The dual role of Zn-acid medium for one-step rapid synthesis of M@rGO (M = Au, Pt, Pd and Ag) hybrid nanostructures at room temperature

We report a new protocol for the synthesis of M@rGO (M = Au, Pt, Pd, Ag and rGO = reduced graphene oxide) hybrid nanostructures at room temperature in Zn-acid medium. The roles of Zn-acid are to reduce the GO by generated hydrogen and the deposition of metal nanoparticles on rGO by galvanic replacement reaction between Zn and Mn+.

Extraction kinetics of cerium(IV) from sulfuric acid medium by the primary amine N1923 using a constant interfacial area cell with laminar flow

BACKGROUND: Thermodynamic studies on Ce(IV) extraction with primary amine N1923 demonstrate that primary amine N1923 is an excellent extractant for separation of Ce(IV) from Re(III). In order to clarify the mechanism of extraction and to optimize the parameters in practical extraction systems used in the rare earth industry, the extraction kinetics was investigated using a constant interfacial area cell with laminar flow in the present work.RESULTS: The data indicate that the rate constant (k(ao).) becomes constant when stirring speed exceeds 250 rpm. The apparent forward extraction rate is calculated to be 10(-1.70). The activation energy (E.) was calculated to be 20.5 kJ/mol from the slope of log kao against 1000/T. The minimum bulk concentration of the extractant necessary to saturate the interface (C-min) is lower than 10(-5) mol L-1.CONCLUSION: Studies of interfacial tension and the effects of stirring rate and specific interfacial area on the extraction rate show that the extraction rate is kinetically controlled, and a mass transfer model has been proposed. The rate equation has been obtained as: -d[Ce(IV)]/dt = 10(-1.70)[Ce(IV)] [(RNH3)(2)SO4](1.376). The rate-controlling step has been evaluated from analysis of the experimental results.

Sol-gel thin-film immobilized soybean peroxidase biosensor for the amperometric determination of hydrogen peroxide in acid medium

An acid-stable soybean-peroxidase biosensor was devel oped by immobilizing the enzyme in a sol-gel thin film. Methylene blue was used as a mediator because of its high electron-transfer efficiency. The sol-gel thin film and enzyme membrane were characterized by FT-IR, and the effects of pH, operating potential, and temperature were explored for optimum analytical performance by using the amperometric method. The H2O2 sensor exhibited a fast response (5 s), high sensitivity (27.5 mu A/mM), as well as good thermostability and long-term stability. In addition, the performance of the biosensor was investigated using flow-injection analysis (FIA).

Spectrophotometric determination of formaldehyde with chromotropic acid in phosphoric acid medium assisted by microwave oven

In the present study. a spectrophotometric method for the determination of formaldehyde by using chromotropic acid was devised. in which the use of potentially hazardous and corrosive concentrated sulfuric acid was eliminated and advantageously C replaced by a mixture of H, concentrated H3PO4 and H2O2. The reaction between formaldehyde and chromotropic acid (CA) in a cone phosphoric acid medium was accelerate by irradiating the mixture with microwave energy for 35 s (1100 W), producing a violetred compound (lambda(max)=570 nm). Beer's Law is obeyed in a concentration range of 0.8-4.8 mg 1(-1) of formaldehyde with a good correlation coefficient (r = 0.9968). The proposed method was applied in the analysis of formaldehyde in commercial disinfectants. Recoveries were within 98.0-100.4%, with standard deviations ranging from 0.03 to 0.13%. (C) 2003 Elsevier B.V All rights reserved.

Electrochemical kinetic study of surface layer growth on natural pyrite in acid medium

This paper presents electrochemical experiments on natural pyrite that combine potentiostatic and voltammetric techniques. X-ray microanalysis is used as an auxiliary technique. The layer growth on pyrite surface is conducted in a wide range of pH and potential range: 3.4 <= pH <= 5.9 with E = 0.80 V (versus SHE), and 0.80 V <= E <= 1.00 V with pH 4.5 (versus SHE) in acetic acid-acetate buffer. This work is unique for two reasons: (1) phenomenological model about layer growth is applied and mathematical-physic consistence is verified and (2) Meyer's hypotheses of chemical mechanism are used to explain kinetic parameters of the phenomenological model. (c) 2005 Elsevier B.V. All rights reserved.

Electrochemical and In Situ FTIR Study of o-Cresol on Platinum Electrode in Acid Medium

The electrochemical behaviour of o-cresol in acidic medium on platinum electrode has been studied by cyclic voltammetry and in situ Fourier transform infrared spectroscopy. The o-cresol suffers hydrolysis during oxidation giving rise to the formation of methyl-p-benzoquinone. In situ FTIR spectroscopic studies also reveal the presence of CO2, formed as a consequence of the rupture of the aromatic ring. Moreover, the oxidation of o-cresol in acidic medium produces a polymeric film on the platinum surface that precludes further oxidation of o-cresol. The reduction of o-cresol at potentials below 0 V produces in the first step the partial reduction of the aromatic ring and when the potential goes to values below 0 V, methyl-cyclohexanone.

Extraction kinetics of Sc(III), Y(III), La(III) and Gd(III) from chloride medium by Cyanex 302 in heptane using the constant interfacial cell with laminar flow

The extraction kinetics of Sc, Y, La and Gd(III) from the hydrochloric acid medium using Cyanex 302 (hereafter HL) in heptane solution have been measured by the constant interfacial cell with laminar flow. Reaction regions are explored at liquid-liquid interface. Extraction regimes are deduced to be diffusion-controlled for Sc(Ill) and mixed controlled for Y, La and Gd(Ill). Extraction mechanisms are discussed according to the dimeric model of Cyanex 302 in non-polar solution. From the temperature dependence of rate measurement, the values of E-a, Delta H-+/-, Delta S-+/- and Delta G(300)(+/-) are calculated and it is found that the absolute values of these parameters keep crescent trend for Sc, Y, La and Gd(III). At the same time, it is found that it can easily achieve the mutual separation among the Sc, Y and La(III) with kinetics extraction methods.

Extraction and stripping of ytterbium (III) from H2SO4 medium by Cyanex 923

The extraction and stripping of ytterbium (III) from sulfuric acid medium using Cyanex 923 in heptane solution was investigated. The effects of extractant concentration, pH and sulfate ion as well as stripping agents, acidity and temperature on the extraction and stripping were studied. The equilibrium constants and thermodynamic parameters, such as Delta H (10.76 kJ(.)mol(-1)), Delta G (-79.26 kJ(.)mol(-1)) and Delta S (292.41 J(.)K(-1.)mol(-1)), were calculated. The extraction mechanism and the complex species extracted were determined by slope analysis and FrIR spectra. Furthermore, it was found that the extraction of Yb (III) from sulfuric acid medium by Cyanex 923 increased with pH, concentration of SO42-, HSO4-, and extractant concentration, and approximately a quantitative extraction of Yb (III) was achieved at an equilibrium pH near 3.0, and the extracted complex was YbSO4(HSO4)(.)2Cyanex923((o)).

Rare earth separation with 1-hexyl-4-ethyloctyl isopropylphosphonic acid extractant

A new extractant 1-hexyl-4-ethyloctyl isopropylphosphonic acid (HHEOIPP or HA) in heptane was employed to extract rare earths from hydrochloric acid medium. The dependence of extraction distribution ratio on equilibrium aqueous pH and the concentration of extractant were investigated. On the basis of slope analysis,it was proposed that two different kinds of extracted species were formed. For rare earth elements (La similar to Ho) the extracted species was LnA(3)(HA)(3) and for heavy rare earth elements (Er similar to Lu) the species was LnClA(2)(HA)(3). The steric hindrance plays an important role in forming the species. The extraction constants and separation factors of the adjacent rare earths were calculated too. Compared with HDEHP and HEH/EHP, HHEOIPP is a valuable extractant with high separation selectivity. The "tetrad effect" between K-ex and atomic number was observed.

Investigating the formation and the properties of monoalkyl carbonates in aqueous medium using capillary electrophoresis with capacitively coupled contactless conductivity detection

Although alkyl carbonic acids (ACAs) and their salts are referred to as instable species in aqueous medium, we demonstrate that a monoalkyl carbonate (MAC) can in fact be easily formed from bicarbonate and an alcohol even in the presence of a high amount of water. A CE system with two capacitively coupled contactless conductivity detectors (C(4)Ds) was used to obtain different parameters about these species and their reactions. Based on the mobilities obtained for a series of alcohols ranging from 1 to 5 carbons, the coefficients of diffusion and the hydrodynamic radii were calculated. When compared with the equivalent carboxylates, MACs have radii systematically smaller. Although the precise pK(a) values of the ACAs could not be obtained, because of the fast decomposition in acid medium, it was possible, for the first time, to show that they are below 4.0. This result suggests that the acidity of an ACA is quite similar to the first hydrogen of H(2)CO(3). Using a new approach to indirectly calibrate the C(4)D, the kinetic constants and the equilibrium constants of formation were also obtained. The results suggest that the increase in the chain length makes the MACs less stable and more inert.

Flow-injection spectrophotometric determination of novalgin in phrmaceuticals using micellar medium

A sensitive flow-injection (FI) procedure with spectrophotometric detection in a micellar medium is proposed for the determination of novalgin. The method is based on the instantaneous formation of a red-orange product (lambda(max) = 510 nm) after the reaction between novalgin and p-dimethylaminocinnamaldehyde (p-DAC) in a dilute acid medium. The sensitivity of this reaction was increased by a factor of 5.6 in the presence of sodium dodecyl sulfate (SDS). Experimental design methodologies were used to optimize the chemical and FI variables. The calibration curve was linear in the range of 1.45 x 10(-6) to 2.90 x 10(-5) mol L-1 with an excellent correlation coefficient (r = 0.9999). The detection limit was 1.31 x 10(-7) mol L-1 (n = 20, RSD = 2.0%). No interferences were observed from the common excipients. The results obtained by the proposed method were favorably compared with those given by the iodometric reference method at 95% confidence level.

Spectrophotometric determination of dipyrone in pharmaceutical preparations by using chromotropic acid

A spectrophotometric method for the determination of dipyrone in pharmaceutical preparations is proposed. This method is based on selective oxidation of dipyrone, in the presence of sulphuric acid, splitting off formaldehyde which reacts with chromotropic acid, also in a sulphuric acid medium, producing a violet-red compound (lambda(max) 575 nm). Beer's law is obeyed in a concentration range of 0.57-5.7 ppm dipyrone with an excellent correlation coefficient (r = 0.9997). The results show a simple, accurate, selective and readily applied method to the determination of dipyrone in pharmaceutical products. The analytical results obtained for these products by the proposed method are in agreement with those of the Brazilian Pharmacopoeia procedure. No interference was observed from common excipients in formulations. Recoveries were within 98.7-101.2%, with standard deviations ranging from 0.2 to 1.7%. (C) 1999 Elsevier B.V. S.A. All rights reserved.

Thermal denaturation and aggregation of hemoglobin of Glossoscolex paulistus in acid and neutral media

The thermal denaturation and aggregation of the HbGp, in the oxy- and cyanomet-forms, was investigated by DSC, AUC, DLS, optical absorption and CD, in the pH range from 5.0 to 7.0. Oxy-HbGp has a denaturation process partially reversible and dependent on the temperature. DSC melting curve is characterized by a single peak with Tc value of 333.4±0.2K for oxy-HbGp, while two peaks with Tc values of 332.2±0.1 and 338.4±0.2K are observed for cyanomet-HbGp, at pH 7.0. In acidic pH oxy- and cyanomet-HbGp are more stable showing higher Tc values and aggregation. AUC data show that, HbGp, at pH 7.0, upon denaturation, remains undissociated at 323K, presenting oligomeric dissociation at 333 (12±3% of tetramer and 88±5% of whole HbGp) and 343K (70±5% of monomer and 30±2% of trimer). DLS data show that the lag period before aggregation is dependent on the temperature and HbGp concentration. Optical absorption and CD results show that the increase of temperature leads to the oxy-HbGp oxidation and aggregation, above 331K, in acidic pH. CD data, for HbGp, present a greater thermal stability in acid medium than at neutral pH, with similar Tc values for both oxidation forms. Our data are consistent with previous studies and represents an advance in understanding the thermal stability of oligomeric HbGp structure. © 2012 Elsevier B.V.

The influence of different co-catalysts in Pt-based ternary and quaternary electro-catalysts on the electro-oxidation of methanol and ethanol in acid media

One of the key objectives in fuel cell technology is to reduce Pt loading by the improvement of its catalytic activity towards alcohol oxidation. Here, a sol-gel based method was used to prepare ternary and quaternary carbon supported nanoparticles by combining Pt-Ru with Mo, Ta, Pb, Rh or Ir, which were used as electro-catalysts for the methanol and ethanol oxidation reactions in acid medium. Structural characterization performed by XRD measurements revealed that crystalline structures with crystallites ranging from 2.8 to 4.1 nm in size and with different alloy degrees were produced. Tantalum and lead deposited as a heterogeneous mixture of oxides with different valences resulting in materials with complex structures. The catalysts activities were evaluated by cyclic voltammetry and by Tafel plots and the results showed that the activity towards methanol oxidation was highly dependent of the alloy degree, while for ethanol the presence of a metal capable to promote the break of C-C bond, such as Rh, was necessary for a good performance. Additionally, the catalysts containing of TaOx or PbOx resulted in the best materials due to different effects: the hi-functional mechanism promoted by TaOx and a better dispersion of the catalysts constituents promoted by PbOx. (C) 2012 Elsevier B.V. All rights reserved.