Etude cinétique de la complexation du cuivre en milieu hydrogénocarbonate par électrochimie

La détermination de la capacité complexante des eaux naturelles est généralement effectuée par titrage ampérométrique du cuivre à pH fixé. Beaucoup, sinon tous les tampons classiques utilisés perturbent les études de spéciation du cuivre par formation de complexes peu stables. Dans ce travail nous nous sommes intéressés à la complexation du cuivre par les ions carbonates généralement présents dans les eaux naturelles. Afin de mener à bien notre étude, nous avons mesuré, dans un milieu synthétique de force ionique et pH contrôlés (KNO3 0,02 M + NaHCO3 2,38.10-3 M) toutes les constantes des divers équilibres prévisibles : produits de solubilité de l'hydroxyde de cuivre Cu(OH)2 et de la malachite Cu2 (OH)2 CO3, constante de formation du carbonate de cuivre dissous CuCO3. A des valeurs de pH suffisamment faibles, la formation du complexe CUOH+ peut étre négligée. Les trois autres réactions ont été suivies race aux mesures combinées, d'une part du pH et, d'autre part, de l'activité en ion Cu2+ libre ou hydraté par ionométrie. Compte tenu des propriétés acido-basiques des diverses espèces, les mesures ont été effectuées à divers pH compris entre 5,5 et 8. Le complexe CuCO30étant l'espèce majoritaire dans ces solutions, sa labilité, pouvant perturber follement les déterminations des capacités complexantes par titrage ampérométrique, a été étudiée par diverses méthodes électrochimiques. La polarographie à tension sinusoïdale surimposée (AC) a indiqué une réduction rapide du cuivre (II) sur électrode de mercure. Deux vagues ont été obtenues en voltampérométrie sur électrode tournante à disque de platine (RDE), ce dédoublement étant d'origine cinétique compte tenu de l'évolution de ces vagues avec la température. Une estimation des valeurs des constantes de vitesse de formation kf et de dissociation kb, a permis de montrer la rapidité des réactions mises en jeu et la labilité du complexe CuCO30.The determination of the complexing capacity of natural waters by amperometric copper (II) titrations must be made in pH-buffered solutions. Most if not all of classical buffers influence copper speciation through the formation of weak complexes. This paper deals with an attempt to use the naturally occurring hydrogenocarbonate buffet. A detailed study of copper (II) chemistry in synthetic solutions at controlled ionic strength and pH (0.02 mol.l-1 KNO3, 2.38 mol.l-1 NaHCO3, controlled Pco2) was carried out. In these solutions copper (Il) chemistry may involve precipitation of copper hydroxide Cu(OH)2, copper hydroxycarbonate Cu2(OH)2 CO3 (malachite) and formation of the soluble complexes CuCO30 and CuOH+. At low enough values of pH CuOH+ formation may be neglected. The three other reactions are studied using copper ionometry with a specific electrode and equilibrium constants determined in the 5.5 to 8.0 pH range. As CuCO30 is a major species in these solutions its lability is of major concern for the validity of the amperometric determination of the complexing capacity by copper (II) titration and bas been studied by several electrochemical approaches. AC polarography indicated a rapid reduction of copper (II) on the mercury electrode. Two waves were obtained for the deposition of copper (Il) by voltamperometry with a rotated platinum disk electrode (RDE) presenting the characteristics of a kinetic control. However the values of the forward (kf) and backward (kb) reaction rate constants for CuCO30 formation or dissociation seem too high for a precise determination

Mise au point de techniques analytiques pour la spéciation du sélénium dans les boues de stations d'épuration d'eaux résiduaires urbaines

Les stations d'épuration d'eaux résiduaires sont une des étapes du cycle du sélénium dans l'environnement et contribuent à sa redistribution dans le milieu naturel. Très peu étudié jusqu'à présent dans ces milieux, le sélénium n'en est pas moins un élément très important du point de vue écotoxicologique, sa teneur dans les boues de stations d'épuration destinées à l'épandage agricole faisant par ailleurs l'objet d'une norme.Nous avons mis au point des techniques permettant la détermination spécifique de l'élément total dans ce type d'échantillon, par minéralisation classique ou assistée par micro-ondes et dosage par Voltamétrie de Redissolution Cathodique Différentielle Pulsée (DPCSV) et Spectrométrie d'Absorption Atomique ElectroThermique (ETAAS). Le contrôle qualité a été effectué sur deux échantillons certifiés fournis par le Bureau Communautaire de Référence (BCR) : la boue CRM 145 R et la boue CRM 007.Cependant, lorsqu'on parle de risque toxicologique, il est important de s'intéresser à la détermination des différentes formes sous lesquelles cet élément peut être présent. Nous avons pour cela réalisé des extractions parallèles (spéciation de phases) du sélénium contenu dans les boues afin de déterminer quel pourcentage du sélénium total est réellement et potentiellement disponible pour les végétaux lors d'un épandage sur sol agricole. La spéciation d'espèces a été brièvement abordée dans le but de déterminer les teneurs en Se(IV) et Se(VI), espèces les plus toxiques.The great effort undertaken for about twenty years to improve the quality of surface waters has led to the construction of numerous waste water treatment plants, generating an increasing amount of sludge. Waste water and sludge treatment processes represent an important point in the hydrological cycle at which the disposal of substantial quantities of trace elements to the environment may be regulated. From the law on waste recovery and disposal in 1975 to the European guideline about wastes in 1991, the priority has been given to waste recovery and recycling. With increasing pressure to ban all sludge dumping at sea, and considering the prohibitive costs of land-filling and incineration, there is a great tendency to dispose of sludge on land (40% in 1988 to 60% in 1992).Although numerous studies have demonstrated the intrinsic value of sludge for soil amendment, given its nitrogen, phosphorus and homogeneous organic matter content, evidence has accumulated in recent years that numerous environmental problems can arise because of the presence in sludges of high amounts of certain trace elements (potentially toxic to plants and to human beings and liable to be concentrated along the food chain), among which selenium is particularly interesting.Selenium presents a complex case, as it is also an essential element for living organisms (including humans). The amendment with sewage sludge is sometimes used to increase the selenium content in crops, and afterwards in cattle, when there is a proven lack of this element in a given place. Nevertheless the boundary between essentiality and toxicity is relatively narrow and is expressed at trace levels. It is thus particularly important to survey the selenium concentrations encountered in sewage sludge, especially as guidelines and regulations concerning these data will probably be strengthened. Presently, in France, sludge must not contain more than 200 mg Se·kg-1 dry weight and must not be used on soils containing more than 10 mg Se·kg-1 dry weight (AFNOR U 44-041 norm). This norm concerns only the total amount of selenium contained in sludge and does not take into account the different species (organic and inorganic Se(-II), Se(0), Se(IV) and Se(VI)) that could be present.First of all we had to develop methods for the classical and microwave-assisted wet digestion of sewage sludge, and the determination of their total selenium concentration by Differential Pulse Cathodic Stripping Voltammetry (DPCSV) and ElectroThermal Atomic Absorption Spectrometry (ETAAS). Quality assurance involved the analysis of two BCR (Community Bureau of Reference) certified sewage sludge reference materials (CRM 145 R and CRM 007) and the different techniques were then applied to natural samples from a representative French sewage treatment plant located in the city of Tarbes (South-West of France). The mixture HNO3-H2O2-H2O led to the best results for the digestion and analysis of certified samples, caused few problems for the analysis by DPCSV and ETAAS, and was therefore retained. The decrease of the digestion duration obtained by the use of microwaves was particularly interesting (from one to three days on a hot plate to less than one hour by the Microdigest 301 (PROLABO, France)), and reproducibility was also acceptable (between 3 and 10%). Concentrations obtained for the sewage sludge from the Tarbes treatment plant were very much lower than those for NF U 44-041: 1.08±0.11 mg Se·kg-1 dry weight.However knowledge of speciation, that is to say the determination of the different physicochemical forms of selenium present in a given medium, is necessary when speaking of the toxicological risk represented by an element. The mobility of selenium and its toxicity to the biosphere are related to its association with various sludge or soil constituents as well as to its total concentration. "Soft" or partial extraction techniques are necessary when the aim of the study to determine trace element speciation. The extractants used must separate selenium from the matrix without inducing any loss or change in the partitioning of individual chemical species. In parallel extractions the mechanisms involved for each extractant must correspond to processes occurring in nature and are then associated with special fractions of selenium: soluble, exchangeable, "oxidizable", and "mineral" fractions .Parallel extractions with three types of extractants were chosen for this study and applied first to CRM 007: warm water (soluble fraction), ammonium phosphate-citric acid (soluble + exchangeable fraction) and sodium hydroxide (soluble + exchangeable + "oxidizable" fraction). The soluble, exchangeable, "oxidizable" and "mineral" fractions represent respectively : 11%, 14%, 39% and 36%. The same procedure was then applied to natural samples from Tarbes giving the following results: 36% soluble, 22% exchangeable, 42% "oxidizable". The sodium hydroxide extraction procedure allowed us to extract the entire Se content of this sludge (1.07±0.03 mg Se·kg-1 dry weight), showing that all the selenium present is potentially available after agricultural land application. It was then possible in this fraction to deal with the species speciation of selenium by the mean of a separation of inorganic and organic species on an Amberlite CG-400 resin and a specific analysis by DPCSV. Se(IV) and Se(VI) represent respectively between 30 and 40% and between 2 and 20% of total selenium in the sludges from Tarbes

Two-dimensional solitons on the surface of magnetic fluids

We report an observation of a stable soliton-like structure on the surface of a ferrofluid, generated by a local perturbation in the hysteretic regime of the Rosensweig instability. Unlike other pattern-forming systems with localized 2D structures, magnetic fluids are characterized by energy conservation; hence their mechanism of soliton stabilization is different from the previously discussed gain/loss balance mechanism. The radioscopic measurements of the soliton's surface profile suggest that locking on the underlying periodic structure is instrumental in its stabilization.Comment: accepted for publication by Physical Review Letter

Two and three-dimensional oscillons in nonlinear Faraday resonance

We study 2D and 3D localised oscillating patterns in a simple model system exhibiting nonlinear Faraday resonance. The corresponding amplitude equation is shown to have exact soliton solutions which are found to be always unstable in 3D. On the contrary, the 2D solitons are shown to be stable in a certain parameter range; hence the damping and parametric driving are capable of suppressing the nonlinear blowup and dispersive decay of solitons in two dimensions. The negative feedback loop occurs via the enslaving of the soliton's phase, coupled to the driver, to its amplitude and width.Comment: 4 pages; 1 figur

Is the Unitarity of the quark-mixing-CKM-matrix violated in neutron β\beta-decay?

We report on a new measurement of neutron $\beta$-decay asymmetry. From the result \linebreak $A_0$ = -0.1189(7), we derive the ratio of the axial vector to the vector coupling constant $\lambda$ = ${\it g_A/g_V}$ = -1.2739(19). When included in the world average for the neutron lifetime $\tau$ = 885.7(7)s, this gives the first element of the Cabibbo-Kobayashi-Maskawa (CKM) matrix $V_{ud}$. With this value and the Particle Data Group values for $V_{us}$ and $V_{ub}$, we find a deviation from the unitarity condition for the first row of the CKM matrix of $\Delta$ = 0.0083(28), which is 3.0 times the stated error

Practical computational toolkits for dendrimers and dendrons structure design

Dendrimers and dendrons offer an excellent platform for developing novel drug delivery systems and medicines. The rational design and further development of these repetitively branched systems are restricted by difficulties in scalable synthesis and structural determination, which can be overcome by judicious use of molecular modelling and molecular simulations. A major difficulty to utilise in silico studies to design dendrimers lies in the laborious generation of their structures. Current modelling tools utilise automated assembly of simpler dendrimers or the inefficient manual assembly of monomer precursors to generate more complicated dendrimer structures. Herein we describe two novel graphical user interface (GUI) toolkits written in Python that provide an improved degree of automation for rapid assembly of dendrimers and generation of their 2D and 3D structures. Our first toolkit uses the RDkit library, SMILES nomenclature of monomers and SMARTS reaction nomenclature to generate SMILES and mol files of dendrimers without 3D coordinates. These files are used for simple graphical representations and storing their structures in databases. The second toolkit assembles complex topology dendrimers from monomers to construct 3D dendrimer structures to be used as starting points for simulation using existing and widely available software and force fields. Both tools were validated for ease-of-use to prototype dendrimer structure and the second toolkit was especially relevant for dendrimers of high complexity and size.Peer reviewe

Cymantrene–Triazole "Click" Products: Structural Characterization and Electrochemical Properties

We report the first known examples of triazole-derivatized cymantrene complexes (η5-[4-substituted triazol-1-yl]cyclopentadienyl)tricarbonylmanganese(I), obtained via a “click” chemical synthesis, bearing a phenyl, 3-aminophenyl, or 4-aminophenyl moiety at the 4-position of the triazole ring. Structural characterization data using multinuclear NMR, UV–vis, ATR-IR, and mass spectrometric methods are provided, as well as crystallographic data for (η5-[4-phenyltriazol-1-yl]cyclopentadienyl)tricarbonylmanganese(I) and (η5-[4-(3-aminophenyl)triazol-1-yl]cyclopentadienyl)tricarbonylmanganese(I). Cyclic voltammetric characterization of the redox behavior of each of the three cymantrene–triazole complexes is presented together with digital simulations, in situ infrared spectroelectrochemistry, and DFT calculations to extract the associated kinetic and thermodynamic parameters. The trypanocidal activity of each cymantrene–triazole complex is also examined, and these complexes are found to be more active than cymantrene alone

Towards functional safety in automotive electronics

International audienceThe part of electronics in automobile design becomes more and more important with an exponential growth during the last 10 years. Nowadays, innovation in automotive industry is driven by electronics. New upcoming electrical/electronic systems (E/E systems) such as advanced driver assistance systems or x-by-wire systems as well as consumer expectation regarding safety will require a dedicated standard to ensure design, development and production of safe products before their introduction on the market.ISO/TC22/SC3/WG16 has been formed to issue the ISO26262 international standard that will specifically address functional safety of E/E systems of automotive industry.This paper provides information about the future ISO26262 which is based on the current results of ISO/TC22/SC3/WG16 [1], those still being subject to changes before the international standard release

Wave patterns generated by an axisymmetric obstacle in a two-layer flow

Gravity waves generated by a moving obstacle in a two-layer stratified fluid are investigated. The experimental configuration is three-dimensional with an axisymmetric obstacle which is towed in one of the two layers. The experimental method used in the present study is based on a stereoscopic technique allowing the 3D reconstruction of the interface between the two layers. Investigation into the wave pattern as a function of the Froude number, Fr, based on the relative density of the fluid layers and the velocity of the towed obstacle is presented. Specific attention is paid to the transcritical regime for which Fr is close to one. Potential energy trapped in the wave field patterns is also extracted from the experimental results and is analyzed as a function of both the Froude number, Fr, and the transcritical similarity parameter Γ. In particular, a remarkable increase in the potential energy around Fr = 1 is observed and a scaling allowing to assemble data resulting from different experimental parameters is proposed

Rhythmic modification in child directed speech

Interval-based rhythm metrics were applied to the speech of English,Catalan and Spanish mothers addressing their children (aged 2, 4 and 6 years) and compared with their speech when addressing other adults. Results show that when mothers speak to their children, their speech is more vocalic (higher %V) and more even-timed (lower variability in vocalic and consonantal interval duration). Little differentiation is made when addressing children of different ages for the window of development investigated here. These results indicate a greater ‘syllable-timed’ quality to child-directed-speech, irrespective of the presumed rhythmic category of the language in question. Characteristic cross-linguistic rhythmic differences observed in adult-directed-speech are, in the main, preserved, although more weakly, suggesting that while modifications in child-directed speech largely occur within the bounds of a presumed rhythmic category, such categories may, in fact, overlap