Equilibrium and ab initio computational studies on the adduct formation of 1,3-diketonato-lithium(I), -sodium(I) and -potassium(I) with 1,10-phenanthroline and its 2,9-dimethyl derivatives.

Highly effective and selective synergistic extraction of Li+ has been found using 2-naphthoyltrifluoroacetone (Hnta) as an acidic chelating agent and 2,9-dimethyl-1,10-phenanthroline (dmp) or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (dmdpp) as a neutral ligand (denoted as L) in toluene. The synergism was ascribed to the adduct formation in the organic phase, and the composition and the formation constants of the adducts for alkali metal ions (M+) were determined by the extraction equilibrium analysis. The adducts found were M(nta)L for Li+ and Na+, while M(nta)L and M(nta)L2 for K+. To understand thermodynamics of the adduct formation with the bidentate amines, quantum chemical calculations of the 1:1 and 1:2 adduct formations with dmp and 1,10-phenanthroline (phen) were performed. The electronic and steric effects of the methyl groups at 2,9-positions of phen on the thermodynamic functions of adduct formation as well as the high lithium selectivity were quantitatively elucidated.

Solid-phase extraction of gallium(III) with hydrophobic 8-quinolinol derivatives-impregnated resin from aqueous acidic and alkaline solutions.

Solid-phase extraction (SPE) of gallium(III) with hydrophobic 8-quinolinol derivatives (HQs)-impregnated resin from aqueous acidic and alkaline solutions has been investigated. The HQs used were 7-(4-ethyl-1-methyloctyl)-8-quinolinol (HEMOQ), 5-octyloxymethyl-8-quinolinol (HO(8)Q), 2-methyl-5-octyloxymethyl-8-quinolinol (HMO(8)Q), 5-dioctylaminomethyl-8-quinolinol (HN(8)Q), 7-bromo-5-octyloxymethyl-8-quinolinol (HBrO(8)Q), and 5-(2-ethylhexyloxymethyl)-8-quinolinol (HOEHQ). Various factors affecting the SPE, such as the substituents of the HQs, HCl and NaOH concentrations in the aqueous phase, the HQ concentration in the resin, and the equilibration time were clarified. The extractability for gallium(III) from the aqueous solution became higher in the following order: HBrO(8)Q < HEMOQ < HO(8)Q < HN(8)Q < HMO(8)Q at 3 mol l(-1) HCl; HMO(8)Q < HO(8)Q < HOEHQ < HEMOQ < HN(8)Q < HBrO(8)Q at pH 0.4; HMO(8)Q < HO(8)Q asymptotically equal to HOEHQ < HN(8)Q < HEMOQ at 3 mol l(-1) NaOH.

Solid phase extraction of phosphorus-containing amino acid-type herbicides and their metabolites from human blood with titania for determination by capillary electrophoresis.

Phosphorus-containing amino acid-type herbicides (PAAHs) and their metabolites in human plasma and whole blood were extracted with titania and determined by capillary electrophoresis (CE). The recoveries of glyphosate (GLYP), aminomethylphosphonic acid (AMPA), gluphosinate (GLUF), and 3-methylphosphonico-propionic acid (MPPA) from human plasma were 84.6, 76.8, 90.4, and 89.6%, respectively. The recoveries of GLYP, AMPA, GLUF, and MPPA from whole blood were 79.6, 84.4, 36.9, and 31.8%, respectively. The low recoveries of GLUF and MPPA from whole blood were improved by the dilution of whole blood with water to 4-fold.

Cloud point extraction equilibrium of lanthanum(III), europium(III) and lutetium(III) using di(2-ethylhexyl)phosphoric acid and Triton X-100.

The cloud point extraction behaviors of lanthanoids(III) (Ln(III)=La(III), Eu(III) and Lu(III)) with and without di(2-ethylhexyl)phosphoric acid (HDEHP) using Triton X-100 were investigated. It was suggested that the extraction of Ln(III) into the surfactant-rich phase without added chelating agent was caused by the impurities contained in Triton X-100. The extraction percentage more than 91% for all Ln(III) metals was obtained using 3.0x10(-5)moldm(-3) HDEHP and 2.0% (v/v) Triton X-100. From the equilibrium analysis, it was clarified that Ln(III) was extracted as Ln(DEHP)(3) into the surfactant-rich phase. The extraction constant of Ln(III) with HDEHP and 2.0% (v/v) Triton X-100 were also obtained.

Association of tris(pentane-2,4-dionato)chromium(III) with modifiers of hydrogen-bond donors in supercritical carbon dioxide.

The solubility of tris(pentane-2,4-dionato)chromium(III) (Cr(acac)(3)) in supercritical carbon dioxide (SC-CO(2)) containing organic modifiers (1,1,1,3,3,3-hexafluoro-2-propanol (HFP) and 3,5-bis(trifluoromethyl)phenol (BTMP)) of hydrogen-bond donors was investigated by UV/VIS spectrophotometry. A great solubility enhancement of Cr(acac)(3) in SC-CO(2) was accomplished by adding HFP and BTMP. The association constant of Cr(acac)(3) with HFP and BTMP in SC-CO(2) could be determined from the relationship of the solubility enhancement against the concentration of the modifier. The association constant linearly increases with an increase in the acid dissociation constant of the modifiers.

Absolute determination method using chirality for glufosinate and bialaphos by gamma-cyclodextrin modified capillary zone electrophoresis.

A novel absolute determination method using chirality without any calibration curves or comparison standards has been proposed for phosphorus-containing amino acid-type herbicides, glufosinate (D,L-GLUF) and bialaphos (BIAL). This method is based on a change in the enantiomeric ratio after the spiking of a known amount of the enantiomers with different enantiomeric ratios to a sample. D,L-GLUF was determined by adding a known amount of L-GLUF to the sample, derivatizing them with dansyl chloride, and measuring the ratio of the peak area of the D-isomer to that of the L-isomer by means of gamma-cyclodextrin modified capillary zone electrophoresis. The accuracy and precision of the method were evaluated using a synthetic sample. The mean values obtained for D- and L-GLUF agreed with the values taken within 1.6%; also the reproducibility was as good as less than 2.8%. The determination of BIAL was achieved by determining GLUF quantitatively produced by the acid hydrolysis of BIAL. The proposed methods were applied to the analysis of commercial herbicides and the validity and usefulness were evaluated.

Cloud point extraction of iron(III) and vanadium(V) using 8-quinolinol derivatives and Triton X-100 and determination of 10(-7)moldm(-3) level iron(III) in riverine water reference by a graphite furnace atomic absorption spectroscopy.

The cloud point extraction behavior of iron(III) and vanadium(V) using 8-quinolinol derivatives (HA) such as 8-quinolinol (HQ), 2-methyl-8-quinolinol (HMQ), 5-butyloxymethyl-8-quinolinol (HO(4)Q), 5-hexyloxymethyl-8-quinolinol (HO(6)Q), and 2-methyl-5-octyloxymethyl-8-quinolinol (HMO(8)Q) and Triton X-100 solution was investigated. Iron(III) was extracted with HA and 4% (v/v) Triton X-100 in the pH range of 1.70-5.44. Above pH 4.0, more than 95% of iron(III) was extracted with HQ, HMQ, and HMO(8)Q. Vanadium(V) was also extracted with HA and 4% (v/v) Triton X-100 in the pH range of 2.07-5.00, and the extractability increased in the following order of HMQ < HQ < HO(4)Q < HO(6)Q. The cloud point extraction was applied to the determination of iron(III) in the riverine water reference by a graphite furnace atomic absorption spectroscopy. When 1.25 x 10(-3)M HMQ and 1% (v/v) Triton X-100 were used, the found values showed a good agreement with the certified ones within the 2% of the R.S.D. Moreover, the effect of an alkyl group on the solubility of 5-alkyloxymethyl-8-quinolinol and 2-methyl-5-alkyloxymethyl-8-quinolinol in 4% (v/v) Triton X-100 at 25 degrees C was also investigated.

Cloud point extraction and preconcentration for the gas chromatography of phenothiazine tranquilizers in spiked human serum.

Cloud point extraction was successfully applied to the preconcentration of phenothiazine derivatives, such as pericyazine (PC), chlorpromazine (CP) and fluphenazine (FUL), for gas chromatography (GC). Phenothiazine derivatives were separated from surfactants by passing the surfactant-rich phase through a cation exchange column after cloud point extraction, permitting the determination of the phenothiazine derivatives extracted in the surfactant-rich phase by GC. The optimal condition for the cloud point extraction of phenothiazine derivatives was also investigated using Triton X-100, Triton X-114, and PONPE10. Triton X-114 provided the most efficient recovery of phenothiazine derivatives among the surfactants used. The addition of sodium chloride and excess ammonia to the sample solution resulted in a decrement of the recovery of the phenothiazine derivatives. The proposed method was applied to the determination of phenothiazine derivatives in spiked human serum by GC. The recoveries of PC, CP, and FUL in spiked human serum were 95.1%, 87.1%, and 84.7%, respectively.

Synergistic cloud point extraction behavior of aluminum(III) with 2-methyl-8-quinolinol and 3,5-dichlorophenol.

The cloud point extraction behavior of aluminum(III) with 8-quinolinol (HQ) or 2-methyl-8-quinolinol (HMQ) and Triton X-100 was investigated in the absence and presence of 3,5-dichlorophenol (Hdcp). Aluminum(III) was almost extracted with HQ and 4(v/v)% Triton X-100 above pH 5.0, but was not extracted with HMQ-Triton X-100. However, in the presence of Hdcp, it was almost quantitatively extracted with HMQ-Triton X-100. The synergistic effect of Hdcp on the extraction of aluminum(III) with HMQ and Triton X-100 may be caused by the formation of a mixed-ligand complex, Al(dcp)(MQ)2.

Co-extraction of lanthanoid(III) with various metal ions in the chelate extraction system with acetylacetone.

The co-extraction phenomenon was found in a typical chelate extraction system, in which the extraction of lanthanoid ion (Ln3+) with acetylacetone (Hacac) was highly enhanced by various metal ions (M(n+)) such as Cu2+, Al3+, and Zr4+. This phenomenon was ascribed to the formation of the 1:1 adduct between Ln(acac)3 and the M(acac),, extracted into the organic phase. The co-extraction occurred more readily for La3+ than that for Lu3+, and increased in the order of Cu2+ < Al3+ < Zr4+. This work elucidated that the co-extraction due to the adduct formation is a rather common phenomenon in the chelate extraction.

Solvent effect on distribution ratio of Pd(II) in supercritical carbon dioxide extraction and solvent extraction using 2-methyl-8-quinolinol.

The distribution ratio (D(M)) of Pd(II) by the extraction with 2-methyl-8-quinolinol (HMQ) was determined using the supercritical carbon dioxide medium (SF-CO(2)) and organic solvent media such as perfluoro-methylcyclohexane, heptane, cyclohexane, carbon tetrachloride and benzene. From experimental results of the slopes of logD(M) versus pH plot and logD(M) versus HMQ concentration plot, the extracted species both in the SF-CO(2) extraction (SFE) and the solvent extraction (SE) were determined to be Pd(MQ)(2). The distribution constant of HMQ (K(D,HMQ)) in the SFE and SE systems were determined from the dependence of the distribution ratio of HMQ (D(HMQ)) on the pH. A linear relationship was observed between logK(D,HMQ) and the solubility parameter (delta) of the extraction medium based on the regular solution theory in both the SFE using SF-CO(2) at the pressure of 8.5-40 MPa and the SE systems. The difference in the slope of the logK(D,HMQ) versus delta plot between the SFE and the SE systems is attributable to the extent of the specific interaction of the solute HMQ with the solvent molecules, i.e. CO(2) molecules and the organic solvent molecules. The D(M) versus delta plot obtained under a given extraction condition using SF-CO(2) (11-40 MPa) and organic solvents showed clear linearity. The D(M) obtained using SF-CO(2) at relatively low pressure range from 8.5 to 11 MPa was independent of the pressure and the delta of SF-CO(2), which coincides with the experimental fact that the solubility of Pd(MQ)(2) in the SF-CO(2) at 8.5-11 MPa was practically constant.

Synergistic effect of 3,5-dichlorophenol and trioctylphosphine oxide on the extraction of vanadium(V) with 2-methyl-8-quinolinol derivatives.

The extraction of vanadium(V) with 2-methyl-8-quinolinol derivatives (HA), such as 2-methyl-8-quinolinol (HMQ), 2-methyl-5-butyloxymethyl-8-quinolinol (HMO4Q), and 2-methyl-5-hexyloxymethyl-8-quinolinol (HMO6Q), from a weakly acidic solution into chloroform was studied in both the absence and presence of 3,5-dichlorophenol (Hdcp) and trioctylphosphine oxide (TOPO) as the synergists. Vanadium(V) was extracted with HA as VO(OH)(A)2 in the absence of synergists, and its extractability increased with an increase in the hydrophobicity of HA. Vanadium(V) was quantitatively extracted from the lower pH region upon the addition of Hdcp and TOPO as VO(OH)(A)2 x Hdcp and VO2(A)(TOPO), respectively. The enhancement of the synergistic effect of Hdcp on the extraction of vanadium(V) with HA increased in the following order: HMQ < HMO4Q < HMO6Q, as opposed to that of TOPO. This result was ascribable to the difference in the mechanisms of the occurrence of the synergistic effect by Hdcp and TOPO.

Supercritical carbon dioxide extraction equilibrium of gallium(III) with 2-methyl-8-quinolinol and 2-methyl-5-butyloxymethyl-8-quinolinol.

This work performed fundamental studies for the extraction of gallium(III) with 2-methyl-8-quinolinol (HMQ) and 2-methyl-5-butyloxymethyl-8-quinolinol (HMO(4)Q) into supercritical carbon dioxide (SF-CO(2)) from a weakly acidic solution. The distribution constants of HMO(4)Q between aqueous and SF-CO(2) phases were determined at 45 degrees C, 8.6-20.4 MPa and I=0.1 M (H, Na)NO(3) (M=mol dm(-3)). At 45 degrees C and 15.7 MPa, gallium(III) was hardly extracted with HMQ into SF-CO(2), but was quantitatively extracted with HMO(4)Q in the pH range of 2.20-2.84. The extraction constant, K(ex, SF-CO(2)) (=[Ga(OH)(MO(4)Q)(2)](SF-CO(2))[H(+)](3)[Ga(3+)](-1)[HMO(4)Q](SF-CO(2))(-2)), of gallium(III) with HMO(4)Q was determined to be 10(-2.6+/-0.1) at 45 degrees C, 15.7 MPa and I=0.1 M (H, Na)NO(3), which was 63 times larger than that in heptane at 45 degrees C and 0.10 MPa. It was also found that the addition of 3,5-dichlorophenol as a synergist enhanced the extractability of gallium(III) with HMO(4)Q into SF-CO(2).

Extraction equilibrium of palladium(II) with 2-methyl-8-quinolinol into supercritical carbon dioxide fluid.

The present study is concerned with the extraction behavior and equilibrium of Pd(II) with 2-methyl-8-quinolinol (HMQ) into supercritical fluid CO(2) (SF-CO(2)). Pd(II)-HMQ complex extracted from a weakly acidic solution (pH 2-3) into SF-CO(2) was determined to be Pd(MQ)(2) on the basis of a slope analysis. The extraction constant K(ex,SF) (=[Pd(MQ)(2)](SF)[H(+)](2)[Cl(-)](4)[PdCl(4)(2-)](-1)[HMQ](-2)) was determined to be 10(4.3+/-0.2) at 8.5 MPa, 45 degrees C and I=0.4 M (H,Na)Cl (1 M=1 mol dm(-3)). The distribution behavior of HMQ between an aqueous and a SF-CO(2) phase was examined so as to discuss quantitatively the extraction equilibrium. The extraction constant (K(ex,Cy)) of Pd(II) with HMQ into cyclohexane with a similar polarity to SF-CO(2) was determined and the K(ex,SF) was compared with the K(ex,Cy). Pd(II) at the concentration range of 10(-5)-10(-4) M in the aqueous solution (pH<3) containing relatively high concentration of chloride ion was found to be extracted efficiently by the SF-CO(2) extraction.