Platinum particles supported on titanium nitride: an efficient electrode material for the oxidation of methanol in alkaline media

In the present study, titanium nitride which shows exceptional stability, extreme corrosion resistance, good electronic conductivity and adhesion behaviour is used to support platinum particles and then used for methanol oxidation in an alkaline medium. The catalyst shows very good CO tolerance for the electrochemical oxidation of methanol. In situ infrared spectroelectrochemical data show the remarkable ability of TiN to decompose water at low over potentials leading to -OH type functional groups on its surface which in turn help in alleviating the carbon monoxide poisoning associated with methanol oxidation. TiN supported catalysts are found to be very good in terms of long term stability, exchange current density and stable currents at low over voltages. Supporting evidence from X-ray photoelectron spectroscopic data and cyclic voltammetry clearly demonstrates the usefulness of TiN supported Pt catalysts for efficient methanol oxidation in alkaline media.

Thermodynamic properties of strontium titanates Sr2TiO4, Sr3Ti2O7, Sr4Ti3O10, and SrTiO3

The chemical potentials of SrO in two-phase fields (TiO2 + SrTiO3) (SrTiO3 + Sr4Ti3O10) (Sr4Ti3O10 + Sr3Ti2O7) and (Sr3Ti2O7 + Sr2TiO4) of the pseudo-binary system (SrO + TiO2) have been measured in the temperature range (900 to 1250) K relative to pure SrO as the reference state using solid-state galvanic cells incorporating single crystal SrF2 as the electrolyte The cells were operated under pure oxygen at ambient pressure The standard Gibbs free energies of formation of strontium titanates SrTiO3 Sr4Ti3O10 Sr3Ti2O7 and Sr2TiO4 from their component binary oxides were derived from the reversible electromotive force (EMF) of the cells For the formation of the four compounds from their component oxides TiO2 with rutile structure and SrO the standard Gibbs free energy changes are given by Delta G((ox))(SrTiO3) +/- 89/(J mol(-1)) = -121878 + 3 881(T/K) Delta G((ox))(Sr4Ti3O10) +/- 284/(J mol(-1)) = -409197 + 14 749(T/K) Delta G((ox))(Sr3Ti2O7) +/- 190/(J mol(-1)) = -285827 + 10 022(T/K) Delta G((ox))(Sr2TiO4) +/- 110/(J mol(-1))= -159385 + 3 770(T/K) The reference state for solid TiO2 is the rutile form The results of this study are in good agreement with Gibbs free energy of formation data reported in the literature for SrTiO3 but differ significantly with data for Sr4Ti3O10 For Si3Ti2O7 and Si2TiO4 experimental measurements are not available in the literature for direct comparison with the results obtained in this study (C) 2010 Elsevier Ltd All rights reserved

Phase relationships in the system Ni-W-O and thermodynamic properties of NiWO,

The phase diagram of the Ni-W-O system at 1200 K was established by metallographic and X-ray identification of the phases present after equilibration at controlled oxygen potentials. The oxygen partial pressures over the samples were fixed by metered streams of CO+CO2 gas mixtures. There was only one ternary oxide, nickel tungstate (NiWO4), in the Ni-W-O system at a total pressure of 1 atm, and this compound decomposed to a mixture of Ni+WO2.72 on lowering the oxygen potential. The Gibbs' free energy of formation of NiWO4 was determined from the measurement of the e.m.f. of the solid oxide galvanic cell, Pt, Ni+NiWO4+WO2.72/CaO-ZrO2/Ni+NiO, Pt and thermodynamic properties of tungsten and nickel oxides available in the literature. For the reaction, NiO(s)+WO3(s)rarrNiWO4(s) DeltaG°=–10500–0.708 T (±250) cal mol–1.

From ‘Afflicted’ to Activists: Structural Violence and Climate Change Discourse in the States of Pernambuco and Paraíba in Northeast Brazil

This study approaches the problem of poverty in the hinterlands of Northeast Brazil through the concept of structural violence, linking the environmental threats posed by climate change, especially those related to droughts, to the broader social struggles in the region. When discussions about potentials and rights are incorporated into the problematic of poverty, a deeper insight is obtained regarding the various factors behind the phenomenon. It is generally believed that climate change is affecting the already marginalized and poor more than those of higher social standing, and will increasingly do so in the future. The data for this study was collected during a three month field work in the states of Pernambuco and Paraíba in Northeast Brazil. The main methods used were semi-structured interviews and participant observation, including attending seminars concerning climate change on the field. The focus of the work is to compare both layman and expert perceptions on what climate change is about, and question the assumptions about its effects in the future, mainly that of increased numbers of ‘climate refugees’ or people forced to migrate due to changes in climate. The focus on droughts, as opposed to other manifestations of climate change, arises from the fact that droughts are not only phenomena that develop over a longer time span than floods or hurricanes, but is also due to the historical persistence of droughts in the region, and both the institutional and cultural linkages that have evolved around it. The instances of structural violence that are highlighted in this study; the drought industry, land use, and the social and power relations present in the region, including those between the civil society, the state and the private agribusiness sector, all work against a backdrop of symbolic and moral realms of value production, where relations between the different actors are being negotiated anew with the rise of the climate change discourse. The main theoretical framework of the study consists of Johan Galtung’s and Paul Farmer’s theory of structural violence, Ulrich Beck’s theory of the risk society, and James Scott’s theory of everyday peasant resistance.

A molecular dynamics study of a PbO.SiO2 glass and melt

The structures of a PbO.SiO2 glass and melt have been studied using molecular dynamics simulation employing Born-Mayer-Huggins pair potentials. Various pair distribution functions are presented and discussed. Pb-Pb correlations persist in the melt, in agreement with experimental observations. The calculated and experimental radial distribution functions are compared.

Time-Dependent Dynamics of a Planar Galaxy Model

Time-dependent models of collisionless stellar systems with harmonic potentials allowing for an essentially exact analytic description have recently been described. These include oscillating spheres and spheroids. This paper extends the analysis to time-dependent elliptic discs. Although restricted to two space dimensions, the systems are richer in that their parameters form a 10-dimensional phase space (in contrast to six for the earlier models). Apart from total energy and angular momentum, two additional conserved quantities emerge naturally. These can be chosen as the areas of extremal sections of the ellipsoidal region of phase space occupied by the system (their product gives the conserved volume). The present paper describes the construction of these models. An application to a tidal encounter is given which allows one to go beyond the impulse approximation and demonstrates the effects of rotation of the perturbed system on energy and angular-momentum transfer. The angular-momentum transfer is shown to scale inversely as the cube of the encounter velocity for an initial configuration of the perturbed galaxy with zero quadrupole moment.

Solid State Electrochemical Sensors in Process Control

The basic principles of operation of gas sensors based on solid-state galvanic cells are described. The polarisation of the electrodes can be minimised by the use of point electrodes made of the solid electrolyte, the use of a reference system with chemical potential close to that of the sample system and the use of graded condensed phase reference electrodes. Factors affecting the speed of response of galvanic sensors in equilibrium and non-equilibrium gas mixtures are considered with reference to products of combustion of fossil fuels. An expression for the emf of non-isothermal galvanic sensors and the criterion for the design of temperature compensated reference electrodes for non-isothermal galvanic sensors are briefly outlined. Non-isothermal sensors are useful for the continuous monitoring of concentrations or chemical potentials in reactive systems at high temperatures. Sensors for oxygen, carbon, and alloying elements (Zn and Si) in liquid metals and alloys are discussed. The use of auxiliary electrodes permits the detection of chemical species in the gas phase which are not mobile in the solid electrolyte. Finally, the cause of common errors in galvanic measurements, and tests for correct functioning of galvanic sensors are given. 60 ref.--AA

Hopping and non-hopping localized ionic motion: β-AgI and β-Ag3SI

In β-AgI and β-Ag3SI the ionic conductivity has been measured at frequencies from 1kHz to 2.6 GHz and from 10 MHz to 10 THz, respectively. In both phases we observe a conductivity increase of some orders of magnitude, due to localized types of motion of the silver ions. In β-AgI the increase is found at about 1 MHz and reflects cooperative back-and-forth hopping processes between adjacent tetrahedral sites. In β-Ag3SI the phenomenon occurs at microwave frequencies. Here it is caused by a non-hopping, non-periodic localized Ag+-motion within shallow potentials.

Chemical potential of oxygen for iron-rutile-ilmenite and iron-ilmenite-ulvospinel equilibria

The chemical potential of oxygen corresponding to the iron-rutile-ilmenite (IRI) and iron-ilmenite-ulvospinel (IIU) equilibria has been measured employing solid-state galvanic cells,$$Pt, Fe + TiO_2 + FeTiO_3 //(Y_2 O_3 ) ZrO_2 //Fe + FeO, Pt$$ and $${\text{Pt, Fe + FeTiO}}_{\text{3}} {\text{ + Fe}}_{\text{2}} {\text{TiO}}_{\text{4}} {\text{//(Y}}_{\text{2}} {\text{0}}_{\text{3}} {\text{) ZrO}}_{\text{2}} {\text{//Fe + FeO, Pt}}$$ in the temperature range of 875 to 1275 K and 900 to 1373 K, respectively. The cells are written such that the right-hand electrodes are positive. The electromotive force (emf) of both the cells was found to be reversible and to vary linearly with temperature over the entire range of measurement. The chemical potential of oxygen for IRI equilibrium is represented by Δμo2(IRI) = -550,724 - 29.445T + 20.374T InT(±210) J mol−1 (875 <-T<- 1184 K) = -620,260 + 369.593T - 27.716T lnT(±210) J mol−1 (1184 <-T<- 1275 K) and that for IIU equilibrium by Δμo2(IIU) = -501,800 - 49.035T + 20.374T lnT(±210) J mol−1 (900 <-T<- 1184 K) = -571,336 + 350.003T− 27.716T lnT(=−210) J mol-1 (1184 <-T<- 1373 K) The standard Gibbs energy changes for IRI and IIU equilibria have been deduced from the measured oxygen potentials. Since ilmenite contains small amounts of Ti³+ ions, a correction for the activity of FeTiO3 has been incorporated by assuming ideal mixing on each cation sublattice in the FeTiO3-Ti2O3 system. Similarly, the ulvospinel contains some Fe³+ ions and a correction for the activity of Fe2TiO4 has been included by modeling the Fe2TiO4-Fe3O4 system. The third-law analysis of the results obtained for IRI equilibrium gives ΔH 298 0 = -575 (±1.0) kJ mol-1 and for IIU equilibrium yields ΔH 298 0 = -523.7 (±0.7) kJ mol−1}. The present results suggest that Fe2+ and Ti4+ cations mix almost ideally on the octahedral site of spinel lattice in Fe2TiO4, giving rise to a configurational contribution of 2R In 2 (11.5256 J mol-1 K-1) to the entropy of Fe2TiO4.

Dynamics of charge transfer in the excited amine complexes of the fullerenes C60 and C70.: A picosecond laser flash photolysis study

In benzene solution, C60 and C70 interact weakly in the ground state with amines having favourable oxidation potentials. Picosecond time-resolved absorption measurements show that on photoexcilation, the weak complexes undergo charge separation to produce ion pairs which in turn undergo fast geminate recombination either to produce the triplet state of the fullerenes or give back the ground slate of the complex, depending on the oxidation potential of the amine. Free-ion yield is generally negligible.

Electrobioleaching of base metal sulfides

Bioleaching of base metal sulfides, such as pyrite, chalcopyrite, and sphalerite, under the influence of applied direct current (DC) potentials is discussed. Contributions toward mineral dissolution from three effects, namely, galvanic, applied potential, and microbiological, are analyzed and compared. Sphalerite could be selectively bioleached in the presence of Thiobacillus ferrooxidans under an applied potential of -500 mV (SCE) from mixed sulfides containing sphalerite, pyrite, and chalcopyrite. Bacterial activity and growth were found to be promoted under electrobioleaching conditions. Probable mechanisms involved in the bioleaching of different sulfides under positive and negative applied potentials are discussed.

The roles of nitrification and nitrate reduction pathways in nitrogen cycling of Baltic Sea

The Baltic Sea is one of the largest brackish water bodies in the world. Primary production in the Baltic Sea is limited by nitrogen (N) availability with the exception of river outlets and the northernmost phosphorus limited basin. The excess human induced N load from the drainage basin has caused severe eutrophication of the sea. The excess N loads can be mitigated by microbe mediated natural N removal processes that are found in the oxic-anoxic interfaces in sediments and water column redoxclines. Such interfaces allow the close coupling between the oxic nitrification process, and anoxic denitrification and anaerobic ammonium oxidation (anammox) processes that lead to the formation of molecular nitrogen gas. These processes are governed by various environmental parameters. The effects of these parameters on N processes were investigated in the northern Baltic Sea sediments. During summer months when the sediment organic content is at its highest, nitrification and denitrification reach their maximum rates. However, nitrification had no excess potential, which was probably because of high competition for molecular oxygen (O2) between heterotrophic and nitrification microbes. Subsequently, the limited nitrate (NO3-) availability inhibited denitrification. In fall, winter and spring, nitrification was limited by ammonium availability and denitrification limited by the availability of organic carbon and occasionally by NO3-. Anaerobic ammonium oxidation (anammox) was not an important N removal process in the northern Baltic Sea. Modeling studies suggest that when hypoxia expands in the Baltic Sea, N removal intensifies. However, the results of this study suggest the opposite because bottom water hypoxia (O2< 2 ml l-1) decreased the denitrification rates in sediments. Moreover, N was recycled by the dissimilatory nitrate reduction to ammonium (DNRA) process instead of being removed from the water ecosystem. High N removal potentials were found in the anoxic water column in the deep basins of the Baltic Proper. However, the N removal in the water column appeared to be limited by low substrate availability, because the water at the depths at which the substrate producing nitrification process occurred, rarely mix with the water at the depths at which N removal processes were found. Overall, the natural N removal capacity of the northern Baltic Sea decreased compared to values measured in mid 1990s and early 2000. The reason for this appears to be increasing hypoxia.

Neurocognitive processing of inflected and derived words

The representation of morphologically complex words in the mental lexicon and their neurocognitive processing has been a vigorously debated topic in psycholinguistics and the cognitive neuroscience of language. This thesis investigates the effect of stimulus modality on morphological processing, the spatiotemporal dynamics of the neural processing of inflected (e.g., work+ed ) and derived (e.g., work+er ) words and their interaction, using the Finnish language. Overall, the results suggest that the constituent morphemes of isolated written and spoken inflected words are accessed separately, whereas spoken derived words activate both their full form and the constituent morphemes. The processing of both spoken and written inflected words elicited larger N400 responses than monomorphemic words (Study I), whereas the responses to spoken derived words did not differ from those to monomorphemic words (Study IV). Spoken inflected words elicited a larger left-lateralized negativity and greater source strengths in the left temporal cortices than derived words (Study IV). Thus, the results suggest different cortical processing for derived and inflected words. Moreover, the neural mechanisms underlying inflection and derivation seem to be not only different, but also independent as indexed by the linear summation of the responses to derived and inflected stimuli in a combined (derivation+inflection) condition (Study III). Furthermore, the processing of meaningless, spoken derived pseudowords was more difficult than for existing derived words, indexed by a larger N400-type effect for the pseudowords. However, no differences were observed between meaningful derived pseudowords and existing derived words (Study II). The results of Study II suggest that semantic compatibility between morphemes seems to have a crucial role in a successful morphological analysis. As a methodological note, time-locking the auditory event-related potentials/fields (ERP/ERF) to the suffix onset revealed the processes related to morphological analysis more precisely (Studies II and IV), which also enables comparison of the neural processes in different modalities (Study I).

Matched thermochemical diagram for vacuum decarburization of ferroalloys

The carbon content of high carbon ferroalloy melts can be reduced by a vacuum treatment. Carbon and oxygen dissolved in the melt react to form CO. Although this process has been suggested in the literature, no comprehensive analysis of the equilibrium partial pressure of CO over an alloy melt with a given carbon and oxygen content has been reported. In this paper, a new type of matched thermochemical diagram is introduced, from which the feasibility of decarburization at reduced CO pressure and the minimum achievable carbon level can be graphically evaluated for any alloy composition and temperature. Carbon and oxygen potentials of different alloys are plotted as functions of temperature on two terminal diagrams. By projecting information from these plots onto a central diagram, containing data on the Gibbs' energy of mixing for the C-O system, equilibrium partial pressures of CO and CO2 are obtained. Nomograms on the central diagram give a direct indication of the equilibrium partial pressures at any given temperature. The carbon and oxygen activities in ferrochromium alloys have been assessed and the results are presented to illustrate the construction and use of the matched thermochemical diagrams.

Synthesis, structure and redox properties of (?-oxo)bis(?-carboxylato)diruthenium(III) complexes containing three different terminal ligands

Blue coloured, unstable, essentially diamagnetic and non-electrolytic diruthenium(III) complexes of the formation [Ru2O(O2CR)4(en)2(PPh3)2] were prepared by reacting [Ru2O(O2CR)4(PPh3)2] with 1,2-diaminoethane (en) in CH2Cl2 (R = C6H4-p-X; X = H, Me and OMe). The molecular structure of the complexes is proposed as [{(?1-O2CR)(?1-en)(PPH3)Ru}2(?-O)(?-O2CR)2] based on the 1H NMR spectral data. The electronic spectra of the complexes display a band near 569 nm with a shoulder at 630 nm. In CH2Cl2-0.1 M [Bun4N]ClO4, the complexes exhibit redox couples Ru2III,III/Ru2III,IV and Ru2III,IV/Ru2IV,IV near 0.1 and 1.2 V (vs SCE), respectively. The potentials are the lowest among diruthenium(III) complexes with a similar core structure.