Aqueous-organic interphase

In Eq. (10.21) subscript i refers to the adsorbed state at the aqueous-organic interphase. The concentrations in brackets refer to the organic phase. The rate of product formation is ... 

Catalysis in Transacylation Reactions. The principal objective of the study was to evaluate 4 as an effective organic soluble lipophilic catalyst for transacylation reactions of carboxylic and phosphoric acid derivatives in aqueous and two-phase aqueous-organic solvent media. Indeed 4 catalyzes the conversion of benzoyl chloride to benzoic anhydride in well-stirred suspensions of CH2CI2 and 1.0 M aqueous NaHCC>3 (Equations 1-3). The results are summarized in Table 1 where yields of isolated acid, anhydride and recovered acid chloride are reported. The reaction is believed to involve formation of the poly(benzoyloxypyridinium) ion intermediate (5) in the organic phase (Equation 1) and 5 then quickly reacts with bicarbonate ion and/or hydroxide ion at the interphase to form benzoate ion (Equation 2 and 3). Apparently most of the benzoate ion is trapped by additional 5 in the organic layer or at the interphase to produce benzoic anhydride (Equation 4), an example of normal phase-... 

The complexes formed with Zr(IV) can lead to the formation of stable emulsions, called cruds (27, 89, 107, 108, 128, 129), present at the aqueous-organic interface and stabilized by microsolid particles. Chemical analysis of interphase precipitate showed that its main components were Zr and HBDP. The precipitation depends on the acidity, the concentration of HDBP, and the concentration of Zr (130). In the solid form, the formula proposed is Zr(N03)2(DBP)2 (101). In solution, several Zr-HDBP complexes have been detected (59, 64,109,110,123,131, 132). 

The reactor is a continuous stirred tank reactor that provides intense mixing of the excess aqueous phase, the organic phase (ratio aqueous/organic phase = 6), and syngas to create enough interphase for effective mass transfer. The reaction exotherm is applied in a falling film evaporator to produce w-butyraldehyde vapor to... 

The degree of polarizability of system can be found from the data calculated by Le Hung [25] with the use of Eqs. (16) and (17). In the equilibrium state of the interphase between the solutions of 0.05 M LiCl in water and 0.05 M TBATPhB in nitrobenzene, the concentrations of Li and CL in the organic phase lower than 10 M, and the concentrations of TBA and TPhB in the aqueous phase are about 3 x 10 M each [3]. These concentrations are too low to establish permanent reversible equilibria. They are, however, significantly higher compared to those of the components present in the mercury-aqueous KF solution system [20]. 

Quite generally, the interphase between an organism and its environment encompasses the elements outlined in Figure 1 of Chapter 1. The scheme shows that the cell membrane, with its hydrophobic lipid bilayer core, has the most prominent function in separating the external aqueous medium from the interior of the cell. The limited and selective permeabilities of the cell membrane towards components of the medium - nutrients as well as toxic species - play a governing role in the transport of material from the medium towards the surface of the organism. 

Sorption/desorption is one of the most important processes influencing movemement of organic pollutants in natural systems. Sorption with reference to a pollutant is its transfer from the aqueous phase to the solid phase on the other hand, desorption is its transfer from the solid phase to the aqueous phase. Similar to all interphase mass-transfers, the sorption/ desorption process can be defined by the final-phase equilibrium of the pollutant at the aqueous-solid phase interface and the time required to approach final equilibrium. 

Reactions carried in aqueous multiphase catalysis are accompanied by mass transport steps at the L/L- as well as at the G/L-interface followed by chemical reaction, presumably within the bulk of the catalyst phase. Therefore an evaluation of mass transport rates in relation to the reaction rate is an essential task in order to gain a realistic mathematic expression for the overall reaction rate. Since the volume hold-ups of the liquid phases are the same and water exhibits a higher surface tension, it is obvious that the organic and gas phases are dispersed in the aqueous phase. In terms of the film model there are laminar boundary layers on both sides of an interphase where transport of the substrates takes place due to concentration gradients by diffusion. The overall transport coefficient /cl can then be calculated based on the resistances on both sides of the interphase (Eq. 1) ... 

The concept sounds attractive, but there is a flaw in the explanation. Assuming an equilibrium situation between the two bulk phases and the interphase, complex formation at the interfacial region requires the same complexes are formed also in the bulk phases. Consequently, in order to produce a considerable amount of the mixed species MA, xBx in the liquid-liquid boundary layer some B must be dissolved in the aqueous, as weU as some A in the organic phase. Since by definition this condition is not met, the relative amount of M present at the interphase region as MAn xBx must be negligible. However, now the metal ion will be distributed between MA in the aqueous phase and MBp in the organic layer (n and p are the... 

The influence of process variables such as the temperature, pressure of H2 and CO on the hydroformylation reaction is well recognized by all researchers. However, other aspects, such as stirring speed, the shape and size of the stirrer, relative amounts of the aqueous and organic phases, etc. are usually overlooked by people working in laboratories far from the actual chemicals production. A few papers in the open literature deal with these questions, of which perhaps the most important concerns the location of the chemical reaction. Does it takes place in the bulk phases or at the interphase region ... 

In this technique, a hydrophobic polymer is dissolved in an organic solvent, such as chloroform, ethyl acetate, or methylene chloride and is emulsified in an aqueous phase containing a stabilizer (e.g., PVA). Just after formation of the nanoemulsion, the solvent diffuses to the external phase until saturation. The solvent molecules that reach the water-air interphase evaporate, which leads to continuous diffusion of the solvent molecules from the inner droplets of the emulsion to the external phase simultaneously, the precipitation of the polymer leads to the formation of nanospheres. The extraction of solvent from the nanodroplets to the external aqueous medium can be induced by adding an alcohol (e.g. isopropanol), thereby increasing the solubility of the organic solvent in the external phase. A purification step is required to assure the elimination of the surfactant in the preparation. This technique is most suitable for the encapsulation of lipophilic drugs, which can be dissolved in the polymer solution. 

A two-phase system (carbon tetrachloride and water) is often used for these reactions. It spears that contact between ruthenium tetroxide and the alkene takes place in the organic phase where they are both most soluble. The mthenium dioxide produced when oxidation occurs is insoluble in all solvents and migrates to the interphase where it contacts the cooxidant (in the aqueous phase) and is reoxidized, as summarized in Scheme 3. Because good contact between all components is essential, best results are obtained when the mixture is shaken or stirred vigorously throughout the course of the reaction. Sharpless and his coworkers have also found that the addition of acetonitrile to the two-phase mixture improves yields. 

Electrosorption is a replacement reaction. We have already discussed the role of the solvent in the interphase, in the context of its effect on the double-layer capacitance. It is most important for our present discussion to know that the electrode is always solvated and that the solvent molecules are held to the surface both by electrostatic and by chemical bonds. Adsorption of a molecule on such a surface requires the removal of the appropriate number of solvent molecules, to make place for the new occupant, so to speak. This is electrosorption. In this chapter we shall restrict our discussion to the electrosorption of neutral organic molecules from aqueous solutions, without charge transfer. Using the notation RH for an unspecified organic molecule, we can then represent electrosorption in general by the reaction... 

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