Spectrophotometric study of reactions of scandium,ytrium and lanthanum ions with some triphenylmethane dyes in the presence of cationic surfactants

Optimum conditions for the formation of ternary complexes of scandium, ytrium and lanthanum ions with chrome azurol S, eriochrome cyanine R and pyrocatechol violet in the presence of cetyltrimethylammonium, cetypyridinium and tetradecyldimethylbenzyl-ammonium (zephiramine) ions are described. The spectrophotometric determination of scandium with chrome azurol S and zephiramine exhibits the greatest sensitivity (? = 1.50 × 10⁵ l mol^?1 cm^?1 at 610 nm). In the spectrophotometric determination of scandium with eriochrome cyanine R and cetylpyridinium ion (? = 9.2 × 10⁴ at 600 nm), the interference caused by yttrium is the least. In the best method for yttrium (with pyrocatechol violet and zephiramine), the molar absorptivity is 3.3 × 10⁴ at 660 nm. Lanthanum does not form ternary complexes of analytical interest in these systems. Some aspects of the formation of ternary complexes with cationic surfactants are discussed.     

Surfactant effects on the spectrophotometry of the gadolinium—chrome azurols complex

Increased molar absorptivities and red-shifted absorbance maxima were noted only upon the addition of cetylpyridinium chloride (CPC), a cationic surfactant. A 1:2:4 gadolinium/chrome azurol S/CPC complex was forned but dissociated at [CPC]/ [Gd³⁺] > 4 apparently because gadolinim(III) was displaced from this complex by additional surfactant monomers. Ternary complexes having different stoichiometries formed in the presence of excess dye. Sodium dodecyl sulfate (SDS), an anionic suffactant, induced dissociation of the binary complex at micellar concentrations, suggesting that dissociation resulted from adsorption of Gd³⁺ cations on the negatively charged micellar surface. Addition of Triton X-100, a nonionic surfactant, had little effect at either micellar or submicellar concentrations. These results confirm that complex stability is an important factor in the use of surfactants as sensitizers in quantitative spectrophotometry.     

A spectrophotometric flow procedure for the determination of cationic surfactants in natural waters using a solenoid micro-pump for fluid propulsion

An automatic flow-analysis procedure for spectrophotometric determination of cationic surfactants in surface water using a solenoid micro-pump for propelling solutions of reagents and sample is described. The proposed method is based on a ternary formation complex between chromazurol S, the Fe(III) ion, and the cationic surfactant. The flow network comprised four solenoid micro-pumps controlled by a microcomputer, which performed the sampling step by loading a reaction coil with sample and reagent solutions and displacing the sample zone through the analytical path. The system is simple, easy to operate, and very flexible, with sufficient sensitivity to determine cationic surfactants in water without any pre-concentration or separation step. After determining the best operational conditions, favourable features such as a linear response between 0.34 and 10.2?mg?L^?1 of surfactant (R?=?0.999), a relative standard deviation of 0.6% (n?=?11) for a sample containing 3.4?mg?L^?1 of surfactant, a detection limit of 0.035?mg?L^?1 of surfactant, and a sampling throughput of 72 determinations per hour were achieved. The system was used to determine cationic surfactant in river-water samples, and recovery values between 91 and 106% were achieved.     

Optical and chromaticity parameters of transition metal complexes with 1-nitroso-2-naphthol-3,6-disulfonic acid in the presence of surfactants

Optimal conditions for the complexation of transition metal ions [Cu(II), Ni(II), Co(II, III), and Fe(II, III)] with 1-nitroso-2-naphthol-2,6-disulfonic acid have been determined by spectrophotometry in the presence of cationic (cetylpyridinium and cetyltrimethylammonium bromides) and nonionic (OP-10, neonol) surfactants. The introduction of nonionic surfactants does not influence the optical parameters of the system, while the introduction of cationic ones leads to hyperchromic and hypsochromic (for the system Fe(III)-NRS-surfactant) effects. The stoichiometric ratios determined by the method of isomolar series and treatment of the saturation curves of cationic surfactants at pH 4.0 are Me(II): R: surfactant = 1: 2: 4, Me(III): R: surfactant = 1: 3: 6. The molar absorption coefficients and chromaticity parameters of ternary complexes have been determined. A 2–5-fold increase in the molar absorption coefficients and chromaticity functions as compared to binary systems has been revealed.     

Spectrophotometric determination of iron(III) with chrome azurol s or eriochrome cyanine r and some cationic surfactants

Sensitive spectrophotometric methods for the determination of iron(III), based on ternary complexes with a triphenylmethane reagent, chrome azurol S (CAS) or eriochrome cyanine R (ECR), and cetyltrimethylammonium (CTA) or cetylpyridinium (CP) ions, are described. For the system Fe—CAS—CTA, the molar absorptivity is 1.35 × 10⁵ l mol^-1 cm^-1 at 645 nm; for Fe—ECR—CTA it is 1.28 × 10⁵ l mol^-1 cm^-1 at 635 nm. Maximum absorbance is attained (at about pH 4) when the molar ratio (to iron) or CAS or ECR is about 20 and that of CTA or CP is 60–80. Citrate, tartrate, oxalate and EDTA interfere. Interference by metals (e.g. Be, Al, Ga, In, Sc, Zr, Th) can be eliminated by preliminary extraction of iron(III) as thiocyanate complex. The method was successfully applied to determining traces of iron in analytical-grade sodium hydroxide.     

The Spectrophotometric Determination of Sc in Eriochrome Canine R(Chrome azurol s)- Phosphatidl Choline System

Abstract

Eriochrome cyanine R(chrome azurol S) is used as a color reagent to determine Sc in the presence of phosphatidyl choline, σ = 3.7 × 10⁴ (4.5 × 10⁴). This method has been connected to extraction separation to determine Sc in the presence of rare earth elements, and good results have been obtained.

Phosphatidyl choline(PC) is a biochemical reagent, which can be used as a surfactant. It has been reported that chrome azurol S(CAS) can be used to determine Be in the presence of PC¹ but it has not been reported that eriochrome cyanine R(ECR) and CAS can be used to determine Sc in the presence of PC. This paper has put forward a method by which Sc can be determined. ECR (CAB) has been used as a color reagent and PC as a surfactant. Conditional experiments have been made and this method has been connected to extraction separation. Tributyl phosphate (TBP) extracts Sc from rare earth elements to make a determination and good results have been obtained.     

Single-step calibration, prediction and real samples data acquisition for artificial neural network using a CCD camera

An artificial neural network (ANN) model is developed for simultaneous determination of Al(III) and Fe(III) in alloys by using chrome azurol S (CAS) as the chromogenic reagent and CCD camera as the detection system. All calibration, prediction and real samples data were obtained by taking a single image. Experimental conditions were established to reduce interferences and increase sensitivity and selectivity in the analysis of Al(III) and Fe(III). In this way, an artificial neural network consisting of three layers of nodes was trained by applying a back-propagation learning rule. Sigmoid transfer functions were used in the hidden and output layers to facilitate nonlinear calibration. Both Al(III) and Fe(III) can be determined in the concentration range of 0.25-4 μg ml⁻¹ with satisfactory accuracy and precision. The proposed method was also applied satisfactorily to the determination of considered metal ions in two synthetic alloys.     

Flow-injection spectrophotometric determination of aluminium based on chrome azurol S and cetylpyridinium chloride

Acidic aluminium solutions (120 μl) are injected into a buffered (pH 5.7) carrier stream and merge with a chrome azurol S/cetylpyridinium chloride stream; a 2.25-m reaction coil is used with a total flow rate of 4 ml min ^?1. Ethanol (30% v/v) in the reagent stream enhances the absorbance of the ternary complex; the molar absorptivity is then 1.34×10 ⁵ l mol ^?1 cm ^?1 at 625 nm. Calibration is linear over the range 0–400 ng ml^?1 aluminium; the limit of determination is 5 ng ml ^?1. Iron is masked in the usual way; fluoride is tolerated at ˇ1 mg l ^?1. The injection rate is about 45 h^?1. The procedure appears to be applicable to tap water.     

The Spectrophotometric Determination of gallium (III) Using O-Hydroxyhydroquinonephathalein in the Presence of Surfactant Micellar

Abstract

The color reaction systems between various metal ions and o-hydroxyhydroquinonephthalein(Qnph) as a xanthene dye, in the presence of various water soluble surfactants(cationic. anionic, non-ionic surfactants) alone or in combination, were systematically investigated at various pH areas. The coexistence of cationic and non-ionic surfactants, such as Zephiramine (Zp) and Brij 35, was most effective for the color reaction systems between Qnph and gallium(III), as a metal ion, at weakly acidic media. By using the color reaction between Qnph and gallium(III) in the coexistence of Zp and Brij 35, an improved and sensitive spectrophotometric determination of gallium(III) was proposed as method 1, and the calibration curve was rectilinear in the range of 0～7.0 μg of gallium(III) in a final solution of 10ml at pH 6.4. The apparent molar absorptivity was 1.5 × 10⁵ 1 mol^?1 cm^?1 at 560 nm, and the interference of foreign ions was decreased by ½～ ¼-fold in comparison with other methods; method 3—in the presence of Zp alone at pH 6.4, method 2—in the presence of Tween or Brij 35 alone, without Zp, at pH 8. Thus, the use of Qnph as a xanthene dye and the combination of cationic and non-ionic surfactants, such as Zp and Brij 35(perhaps, on the mixed micellar media), was most effective and its color reaction was used for the separative assay of gallium(III).     

Determination of Anionic Surfactant in Fresh Water and in Sea Water

Ion pairs formed from suitable cationic dye and anionic surfactant in water were separated by solvent extraction. The extracts were used subsequently for spectrophotometric determinations. The extraction of ion pairs with various combinations is described. Of the dyes and solvents examined, ethyl violet and p-xylene are the most useful combination as the cationic dye and extraction solvent. The extracts are determined spectrophotometrically at 611.5 nm; the molar absorptivity is 1, 01 × 10⁵ M^?1 cm^?1. The detection limit is 1.4 ppb in water. The method is simple, rapid and sensitive. It can also be applied to the determination of anionic surfactants in sea water.     

Sensitive spectrophotometric determination of aluminium using thermal lens spectrometry

The determination of Al³⁺ in solution using a continuous-wave mode mismatched thermal lens spectrometer is reported and two spectrophotometric procedures are compared. The reagent investigated were bromopyrogallol red—tetradecyltrimethylammonium bromide (BPR—TDTA) and chrome azurol S—cetylpyridinium chloride (CAS—CPC). The CAS—CPC system gave a superior detection limit (0.17 μg 1^?1) to the BPR—TDTA system (1.15 mg 1^?1) owing to the higher reagent blanks and concomitant laser noise in the latter system.     

Effects of alkyltrimethylammonium bromide surfactants on the kinetics of the oxidation of tris(1,10-phenanthroline)iron(II) by azido-pentacyanocobaltate(III) complex

The redox reaction between tris(1,10-phenanthroline)iron(II), [Fe(phen)₃]²⁺, and azido-pentacyanocobaltate(III), [Co(CN)₅N₃]^3? was investigated in three cationic surfactants: dodecyltrimethylammonium bromide (DTAB), tetradecyltrimethylammonium bromide (TTAB) and cetyltrimethylammonium bromide (CTAB) in the presence of 0.1?M NaCl at 35°C. Second-order rate constant in the absence and presence of surfactant, k_w and k_ψ, respectively, were obtained in the concentration ranges DTAB?=?0???4.667?×?10^?4?mol?dm^?3, TTAB?=?0–9.364?×?10^?5?mol?dm^?3, CTAB?=?0???6.220?×?10^?5?mol?dm^?3. Electron transfer rate was inhibited by the surfactants with premicelllar activity. Inhibition factors, k_w/k_ψ followed the trend CTAB?>?TTAB?>?DTAB with respect to the surfactant concentrations used. The magnitudes of the binding constants obtained suggest significant electrostatic and hydrophobic interactions. Activation parameters ΔH^≠, ΔS^≠, and E_a have larger positive values in the presence of surfactants than in surfactant-free medium. The electron transfer is proposed to proceed via outer-sphere mechanism in the presence of the surfactants.     

Effect of Surfactants on the Formation,Morphology, and Surface Property of Synthesized SiO2 Nanoparticles

Abstract

This study investigated the effect of cationic, anionic (saturated and unsaturated), and nonionic surfactants on the formation, morphology, and surface properties of silica nanoparticles synthesized by the ammonium‐catalyzed hydrolysis of tetraethoxysilane in alcoholic media. Results indicate that at a relatively low surfactant concentration (1 × 10^?3–1 × 10^?6 M), cationic surfactants significantly affected the growth of silica particles as measured by dynamic light scattering and transmission electron microscopic analyses. In contrast, the anionic and nonionic surfactants showed relatively minor effects in the low concentration range. The magnitude of negative zeta potential was reduced for silica colloids that were synthesized in the presence of cationic surfactant because of charge neutralization. The presence of anionic surfactants only slightly increased the negative zeta potential while the nonionic surfactant showed no obvious effects. At high surfactant concentrations (>1 × 10^?3 M), cationic and anionic surfactants both induced colloid aggregation, while the nonionic surfactant showed no effect on particle size. Raman spectroscopic analysis suggests that molecules of cationic surfactants adsorb on silica surfaces via head groups, aided by favorable electrostatic attraction, while molecules of anionic and nonionic surfactants adsorb via their hydrophobic tails.     

Spectrophotometric study of the formation of ternary complexes of iron(III) with some triphenylmethane dyes and cationic surfactants

The optimum conditions have been found for the formation of the ternary complexes of iron(III) with Chrome Azurol S (CAS), Eriochrome Cyanine R, and Pyrocatechol Violet in the presence of cetyltrimethylammonium (CTA), cetylpyridinium, or tetradecyldimethyl-benzylammonium ions. The pH range of the complex formation is limited mainly by the pertinent hydrolysis constants of the metal ions. The maximum absorbances were obtained for excess R and cationic surfactants, ensuring the formation of complexes with the highest R:Fe molar ratio. The method based on the Fe-CAS-CTA system (ε = 1.32 × 10⁵ liter mol⁻¹ cm⁻¹ at 628 nm) is most sensitive and is recommended for the spectrophotometric determination of iron.     

Spectrophotometric determination of aluminium with chrome azurol s

A comprehensive investigation of the spcctrophotometric determination of aluminium with chrome azurol S is described. No heating is required for colour formation, and the method is considerably more reproducible and selective than either the eriochrome cyanine R or aluminon methods. In the presence of suitable masking agents, only Be²⁺, Zr⁴⁺, and F-cause serious interference. A molar absorptivity of 21,500 at 567.5 mμ was found for the aluminium-chrome azurol S lake, with a relative standard deviation of ± 0.4% at the 20 μg Al level. Beer's law is obeyed from 0 to 1.2 mg Al/ml.     

Kinetics and mechanism of the redox reaction between malachite green and iron(III) in aqueous and micellar media

The kinetics of the oxidation of malachite green (MG⁺) by Fe(III) were investigated spectrophotometrically by monitoring the absorbance change at 618 nm in aqueous and micellar media at a temperature range 20–40 °C; I = 0.10 mol dm^?3 for [H⁺] range (2.50–15.00) × 10^?4 mol dm^?3. The rate of reaction increases with increasing [H⁺]. The reaction was carried out under pseudo-first-order conditions by taking the [Fe(III)] (>10-fold) the [MG⁺]. A mechanism of the reaction between malachite green and Fe(III) is proposed, and the rate equation derived from the mechanism was consistent with the experimental rate law as follows: Rate = (k ₄ + K ₁ k ₅[H⁺]) [MG⁺][Fe(III)]. The effect of surfactants, such as cetyltrimethylammonium bromide (CTAB, a cationic surfactant) and sodium dodecylsulfate (SDS, an anionic surfactant), on the reaction rate has been studied. CTAB has no effect on the rate of reaction while SDS inhibits it. Also, the effect of ligands on the reaction rate has been investigated. It is proposed that electron transfer proceeds through an outer-sphere mechanism. The enthalpy and the entropy of the activation were calculated using the transition state theory equation.     

Estimation of free acidity in some hydrolysable metal ions present in reprocessing streams by fiber optic aided spectrophotometry

A fiber optic aided spectrophotometric technique has been developed for the determination of free acidity in nuclear fuel reprocessing streams. In this method, nitric acid forms yellow colour complex with chrome azurol s. The system obeys Lambert–Beer’s law at 542 nm in the range of acidity 4–14 M. The molar absorption coefficient (ε) and Sandell’s sensitivity (S) of complex are 5.23 × 10³ L.mol^?1.cm^?1 and 1.91 × 10^?4 µg/cm² respectively. Relative standard deviation is less than 1 % and correlation coefficient is 0.999. Results of the present method are in good agreement with those obtained by the standard procedure.     

Interaction between biosurfactant surfactin and cationic surfactant cetyl trimethyl ammonium bromide in mixed micelle

An anionic/cationic mixed surfactant aqueous system of surfactin and cetyl trimethyl ammonium bromide (CTAB) at different molar ratios was studied by surface tension and fluorescence methods (pH 8.0). Various parameters that included critical micelle concentration (cmc), micellar composition (X ₁), and interaction parameter (β ^m) as well as thermodynamic properties of mixed micelles were determined. The β ^m was found to be negative and the mixed system was found to have much lower cmc than pure surfactant systems. There exits synergism between anionic surfactin and cationic CTAB surfactants. The degree of participation of surfactin in the formation of mixed micelle changes with mixing ratio of the two surfactants. The results of aggregation number, fluorescence anisotropy, and viscosity indicate that more packed and larger aggregates were formed from mixed surfactants than unmixed, and the mixed system may be able to form vesicle spontaneously at high molar fraction of surfactin.     

Indirect atomic absorption spectrometric determination of some cationic surfactants by continuous liquid/liquid extraction with tetrathiocyanatocobaltate

The method involves the extraction of the detergent/tetrathiocyanatocobaltate(II) ion-pair into 4-methyl-2-pentanone. The overall concentration of cationic surfactant can be determined indirectly by measuring the cobalt in the organic layer by a.a.s. The optimum conditions for determining dodecyltrimethylammonium and tetraheptylammonium bromide (0.4–9.0 μg ml^?1) are described. The relative standard deviation is 1.2%. The method is selective and free from the interference of nonionic surfactants, and is applied to the determination of cationic surfactants added to water samples.     

A Novel Spectrophotometric Method for the Determination of Levodopa with the Detection System of Potassium Ferricyanide‐Fe(III)

In this paper, a novel method has been established to determine levodopa with the detection system of potassium ferricyanide‐Fe(III). In the presence of potassium ferricyanide, it has been demonstrated that Fe(III) is reduced to Fe(II) by levodopa at pH 4.0. In addition, the in situ formed Fe(II) reacts with potassium ferricyanide to form soluble prussian blue (KFe^III[Fe^II(CN)₆]). Beer's law is obeyed in the range of levodopa concentrations of 0.01–4.00 μg mL^?1 at the maximal absorption wavelength of 735 nm. The linear regression equation is A = 0.0082 + 0.61365 C (μg mL^?1) with a correlation coefficient of 0.9996. The detection limit (3σ/k) is 9 ng mL^?1, and R.S.D. is 0.73% (n = 11). Moreover, the apparent molar absorption coefficient of indirect determination of levodopa is 1.2 × 10⁵ Lmol^?1cm^?1. The parameters with regard to determination are optimized, and the reaction mechanism is discussed. This method has been successfully applied to determine levodopa in pharmaceutical, serum and urine samples. Analytical results obtained with this novel assay are satisfactory.