Transfer solid-phase

There are five modelsl l which can be used to represent the kinetics in ion exchange systems which involve liquid exchange phase mass transfer, solid phase mass transfer, and chemical reaction at the exchange group. 

The protected nucleoside-3-phosphoramidite monomer units such as 671 are used in the solid-phase oligonucleotide synthesis. In the 60mer synthesis, 104 allylic protective groups are removed in almost 100% overall yield by the single Pd-catalyze reaction with formic acid and BuNH2[432], N,(9-protection of uridine derivatives was carried out under pha.se-transfer conditions[433]. 

Solid-phase microextractions also have been developed. In one approach, a fused silica fiber is placed inside a syringe needle. The fiber, which is coated with a thin organic film, such as poly(dimethyl siloxane), is lowered into the sample by depressing a plunger and exposed to the sample for a predetermined time. The fiber is then withdrawn into the needle and transferred to a gas chromatograph for analysis. 

Caffeine is extracted from beverages by a solid-phase microextraction using an uncoated fused silica fiber. The fiber is suspended in the sample for 5 min and the sample stirred to assist the mass transfer of analyte to the fiber. Immediately after removing the fiber from the sample it is transferred to the gas chromatograph s injection port where the analyte is thermally desorbed. Quantitation is accomplished by using a C3 caffeine solution as an internal standard. 

Contactive (Direct) Heat Transfer Contactive heat-transfer equipment is so constructed that the particulate burden in solid phase is directly exposed to and permeated by the heating or cooling medium (Sec. 20). The carrier may either heat or cool the solids. A large amount of the industrial heat processing of sohds is effected by this mechanism. Physically, these can be classified into packed beds and various degrees of agitated beds from dilute to dense fluidized beds. 

Combined Pore and Solid Diffusion In porous adsorbents and ion-exchange resins, intraparticle transport can occur with pore and solid diffusion in parallel. The dominant transport process is the faster one, and this depends on the relative diffusivities and concentrations in the pore fluid and in the adsorbed phase. Often, equilibrium between the pore fluid and the solid phase can be assumed to exist locally at each point within a particle. In this case, the mass-transfer flux is expressed by ... 

FIG. 16-12 Correction factors for addition of mass-transfer resistances, relative to effective overall solid phase or fluid phase rates, as a function of the mechanism parameter. Each curve corresponds to both and hj over its entire range. 

Rotating-drum-type and belt-type heat-transfer equipment forms granular products directly from fluid pastes and melts without intermediate preforms. These processes are described in Sec. 5 as examples of indirect heat transfer to and from the solid phase. When solidification results from melt freezing, the operation is known as flaking. If evaporation occurs, solidification is by diying. 

The dominant mechanism of purification for column ciystallization of sohd-solution systems is reciystallization. The rate of mass transfer resulting from reciystallization is related to the concentrations of the solid phase and free hquid which are in intimate contac t. A model based on height-of-transfer-unit (HTU) concepts representing the composition profQe in the purification sec tion for the high-melting component of a binaiy solid-solution system has been reported by Powers et al. (in Zief and Wilcox, op. cit., p. 363) for total-reflux operation. Typical data for the purification of a solid-solution system, azobenzene-stilbene, are shown in Fig. 22-10. The column ciystallizer was operated... 

When a gas reacts with a solid, heat will be transfened from the solid to the gas when the reaction is exothermic, and from gas to solid during an endothermic reaction. The energy which is generated will be distributed between the gas and solid phases according to the temperature difference between the two phases, and their respective thermal conductivities. If the surface temperature of the solid is T2 at any given instant, and that of the bulk of the gas phase is Ti, the rate of convective heat transfer from the solid to the gas may be represented by the equation... 

Equivalent rates of mass transfer, where mass transfer is occuiTing between a liquid and a solid phase, between liquid-liquid phases, or between gas and liquid phases, and the rates are identical. 

Extraction (sometimes called leaching) encompasses liquid-liquid as well as liquid-solid systems. Liquid-liquid extraction involves the transfer of solutes from one liquid phase into another liquid solvent it is normally conducted in mixer settlers, plate and agitated-tower contacting equipment, or packed or spray towers. Liquid-solid extraction, in which a liquid solvent is passed over a solid phase to remove some solute, is carried out in fixed-bed, moving-bed, or agitated-solid columns. 

Other PK variations include microwave conditions, solid-phase synthesis, and the fixation of atmospheric nitrogen as the nitrogen source (27—>28). Hexamethyldisilazane (HMDS) is also an excellent ammonia equivalent in the PK synthesis. For example, 2,5-hexanedione and HMDS on alumina gives 2,5-dimethylpyrrole in 81% yield at room temperature. Ammonium formate can be used as a nitrogen source in the PK synthesis of pyrroles from l,4-diaryl-2-butene-l,4-diones under Pd-catalyzed transfer hydrogenation conditions. 

Supercritical fluid extraction (SFE) and Solid Phase Extraction (SPE) are excellent alternatives to traditional extraction methods, with both being used independently for clean-up and/or analyte concentration prior to chromatographic analysis. While SFE has been demonstrated to be an excellent method for extracting organic compounds from solid matrices such as soil and food (36, 37), SPE has been mainly used for diluted liquid samples such as water, biological fluids and samples obtained after-liquid-liquid extraction on solid matrices (38, 39). The coupling of these two techniques (SPE-SFE) turns out to be an interesting method for the quantitative transfer... 

When a first column of a very short length (and therefore a low selectivity) is used (this is especially suitable for multiresidue methods), we talk about an on-line precolumn (PC) switching technique coupled to LC (PC-LC or solid-phase extraction (SPE)-LC). This is particulary useful for the enrichment of analytes, and enables a higher sample volume to be injected into the analytical column and a higher sensitivity to be reached. The sample is passed through the precolumn and analytes are retained, while water is eliminated then, by switching the valve, the analytes retained in the precolumn are transferred to the analytical column by the mobile phase, and with not just a fraction, as in the previous cases. 

In some circumstances, separation of solid from a liquid is better achieved by use of a centrifuge than by filtration, and a small, electrically driven centrifuge is a useful piece of equipment for an analytical laboratory. It may be employed for removing the mother liquor from recrystallised salts, for collecting difficultly filterable precipitates, and for the washing of certain precipitates by decantation. It is particularly useful when small quantities of solids are involved centrifuging, followed by decantation and re-centrifuging, avoids transference losses and yields the solid phase in a compact form. Another valuable application is for the separation of two immiscible phases. 

Sublimation (diffusion) printing is a textile process in which color patterns in dry die crystals are transferred from a release film to the fabric under high heat and pressure. The process has been adapted to plastics. The equipment used is very similar to that used for hot stamping. Under heat and pressure, the dye crystals sublime (go directly to the vapor phase from the solid phase without melting) and the vapor penetrates the plastic product. As a result, the decoration is very durable and wear resistant. It is also cost competitive against other processes such as two-step injection molding or silk screening. 

Fig. 11. Change of the fluorescence spectra of polyfpropynoic acid)s as a result of transfer from solution [(1) PPAL, (2) PPASJ to the solid phase [(3) PPAL, (4) PPASJ. Concentration of aqueous solutions 10 4 mol/1. The fluorescence spectra of the samples in solid phase were taken from powdered polymers placed between two quartz plates. Slit width 0.2 mm sensitivity 3,0 excitation = 365 nm. / = intensity...

A similar derivation can be made for the rate of mass transfer from the gas phase to the solid phase. 

The basic approach taken in the analytical studies of composite-propellant combustion represents a modification of the studies of double-base propellants. For composite propellants, it has been assumed that the solid fuel and solid oxidizer decompose at the solid surface to yield gaseous fuel and oxidizing species. These gaseous species then intermix and react in the gas phase to yield the final products of combustion and to establish the flame temperature. Part of the gas-phase heat release is then transferred back to the solid phase to sustain the decomposition processes. The temperature profile is assumed to be similar to the situation associated with double-base combustion, and, in this sense, combustion is identical in the two different types of propellants. 

These studies have indicated that the independent parameters controlling the postulated solid-phase reactions significantly affect the resulting acoustic admittance of the combustion zone, even though these reactions were assumed to be independent of the pressure in the combustion zone. In this combustion model, the pressure oscillations cause the flame zone to move with respect to the solid surface. This effect, in turn, causes oscillations in the rate of heat transfer from the gaseous-combustion zone back to the solid surface, and hence produces oscillations in the temperature of the solid surface. The solid-phase reactions respond to these temperature oscillations, producing significant contributions to the acoustical response of the combustion zone. 

The gas-liquid-particle processes considered in this paper may be grouped into two major classes. In the first, components of all three phases participate in the chemical reaction. In the second, components of only the gaseous and the solid phases participate in the chemical reaction, the liquid phase functioning as a chemically inactive medium for the transfer of momentum, heat, and mass. Important examples of these two types of processes are described, respectively, in Sections II,A and II,B. 

In a number of these processes, a liquid heat- and mass-transfer medium is in direct contact with the catalyst and the reaction mixture. The main function of the liquid is to act as a heat sink and as a medium for convective heat transfer. However, since the liquid may be assumed to cover the solid particles and in this way act as a barrier between the gaseous and the solid phases, it must therefore also function as a mass-transfer medium. 

Equation (15) is derived under the assumption that the amount of adsorbed component transferred by flow or diffusion of the solid phase may be neglected. This assumption is clearly justified in cases of fixed-bed operation, and it is believed to be permissible in many cases of slurries or fluidized beds, since the absolute amount of adsorbed component will probably be quite low due to its low diffusivity in the interior of the catalyst pellet. The assumption can, however, be waived by including in Eq. (15) the appropriate diffusive and convective terms. 

Bubble-column slurry operations are usually characterized by zero net liquid flow, and the particles are held suspended by momentum transferred from the gas phase to the solid phase via the liquid medium. The relationships between solids holdup and gas flow rate is of importance for design of bubble-column slurries, and some studies of this aspect will be reviewed prior to the discussion of transport phenomena. 

Recently it has been shown that the microwave-assisted decoration of the 2(lff)-pyrazinone scaffold can allow an easy introduction of different substituents at the C-3 and even to the less reactive C-5 position [29]. Taking full advantage of combinatorial principles, some of these pathways were transferred to microwave-enhanced solid-phase chemistry, opening the way for the generation of many biologically interesting structures [108]. 

Unsymmetrical as well as symmetrical anhydrides are often prepared by the treatment of an acyl halide with a carboxylic acid salt. The compound C0CI2 has been used as a catalyst. If a metallic salt is used, Na , K , or Ag are the most common cations, but more often pyridine or another tertiary amine is added to the free acid and the salt thus formed is treated with the acyl halide. Mixed formic anhydrides are prepared from sodium formate and an aryl halide, by use of a solid-phase copolymer of pyridine-l-oxide. Symmetrical anhydrides can be prepared by reaction of the acyl halide with aqueous NaOH or NaHCOa under phase-transfer conditions, or with sodium bicarbonate with ultrasound. 

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