Micelle-mediated cloud point extraction and spectrophotometric determination of rhodamine B using Triton X-100

A new micelle-mediated cloud point extraction method is described for sensitive and selective determination of trace amounts of rhodamine B by spectrophotometry. The method is based on the cloud point extraction of rhodamine B from aqueous solution using Triton X-100 in acidic media. The extracted surfactant rich phase is diluted with water and its absorbance is measured at 563 nm by a spectophotometer. The effects of different operating parameters such as concentration of surfactant and salt, temperature and pH on the cloud point extraction of rhodamine B were studied in details and a set of optimum conditions were obtained. Under optimum conditions a linear calibration graph in the range of 5-550 ng mL⁻¹ of rhodamine B in the initial solution with r = 0.9991 (n = 15) was obtained. Detection limit based on three times the standard deviation of the blank (3S_b) was 1.3 ng mL⁻¹ (n = 10) and the relative standard deviation (R.S.D.) for 50 and 350 ng mL⁻¹ of rhodamine B was 2.40 and 0.87% (n = 10), respectively. The method was applied for the determination of rhodamine B in soft pastel, hand washing liquid soap, matches tip and textile dyes mixture samples.     

Cloud point extraction of lanthanide(III) ions via use of Triton X-100 without and with water-soluble calixarenes as added chelating agents

The use of water-soluble calixarenes: p-sulfonato thiacalixarene (ST), tetra-sulfonatomethylated calix[4]resorcinarene (SR), calix[4]resorcinarene phosphonic acid (PhR) as chelating agents in cloud point extraction (CPE) of La(III), Gd(III) and Yb(III) ions using Triton X-100 as non-ionic surfactant is introduced. The data obtained indicate that both complexation ability and structure of calixarenes govern the extraction efficiency of lanthanides. In particular ST and SR, forming 1:1 lanthanide complexes with similar stability in aqueous media, exhibit different extractability when used as chelating agents in CPE. First synthesized PhR was found to be the most efficient chelating agent exhibiting pH-dependent selectivity within La(III), Gd(III) and Yb(III) in CPE.     

Spectrophtometric determination of malachite green in fish farming water samples after cloud point extraction using nonionic surfactant Triton X-100

A novel and sensitive cloud point extraction procedure for the determination of trace amounts of malachite green by spectrophotometry was developed. Malachite green was extracted at pH 2.5 mediated by micelles of nonionic surfactant Triton X-100. The extracted surfactant-rich phase was diluted with ethanol and its absorbance was measured at 630 nm. The effect of different variables such as pH, Triton X-100 concentration, cloud point temperature and time and diverse ions was investigated and optimum conditions were established. The calibration graph was linear in the range of 4-500 ng mL⁻¹ of malachite green in the initial solution with r = 0.9996 (n = 10). Detection limit based on three times the standard deviation of the blank (3S_b) was 1.2 ng mL⁻¹ and the relative standard deviation (R.S.D.) for 20 and 300 ng mL⁻¹ of malachite green was 1.48 and 1.13% (n = 8), respectively. The method was applied to the determination of malachite green in different fish farming and river water samples.     

Solid phase extraction of zinc(II) using a PVC-based polymer inclusion membrane with di(2-ethylhexyl)phosphoric acid (D2EHPA) as the carrier

A polymer inclusion membrane (PIM) is reported consisting of 45% (m/m) di(2-ethylhexyl)phosphoric acid (D2EHPA) immobilized in poly(vinyl chloride) (PVC) for use as a solid phase absorbent for selectively extracting Zn(II) from aqueous solutions in the presence of Cd(II), Co(II), Cu(II), Ni(II) and Fe(II). Interference from Fe(III) in the sample is eliminated by precipitation with orthophosphate prior to the extraction of Zn(II). Studies using a dual compartment transport cell have shown that the Zn(II) flux (2.58 × 10⁻⁶ mol m⁻² s⁻¹) is comparable to that observed for supported liquid membranes. The stoichiometry of the extracted complex is shown to be ZnR₂·HR, where R is the D2EHPA anion.     

Adsorption of lanthanides(III) from aqueous solutions by fullerene black modified with di(2-ethylhexyl)phosphoric acid

Fullerene black (FB) - a product of electric arc graphite vaporization after extraction of fullerenes - was modified with the di(2-ethylhexyl)phosphoric acid (D2EHPA). The distribution of D2EHPA between FB and aqueous HNO₃ solutions has been studied. The effect of HNO₃ concentration in the aqueous phase and that of D2EHPA concentration in the sorbent phase on the adsorption of microquantities of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y nitrates from HNO₃ solutions by D2EHPA-modified FB are considered. The stoichiometry of the sorbed complexes has been determined by the slope analysis method. The efficiency of lanthanides’ adsorption increases with an increase in the element atomic number. A considerable synergistic effect has been observed upon the addition of the neutral bidentate tetraphenylmethylenediphosphine dioxide ligand to D2EHPA in the sorbent phase.      

The effect of diluents on extraction of copper(II) with di(2-ethylhexyl)phosphoric acid

The liquid–liquid extraction of copper(II) from sulfate medium with di(2-ethylhexyl)phosphoric acid (D2EHPA, HL) at 25°C is studied with the following parameters: pH, concentration of the extractant, and the nature of diluent. The effect of the diluent using polar and nonpolar solvents in the extraction of copper(II) is discussed. The extracted copper(II) species were CuL₂ in 1-octanol and methyl isobutyl ketone and CuL₂ · 2HL in toluene, carbon tetrachloride, and cyclohexane. The extraction constants are evaluated for different diluents.     

Reversed phase partition chromatographic separation of antimony (III) with bis(2-ethylhexyl) phosphoric acid

A new method is proposed for the extractive Chromatographic separation of antimony. Antimony is extracted from 0.001–0.5M hydrochloric acid by a silica gel column coated with bis (2-ethylhexyl) phosphoric acid stripped with 2–8M hydrochloric, nitric or sulphuric acid, and determined spectrophotometrically at 555 nm as its complex with phenylfluorone. Antimony can thus be separated from a large number of elements, including iron, manganese, copper and thallium. Arsenic, antimony, bismuth and tin can be sequentially separated.     

Thermodynamics of non-ionic surfactant Triton X-100-cationic surfactants mixtures at the cloud point

This study investigates the effects of gemini and conventional cationic surfactants on the cloud point (CP) of the non-ionic surfactant Triton X-100 (TX-100) in aqueous solutions. Instead of visual observation, a spectrophotometer was used for measurement of the cloud point temperatures. The thermodynamic parameters of these mixtures were calculated at different cationic surfactant concentrations. The gemini surfactants of the alkanediyl-α-ω-bis (alkyldimethylammonium) dibromide type, on the one hand, with different alkyl groups containing m carbon atoms and an ethanediyl spacer, referred to as “m-2-m” (m = 10, 12, and 16) and, on the other hand, with –C₁₆ alkyl groups and different spacers containing s carbon atoms, referred to as “16-s-16” (s = 6 and 10) were synthesized, purified and characterized. Additions of the cationic surfactants to the TX-100 solution increased the cloud point temperature of the TX-100 solution. It was accepted that the solubility of non-ionic surfactant containing polyoxyethylene (POE) hydrophilic chain was a maximum at the cloud point so that the thermodynamic parameters were calculated at this temperature. The results showed that the standard Gibbs free energy , the enthalpy and the entropy of the clouding phenomenon were found positive in all cases. The standard free energy increased with increasing hydrophobic alkyl chain for both gemini and conventional cationic surfactants; however, it decreased with increasing surfactant concentration.     

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 (HO₄Q), 5-hexyloxymethyl-8-quinolinol (HO₆Q), and 2-methyl-5-octyloxymethyl-8-quinolinol (HMO₈Q) 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 HMO₈Q. 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 < HO₄Q < HO₆Q. 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 × 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 °C was also investigated.     

有机酸对非离子型表面活性剂浊点的影响

有机酸对非离子表面活性剂TritonX-100浊点的影响与酸的亲水性能、空间效应及其在胶束中的增溶位置有关。直链一元酸的加入均使浊点下降,且酸的碳链越长影响越大。直链二元酸对TritonX-100浊点下降的影响小于直链一元酸,且碳原子数nc<6时,使得浊点略有升高;nc≥6时,使得浊点下降。由于空间位阻作用,支链酸和取代酸使TritonX-100浊点降低幅度较小。     

Atomic absorption determination of indium after extraction with di-(2-ethylhexyl)phosphoric acid

The equilibrium data show that indium can be quickly extracted from acidic aqueous solutions by di-(2-ethylhexyl)phosphoric acid in methyl isobutyl ketone. In this polar solvent the species ML₃·HL is extracted. The overall extraction constant is higher than that for other tervalent metals. The extraction process can be combined with AAS determination of the indium. The method is fast because stripping is not necessary, and the organic phase can be analysed directly by AAS. Use of a 51 v/v aqueous: organic phase ratio increases the sensitivity. In the pH-range used the method has good selectivity.     

Role of Cloud Point of the Capping Agent (Nonionic Surfactant,Triton X-100) on the Synthesis of Silver Nanoparticles

The solution behavior of the nonionic surfactants below and above the cloud point (CP) is quite different. Below CP, a single phase of molecular or micellar solution exists, whereas above the CP, the solution separates into two phases: the first one is denser and smaller phase and contains most of the surfactant and the other one is relatively a voluminous aqueous phase and has surfactant concentration close to the critical micelle concentration (cmc). There are many reports available where nonionic surfactant is used as capping agent. But, to the best of our knowledge, there is no report on the CP's role on the synthesis of nanoparticles (NPs). Therefore, it is very important to understand the role of the CP on the synthesis of NPs. In the present work, we report the role of the clouding of the nonionic surfactant Triton X-100 (using as capping agent) on the synthesis of AgNPs below and above the CP. The morphology of AgNPs was studied by transmission electron microscopy (TEM), dynamic light scattering (DLS), UV–Vis absorption, etc., techniques. Below the CP, spherical polydisperse particles of 12 ± 5 nm mean diameter were found, whereas above the CP, the aggregated particles with higher diameter were found.     

Kinetics,mechanism and cloud point measurements in the oxidative degradation of non-ionic Triton X-100 surfactant in acidic permanganate solutions

The polyoxyethylene chain of non-ionic surfactant Triton X-100 [4-(1,1,3,3-tetramethylbutyl) phenyl polyethylene glycol,TX-100] was degraded by permanganate in the presence of HClO₄. The oxidative degradation rate and cloud point have been obtained as a function of [surfactant], [permanganate], [HClO₄], and temperature. Dependence of the reaction rate on adding inorganic salts (Na₄P₂O₇, NaF and MnCl₂) was also examined. The oxidation rate increased with increase in [TX-100] and [H⁺]. The higher order kinetics with respect to [TX-100] at lower [H⁺] shifted to lower order at higher [H⁺]. The cloud point of TX-100 (67°C) shifted to lower temperature (23±0.5°C) after oxidative degradation of the polyoxyethylene chain. Evidence of complex formation between TX-100 and MnO ₄ ⁻ was obtained spectrophotometrically. Presence of the primary alcoholic (–OH) group in the TX-100 skeleton is responsible for the degradation of oxyethylene chain. Both monomeric and aggregated TX-100 molecules are oxidized by permanganate. A catalytic oxidation mechanism is proposed on the basis of the experimental findings.     

二(2-乙基己基)磷酸对氨基酸的萃取平衡

二（２－乙基己基）磷酸对氨基酸的萃取平衡曹汉瑾,王德宝,刘沛妍,吴子生,严忠（东北师范大学化学系,长春,１３００２４）关键词氨基酸,二（２－乙基己基）磷酸,萃取平衡,分配比迄今为止,有关氨基酸溶剂萃取的文献报道还不多［１～３］．本实验以二（２－乙基己...     

The Micellization and Clouding Phenomena of a Nonionic Surfactant,Poly(ethylene glycol) t-octylphenyl ether (Triton X-100): Effect of (Chloride Salt) Electrolytes

Herein, we report the micellization and the clouding of a nonionic surfactant, poly(ethylene glycol) t-octylphenyl ether (Triton X-100), in aqueous solutions in the absence and presence of (chloride salt) electrolytes. In the absence and presence of electrolytes, the critical micelle concentration (CMC) of Triton X-100 was measured by surface tension measurements. Upon increasing the temperature as well as the concentration of electrolytes, the CMCs decreased. The surface properties and the thermodynamic parameters of the micellar systems were evaluated. From these evaluated thermodynamic parameters, it was found that in the presence of an electrolyte, the stability of the micellar system is high. The cloud points (CPs) of Triton X-100 were also measured in the absence and presence of metallic ions of electrolytes. Upon the addition of metallic ions of chloride salts (electrolytes), the decrease in CP values was observed and the order was found to be: K⁺ > Na⁺ > Li⁺ > NH⁺₄.     

Fundamental- and Second-Harmonic Tensammetry of DI-(2-ethylhexyl)phosphoric Acid

Abstract

The tenaammetric behavior of di-(2-ethylhexyl)phosphoric acid (D2KHPA) was investigated by non-phase-selective AC polarography. D2EHPA produces in alkali sulfate supporting electrolytes a decrease of the capacitive current in the region of zero-charge potential, as well as a tensammetric peak located between -1.0 and -1.3 V vs. SCE. In the same range, the second harmonic has a characteristic maximum. The pH of the solution and the nature of the cation in the supporting electrolyte affect both the height and the position of the tensammetric peaks. The tensammetric method allows determination of D2EHPA at concentrations ranging from 0.5 to 200 mg/1. Maximum sensitivity is obtained by measuring the second harmonic.     

Kinetic study of l-isoleucine transport through a liquid membrane containing di(2-ethylhexyl) phosphoric acid in kerosene

A kinetic study of l-isoleucine transport through a liquid membrane containing di(2-ethylhexyl) phosphoric acid (D2EHPA) in kerosene is presented. The influences of pH in the aqueous feed solution, D2EHPA concentration in the organic phase, the stripping solution composition and H₂SO₄ concentration in the stripping solution were investigated, and the effects of stirring speed and temperature on the transport of l-isoleucine through a bulk liquid membrane (BLM) were studied. The kinetics of l-isoleucine transport could be analyzed in the formalism of a reversible pseudo-first-order reaction followed by an irreversible pseudo-first-order reaction. The pseudo-first-order apparent rate constants of the interfacial transport of l-isoleucine species are determined for the liquid membrane, at various temperatures. The apparent activation energy values are 21.3±1.9, 57.6±5.1 and 31.8±2.7 kJ mol⁻¹ for the extraction reaction, extraction back reaction and stripping reaction, respectively.     

Cloud point extraction: an alternative to traditional liquid-liquid extraction for lanthanides(III) separation

Cloud point extraction (CPE) was used to extract and separate lanthanum(III) and gadolinium(III) nitrate from an aqueous solution. The methodology used is based on the formation of lanthanide(III)-8-hydroxyquinoline (8-HQ) complexes soluble in a micellar phase of non-ionic surfactant. The lanthanide(III) complexes are then extracted into the surfactant-rich phase at a temperature above the cloud point temperature (CPT). The structure of the non-ionic surfactant, and the chelating agent-metal molar ratio are identified as factors determining the extraction efficiency and selectivity. In an aqueous solution containing equimolar concentrations of La(III) and Gd(III), extraction efficiency for Gd(III) can reach 96% with a Gd(III)/La(III) selectivity higher than 30 using Triton X-114. Under those conditions, a Gd(III) decontamination factor of 50 is obtained.     

Polarographic behaviour of 1,3-bis[(2-pyridyl)methyleneamino]thiourea (PMAT) in absence and presence of Triton X-100

The polarographic behaviour of 1,3-bis[(2-pyridyl)methyleneamino]thiourea (PMAT) in solutions of varyingpH has been studied both in the absence and presence of Triton X-100 (T.X-100). The mechanism for the reduction process is discussed. The adsorption effect of electrochemically inactive T.X-100 on the polarographic waves ofPMAT has been investigated. The values of the kinetic parameters for the electrode reaction at differentpH values have been computed. The applicability of the polarographic method for determination ofPMAT is also discussed.

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Das polarographische Verhalten von 1,3-Bis[(2-pyridyl)methylenamino]-thioharnstoff (PMAT) in Anwesenheit und Abwesenheit von Triton X-100. Die polarographische Bestimmung vonPMAT

Zusammenfassung Es wurde das polarographische Verhalten vonPMAT in Lösungen mit verschiedenempH sowohl in Gegenwart als auch ohne Triton X-100 (T.X-100) untersucht. Es wird ein Mechanismus für den Reduktionsprozeß diskutiert. Der Adsorptionseffekt des elektrochemisch inaktiven T.X-100 wurde hinsichtlich der polarographischen Wellen vonPMAT untersucht. Die kinetischen Parameter der Elektrodenreaktion wurden für verschiedenepH-Werte ermittelt. Ebenso wird die Anwendbarkeit der polarographischen Methode für die Bestimmung vonPMAT diskutiert.

     

二（2—乙基己基）单硫代磷酸萃取铟的研究

目前采用二(2-乙基己基)磷酸(D2EHPA)从硫酸溶液中萃取铟在生产上虽获得广泛应用,但反萃取又转入盐酸体系,腐蚀刺激性较强.改用D2EHMTPA萃取铟可能较好,有关这方面的研究至今尚未见报道,本文从硫酸溶液中考察了D2EHMTPA萃取铟的性能,并与D2-EHPA和二(2-乙基己基)二硫代磷酸(D2EHDTPA)作比较,以了解这类萃取剂结构上的差别对萃取铟的影响,这对选择及合成高效能萃取剂分子也是有意义的,还应用斜率法、饱和法确定了萃取平衡反应及萃合物组成,根据IR与NMR探讨了D2EHMTPA萃取铟的机理。