Adsorbents, dehydration

In Eqns. 5-85 and 5-86, we have distinguished the charge a of surface states from the charge of adsorbed dehydrated ions. Since these two charges are on the same semiconductor surface, it is apparently difficult to distinguish... 

Helmholtz Double Layer A simplistic description of the electric double layer as a condenser (the Helmholtz condenser) in which the condenser plate separation distance is the Debye length. The Helmholtz layer is divided into an inner Helmholtz plane (IHP) of adsorbed, dehydrated ions immediately next to a surface, and an outer Helmholtz plane (OHP) at the center of a next layer of hydrated, adsorbed ions just inside the imaginary boundary where the diffuse double layer begins. That is, both Helmholtz planes are within the Stern layer. 

The hydration shell is formed with the increasing of the water content of the sample and the NA transforms from the unordered to A- and then to B form, in the case of DNA and DNA-like polynucleotides and salt concentrations similar to in vivo conditions. The reverse process, dehydration of NA, results in the reverse conformational transitions but they take place at the values of relative humidity (r.h.) less than the forward direction [12]. Thus, there is a conformational hysteresis over the hydration-dehydration loop. The adsorption isotherms of the NAs, i.e. the plots of the number of the adsorbed water molecules versus the r.h. of the sample at constant temperature, also demonstrate the hysteresis phenomena [13]. The hysteresis is i( producible and its value does not decrease for at least a week. 

Both forms sublime very readily, even at room temperature a small sample on exposure to the air will completely volatilise in a short time, particularly on a warm day or if the sample is exposed to a gentle current of air. Hence the above method for rapid drying. A sample confined in an atmospheric desiccator over calcium chloride rapidly disappears as the vapour is adsorbed by the calcium chloride. A sample of the hexahydrate similarly confined over sodium hydroxide undergoes steady dehydration with initial liquefaction, for the m.p. of the hydrated-anhydrous mixture is below room temperature as the dehydration proceeds to completion, complete resolidification occurs. 

The intercept on the adsorption axis, and also the value of c, diminishes as the amount of retained nonane increases (Table 4.7). The very high value of c (>10 ) for the starting material could in principle be explained by adsorption either in micropores or on active sites such as exposed Ti cations produced by dehydration but, as shown in earlier work, the latter kind of adsorption would result in isotherms of quite different shape, and can be ruled out. The negative intercept obtained with the 25°C-outgassed sample (Fig. 4.14 curve (D)) is a mathematical consequence of the reduced adsorption at low relative pressure which in expressed in the low c-value (c = 13). It is most probably accounted for by the presence of adsorbed nonane on the external surface which was not removed at 25°C but only at I50°C. (The Frenkel-Halsey-Hill exponent (p. 90) for the multilayer region of the 25°C-outgassed sample was only 1 -9 as compared with 2-61 for the standard rutile, and 2-38 for the 150°C-outgassed sample). 

During the adsorption or occlusion of various molecules, the micropores fill and empty reversibly. Adsorption in zeoHtes is a matter of pore filling, and the usual surface area concepts are not appHcable. The pore volume of a dehydrated zeoHte and other microporous soHds which have type 1 isotherms may be related by the Gurvitch rule, ie, the quantity of material adsorbed is assumed to fill the micropores as a Hquid having its normal density. The total pore volume D is given by... 

The 2eohte sodium X (type 13X) has a crystallographic aperture of 0.74 nm. This compares well with the adsorbate value of 0.81 nm. ZeoHte calcium X exhibits a smaller apparent pore si2e of 0.78 nm (lOX). This difference is probably due to some distortion of the aluminosihcate framework upon dehydration and calcium ion migration. 

Molecular sieves have had increasing use in the dehydration of cracked gases in ethylene plants before low temperature fractionation for olefin production. The Type 3A molecular sieve is size-selective for water molecules and does not co-adsorb the olefin molecules. 

Favor adsorption for processes that require essentially complete removal of water vapor (adsorptive dehydration is capable of achieving dew point depres >45° C (80°F) molecular sieves are favored adsorbents. 

Trinidad asphalt has a relatively uniform composition of 29% water and gas, 39% bitumen soluble in carbon disulfide, 27% mineral matter on ignition, and 5% bitumen that remains adsorbed on the mineral matter. Refining is essentially a process of dehydration by heating the cmde asphalt to ca 165°C. The refined product averages 36% mineral ash with a penetration at 25°C of about 2 (0.2 mm), a softening point (ring and ball method) of 99°C, a flash point (Cleveland open cup) of 254°C, a sulfur content of 3.3%, and a saponification value of 45 mg KOH/g. The mineral matter typically contains... 

Adsorbent drying systems are typicaHy operated in a regenerative mode with an adsorption half-cycle to remove water from the process stream and a desorption half-cycle to remove water from the adsorbent and to prepare it for another adsorption half-cycle (8,30,31). UsuaHy, two beds are employed to aHow for continuous processing. In most cases, some residual water remains on the adsorbent after the desorption half-cycle because complete removal is not economically practical. The difference between the amount of water removed during the adsorption and desorption half-cycle is termed the differential loading, which is the working capacity available for dehydration. 

Fig. 14. Position of water front in packed bed of adsorbent during dynamic dehydration. Conditions 50% rh 10.2 cm/s air particle size = caO.167 cm ...

Activation of zeolites is a dehydration process aceomplished by the application of heat in a high vacuum. Some zeolite crystals show behavior opposite to that of activated carbon in that they selectively adsorb water in the presence of nonpolar solvents. Zeolites can be made to have specifie pore sizes that will increase their seleetive nature due to the size and orientation of the molecules to be adsorbed. Moleeules above a specific size could not enter the pores and therefore would not be adsorbed. 

Molecular sieves are an adsorbent that is produced by the dehydration of naturally occurring or synthetic zeolites (crystalline alkali-metal aluminosilicates). The dehydration leaves inter-crystalline cavities into which normal paraffin molecules are selectively retained and other molecules are excluded. This process is used to remove normal paraffins from gasoline fuels for improved combustion. Molecular sieves are used to manufacture high-purity solvents. 

Silica gel and aluminium oxide layers are highly active stationary phases with large surface areas which can, for example, — on heating — directly dehydrate, degrade and, in the presence of oxygen, oxidize substances in the layer This effect is brought about by acidic silanol groups [93] or is based on the adsorption forces (proton acceptor or donor effects, dipole interactions etc) The traces of iron in the adsorbent can also catalyze some reactions In the case of testosterone and other d -3-ketosteroids stable and quantifiable fluorescent products are formed on layers of basic aluminium oxide [176,195]... 

Multiple desiccant beds are used in cyclic operation to dry the gas on a continuous basis. The number and arrangement of the desiccant beds may vary from two towers, adsorbing alternately, to many towers. Three separate functions or cycles must alternately be performed in each dehydrator. They are an adsorbing or gas drying cycle, a heating or regeneration cycle, and a cooling cycle. 

In its simplest form, an adsorber is normally a cylindrical tower filled with a solid desiccant. The depth of the desiccant may vary from a few feet to 30 ft or more. The vessel diameter may be from a few inches to 10 or 15 ft. A bed height to diameter (L/D) ratio of higher than 2.5 is desirable. Ratios as low as 1 1 are sometimes used however, poor gas dehydration, caused by non-uniform flow, channeling and an inadequate contact time between the wet gas and the desiccant sometimes result. 

An important variable that determines the size of a given desiccant bed is the relative saturation of the inlet gas. This variable is the driving force that affects the transfer of water to the adsorbent. If saturated gas (100% relative humidity) is being dried, higher useful capacities can be expected for most desiccants than when drying partially saturated gases. However, in most field gas dehydration installations the inlet gas is samrated with water vapor and this is not a variable that must be considered. 

Adsorption processes use a solid material (adsorbent) possessing a large surface area and the ability to selectively adsorb a gas or a liquid on its surface. Examples of adsorbents are silica (Si02), anhydrous alumina (AI2O3), and molecular sieves (crystalline silica/alumina). Adsorption processes may be used to remove acid gases from natural gas and gas streams. For example, molecular sieves are used to dehydrate natural gas and to reduce its acid gases. 

A large amount of water is added to the dehydrated material in order to cause it to swell the swollen structure is preserved when the material is frozen and subsequently dried in vacuo (in the frozen state) to a low moisture content. Some leaching occurs during the treatment with water and this, undoubtedly, further contributes to the increase in the porosity of the solid. Drying of the lyophilized substance can.be completed in a relatively short time in a vacuum oven at an elevated temperature, or at room temperature in the presence of an efficient water adsorbent. 

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