On-line mass spectrometry of the electro-oxidation of methanol in acidic media on tungsten carbide

The electro-oxidation of methanol at supported tungsten carbide (WC) nanoparticles in sulfuric acid solution was studied using cyclic voltammetry, potentiostatic measurements, and differential electrochemical mass spectroscopy (DEMS). The catalyst was prepared by a sonochemical method and characterized by X-ray diffraction. Over the WC catalyst, the oxidation of methanol (1 M in a sulfuric acid electrolyte) begins at a potential below 0.5 V/RHE during the anodic sweep. During potentiostatic measurements, a maximum current of 0.8 mA mg(-1) was obtained at 0.4 V. Measurements of DEMS showed that the methanol oxidation reaction over tungsten carbide produces CO2 (m/z=44); no methylformate (m/z=60) was detected. These results are discussed in the context of the continued search for alternative materials for the anode catalyst of direct methanol fuel cells.

Chromotropic acid-formaldehyde reaction in strongly acidic media. The role of dissolved oxygen and replacement of concentrated sulphuric acid

The procedure for formaldehyde analysis recommended by the National Institute for Occupational Safety and Health (NIOSH) is the Chromotropic acid spectrophotometric method, which is the one that uses concentrated sulphuric acid. In the present study the oxidation step associated with the aforementioned method for formaldehyde determination was investigated. Experimental evidence has been obtained indicating that when concentrated H2SO4 (18 mol l(-1)) is used (as in the NIOSH procedure) that acid is the oxidizing agent. on the other hand, oxidation through dissolved oxygen takes place when concentrated H2SO4 is replaced by concentrated hydrochloric (12 mol l(-1)) and phosphoric (14.7 mol l(-1)) acids as well as by diluted H2SO4 (9.4 mol l(-1)). Based on investigations concerning the oxidation step, a modified procedure was devised, in which the use of the potentially hazardous and corrosive concentrated H2SO4 was eliminated and advantageously replaced by a less harmful mixture of HCl and H2O2. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Aniline-1,4-benzoquinone as a model system for the characterization of products from aniline oligomerization in low acidic media

Increase in the pH medium of aniline polymerization is used for giving products of different morphologies, which are often wrongly attributed to PANI chains. Infrared and Raman spectroscopic data, supported by quantum chemical calculations, show that aniline-1,4-benzoquinone (AnBzq) is a model system for the characterization of the products of aniline oligomerization in low acidic media. The Raman spectra excited at different laser lines reveal the bichromophoric nature of AnBzq, whose absorption bands at 550 nm and 440 nm can be attributed to pi-pi* transitions of the delocalized benzoquinone and amino-phenyl moieties, respectively. (C) 2012 Elsevier B.V. All rights reserved.

The influence of the Pt crystalline surface orientation on the glycerol electro-oxidation in acidic media

We investigated the electrochemical oxidation of glycerol on low-index Pt single crystals in acidic media (H2SO4 and HClO4) by cyclic voltammetry and Fourier Transform Infrared (FTIR) spectroscopy and we verified that this is a surface sensitive reaction. Pt(100) and Pt(110) surface structures favor the breaking of the C-C-C bond at low potentials (say 0.05 V), as seen by the formation of CO, one of the adsorbed residues of the glycerol dissociation, which poisons these surfaces even at high potentials. Pt(111) surface structure does not favor the C-C-C bond breaking at potentials as low as 0.05 V. However, Pt(111) is less poisoned by residues of glycerol dissociation and, for this reason, it is more active for glycerol oxidation than Pt(100) and Pt(110) at low potentials. Carbonyl containing compounds and CO2 were detected as reaction products of the glycerol oxidation on all investigated single-crystal Pt surfaces. The ratio between CO2 and carbonyl containing compounds is clearly much higher for Pt(100) and Pt(110) than for Pt(111). (C) 2012 Elsevier Ltd. All rights reserved.

OSCILLATORY DYNAMICS IN SYSTEMS CONTAINING BROMATE AND 1,4-CYCLOHEXANEDIONE IN ACIDIC MEDIA. I. THE EFFECT OF TEMPERATURE.

OSCILLATORY DYNAMICS IN SYSTEMS CONTAINING BROMATE AND 1,4-CYCLOHEXANEDIONE IN ACIDIC MEDIA. I. THE EFFECT OF TEMPERATURE. We present in this work the influence of temperature on the dynamics of homogeneous chemical systems containing bromate and 1,4-cyclohexanedione (1,4-CHD) in acidic media. In particular, the following systems were studied: bromate/1,4-CHD/acid, bromate/1,4-CHD/ferroin/acid and bromate/1,4-CHD/trisbipyridine ruthenium/acid. Investigations were carried out by means of an electrochemical probe, at five temperatures between 5 and 45 degrees C. Activation energies (E-a) were estimated in different ways for the pre-oscillatory and oscillatory regimes. In any case, the E-a was found to depend on the catalyst, composition and initial concentrations. In addition, it was observed that ferroin and trisbipyridine ruthenium act as catalysts only during the transition between the induction period and oscillatory regime.

Electrochemical features of Pt(S)[n(110) × (100)] surfaces in acidic media

Experiments have been carried out in sulfuric and perchloric acid solutions on Pt(S)[n(110) × (100)] electrodes. The comparison between the two different electrolytic media reveals an important influence of the anion in the voltammetric features. Total charge curves have been obtained with the CO charge displacement method in combination with voltammetric measurements. From these curves, the dependence of the pztc with the step density and the strength of the anion adsorption have been analyzed. The problem of the so-called third peak is treated for a series of electrodes that contain (110) terraces, revealing the requirement of (110) domains for occurrence of this adsorption state.

Natural Arabidopsis brx loss-of-function alleles confer root adaptation to acidic soil.

Soil acidification is a major agricultural problem that negatively affects crop yield. Root systems counteract detrimental passive proton influx from acidic soil through increased proton pumping into the apoplast, which is presumably also required for cell elongation and stimulated by auxin. Here, we found an unexpected impact of extracellular pH on auxin activity and cell proliferation rate in the root meristem of two Arabidopsis mutants with impaired auxin perception, axr3 and brx. Surprisingly, neutral to slightly alkaline media rescued their severely reduced root (meristem) growth by stimulating auxin signaling, independent of auxin uptake. The finding that proton pumps are hyperactive in brx roots could explain this phenomenon and is consistent with more robust growth and increased fitness of brx mutants on overly acidic media or soil. Interestingly, the original brx allele was isolated from a natural stock center accession collected from acidic soil. Our discovery of a novel brx allele in accessions recently collected from another acidic sampling site demonstrates the existence of independently maintained brx loss-of-function alleles in nature and supports the notion that they are advantageous in acidic soil pH conditions, a finding that might be exploited for crop breeding.

Platinum–rhodium–tin/carbon electrocatalysts for ethanol oxidation in acid media: effect of the precursor addition order and the amount of tin

Carbon-supported Pt x –Rh y –Sn z catalysts (x:y:z = 3:1:4, 6:2:4, 9:3:4) are prepared by Pt, Rh, and Sn precursors reduction in different addition order. The materials are characterized by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy techniques and are evaluated for the electrooxidation of ethanol in acidic media by cyclic voltammetry, chronoamperometry, and anode potentiostatic polarization. The influence of both the order in which the precursors are added and the composition of metals in the catalysts on the electrocatalytic activity and physico-chemical characteristics of Pt x –Rh y –Sn z /C catalysts is evaluated. Oxidized Rh species prevail on the surface of catalysts synthesized by simultaneous co-precipitation, thus demonstrating the influence of synthesis method on the oxidation state of catalysts. Furthermore, high amounts of Sn in composites synthesized by co-precipitation result in very active catalysts at low potentials (bifunctional effect), while medium Sn load is needed for sequentially deposited catalysts when the electronic effect is most important (high potentials), since more exposed Pt and Rh sites are needed on the catalyst surface to alcohol oxidation. The Pt3–Rh1–Sn4/C catalyst prepared by co-precipitation is the most active at potentials lower than 0.55 V (related to bifunctional effect), while the Pt6–Rh2–Sn4/C catalyst, prepared by sequential precipitation (first Rh and, after drying, Pt + Sn), is the most active above 0.55 V.

Um novo método para quantificar mercúrio orgânico (Hg orgânico) empregando a espectrometria de fluorescência atômica do vapor frio

In this work a simple and sensitive procedure to extract organic mercury from water and sediment samples, using methylene chloride in acidic media followed by CVAFS quantification has been developed. The method was evaluated for possible interferents, using different inorganic mercury species and humic acid, no effects being observed. The detection limit for organic mercury was 160 pg and 396 pg for water and sediment samples respectively. The accuracy of the method was evaluated using a certified reference material of methylmercury (BCR-580, estuarine sediment). Recovery tests using methylmercury as surrogate spiked with 1.0 up to 30.0 ng L-1 ranged from 90 up to 109% for water samples, whereas for sediments, recoveries ranged from 57 up to 97%.

Co-eletrodeposição oscilatória de cobre e estanho

It is investigated in the present contribution the oscillatory co-electrodeposition of CuSn on a polycrystalline gold surface in the presence of Triton X-100 surfactant and citric acid as additive, in acidic media. The experiments were conducted under potentiostatic control and the system dynamics characterized in terms of the morphology and stability of the current oscillations. Besides modulations in the frequency and amplitude of the current oscillations, several patterned states were observed, including relaxation-like and mixed mode oscillations. The oscillations were found to be very robust and some time series presented regular motions up to about two hours.

Direct evidence of singlet molecular oxygen generation from peroxynitrate, a decomposition product of peroxynitrite

The decomposition of peroxynitrite to nitrite and dioxygen at neutral pH follows complex kinetics, compared to its isomerization to nitrate at low pH. Decomposition may involve radicals or proceed by way of the classical peracid decomposition mechanism. Peroxynitrite (ONOOH/ONOO(-)) decomposition has been proposed to involve formation of peroxynitrate (O(2)NOOH/O(2)NOO(-)) at neutral pH (D. Gupta, B. Harish, R. Kissner and W. H. Koppenol, Dalton Trans., 2009, DOI: 10.1039/b905535e, see accompanying paper in this issue). Peroxynitrate is unstable and decomposes to nitrite and dioxygen. This study aimed to investigate whether O(2)NOO(-) formed upon ONOOH/ONOO(-) decomposition generates singlet molecular oxygen [O(2) ((1)Delta(g))]. As unequivocally revealed by the measurement of monomol light emission in the near infrared region at 1270 nm and by chemical trapping experiments, the decomposition of ONOO(-) or O(2)NOOH at neutral to alkaline pH generates O(2) ((1)Delta(g)) at a yield of ca. 1% and 2-10%, respectively. Characteristic light emission, corresponding to O(2) ((1)Delta(g)) monomolecular decay was observed for ONOO(-) and for O(2)NOOH prepared by reaction of H(2)O(2) with NO(2)BF(4) and of H(2)O(2) with NO(2)(-) in HClO(4). The generation of O(2) ((1)Delta(g)) from ONOO(-) increased in a concentration-dependent manner in the range of 0.1-2.5 mM and was dependent on pH, giving a sigmoid pro. le with an apparent pK(a) around pD 8.1 (pH 7.7). Taken together, our results clearly identify the generation of O(2) ((1)Delta(g)) from peroxynitrate [O(2)NOO(-) -> NO(2)(-) + O(2) ((1)Delta(g))] generated from peroxynitrite and also from the reactions of H(2)O(2) with either NO(2)BF(4) or NO(2)(-) in acidic media.

FIA potentiometric system based on periodate polymeric membrane sensors for the assessment of ascorbic acid in commercial drinks

Ascorbic acid is found in many food samples. Its clinical and technological importance demands an easyto- use, rapid, robust and inexpensive method of analysis. For this purpose, this work proposes a new flow procedure based on the oxidation of ascorbic acid by periodate. A new potentiometric periodate sensor was constructed to monitor this reaction. The selective membranes were of PVC with porphyrin-based sensing systems and a lipophilic cation as additive. The sensor displayed a near-Nernstian response for periodate over 1.0x10-2–6.0x10-6 M, with an anionic slope of 73.9 ± 0.9 mV decade-1. It was pH independent in acidic media and presented good selectivity features towards several inorganic anions. The flow set-up operated in double-channel, carrying a 5.0x10-4 M IO- 4 solution and a suitable buffer; these were mixed in a 50-cm reaction coil. The overall flow rate was 7 ml min-1 and the injection volume 70 µl. Under these conditions, a linear behaviour against concentration was observed for 17.7–194.0 µg ml-1, presenting slopes of 0.169 mV (mg/l)-1, a reproducibility of ±1.1 mV (n = 5), and a sampling rate of ~96 samples h-1. The proposed method was applied to the analysis of beverages and pharmaceuticals.

Artifacts in the analysis of thioridazine and other neuroleptics.

Although the sensitivity to light of thioridazine and its metabolites has been described, the problem does not seem to be widely acknowledged. Indeed, a survey of the literature shows that assays of these compounds under light-protected conditions have been performed only in a few of the numerous analytical studies on this drug. In the present study, thioridazine, its metabolites, and 18 other neuroleptics were tested for their sensitivity to light under conditions used for their analysis. The results show that light significantly affects the analysis of thioridazine and its metabolites. It readily causes the racemization of the isomeric pairs of thioridazine 5-sulphoxide and greatly decreases the concentration of thioridazine. This sensitivity to light varied with the medium used (most sensitive in acidic media) and also with the molecule (in order of decreasing sensitivity: thioridazine > mesoridazine > sulforidazine). Degradation in neutral or basic media was slow, with the exception of mesoridazine in a neutral medium. Twelve other phenothiazines tested, as well as chlorprotixene, a thioxanthene drug, were found to be sensitive to light in acidic media, whereas flupenthixol and zuclopenthixol (two thioxanthenes), clozapine, fluperlapine, and haloperidol (a butyrophenone) did not seem to be affected. In addition to being sensitive to light, some compounds may be readily oxidized by peroxide-containing solvents.

Photocatalytic oxidation of humic substances and lignins in aqueous solutions

Tässä tutkimuksessa tarkastellaan kahden yleisen, veden ympäristökuormitusta aiheuttavan kemikaaliryhmän, ligniinin ja humusaineiden, fotokatalyyttistahapetusta (photocatalytic oxidation, PCO) vesiliuoksessa. Fotokatalyyttina käytettiin titaanidioksidia, jota säteilytettiin ultraviolettivalolla. Työssä selvitettiin useiden eri olosuhdeparametrien vaikutusta fotokatalyysiin. Tutkittavia parametreja olivat mm. kontaminanttien alkukonsentraatio, pH, vetyperoksidilisäys, rauta-ionien lisäys, fotokatalyysimenetelmä, fotokatalyytin pintakonsentraatioja titaanidioksidin määrä lasisissa mikropartikkeleissa. Ultraviolettivalon lähteinä käytettiin sekä keinovaloa että auringonvaloa. Katalyytin kantoaineena käytettiin huokoisia lasisia mikropartikkeleita, joiden pintaan kiinnittynyt titaanidioksidi pystyi hyvin vähentämään kontaminanttien määrää vedessä. Fotokatalyysin tehokkuus kasvoi humusaine- ja ligniinikonsentraatioiden kasvaessa. Korkeimmat hapetustehokkuudet kumallakin kontaminantilla saavutettiin neutraaleissa jalievästi emäksisissä olosuhteissa huolimatta siitä, että paras adsorboituminen tapahtui happamissa olosuhteissa. Tämän perusteella voidaan olettaa, että humusaineiden ja ligniinin hapetus tapahtuu pääosin radikaalimekanismilla. Vetyperoksidin lisääminen humusaineliuokseen lisäsi hapettumisnopeutta, vaikka näennäinen hapetustehokkuus ei muuttunut. Tämän perusteella vetyperoksidi hapetti myös humusaineita referenssinäytteessä. Ligniinin fotokatalyyttinen hapettuminen parani vetyperoksidilisäyksellä happamissa olosuhteissa johtuen lisääntyneestä OH-radikaalien muodostumisesta. Ligniini ei hapettunut vetyperoksidilla, jos fotokatalyyttiä ei¿ollut läsnä. Rauta-ionit eivät lisänneet humushappojen fotokatalyyttistähapettumista, mutta Fe2+-ionien lisäys aina konsentraatioon 0.05 mM johti ligniinin hapettumistehokkuuden voimakkaaseen kasvuun. Rauta-ionikonsentraation kasvattaminen edelleen johti ligniinin hapetustehokkuuden alenemiseen.