are ia equiUbrium ia the bulk of the bed. This assumption eliminates iatraparticle resistances from further consideration and is reasonable for rotary kiln appHcations. The two remaining resistances are associated with hydrocarbon diffusion out of the bed and with convection from the bed surface to the bulk gases. The flux of species Fi from the desorbiag bed becomes... 

The I2 formed stays in solution, exerting a certain vapor pressure, and is extracted from the brine in a countercurrent air blow-out process. The extracted brine leaves the extraction tower and is discarded or reinjected into the wells to avoid sinking of the soil. The iodine-loaded air is then submitted to a cocurrent desorption process by means of an acidic iodide solution to which SO2 is added. By this solution the iodine is reduced to iodide by the following reaction ... 

There are seven commercial processes in operation six operate in the vapor phase. The Universal Oil Products process operates in the Hquid phase and is unique in the simulation of a moving bed. The adsorption unit consists of one vessel segmented into sections with multiple inlet and oudet ports. Flow to the various segments is accompHshed by means of a rotary valve which allows each bed segment to proceed sequentially through all the adsorption/desorption steps. 

Dj IE, ratio of a crack is held constant but the dimensions approach molecular dimensions, the crack becomes more retentive. At room temperature, gaseous molecules can enter such a crack direcdy and by two-dimensional diffusion processes. The amount of work necessary to remove completely the water from the pores of an artificial 2eohte can be as high as 400 kj/mol (95.6 kcal/mol). The reason is that the water molecule can make up to six H-bond attachments to the walls of a pore when the pore size is only slightly larger. In comparison, the heat of vaporization of bulk water is 42 kJ /mol (10 kcal/mol), and the heat of desorption of submonolayer water molecules on a plane, soHd substrate is up to 59 kJ/mol (14.1 kcal/mol). The heat of desorption appears as a exponential in the equation correlating desorption rate and temperature (see Molecularsieves). 

Thermal treatment is used to destroy, break down, or aid in the desorption of contaminants in gases, vapors, Hquids, sludges, and soHds. There are a variety of thermal processes that destroy contaminants, most of which are classified as incineration. Incineration HteraHy means to become ash (from Medieval Latin, incinerare in or into ashes). With respect to the incineration of hazardous wastes regulated in the United States, however, there is a strict legal definition of what constitutes an incinerator. The Resource Conservation and Recovery Act (RCRA) definition of incinerator at 40 CFR 260.10 is... 

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