Aqueous phase effect

C. S. Callam, S. J. Singer, T. F. Fowary, and C. M. Hadad, Computational analysis of the potential energy surfaces of glycerol in the gas and aqueous phases Effects of level of theory, basis set, and solvation on strongly intramolecularly hydrogen bonded systems. J. Am. Chem. Soc. 123, 11743 11754 (2001). 

One requirement for a reaction to occur is that the chemicals involved must be able to mix and interact with one another. Thus the physical state of the reactants can be important. In particular, an aqueous solution is often used as the medium for a reaction. To describe reactions in the aqueous phase effectively, we often need to specify the molar concentration of the solutions used. We also have options about how to write the chemical reaction itself—as a molecular equation, for example, or a net ionic equation. Several classes of chemical reactions, such as precipitation reactions or acid-base neutralizations, are sufficiently common that additional definitions have been established to improve our ability to communicate about them. 

Thus, the role of polymer here is to improve the mobility ratio between the fluids by either increasing aqueous-phase viscosity or reducing the aqueous-phase effective permeability (see Chapter 5) or both. This lowered mobility ratio will improve both the linear and areal displacement efficiency, thus leading to improved oil recovery. 

The effects of 4-substituents on the gas-phase base strengths of pyridine have been more extensively studied [87]. The results are shown for series 4 of Table 9. The gas-phase substituent effects RAGfg) are roughly linear with the corresponding aqueous-phase effects 5 iAG( q), as shown in Figure 5. However, the points for — R (71-electron donor) substituents all lie above the relatively precise correlation line for H and 4-R substituents (CF3, CN, and NO2). Data for both phases are described with precision (c/. Table 9) by the dual-substituent parameter treatment [92] ... 

The kinetic data are essentially always treated using the pseudophase model, regarding the micellar solution as consisting of two separate phases. The simplest case of micellar catalysis applies to unimolecTilar reactions where the catalytic effect depends on the efficiency of bindirg of the reactant to the micelle (quantified by the partition coefficient, P) and the rate constant of the reaction in the micellar pseudophase (k ) and in the aqueous phase (k ). Menger and Portnoy have developed a model, treating micelles as enzyme-like particles, that allows the evaluation of all three parameters from the dependence of the observed rate constant on the concentration of surfactant". ... 

The extraction efficiency, therefore, is almost 75%. When the same calculation is carried out at a pH of 5.00, the extraction efficiency is 60%, but the extraction efficiency is only 3% at a pH of 7.00. As expected, extraction efficiency is better at more acidic pHs when HA is the predominate species in the aqueous phase. A graph of extraction efficiency versus pH for this system is shown in Figure 7.23. Note that the extraction efficiency is greatest for pHs more acidic than the weak acid s piQ and decreases substantially at pHs more basic than the pi A- A ladder diagram for HA is superimposed on the graph to help illustrate this effect. 

Monomer compositional drifts may also occur due to preferential solution of the styrene in the mbber phase or solution of the acrylonitrile in the aqueous phase (72). In emulsion systems, mbber particle size may also influence graft stmcture so that the number of graft chains per unit of mbber particle surface area tends to remain constant (73). Factors affecting the distribution (eg, core-sheU vs "wart-like" morphologies) of the grafted copolymer on the mbber particle surface have been studied in emulsion systems (74). Effects due to preferential solvation of the initiator by the polybutadiene have been described (75,76). 

Initia.tors, The initiators most commonly used in emulsion polymerization are water soluble although partially soluble and oil-soluble initiators have also been used (57). Normally only one initiator type is used for a given polymerization. In some cases a finishing initiator is used (58). At high conversion the concentration of monomer in the aqueous phase is very low, leading to much radical—radical termination. An oil-soluble initiator makes its way more readily into the polymer particles, promoting conversion of monomer to polymer more effectively. 

The distribution of highly extractable solutes such as and Pu between the aqueous and organic phases is strongly dependent upon the nitrate anion concentration in the aqueous phase. This salting effect permits extraction or reextraction (stripping) of the solute by controlling the nitric acid concentration in the aqueous phase. The distribution coefficient, D, of the solute is expressed as... 

A variety of methods have been devised to stabilize shales. The most successful method uses an oil or synthetic mud that avoids direct contact between the shale and the emulsified water. However, preventing direct contact does not prevent water uptake by the shale, because the organic phase forms a semipermeable membrane on the surface of the wellbore between the emulsified water in the mud and the water in the shale. Depending on the activity of the water, it can be drawn into the shale (activity lower in the shale) or into the mud (activity higher in the shale) (95—97). This osmotic effect is favorable when water is drawn out of the shale thus the aqueous phase of the oil or synthetic mud is maintained at a low water activity by a dding a salt, either sodium chloride or more commonly, calcium chloride. The salt concentration is carried somewhat above the concentration required to balance the water activity in the shale to ensure water movement into the mud. 

The total antioxidant activity of teas and tea polyphenols in aqueous phase oxidation reactions has been deterrnined using an assay based on oxidation of 2,2 -azinobis-(3-ethylbenzothiazoline-sulfonate) (ABTS) by peroxyl radicals (114—117). Black and green tea extracts (2500 ppm) were found to be 8—12 times more effective antioxidants than a 1-mAf solution of the water-soluble form of vitamin E, Trolox. The most potent antioxidants of the tea flavonoids were found to be epicatechin gallate and epigallocatechin gallate. A 1-mAf solution of these flavanols were found respectively to be 4.9 and 4.8 times more potent than a 1-mAf solution of Trolox in scavenging an ABT radical cation. 

High molecular weight primary, secondary, and tertiary amines can be employed as extractants for zirconium and hafnium in hydrochloric acid (49—51). With similar aqueous-phase conditions, the selectivity is in the order tertiary > secondary > primary amines. The addition of small amounts of nitric acid increases the separation of zirconium and hafnium but decreases the zirconium yield. Good extraction of zirconium and hafnium from ca 1 Af sulfuric acid has been effected with tertiary amines (52—54), with separation factors of 10 or more. A system of this type, using trioctylarnine in kerosene as the organic solvent, is used by Nippon Mining of Japan in the production of zirconium (55). 

The use of an extractant depends on loading capacity, extraction rate, pH range, and the cost of the reagent and the diluent. Loss of the extractant must be minimised because of its high cost. Organic losses to the aqueous phase are also undesirable because of the deleterious effect on cathode deposits. Advances in SX—EW processes are described in Reference 38. 

Skim milk was initially used as the aqueous phase in margarine. Where the law allows, margarines may contain caseinates, whey proteins, or soy proteins as the proteins component in the aqueous phase. The addition to margarine of 0.01—0.1 wt % sodium caseinate in place of milk has been proposed to eliminate sticking during frying. Substituting soy proteins for milk would have the same effect. 

Because phenols are weak acids, they can be freed from neutral impurities by dissolution in aqueous N sodium hydroxide and extraction with a solvent such as diethyl ether, or by steam distillation to remove the non-acidic material. The phenol is recovered by acidification of the aqueous phase with 2N sulfuric acid, and either extracted with ether or steam distilled. In the second case the phenol is extracted from the steam distillate after saturating it with sodium chloride (salting out). A solvent is necessary when large quantities of liquid phenols are purified. The phenol is fractionated by distillation under reduced pressure, preferably in an atmosphere of nitrogen to minimise oxidation. Solid phenols can be crystallised from toluene, petroleum ether or a mixture of these solvents, and can be sublimed under vacuum. Purification can also be effected by fractional crystallisation or zone refining. For further purification of phenols via their acetyl or benzoyl derivatives (vide supra). 

Compounds such as hydrogen sulfide and cyanides are the most common metal surface poisoners occurring in process units subject to aqueous-phase hydrogen attack. In many process units, these compounds can be effectively eliminated and hydrogen diffusion stopped by adding ammonium polysulfides and oxygen to the process streams which converts the compounds to polysulfides and thiocyanates, provided the pH is kept on the alkaline side. 

Repeat the above steps for dissociation of HCl in waU (label the vertical axis aqueous phase energy). T1 energies contained in this sequence have been obtaine by calculating the effect a polar medium like water won have on the dissolved species. How many energy minin are there What species do these minima correspond t(... 

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