Optimization of cloud point extraction of copper with neocuproine from aqueous solutions using Taguchi fractional factorial design

Taguchi method was applied to optimize cloud point extraction (CPE) conditions for preconcentration and determination of trace amounts of copper by UV-Vis spectrophotometry. Briefly, the copper ions formed complexes with neocuproine in aqueous solution; then, Triton X-114 (0.15%, w/v) was added and phase separation occurred upon heating to 60°C. The copper complexes were preconcentrated into the small volume of the surfactant-rich phase; after centrifugation, the surfactant-rich phase was diluted with methanol and absorbance was measured at 455 nm. The main factors affecting the CPE were evaluated and optimized with Taguchi orthogonal array design (OA ₂₅). Under the optimum conditions, the calibration curve was linear in the range 2–500 μg/L (r ² > 0.997). The limit of detection and preconcentration factor were 1.8 μg/L and 37.2, respectively. The applicability of the proposed method was successfully confirmed by preconcentration and determination of trace amounts of copper in water samples and satisfactory results were obtained.     

Application of a fractional factorial design for the determination of cadmium by ETA-AAS in different atomization systems

A multivariate study was applied to the investigation of the variables affecting the cadmium sensitivity in a graphite furnace, with and without platform atomization or matrix modifier. The results indicated that, depending on the atomization system used, the factors studied (drying, ashing, atomization, calibration curve) exert an influence on the analysis. The interactions between the factors were also analyzed.     

Application of the fractional factorial design in multiple W/O/W emulsions

In presented research, multiple W/O/W emulsions were developed by using experimental design method. A 24-1 fractional factorial design was performed by varying the following input parameters: primary polymeric emulsifier (PEG 30-dipolyhydroxystearate) concentration (0.8% and 2.4%), secondary polymeric emulsifier (Poloxamer 407) concentration (0.8% and 1.2%), electrolyte magnesium sulfate heptahydrate (0.08% and 0.4%) and electrolyte sodium chloride (0.08% and 0.4%). Multiple emulsions were prepared by a two-step emulsification process. Obtained emulsions were characterized with rheological measurements, conductivity and centrifugation tests. Factorial analysis revealed that the concentration of the primary emulsifier was the predominant factor influencing the phase separation, conductivity and maximal apparent viscosity. Additionally, electrolyte magnesium sulfate heptahydrate was more efficient in stabilizing these systems, compared to sodium chloride. The applied fractional factorial design method enabled determination of the optimal concentrations of the primary and secondary emulsifier, as well as the concentration of electrolytes, in order to obtain W/O/W emulsions with desired maximal apparent viscosities, low values of conductivity and without phase separation after centrifugation.     

Carbon dioxide adsorption over DIPA functionalized MCM-41 and SBA-15 molecular sieves

The capture of carbon dioxide was carried out using MCM-41 and SBA-15 as adsorbents. These mesoporous materials were synthesized by the hydrothermal method, and subsequently functionalized with the di-iso-propylamine (DIPA). Then, they were characterized by XRD, BET, and TG/DTG. The X-ray diffraction patterns of the synthesized samples showed the characteristic peaks of MCM-41 and SBA-15, indicating that the structures of these materials were obtained. The functionalized samples presented a decrease of the intensities of these peaks, suggesting a decreasing in the structural organization of the material; however, the mesoporous structure was preserved. For the adsorption capacity measurements, the materials were previously saturated with carbon dioxide at 75 °C, and then desorbed in a thermobalance in the temperature range of 25–900 °C, under helium atmosphere. Desorption tests showed that the functionalized MCM-41 presented a weight loss of 7.5 wt%, against 5.9 wt% for SBA-15. The obtained values indicate that these nanostructured materials can be used as adsorbent for carbon dioxide capture.     

Extraction of PCDD/PCDF from soil with supercritical CO2: Optimization by a three-level factorial design approach

A highly sensitive and selective voltammetric procedure is described for the simultaneous determination of eleven elements (Cd, Pb, Cu, Sb, Bi, Se, Zn, Mn, Ni, Co and Fe) in water samples. Firstly, differential pulse anodic stripping voltammetry (DPASV) with a hanging mercury drop electrode (HMDE) is used for the direct simultaneous determination of Cd, Pb, Cu, Sb and Bi in 0.1 M HCl solution (pH = 1) containing 2 M NaCl. Then, differential pulse cathodic stripping voltammetry (DPCSV) is used for the determination of Se in the same solution. Zn is subsequently determined by DPASV after raising the pH of the same solution to pH 4. Next, the pH of the medium is raised to pH 8.5 by adding NH₃/NH₄Cl buffer solution for the determination of Mn by DPASV. Ni and Co are determined in the same solution by differential pulse adsorptive stripping voltammetry (DPAdSV) after adding DMG (1 × 10^–4 M). Finally, 1 × 10^–5 M 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) is added to the solution for the determination of Fe by DPAdSV. The optimal conditions are described. Relative standard deviations and relative errors are calculated for the eleven elements at three different concentration levels. The lower detection limits for the investigated elements range from 1.11 × 10^–10 to 1.05 × 10^–9 M, depending on the element determined. The proposed analysis scheme was applied for the determination of these eleven elements in some ground water samples.     

A factorial design for optimizing a flow injection analysis system

The use of a factorial design for the response exploration of a flow injection (FI) system is described and illustrated by FI spectrophotometric determination of paraquat. Variable response (absorbance) is explored as a function of the factors flow rate and length of the reaction coil. The present study was found to be useful to detect and estimate any interaction among the factors that may affect the optimal conditions for the maximal response in the optimization of the FI system, which is not possible with a univariate design. In addition, this study showed that factorial experiments enable economy of experimentation and yield results of high precision due to the use of the whole data for calculating the effects.     

A factorial design for optimizing a flow injection analysis system

The use of a factorial design for the response exploration of a flow injection (FI) system is described and illustrated by FI spectrophotometric determination of paraquat. Variable response (absorbance) is explored as a function of the factors flow rate and length of the reaction coil. The present study was found to be useful to detect and estimate any interaction among the factors that may affect the optimal conditions for the maximal response in the optimization of the FI system, which is not possible with a univariate design. In addition, this study showed that factorial experiments enable economy of experimentation and yield results of high precision due to the use of the whole data for calculating the effects.     

Influence of different extraction parameters on a solid-phase dynamic extraction for the gas chromatographic determination of d-limonene degradation products by using a fractional factorial design

Through the application of a solid-phase dynamic extraction (SPDE) method for the determination of volatile substances, different parameters may influence the extraction and desorption process and are, therefore, vital for the determination of the extracted substances via gas chromatography (GC). In this study, the influence of extraction und desorption parameters of an SPDE-GC method for the determination of the d-limonene degradation products, namely, alpha-terpineol, (-)-carveol, and (S)-carvone, in an aqueous model system was evaluated using a factorial fractional design. The aim was to reduce the number of factors that should be considered for the optimization of an SPDE procedure for different applications. It could be shown that the extraction efficiency of alpha-terpineol, (-)-carveol, and (S)-carvone is significantly influenced by the extraction parameters incubation temperature, number of extraction strokes, and amount of added NaCl. All 3 parameters have a positive effect on the extraction and determination of the examined d-limonene degradation products. Due to the identification of significant factors on the basis of an experimental design, the results of this study can be very useful for further development of SPDE methods for different applications.     

Development of a simultaneous liquid-liquid extraction and chiral derivatization method for stereospecific GC-MS analysis of amphetamine-type stimulants in human urine using fractional factorial design

A stereospecific gas chromatography-mass spectrometry analysis method for amphetamine-type stimulants in human urine was recently developed. For maximum efficiency, liquid-liquid extraction and chiral derivatization of the analytes using (R)-(-)-alpha-methoxy-alpha-(trifluoromethyl)phenylacetyl chloride were performed simultaneously. The effects of (1) use of saturated sodium chloride in 2.0 m sodium hydroxide, (2) extraction solvent volume, (3) percentage of triethylamine, (4) derivatization reagent volume, (5) sample mixing time, (6) incubation temperature and (7) incubation time on method sensitivity and variability were assessed using a two-level, eight-run Plackett-Burman design followed by a fold-over design. The use of saturated sodium chloride solution and the derivatization reagent volume were significant factors (ANOVA, p < 0.01). The saturated sodium chloride solution decreased sensitivity whereas an increased volume of derivatization reagent increased sensitivity. Calibration curves for all analytes were linear between 5 and 500 microg/L, with correlation coefficients of >0.99. Detection limits were 相似文献   

Amorphous and ordered organosilicas functionalized with amine groups as sorbents of platinum (II) ions

Two groups of amine-functionalized organosilicas have been synthesized: amorphous polysiloxane xerogels (APX) and ordered mesoporous organosilicas (OMO) by co-condensation of tetraethoxysilane and appropriate alkoxysilanes: aminopropyltriethoxysilane and N-[3-(trimethoxysilyl)propyl]ethylenediamine. The obtained materials were characterized by sorption measurements, X-ray diffractometry, elemental analysis, transmission electron microscopy, and scanning electron microscopy. The OMO samples have well developed porous structure—the values of specific surface area are in the range 740–840 m²/g. While the APX samples are less porous having the corresponding values in the range 280–520 m²/g. The sizes of the ordered mesopores of OMO are in the range 5.9–6.5 nm while for the APX they are 2.9–12.1 nm indicating structural differences between both groups of the samples. All samples were tested as the sorbents of Pt(II) ions. The influence of various parameters such as pH, contact time, equilibrium concentration on Pt(II) adsorption ability onto prepared adsorbents was studied in detail. Additionally, the effect of chloride concentration on Pt(II) adsorption was investigated. The values of static sorption capacities were in the range of 32–102 mg_Pt(II)/g and 20–139 mg_Pt(II)/g for OMO and APX series, respectively.     

Carbon deposition in methane reforming with carbon dioxide

Coke formation in the dry reforming of methane was studied using a thermobalance (TG) and with a catalytic microreactor in the temperature range 800–950 K. Silica-supported and lanthana-supported nickel catalysts were examined. The effects of process variables such as temperature and gas composition (He dilution, CH₄/CO₂ ratio) on the coke formation rate were determined. The reactivity of H₂ on several kinds of carbon was also investigated. The morphology of the coke was studied by scanning electron microscopy (SEM). The induction times for coke formation were significantly affected by temperature and by the CO content in the feed gas. The results of catalytic tests were consistent with the TG measurements. The behaviour of SiO₂ and La₂O₃ supported Ni catalysts agree with a mechanism in which the lanthana support plays an important role in the carbon deposition.     

Carbon dioxide evolution in a Belousov-Zhabotinsky type oscillating reaction with acetonedicarboxylic acid

Oscillations in the platinum redox potential during the reaction of bromate ions with acetonedicarboxylic acid catalyzed by Mn(II) ions were observed. The volume of gaseous carbon dioxide produced was measured. A nonoscillatory course was found both at the slow and rapid stirring rates for carbon dioxide evolution. The perturbation experiments suggest supersaturation during the Belousov-Zhabotinsky reaction with acetonedicarboxylic acid. Possible reasons for such observations are discussed.     

Application of factorial design to improve a FIA system for penicillin determination

A potentiometric FIA system for penicillin determination, employing penicillinase [E.C. 3.5.2.6] immobilized on silica gel, packed into a reactor, was improved by the use of statistically designed experiments. A two-level and three-factor factorial was used to find the best working conditions evaluating the influence of some parameters on the signal response of the system and the number of determinations per hour. These parameters were analyzed individually obtaining two level of the variables to be used in the factorial design: length of the reactor (1.5 and 2.0 cm), carrier flow rate (1.6 and 2.2 ml min⁻¹) and sample volume (100 and 150 μl). The pure error on the measurements was estimated by authentic repetitions. The ideal working conditions taking into account a compromise between the best response signal and the number of determinations per hour (with the same importance) being chosen the level of factors: length of reactor 1.5 cm, carrier flow rate 2.2 ml min⁻¹ and sample volume of 150 μl. Under these conditions the system allowed to analyze was about 45 samples per hour, during 73 days, with a standard deviation of 2.4% at concentration range between 10⁻¹ and 10⁻³ mol l⁻¹.     

Fractional factorial design study of a pressure swing adsorption-solvent vapor recovery process

A two-level fractional factorial study was performed by computer simulation on the periodic state process performance of a pressure swing adsorption-solvent vapor recovery process (PSA-SVR). The goal was to investigate factor (parameter) interaction effects on the process performance, i.e., interaction effects that cannot be ascertained from the conventional “one-at-a-time” approach. Effects of seven factors, i.e., the purge to feed ratio, pressure level, pressure ratio, heat transfer coefficient, feed concentration, feed volumetric flow rate and bed length to diameter ratio, on the process performance were investigated. The results were judged in terms of the light product purity, heavy product enrichment (and relative enrichment) and recovery, and bed capacity factor. Only the purge to feed ratio, pressure ratio, and feed concentration had significant effects on the benzene vapor enrichment (and relative enrichment); and no two-factor and higher interactions were observed. The light product purity was affected by all seven factors; and the relative importance of the effect of each factor depended on the levels of the other factors, i.e., significant two-factor interaction effects existed. Two-factor interaction effects also existed on the benzene vapor recovery, although the effects of all seven factors and their interactions were relatively small. The bed capacity factor was affected mainly by the purge to feed ratio, the heat transfer coefficient and the feed concentration; two factor and higher order interaction effects were insignificant. Overall, this study demonstrated the utility of fractional factorial design for revealing factor interactions and their effects on the performance of a PSA-SVR process.     

Fractional factorial design study of a pressure swing adsorption-solvent vapor recovery process

A two-level fractional factorial study was performed by computer simulation on the periodic state process performance of a pressure swing adsorption-solvent vapor recovery process (PSA-SVR). The goal was to investigate factor (parameter) interaction effects on the process performance, i.e., interaction effects that cannot be ascertained from the conventional one-at-a-time approach. Effects of seven factors, i.e., the purge to feed ratio, pressure level, pressure ratio, heat transfer coefficient, feed concentration, feed volumetric flow rate and bed length to diameter ratio, on the process performance were investigated. The results were judged in terms of the light product purity, heavy product enrichment (and relative enrichment) and recovery, and bed capacity factor. Only the purge to feed ratio, pressure ratio, and feed concentration had significant effects on the benzene vapor enrichment (and relative enrichment); and no two-factor and higher interactions were observed. The light product purity was affected by all seven factors; and the relative importance of the effect of each factor depended on the levels of the other factors, i.e., significant two-factor interaction effects existed. Two-factor interaction effects also existed on the benzene vapor recovery, although the effects of all seven factors and their interactions were relatively small. The bed capacity factor was affected mainly by the purge to feed ratio, the heat transfer coefficient and the feed concentration; two factor and higher order interaction effects were insignificant. Overall, this study demonstrated the utility of fractional factorial design for revealing factor interactions and their effects on the performance of a PSA-SVR process.Nomenclature BCF bed capacity factor, % - b, b ₀ isotherm parameters, m³/(mol K^0.5) - C _pg gas phase heat capacity, kJ/(kg K) - C _ps solid phase heat capacity, kJ/(kg K) - E enrichment - E _I ideal enrichment - E _R relative enrichment - H heat transfer coefficient, kJ/m² s K) - H heat of adsorption, kJ/mol - k number of factors, or mass transfer coefficient, l/s - l number of levels - L bed length, m - LD bed length to diameter ratio - PF purge to feed ratio - P _H adsorption high pressure, kPa - P _L desorption pressure, kPA - PL pressure level, represented byP _I - PR pressure ratio - q amount adsorbed, mol/kg - q ^xx equilibrium amount adsorbed, mol/kg - q ^xx _j equilibrium amount adsorbed at the feed conditions, mol/kg - r _b bed radius, m - R solvent vapor recovery, % or gas constant, m³ (mole K) - T temperature, K - T ₀ ambient temperature, K - t time, s - u interstitial velocity, m/s - VF volumetric feed flow rate, m³ STP/s - YF feed mole fraction - Y _p light product mole fraction - z axial coordinate, m Greek Symbols _g gas phase density, kg/m³ - _s solid phase density, kg/m³ - bed void fraction     

Robustness testing of a reversed-phase high-performance liquid chromatographic assay: comparison of fractional and asymmetrical factorial designs

Robustness tests were performed on a reversed-phase HPLC assay for triadimenol. Different experimental designs were compared. Two-level fractional factorial designs with different resolutions were used to study the influence of procedure-related factors. The factors chromatographic column manufacturer at four levels and instrument at three levels were stepwise included in the study using asymmetrical factorial designs. The significance of the factor effects was determined statistically, using two types of error estimates in the calculation of critical effects, and graphically, by means of half-normal plots. The asymmetrical designs turned out to be an efficient and economic method to examine the influence of factors at different numbers of levels in the robustness testing of analytical methods.     

一氧化碳与烯烃共聚及其功能高分子

本文综述了一氧化碳与烯烃共聚合成聚酮的方法，共聚反应机理以及聚酮在合成其他功能高分子方面的应用。