Studies on the Distribution of Phenoxyacetic Acid in Two-Phase Systems: n -Aliphatic Hydrocarbon – Water

Phenoxyacetic acid distribution in two-phase systems n-aliphatic hydrocarbon (C₅–C₈) – water and its dimerization in organic phase were investigated. The values of distribution coefficient (D _HR), distribution constant (K _D), and dimerization constant (K _dim) of acid were obtained. The empirical correlations of these quantities with Hildebrand solubility parameter of organic solvents were established. The influence of pH of the aqueous phase as well as the polarity of the applied organic solvents on phenoxyacetic acid physical chemistry in the two-phase systems was described.     

Studies on the Distribution of Phenoxyacetic Acid in Two-Phase Systems: <Emphasis Type="Italic">n</Emphasis>-Aliphatic Hydrocarbon – Water

Summary. Phenoxyacetic acid distribution in two-phase systems n-aliphatic hydrocarbon (C₅–C₈) – water and its dimerization in organic phase were investigated. The values of distribution coefficient (D _HR), distribution constant (K _D), and dimerization constant (K _dim) of acid were obtained. The empirical correlations of these quantities with Hildebrand solubility parameter of organic solvents were established. The influence of pH of the aqueous phase as well as the polarity of the applied organic solvents on phenoxyacetic acid physical chemistry in the two-phase systems was described.     

Studies on the Physical Chemistry of (2,4-Dichlorophenoxy)acetic Acid in Two-phase Systems: Organic Solvent-Water

The dissociation constants (p _s K _a ) of 2,4-D acid were determined in methanol-water mixtures of 10.9 to 38.9 wt.% methanol content. The Yasuda-Shedlovsky procedure was used to obtain the pK _a value in zero-% methanol. The distribution of 2,4-D acid in twelve two-phase organic solvent + water systems and its dimerization in the organic phase were investigated. Values of the distribution coefficient (D _HR), distribution constant (K _D ), and dimerization constant (K _dim) of 2,4-D were obtained. The influence of the structure and polarity of the investigated organic solvents, as well as that of pH of the aqueous phase, on the physical chemistry of 2,4-D in the two-phase systems are described.     

Potentiometric Studies on the Equilibria of Flufenamic Acid in Aqueous Solutions and in Two-phase Organic Solvent + Water Systems

In this paper, the flufenamic acid equilibria in aqueous solution and in two-phase organic solvent + aqueous solution are described and presented. The dissociation constants K _a1 and K _a2 were determined in MDM + water mixtures. The Yashuda-Shedlovsky extrapolation procedure has been used to obtain the values of K _a1 and K _a2 in aqueous solutions. The distribution ratio D was measured in the toluene + water system over a wide range of pH by the shaking flask method. Based on the results of potentiometric titrations in two-phase organic solvent (benzene, ethylbenzene, toluene, carbon tetrachloride, chloroform, chlorobenzene, and bromobenzene) + aqueous systems, and using models of single and multistep equilibria, the values of distribution constants K _D and dimerization constants K _dim were calculated. The influences of polarity of the applied solvents and pH of the aqueous phase, on the speciation of the particular forms of flufenamic acid in both phases, were demonstrated.     

Automatic potentiometric two-phase titration in pharmaceutical analysis : Part 3. Titrimetric Identification of Drugs

The conditional acidity constant in a liquid-liquid two-phase system (pK^*_HA + value) can be used as an identity parameter for drug compounds. The pK^*_HA + value can be calculated if the phase ratio and the acidity and distribution constants are known. Selectivity is obtained mainly by the choice of the organic phase. An excess of hydrochloric acid is first added to the sample in the two-phase system. The hydrochloric acid and the sample are then titrated sequentially with sodium hydroxide. The proposed titration procedure makes it possible to calibrat the electrodes, determine the pK^*_HA + value(s), quantify one or more compounds, and check the performance of the electrodes in one and the same experimental run. Lidocaine was “identified” and assayed in different dosage forms such as ointment and solution for injection. The results were in agreement with those obtained by liquid chromatography.     

Separation of fuel additive levulinic acid using toluene,xylene, and octanol from water stream

Levulinic acid is an important fuel additive due to its multifunctionality with keto and carboxylic functional groups. It also carries the potential to produce some other fuel additives viz. γ-valerolactone, ethyl levulinate, and 2-methyl tetrahydrofuran. These substances can be combined with petroleum-derived transportation fuels similarly to bioethanol without modifying in engines. The wastewater and solid wastes from various industries contain organic acids in the downstreams. The recovery and separation of organic acids from wastewater is challenging due to its dilute concentrations and other issues. The presented study involves the separation of levulinc acid from the waste-water stream using various solvents such as toluene, xylene, and octanol at 25°C. The experimental results were described in terms of the partition constant (P_c), dimerization constant (D_c), distribution coefficients (K_D), and extraction efficiency (E_η). The present study can significantly contribute to the recovery of levulinic acid as fuel additive levulinic with low-cost process.     

Solvent effect of ionic liquids on the distribution constant of 2-thenoyltrifluoroacetone and its nickel(II) and copper(II) chelates and the evaluation of the solvent properties based on the regular solution theory

Distribution constants of 2-thenoyltrifluoroacetone (Htta) and its Ni(II)and Cu(II) chelates between 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (C_nmimTf₂N; n = 4, 6, and 8) as ionic liquid (IL) and an aqueous phase were determined. The enol fraction of Htta in ILs was spectrophotometrically measured to calculate the distribution constant of the enol form (K_D,HE) of Htta. The K_D,HE values in ILs were evaluated by comparing those in various molecular solvents such as alkanes, aromatic hydrocarbons, chlorohydrocarbons, ethers, ketones, and esters previously reported on the basis of the regular solution theory (RST). It was elucidated that the IL solutions of Htta (enol) can be taken as apparently regular solutions as expected in the organic solvents. On the other hand, the effect of ILs on the distribution constant of metal(II) chelates (K_D,M) was fairly complicated. The Cu(tta)₂-IL solutions behaved like the alkane and aromatic hydrocarbon solutions but the Ni(tta)₂-IL (C₄mimTf₂N) like ether and ketone solutions. In the Ni(II) case, some specific interactions between the Ni(II) chelate and IL was suggested. Finally, the solubility parameters of ILs were calculated using K_D,HE by RST and were in good agreement with the literature values obtained by the enthalpy of vaporization.     

Laser-induced fluorescence and infrared spectroscopic studies on the specific solvation of tris(1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedionato)europium(III) in an ionic liquid

The extraction constant and the two-phase stability constant (K_D,Mβ₃) of tris(2-thenoyltrifluoroacetonato)europium(III) between 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C₄mim][Tf₂N]) as an ionic liquid and an aqueous phase were determined by considering the extraction equilibria including anionic tetrakis(2-thenoyltrifluoroacetonato)europate(III). Specific solute-solvent interactions between the neutral Eu(III) chelate and [C₄mim][Tf₂N] molecules were revealed from the relationships between the distribution constant of the enol form of 2-thenoyltrifluoroacetone (Htta) as a proton chelate and the distribution constant (K_D,M) of the neutral Eu(III) chelate because the [C₄mim][Tf₂N] system gave the high K_D,Mβ₃ value compared with those in conventional molecular solvents such as benzene and 1,2-dichloroethane. The coordination environment of Eu³⁺ in the neutral Eu(III) chelate in [C₄mim][Tf₂N] was investigated by time-resolved laser-induced fluorescence spectroscopy and infrared absorption spectroscopy. Both methods consistently indicated that not only the Eu(III) chelate extracted but also Eu(tta)₃(H₂O)₃ synthesized as a solid crystal were almost completely dehydrated in [C₄mim][Tf₂N] saturated with water. Consequently, the higher K_D,M or extractability of the neutral Eu(III) chelate in the [C₄mim][Tf₂N] system can be ascribed to the dehydration of the Eu(III) chelate, which is caused by the specific solvation with [C₄mim][Tf₂N] molecules.     

Enantioselective Extraction System Containing Binary Chiral Selectors and Chromatographic Enantioseparation Method for Determination of the Absolute Configuration of Enantiomers of Cyclopentolate

The distribution coefficients and enantioseparation of cyclopentolate were studied in an extraction system containing d-tartaric acid ditertbutyl ester in organic phase and 2-hydroxypropyl-β-cyclodextrin (HP-β-CD) in aqueous phase. Various parameters involved in the enantioseparation such as the type and the concentration of chiral selectors, pH value and a wide range of organic solvents were investigated. The maximum enantioselectivity (α = 2.13) and optimum distribution coefficients (K _R = 0.85, K _S = 0.40) were obtained under the following conditions: 0.10 mol/L HP-β-CD in aqueous phase and 0.20 mol/L d-tartaric acid ditertbutyl ester in decanol as organic phase. Cyclopentolate is present as a racemic mixture to the aqueous phase. The potentially different biological activities of cyclopentolate enantiomers have not been examined yet. Two chiral liquid chromatography methods have been developed for the direct separation of the enantiomers of cyclopentolate. First method was used for the quantification analysis of cyclopentolate enantiomers in aqueous phase. Second method used two chiroptical detectors: electronic circular dichroism (ECD) and optical rotation (OR) for the identification of individual cyclopentolate enantiomers from the organic phase enriched with (R)-enantiomer. The absolute stereochemistry was determined by means of the comparison of the experimental and computed ECD spectra and signs of OR. The ECD spectra of chiral analytes were measured on-line using HPLC-ECD technique.     

Investigation of phase equilibria of levulinic acid distribution between aqueous phase to organic phase by Aliquat 336 in different modifiers

The extraction of levulinic acid by tricaprylmethylammonium chloride (Aliquat 336) dissolved in five alcohols solvents (isoamyl alcohol, hexan-1-ol, octan-1-ol, nonan-1-ol, decan-1-ol) and five esters solvents (dimethyl phthalate, dimethyl adipate, dimethyl succinate, dimethyl glutarate, diethyl carbonate), two ketones (diisobutyl ketone (DIBK), methyl isobutyl ketone (MIBK)) were investigated to understand effect of modifier on levulinic acid extraction. In addition to these Aliquat 336 + modifier system, the experiments were done also with single solvents. All measurements were carried out T = 298.15 K. Organic solutions of Aliquat 336 are being used increasingly to separate organic acids from aqueous mixture solutions by reactive extraction. The extent to which the organic phase may be loaded with levulinic acid is explained as a loading ratio, Z_Z, extraction efficiency E and, distribution coefficients K_D were calculated. The maximum extraction efficiency was obtained value of 72.1 for isoamyl alcohol. The extraction equilibrium constant, K_E, has been calculated for each modifier. Furthermore, Freundlich, Langmuir, and LSER model equations have been obtained for experimental data of alcohols.     

Tautomeric reaction equilibrium of ethyl acetoacetate in CO2–n-pentane and CO2–ethanol mixed solvents in the critical region

The tautomeric equilibrium constant K_C of ethyl acetoacetate (EAA) in CO₂–n-pentane and CO₂–ethanol was studied by UV–VIS spectroscopy at 308.2 K over the pressure range from 6.5 to 9.0 MPa. This work focuses on how the tautomeric equilibrium changes with pressure and composition of the mixed solvents in the near critical region. The results showed that the effect of pressure on K_C was very limited at pressures much higher than the phase separation pressures. However, the K_C increased sharply as the pressure approached the critical point or the bubble point of the mixed solvents.     

Physicochemical properties of 4-tert-butylbenzoic acid N′,N′-dialkylhydrazides

Properties of hydrazides of 4-tert-butylbenzoic acid, important for their application in extraction technology, have been studied: solubility, acid-base properties, distribution between immiscible liquids, and hydrolytic stability. pH ranges of existence of different forms of the compounds have been determined. The N′,N′-dialkyl derivatives with alkyl chains longer than C₆ are readily soluble in nonpolar solvents, are not transferred into aqueous phase, and are stable with respect to hydrolysis in acidic and basic media. Linear correlations of the studied physicochemical parameters with the compounds structure and the medium properties have been elucidated.     

Enantioseparation of mandelic acid enantiomers in ionic liquid aqueous two-phase extraction systems

In the past decade, ionic liquids have received great attention owing to their potential as green solvent alternatives to conventional organic solvents. In this work, hydrophobic achiral ionic liquids (1-butyl-3-methylimidazolium-hexafluorophosphate([bmim][PF₆]), 1-octyl-3-methylimidazolium tetrafluoroborate([omim][BF₄])) were used as solvents in chiral liquid-liquid extraction separation of mandelic acid (MA) enantiomers with β-cyclodextrin (β-CD) derivatives as hydrophilic chiral selectors preferentially forming complexes with (R)-enantiomers. Factors affecting the separation efficiency were optimised, namely the type of the extraction solvents and β-CD derivatives, concentrations of the β-CD derivatives and MA enantiomers, pH, and temperature. Excellent enantioseparation of MA enantiomers was achieved in the ionic liquid aqueous two-phase extraction systems under the optimal conditions of pH 2.5 and temperature of 5°C with the maximum enantioselectivity (α) of 1.74. The experimental results demonstrated that the ionic liquid aqueous two-phase extraction systems with a β-CD derivative as the chiral selector have a strong chiral recognition ability, which might extend the application of ionic liquids in chiral separation.     

The use of14C,59Fe and65Ni radionuclides for the study of solvent effects on the extraction equilibria with n-caprylic acid

The distribution of n-caprylic acid between an aqueous sodium sulphate solution and several organic diluents of various properties has been investigated, using¹⁴C-labelled n-caprylic acid. The distribution coefficients of the monomeric capyrlic acid and its dimerization constants in the organic phase were determined. The extraction of Fe(III) and Ni(II) with n-caprylic acid solutions in various diluents was studied using the AKUFVE solvent extraction equipment. The composition of the extracted compound of Fe(III) has been determined and the extraction constants for all the studied systems have been calculated. For the extraction of Ni(II) the constants of the extraction of nickel caprylate monomers and its dimerization constants in the organic phase have been calculated.     

(Liquid + liquid) equilibria for (acetate-based ionic liquids + inorganic salts) aqueous two-phase systems

In the present work, (liquid + liquid) equilibrium data have been determined experimentally for aqueous two-phase systems formed by the imidazolium ionic liquids of [C_nmim][CH₃COO] (n = 4, 6, 8) and inorganic salts of K₃PO₄, K₂HPO₄, and K₂CO₃ at T = 298.15 K. Combined with available data in the literature, the effect of alkyl chain length of cations, type of anions of the ionic liquids, and nature of the inorganic salts were examined on the binodal curves of the systems. Then the binodal curves were fitted to a four-parameter empirical equation, and the tie-lines were described by the Othmer–Tobias and Bancroft equations. In addition, the extraction capacity of the {[C_nmim][CH₃COO] (n = 4, 6, 8) + K₃PO₄} aqueous two-phase systems was evaluated through their application to the extraction of l-tryptophan. The high extraction efficiency suggests that these aqueous two-phase systems are feasible to be used in the extraction and separation process.     

Thermodynamics and Fluorescence Spectra of 1,10-Phenanthroline in Micelles of Poly (Ethylene Oxide)-Type Nonionic Surfactant

The distribution of 1,10-phenanthroline (phen) in micellar solutions of the nonionic surfactants Triton X and C₁₂E _n with varying poly (ethylene oxide) chain lengths has been studied by potentiometry, calorimetry, and fluorometry at 298 K. Micelles accommodate 1,10-phenanthroline according to the reaction, phen + Y_m = Y_m(phen), where Y_m denotes a surfactant molecule aggregated in micelles. The constant K _m for the reaction of Triton X increases as a linear function of n*, the number of ethylene oxide (EO) groups, as K _m = K_EO n* + K_c. Nonzero K _EO and K _c values suggest a heterogeneous inner structure of the micelle, i.e., the hydrophobic core surrounded by a hydrophilic poly (ethylene oxide) (PEO) shell. On the basis of molar volumes, the intrinsic thermodynamic parameters of transfer of 1,10-phenantholine were extracted. The enthalpy and entropy of transfer of 1,10-phenanthroline from the PEO shell to the core are found to be small and negative. By using K _EO and K _c values for C₁₂E _n obtained by fluorometry, individual fluorescence spectra of 1,10-phenanthroline in the PEO shell and core were extracted. The fluorescence intensity of 1,10-phenathroline accommodated in the core, like in organic solvents, is significantly reduced relative to that in water. These facts indicate that the aromatic rings of 1,10-phenanthroline penetrate into the hydrophobic core, while its hydrophilic N site is still hydrated in the PEO shell.     

A generalized form of the extraction constant for the partition of a metal chelate between immiscible aqueous and organic phases

The theory underlying the partition of sparingly soluble reagents and their formally neutral metal chelates between an aqueous phase and any immisicible organic phase leads to a generalized extraction constant K^*_ex=K_exSⁿ_r,0/S_c,o where K_ex is the conventional extraction constant and S_r,oS_c,o are the molar solubilities of reagent and metal complex, respectively, in the same organic solvent. The predicted constancy of K^*_ex is confirmed for measurements in seven solvents and for systems involving mono-, di- and tridithizonates of Ag⁺, Zn²⁺ and Bi³⁺, respectively.     

Aqueous two-phase system of an anionic gemini surfactant and a cationic conventional surfactant mixture

The aqueous two-phase system formed by the mixture of dodecyltrimethylammonium bromide (DTAB) with a gemini surfactant O,O′-bis(sodium 2-lauricate)-p-benzenediol (C₁₁pPHCNa) has been studied. Two two-phase regions were observed, one was a wide region in the cationic surfactant-rich side and the other in the vicinity of R = 1:1, where R is the mixing mole ratio of DTAB to C₁₁pPHCNa in global solution. Multi-lamellar vesicles are formed in the concentrated upper phase of cationic surfactant-rich systems and spherical aggregates in the concentrated bottom phase at R = 1:1. The microstructure of the solution and the phase behavior of the aqueous two-phase system strongly depended on the total concentration and the composition of the system.