Oscillating chemical reactions, which are far from equilibrium, are extremely sensitive to certain species and may provide new analytical methods using the regular oscillations as well as the non-equilibrium stationary state after system bifurcation. This review of their application to analytical chemistry from 2005 to 2012 includes other appropriate references. Both organic and inorganic analytes are included.
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A simple analytical method for the determination of p-nitrobenzene-azo-naphthol was proposed by a sequential perturbation with different amounts of p-nitrobenzene-azo-naphthol on an oscillating chemical system. The method involves a Cu(II)-catalysed oscillating reaction between hydrogen peroxide and sodium thiocyanate in alkaline medium with the aid of continuous-flow stirred tank reactor (CSTR). A good linear relationship between the changes, oscillation amplitude or/and period, and the concentration of p-nitrobenzene-azo-naphthol was obtained. The use of analyte pulse perturbation technique provides a possibility of sequential determination in a same oscillating system, due to a new steady state that reappeared rapidly after each perturbation. The calibration curve fits a linear equation very well when the concentration of p-nitrobenzene-azo-naphthol ranging from 5.2×10−7 to 3.3×10−3M. Influence of temperature, injection point, flow rate and reactants variables on this system were investigated in detail.
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The solvent extraction behavior of precious metal palladium with 1-phenyl-3-methyl-4-benzoyl-5-pyrazone (PMBP) into molten paraffin wax has been studied in the temperature range from 55 to 75 °C. The complex consisting of PMBP and palladium was extracted into molten wax phase in the pH range from 1.0 to 3.5 at 60 °C. The extraction efficiency was up to 97% at the experimental pH. The stoichiometry of the extracted species of palladium was determined on the basis of slope analysis method. The effects of time to achieve equilibrium, temperature, and extractant concentration on the extraction were discussed. The thermodynamic data indicate that the extraction is an endothermic reaction and the increase of temperature promotes the extraction of palladium into molten paraffin wax and the extraction of palladium with PMBP is entropy controlled at high temperatures. [...]
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A stable superhydrophobic surface of stearic acid grafted zinc was fabricated with two steps, that is, the zinc surface was firstly treated with glow discharge electrolysis plasma (GDEP) and then followed by a grafted reaction of stearic acid onto the treated zinc surface. Results indicated that the wettability of zinc substrate changed from superhydrophily to superhyphodrobicity with a water contact angle (CA) up to 158° and a water sliding angle (SA) less than 5°. The surface morphology and composition were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. [...]
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A sensitive and convenient method for the determination of trace europium ions using an oscillating chemical reaction involving Ce(IV) - KBrO3 - acetone - oxalic acid - H2SO4 was proposed. The results indicated that the changes in oscillating period (T) was linearly proportional to the negative logarithmic concentration of Eu3+ (-log C) in the range of 1.41 × 10−8 ˜ 1.41 × 10−4 mol L−1 (r = 0.9982) with a detection limit of 1.04 × 10−9 mol L−1. The recoveries were limited to the range of 99.5% to 100.8%. Under the same conditions, other rare earth ions did not interfere with the determination of Eu3+. In addition, a perturbation mechanism was also discussed briefly. [...]
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Non-equilibrium plasma makes it is possible to modify surface chemistry, synthetize polymer materials, and oxidize some organic compounds completely by generation of energetic and chemically active species in gas or liquid phases. Glow-discharge electrolysis plasma (GDEP) has been intensely studied for applications in chemistry and in material, environmental, and biomedical engineering during the last few years because of the very highly active chemical species produced during the glow-discharge electrolysis (GDE) process. A brief review is already available regarding applications of glow-discharge electrolysis plasma technique in chemistry and environmental science during the past decade. For convenience of discussion, some papers from prior years are also cited. The contents of this review are focused on the degradation of persistent pollutants, surface modification of materials, and preparation of functional polymers.
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An acrylic acid/poly(ethylene glycol) (AAc/PEG) hydrogel was synthesized in aqueous solution by a simple one-step method using glow-discharge electrolysis plasma (GDEP) technique. The structure of AAc/PEG hydrogel was characterized by Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). Factors influencing the adsorption of heavy-metal ions such as solution pH, contact time, initial heavy-metal ion concentration were examined systematically by batch experiments. Results showed that both chemical complexation and ion exchange played an important role for heavy-metal ion adsorption onto AAc/PEG hydrogel. The adsorption isothermals followed the Langmuir isotherm and the adsorption kinetics fitted the pseudo-second-order model at 25°C with a pH 6. In addition, AAc/PEG hydrogel can be also regenerated and re-used. [...]
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This paper described the determination of p-nitroaniline in a double organic substrate oscillating system of tartrate-acetone-Mn2+-KBrO3-H2SO4. Under the optimum conditions, temperature was chosen as a control parameter to design the bifurcation point and proposed a convenient method for determination of p-nitroaniline. Results showed that the system consisting of 3.5 mL 0.06 mol L−1 tartrate, 4.0 mL 0.7 mol L−1 H2SO4, 1.5 mL 1.5×10−4 mol L−1 MnSO4, 4.0 mL 0.4 mol L−1 acetone and 7.0 mL 0.05 mol L−1 KBrO3 was very sensitive to the surrounding at 33.5°C. A good linear relationship between the potential difference and the negative logarithm concentration of p-nitroaniline was obtained to be in the range of 2.50×10−7∼3.75×10−5 mol L−1 with a lower detection limit of 2.50×10−8 mol L−1. [...]
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A plasma induced degradation process has been studied to treat 4-nitrotoluene (4-NT) present as an aqueous pollutant. The plasma was locally generated from a glow discharge around a tip of a platinum anode in an electrolytic solution. The influence of initial pH and Fe2+ on the degradation was examined. Major intermediates resulting from the degradation process were identified. Amongst the aromatic intermediates, p-hydroxybenzoic acid was the predominant degradation product. The formation of oxalic acid, malic acid was also observed. The final products of degradation were NH4+, NO3− and CO2. Based on the analysis of intermediates and the kinetic considerations, the degradation was shown to follow a pseudo-first order reaction hence, a possible reaction pathway was proposed.
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A rapid, simple and reliable capillary electrophoresis method for the separation and quantitation of inorganic cations with indirect UV detection at 214 nm was developed. The electrolyte was: 12 mM imidazole as background absorbance provider; 5 mM malic acid and 1.0 mM 18-crown-6 ether as complexing agents; and 20% D2O (v/v) to improve ion mobility. The pH was 4.25. The applied voltage was 22 kV at 22°C. Nine ions were completely separated and determined with correlation coefficients of 0.9979-0.9992. The relative standard deviations (RSD) were less than 0.5% for migration time and less than 5.2% for peak area (n=8). The detection limits (S/N=3) were from 0.08 mg L−1 (for Na+) to 0.51 mg L−1 (for Cu2+). To assess the reliability atomic absorption (AA) was also used to determine the same samples. Satisfactory results were obtained for real samples of jasmine tea drink and coconut milk. [...]
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A convenient and sensitive method for determination of sulfanilamide (SNA) was described based on the Mn(II)-catalyzed oscillating chemical reaction. Under optimum conditions, a linear relationship existed between the changes of oscillating period or amplitude and the negative of logarithm of SNA concentration in the range of 4.27 × 10−8 mol ·L−1 ∼ 7.41 × 10−6 mol ·L−1 (RSD, 0.85%) and 9.33 × 10−8 mol ·L−1 ∼ 3.02 × 10−6 mol ·L−1 (RSD, 1.08%), respectively. The lower limit of detection was found to be 2.69 × 10−8 mol ·L−1 and 6.03 × 10−8 mol ·L−1, respectively. [...]
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