Simultaneous Adsorption

The triple layer model attempts to take into account inner sphere complex formation and electrostatic adsorption simultaneously by considering "specifically adsorbed" ions which are supposed to be maintained very close to the surface, whether it be through the formation of covalent bonds with some surface groups, or of some outer sphere complex. No specific interpretation of the bonding is required, provided one can define a plane of specific adsorption, located a few A from the surface and containing those ions this is called the Stem layer. The theory distinguishes then between three successive parallel layers the surface plane proper, the Stem layer, and the diffuse layer. 

Figure 10. Reduction of fibrinogen adsorption (simultaneous albumin incubation) with 0 8 alkylated polyurethanes. Abscissa enhancement of albumin adsorption on a duplicate treated sample, using identical methodology. (Reproduced with permission from Ref. 25. Copyright 1983 American Society for Artificial Internal Organs.)...

The model equations (11.6-2) to (11.6-4) are validated with the experimental data of binary and ternary systems of ethane, propane and n-butane onto activated carbon. All the necessary equilibrium and kinetic parameters are obtained from the single component fitting as done in the last section. In this sense the multicomponent model is the predicting tool, and it has been shown in Do (1997) that this multicomponent heterogeneous model is a good predictive model. It is capable of predicting well simultaneous adsorption, simultaneous desorption and displacement. Readers are referred to a review paper by Do (1997) for further details. 

Adsorption refers to the accumulation of any species from one of the continuous phases at the interface between two phases. If the solid-liquid (S/L) interface is in question [i.e., adsorption of a dissolved material (solute) is studied], the wetting of solid material (adsorbent) by the liquid (medium in which adsorbent is dispersed) and the solubdilty of solute in the given liquid (here, solvent) have to be considered in addition to adsorption. Simultaneous equilibria of adsorption, wetting, and solubility exist between the components (adsorbent, solvent, and solute). Competition of solvent and solute molecules for surface sites and also competition of surface and solvation forces for solute molecules are always present in the S/L adsorption systems. Therefore, a better understanding of adsorption from solutions requires that the interaction of a solute with a surface be characterized in terms of the frmdamental physical and chemical properties of aU the three components (solute, adsorbent, and solvent) of adsorption. 

The swelling of the adsorbent can be directly demonstrated as in the experiments of Fig. 4.27 where the solid was a compact made from coal powder and the adsorbate was n-butane. (Closely similar results were obtained with ethyl chloride.) Simultaneous measurements of linear expansion, amount adsorbed and electrical conductivity were made, and as is seen the three resultant isotherms are very similar the hysteresis in adsorption in Fig. 4.27(a), is associated with a corresponding hysteresis in swelling in (h) and in electrical conductivity in (c). The decrease in conductivity in (c) clearly points to an irreversible opening-up of interparticulate junctions this would produce narrow gaps which would function as constrictions in micropores and would thus lead to adsorption hysteresis (cf. Section 4.S). 

Mechanisms of Leukocyte Adsorption. The exact mechanism of leukocyte adhesion to filter media is not yet fuUy understood. Multiple mechanisms simultaneously contribute to the adhesion of cells to biomaterials, however, physical and biological mechanisms have been distinguished. Physical mechanisms include barrier phenomenon, surface tension, and electrostatic charge biological mechanisms include cell activation and cell to cell binding. 

Uranium Purification. Subsequent uranium cycles provide additional separation from residual plutonium and fission products, particularly zirconium— niobium and mthenium (30). This is accompHshed by repeating the extraction/stripping cycle. Decontamination factors greater than 10 at losses of less than 0.1 wt % are routinely attainable. However, mthenium can exist in several valence states simultaneously and can form several nitrosyl—nitrate complexes, some for which are extracted readily by TBP. Under certain conditions, the nitrates of zirconium and niobium form soluble compounds or hydrous coUoids that compHcate the Hquid—Hquid extraction. SiUca-gel adsorption or one of the similar Hquid—soHd techniques may also be used to further purify the product streams. 

Work in the area of simultaneous heat and mass transfer has centered on the solution of equations such as 1—18 for cases where the stmcture and properties of a soHd phase must also be considered, as in drying (qv) or adsorption (qv), or where a chemical reaction takes place. Drying simulation (45—47) and drying of foods (48,49) have been particularly active subjects. In the adsorption area the separation of multicomponent fluid mixtures is influenced by comparative rates of diffusion and by interface temperatures (50,51). In the area of reactor studies there has been much interest in monolithic and honeycomb catalytic reactions (52,53) (see Exhaust control, industrial). Eor these kinds of appHcations psychrometric charts for systems other than air—water would be useful. The constmction of such has been considered (54). 

There are two general theories of the stabUity of lyophobic coUoids, or, more precisely, two general mechanisms controlling the dispersion and flocculation of these coUoids. Both theories regard adsorption of dissolved species as a key process in stabilization. However, one theory is based on a consideration of ionic forces near the interface, whereas the other is based on steric forces. The two theories complement each other and are in no sense contradictory. In some systems, one mechanism may be predominant, and in others both mechanisms may operate simultaneously. The fundamental kinetic considerations common to both theories are based on Smoluchowski s classical theory of the coagulation of coUoids. 

A novel sensitive and seleetive adsorptive stripping proeedure for simultaneous determination of eopper, bismuth and lead is presented. The method is based on the adsorptive aeeumulation of thymolphetalexone (TPN) eomplexes of these elements onto a hanging mereury drop eleetrode, followed by reduetion of adsorbed speeies by voltammetrie sean using differential pulse modulation. The optimum analytieal eonditions were found to be TPN eoneentration of 4.0 p.M, pH of 9.0, and aeeumulation potential at -800 mV vs. Ag/AgCl with an aeeumulation time of 80 seeonds. The peak eurrents ai e proportional to the eoneentration of eopper, bismuth and lead over the 0.4-300, 1-200 and 1-100 ng mL ranges with deteetion limits of 0.4, 0.8 and 0.7 ng mL respeetively. The proeedure was applied to the simultaneous determination of eopper, bismuth and lead in real and synthetie samples with satisfaetory results. 

There was studied dependence of sorption rate values of microamounts high listed elements from time of their contact with sorbents, pH media and means of equilibrium concentration. It is shown that owing to exchange of sorbents surface characteristics, its hydrating rate value and heterogeneity of sorbate and hydrolyzed forms of metals investigated interaction with surface can simultaneously proceed on several mechanisms. The contributions of various factors into adsorption of elements-analogues are depended from sorption conditions and nature of sorbent surface. 

Subsequently, biological/physical treatment of leachate with an activated carbon-enhanced sequencing batch bioreactor (PAC-SBR) was analyzed to determine whether the improved treatment by simultaneous adsorption and biodegradation in the SBR would produce an acceptable effluent without post-treatment in the existing granular activated carbon adsorber (Ying et al., 1986). 

In the desorption step, ammonia is passed downflow through the bed which has completed the adsorption cycle. The ammonia is heated to approximately the same temperature as that of the feed in the adsorption step in order to maintain a nominally isothermal operation. The first portion of the desorbate, although rich in n-paraffms, contains impurities and is recycled to the second bed which is simultaneously operating on the adsorption cycle. The remaining product is condensed and separated from ammonia. The product is freed of dissolved ammonia by distillation. 

Six potential MSAs should be simultaneously screened. Riese include absoiption in water. Si. adsorption onto activated carbon, Sj, absorption in chilled methanol, S3, and the use of the following reactive solvents diethanolamine (DEA), S4, hot potassium carbonate, Sj, and diisc ir ranolamine (DIPA), S. ... 

The terms proportional to and describe adsorption on, and desorption from, the reconstructed and unreconstructed surfaces, respectively, without a simultaneous change in the surface structure. The term with accounts for the spontaneous reconstruction and the spontaneous lifting of the reconstruction in the absence of an adsorbate. The expressions with w r and Wsu give the rates of adsorption and desorption with concurrent reconstruction or lifting of the reconstruction. Finally, the terms proportional to... 

In sulphur dioxide linear kinetics are generally observed due to control by phase boundary reactions, i.e. adsorption of SOj. RahmeF suggested that this is one of the conditions which favours simultaneous nucleation of sulphide and oxide at the gas/scale interface. The main reaction products are NiO, NijSj, Ni-S,j, and NiS04, depending on the temperature and gas pressure for example, according to the following reaction ... 

In the case of ions, the repulsive interaction can be altered to an attractive interaction if an ion of opposite charge is simultaneously adsorbed. In a solution containing inhibitive anions and cations the adsorption of both ions may be enhanced and the inhibitive efficiency greatly increased compared to solutions of the individual ions. Thus, synergistic inhibitive effects occur in such mixtures of anionic and cationic inhibitors . These synergistic effects are particularly well defined in solutions containing halide ions, I. Br , Cl", with other inhibitors such as quaternary ammonium cations , alkyl benzene pyridinium cations , and various types of amines . It seems likely that co-ordinate-bond interactions also play some part in these synergistic effects, particularly in the interaction of the halide ions with the metal surfaces and with some amines . 

The effects of adsorbed inhibitors on the individual electrode reactions of corrosion may be determined from the effects on the anodic and cathodic polarisation curves of the corroding metaP . A displacement of the polarisation curve without a change in the Tafel slope in the presence of the inhibitor indicates that the adsorbed inhibitor acts by blocking active sites so that reaction cannot occur, rather than by affecting the mechanism of the reaction. An increase in the Tafel slope of the polarisation curve due to the inhibitor indicates that the inhibitor acts by affecting the mechanism of the reaction. However, the determination of the Tafel slope will often require the metal to be polarised under conditions of current density and potential which are far removed from those of normal corrosion. This may result in differences in the adsorption and mechanistic effects of inhibitors at polarised metals compared to naturally corroding metals . Thus the interpretation of the effects of inhibitors at the corrosion potential from applied current-potential polarisation curves, as usually measured, may not be conclusive. This difficulty can be overcome in part by the use of rapid polarisation methods . A better procedure is the determination of true polarisation curves near the corrosion potential by simultaneous measurements of applied current, corrosion rate (equivalent to the true anodic current) and potential. However, this method is rather laborious and has been little used. 

A number of metals have the ability to absorb hydrogen, which may be taken into solid solution or form a metallic hydride, and this absorption can provide an alternative reaction path to the desorption of H,. as gas. In the case of iron and iron alloys, both hydrogen adsorption and absorption occur simultaneously, and the latter thus gives rise to another equilibrium involving the transfer of H,<,s across the interface to form interstitial H atoms just beneath the surface ... 

Simultaneously with the decrease of the number of variables, the number of the parameters to be determined also decreases the remaining parameters are, of course, only relative values of, in our case, the rate constants and adsorption coefficients... 

The simplest case to be analyzed is the process in which the rate of one of the adsorption or desorption steps is so slow that it becomes itself rate determining in overall transformation. The composition of the reaction mixture in the course of the reaction is then not determined by kinetic, but by thermodynamic factors, i.e. by equilibria of the fast steps, surface chemical reactions, and the other adsorption and desorption processes. Concentration dependencies of several types of consecutive and parallel (branched) catalytic reactions 52, 53) were calculated, corresponding to schemes (Ila) and (lib), assuming that they are controlled by the rate of adsorption of either of the reactants A and X, desorption of any of the products B, C, and Y, or by simultaneous desorption of compounds B and C. 

Fig. 4. Dependence of relative concentrationa nj/nt of reaction components A, B, and C on time variable r (arbitrary units) in the case of consecutive (— — ) reactions according to scheme (Ha) or parallel (C ) reactions according to scheme (lib). Ads X, Ads A, Des Y denotes that the rate determining step in the overall transformation is adsorption or desorption of the respective substance Des (B + C) denotes that the overall rate is determined by simultaneous desorption of the substance B and C. Ki/Ki = 0.5 for consecutive, and Ki /Ki — 0.5 for parallel reactions, b nxVn. 0 = 2.5 for consecutive reactions Kt = 0.5, and for parallel reactions Ki/Ki — 0.5. c nxVnA0 = 2.5 fcdesBKi Ky/fcdesoXj Kx = 10 [cf. (53)]. d Ki = 1.75 for consecutive, and Ki/Ki = 1.75 for parallel reactions.

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