Removal of hexavalent chromium from aqueous solutions by micellar compounds

The recovery of toxic metal compounds is a deep concern in all industries. Hexavalent chromium is particularly worrying because of its toxic influence on human health [1], [2] and [3]. Actually the wastewater norm (0.1 mg/l) is very strict and will become more severe in the near future. We present in this paper the experimental results of the metal ion which is bound on micellar compounds and then retained by ultrafiltration membrane. A well known surfactant cetyltrimethylammonium bromide (CTABr) is used as an adsorbent to remove hexavalent chromium from wastewaters. The effects of various experimental parameters on equilibrium adsorption of Cr(VI) on the surfactant have been investigated using batch adsorption experiments. It was found that the capacity of chromium adsorption on CTABr increases with initial metal concentration and in a lesser extent with pH solution. Total chromium adsorption decreased slightly with a rise in temperature suggesting an exothermic adsorption of chromium, thermodynamic parameters are evaluated. It has also been observed that the capacity of chromium adsorption decreases with the mass of adsorbent and concentration of other ions present in the solution. The metal ion adsorption on surfactant is well represented by the Freundlich isotherm.     

Lecithin in oil-in-water emulsions

Summary A study was made to investigate the use of purified phosphatide in I.V. emulsions. Lecithin isolated from egg yolk and purified by alumina and silica chromatography was analyzed by chromatographic strip techniques as a one-component material. Highly purified lecithin was found to be an inefficient emulsifier. Moreover emulsions containing highly purified lecithin were heat-sensitive. An emulsion physical stability test was developed to evaluate emulsifier formulations containing purified phosphatides for use with small amounts of emulsions (approximately 50 g.). Using this procedure, a considerable number of substances were tested as additives to enhance the purified lecithin's emulsifying power. None were found to be as effective as natural soybean phosphatide, which was used as a control. From these observations it is indicated that pure phosphatides are inefficient emulsifiers and that those phosphatide preparations possessing good emulsifying characteristics are presumably mixtures or complexes of the phosphatides with other substances. This investigation was supported in part by funds from the Office of the Surgeon General. One of the laboratories of the Southern Utilization Research and Development Division. Agricultural Research Service, United States Department of Agriculture.     

Electrochemical oxidation of 2-mercaptopyridine N-oxide on mercury electrodes in aqueous solutions

The oxidation mechanism of 2-mercaptopyridine N-oxide (NOS) is studied in aqueous media. Polarographic, classical and differential pulse, and voltammetic studies were made. The effect of pH, reactant concentration and scan rate on the electrochemical parameters is studied. The results indicate that the anionic form of NOS is oxidized at the mercury electrode to yield a radical. At pH 2 > 4.5 the dissociation of NOS precedes the electrochemical process.At low concentration values the reversible oxidation of NOS to yield the strongly adsorbed radical takes place, whereas at high concentrations this process is accompanied by the diffusional reversible oxidation. Both processes appear at different potentials due to the contribution of ΔG_ads, which has been determined from polarographic and voltammetric measurements, having a value of −7.7 kJ mol⁻¹. The oxidation potential of the NOS⁻/NOS redox couple has been also calculated as E ° = 274 ± 5 mV vs. the Ag/AgCl/KCl_sat electrode.     

Electrochemical oxidation of carbon fibres in aqueous solutions and analysis of the surface oxides

Carbon fibres with notably different surface oxides can be prepared by varying the electrochemical oxidation conditions. Through correlation of voltammetric analysis and mass spectroscopy, interpretation of the reduction peaks of the surface oxides on the basis of their potential and width is possible. Narrow voltammetric reduction peaks at strongly negative potential are indicative of the predominance of –COOH type groups, while wide peaks at more positive potential are indicative of the presence of an excess of type groups. A quantitative determination of the surface acidic groups (–COOH and) is achieved by combination of Ag⁺ ion exchange and esterification of groups with 3,5-dinitrobenzoyl chloride. All results are confirmed by the independent method of –COOH group determination via their electrocatalytic behaviour in the reduction of azobenzene in methanol. The amounts of the –COOH and groups formed depend notably on the conditions of the electrochemical oxidation of the carbon fibres. The ratio between –COOH and groups coincides in all cases with that obtained by the mass spectrosopic data.     

Electrochemical oxidation of urea in aqueous solutions using a boron-doped thin-film diamond electrode

In the present paper, the electrocatalytic abatement of urea in aqueous solutions has been studied by means of cyclic voltammetry and galvanostatic electrolysis, using different anodes such as Pt, Ti–Ru oxide, boron-doped diamond (BDD) and antimony-doped tin oxide. HPLC analysis, total organic carbon (TOC) and ionic chromatography have been used to evaluate the oxidation and the mineralization of the treated aqueous solutions. The results of the cyclic voltammetries have shown that, in the case of Pt and Ti–Ru oxides a decrease in current density in the oxygen evolution region can be observed in the presence of urea, due to the blockage of the electrode active oxygen evolution sites as a consequence of the reversible adsorption of urea. Instead, a notable increase in the current density has been observed in the region of the oxygen evolution for the BDD and antimony-doped tin oxide electrodes, in the presence of urea, indicating that the oxidation of urea involves hydroxyl radicals.The bulk electrolysis tests have shown that the complete removal of urea and TOC can only be achieved using a boron-doped diamond and that Pt, the Ti–Ru oxide and antimony-doped tin oxide only permit a partial oxidation of urea. On the basis of the TOC evolution and the identification of the organic intermediates and inorganic ions released during the treatment, a total mineralization has been proposed. Finally, electrolysis has been performed in the presence of chloride ions, which act as oxidation mediator, and a comparison has been done between direct and mediated electro-oxidation.     

Flow behaviour of oil-in-water emulsions

The rheological behaviour of concentrated oil-in-water emulsions has been investigated using the Weissenberg Rheogoniometer. The oil concentration has been varied from 40 to 95 volume percent. The effects of shear rate and oil concentration on the viscosity have been determined. From the rheological data, the maximum attainable oil concentration in the emulsion has been estimated and is introduced as a parameter in the relationship between relative viscosity and oil concentration to account for certain variations in the emulsion characteristics. Empirical equations have been obtained which correlate zero shear rate viscosity and infinite shear viscosity as a function of reduced oil concentration. Comparison has been made between the emulsion viscosity and the solid-liquid suspension viscosity at high dispersed phase concentration. Estimated maximum attainable oil concentration is found to be in close agreement with the actual maximum concentration that could be achieved experimentally.     

Electrochemical oxidation of 1,3,5-trimethoxybenzene in aqueous solutions at gold oxide and lead dioxide electrodes

A kinetic study of the electrochemical oxidation of 1,3,5-trimethoxybenzene (TMB) by direct electron transfer at treated gold disk was combined with results of electrolysis in order to produce total degradation into CO₂ and H₂O at Ta/PbO₂ anode. The oxidation of TMB at gold electrode was studied by cyclic voltammetry. The cyclic voltammogram shows one irreversible anodic peak (I) corresponding to the oxidation of adsorbed TMB molecules. The proposed mechanism is based on the hypothesis of two-electron oxidation of TMB molecule leading, via intermediate of a radical cation, to the formation of the 2,4,6-trimethoxyphenol (TMP) and an adsorbed polymeric film. The TMP molecule undergoes a rapid oxidation leading to the formation of 2,6-dimethoxy-p-benzoquinone (DMBQ) as a major product. Degradation of TMB was studied by galvanostatic electrolysis using Ta/PbO₂ anode. The influence of initial TMB concentration and applied current density was investigated. Measurement of total organic carbon (TOC) and analysis by HPLC were used to follow this degradation. The experimental data indicated that the removal of TMB follows a pseudo first-order kinetic. The efficiency of the electrochemical process increases at lower current density and higher TMB initial concentration while it decreases with the TOC removal progress.     

Effect of droplet size on lipid oxidation rates of oil-in-water emulsions stabilized by protein

In emulsions lipid oxidation is mainly influenced by the properties of the interface. The aim of this work was to investigate the effects of droplet size and interfacial area on lipid oxidation in protein-stabilized emulsions. Emulsions, made of stripped sunflower oil (30% vol/vol) and stabilized by BSA were characterized by surface area values equal to 0.7, 5.1, and 16.3 m²·cm⁻³ oil. The kinetics of O₂ consumption and conjugated diene (CD) formation, performed on emulsions and nonemulsified controls, showed that emulsification prompted oxidation at an early stage. On condition that oxygen concentration was not limiting, the rates of O₂ consumption and CD formation were higher when the interfacial area was larger. Protein adsorbed at the interface probably restrained this pro-oxidant effect. Once most of the O₂ in the system was consumed (6–8 h), CD remained steady at a level depending directly on the ratio between oxidizable substrate and total amount of oxygen. At this stage of aging, the amounts of primary oxidation products were similar whatever the droplet size of the emulsion. Hexanal and pentane could be detected in the headspace of emulsions only at this stage. They were subsequently produced at rates not depending on oil droplet size and interfacial area.     

Catalytic oxidation of phenol in aqueous solutions

The objective of this work is to investigate catalyst systems for the oxidation of phenol in water in a batch autoclave. The main experimental variables are the type and the composition of the catalyst, the catalyst loading, temperature, oxygen partial pressure, initial phenol concentration and the stirrer speed. Commercial catalysts were used. Experimental work was conducted in two different laboratories. In one laboratory, the catalysts tested were 35% CuO+65% ZnO; 5–15% CuO+85–95% Al₂O₃; 26% CuO+74% Cu Chromite. In the other laboratory, the catalysts tested included 35% CuO+65% ZnO; 5–10% Ba₂CO₃+<5% C+30–40% CuO+60–70% ZnO; and 8–15% Al₂O₃+1–5% C+35–45% CuO+40–50% ZnO. With some of these catalysts depending on the operating conditions, complete phenol conversion could be obtained within 90 min. Under certain experimental conditions, the reaction underwent an induction period after which there was a transition to a much higher activity regime. The induction period may be due to an autocatalytic reaction system or to a very slow rate of formation of hydroquinone and catechol which then readily oxidize to o- and p-benzoquinone. An increase in the temperature and the oxygen partial pressure decreased the induction period, which increased as the catalyst to phenol ratio increased. 26% CuO+74% Cu Chromite and 8–15% Al₂O₃+1–5% C+35–45% CuO+40–50% ZnO were found to be the most active catalysts.     

Argan oil-in-water emulsions: Preparation and stabilization

We prepared stable oil-in-water emulsions of argan oil with two different types of mixtures of nonionic emulsifiers. Three different types of oil (Israeli argan oil, Moroccan argan oil, and soybean oil) were emulsified with mixtures of Span 80 and Tween 80. The optimum HLB value for argon oil was 11.0 (±1.0). The argan oil-in-water emulsions were stable for more than 5 mon at 25°C. Synergistic effects were found in enhancing stability of emulsions prepared with sucrose monostearate. The origin of the oil and the internal content of natural emulsifiers, such as monoglycerides and phospholipids, have a profound influence on its interfacial properties and on the stability of the argan oil-in-water emulsions.     

Electrochemical oxidation of acetaminophen in aqueous solutions: Kinetic evaluation of hydrolysis, hydroxylation and dimerization processes

Electrochemical oxidation of acetaminophen (paracetamol) has been studied in various pHs using cyclic voltammetry and controlled-potential coulometry. The results indicate that electrochemically generated N-acetyl-p-benzoquinone-imine (NAPQI) participates in different type reactions based on solution's pH. It is hydrolyzed in strong acidic media and hydroxylated in strong alkaline media and also, it is dimerized in intermediate pHs. Furthermore, in this work, a simple method for electrochemical synthesis of acetaminophen's dimer is described. In addition, in various pHs, based on related mechanism, the observed homogeneous rate constants (k_obs) of hydrolysis, hydroxylation and dimerization reactions were estimated by comparing the experimental cyclic voltammetric responses with the digital-simulated results. The most amounts of k_obs are calculated in pHs less than 2 and more than 9. In this study, the least observed homogeneous rate constant (k_obs) belongs to pHs 5.0 and 9.0.     

Inhibition of oxidation in 10% oil-in-water emulsions by β-carotene with α- and γ-tocopherols

The effects of low concentrations of β-carotene, α-, and γ-tocopherol were evaluated on autoxidation of 10% oil-in-water emulsions of rapeseed oil triacylglycerols. At concentrations of 0.45, 2, and 20 μg/g, β-carotene was a prooxidant, based on the formation of lipid hydroperoxides, hexanal, or 2-heptenal. In this emulsion, 1.5, 3, and 30 μg/g of γ-tocopherol, as well as 1.5 μg/g of α-tocopherol, acted as antioxidants and inhibited both the formation and decomposition of lipid hydroperoxides. Moreover, at a level of 1.5 μg/g, γ-tocopherol was more effective as an antioxidant than α-tocopherol. At levels of 0.5 μg/g, both α- and γ-tocopherol significantly inhibited the formation of hexanal but not the formation of lipid hydroperoxides. Oxidation was effectively retarded by combinations of 2 μg/g β-carotene and 1.5 μg/g γ- or α-tocopherol. The combination of β-carotene and α-tocopherol was significantly better in retarding oxidation than α-tocopherol alone. While γ-tocopherol was an effective antioxidant, a synergistic effect between β-carotene and γ-tocopherol could not be shown. The results indicate that there is a need to protect β-carotene from oxidative destruction by employing antioxidants, such as α- and γ-tocopherol, should β-carotene be used in fat emulsions.     

Electrochemical treatment of aqueous solutions containing urea

Investigations on the anodic decomposition of urea using Ti/Pt and Ti/(RuO₂–TiO₂)_40:60 electrodes were carried out. The kinetics of the process were examined in a periodic electrolyser. The effect of anodic current density, initial urea concentration, and sodium chloride concentration on the effectiveness of the basic process (average rate of urea decomposition, current efficiency, and unit power consumption) is discussed. When a Ti/Pt electrode is applied for urea removal from aqueous solution urea is not decomposed directly at the surface of the electrode, but rather in the bulk of the solution by hypochlorite formed during the process. When the Ti/(RuO₂–TiO₂)_40:60 electrode is used for the removal of urea from aqueous solutions, the reaction of urea with chlorine adsorbed at the electrode predominates. In both cases non-toxic products of urea decomposition (N₂, CO₂,) are formed. Comparison of the effectiveness of anodic decomposition of urea for the Ti/Pt and Ti/(RuO₂–TiO₂)_40:60 electrodes in the periodic electrolyser at optimum process parameters has revealed that the former electrode is more favorable.     

Electrochemical oxidation of 4-morpholinoaniline in aqueous solutions: Synthesis of a new trimer of 4-morpholinoaniline

Electrochemical oxidation of 4-morpholinoaniline has been studied in various pHs using cyclic voltammetry and controlled-potential coulometry. The electrochemical trimerization of 4-morpholinoaniline is described and its mechanism has been studied in aqueous solution. This method provides a green, reagent-less, and environmentally friendly procedure with high atom economy, for the synthesis of “4-morpholinoaniline-trimer” using a carbon electrode in an undivided cell in good yield and purity.     

Catalytic oxidation of organic compounds in aqueous media

Ru, Pt and Rh catalysts supported on titania, ceria or active carbon and a Mn/Ce composite oxide catalysts were prepared and their catalytic behavior in Wet Air Oxidation ( 20 bar O₂) of phenol and acetic acid were investigated. Phenol was found to be an easily oxidizable compound as 170°C, while acetic acid was a very refractory molecule, even at 200°C. Ru(5 wt.-%)/C is a very efficient catalyst for the WAO of acetic acid without any leaching of noble metal.     

Electrochemical degradation of polyfuran in wet acetonitrile and aqueous solutions

The degradation of polyfuran in a wet acetonitrile solution and in an aqueous solution has been investigated with a cyclic voltammetry technique, along with Fourier transform infrared and Fourier transform Raman spectroscopy techniques. Infrared spectroscopy shows that the main defects that exist in polyfuran after cycling in dried acetonitrile are mainly saturated C? H structures, whereas those after cycling in an aqueous solution are mainly carbonyl groups in the polymer chain. This may be because polyfuran can undergo degradation through a crosslinking mechanism in a dried acetonitrile solution, whereas in an aqueous solution, it undergoes degradation through a nucleophilic attack mechanism. Raman spectroscopy shows that not all the furan rings are involved in the degradation process, although the electrochemical activity of polyfuran is totally lost in an aqueous solution after only one cycle. The sites that are sensitive to the degradation process may be the electrochemically active sites, that is, the positively charged sites in polyfuran chains. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3160–3165, 2002     

Catalytic oxidation of sulphite in diluted aqueous solutions

The rate of reaction of dissolved oxygen and sulphite ions in diluted aqueous solutions, which has industrial importance in abatement of air pollution by sulphur dioxide, was investigated in homogeneous and in heterogeneous systems. Cobaltous sulphate was used as a catalyst.The rate of sulphite oxidation was found to be zero order with respect to oxygen and three-halves order with respect to sulphite. The influence of the catalyst concentration was found to follow a square root dependence. The reaction rate constant increased with pH. The heterogeneous conditions resulted in a reaction rate that was about one order of magnitude lower than that under homogeneous conditions. This difference indicates an induction period of the sulphite oxidation.     

Solubilization in aqueous mixed micellar solutions: Water-potassium oleate-1-pentanol-benzene

Spectral parameters of the UV absorption and emission spectrum of benzene dissolved in aqueous solutions of potassium oleate and 1-pentanol were measured. By comparing these parameters with those for solutions of benzene in hydrocarbon solvents, it was concluded that the major portion of the benzene solubilized in the mixed micelles was in a relatively nonpolar environment. These results agree with previous studies of benzene dissolved in sodium lauryl sulfate solutions. Estimations of the energy of transfer of benzene from water to the mixed micelle also support this conclusion.     

The oxidation of aqueous sodium sulphite solutions

In this paper new experimental work on the kinetics of the absorption of oxygen in an aqueous solution of sodium sulphite with cobaltous sulphate as a catalyst, has been presented and compared with already published data. It is shown that the reaction of oxygen with sodium sulphite is zero order in sulphite, first order in cobalt and second order in oxygen for 2 × 10⁴ N/m² <p_O2 < 10⁵ N/m², 150°C <T < 60°C, 3 × 10^?6 kmol/m³ <c_Co⁺⁺ < 3 × 10^?3 kmol/m 7.50 < pH < 8.50 and 0.4 kmol/m² <c_SO2-- < 0.8 kmol/m³. The reaction rate constant can be varied by more than two decades by changing the cobalt concentration, pH and temperature.The specific interfacial areas, a, and mass transfer coefficients, k_L, measured by DeWaal and Beek [14, 15] using an incorrect kinetic model of this reaction, are reinterpreted with the results of the present kinetic investigation. It is shown that their values of a and k_L are a factor 2.2 too low and too high, respectively, but that their values of k_La are correct.     

Electrochemical removal of gallic acid from aqueous solutions

Removal of gallic acid from aqueous solutions of different concentrations has been performed by electroprecipitation using a sacrificial iron anode, by indirect electrochemical oxidation carried out via electro- and photoelectro-Fenton processes using an oxygen-diffusion cathode, and by a combination of the first two methods (peroxicoagulation process). In all cases, chromatographic analyses have shown a very quick disappearance of gallic acid and its aromatic by-products within 30-90 min of electrolysis, depending on the method. A pseudo first-order kinetic decay of gallic acid was always observed under galvanostatic conditions. A decay of TOC and COD close to 90 and 95% is observed with electroprecipitation and peroxicoagulation processes, respectively, after electrolysis time lower than 2 h. The specific charge utilised in these two processes was about half of that theoretically required for the complete direct oxidation process (mineralisation). During electrolyses some carboxylic acids have been detected as main intermediates, which completely disappear at the end of the process, except oxalic acid in the case of electro-Fenton method.