Selective neutralization, sodium

A. Amirav, U. Even, and J. Jortner, Electronic-Vibrational Excitations of Aromatic Molecules in Large Argon Clusters , J. Phys. Chem. 86, 3345 (1982). L. Bewig, U. Buck, C. Mehlmann, and M. Winter, Ionization Induced Fragmentation of Size Selected Neutral Sodium Clusters , J. Chem. Phys. 100, 2765 (1994). 

The aqueous sodium naphthenate phase is decanted from the hydrocarbon phase and treated with acid to regenerate the cmde naphthenic acids. Sulfuric acid is used almost exclusively, for economic reasons. The wet cmde naphthenic acid phase separates and is decanted from the sodium sulfate brine. The volume of sodium sulfate brine produced from dilute sodium naphthenate solutions is significant, on the order of 10 L per L of cmde naphthenic acid. The brine contains some phenolic compounds and must be treated or disposed of in an environmentally sound manner. Sodium phenolates can be selectively neutralized using carbon dioxide and recovered before the sodium naphthenate is finally acidified with mineral acid (29). Recovery of naphthenic acid from aqueous sodium naphthenate solutions using ion-exchange resins has also been reported (30). 

There are two general classes of naturally-occurring antibiotics which influence the transport of alkali metal cations through natural and artificial membranes. The first category contains neutral macrocyclic species which usually bind potassium selectively over sodium. The second (non-cyclic) group contains monobasic acid functions which help render the alkaline metal complexes insoluble in water but soluble in non-polar solvents (Lauger, 1972 Painter Pressman, 1982). The present discussion will be restricted to (cyclic) examples from the first class. 

Metal hydroxides in general are anion-selective in acid solution and turn to be cation-selective beyond a certain pH, called the point of the iso-selectivity, pHpjS it is pHpjS = 10.3 for ferric oxide and pHpis = 5.8 for ferric-ferrous oxide [72]. Adsorption of multivalent ions may also control the ion selectivity of hydrous metal oxides because of its effect on the fixed charge in the oxides. For instance, hydrous ferric oxide, which is anion-selective in neutral sodium chloride solution, turns to be cation-selective by the adsorption of such ions as divalent sulfate ions, divalent molybdate ions, and trivalent phosphate ions [70,73]. It is worth emphasizing that such an ion-selectivity change due to the adsorption of multivalent ions frequently plays a decisive role in the corrosion of metals. 

For the neutral sodium dimer and trimer, beautifully resolved optical spectra are available, which are in excellent agreement with quantum-chemistry-type calculations [10, 11]. The early experiments on larger neutral clusters [12] gave many beautiful results but had one serious drawback. At best it is very difficult to mass-select neutral clusters, so that one has nearly always to work with a broad distribution of masses. In some cases it was possible, nevertheless, to deduce optical data [5, 12]. 

We can convert an acyl chloride into an aldehyde by hydride reduction. In this transformation, we again face a selectivity problem Sodium borohydride and lithium aluminum hydride convert aldehydes into alcohols. To prevent such overreduction, we must modify LiAlH4 by letting it react first with three molecules of 2-methyl-2-propanol (fert-butyl alcohol see Section 8-6). This treatment neutralizes three of the reactive hydride atoms, leaving one behind that is nucleophilic enough to attack an acyl chloride but not the resulting aldehyde. 

The pH must be kept at 7.0—7.2 for this method to be quantitative and to give a stable end poiut. This condition is easily met by addition of soHd sodium bicarbonate to neutralize the HI formed. With starch as iudicator and an appropriate standardized iodine solution, this method is appHcable to both concentrated and dilute (to ca 50 ppm) hydraziue solutious. The iodiue solutiou is best standardized usiug mouohydraziuium sulfate or sodium thiosulfate. Using an iodide-selective electrode, low levels down to the ppb range are detectable (see Electro analytical techniques) (141,142). Potassium iodate (143,144), bromate (145), and permanganate (146) have also been employed as oxidants. 

The sodium form of weakacid resins has exceptionally high selectivity for divalent cations in neutral, basic, and slightly acidic solutions. 

Weak base resins when in the free base (hydroxyl) form are not capable of splitting neutral salts such as sodium chloride. Salt forms of weak base resins release anions to the Hquid phase if other ions for which the resin has a greater selectivity are present. 

Acid-cataly2ed hydroxylation of naphthalene with 90% hydrogen peroxide gives either 1-naphthol or 2-naphthiol at a 98% yield, depending on the acidity of the system and the solvent used. In anhydrous hydrogen fluoride or 70% HF—30% pyridine solution at — 10 to + 20°C, 1-naphthol is the product formed in > 98% selectivity. In contrast, 2-naphthol is obtained in hydroxylation in super acid (HF—BF, HF—SbF, HF—TaF, FSO H—SbF ) solution at — 60 to — 78°C in > 98% selectivity (57). Of the three commercial methods of manufacture, the pressure hydrolysis of 1-naphthaleneamine with aqueous sulfuric acid at 180°C has been abandoned, at least in the United States. The caustic fusion of sodium 1-naphthalenesulfonate with 50 wt % aqueous sodium hydroxide at ca 290°C followed by the neutralization gives 1-naphthalenol in a ca 90% yield. 

Anionic and neutral polymers are usually analyzed successfully on Syn-Chropak GPC columns because they have minimal interaction with the appropriate mobile-phase selection however, cationic polymers adsorb to these columns, often irreversibly. Mobile-phase selection for hydrophilic polymers is similar to that for proteins but the solubilities are of primary importance. Organic solvents can be added to the mobile phase to increase solubility. In polymer analysis, ionic strength and pH can change the shape of the solute from mostly linear to globular therefore, it is very important to use the same conditions during calibration and analysis of unknowns (8). Many mobile phases have been used, but 0.05-0.2 M sodium sulfate or sodium nitrate is common. 

Cholanic acid also possesses the ability of transporting cations across a lipophilic membrane but the selectivity is not observed because it contains no recognition sites for specific cations. In the basic region, monensin forms a lipophilic complex with Na+, which is the counter ion of the carboxylate, by taking a pseudo-cyclic structure based on the effective coordination of the polyether moiety. The lipophilic complex taken up in the liquid membrane is transferred to the active region by diffusion. In the acidic region, the sodium cation is released by the neutralization reaction. The cycle is completed by the reverse transport of the free carboxylic ionophore. 

Figure 23.8 shows the readings of a glass electrode [the measured values of of a cell of the type (23.5)] as a function of solution pH. In the range from acidic to neutral solutions, this curve perfectly obeys Eq. (23.7) (i.e., the potential varies linearly by 0.06 V per unit of pH). However, in alkaline solutions the curve departs from this function ( alkali error of the glass electrode ) in strongly alkaline solutions the readings of the electrode are practically independent of solution pH. This is due to violation of the selectivity conditions. At a pH value of 10 and a sodium ion... 

Subsequently, cationic rhodium catalysts are also found to be effective for the regio- and stereoselective hydrosilation of alkynes in aqueous media. Recently, Oshima et al. reported a rhodium-catalyzed hydrosilylation of alkynes in an aqueous micellar system. A combination of [RhCl(nbd)]2 and bis-(diphenylphosphi no)propanc (dppp) were shown to be effective for the ( >selective hydrosilation in the presence of sodium dodecylsulfate (SDS), an anionic surfactant, in water.86 An anionic surfactant is essential for this ( )-selective hydrosilation, possibly because anionic micelles are helpful for the formation of a cationic rhodium species via dissociation of the Rh-Cl bond. For example, Triton X-100, a neutral surfactant, gave nonstereoselective hydrosilation whereas methyltrioctylammonium chloride, a cationic surfactant, resulted in none of the hydrosilation products. It was also found that the selectivity can be switched from E to Z in the presence of sodium iodide (Eq. 4.47). 

Seiler K., Wang K., Bakker E., Morf W.E., Rusterholz B., Spichiger U.E., Simon W., Characterization of sodium-selective optode membranes based on neutral ionophores and assay of sodium in plasma, Clinical Chemistry 1991 37 1350-1355. 

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