Aqueous Mixtures

We have considered the surface tension behavior of several types of systems, and now it is desirable to discuss in slightly more detail the very important case of aqueous mixtures. If the surface tensions of the separate pure liquids differ appreciably, as in the case of alcohol-water mixtures, then the addition of small amounts of the second component generally results in a marked decrease in surface tension from that of the pure water. The case of ethanol and water is shown in Fig. III-9c. As seen in Section III-5, this effect may be accounted for in terms of selective adsorption of the alcohol at the interface. Dilute aqueous solutions of organic substances can be treated with a semiempirical equation attributed to von Szyszkowski [89,90]... 

Figure C2.6.11. SEM of AB2 stmcture, fonned in aqueous mixtures of PS latex spheres witli <3 = 68 nm and a = 264 nm (courtesy of Prof R H Ottewill).

An illustrative example generates a 2 x 2 calibration matrix from which we can determine the concentrations xi and X2 of dichromate and permanganate ions simultaneously by making spectrophotometric measurements yi and j2 at different wavelengths on an aqueous mixture of the unknowns. The advantage of this simple two-component analytical problem in 3-space is that one can envision the plane representing absorbance A as a linear function of two concentration variables A =f xuX2). 

The benzoic acid may be separated by steam distillation or by saturating the aqueous mixture of sodium salts with sulphur dioxide whilst maintaining the temperature below 40° the benzoic acid precipitates and can be separated by filtration or extraction with ether. Acidification of the filtrate with hydrochloric acid liberates the pyruvic acid. The pjTuvic acid may be oxidised < lth hydrogen peroxide to the arylacetic acid, for example ... 

The following are examples of the above procedure. A mixture of diethylamine and re-butyl alcohol may be separated by adding sufficient dilute sulphuric acid to neutralise the base steam distillation will remove the alcohol. The amine can be recovered by adding sodium hydroxide to the residue and repeating the distillation. A mixture of diethyl ketone and acetic acid may be treated with sufficient dilute sodium hydroxide solution to transform the acid into sodium acetate and distilling the aqueous mixture. The ketone will pass over in the steam and the non-volatile, stable salt will remain in the flask. Acidification with dilute sulphuric acid hberates acetic acid, which can be isolated by steam distillation or by extraction. 

Using Figure 7.27, explain how an aqueous mixture of Cu +, Pb +, and Cd + can be separated by extraction with dithizone in CCI4. 

Although acetic acid and water are not beheved to form an azeotrope, acetic acid is hard to separate from aqueous mixtures. Because a number of common hydrocarbons such as heptane or isooctane form azeotropes with formic acid, one of these hydrocarbons can be added to the reactor oxidate permitting separation of formic acid. Water is decanted in a separator from the condensate. Much greater quantities of formic acid are produced from naphtha than from butane, hence formic acid recovery is more extensive in such plants. Through judicious recycling of the less desirable oxygenates, nearly all major impurities can be oxidized to acetic acid. Final acetic acid purification follows much the same treatments as are used in acetaldehyde oxidation. Acid quahty equivalent to the best analytical grade can be produced in tank car quantities without difficulties. 

Chlorine in the presence of hydrogen chloride in an anhydrous organic solvent yields 2,4,6-trichloroariiline [634-93-5] (36,37). A mixture of aniline vapor and chlorine, diluted with an inert gas, over activated carbon at 400°C yields o-chloroaruline [95-51-2] (38). Aniline when treated with chlorine gas, in an aqueous mixture of sulfuric acid and acetic acid, at 105—115°C gives an 85—95% yield of -chlorarul [118-75-2] (39). 

The acid occurs both as colorless triclinic prisms (a-form) and as monoclinic prisms ( 3-form) (8). The P-form is triboluminescent and is stable up to 137°C the a-form is stable above this temperature. Both forms dissolve in water, alcohol, diethyl ether, glacial acetic acid, anhydrous glycerol, acetone, and various aqueous mixtures of the last two solvents. Succinic acid sublimes with partial dehydration to the anhydride when heated near its melting point. 

In wet-air oxidation, the aqueous mixture is heated under pressure ia the presence of air, which oxidi2es the organic material. The efficiency of the oxidation process is a function of reaction time and temperature. The oxidation products are generally less complex and can be treated by conventional biological methods (31). The reactor usually operates between 177 and 321°C with pressures of 2.52—20.8 MPa (350—3000 psig). 

A 600-mL, three-necked, round-bottomed flask 1s equipped with a mechanical stirrer, a short gas inlet tube, and an efficient reflux condenser fitted with a potassium hydroxide drying tube. The flask is charged with 13.4 g (0.05 mol) of 3-ben2y1-5-(2-hydroxyethyl)-4-methyl-l,3-th1azol1um chloride (Note 11, 72.1 g (1.0 mol) of butyraldehyde (Note 2). 30.3 g (0.3 mol) of triethylamine (Note 2), and 300 raL of absolute ethanol. A slow stream of nitrogen (Note 3) is begun, and the mixture is stirred and heated In an oil bath at 80°C. After 1.5 hr the reaction mixture is cooled to room temperature and concentrated by rotary evaporation. The residual yellow liquid Is poured Into 500 mL of water contained 1n a separatory funnel, and the flask is rinsed with 150 mL of dichloromethane which is then used to extract the aqueous mixture. The aqueous layer is extracted with a second 150-mL portion of... 

Ion-exchange chromatography involves an electrostatic process which depends on the relative affinities of various types of ions for an immobilised assembly of ions of opposite charge. The stationary phase is an aqueous buffer with a fixed pH or an aqueous mixture of buffers in which the pH is continuously increased or decreased as the separation may require. This form of liquid chromatography can also be performed at high inlet pressures of liquid with increased column performances. 

The reason for this relationship is not clear, but as there is poor interaction between the solutes and methanol due to their highly dispersive character, they may need to interact with two methanol molecules in order to become sufficiently solvated to disperse in the aqueous mixtures. 

I rcdici.s properties and lompuics ihcmical and solid-liquid phase equilibrium for aqueous mixtures. Up to 20 composition data sets may be handled in memory at once. Requires 512K memory. 

The thiocyanatohydrin is dissolved in a minimal amount of dry pyridine and cooled in an ice bath. Methanesulfonyl chloride (1 ml/g of thiocyanatohydrin) is added to the above solution. The reaction mixture is allowed to stand at 0° in a refrigerator for ca. 24 hr and is then poured into ice water. An ether extract of the aqueous mixture is washed successively with dil. hydrochloric acid, water, sodium carbonate solution and water, dried (MgS04), and evaporated. The solvent used for recrystallization is dependent on the other substituents present in the steroid. 

FIGURE 16.5 Broad standard calibration (linear mode) of a semipreparative Sephacryl S-IOOO system (95 x 1.6 cm) with an aqueous mixture of Blue Dextran, Dextran T-SOO, and glucose eluent 0.005 M NaOH V, i = 75 ml. = 162 ml. 

When the range of chemieal types is restricted, regular behavior is often observed. For example, one might choose to study a series of hydroxylic solvents, thus holding approximately constant the H-bonding capabilities within the series. This is a motivation, also, for solvent studies in a series of binary mixed solvents, often an organic-aqueous mixture whose composition may be varied from pure water to pure organic. Mukerjee et al. defined a quantity H for hydroxylic and mixed hydroxyiic-water solvents by Eq. (8-17). 

Table 8-8 gives some nonelectrolyte transfer free energies, and Table 8-9 lists single ion transfer activity coefficients. Note especially the remarkable values for anions in dipolar aprotic solvents, indicating extensive desolvation in these solvents relative to methanol. This is consistent with the enhanced nucleophilic reactivity of anions in dipolar aprotic solvents. Parker and Blandamer have considered transfer activity coefficients for binary aqueous mixtures. 

A partial solution to the problem of producing sharp peaks at low elution temperatures is to add a small amount of a higher-boiling co-solvent to the main solvent. As suggested by Grob and Muller (23, 24), butoxyethanol can be used as a suitable cosolvent for aqueous mixtures in such cases. 

A 250-mI round-bottom flask fitted with a condenser (drying tube) is charged with a mixture of 2-bromocholestanone (4.7 g, 0.01 mole), lithium carbonate (7.4 g, 0.10 mole), and 100 ml of dimethylformamide. The system is flushed with nitrogen and then refluxed (mantle) for 18-24 hours. After the reflux period, the solution is cooled and poured into 500 ml of water. The aqueous mixture is extracted with 50 ml of ether, the ether extract is dried (sodium sulfate), and the ether is removed (rotary evaporator). The residue may be recrystallized from ethanol or methanol. J -Cholestenone is a white solid, mp 98-100°. 

The second apparatus, shown in Fig. A3.lib, is used with organic solvents more dense than water. The operating principles are identical, except that the return of the solvent occurs from beneath the aqueous mixture. 

The known methods for the preparation of D- -)-a-aminobenzylpenicillin by the acylation of 6-aminopenicillanic acid result in the preparation of aqueous mixtures which contain, in addition to the desired penicillin, unreacted 6-aminopenicillanic acid, hydrolyzed acylat-ing agent, and products of side reactions such as the products of the acylating agent reacted with itself and/or with the desired penicillin, as well as other impurities. 

The crude benzhydryl ether was a clear reddish oil. It was dissolved in 75 ml of 20% hydrochloric acid and the aqueous acid solution then washed three times with 50 ml portions each of ethyl ether. The aqueous acid solution was then decolorized with activated carbon and thereafter slowly admixed with 75 ml of 28% aqueous ammonia. The benzhydryl ether separated as an oily material and was removed from the aqueous mixture by extraction with three 50 ml portions of ethyl ether. 

A mixture of 30 parts of 17o -ethvnvl-19-norandrost-4-ene-30,17(3-diol, 360 parts of dry pyridine, and 111 parts of acetic anhydride, under nitrogen, is stirred and heated at the reflux temperature for about 5 hours. This reaction mixture is cooled, then poured into approximately 3,500 parts of cold water and the resulting aqueous mixture is stirred at room temperature for about 0.5 hour. The precipitate which forms is collected by filtration, then is washed on the filter with water and dried in air. This solid material is extracted into ether, and the ether solution is washed successively with 10% aqueous hydrochloric acid and 5% aqueous sodium bicarbonate. 

The catalyst is prepared by suspending 5 kg of catalyst grade charcoal in 200 liters of water, in a pressure vessei, and adding thereto 25 liters of 4% (as Pd metal) aqueous palladous chloride. Air is displaced from the vessel and then hydrogen is passed into the aqueous mixture at a pressure of 3 to 5 psi, while stirring, until no further absorption is noted and the chloride is completely reduced to metal. 

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