High temperature stability of oxysulfides containing Ce3+ and Y3+ ions

Standard Gibbs energies of formation of oxysulfides of cerium and yttrium from their respective oxedes were determined using solid oxide galvanic cells incorporating calcia-stabilized zirconia as the electrolyte in the temperature range 870���1120 K. The sulfur potential over the electrode containing the oxide and oxysulfide was fixed by a buffer mixture of Ag + Ag2S. A small amount of CaH2 was added to the buffer to generate an equilibrium ratio of H2S and H2 species in a closed system containing the buffer and the electrode. The sulfur potential is transmitted to the electrode via the gas phase. The results can be summarized by the equations 2left angle bracketCeO2right-pointing angle bracket+1/2(S2)���left angle bracketCe2O2Sright-pointing angle bracket+(O2) ��G��=430600���109��7T(��400)J mol���1 left angle bracketY2O3right-pointing angle bracket+1/2(S2)���left angle bracketY2O2Sright-pointing angle bracket+1/2(O2) ��G��=114780���1��45T(��200)J mol���1 The values are compared with data reported in the literature. The stability field diagram for the Ce---O---S system has been developed using the results of this study for Ce2O2S and data for other phases from the literature.

Electron energy loss spectroscopy (EELS) of H2O, H2S, H2Se and H2Te

Electronic excitation in H2O, H2S, H2Se and H2Te molecules has been studied by the EELS technique. Spectra of H2S and H2Se are remarkably similar with the 1b1-nd transition most intense. The intensity of the first transition 1b1-nsa1 decreases through H2O to H2Se and this transition is absent in H2Te. Transitions observed by EELS have been compared with optical absorption studies. A correlation diagram of the occupied and the excited states has been provided for these four molecules by making use of UVPES and EELS.

Hydroxylation of oxygen-covered Cu(110) and Zn(0001) surfaces by interaction with CH3OH, (CH3)2NH, H2S, HCl and other proton donor molecules

EELS studies provide definitive evidence for the hydroxylation of oxygen-covered Cu(110) and Zn(0001) surfaces on interaction with proton donor molecules such as H2O, CH3OH, HCOOH, NH3 and (CH3)2NH. The occurrence of surface hydroxylation is unambigouusly shown by a study of the interaction of H2S and HCl with an oxygen covered Cu(110) surface.

Immediate and residual effects of heat stress and restricted intake on milk protein and casein composition and energy metabolism

The effects of heat stress on dairy production can be separated into 2 distinct causes: those effects that are mediated by the reduced voluntary feed intake associated with heat stress, and the direct physiological and metabolic effects of heat stress. To distinguish between these, and identify their effect on milk protein and casein concentration, mid-lactation Holstein-Friesian cows (n = 24) were housed in temperature-controlled chambers and either subjected to heat stress HS; temperature-humidity index (THI) ~78 or kept in a THI < 70 environment and pair-fed with heat-stressed cows (TN-R) for 7 d. A control group of cows was kept in a THI < 70 environment with ad libitum feeding (TN-AL). A subsequent recovery period (7 d), with THI < 70 and ad libitum feeding followed. Intake accounted for only part of the effects of heat stress. Heat stress reduced the milk protein concentration, casein number, and casein concentration and increased the urea concentration in milk beyond the effects of restriction of intake. Under HS, the proportion in total casein of ��S1-casein increased and the proportion of ��S2-casein decreased. Because no effect of HS on milk fat or lactose concentration was found, these effects appeared to be the result of specific downregulation of mammary protein synthesis, and not a general reduction in mammary activity. No residual effects were found of HS or TN-R on milk production or composition after THI < 70 and ad libitum intake were restored. Heat-stressed cows had elevated blood concentrations of urea and Ca, compared with TN-R and TN-AL. Cows in TN-R had higher serum nonesterified fatty acid concentrations than cows in HS. It was proposed that HS and TN-R cows may mobilize different tissues as endogenous sources of energy.

Some studies on a solid state sulphur probe for coal gasification system

Measurements on the solid electrolyte cell(Ar -b H2 ~ H2S/CaS + CaF2 ~- ( P t ) / / C a F 2 / / ( P t )-~- CaF2 ~ CaS/H2S ~- H2 ~- At) show that the emf of the cell is directly related through the Nernst equation to the difference in sulfur potentials established at the two Ar ~- H2 ~ H2S/electrode interfaces. The electrodes are designed to convert the sulfur potential gradient across the calcium fluoride electrolyte into an equivalent fluorine potential gradient with the aid of the reaction, CaF2(s) ~ 1~ S2(g)-e CaS(s) ~- F2(g). The response time of the probe varies from approximately 9 hr at 990~ to 2.5 hr at 1225~ The conversion of calcium sulfide and/or calcium fluoride into calcium oxide should not be a problem in anticipated commercial coal gasification systems. Suggestions are presented for improving the cell for such commercial applications.

Corrosion of 310 stainless steel in H2 H2O-H2S gas mixtures; studies at constant temperature and fixed oxygen potential

Corrosion of SAE 310 stainless steel in H2-H2O-H2S gas mixtures was studied at a constant temperature of 1150 K. Reactive gas mixtures were chosen to yield a constant oxygen potential of approximately 6 �� 10-13 Nm-2 and sulfur potentials ranging from 0.19 �� 10-2 Nm-2 to 33 �� 10-2 Nm-2. The kinetics of corrosion were determined using a thermobalance, and the scales were analyzed using metallography, scanning electron microscopy, and energy dispersive X-ray analysis. Two corrosion regimes, which were dependent on sulfur potential, were identified. At high sulfur potentials (P S 2 �� 2.7 �� 10-2 Nm-2) the corrosion rates were high, the kinetics obeyed a linear rate equation, and the scales consisted mainly of sulfide phases similar to those observed from pure sulfidation. At low sulfur potentials (P S 2 �� 0.19 �� 10-2 Nm-2) the corrosion rates were low, the kinetics obeyed a parabolic rate equation, and scales consisted mainly of oxide phases. Thermochemical diagrams for the Fe-Cr-S-O, Fe-Ni-S-O, Cr-Ni-S-O, and Si-Cr-S-O systems were constructed, and the experimental results are discussed in relation to these diagrams. Based on this comparison, reasonable corrosion mechanisms were developed. At high sulfur potentials, oxide and sulfide phases initially nucleate as separate islands. Overgrowth of the oxide by the sulfide occurs and an exchange reaction governs the corrosion process. Preoxidation at low oxygen potentials and 1150 K is beneficial in suppressing sulfidation at high sulfur potentials.

Microwave, infrared-microwave double resonance, and theoretical studies of C2H4 center dot center dot center dot H2S complex

In this manuscript, rotational spectra of four new isotopologues of the S-H center dot center dot center dot pi bonded C2H4 center dot center dot center dot H2S complex, i.e., C2D4 center dot center dot center dot H2S, C2D4 center dot center dot center dot D2S, C2D4 center dot center dot center dot HDS, and (CCH4)-C-13 center dot center dot center dot H2S have been reported and analyzed. All isotopologues except C2D4 center dot center dot center dot HDS show a four line pattern whereas a doubling of the transition frequencies was observed for C2D4 center dot center dot center dot HDS. These results together with our previous report on the title complex M. Goswami, P. K. Mandal, D. J. Ramdass, and E. Arunan, Chem. Phys. Lett. 393(1-3), 22-27 (2004)] confirm that both subunits (C2H4 and H2S) are involved in large amplitude motions leading to a splitting of each rotational transition to a quartet. Further, the results also confirm that the motions which are responsible for the observed splittings involve both monomers. Molecular symmetry group analysis, considering the interchange of equivalent H atoms in H2S and C2H4 could explain the observed four line pattern and their intensities in the microwave spectrum. In addition, hydride stretching fundamentals of the complex were measured using coherence-converted population transfer Fourier Transform Microwave-infrared (IR-MW double resonance) experiments in the S-H and C-H stretch regions. Changes in the tunneling splittings upon vibrational excitation are consistent with the isotopic dependence of pure rotational transitions. A complexation shift of 2.7-6.5 cm(-1) has been observed in the two fundamental S-H stretching modes of the H2S monomer in the complex. Vibrational pre-dissociation in the bound S-H stretch has been detected whereas the instrument-limited line-shapes in other S-H and C-H stretches indicate slower pre-dissociation rate. Some local perturbations in the vibrational spectra have been observed. Two combination bands have been observed corresponding to both the S-H stretching fundamentals and what appears to be the intermolecular stretching mode at 55 cm(-1). The tunneling splitting involved in the rotation of C2H4 unit has been deduced to be 1.5 GHz from the IR-MW results. In addition, ab initio barrier heights derived for different motions of the monomers support the experimental results and provide further insight into the motions causing the splitting. (C) 2013 AIP Publishing LLC.

H2O-CH4 and H2S-CH4 complexes: a direct comparison through molecular beam experiments and ab initio calculations

New molecular beam scattering experiments have been performed to measure the total ( elastic plus inelastic) cross sections as a function of the velocity in collisions between water and hydrogen sulfide projectile molecules and the methane target. Measured data have been exploited to characterize the range and strength of the intermolecular interaction in such systems, which are of relevance as they drive the gas phase molecular dynamics and the clathrate formation. Complementary information has been obtained by rotational spectra, recorded for the hydrogen sulfide-methane complex, with a pulsed nozzle Fourier transform microwave spectrometer. Extensive ab initio calculations have been performed to rationalize all the experimental findings. The combination of experimental and theoretical information has established the ground for the understanding of the nature of the interaction and allows for its basic components to be modelled, including charge transfer, in these weakly bound systems. The intermolecular potential for H2S-CH4 is significantly less anisotropic than for H2O-CH4, although both of them have potential minima that can be characterized as `hydrogen bonded'.

Evaluacion de la produccion de chilote en el cultivo de maiz (Zea mays L.) variedad HS-5G utilizando sustratos mejorados y determinacion de los coeficientes "Kc" y "Ky", bajo riego, Finca Las Mercedes, Managua 2009

El presente trabajo de investigaci��n se estableci�� el 20 de Abril al 16 Junio del 2009, en la Unidad Productiva Hacienda Las Mercedes propiedad de la Universidad Nacional Agraria, ubicada en el municipio de Managua Departamento de Managua km 11 carretera Norte, entrada al carnic 2 km al lago, teniendo su ubicaci��n geogr��fica en las siguientes coordenadas: 12��10���14��� a 12��08���05��� de latitud Norte y 86��10���22��� a 86��09���44��� longitud Oeste, a 56 msnm. La temperatura promedio es de 32.7��C, con una precipitaci��n de 1400-1450 mm anuales, humedad relativa de 72% y una velocidad m��xima del viento de 25.2Km/h. El prop��sito del experimento fue Evaluar la producci��n de chilote en el cultivo de ma��z (Zea mays, L. ) variedad HS-5G, con los diferentes tratamientos Compost, Bocashi, Biofertilizante, Qu��mico (Urea 46%) y la obtenci��n de los coeficientes de cultivos ���Kc��� y el rendimiento ���Ky���, bajo el sistema de riego por aspersi��n en la finca Hacienda Las Mercedes. Las dosis utilizadas fueron calculadas a parti r de los requerimientos del cultivo y un an��lisis de suelo realizado previo a la siembra, se aplicaron las dosis de 17,857 kg.h-1 de compost, 10,521 kg.h-1 de Bocashi 26,450 gal.h-1 de Biofertilizante todos estos abonos org��nicos fueron elaborados como parte de la investigaci��n haciendo uso de los distintos materiales que se tienen en la finca para su composici��n, el fertilizante mineral con 214 kg.h- 1 urea 46%. El ensayo se estableci�� en un dise��o de bloque completo al azar (BCA) con cuatro tratamientos y cuatro repeticiones. La dimensi��n Total del ensayo es de 585m2 (26m x 22.5m), cada parcela era de 14m2 (4m x 3.5m) 1.5 m2 para la parcela ��til. La distancia entre bloque fue de 2 m y de 1.5 m entre parcela. Las variables cuantitativas evaluadas fueron Altura de la planta, N��mero de hojas, Di��metro del tallo y en los componentes del rendimiento: Altura del chilote, Peso con braquia, Peso sin braquia, Longitud del chilote, Di��metro del chilote y Rendimiento por tratamiento. A los datos obtenidos se les someti�� a un an��lisis de varianza (ANDEVA) y separaci��n de medias mediante el uso de la prueba de Diferencias M��nimas Signi ficativas (LSD ��=0.05). Utilizando Software estad��stico Infostat. Los resultados muestran que la ��nica variable que present�� diferencias significativas fue la altura de planta a los 8 d��as despu��s de siembra encontr��ndose alturas mayor de 5.99 cm cuando el cultivo fue fertilizado con Bocashi ya que el bocashi retiene mayor humedad. Serealizo un an��lisis econ��mico, logrando un beneficio neto de C$517,165 el fertilizante sint��tico urea 46% obtuvo una tasa de retorno marginal (37.93 %). Con respecto a las variables de riego, tomando en cuenta las etapas fonol��gicas del cultivo se le aplico mayor volumen de agua en la fase de emergencia y crecimiento vegetativo para todos los tratamientos se obtuvo un coeficiente decultivo uniforme y un coeficiente de rendimiento por lo que el qu��mico fue el que obtuvo una menor p��rdida con respecto a los otros tratamientos.

Reutilizaci��n de escoria negra de acer��a como soporte en biofiltros para la eliminaci��n de H2S del biog��s.

[EN]Due to the limitations associated with fossil fuels it is necessary to promote energy sources that are renewable as well as eco-friendly, such as biogas generated in anaerobic digesters. The biogas, composed principally of methane and CO2, is the result of the biodegradation of organic matter under anaerobic conditions. Its use as fuel is limited by the presence of minority compounds such as hydrogen sulphide (H2S); therefore, its pre-treatment is necessary. Currently there are various technologies for the removal of H2S from a gas stream, but most of them are based on physic-chemical treatments which have a number of drawbacks as reactive consumption, generation of secondary flows, etc. Biofiltration has been used as an efficient and low cost alternative to conventional purification processes, and excellent results for the degradation of H2S have been obtained. However process can be limited due to the progressive ageing of the support material, along with the loss of nutrients and other specific characteristics necessary for the good development of biomass. The purpose of this project is to develop a mixed support consisting of a mixture of an organic material and an inorganic support for its application in the removal of the H2S from biogas. This support material helps to optimize the characteristics of the bed and extend its lifespan. The development of such material will contribute to the implementation of biofiltration for treating biogas from anaerobic digesters for its use as biofuel. The inorganic material used is electric arc furnace (EAF) black slag, a by-product generated in large quantities in the production of steel in the Basque Country. Although traditionally the slag has been used in civil engineering, its physicochemical characteristics make it suitable for reuse as a filter medium in biofiltration. The main conclusion drawn from the experimental results is that EAF black slag is a suitable co-packing material in organic biofilters treating H2S-polluted gaseous streams. High pollutant removal rates have been achieved during the whole experimental period. The removal capacity recorded in biofilters with less inorganic material was higher than in those with higher slag portion. Nevertheless, all the biofilters have shown a satisfactory response even at high inlet loads (48 g��m-3��h-1), where the RE has not decreased over 82%.

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