Phenol water mixtures

Rhim JW, Sohn MY, and Lee KH. Pervaporation separation of binary organic-aqueous liquids mixtures using crosshnked PVA membranes II phenol-water mixture. J. App. Poly. Sci. 1994 52(9) 1217-1222. 

Fig. 7.2. Partial miscibility of phenol-water mixtures as a function of temperature.

Extractions and precipitations in chemistry are well-established for organic systems. For example, nucleic acids may be extracted in a phenol/water mixture (J.). The use of aqueous extractions has several advantages over these and other widely used methods of separation. 1) Chemical components, such as polymers and/or salts, may be chosen to minimize denaturation due to solvency or interfacial tension < 2). Solvent/water mixtures, such as phenol/water, produce interfacial tensions in the range of 50 dyne/cm, compared to 0.1 dyne/cm in aqueous systems( ). 2)... 

Experiment 14.1 Demonstration of the presence of a miscibility gap with the help of the systems phenolfwater and triethylaminel water. When heated, a heterogeneous mixture of phenol and water will become a homogeneous solution when the upper critical solution temperature (approx. 339 K) is exceeded. However, even at higher temperatures, a heterogeneous mixture of triethylamine and water remains separated, but when cooled with ice to below the lower critical solution temperature (approx. 292 K), it will become a homogeneous solution. The phenol-water mixture, however, continues to consist of two phases after cooling. 

Figure 9.20 Txx diagram for phenol-water mixtures at 1 bar. These mixtures are partially immiscible as liquids and completely immiscible as solids. Sp = pure phenol solid = pure ice. Note the eutectic for nearly jnire-water mixtures. Data from [8-11].

Mitchell, J.K. 1831. On the penetrativeness of fluids. J. Roy. Inst. Great Britain 2 101-307. Mixa, A. and Staudt, C. 2008. Membrane-based separation of phenol/water mixtures using ionically and covalently crosslinked ethylene-methacylic acid copolymer. Int. J. Chem. Eng. ID 319392 12. 

If the third substance dissolves in both liquids (and the solubility in each of the liquids is of the same order), the mutual solubility of the liquids will be increased and an upper C.S.T. will be lowered, as is the case when succinic acid or sodium oleate is added to the phenol - water system. A 0 083 molar solution of sodium oleate lowers the C.S.T. by 56 -7° this large effect has been applied industrially in the preparation of the disinfectant sold under the name of Lysol. Mixtures of tar acids (phenol cresols) do not mix completely with water at the ordinary temperature, but the addition of a small amount of soap ( = sodium oleate) lowers the miscibility temperature so that Lysol exists as a clear liquid at the ordinary temperature. 

Aqueous dispersions are alternatives to solutions of Hquid and soHd resins. They are usuaUy offered in 50% soHds and may contain thickeners and cosolvents as stabilizers and to promote coalescence. Both heat-reactive (resole) and nonheat-reactive (novolak) systems exist that contain unsubstituted or substituted phenols or mixtures. A related technology produces large, stable particles that can be isolated as discrete particles (44). In aqueous dispersion, the resin stmcture is designed to produce a hydrophobic polymer, which is stabilized in water by an interfacial agent. 

An interesting observation reported in Table XLIX is the increase in the hydroquinone/catechol ratio from 1.44 to 1.99 when the dielectric constant of the medium is decreased from 58.9 to 39.2 by addition of methanol to water. A similar increase in the hydroquinone/catechol ratios was also observed in phenol hydroxylation catalyzed by TS-1 (266) in dioxane-water and tert-butyl alcohol-water mixtures. The para/ortho ratio increased nearly 10-fold when 10% dioxane was added to water. Similarly, the para/ortho ratio more than doubled (1.3-3.0) when 10% tert-butyl alcohol was added to water. An opposite trend, namely, a decrease in the para/ortho ratio from 1.4 to 0.6, was observed when 10% formamide (s = 108) was added to water. Because of geometric constraints in the MFI pores, catechol is expected to be formed more easily on the external surface of TS-1 crystallites than in the pores (91). Hydroquinone, less spatially demanding, can form in the TS-1 channels. A greater coverage of the hydrophobic... 

Gastrointestinal Effects. During the first few days after a man splashed a phenol-water solution (concentration not stated) on his face, chest wall, hand, and both arms, he complained of nausea and vomited twice (Horch et al. 1994). A worker who was partially immersed for only a few seconds in a shallow vat containing a mixture of 40% phenol in dichloromethane, collapsed after showering and was taken to a hospital where he was found to have bums over 50% of his body. Initial observations were stable however, after drinking fluids, he developed nausea and vomiting (Foxall et al. 1989). 

Kralj, F. and Sincic, D. Mutual solubilities of phenol, salicyaldehyde, phenol-salicyaldehyde mixture, and water with and without the presence of sodium chloride and sodium chloride plus sodium sulfate, J. Chem. Eng. Data, 25 (4) 335-338,1980. Kramer, C.R. and Henze, U. Partitioning properties of benzene derivatives. 1. Temperature dependence of the partitioning of monosubstituted benzenes and nitrobenzenes in the n-octanol/water system, Z. Phys. Chem., 271(3) 503-513,1990. Krasnoshchekova, R.Ya. and Gubergrits, M. Solubility of paraffin hydrocarbons in fresh and salt water, Neftekhlmlya, 13(6) 885-888, 1973. 

Roses, M., Rived, F., and Bosch, E. Dissociation constants of phenols in methanol-water mixtures. 7 Chromatogr. A, 867(l) 45-56, 2000. 

Fio. 23. Dependence of ralentioa bctor on eolvent oompoiitkm. using methanol-water mixture as the eluent. The data, plotted on a togaritlunic scaie, were obtained with butanol, jwntanol, and phenol as the ehute on Si-100 which had been treated, with trichlorobu-tylsilane (—) or with trichlorpoctadecylsilane (——). Reprinted with permission from Karch el al. (143). 

Many papers concerning salt effect on vapor-liquid equilibrium have been published. The systems formed by alcohol-water mixtures saturated with various salts have been the most widely studied, with those based on the ethyl alcohol-water binary being of special interest (1-6,8,10,11). However, other alcohol mixtures have also been studied methanol (10,16,17,20,21,22), 1-propanol (10,12,23,24), 2-propanol (12,23,25,26), butanol (27), phenol (28), and ethylene glycol (29,30). Other binary solvents studied have included acetic acid-water (22), propionic acid-water (31), nitric acid-water (32), acetone-methanol (33), ethanol-benzene (27), pyridine-water (25), and dioxane-water (26). 

A potentiometric method for determination of ionization constants for weak acids and bases in mixed solvents and for determination of solubility product constants in mixed solvents is described. The method utilizes glass electrodes, is rapid and convenient, and gives results in agreement with corresponding values from the literature. After describing the experimental details of the method, we present results of its application to three types of ionization equilibria. These results include a study of the thermodynamics of ionization of acetic acid, benzoic acid, phenol, water, and silver chloride in aqueous mixtures of acetone, tetrahydrofuran, and ethanol. The solvent compositions in these studies were varied from 0 to ca. 70 mass % nonaqueous component, and measurements were made at several temperatures between 10° and 40°C. 

Octaethylporphinato complexes of the type [M(OEP)(02CMe)2] (M = Zr or Hf) have been prepared by reaction of H2OEP and [M(acac)4] in molten phenol at 210-240 °C followed by crystallization from pyridine-acetic acid-water mixtures. The complexes have been characterized by IR and mass spectra703,704 and by electronic absorption and emission spectra.703 They have an eight-coordinate square antiprismatic structure (48) in which the four porphinato nitrogen atoms occupy the coordination sites on one square face and the two bidentate acetate... 

Azeotropic and Partially Miscible Systems. Azeotropic mixtures are those whose vapor and liquid equilibrium compositions are identical. Their x-y lines cross or touch the diagonal. Partially miscible substances form a vapor phase of constant composition over the entire range of two-phase liquid compositions usually the horizontal portion of the x-y plot intersects the diagonal, but those of a few mixtures do not, notably those of mixtures of methylethylketone and phenol with water. Separation of azeotropic mixtures sometimes can be effected in several towers at different pressures, as illustrated by Example 13.6 for ethanol-water mixtures. Partially miscible constant boiling mixtures usually can be separated with two towers and a condensate phase separator, as done in Example 13.7 for n-butanol and water. 

Figure 13.23. Examples of vapor-liquid equilibria in presence of solvents, (a) Mixture of-octane and toluene in the presence of phenol, (b) Mixtures of chloroform and acetone in the presence of methylisobutylketone. The mole fraction of solvent is indicated, (c) Mixture of ethanol and water (a) without additive (b) with 10gCaCl2 in 100 mL of mix. (d) Mixture of acetone and methanol (a) in 2.3Af CaCl2 ip) salt-free, (e) Effect of solvent concentration on the activity coefficients and relative volatility of an equimolal mixture of acetone and water (Carlson and Stewart, in Weissbergers Technique of Organic Chemistry IV, Distillation, 1965). (f) Relative volatilities in the presence of acetonitrile. Compositions of hydrocarbons in liquid phase on solvent-free basis (1) 0.76 isopentane + 0.24 isoprene (2) 0.24 iC5 + 0.76 IP (3) 0.5 iC5 + 0.5 2-methylbutene-2 (4) 0.25-0.76 2MB2 + 0.75-0.24 IP [Ogorodnikov et al., Zh. Prikl. Kh. 34, 1096-1102 (1961)].

Commonly used extraction solvents are ethyl acetate, diethyl ether, methanol, and aqueous methanol, but the majority of the free phenolic compounds can be extracted with alcohols (methanol or ethanol) or alcohol-water mixtures (1). Due to the differences in polarity between components (40), neither diethyl ether nor ethyl acetate are able to extract completely all the phenolic compounds in a liquid-liquid extraction. Thus, successive extraction with diethyl ether and then ethyl acetate has been used for phenolics in fruit juices (41). When using alcohol-water mixtures (40), repeated extraction or reflux for 1 h are necessary to extract free phenolic acids as well as their glycosides. 

Conversion of 2 ,4, 6 -trihydroxyacetophenone to the tricarbonate proceeded smoothly in 87% yield on treatment with 3.3 equivalents of methyl chloroformate and triethylamine in THF at 0°C. Treatment of this tricarbonate with 4 equivalents of sodium borohydride in a 1 1 THF/water mixture at 0°C to ambient temperature gave the phenol 1 in 83% yield. 

The vaccine formulation comprises a mixture of the outer-membrane lipopolysaccharides from bacteria of the seven different serotypes. The lipopolysaccharides may be obtained from cultures of each of the seven types by the standard procedure of Westphal (11), involving phenol—water extraction of the cells. However, for large-scale purposes, the older procedure of Boivin, (12) involving extraction of the cells with trichloroacetic acid, was... 

Many different solvent developers have been used in the separation of sugars and related compounds. Three of these, phenol-water, collidine-water, and 1-butanol-acetic acid-water,27 also commonly employed in the resolution of amino acid mixtures, are widely used. Other commonly used solvent developers are 1-butanol-ammonia-water, 1-butanol-ethanol-water,27 1-butanol-pyridine-water,61 ethyl acetate-acetic acid-water, and ethyl acetate-pyridine-water.26... 

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