Absence of respiratory inflammatory reaction of elemental sulfur using the California Pesticide Illness Database and a mouse model.

Science.gov (United States)

Lee, Kiyoung; Smith, Jodi L; Last, Jerold A

2005-01-01

Elemental sulfur, a natural substance, is used as a fungicide. Elemental sulfur is the most heavily used agricultural chemical in California. In 2003, annual sulfur usage in California was about 34% of the total weight of pesticide active ingredient used in production agriculture. Even though sulfur is mostly used in dust form, the respiratory health effects of elemental sulfur are not well documented. The purpose of this paper is to address the possible respiratory effect of elemental sulfur using the California Pesticide Illness Database and laboratory experiments with mice. We analyzed the California Pesticide Illness Database between 1991 and 2001. Among 127 reports of definite, probable, and possible illness involving sulfur, 21 cases (16%) were identified as respiratory related. A mouse model was used to examine whether there was an inflammatory or fibrotic response to elemental sulfur. Dust solutions were injected intratracheally into ovalbumin sensitized mice and lung damage was evaluated. Lung inflammatory response was analyzed via total lavage cell counts and differentials, and airway collagen content was analyzed histologically and biochemically. No significant differences from controls were seen in animals exposed to sulfur particles. The findings suggest that acute exposure of elemental sulfur itself may not cause an inflammatory reaction. However, further studies are needed to understand the possible health effects of chronic sulfur exposure and environmental weathering of sulfur dust.

Contribution to the study of sulfur trioxide formation and determination of the sulfuric acid dew point in boiler plants

Energy Technology Data Exchange (ETDEWEB)

Mueller, H.

1983-11-01

This paper analyzes chemical reaction kinetics of the formation of sulfur trioxide and sulfuric acid in combustion air and flue gas of steam generators. Formulae for sulfuric acid equilibrium reactions according to Wahnschaffe (W. Grimm, 1972) and R. Hasse, H.W. Borgmann (1962) are presented. Theoretical acid dew point, combustion parameters with influence on the dew point temperature and formation of sulfates are further discussed. Sulfur trioxide formation at temperatures above 1,000 C as a non-equilibrium reaction is outlined as another variant of chemical reactions. A graphic evaluation is made of dew point conditions in brown coal dust fired, and heating oil fired steam generators. (11 refs.)

Isotope effects of sulfur in chemical reactions

International Nuclear Information System (INIS)

Mikolajczuk, A.

1999-01-01

Sulfur is an important component of organic matter because it forms compounds with many elements. Due to high chemical activity of sulfur, it takes part in biological and geological processes in which isotope effects are occurring. It has been shown during last years research of isotope effects that we have take into account not only mass difference but also many other physical properties of nuclides e.g. even or odd number of neutrons in nuclei, shape and distribution of charge, turn of nuclear spin etc. The factor remains that new theoretical ideas have been formed on the base of data, being obtained in fractionation processes of heavy element isotope, particularly uranium. Now it is being well known that effects unconnected with vibration energy have also caused an effect on fractionation of considerably lighter elements like iron and magnesium. The important question is, if these effects would come to light during the separation of sulfur isotopes. Sulfur have three even isotopes M = (32, 34, 36) and one odd M 33). This problem is still open. (author)

Application of atomic mutations included in nuclear reactions, 40Ar(γ, p)39Cl(β decay)39Ar, to surface study

International Nuclear Information System (INIS)

Ohkuma, Juzo

1987-01-01

It has been found that the nuclear transformation processes which are initiated by photonuclear reactions can be used for studying the adsorption and chemical reactions taking place on solid surfaces. Chemically reactive 39 Cl was produced by irradiating 40 Ar with high-energy bremsstrahlung, and its blow was directed onto several material surfaces. The amount of chlorine adsorption was ascertained by detecting its radioactivity. Desorption without heating the adsorber samples inevitably occurred owing to the nuclear decay of 39 Cl. The adsorption and desorption rates were compared for several elements. A fast growth of oxide islands on sample surfaces was observed during the adsorption-desorption process. (author)

In-situ sulfuration synthesis of sandwiched spherical tin sulfide/sulfur-doped graphene composite with ultra-low sulfur content

Science.gov (United States)

Zhao, Bing; Yang, Yaqing; Wang, Zhixuan; Huang, Shoushuang; Wang, Yanyan; Wang, Shanshan; Chen, Zhiwen; Jiang, Yong

2018-02-01

SnS is widely studied as anode materials since of its superior structural stability and physicochemical property comparing with other Sn-based composites. Nevertheless, the inconvenience of phase morphology control and excessive consumption of sulfur sources during synthesis hinder the scalable application of SnS nanocomposites. Herein, we report a facile in-situ sulfuration strategy to synthesize sandwiched spherical SnS/sulfur-doped graphene (SnS/S-SG) composite. An ultra-low sulfur content with approximately stoichiometric ratio of Sn:S can effectively promote the sulfuration reaction of SnO2 to SnS and simultaneous sulfur-doping of graphene. The as-prepared SnS/S-SG composite shows a three-dimensional interconnected spherical structure as a whole, in which SnS nanoparticles are sandwiched between the multilayers of graphene sheets forming a hollow sphere. The sandwiched sphere structure and high S doping amount can improve the binding force between SnS and graphene, as well as the structural stability and electrical conductivity of the composite. Thus, a high reversibility of conversion reaction, promising specific capacity (772 mAh g-1 after 100 cycles at 0.1 C) and excellent rate performance (705 and 411 mAh g-1 at 1 C and 10 C, respectively) are exhibited in the SnS/S-SG electrode, which are much higher than that of the SnS/spherical graphene synthesized by traditional post-sulfuration method.

Directional Track Selection Technique in CR39 SSNTD for lowyield reaction experiments

Science.gov (United States)

Ingenito, Francesco; Andreoli, Pierluigi; Batani, Dimitri; Bonasera, Aldo; Boutoux, Guillaume; Burgy, Frederic; Cipriani, Mattia; Consoli, Fabrizio; Cristofari, Giuseppe; De Angelis, Riccardo; Di Giorgio, Giorgio; Ducret, Jean Eric; Giulietti, Danilo; Jakubowska, Katarzyna

2018-01-01

There is a great interest in the study of p-11B aneutronic nuclear fusion reactions, both for energy production and for determination of fusion cross-sections at low energies. In this context we performed experiments at CELIA in which energetic protons, accelerated by the laser ECLIPSE, were directed toward a solid Boron target. Because of the small cross-sections at these energies the number of expected reactions is low. CR39 Solid-State Nuclear Track Detectors (SSNTD) were used to detect the alpha particles produced. Because of the low expected yield, it is difficult to discriminate the tracks due to true fusion products from those due to natural background in the CR39. To this purpose we developed a methodology of particle recognition according to their direction with respect to the detector normal, able to determine the position of their source. We applied this to the specific experiment geometry, so to select from all the tracks those due to particles coming from the region of interaction between accelerated protons and solid boron target. This technique can be of great help on the analysis of SSNTD in experiments with low yield reactions, but can be also generally applied to any experiment where particles reach the track detector with known directions, and for example to improve the detection limit of particle spectrometers using CR39.

Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells

Science.gov (United States)

Zhang, Yuegang; Cairns, Elton J.; Ji, Liwen; Rao, Mumin

2017-06-06

The loss of sulfur cathode material as a result of polysulfide dissolution causes significant capacity fading in rechargeable lithium/sulfur cells. Embodiments of the invention use a chemical approach to immobilize sulfur and lithium polysulfides via the reactive functional groups on graphene oxide. This approach obtains a uniform and thin (.about.tens of nanometers) sulfur coating on graphene oxide sheets by a chemical reaction-deposition strategy and a subsequent low temperature thermal treatment process. Strong interaction between graphene oxide and sulfur or polysulfides demonstrate lithium/sulfur cells with a high reversible capacity of 950-1400 mAh g.sup.-1, and stable cycling for more than 50 deep cycles at 0.1 C.

Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yuegang; Cairns, Elton J.; Ji, Liwen; Rao, Mumin

2017-12-26

The loss of sulfur cathode material as a result of polysulfide dissolution causes significant capacity fading in rechargeable lithium/sulfur cells. Embodiments of the invention use a chemical approach to immobilize sulfur and lithium polysulfides via the reactive functional groups on graphene oxide. This approach obtains a uniform and thin (.about.tens of nanometers) sulfur coating on graphene oxide sheets by a chemical reaction-deposition strategy and a subsequent low temperature thermal treatment process. Strong interaction between graphene oxide and sulfur or polysulfides demonstrate lithium/sulfur cells with a high reversible capacity of 950-1400 mAh g.sup.-1, and stable cycling for more than 50 deep cycles at 0.1 C.

Nanostructured sulfur cathodes

KAUST Repository

Yang, Yuan

2013-01-01

Rechargeable Li/S batteries have attracted significant attention lately due to their high specific energy and low cost. They are promising candidates for applications, including portable electronics, electric vehicles and grid-level energy storage. However, poor cycle life and low power capability are major technical obstacles. Various nanostructured sulfur cathodes have been developed to address these issues, as they provide greater resistance to pulverization, faster reaction kinetics and better trapping of soluble polysulfides. In this review, recent developments on nanostructured sulfur cathodes and mechanisms behind their operation are presented and discussed. Moreover, progress on novel characterization of sulfur cathodes is also summarized, as it has deepened the understanding of sulfur cathodes and will guide further rational design of sulfur electrodes. © 2013 The Royal Society of Chemistry.

Menaquinone-7 in the reaction center complex of the green sulfur bacterium Chlorobium vibrioforme functions as the electron acceptor A1

DEFF Research Database (Denmark)

Kjaer, B; Frigaard, N-U; Yang, F

1998-01-01

Photosynthetically active reaction center complexes were prepared from the green sulfur bacterium Chlorobium vibrioforme NCIMB 8327, and the content of quinones was determined by extraction and high-performance liquid chromatography. The analysis showed a stoichiometry of 1.7 molecules of menaqui......Photosynthetically active reaction center complexes were prepared from the green sulfur bacterium Chlorobium vibrioforme NCIMB 8327, and the content of quinones was determined by extraction and high-performance liquid chromatography. The analysis showed a stoichiometry of 1.7 molecules...

Performance evaluation of the sulfur-redox-reaction-activated up-flow anaerobic sludge blanket and down-flow hanging sponge anaerobic/anoxic sequencing batch reactor system for municipal sewage treatment.

Science.gov (United States)

Hatamoto, Masashi; Ohtsuki, Kota; Maharjan, Namita; Ono, Shinya; Dehama, Kazuya; Sakamoto, Kenichi; Takahashi, Masanobu; Yamaguchi, Takashi

2016-03-01

A sulfur-redox-reaction-activated up-flow anaerobic sludge blanket (UASB) and down-flow hanging sponge (DHS) system, combined with an anaerobic/anoxic sequencing batch reactor (A2SBR), has been used for municipal sewage treatment for over 2 years. The present system achieved a removal rate of 95±14% for BOD, 74±22% for total nitrogen, and 78±25% for total phosphorus, including low water temperature conditions. Sludge conversion rates during the operational period were 0.016 and 0.218 g-VSS g-COD-removed(-1) for the UASB, and DHS, respectively, which are similar to a conventional UASB-DHS system, which is not used of sulfur-redox-reaction, for sewage treatment. Using the sulfur-redox reaction made advanced treatment of municipal wastewater with minimal sludge generation possible, even in winter. Furthermore, the occurrence of a unique phenomenon, known as the anaerobic sulfur oxidation reaction, was confirmed in the UASB reactor under the winter season. Copyright © 2016. Published by Elsevier Ltd.

Radiation induced sulfur dioxide removal

International Nuclear Information System (INIS)

Chmielewski, A.G.

2000-01-01

The biggest source of air pollution is the combustion of fossil fuels, were pollutants such as particulate, sulfur dioxide (SO 2 ), nitrogen oxides (NO x ), and volatile organic compounds (VOC) are emitted. Among these pollutants, sulfur dioxide plays the main role in acidification of the environment. The mechanism of sulfur dioxide transformation in the environment is partly photochemical. This is not direct photooxidation, however, but oxidation through formed radicals. Heterogenic reactions play an important role in this transformation as well; therefore, observations from environmental chemistry can be used in air pollution control engineering. One of the most promising technologies for desulfurization of the flue gases (and simultaneous denitrification) is radiation technology with an electron accelerator application. Contrary to the nitrogen oxides (NO x ) removal processes, which is based on pure radiation induced reactions, sulfur dioxide removal depends on two pathways: a thermochemical reaction in the presence of ammonia/water vapor and a radiation set of radiochemical reactions. The mechanism of these reactions and the consequent technological parameters of the process are discussed in this paper. The industrial application of this radiation technology is being implemented in an industrial pilot plant operated by INCT at EPS Kaweczyn. A full-scale industrial plant is currently in operation in China, and two others are under development in Japan and Poland. (author)

Sulfur and Its Role In Modern Materials Science.

Science.gov (United States)

Boyd, Darryl A

2016-12-12

Although well-known and studied for centuries, sulfur continues to be at the center of an extensive array of scientific research topics. As one of the most abundant elements in the Universe, a major by-product of oil refinery processes, and as a common reaction site within biological systems, research involving sulfur is both broad in scope and incredibly important to our daily lives. Indeed, there has been renewed interest in sulfur-based reactions in just the past ten years. Sulfur research spans the spectrum of topics within the physical sciences including research on improving energy efficiency, environmentally friendly uses for oil refinery waste products, development of polymers with unique optical and mechanical properties, and materials produced for biological applications. This Review focuses on some of the latest exciting ways in which sulfur and sulfur-based reactions are being utilized to produce materials for application in energy, environmental, and other practical areas. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization of desulfurization, denitrogenation and process sulfur transfer during hydropyrolysis of Chinese high sulfur coals

Energy Technology Data Exchange (ETDEWEB)

Sun Chenggong; Li Baoqing [Chinese Academy of Sciences, Taiyuan (China). State Key Lab. of Coal Conversion; Snape, C.E. [Strathclyde Univ., Glasgow (United Kingdom). Dept. of Pure and Applied Chemistry

1997-12-31

The process desulphurization and denitrogenation of Chinese high sulfur coals and the characteristics of sulfur transformation during non-catalytic hydropyrolysis were investigated by a 10 g fixed-bed reactor and a small-scaled reactor with online spectrometry respectively. It was indicated that more than 70% of the total sulfur of the two high sulfur coals and almost all pyritic sulfur are removed as H{sub 2}S, leaving the char and tar products with much less sulfur distribution. The liability of sulfur transformation to tar products is closely related to the thiophenic structure forms rather than sulfidic forms. At the same time, the formation of trace amount of sulfur dioxide indicates the presence of inherent sulfur oxidation reactions inside coal frame structures even under H{sub 2} pressure. (orig.)

Sulfur isotope studies of biogenic sulfur emissions at Wallops Island, Virginia

International Nuclear Information System (INIS)

Hitchcock, D.R.; Black, M.S.; Herbst, R.P.

1978-03-01

This research attempted to determine whether it is possible to measure the stable sulfur isotope distributions of atmospheric particulate and gaseous sulphur, and to use this information together with measurements of the ambient levels of sulfur gases and particulate sulfate and sodium in testing certain hypotheses. Sulfur dioxide and particulate sulfur samples were collected at a coastal marine location and their delta (34)S values were determined. These data were used together with sodium concentrations to determine the presence of biogenic sulfur and the identity of the biological processes producing it. Excess (non-seasalt) sulfate levels ranged from 2 to 26 micrograms/cu m and SO2 from 1 to 9 ppb. Analyses of air mass origins and lead concentrations indicated that some anthropogenic contaminants were present on all days, but the isotope data revealed that most of the atmospheric sulfur originated locally from the metabolism of bacterial sulfate reducers on all days, and that the atmospheric reactions leading to the production of sulfate from this biogenic sulfur source are extremely rapid. Delta 34 S values of atmospheric sulfur dioxide correlated well with those of excess sulfate, and implied little or no sulfur isotope fractionation during the oxidation of sulfur gases to sulfate

Sulfur Isotope Exchange between S-35 Labeled Inorganic Sulfur-Compounds in Anoxic Marine-Sediments

DEFF Research Database (Denmark)

FOSSING, H.; THODEANDERSEN, S.; JØRGENSEN, BB

1992-01-01

of isotope exchange, specific radioactivities of the reduced sulfur pools were poorly defined and could not be used to calculate their rates of formation. Such isotope exchange reactions between the reduced inorganic sulfur compounds will affect the stable isotope distribution and are expected to decrease...

Air Quality Criteria for Sulfur Oxides.

Science.gov (United States)

National Air Pollution Control Administration (DHEW), Washington, DC.

Included is a literature review which comprehensively discusses knowledge of the sulfur oxides commonly found in the atmosphere. The subject content is represented by the 10 chapter titles: Physical and Chemical Properties and the Atmospheric Reactions of the Oxides of Sulfur; Sources and Methods of Measurements of Sulfur Oxides in the Atmosphere;…

Sulfurized carbon: a class of cathode materials for high performance lithium/sulfur batteries

Directory of Open Access Journals (Sweden)

Sheng S. Zhang

2013-12-01

Full Text Available Liquid electrolyte lithium/sulfur (Li/S batteries cannot come into practical applications because of many problems such as low energy efficiency, short cycle life, and fast self-discharge. All these problems are related to the dissolution of lithium polysulfide, a series of sulfur reduction intermediates, in the liquid electrolyte, and resulting parasitic reactions with the Li anode. Covalently binding sulfur onto carbon surface is a solution to completely eliminate the dissolution of lithium polysulfide and make the Li/S battery viable for practical applications. This can be achieved by replacing elemental sulfur with sulfurized carbon as the cathode material. This article reviews the current efforts on this subject and discusses the syntheses, electrochemical properties, and prospects of the sulfurized carbon as a cathode material in the rechargeable Li/S batteries.

Relationship between corrosion and the biological sulfur cycle: A review

Energy Technology Data Exchange (ETDEWEB)

Little, B.J.; Ray, R.I.; Pope, R.K.

2000-04-01

Sulfur and sulfur compounds can produce pitting, crevice corrosion, dealloying, stress corrosion cracking, and stress-oriented hydrogen-induced cracking of susceptible metals and alloys. Even though the metabolic by-products of the biological sulfur cycle are extremely corrosive, there are no correlations between numbers and types of sulfur-related organisms and the probability or rate of corrosion, Determination of specific mechanisms for corrosion caused by microbiologically mediated oxidation and reduction of sulfur and sulfur compounds is complicated by the variety of potential metabolic-energy sources and by-products; the coexistence of reduced and oxidized sulfur species; competing reactions with inorganic and organic compounds; and the versatility and adaptability of microorganisms in biofilms. The microbial ecology of sulfur-rich environments is poorly understood because of the association of aerobes and anaerobes and the mutualism or succession of heterotrophs to autotrophs. The physical scale over which the sulfur cycle influences corrosion varies with the environment. The complete sulfur cycle of oxidation and reduction reactions can take place in macroenvironments, including sewers and polluted harbors, or within the microenvironment of biofilms. In this review, reactions of sulfur and sulfur compounds resulting in corrosion were discussed in the context of environmental processes important to corrosion.

From melamine sponge towards 3D sulfur-doping carbon nitride as metal-free electrocatalysts for oxygen reduction reaction

Science.gov (United States)

Xu, Jingjing; Li, Bin; Li, Songmei; Liu, Jianhua

2017-07-01

Development of new and efficient metal-free electrocatalysts for replacing Pt to improve the sluggish kinetics of oxygen reduction reaction (ORR) is of great importance to emerging renewable energy technologies such as metal-air batteries and polymer electrolyte fuel cells. Herein, 3D sulfur-doping carbon nitride (S-CN) as a novel metal-free ORR electrocatalyst was synthesized by exploiting commercial melamine sponge as raw material. The sulfur atoms were doping on CN networks uniformly through numerous S-C bonds which can provide additional active sites. And it was found that the S-CN exhibited high catalytic activity for ORR in term of more positive onset potential, higher electron transfer number and higher cathodic density. This work provides a novel choice of metal-free ORR electrocatalysts and highlights the importance of sulfur-doping CN in metal-free ORR electrocatalysts.

Oxidation of inorganic sulfur compounds in acidophilic prokaryotes

Energy Technology Data Exchange (ETDEWEB)

Rohwerder, T.; Sand, W. [Universitaet Duisburg-Essen, Biofilm Centre, Aquatic Biotechnology, Duisburg (Germany)

2007-07-15

The oxidation of reduced inorganic sulfur compounds to sulfuric acid is of great importance for biohydrometallurgical technologies as well as the formation of acidic (below pH 3) and often heavy metal-contaminated environments. The use of elemental sulfur as an electron donor is the predominant energy-yielding process in acidic natural sulfur-rich biotopes but also at mining sites containing sulfidic ores. Contrary to its significant role in the global sulfur cycle and its biotechnological importance, the microbial fundamentals of acidophilic sulfur oxidation are only incompletely understood. Besides giving an overview of sulfur-oxidizing acidophiles, this review describes the so far known enzymatic reactions related to elemental sulfur oxidation in acidophilic bacteria and archaea. Although generally similar reactions are employed in both prokaryotic groups, the stoichiometry of the key enzymes is different. Bacteria oxidize elemental sulfur by a sulfur dioxygenase to sulfite whereas in archaea, a sulfur oxygenase reductase is used forming equal amounts of sulfide and sulfite. In both cases, the activation mechanism of elemental sulfur is not known but highly reactive linear sulfur forms are assumed to be the actual substrate. Inhibition as well as promotion of these biochemical steps is highly relevant in bioleaching operations. An efficient oxidation can prevent the formation of passivating sulfur layers. In other cases, a specific inhibition of sulfur biooxidation may be beneficial for reducing cooling and neutralization costs. In conclusion, the demand for a better knowledge of the biochemistry of sulfur-oxidizing acidophiles is underlined. (Abstract Copyright [2007], Wiley Periodicals, Inc.)

Surface reaction modification: The effect of structured overlayers of sulfur on the kinetics and mechanism of the decomposition of formic acid on Pt(111)

Science.gov (United States)

Abbas, N.; Madix, R. J.

The reaction of formic acid (DCOOH) on Pt(111), Pt(111)-(2×2)S and Pt(111)-(√3×√3)R30°S surfaces was examined by temperature programmed reaction spectroscopy. On the clean surface formic acid decomposed to yield primarily carbon dioxide and the hydrogenic species (H 2, HD and D 2) at low coverages. Although the formation of water and carbon monoxide via a dehydration reaction was observed at these coverages, the yield of these products was small when compared to the other products of reaction. The evolution of CO 2 at low temperature was ascribed to the decomposition of the formate intermediate. In the presence of sulfur the amount of molecularly adsorbed formic acid decreased up to a factor of three on the (√3×√3)R30°S surface, and a decline in the reactivity of over an order of magnitude was also observed. The only products formed were the hydrogenic species and carbon dioxide. The absence of carbon monoxide indicated that the dehydration pathway was blocked by sulfur. In addition to the low temperature CO 2 peak a high temperature CO 2-producing path was also evident. It was inferred from both the stoichiometry and the coincident evolution of D 2 and CO 2 in the high temperature states that these products also evolved due to the decomposition of the formate intermediate. On increasing the sulfur coverage to one-third monolayer this intermediate was further stabilized, and a predominance of the decomposition via the high temperature path was observed. Stability of the formate intermediate was attributed to inhibition of the decomposition reaction by sulfur atoms. The activation energy for formate decomposition increased from 15 kcal/gmole on the clean surface to 24.3 kcal/gmol on the (√3×√3)R30°S overlayer.

Graphene derived carbon confined sulfur cathodes for lithium-sulfur batteries: Electrochemical impedance studies

International Nuclear Information System (INIS)

Ganesan, Aswathi; Varzi, Alberto; Passerini, Stefano; Shaijumon, Manikoth M.

2016-01-01

Highlights: • Graphene-derived carbon (GDC) with distinctive porosity characteristics are prepared. • Effect of micro-/mesoporosity of GDC for improved Li-S battery performance is studied. • Impedance studies reveal insights into Li-S redox reactions and capacity fading phenomena. - Abstract: Sulfur nanocomposites are prepared by using graphene derived carbon (GDC), with controlled porosity characteristics, as confining matrix and are studied as efficient cathodes for lithium-sulfur (Li-S) batteries. To understand the effect of micro-/mesoporosity in porous carbon for the effective encapsulation of sulfur and polysulfides towards improved Li-S battery performance, two different GDC samples with controlled porosity characteristics, one with predominantly micropores (GDC-1) and a surface area of 1970 m 2 g −1 and the other with a surface area of 3239 m 2 g −1 , having more or less equal contribution of micro- and mesopores (GDC-2), are used to synthesize nanocomposite sulfur electrodes following melt diffusion process. Electrochemical studies are carried out by using cyclic voltammetry, galvanostatic charge/discharge cycling and electrochemical impedance spectroscopy (EIS). EIS spectra collected at different depth of discharge (DOD) in the first cycle as well as upon cycling give valuable insights into the Li-S redox reactions and capacity fading phenomena in these electrodes. The impedance response of GDC-S electrodes suggests a detrimental effect of the mesopores, where insoluble reaction products can easily accumulate, resulting in the loss of active material leading to capacity fading of Li-S cells.

The GC/AED studies on the reactions of sulfur mustard with oxidants

International Nuclear Information System (INIS)

Popiel, StanisIaw; Witkiewicz, Zygfryd; Szewczuk, Aleksander

2005-01-01

A gas chromatograph coupled with an atomic emission detector was used to identify and to determine the products formed on oxidation of sulfur mustard. The oxidation rate and the resulting oxidates were studied in relation to oxidant type and reaction medium parameters. Hydrogen peroxide, sodium hypochlorite, sodium perborate, potassium monopercarbonate, ammonium peroxydisulfate, potassium peroxymonosulfate (oxone), and tert-butyl peroxide were used as oxidants. Oxidations were run in aqueous media or in solvents of varying polarities. The oxidation rate was found to be strongly related to oxidant type: potassium peroxymonosulfate (oxone) and sodium hypochlorite were fast-acting oxidants; sodium perborate, hydrogen peroxide, ammonium peroxydisulfate, and sodium monopercarbonate were moderate oxidants; tert-butyl peroxide was the slowest-acting oxidant. In non-aqueous solvents, the oxidation rate was strongly related to solvent polarity. The higher the solvent polarity, the faster the oxidation rate. In the acid and neutral media, the mustard oxidation rates were comparable. In the alkaline medium, oxidation was evidently slower. A suitable choice of the initial oxidant-to-mustard concentration ratio allowed to control the type of the resulting mustard oxidates. As the pH of the reaction medium was increased, the reaction of elimination of hydrogen chloride from mustard oxidates becomes more and more intensive

MATHEMATICAL SIMULATION OF THE INTERACTIONS AMONG CYANOBACTERIA, PURPLE SULFUR BACTERIA AND CHEMOTROPIC SULFUR BACTERIA IN MICROBIAL MAT COMMUNITIES

NARCIS (Netherlands)

DEWIT, R; VANDENENDE, FP; VANGEMERDEN, H

A deterministic one-dimensional reaction diffusion model was constructed to simulate benthic stratification patterns and population dynamics of cyanobacteria, purple and colorless sulfur bacteria as found in marine microbial mats. The model involves the major biogeochemical processes of the sulfur

Thermal dynamic analysis of sulfur removal from coal by electrolysis

Energy Technology Data Exchange (ETDEWEB)

Li, D.; Gao, J.; Meng, F. [Qinghua University, Beijing (China). Dept. of Thermal Engineering

2002-06-01

The electrolytic reactions about sulfur removal from coal were studied by using chemical thermal dynamic analysis. According to the thermodynamical data, the Gibbs free energy value of the electrolytic reactions of pyritic and organic sulfur removal from coal is higher than zero. So, these electrolytic reactions are not spontaneous chemical reactions. In order to carry out desulfurisation by electrolysis, a certain voltage is necessary and important. Because theoretic decomposition voltage of pyrite and some parts of organic sulfur model compound is not very high, electrolysis reactions are easily to be carried out by using electrolysis technology. Mn ion and Fe ion are added into electrolysis solutions to accelerate the desulfurisation reaction. The electrolytic decomposition of coal is discussed. Because the theoretical decomposition voltage of some organic model compound is not high, the coal decomposition might happen. 17 refs., 4 tabs.

Reactions of sulfur atoms. XV. Absolute rate parameters for the S(3P210) + alkyne reactions

International Nuclear Information System (INIS)

van Roodselaar, A.; Safarik, I.; Strausz, O.P.; Gunning, H.E.

1978-01-01

Using flash photolysis with vacuum uv kinetic absorption spectroscopy, absolute rate constants and Arrhenius parameters have been measured for the addition of ground state S( 3 P 2 , 1 , 0 ) atoms to alkynes. The decay of sulfur atoms in COS, alkyne, and CO 2 -diluent mixtures is first order in sulfur atom concentration and the first-order decay rate constants are proportional to the alkyne concentration. The following rate constants were determined at room temperature: k(C 2 H 2 ) = k(C 2 D 2 ) + (2.3 +- 0.4) x 10 8 ; k(CHCCH 3 ) = (4.8 +- 0.2) x 10 9 ; k(CHCC 2 H 5 ) = (3.3 +- 0.2) x 10 9 ; k(CH 3 CCCH 3 ) = 1.6 +- 0.2) x 10 10 ; k(CH 3 CCC 2 C 5 ) = 1.8 +- 0.3) x 10 10 ; and k(CF 3 CCCF 3 ) = (2.1 +- 0.4) x 10 8 L mol -1 s -1 . The Arrhenius parameters determined are k(C 2 H 2 ) = (3.4 +- 1.9) x 10 10 exp[(-3000 +- 400)/RT] L mol -1 s -1 and k(CHCCH 3 ) = (2.0 +- 1.2) x 10 10 exp[(-900 +- 200)/RT] L mol -1 s -1 where error limits represent standard deviations. The rate parameters are compared to those obtained for the addition of other electrophilic reagents to alkynes and the results discussed in terms of structural and kinetic factors. Theoretical treatment of the secondary H/D isotope effect in the acetylene reaction satisfactorily reproduces the experimental value. 5 tables, 4 figures, 59 references

Transformation of sulfur during pyrolysis and hydropyrolysis of coal

Energy Technology Data Exchange (ETDEWEB)

Chen, H.; Li, B.; Yang, J.; Zhang, B. [Chinese Academy of Sciences, Taiyuan (China). Inst. of Coal Chemistry

1998-05-01

It is reported that the transformation of sulfur during pyrolysis (Py) under nitrogen and hydropyrolysis (HyPy) of Chinese Yanzhou high sulfur bituminous coal and Hongmiao lignite was studied in a fixed-bed reactor. The volatile sulfur-containing products were determined by gas chromatography with flame photometric detection. The sulfur in initial coal and char (mainly aliphatic and thiophenic sulfur forms) was quantitatively analyzed using X-ray photoelectron spectroscopy (XPS). The desulfurization yield was calculated by elemental analysis. The main volatile sulfur-containing gas was H{sub 2}S in both Py and HyPy. Both the elemental analysis and XPS results indicated that more sulfur was removed in HyPy than in Py under nitrogen. Thiophenic sulfur can be partially hydrogenated and removed in HyPy. Pyrite can be reduced to a ferrous sulfide completely even as low as 400{degree}C in HyPy while in Py the reduction reaction continues up to 650{degree}C. Mineral matter can not only fix H{sub 2}S produced in Py and HyPy to form higher sulfur content chars but also catalyses the desulfurization reactions to form lower sulfur content tars in HyPy. 24 refs., 8 figs., 4 tabs.

40 CFR 721.9672 - Amides, tall-oil fatty, N-[2-[2-hydroxyethyl)amino]ethyl], reaction products with sulfur dioxide...

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Amides, tall-oil fatty, N-[2-[2... Significant New Uses for Specific Chemical Substances § 721.9672 Amides, tall-oil fatty, N-[2-[2-hydroxyethyl... identified as amides, tall-oil fatty, N-[2-[2-hydroxyethyl)amino]ethyl], reaction products with sulfur...

Kinetics of reactions of the Actinomadura R39 DD-peptidase with specific substrates.

Science.gov (United States)

Adediran, S A; Kumar, Ish; Nagarajan, Rajesh; Sauvage, Eric; Pratt, R F

2011-01-25

The Actinomadura R39 DD-peptidase catalyzes the hydrolysis and aminolysis of a number of small peptides and depsipeptides. Details of its substrate specificity and the nature of its in vivo substrate are not, however, well understood. This paper describes the interactions of the R39 enzyme with two peptidoglycan-mimetic substrates 3-(D-cysteinyl)propanoyl-D-alanyl-D-alanine and 3-(D-cysteinyl)propanoyl-D-alanyl-D-thiolactate. A detailed study of the reactions of the former substrate, catalyzed by the enzyme, showed DD-carboxypeptidase, DD-transpeptidase, and DD-endopeptidase activities. These results confirm the specificity of the enzyme for a free D-amino acid at the N-terminus of good substrates and indicated a preference for extended D-amino acid leaving groups. The latter was supported by determination of the structural specificity of amine nucleophiles for the acyl-enzyme generated by reaction of the enzyme with the thiolactate substrate. It was concluded that a specific substrate for this enzyme, and possibly the in vivo substrate, may consist of a partly cross-linked peptidoglycan polymer where a free side chain N-terminal un-cross-linked amino acid serves as the specific acyl group in an endopeptidase reaction. The enzyme is most likely a DD-endopeptidase in vivo. pH-rate profiles for reactions of the enzyme with peptides, the thiolactate named above, and β-lactams indicated the presence of complex proton dissociation pathways with sticky substrates and/or protons. The local structure of the active site may differ significantly for reactions of peptides and β-lactams. Solvent kinetic deuterium isotope effects indicate the presence of classical general acid/base catalysis in both acylation and deacylation; there is no evidence of the low fractionation factor active site hydrogen found previously in class A and C β-lactamases.

Study of the reduction of sulfur dioxide to elemental sulfur by carbon monoxide on a La/sub 0/ /sub 5/ Sr/sub 0/ /sub 5/ CoO/sub 3/ catalyst

Energy Technology Data Exchange (ETDEWEB)

Hibbert, D B; Tseung, A C.C.

1979-12-01

A study of the reduction of sulfur dioxide to elemental sulfur by carbon monoxide on a La/sub 0/ /sub 5/ Sr/sub 0/ /sub 5/ CoO/sub 3/ catalyst a perovskite oxide, to determine the effects of oxygen and water on SO2 reduction showed that in the presence of 5 to 16% oxygen, the reaction between sulfur dioxide and carbon monoxide still occurred if there was sufficient carbon monoxide in the gas to react with all the oxygen. At 600C, all the sulfur dioxide was removed at 5 to 16% oxygen levels. Water vapor at 2% did not adversely affect the reaction. The unwanted by-products, hydrogen disulfide and carbonyl sulfide, were reduced at contact times below 0.25 sec. During the reaction, the catalyst itself reacted with sulfur to give metal sulfides. When reagent grade CO/sub 2/O/sub 3/ was substituted for perovskite oxide, the maximum conversion of 98% of sulfur dioxide was attained at 550C, but an unacceptably high concentration of carbonyl sulfide was formed; within 1 hr, the sulfur dioxide conversion fell to 60%. The perovskite oxide reaction may be useful in removing sulfur dioxide from fosill fuel stack gases.

Comparative study of reactions between µ-nitrido- or µ-oxo-bridged iron tetrasulfophthalocyanines and sulfur-containing reductants

Directory of Open Access Journals (Sweden)

Dereven’kov Ilia A.

2013-01-01

Full Text Available A comparative study of reactivity of μ-nitrido- and μ-oxo-dimers of iron tetrasulfophthalocyanine has been performed in aqueous solutions of various acidity. The substantially higher stability of nitrido-bridged structure under both strongly acidic and strongly alkaline environments was demonstrated. Reactions of the complexes with sulfur-containing reductants (sodium dithionite, thiourea dioxide, sodium hydroxymethanesulfinate, L-cysteine has been studied. Differences in reduction processes were explained.

Dew point of gases with low sulfuric acid content

Energy Technology Data Exchange (ETDEWEB)

Fieg, J.

1981-07-01

Discusses control of air pollution caused by sulfur compounds in solid fuels during combustion. Excessive amount of oxygen during combustion leads to formation of sulfur trioxide. Sulfur trioxide reacts with water vapor and forms sulfuric acid. Chemical reactions which lead to formation of sulfuric acid are described. Conditions for sulfuric acid condensation are analyzed. Several methods for determining dew point of flue gases with low sulfuric acid content are reviewed: methods based on determination of electric conductivity of condensed sulfuric acid (Francis, Cheney, Kiyoure), method based on determination of sulfuric acid concentration in the gaseous phase and in the liquid phase after cooling (Lee, Lisle and Sensenbaugh, Ross and Goksoyr). (26 refs.) (In Polish)

Reevaluation of the phenol-sulfuric acid reaction for the estimation of hexoses and pentoses.

Science.gov (United States)

Rao, P; Pattabiraman, T N

1989-08-15

Evidence is provided to show that in the conventional phenol-sulfuric acid reaction procedure, phenol underwent sulfonation in situ and the phenolsulfonic acid formed decreased the color intensity for hydroxymethyl furfural (HMF), furfural, and many hexoses and pentoses tested. A modified method is described to overcome this problem in which phenol was added after the dehydration of carbohydrates by sulfuric acid and after cooling the system. The color intensity around 475-485 nm for different compounds was fairly proportional to the amount of furfural derivatives (absorption at 310-320 nm) formed from the sugars in the modified method unlike in the conventional procedure. The studies also show that for condensation of HMF derivatives with phenol, heat is not necessary. The color intensity in the modified method also increased compared to that in the conventional method. The increase in the modified method compared to that in the conventional method was 6.0-fold for furfural, 9.1-fold for hydroxymethyl furfural, 3.7-fold for fructose, 2.3-fold for xylose, and 2.0-fold for glucose and arabinose. The possible reasons for this differential increase are discussed.

Chemiluminescence behavior based on oxidation reaction of rhodamine B with cerium(IV) in sulfuric acid medium

International Nuclear Information System (INIS)

Ma Yongjun; Jin Xiaoyong; Zhou Min; Zhang Ziyu; Teng Xiulan; Chen Hui

2003-01-01

The chemiluminescence (CL) of the rhodamine B (RhB)-cerium(IV) system was investigated by flow-injection. Rhodamine B was suggested to be a suitable chemiluminescent reagent in acidic conditions. When the concentration of rhodamine B was 100 mg l -1 and cerium sulfate was 1.6 mmol l -1 in sulfuric acid, the chemiluminescent intensity was found to be highest by using 0.3 mol l -1 sulfuric acid as a carrier solution. The particular chemiluminescent system could tolerate such distinct acidic environments that it was utilized for detecting many compounds that are stable in acidic solutions. Furthermore, by virtue of IR, UV-Vis and luminescence spectroscopic measurements, the chemiluminescent behavior of rhodamine B was studied and a possible mechanism for this chemiluminescent reaction was proposed. The emitter was affirmed to be a radical species due to one of the oxidation products of RhB; the chemiluminescent emissive wavelength was about 425 nm

Chemiluminescence behavior based on oxidation reaction of rhodamine B with cerium(IV) in sulfuric acid medium

Energy Technology Data Exchange (ETDEWEB)

Ma Yongjun; Jin Xiaoyong; Zhou Min; Zhang Ziyu; Teng Xiulan; Chen Hui

2003-08-18

The chemiluminescence (CL) of the rhodamine B (RhB)-cerium(IV) system was investigated by flow-injection. Rhodamine B was suggested to be a suitable chemiluminescent reagent in acidic conditions. When the concentration of rhodamine B was 100 mg l{sup -1} and cerium sulfate was 1.6 mmol l{sup -1} in sulfuric acid, the chemiluminescent intensity was found to be highest by using 0.3 mol l{sup -1} sulfuric acid as a carrier solution. The particular chemiluminescent system could tolerate such distinct acidic environments that it was utilized for detecting many compounds that are stable in acidic solutions. Furthermore, by virtue of IR, UV-Vis and luminescence spectroscopic measurements, the chemiluminescent behavior of rhodamine B was studied and a possible mechanism for this chemiluminescent reaction was proposed. The emitter was affirmed to be a radical species due to one of the oxidation products of RhB; the chemiluminescent emissive wavelength was about 425 nm.

Physiology and application of sulfur-reducing microorganisms from acidic environments

NARCIS (Netherlands)

Florentino, Anna Patrícya

2017-01-01

Sulfur cycle is one of the main geochemical cycles on Earth. Oxidation and reduction reactions of sulfur are mostly biotic and performed by microorganisms. In anaerobic conditions – marine and some freshwater systems, dissimilatory sulfur- and sulfate-reducing bacteria and archaea are key players

Selective catalytic reduction of sulfur dioxide to elemental sulfur. Final report

Energy Technology Data Exchange (ETDEWEB)

Liu, W.; Flytzani-Stephanopoulos, M.; Sarofim, A.F.

1995-06-01

This project has investigated new metal oxide catalysts for the single stage selective reduction of SO{sub 2} to elemental sulfur by a reductant, such as CO. Significant progress in catalyst development has been made during the course of the project. We have found that fluorite oxides, CeO{sub 2} and ZrO{sub 2}, and rare earth zirconates such as Gd{sub 2}Zr{sub 2}O{sub 7} are active and stable catalysts for reduction Of SO{sub 2} by CO. More than 95% sulfur yield was achieved at reaction temperatures about 450{degrees}C or higher with the feed gas of stoichiometric composition. Reaction of SO{sub 2} and CO over these catalysts demonstrated a strong correlation of catalytic activity with the catalyst oxygen mobility. Furthermore, the catalytic activity and resistance to H{sub 2}O and CO{sub 2} poisoning of these catalysts were significantly enhanced by adding small amounts of transition metals, such as Co, Ni, Co, etc. The resulting transition metal-fluorite oxide composite catalyst has superior activity and stability, and shows promise in long use for the development of a greatly simplified single-step sulfur recovery process to treat variable and dilute SO{sub 2} concentration gas streams. Among various active composite catalyst systems the Cu-CeO{sub 2} system has been extensively studied. XRD, XPS, and STEM analyses of the used Cu-CeO{sub 2} catalyst found that the fluorite crystal structure of ceria was stable at the present reaction conditions, small amounts of copper was dispersed and stabilized on the ceria matrix, and excess copper oxide particles formed copper sulfide crystals of little contribution to catalytic activity. A working catalyst consisted of partially sulfated cerium oxide surface and partially sulfided copper clusters. The overall reaction kinetics were approximately represented by a first order equation.

Toluene destruction in the Claus process by sulfur dioxide: A reaction kinetics study

KAUST Repository

Sinha, Sourab

2014-10-22

The presence of aromatics such as benzene, toluene, and xylene (BTX) as contaminants in the H2S gas stream entering Claus sulfur recovery units has a detrimental effect on catalytic reactors, where BTX forms soot particles and clogs and deactivates the catalysts. BTX oxidation, before they enter catalyst beds, can solve this problem. A theoretical investigation is presented on toluene oxidation by SO2. Density functional theory is used to study toluene radical (benzyl, o-methylphenyl, m-methylphenyl, and p-methylphenyl)-SO2 interactions. The mechanism begins with SO2 addition on the radical through one of the O atoms rather than the S atom. This exothermic reaction involves energy barriers of 4.8-6.1 kJ/mol for different toluene radicals. Thereafter, O-S bond scission takes place to release SO. The reaction rate constants are evaluated to facilitate process simulations. Among four toluene radicals, the resonantly stabilized benzyl radical exhibited lowest SO2 addition rate. A remarkable similarity between toluene oxidation by O2 and by SO2 is observed.

Toluene destruction in the Claus process by sulfur dioxide: A reaction kinetics study

KAUST Repository

Sinha, Sourab; Raj, Abhijeet Dhayal; Alshoaibi, Ahmed S.; Alhassan, Saeed M.; Chung, Suk-Ho

2014-01-01

The presence of aromatics such as benzene, toluene, and xylene (BTX) as contaminants in the H2S gas stream entering Claus sulfur recovery units has a detrimental effect on catalytic reactors, where BTX forms soot particles and clogs and deactivates the catalysts. BTX oxidation, before they enter catalyst beds, can solve this problem. A theoretical investigation is presented on toluene oxidation by SO2. Density functional theory is used to study toluene radical (benzyl, o-methylphenyl, m-methylphenyl, and p-methylphenyl)-SO2 interactions. The mechanism begins with SO2 addition on the radical through one of the O atoms rather than the S atom. This exothermic reaction involves energy barriers of 4.8-6.1 kJ/mol for different toluene radicals. Thereafter, O-S bond scission takes place to release SO. The reaction rate constants are evaluated to facilitate process simulations. Among four toluene radicals, the resonantly stabilized benzyl radical exhibited lowest SO2 addition rate. A remarkable similarity between toluene oxidation by O2 and by SO2 is observed.

Extractive de-sulfurization and de-ashing of high sulfur coals by oxidation with ionic liquids

International Nuclear Information System (INIS)

Saikia, Binoy K.; Khound, Kakoli; Baruah, Bimala P.

2014-01-01

Highlights: • Extractive de-sulfurization and de-ashing process for cleaning high sulfur coals. • The process removes inorganic as well as organic sulfur components from high sulfur coals. • The process has less risk to chemists and other surroundings. - Abstract: The environmental consequences of energy production from coals are well known, and are driving the development of desulfurization technologies. In this investigation, ionic liquids were examined for extractive desulfurization and de-ashing in industrially important high sulfur sub-bituminous Indian coals. The ionic liquids, namely, 1-n-butyl-3-methylimidazolium tetrafluoroborate (IL1) and 1-n-butyl 3-methylimidazolium chloride (IL2) were employed for desulfurization of a few Indian coal samples in presence of HCOOH/H 2 O 2 and V 2 O 5 . Results show the maximum removal of 50.20% of the total sulfur, 48.00% of the organic sulfur, and 70.37 wt% of the ash in this process. The ionic liquids were recovered and subsequently used for further desulfurization. FT-IR spectra reveal the transformation of organic sulfur functionalities into the sulfoxides (S=O) and sulfones (-SO 2 ) due to the oxidative reactions. The sulfate, pyrite and sulfides (aryls) signals in the near edge X-ray absorption fine structure (NEXAFS) of the oxidized coal samples showed sulfur transformation during the desulfurization process. The study demonstrates the removal of significant amount of inorganic as well as organic sulfur (aryls) components from the original high sulfur coal samples to make them cleaner

Bifluoride-catalysed sulfur(VI) fluoride exchange reaction for the synthesis of polysulfates and polysulfonates

Science.gov (United States)

Gao, Bing; Zhang, Linda; Zheng, Qinheng; Zhou, Feng; Klivansky, Liana M.; Lu, Jianmei; Liu, Yi; Dong, Jiajia; Wu, Peng; Sharpless, K. Barry

2017-11-01

Polysulfates and polysulfonates possess exceptional mechanical properties making them potentially valuable engineering polymers. However, they have been little explored due to a lack of reliable synthetic access. Here we report bifluoride salts (Q+[FHF]-, where Q+ represents a wide range of cations) as powerful catalysts for the sulfur(VI) fluoride exchange (SuFEx) reaction between aryl silyl ethers and aryl fluorosulfates (or alkyl sulfonyl fluorides). The bifluoride salts are significantly more active in catalysing the SuFEx reaction compared to organosuperbases, therefore enabling much lower catalyst-loading (down to 0.05 mol%). Using this chemistry, we are able to prepare polysulfates and polysulfonates with high molecular weight, narrow polydispersity and excellent functional group tolerance. The process is practical with regard to the reduced cost of catalyst, polymer purification and by-product recycling. We have also observed that the process is not sensitive to scale-up, which is essential for its future translation from laboratory research to industrial applications.

Unifying principles in homodimeric type I photosynthetic reaction centers: properties of PscB and the FA, FB and FX iron-sulfur clusters in green sulfur bacteria.

Science.gov (United States)

Jagannathan, Bharat; Golbeck, John H

2008-12-01

The photosynthetic reaction center from the green sulfur bacterium Chlorobium tepidum (CbRC) was solubilized from membranes using Triton X-100 and isolated by sucrose density ultra-centrifugation. The CbRC complexes were subsequently treated with 0.5 M NaCl and ultrafiltered over a 100 kDa cutoff membrane. The resulting CbRC cores did not exhibit the low-temperature EPR resonances from FA- and FB- and were unable to reduce NADP+. SDS-PAGE and mass spectrometric analysis showed that the PscB subunit, which harbors the FA and FB clusters, had become dissociated, and was now present in the filtrate. Attempts to rebind PscB onto CbRC cores were unsuccessful. Mössbauer spectroscopy showed that recombinant PscB contains a heterogeneous mixture of [4Fe-4S]2+,1+ and other types of Fe/S clusters tentatively identified as [2Fe-2S]2+,1+ clusters and rubredoxin-like Fe3+,2+ centers, and that the [4Fe-4S]2+,1+ clusters which were present were degraded at high ionic strength. Quantitative analysis confirmed that the amount of iron and sulfide in the recombinant protein was sub-stoichiometric. A heme-staining assay indicated that cytochrome c551 remained firmly attached to the CbRC cores. Low-temperature EPR spectroscopy of photoaccumulated CbRC complexes and CbRC cores showed resonances between g=5.4 and 4.4 assigned to a S=3/2 ground spin state [4Fe-4S]1+ cluster and at g=1.77 assigned to a S=1/2 ground spin state [4Fe-4S]1+ cluster, both from FX-. These results unify the properties of the acceptor side of the Type I homodimeric reaction centers found in green sulfur bacteria and heliobacteria: in both, the FA and FB iron-sulfur clusters are present on a salt-dissociable subunit, and FX is present as an interpolypeptide [4Fe-4S]2+,1+ cluster with a significant population in a S=3/2 ground spin state.

Kinetics of reaction of peroxynitrite with selenium- and sulfur-containing compounds

DEFF Research Database (Denmark)

Storkey, Corin; Pattison, David I.; Ignasiak, Marta T.

2015-01-01

with peroxynitrite with high rate constants. Low molecular mass selenols react particularly rapidly with peroxynitrite, with second order rate constants k2 in the range 5.1×105-1.9×106 M-1 s-1, and 250-830 fold faster than the corresponding thiols (RSH) and many other endogenous biological targets. Reactions......Peroxynitrite (the physiological mixture of ONOOH and its anion, ONOO-) is a powerful biologically-relevant oxidant capable of oxidizing and damaging a range of important targets including sulfides, thiols, lipids, proteins, carbohydrates and nucleic acids. Excessive production of peroxynitrite...... of peroxynitrite with selenides, including selenosugars are approximately 15-fold faster than their sulfur homologs with k2 approximately 2.5×103 M-1 s-1. The rate constants for diselenides and sulfides were slower with k2 0.72-1.3×103 M-1 s-1 and approximately 2.1×102 M-1 s-1 respectively. These studies...

Sulfur isotopes in coal constrain the evolution of the Phanerozoic sulfur cycle

DEFF Research Database (Denmark)

Canfield, Donald Eugene

2013-01-01

Sulfate is the second most abundant anion (behind chloride) in modern seawater, and its cycling is intimately coupled to the cycling of organic matter and oxygen at the Earth’s surface. For example, the reduction of sulfide by microbes oxidizes vast amounts of organic carbon and the subsequent......, these compositions do not deviate substantially from the modern surface-water input to the oceans. When applied to mass balance models, these results support previous interpretations of sulfur cycle operation and counter recent suggestions that sulfate has been a minor player in sulfur cycling through...... reaction of sulfide with iron produces pyrite whose burial in sediments is an important oxygen source to the atmosphere. The concentrations of seawater sulfate and the operation of sulfur cycle have experienced dynamic changes through Earth’s history, and our understanding of this history is based mainly...

Disproportionation of elemental sulfur by haloalkaliphilic bacteria from soda lakes.

Science.gov (United States)

Poser, Alexander; Lohmayer, Regina; Vogt, Carsten; Knoeller, Kay; Planer-Friedrich, Britta; Sorokin, Dimitry; Richnow, Hans-H; Finster, Kai

2013-11-01

Microbial disproportionation of elemental sulfur to sulfide and sulfate is a poorly characterized part of the anoxic sulfur cycle. So far, only a few bacterial strains have been described that can couple this reaction to cell growth. Continuous removal of the produced sulfide, for instance by oxidation and/or precipitation with metal ions such as iron, is essential to keep the reaction exergonic. Hitherto, the process has exclusively been reported for neutrophilic anaerobic bacteria. Here, we report for the first time disproportionation of elemental sulfur by three pure cultures of haloalkaliphilic bacteria isolated from soda lakes: the Deltaproteobacteria Desulfurivibrio alkaliphilus and Desulfurivibrio sp. AMeS2, and a member of the Clostridia, Dethiobacter alkaliphilus. All cultures grew in saline media at pH 10 by sulfur disproportionation in the absence of metals as sulfide scavengers. Our data indicate that polysulfides are the dominant sulfur species under highly alkaline conditions and that they might be disproportionated. Furthermore, we report the first organism (Dt. alkaliphilus) from the class Clostridia that is able to grow by sulfur disproportionation.

Development of an Analytic Method for Sulfur Compounds in Aged Garlic Extract with the Use of a Postcolumn High Performance Liquid Chromatography Method with Sulfur-Specific Detection.

Science.gov (United States)

Matsutomo, Toshiaki; Kodera, Yukihiro

2016-02-01

Garlic and its processed preparations contain numerous sulfur compounds that are difficult to analyze in a single run using HPLC. The aim of this study was to develop a rapid and convenient sulfur-specific HPLC method to analyze sulfur compounds in aged garlic extract (AGE). We modified a conventional postcolumn HPLC method by employing a hexaiodoplatinate reagent. Identification and structural analysis of sulfur compounds were conducted by LC-mass spectrometry (LC-MS) and nuclear magnetic resonance. The production mechanisms of cis-S-1-propenylcysteine (cis-S1PC) and S-allylmercaptocysteine (SAMC) were examined by model reactions. Our method has the following advantages: less interference from nonsulfur compounds, high sensitivity, good correlation coefficients (r > 0.98), and high resolution that can separate >20 sulfur compounds, including several isomers, in garlic preparations in a single run. This method was adapted for LC-MS analysis. We identified cis-S1PC and γ-glutamyl-S-allyl-mercaptocysteine in AGE. The results of model reactions suggest that cis-S1PC is produced from trans-S1PC through an isomerization reaction and that SAMC is produced by a reaction involving S-allylcysteine/S1PC and diallyldisulfide during the aging period. We developed a rapid postcolumn HPLC method for both qualitative and quantitative analyses of sulfur compounds, and this method helped elucidate a potential mechanism of cis-S1PC and SAMC action in AGE. © 2016 American Society for Nutrition.

High-spin states in the A=39 mirror nuclei 39Ca and 39K

International Nuclear Information System (INIS)

Andersson, T.; Rudolph, D.; Fahlander, C.; Eberth, J.; Thomas, H.G.; Haslip, D.; Svensson, C.E.; Waddington, J.C.; LaFosse, D.R.; Sarantites, D.G.; Weintraub, W.; Wilson, J.N.; Brown, B.A.

1999-01-01

High-spin states of the mass A=39 mirror pair 39 K and 39 Ca were investigated via the fusion-evaporation reaction 28 Si+ 16 O at 125 MeV beam energy. The gammasphere array in conjunction with the 4π charged-particle detector array microball and neutron detectors was used to detect γ rays in coincidence with evaporated light particles. The results of the first high-spin study of the T z =-1/2 nucleus 39 Ca are discussed in terms of mirror symmetry and compared to spherical shell-model calculations in the 1d 3/2 -1f 7/2 configuration space. (orig.)

A Li+-conductive microporous carbon–sulfur composite for Li-S batteries

International Nuclear Information System (INIS)

Zhang, Wenhua; Qiao, Dan; Pan, Jiaxin; Cao, Yuliang; Yang, Hanxi; Ai, Xinping

2013-01-01

Highlights: ► A carbon–sulfur composite was prepared by vaporizing sulfur into the nanopores of Li + -conductive carbon microspheres. ► The redox reaction of S 8 molecules embedded in the nanopores of carbon microspheres proceeds through a solid–solid mechanism at the S/C interfaces. ► The carbon–sulfur composite exhibits a stable cycling performance and a superior high coulombic efficiency of 100%. - Abstract: In this paper, we propose a new strategy to develop high performance sulfur electrode by impregnating sulfur into the micropores of a Li + -insertable carbon matrix with the simultaneous use of a carbonate electrolyte, which does not dissolve polysulfides, to restrain the solution of the reaction intermediates of sulfur. To proof this concept, we prepared a Li + -insertable microporous carbon–sulfur composite by vaporizing sulfur into the micropores of the nanofiber-wired carbon microspheres. The experimental results demonstrate that, in the carbonate electrolyte of 1 M LiPF 6 /PC-EC-DEC, such S/C composite electrode exhibits not only stable cycling performance with a reversible capacity of 720 mAh g −1 after 100 cycles, but also superior high coulombic efficiency of ∼100% upon extended cycling (except the first three cycles). The structural and electrochemical analysis indicates that the improved electrochemical behaviors of the S/C composite arise from a new reaction mechanism, in which Li + ions and electrons transport through the carbon matrix into the interior of the cathode and then react with the embedded sulfur in the S/C solid–solid interfaces, avoiding the solution of the intermediates into the bulk electrolyte. More significantly, the structural design and working mechanism of such a sulfur cathode could be extended to a variety of poorly conductive and easily soluble redox-active materials for battery applications.

Analysis of sulfur-iodine thermochemical cycle for solar hydrogen production. Part 1: decomposition of sulfuric acid

Energy Technology Data Exchange (ETDEWEB)

Huang, Cunping; T-Raissi, Ali [Central Florida Univ., Florida Solar Energy Center, Cocoa, FL (United States)

2005-05-01

The sulfur-iodine (S-I) thermochemical water splitting cycle is one of the most studied cycles for hydrogen (H{sub 2}) production. S-I cycle consists of four sections: (I) acid production and separation and oxygen purification, (II) sulfuric acid concentration and decomposition, (III) hydroiodic acid (HI) concentration, and (IV) HI decomposition and H{sub 2} purification. Section II of the cycle is an endothermic reaction driven by the heat input from a high temperature source. Analysis of the S-I cycle in the past thirty years have been focused mostly on the utilization of nuclear power as the high temperature heat source for the sulfuric acid decomposition step. Thermodynamic as well as kinetic considerations indicate that both the extent and rate of sulfuric acid decomposition can be improved at very high temperatures (in excess of 1000 deg C) available only from solar concentrators. The beneficial effect of high temperature solar heat for decomposition of sulfuric acid in the S-I cycle is described in this paper. We used Aspen Technologies' HYSYS chemical process simulator (CPS) to develop flowsheets for sulfuric acid (H{sub 2}SO{sub 4}) decomposition that include all mass and heat balances. Based on the HYSYS analyses, two new process flowsheets were developed. These new sulfuric acid decomposition processes are simpler and more stable than previous processes and yield higher conversion efficiencies for the sulfuric acid decomposition and sulfur dioxide and oxygen formation. (Author)

Nuclear Data Sheets for A=39

Science.gov (United States)

Chen, Jun

2018-03-01

Experimental nuclear structure data from various reactions and decays have been evaluated for all known nuclides of mass 39 (Mg, Al, Si, P, S, Cl, Ar, K, Ca, Sc, Ti). Detailed evaluated nuclear structure information is presented for each reaction and decay and the best values combining all available data are recommended for level energies, half-lives, γ-ray energies and intensities, decay properties (energies, intensities and placement of radiations), and other spectroscopic data. The 39K, 39Ca and 39Ar are the most extensively studied nuclides; no excited states are known in 39Mg and 39Ti. This work supersedes the earlier full evaluation of A=39 by B. Singh and J. Cameron (2006Si02).

34S/32S fractionation in sulfur cycles catalyzed by anaerobic bacteria

Science.gov (United States)

Fry, B.; Gest, H.; Hayes, J. M.

1988-01-01

Stable isotopic distributions in the sulfur cycle were studied with pure and mixed cultures of the anaerobic bacteria, Chlorobium vibrioforme and Desulfovibrio vulgaris. D. vulgaris and C. vibrioforme can catalyze three reactions constituting a complete anaerobic sulfur cycle: reduction of sulfate to sulfide (D. vulgaris), oxidation of sulfide to elemental sulfur (C. vibrioforme), and oxidation of sulfur to sulfate (C. vibrioforme). In all experiments, the first and last reactions favored concentration of the light 32S isotope in products (isotopic fractionation factor epsilon = -7.2 and -1.7%, respectively), whereas oxidation of sulfide favored concentration of the heavy 34S isotope in products (epsilon = +1.7%). Experimental results and model calculations suggest that elemental sulfur enriched in 34S versus sulfide may be a biogeochemical marker for the presence of sulfide-oxidizing bacteria in modern and ancient environments.

Synthesis of l-cysteine derivatives containing stable sulfur isotopes and application of this synthesis to reactive sulfur metabolome.

Science.gov (United States)

Ono, Katsuhiko; Jung, Minkyung; Zhang, Tianli; Tsutsuki, Hiroyasu; Sezaki, Hiroshi; Ihara, Hideshi; Wei, Fan-Yan; Tomizawa, Kazuhito; Akaike, Takaaki; Sawa, Tomohiro

2017-05-01

Cysteine persulfide is an L-cysteine derivative having one additional sulfur atom bound to a cysteinyl thiol group, and it serves as a reactive sulfur species that regulates redox homeostasis in cells. Here, we describe a rapid and efficient method of synthesis of L-cysteine derivatives containing isotopic sulfur atoms and application of this method to a reactive sulfur metabolome. We used bacterial cysteine syntheses to incorporate isotopic sulfur atoms into the sulfhydryl moiety of L-cysteine. We cloned three cysteine synthases-CysE, CysK, and CysM-from the Gram-negative bacterium Salmonella enterica serovar Typhimurium LT2, and we generated their recombinant enzymes. We synthesized 34 S-labeled L-cysteine from O-acetyl-L-serine and 34 S-labeled sodium sulfide as substrates for the CysK or CysM reactions. Isotopic labeling of L-cysteine at both sulfur ( 34 S) and nitrogen ( 15 N) atoms was also achieved by performing enzyme reactions with 15 N-labeled L-serine, acetyl-CoA, and 34 S-labeled sodium sulfide in the presence of CysE and CysK. The present enzyme systems can be applied to syntheses of a series of L-cysteine derivatives including L-cystine, L-cystine persulfide, S-sulfo-L-cysteine, L-cysteine sulfonate, and L-selenocystine. We also prepared 34 S-labeled N-acetyl-L-cysteine (NAC) by incubating 34 S-labeled L-cysteine with acetyl coenzyme A in test tubes. Tandem mass spectrometric identification of low-molecular-weight thiols after monobromobimane derivatization revealed the endogenous occurrence of NAC in the cultured mammalian cells such as HeLa cells and J774.1 cells. Furthermore, we successfully demonstrated, by using 34 S-labeled NAC, metabolic conversion of NAC to glutathione and its persulfide, via intermediate formation of L-cysteine, in the cells. The approach using isotopic sulfur labeling combined with mass spectrometry may thus contribute to greater understanding of reactive sulfur metabolome and redox biology. Copyright © 2017 Elsevier Inc

Vapor phase elemental sulfur amendment for sequestering mercury in contaminated soil

Science.gov (United States)

Looney, Brian B.; Denham, Miles E.; Jackson, Dennis G.

2014-07-08

The process of treating elemental mercury within the soil is provided by introducing into the soil a heated vapor phase of elemental sulfur. As the vapor phase of elemental sulfur cools, sulfur is precipitated within the soil and then reacts with any elemental mercury thereby producing a reaction product that is less hazardous than elemental mercury.

Reaction of (carbonylimido)sulfur(IV) derivatives with TAS-fluoride, (Me2N)3S+Me3SiF2-.

Science.gov (United States)

Lork, E; Viets, D; Mews, R; Oberhammer, H

2000-10-16

In the reaction of TAS-fluoride, (Me2N)3S+Me3SiF2-, with carbonyl sulfur difluoride imides RC(O)NSF2 (R = F, CF3), C-N bond, cleavage is observed, and TAS+RC(O)F2- and NSF are the final products. From TASF and RC(O)NS(CF3)F, the salts TAS+RC(O)NS(CF3)F2- (R = F (14), CF3 (15)), with psi-pentacoordinate sulfur centers in the anions, are formed. An X-ray structure investigation of 14 shows that the fluorine atoms occupy axial positions and CF3, NC(O)F, and the sulfur lone pair occupy equatorial positions of the trigonal bipyramid. The -C(O)F group lies in the equatorial plane with the CO bond synperiplanar to the SN bond. According to B3LYP calculations, this structure corresponds to a global minimum and the expected axial orientation of the -C(O)F group represents a transition state. Calculations for the unstable FC(O)NSF3- anion show a different geometry. The -C(O)F group deviates 40 degrees from axial orientation, and the equatorially bonded fluorine is, in contrast to the -CF3 group in 14, syn positioned.

Extraction of sulfuric acid with TOPO

International Nuclear Information System (INIS)

Shuyun, Xue; Yonghui, Yang; Yanzhao, Yang; Sixiu, Sun; Borong, Bao

1998-01-01

A study on solvent extraction of sulfuric acid by tri-octylphosphine oxide (TOPO) in n-heptane has been made. Extraction coefficients of H 2 SO 4 as a function of H 2 SO 4 concentration in aqueous phase, and extractant concentrations in organic phase have been studied. The composition of extracted species, equilibrium constants of extraction reaction have been evaluated. These results are important for interpreting extraction equilibrium data of uranium(VI) or other metal ions with TOPO in sulfuric acid media. (author)

Sulfur deactivation of fatty ester hydrogenolysis catalysts

Energy Technology Data Exchange (ETDEWEB)

Brands, D.S.; U-A-Sai, G.; Poels, E.K.; Bliek, A. [Univ. of Amsterdam (Netherlands). Dept. of Chemical Engineering

1999-08-15

Trace organosulfur compounds present as natural impurities in oleochemical feedstocks may lead to activation of copper-containing catalysts applied for hydrogenolysis of esters toward fatty alcohols. In this paper, the sulfur deactivation of Cu/SiO{sub 2} and Cu/ZnO/SiO{sub 2} catalysts was studied in the liquid-phase hydrogenolysis of methyl palmitate. The rate of deactivation is fast and increases as a function of the sulfur-containing compound present: octadecanethiol {approx} dihexadecyl disulfide < benzyl isothiocyanate < methyl p-toluene sulfonate < dihexadecyl sulfide < dibenzothiophene. The rapid deactivation is caused by the fact that sulfur is quantitatively removed from the reaction mixture and because mainly surface sulfides are formed under hydrogenolysis conditions. The life time of a zinc-promoted catalyst is up to two times higher than that of the Cu/SiO{sub 2} catalyst, most likely due to zinc surface sulfide formation. The maximum sulfur coverage obtained after full catalyst deactivation with dibenzothiophene and dihexadecyl sulfide--the sulfur compounds that cause the fastest deactivation--may be as low as 0.07. This is due to the fact that decomposition of these compounds as well as the hydrogenolysis reaction itself proceeds on ensembles of copper atoms. Catalyst regeneration studies reveal that activity cannot be regained by reduction or combined oxidation/reduction treatments. XRD, TPR, and TPO results confirm that no distinct bulk copper or zinc sulfide or sulfate phases are present.

The effects of retrograde reactions and of diffusion on 39Ar-40Ar ages of micas

DEFF Research Database (Denmark)

Allaz, Julien; Engi, Martin; Berger, Alfons

2011-01-01

Effects of metamorphic reactions occurring during decompression were explored to understand their influence on 39Ar-40Ar ages of micas. Monometamorphic metasediments from the Lepontine Alps (Switzerland) were studied. Collected samples reached lower amphibolite facies during the Barrovian....... XRD-data indicated that some mineral separates prepared for Ar-Ar stepwise heating analysis were monomineralic, whereas others were composed of two white micas (muscovite with paragonite or margarite), or biotite and chlorite. In monomineralic samples 37Ar/39Ar and 38Ar/39Ar (proportional to Ca....../K and Cl/K ratios) did not change and the resulting ages can be interpreted unambiguously. In mineral separates containing two white micas, Ca/K and Cl/K ratios were variable, reflecting non-simultaneous laboratory degassing of the two heterochemical Ar-reservoirs. These ratios were used to identify each...

Nitrogen-doped graphene nanosheets/sulfur composite as lithium–sulfur batteries cathode

Energy Technology Data Exchange (ETDEWEB)

Hao, Yong [Department of Mechanical and Materials Engineering, Florida International University, 10555 W. Flagler Street, Miami, FL 33174 (United States); Li, Xifei; Sun, Xueliang [Nanomaterials and Energy Lab, Department of Mechanical and Materials Engineering, Western University, London, Ontario N6A 5B9 (Canada); Energy and Materials Engineering Centre, College of Physics and Materials Science, Tianjin Normal University, Tianjin 300387 (China); Wang, Chunlei, E-mail: wangc@fiu.edu [Department of Mechanical and Materials Engineering, Florida International University, 10555 W. Flagler Street, Miami, FL 33174 (United States)

2016-11-15

Highlights: • NGNSs are synthesized with amino-N and pyridine-N-oxide groups. • NGNSs provide a matrix with high surface area and conductivity. • N groups facilitate immobilization of polysulfides for Li–S batteries. - Abstract: Lithium–sulfur batteries have been receiving unprecedented attentions in recent years due to their exceptional high theoretical capacity and energy density, low cost and environmental friendliness. Yet their practical applications are still hindered by short cycle life, low efficiency and poor conductivity which are mainly caused by the insulating nature of sulfur and dissolution of polysulfides. Here, a nitrogen-doped graphene nanosheets/sulfur (NGNSs/S) composite was synthesized via a facile chemical reaction deposition. In this composite, NGNSs was employed as a conductive host to entrap S/polysulfides in the cathode part. The NGNSs/S composite delivered an initial discharge capacity of 856.7 mAh g{sup −1} and a reversible capacity of 319.3 mAh g{sup −1} at 0.1 C with good recoverable rate capability.

Two-step rapid sulfur capture. Final report

Energy Technology Data Exchange (ETDEWEB)

NONE

1994-04-01

The primary goal of this program was to test the technical and economic feasibility of a novel dry sorbent injection process called the Two-Step Rapid Sulfur Capture process for several advanced coal utilization systems. The Two-Step Rapid Sulfur Capture process consists of limestone activation in a high temperature auxiliary burner for short times followed by sorbent quenching in a lower temperature sulfur containing coal combustion gas. The Two-Step Rapid Sulfur Capture process is based on the Non-Equilibrium Sulfur Capture process developed by the Energy Technology Office of Textron Defense Systems (ETO/TDS). Based on the Non-Equilibrium Sulfur Capture studies the range of conditions for optimum sorbent activation were thought to be: activation temperature > 2,200 K for activation times in the range of 10--30 ms. Therefore, the aim of the Two-Step process is to create a very active sorbent (under conditions similar to the bomb reactor) and complete the sulfur reaction under thermodynamically favorable conditions. A flow facility was designed and assembled to simulate the temperature, time, stoichiometry, and sulfur gas concentration prevalent in the advanced coal utilization systems such as gasifiers, fluidized bed combustors, mixed-metal oxide desulfurization systems, diesel engines, and gas turbines.

Electrochemical reduction of sulfur dioxide in sulfolane

Energy Technology Data Exchange (ETDEWEB)

Vorob' ev, A.S.; Gavrilova, A.A.; Kolosnitsyn, V.S.; Nikitin, Yu.E.

1985-09-01

Solutions of sulfur dioxide in aproptic media are promising electrolyte oxidizing agents for chemical current sources with anodes of active metals. This work describes the electrochemical reduction of sulfur dioxide in sulfolane in a lithium halide supporting electrolyte which was investigated by the methods of voltamperometry and chronopotentiometry. The dependence of the current of the cathodic peak on the concentration of the supporting electrolyte salts, sulfur dioxide and water, was studied. On the basis of the data obtained, a hypothesis was advanced on the nature of the limiting step. The investigation showed that at low polarizing current densities, a substantial influence on the reduction of sulfur dioxide in sulfolane in a lithium halide supporting electrolyte is exerted by blockage of the electrode surface by sparingly soluble reaction products.

SULFUR POLYMER ENCAPSULATION

International Nuclear Information System (INIS)

KALB, P.

2001-01-01

recommended for treatment of wastes containing high concentrations of nitrates because of potentially dangerous reactions between sulfur, nitrate, and trace quantities of organics. Recently, the process has been adapted for the treatment of liquid elemental mercury and mercury contaminated soil and debris

Non-mass-dependent fractionation of sulfur and oxygen isotopes during UV photolysis of sulfur dioxide

Science.gov (United States)

Pen, Aranh

Since the discovery of anomalous sulfur isotope abundance in the geological record in sulfate and sulfide minerals (Farquhar et al., 2000), much effort has been put into understanding their origin to provide new insights into the environmental conditions on the early Earth (Farquhar et al., 2001; Pavlov and Kasting, 2002; Ono et al., 2003; Zahnle et al., 2006; Farquhar et al., 2007; Lyons, 2007; Lyons, 2008). This discovery gained immense interest because of its implications for both the lack of oxygen in the atmosphere during the Archean era 2.5-3.8 Gya (billion years ago), and for rise of oxygen, or the "Great Oxidation Event", that occurred 2.2-2.4 Gya (Holland, 2002). These signatures are believed to be produced in an anticorrelation to oxygen abundance in the early atmosphere, which will aid in quantifying the rate of oxygenation during the "Great Oxidation Event". According to Farquhar et al. (2000), the non-mass-dependent (NMD), or anomalous, fractionation signatures were produced by photochemical reactions of volcanic sulfur species in Earth's early atmosphere (> 2.3 Gya) due to the lack of an oxygen and ozone shield, resulting in an atmosphere transparent to solar ultraviolet (UV) radiation (Farquhar et al., 2001). Interpretation of the anomalous rock records, though, depends on the identification of (1) chemical reactions that can produce the NMD signature (Farquhar and Wing, 2003); and (2) conditions necessary for conversion of the gas-phase products into solid minerals (Pavlov and Kasting, 2002). The focus of my research addresses the first step, which is to determine whether the chemical reactions that occurred in Earth's early atmosphere, resulting in NMD fractionation of sulfur isotopes, were due to broadband UV photochemistry, and to test isotopic self-shielding as the possible underlying mechanism. In this project, our goals were to test isotopic self-shielding during UV photolysis as a possible underlying mechanism for anomalous sulfur isotopic

Process for removal of sulfur oxides from hot gases

International Nuclear Information System (INIS)

Bauerle, G. L.; Kohl, A. L.

1984-01-01

A process for the removal of sulfur oxides from two gas streams containing the same. One gas stream is introduced into a spray dryer zone and contacted with a finely dispersed spray of an aqueous medium containing an absorbent for sulfur oxides. The aqueous medium is introduced at a controlled rate so as to provide water to the gas in an amount to produce a cooled product gas having a temperature at least 7 0 C. above its adiabatic saturation temperature and from about 125-300% of the stoichiometric amount of absorbent required to react with the sulfur oxides to be removed from the gas stream. The effluent from the spray dryer zone comprises a gas stream of reduced sulfur oxide content and contains entrained dry particulate reaction products including unreacted absorbent. This gas stream is then introduced into a particulate removal zone from which is withdrawn a gas stream substantially free of particles and having a reduced sulfur oxide content. the dry particulate reaction products are collected and utilized as a source of absorbent for a second aqueous scrubbing medium containing unreacted absorbent for the sulfur oxides. An effluent gas stream is withdrawn from the aqueous scrubbing zone and comprises a water-saturated gas stream of reduced sulfur oxide content and substantially free of particles. The effluent gas streams from the particulate removal zone and the aqueous scrubbing zone are combined in such proportions that the combined gas stream has a temperature above its adiabatic saturation temperature

Sulfur-doped porous reduced graphene oxide hollow nanosphere frameworks as metal-free electrocatalysts for oxygen reduction reaction and as supercapacitor electrode materials.

Science.gov (United States)

Chen, Xi'an; Chen, Xiaohua; Xu, Xin; Yang, Zhi; Liu, Zheng; Zhang, Lijie; Xu, Xiangju; Chen, Ying; Huang, Shaoming

2014-11-21

Chemical doping with foreign atoms is an effective approach to significantly enhance the electrochemical performance of the carbon materials. Herein, sulfur-doped three-dimensional (3D) porous reduced graphene oxide (RGO) hollow nanosphere frameworks (S-PGHS) are fabricated by directly annealing graphene oxide (GO)-encapsulated amino-modified SiO2 nanoparticles with dibenzyl disulfide (DBDS), followed by hydrofluoric acid etching. The XPS and Raman spectra confirmed that sulfur atoms were successfully introduced into the PGHS framework via covalent bonds. The as-prepared S-PGHS has been demonstrated to be an efficient metal-free electrocatalyst for oxygen reduction reaction (ORR) with the activity comparable to that of commercial Pt/C (40%) and much better methanol tolerance and durability, and to be a supercapacitor electrode material with a high specific capacitance of 343 F g(-1), good rate capability and excellent cycling stability in aqueous electrolytes. The impressive performance for ORR and supercapacitors is believed to be due to the synergistic effect caused by sulfur-doping enhancing the electrochemical activity and 3D porous hollow nanosphere framework structures facilitating ion diffusion and electronic transfer.

Quantitative analysis of sulfur forms of coal and the pyrolysis behavior of sulfur compounds; Sekitanchu no io kagobutsu no keitaibetsu gan`yuryo no teiryo to sono netsubunkai kyodo

Energy Technology Data Exchange (ETDEWEB)

Mae, K.; Miura, K.; Shimada, M. [Kyoto University, Kyoto (Japan). Faculty of Engineering

1996-10-28

As part of the studies on coal utilization basics, considerations were given on quantification of sulfur forms of coal and the pyrolysis behavior of sulfur compounds. With the temperature raising oxidation method, a thermo-balance was connected directly to a mass analyzer, and the coal temperature was raised at a rate of 5{degree}C per minute and gasified. Peak division was performed on SO2 and COS production to derive sulfur forms of coal. Using the slow-speed pyrolysis method, production rates of H2S, COS, SO2 and mercaptans were measured at a temperature raising rate of 20{degree}C per minute. Sulfur content in char was also measured. With the quick pyrolysis method, a Curie point pyrolyzer was connected directly to a gas chromatograph, by which secondary reaction is suppressed, and initial pyrolytic behavior can be tracked. All kinds of coals produce a considerable amount of SO2 in the slow-speed pyrolysis, but very little in the quick pyrolysis. Instead, H2S and mercaptans are produced. Sulfur compound producing mechanisms vary depending on the temperature raising rates. By using a parallel primary reaction model, analysis was made on reactions of H2S production based on different activation energies, such as those generated from pyrite decomposition and organic sulfur decomposition. The analytic result agreed also with that from the temperature raising oxidation method. 4 refs., 6 figs., 1 tab.

Anode Improvement in Rechargeable Lithium-Sulfur Batteries.

Science.gov (United States)

Tao, Tao; Lu, Shengguo; Fan, Ye; Lei, Weiwei; Huang, Shaoming; Chen, Ying

2017-12-01

Owing to their theoretical energy density of 2600 Wh kg -1 , lithium-sulfur batteries represent a promising future energy storage device to power electric vehicles. However, the practical applications of lithium-sulfur batteries suffer from poor cycle life and low Coulombic efficiency, which is attributed, in part, to the polysulfide shuttle and Li dendrite formation. Suppressing Li dendrite growth, blocking the unfavorable reaction between soluble polysulfides and Li, and improving the safety of Li-S batteries have become very important for the development of high-performance lithium sulfur batteries. A comprehensive review of various strategies is presented for enhancing the stability of the anode of lithium sulfur batteries, including inserting an interlayer, modifying the separator and electrolytes, employing artificial protection layers, and alternative anodes to replace the Li metal anode. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Powering Lithium-Sulfur Battery Performance by Propelling Polysulfide Redox at Sulfiphilic Hosts.

Science.gov (United States)

Yuan, Zhe; Peng, Hong-Jie; Hou, Ting-Zheng; Huang, Jia-Qi; Chen, Cheng-Meng; Wang, Dai-Wei; Cheng, Xin-Bing; Wei, Fei; Zhang, Qiang

2016-01-13

Lithium-sulfur (Li-S) battery system is endowed with tremendous energy density, resulting from the complex sulfur electrochemistry involving multielectron redox reactions and phase transformations. Originated from the slow redox kinetics of polysulfide intermediates, the flood of polysulfides in the batteries during cycling induced low sulfur utilization, severe polarization, low energy efficiency, deteriorated polysulfide shuttle, and short cycling life. Herein, sulfiphilic cobalt disulfide (CoS2) was incorporated into carbon/sulfur cathodes, introducing strong interaction between lithium polysulfides and CoS2 under working conditions. The interfaces between CoS2 and electrolyte served as strong adsorption and activation sites for polar polysulfides and therefore accelerated redox reactions of polysulfides. The high polysulfide reactivity not only guaranteed effective polarization mitigation and promoted energy efficiency by 10% but also promised high discharge capacity and stable cycling performance during 2000 cycles. A slow capacity decay rate of 0.034%/cycle at 2.0 C and a high initial capacity of 1368 mAh g(-1) at 0.5 C were achieved. Since the propelling redox reaction is not limited to Li-S system, we foresee the reported strategy herein can be applied in other high-power devices through the systems with controllable redox reactions.

Sulfur Based Thermochemical Heat Storage for Baseload Concentrated Solar Power Generation

Energy Technology Data Exchange (ETDEWEB)

Wong, Bunsen [General Atomics, San Diego, CA (United States)

2014-11-01

This project investigates the engineering and economic feasibility of supplying baseload power using a concentrating solar power (CSP) plant integrated with sulfur based thermochemical heat storage. The technology stores high temperature solar heat in the chemical bonds of elemental sulfur. Energy is recovered as high temperature heat upon sulfur combustion. Extensive developmental and design work associated with sulfur dioxide (SO₂) disproportionation and sulfuric acid (H₂SO₄) decomposition chemical reactions used in this technology had been carried out in the two completed phases of this project. The feasibility and economics of the proposed concept was demonstrated and determined.

Vulcanization Kinetics of Natural Rubber Based On Free Sulfur Determination

Directory of Open Access Journals (Sweden)

Abu Hasan

2013-05-01

Full Text Available The determination of free sulfur in the rubber vulcanizates provided significant representation of vulcanization reaction. In this research, the effects of vulcanization temperature, the mixing method of carbon black into rubber, the ingredients mixing sequence and the type of carbon black were studied on masticated and milled natural rubber in which the reaction was observed by un-reacted sulfur determination. The results showed that higher vulcanization temperature provided faster vulcanization reaction and greater reaction rate constant. Similarly, the mixing sequence of ingredient and carbon black into rubber influenced the rate of vulcanization reaction. The subsequent ingredients mixing sequence, in this case, resulted in higher vulcanization rate compared to that of the simultaneous one. However, the mixing method of carbon black into rubber brought small effect on the rate of vulcanization reaction. The type of carbon black applied was observed to influence the reaction rate of vulcanization. Smaller particle sizes of carbon black gave larger reaction rate constant. In this case, the type of carbon black N 330 gave faster vulcanization rate than that of N 660.

Surface structure-dependent pyrite oxidation in relatively dry and moist air: Implications for the reaction mechanism and sulfur evolution

Science.gov (United States)

Zhu, Jianxi; Xian, Haiyang; Lin, Xiaoju; Tang, Hongmei; Du, Runxiang; Yang, Yiping; Zhu, Runliang; Liang, Xiaoliang; Wei, Jingming; Teng, H. Henry; He, Hongping

2018-05-01

Pyrite oxidation not only is environmentally significant in the formation of acid mine (or acid rock) drainage and oxidative acidification of lacustrine sediment but also is a critical stage in geochemical sulfur evolution. The oxidation process is always controlled by the reactivity of pyrite, which in turn is controlled by its surface structure. In this study, the oxidation behavior of naturally existing {1 0 0}, {1 1 1}, and {2 1 0} facets of pyrite was investigated using a comprehensive approach combining X-ray photoelectron spectroscopy, diffuse reflectance Fourier transform infrared spectroscopy, and time-of-flight secondary-ion mass spectrometry with periodic density functional theoretical (DFT) calculations. The experimental results show that (i) the initial oxidation rates of both pyrite {1 1 1} and {2 1 0} are much greater than that of pyrite {1 0 0}; (ii) the initial oxidation rate of pyrite {2 1 0} is greater than that of pyrite {1 1 1} in low relative humidity, which is reversed in high relative humidity; and (iii) inner sphere oxygen-bearing sulfur species are originally generated from surface reactions and then converted to outer sphere species. The facet dependent rate law can be expressed as: r{hkl} =k{hkl}haP0.5(t + 1) - 0.5 , where r{hkl} is the orientation dependent reaction rate, k{hkl} is the orientation dependent rate constant, h is the relative humidity, P is the oxygen partial pressure, and t is the oxidation time in seconds. {1 1 1} is the most sensitive facet for pyrite oxidation. Combined with DFT theoretical investigations, water catalyzed electron transfer is speculated as the rate-limiting step. These findings disclose the structure-reactivity dependence of pyrite, which not only presents new insight into the mechanism of pyrite oxidation but also provides fundamental data to evaluate sulfur speciation evolution, suggesting that the surface structure sensitivity should be considered to estimate the reactivity at the mineral

Physiology and genetics of sulfur-oxidizing bacteria.

Science.gov (United States)

Friedrich, C G

1998-01-01

Reduced inorganic sulfur compounds are oxidized by members of the domains Archaea and Bacteria. These compounds are used as electron donors for anaerobic phototrophic and aerobic chemotrophic growth, and are mostly oxidized to sulfate. Different enzymes mediate the conversion of various reduced sulfur compounds. Their physiological function in sulfur oxidation is considered (i) mostly from the biochemical characterization of the enzymatic reaction, (ii) rarely from the regulation of their formation, and (iii) only in a few cases from the mutational gene inactivation and characterization of the resulting mutant phenotype. In this review the sulfur-metabolizing reactions of selected phototrophic and of chemotrophic prokaryotes are discussed. These comprise an archaeon, a cyanobacterium, green sulfur bacteria, and selected phototrophic and chemotrophic proteobacteria. The genetic systems are summarized which are presently available for these organisms, and which can be used to study the molecular basis of their dissimilatory sulfur metabolism. Two groups of thiobacteria can be distinguished: those able to grow with tetrathionate and other reduced sulfur compounds, and those unable to do so. This distinction can be made irrespective of their phototrophic or chemotrophic metabolism, neutrophilic or acidophilic nature, and may indicate a mechanism different from that of thiosulfate oxidation. However, the core enzyme for tetrathionate oxidation has not been identified so far. Several phototrophic bacteria utilize hydrogen sulfide, which is considered to be oxidized by flavocytochrome c owing to its in vitro activity. However, the function of flavocytochrome c in vivo may be different, because it is missing in other hydrogen sulfide-oxidizing bacteria, but is present in most thiosulfate-oxidizing bacteria. A possible function of flavocytochrome c is discussed based on biophysical studies, and the identification of a flavocytochrome in the operon encoding enzymes involved

Analysis of a Mathematical Model of Lithium-Sulfur Cells Part III: Electrochemical Reaction Kinetics, Transport Properties and Charging

International Nuclear Information System (INIS)

Ghaznavi, Mahmoudreza; Chen, P.

2014-01-01

Highlights: • The discharge behavior of Li-S cells in wide range of exchange current densities of electrochemical reactions is studied. • Among all reduction reactions, 1/2 S 8(l) +e − ⇌1/2 S 8 2− and 1/2 S 2 2− +e − ⇌2S 2− play the most important role in capacity performance. • Low diffusion increases the precipitation of polysulfides in separator which may block the anode surface. • Large solubility of Li 2 S is needed for the model to be able to simulate the charging process. - Abstract: Sensitivity analysis of a mathematical model of a lithium-sulfur (Li-S) battery was performed by investigating the response of the model to variation of the exchange current densities, diffusion coefficients, and cathode thickness over a wide range; the results of the analysis were used to explain the some aspects of the behavior of the system which may be seen in experiments. In particular, among all the exchange current densities, the exchange current density of the elemental sulfur reduction has the most significant effect on the discharge capacity of the cell. The variation of the diffusion coefficients was also analyzed, providing information on the non-uniformity of precipitants in the cell after discharge. An optimum cathode thickness was presented to gain the highest capacity of the cell. Finally, the simulation of charging was studied, showing that the model needs a large solubility product of di-lithium sulfide to be able to simulate the charge process of a cell

Preparation and enhanced electrochemical properties of nano-sulfur/poly(pyrrole-co-aniline) cathode material for lithium/sulfur batteries

International Nuclear Information System (INIS)

Qiu Linlin; Zhang Shichao; Zhang Lan; Sun, Mingming; Wang Weikun

2010-01-01

Poly(pyrrole-co-aniline) (PPyA) copolymer nanofibers were prepared by chemical oxidation method with cetyltrimethyl ammonium chloride (CTAC) as template, and the nano-sulfur/poly(pyrrole-co-aniline) (S/PPyA) composite material in lithium batteries was achieved via co-heating the mixture of PPyA and sublimed sulfur at 160 deg. C for 24 h. The component and structure of the materials were characterized by FTIR, Raman, XRD, and SEM. PPyA with nanofiber network structure was employed as a conductive matrix, adsorbing agent and firm reaction chamber for the sulfur cathode materials. The nano-dispersed composite exhibited a specific capacity up to 1285 mAh g -1 in the initial cycle and remained 866 mAh g -1 after 40 cycles.

Effects of compatibility of polymer binders with solvate ionic liquid electrolytes on discharge and charge reactions of lithium-sulfur batteries

Science.gov (United States)

Nakazawa, Toshitada; Ikoma, Ai; Kido, Ryosuke; Ueno, Kazuhide; Dokko, Kaoru; Watanabe, Masayoshi

2016-03-01

Electrochemical reactions in Li-S cells with a solvate ionic liquid (SIL) electrolyte composed of tetraglyme (G4) and Li[TFSA] (TFSA: bis(trifluoromethanesulfonyl)amide) are studied. The sulfur cathode (S cathode) comprises sulfur, carbon powder, and a polymer binder. Poly(ethylene oxide) (PEO) and poly(vinyl alcohol) (PVA-x) with different degrees of saponification (x%) are used as binders to prepare the composite cathodes. For the Li-S cell containing PEO binder, lithium polysulfides (Li2Sm, 2 ≤ m ≤ 8), reaction intermediates of the S cathode, dissolve into the electrolyte, and Li2Sm acts as a redox shuttle in the Li-S cell. In contrast, in the Li-S cell with PVA-x binder, the dissolution of Li2Sm is suppressed, leading to high columbic efficiencies during charge-discharge cycles. The compatibility of the PVA-x binder with the SIL electrolyte changes depending on the degree of saponification. Decreasing the degree of saponification leads to increased electrolyte uptake by the PVA-x binder, increasing the charge and discharge capacities of Li-S cell. The rate capability of Li-S cell is also enhanced by the partial swelling of the PVA-x binder. The enhanced performance of Li-S cell containing PVA-x is attributed to the lowering of resistance of Li+ ion transport in the composite cathode.

New treating processes for sulfur-containing natural gases

Energy Technology Data Exchange (ETDEWEB)

Kislenko, N.; Aphanasiev, A.; Nabokov, S.; Ismailova, H. [VNIIGAS, Moscow (Russian Federation)

1996-12-31

The traditional method of removing H{sub 2}S from sour natural gases is first to treat the gas with a solvent and then to recover the H{sub 2}S from the sour stream in a Claus plant. This method recovers up to 97% of the sulfur when a three-stage Claus unit is employed. Amine/Claus units have operating difficulties for small sulfur capacities (up to 5 tons/day) because the operation of the fired equipment (reaction furnace) is much more difficult. Therefore, for small scale sulfur recovery plants redox processes which exhibit a significant reduction in investment and operating costs are normally used. Many different factors influence the choice of gas desulfurization technology--composition and gas flow, environmental sulfur recovery requirements and CO{sub 2}/H{sub 2}S ratio.

Reduced graphene oxide encapsulated sulfur spheres for the lithium-sulfur battery cathode

Directory of Open Access Journals (Sweden)

Feiyan Liu

Full Text Available Reduced graphene oxide (rGO encapsulated sulfur spheres for the Li-S batteries were prepared via the redox reaction between sodium polysulfide. XRD spectra showed that the diffraction peak of graphite oxide (GO at 10° disappeared, while the relatively weak diffraction peak at 27° belongs to graphene emerged. FT-IR spectra showed that the vibrations of the functional groups of GO, such as 3603 cm−1, 1723 cm−1and 1619 cm−1 which contributed from OH, COC and CO respectively, disappeared when compared to the spectra of GSC. SEM observations indicated that the optimum experimental condition followed as: mass ratio of GO and S was 1:1, 10% NaOH was used to adjust the pH. EDX analysis showed that the sulfur content reached at 68.8% of the composite material. The resultant electric resistance was nearly less than GO’s resistance in three orders of magnitude under same condition. Further electrochemical performance tests showed a coulombic efficiency was 96% from the first cycle capacity was 827 mAh g−1, to 388 mAh g−1 in the 100 cycles. This study carries substantial significance to the development of Li-S battery cathode materials. Keywords: Lithium-sulfur battery, Graphene, Sulfur spheres, Cathode material

Particle spectra and correlations in sulfur-nucleus reactions at 200 GeV per nucleon

International Nuclear Information System (INIS)

Alber, T.

1995-08-01

In this work the production of negatively charged particles and two-particle correlations in nucleus-nucleus reactions at high energies are studied. The range of the acceptance of experiment NA35 at the CERN-SPS was increased in 1990 by adding a large volume Time Projection Chamber downstream of the streamer chamber. The analysis of the data taken during the run period 1991 shows that such a detector faces no basic problems when operated in a high multiplicity experiment. The scenario of particle production in sulfur-nucleus reactions is studied via the measurement of rapidity and transverse momentum distributions which show good agreement with the results from other data-sets of the same experiment. The width of the rapidity distribution is only a little narrower than observed in nucleon-nucleon collisions and is in contradiction to the assumption of a static source with isotropic particle emission. The shape of the transverse momentum distribution indicates an effective temperature at freeze-out of about 150 MeV. The analysis of the two-particle correlation benefits particularly from the high statistics collected for different reactions in different phase-space regions. This allows a differential analysis of the correlation function for the different components of the momentum difference in various regions of rapidity and transverse momentum. It is recalled that for an expanding source the experimentally obtained radius parameters are not a direct measure of the geometrical size of the source but measure a so-called region of homogeneity. This expectation is also confirmed by a microscopic simulation of the reaction. The experimental results for the radius parameters support such a description of the particle production mechanism in terms of an expanding source. (orig.)

Sulfur Isotope Exchange between S-35 Labeled Inorganic Sulfur-Compounds in Anoxic Marine-Sediments

DEFF Research Database (Denmark)

FOSSING, H.; THODEANDERSEN, S.; JØRGENSEN, BB

1992-01-01

Isotope exchange reactions between S-35-labeled sulfur compounds were studied in anoxic estuarine sediment slurries at 21-degrees-C and pH 7.4-7.7. Two experiments labeled with radioactive elemental sulfur (S-35-degrees) and one labeled with radioactive sulfate ((SO42-)-S-35) were performed as time......% of the total S-35 was recovered in the SIGMA-HS- pool in less than 1.5 h. With no detectable SIGMA-HS- (less than 1-mu-M) in the slurry, 58% of the total S-35 was observed in the pyrite pool within 1.5 h. The FeS pool received up to 31% of all S-35 added. The rapid S-35 incorporation from S-35-degrees...... into SIGMA-HS- and FeS pools was explained by isotope exchange reactions. In contrast, there was evidence that the radioactivity observed in the 'pyrite pool' was caused by adhesion of the added S-35-degrees to the FeS2 grains. In all S-35-degrees-labeled experiments we also observed oxidation...

Comparative analysis of the mechanisms of sulfur anion oxidation and reduction by dsr operon to maintain environmental sulfur balance.

Science.gov (United States)

Ghosh, Semanti; Bagchi, Angshuman

2015-12-01

Sulfur metabolism is one of the oldest known redox geochemical cycles in our atmosphere. These redox processes utilize different sulfur anions and the reactions are performed by the gene products of dsr operon from phylogenetically diverse sets of microorganisms. The operon is involved in the maintenance of environmental sulfur balance. Interestingly, the dsr operon is found to be present in both sulfur anion oxidizing and reducing microorganisms and in both types of organisms DsrAB protein complex plays a vital role. Though there are various reports regarding the genetics of dsr operon there are practically no reports dealing with the structural aspects of sulfur metabolism by dsr operon. In our present study, we tried to compare the mechanisms of sulfur anion oxidation and reduction by Allochromatium vinosum and Desulfovibrio vulgaris respectively through DsrAB protein complex. We analyzed the modes of bindings of sulfur anions to the DsrAB protein complex and observed that for sulfur anion oxidizers, sulfide and thiosulfate are the best substrates whereas for reducers sulfate and sulfite have the best binding abilities. We analyzed the binding interaction pattern of the DsrA and DsrB proteins while forming the DsrAB protein complexes in Desulfovibrio vulgaris and Allochromatium vinosum. To our knowledge this is the first report that analyzes the differences in binding patterns of sulfur substrates with DsrAB protein from these two microorganisms. This study would therefore be essential to predict the biochemical mechanism of sulfur anion oxidation and reduction by these two microorganisms i.e., Desulfovibrio vulgaris (sulfur anion reducer) and Allochromatium vinosum (sulfur anion oxidizer). Our observations also highlight the mechanism of sulfur geochemical cycle which has important implications in future study of sulfur metabolism as it has a huge application in waste remediation and production of industrial bio-products viz. vitamins, bio-polyesters and bio

Kinetics of uncatalyzed thermochemical sulfate reduction by sulfur-free paraffin

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Zhang, Tongwei; Ellis, Geoffrey S.; Ma, Qisheng; Amrani, Alon; Tang, Yongchun

2012-01-01

To determine kinetic parameters of sulfate reduction by hydrocarbons (HC) without the initial presence of low valence sulfur, we carried out a series of isothermal gold-tube hydrous-pyrolysis experiments at 320, 340, and 360 °C under a constant confined pressure of 24.1 MPa. The reactants used consisted of saturated HC (sulfur-free) and CaSO4 in an aqueous solution buffered to three different pH conditions without the addition of elemental sulfur (S8) or H2S as initiators. H2S produced in the course of reaction was proportional to the extent of the reduction of CaSO4 that was initially the only sulfur-containing reactant. Our results show that the in situ pH of the aqueous solution (herein, in situ pH refers to the calculated pH value of the aqueous solution at certain experimental conditions) can significantly affect the rate of the thermochemical sulfate reduction (TSR) reaction. A substantial increase in the TSR reaction rate was observed with a decrease in the in situ pH. Our experimental results show that uncatalyzed TSR is a first-order reaction. The temperature dependence of experimentally measured H2S yields from sulfate reduction was fit with the Arrhenius equation. The determined activation energy for HC (sulfur-free) reacting with View the MathML sourceHSO4− in our experiments is 246.6 kJ/mol at pH values ranging from 3.0 to 3.5, which is slightly higher than the theoretical value of 227.0 kJ/mol using ab initio quantum chemical calculations on a similar reaction. Although the availability of reactive sulfate significantly affects the rate of reaction, a consistent rate constant was determined by accounting for the HSO4− ion concentration. Our experimental and theoretical approach to the determination of the kinetics of TSR is further validated by a reevaluation of several published experimental TSR datasets without the initial presence of native sulfur or H2S. When the effect of reactive sulfate concentration is appropriately accounted for, the

Investigation of the impact of the $^{39}$Ar(n , $\\alpha)^{36}$S reaction on the nucleosynthesis of the rare isotope $^{36}$S

CERN Multimedia

Geltenbort, P

2002-01-01

The origin of the rare, neutron rich isotope $^{36}$S remains a debated question. One of the key reactions in the s-process nucleosynthesis network leading to $^{36}$S is $^{39}$Ar(n , $\\alpha) ^{36}\\!$S. This reaction has never been studied so far, which is due to the fact that $^{39}$Ar is a radioactive (T$_{1/2}$ = 269 y) gas, which is not commercially available. During a three days experimental campaign, an optimized $^{39}$Ar sample was prepared at ISOLDE. A dedicated titaniumoxide target (8 g/cm$^{2}$) was bombarded with 1 GeV protons from the PS Booster. In order to obtain a pure argon beam, a water-cooled transfer line was used to freeze-out less volatile isobars before they can reach the ion source. Adding stable argon with a calibrated leak to the ion source enabled to determine the ionization efficiency (3.5%). For the isotope separation, the low-mass side (GLM) of the General Purpose Separator was used. After magnetic separation, $^{39}$Ar ions (1+) were implanted at 60 keV in a 12 mm thick alumin...

Room-Temperature, Ambient-Pressure Chemical Synthesis of Amine-Functionalized Hierarchical Carbon-Sulfur Composites for Lithium-Sulfur Battery Cathodes.

Science.gov (United States)

Chae, Changju; Kim, Jinmin; Kim, Ju Young; Ji, Seulgi; Lee, Sun Sook; Kang, Yongku; Choi, Youngmin; Suk, Jungdon; Jeong, Sunho

2018-02-07

Recently, the achievement of newly designed carbon-sulfur composite materials has attracted a tremendous amount of attention as high-performance cathode materials for lithium-sulfur batteries. To date, sulfur materials have been generally synthesized by a sublimation technique in sealed containers. This is a well-developed technique for the synthesizing of well-ordered sulfur materials, but it is limited when used to scale up synthetic procedures for practical applications. In this study, we suggest an easily scalable, room-temperature/ambient-pressure chemical pathway for the synthesis of highly functioning cathode materials using electrostatically assembled, amine-terminated carbon materials. It is demonstrated that stable cycling performance outcomes are achievable with a capacity of 730 mAhg -1 at a current density of 1 C with good cycling stability by a virtue of the characteristic chemical/physical properties (a high conductivity for efficient charge conduction and the presence of a number of amine groups that can interact with sulfur atoms during electrochemical reactions) of composite materials. The critical roles of conductive carbon moieties and amine functional groups inside composite materials are clarified with combinatorial analyses by X-ray photoelectron spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy.

Precipitation of the rare earth double sodium and rare earths from the sulfuric liquor and the conversion into rare earth hydroxides through meta ethic reaction

International Nuclear Information System (INIS)

Abreu, Renata D.; Oliveira, Ester F.; Brito, Walter de; Morais, Carlos A.

2007-01-01

This work presents the purification study of the rare earths through precipitation of rare earth and sodium (Na TR (SO 4 ) 2 . x H 2 O)) double sulfate and his conversion to rare earths hydroxide TR(OH) 3 by meta ethic reaction through the addition of sodium hydroxide solution to the solid double sulfate. The study used the sulfuric liquor as rare earth sample, generated in the chemical processing of the monazite with sulfuric acid by the Industrias Nucleares do Brasil - INB, Brazil, after the thorium and uranium extraction. The work investigated the influence of the main variables involved in the precipitation of Na TR(SO 4 ) 2 .xH 2 O and in the conversion for the TR(OH) 3 , as follows: type and excess of the precipitation agent, temperature and time reaction. The obtained solid composites were characterized by X-ray diffraction, infrared and chemical analysis. The double sulfate diffractogram indicated the Na TR(SO 4 ) 2 mono-hydrated. The characterization of the metatese products has shown that, for obtaining the complete conversion of NaTR(SO 4 ) 2 .H 2 O into TR(OH) 3 , the reaction must be hot processed (∼70 deg C) and with small excess of Na OH (≤ 5 percent). (author)

Biogeochemistry of sulfur and iron in Thioploca-colonized surface sediments in the upwelling area off central chile

Science.gov (United States)

Zopfi, Jakob; Böttcher, Michael E.; Jørgensen, Bo Barker

2008-02-01

The biogeochemistry of sedimentary sulfur was investigated on the continental shelf off central Chile at water depths between 24 and 88 m under partial influence of an oxygen minimum zone. Dissolved and solid iron and sulfur species, including the sulfur intermediates sulfite, thiosulfate, and elemental sulfur, were analyzed at high resolution in the top 20 cm. All stations were characterized by high rates of sulfate reduction, but only the sediments within the Bay of Concepción contained dissolved sulfide. Due to advection and/or in-situ reoxidation of sulfide, dissolved sulfate was close to bottom water values. Whereas the concentrations of sulfite and thiosulfate were mostly in the submicromolar range, elemental sulfur was by far the dominant sulfur intermediate. Although the large nitrate- and sulfur-storing bacteria Thioploca were abundant, the major part of S 0 was located extracellularly. The distribution of sulfur species and dissolved iron suggests the reaction of sulfide with FeOOH as an important pathway for sulfide oxidation and sulfur intermediate formation. This is in agreement with the sulfur isotope composition of co-existing elemental sulfur and iron monosulfides. In the Bay of Concepción, sulfur isotope data suggest that pyrite formation proceeds via the reaction of FeS with polysulfides or H 2S. At the shelf stations, on the other hand, pyrite was significantly depleted in 34S relative to its potential precursors FeS and S 0. Isotope mass balance considerations suggest further that pyritization at depth includes light sulfide, potentially originating from bacterial sulfur disproportionation. The δ 34S-values of pyrite down to -38‰ vs. V-CDT are among the lightest found in organic-rich marine sediments. Seasonal variations in the sulfur isotope composition of dissolved sulfate indicated a dynamic non-steady-state sulfur cycle in the surface sediments. The 18O content of porewater sulfate increased with depth at all sites compared to the

Comparison of comprehensive two-dimensional gas chromatography coupled with sulfur-chemiluminescence detector to standard methods for speciation of sulfur-containing compounds in middle distillates.

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Ruiz-Guerrero, Rosario; Vendeuvre, Colombe; Thiébaut, Didier; Bertoncini, Fabrice; Espinat, Didier

2006-10-01

The monitoring of total sulfur content and speciation of individual sulfur-containing compounds in middle distillates is required for efficient catalyst selection and for a better understanding of the kinetics of the reactions involved in hydrotreament processes. Owing to higher resolution power and enhanced sensitivity, comprehensive two-dimensional gas chromatography (GCxGC) hyphenated to sulfur chemiluminescence detection (SCD) has recently evolved as a powerful tool for improving characterization and identification of sulfur compounds. The aim of this paper is to compare quantitatively GCxGC-SCD and various other methods commonly employed in the petroleum industry, such as X-ray fluorescence, conventional GC-SCD, and high-resolution mass spectrometry, for total sulfur content determination and speciation analysis. Different samples of middle distillates have been analyzed to demonstrate the high potential and important advantages of GCxGC-SCD for innovative and quantitative analysis of sulfur-containing compounds. More accurate and detailed results for benzothiophenes and dibenzothiophenes are presented, showing that GCxGC-SCD should become, in the future, an essential tool for sulfur speciation analysis.

Bunsen Reaction using a HIx Solution (HI-I2-H2O with Countercurrent Flow for Sulfur-Iodine Hydrogen Production Process

Directory of Open Access Journals (Sweden)

Kim Hyo-Sub

2016-01-01

Full Text Available In the sulfur-iodine hydrogen production process, the Bunsen reaction is a crucial section because of the linkage with the H2SO4 and HI decomposition sections. The HIx solution (HI-I2-H2O mixture was fed to the Bunsen reaction section as a reactant from the HI decomposition section. In this study, the Bunsen reaction using the HIx solution with countercurrent flow was performed. The production rate of HIx phase solution increased while that of H2SO4 phase solution was maintained constant when increasing the flow rate of HIx solution. As the SO2 flow rate increased, the production rates of H2SO4 and HIx phase solutions increased. The amount of resultant H2SO4 phase was very lower than that of resultant HIx phase under the conditions examined in this study.

Sugar Dehydration without Sulfuric Acid: No More Choking Fumes in the Classroom!

Science.gov (United States)

Silverstein, Todd P.; Zhang, Yi

1998-06-01

Sugar is a common reagent often used in colorful classroom demonstrations. It produces a growing column of black ash when dehydrated by concentrated sulfuric acid, and it produces a brilliant purple flame when combusted with potassium chlorate. Unfortunately, both of these reactions also produce copious quantities of noxious fumes which make them problematic as lecture demonstrations. We have modified and combined these two reactions. Our demonstration uses no sulfuric acid, yields relatively little smoke, and produces an exciting and unpredictable growing column of black carbon.

Unique aqueous Li-ion/sulfur chemistry with high energy density and reversibility.

Science.gov (United States)

Yang, Chongyin; Suo, Liumin; Borodin, Oleg; Wang, Fei; Sun, Wei; Gao, Tao; Fan, Xiulin; Hou, Singyuk; Ma, Zhaohui; Amine, Khalil; Xu, Kang; Wang, Chunsheng

2017-06-13

Leveraging the most recent success in expanding the electrochemical stability window of aqueous electrolytes, in this work we create a unique Li-ion/sulfur chemistry of both high energy density and safety. We show that in the superconcentrated aqueous electrolyte, lithiation of sulfur experiences phase change from a high-order polysulfide to low-order polysulfides through solid-liquid two-phase reaction pathway, where the liquid polysulfide phase in the sulfide electrode is thermodynamically phase-separated from the superconcentrated aqueous electrolyte. The sulfur with solid-liquid two-phase exhibits a reversible capacity of 1,327 mAh/(g of S), along with fast reaction kinetics and negligible polysulfide dissolution. By coupling a sulfur anode with different Li-ion cathode materials, the aqueous Li-ion/sulfur full cell delivers record-high energy densities up to 200 Wh/(kg of total electrode mass) for >1,000 cycles at ∼100% coulombic efficiency. These performances already approach that of commercial lithium-ion batteries (LIBs) using a nonaqueous electrolyte, along with intrinsic safety not possessed by the latter. The excellent performance of this aqueous battery chemistry significantly promotes the practical possibility of aqueous LIBs in large-format applications.

Complex chemical composition of colored surface films formed from reactions of propanal in sulfuric acid at upper troposphere/lower stratosphere aerosol acidities.

Science.gov (United States)

Van Wyngarden, A L; Pérez-Montaño, S; Bui, J V H; Li, E S W; Nelson, T E; Ha, K T; Leong, L; Iraci, L T

Particles in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40-80 wt %) in water. However, airborne measurements have shown that these particles also contain a significant fraction of organic compounds of unknown chemical composition. Acid-catalyzed reactions of carbonyl species are believed to be responsible for significant transfer of gas phase organic species into tropospheric aerosols and are potentially more important at the high acidities characteristic of UT/LS particles. In this study, experiments combining sulfuric acid (H 2 SO 4 ) with propanal and with mixtures of propanal with glyoxal and/or methylglyoxal at acidities typical of UT/LS aerosols produced highly colored surface films (and solutions) that may have implications for aerosol properties. In order to identify the chemical processes responsible for the formation of the surface films, attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and 1 H nuclear magnetic resonance (NMR) spectroscopies were used to analyze the chemical composition of the films. Films formed from propanal were a complex mixture of aldol condensation products, acetals and propanal itself. The major aldol condensation products were the dimer (2-methyl-2-pentenal) and 1,3,5-trimethylbenzene that was formed by cyclization of the linear aldol condensation trimer. Additionally, the strong visible absorption of the films indicates that higher-order aldol condensation products must also be present as minor species. The major acetal species were 2,4,6-triethyl-1,3,5-trioxane and longer-chain linear polyacetals which are likely to separate from the aqueous phase. Films formed on mixtures of propanal with glyoxal and/or methylglyoxal also showed evidence of products of cross-reactions. Since cross-reactions would be more likely than self-reactions under atmospheric conditions, similar reactions of aldehydes like propanal with common aerosol organic species like glyoxal

Behaviour of organic sulfur compounds in HPLC

International Nuclear Information System (INIS)

Freyholdt, T.

1982-01-01

The retention behaviour of organic sulfur compounds in the reverse-bonded-phase chromatography is characterized by determining the retention indices according to Kovats. The results of these studies show that the solubility of organic compounds in the eluting agent and the molar sorption surfaces of the solutes are the main factors determining the retention behaviour. Knowledge of the retention indices of above-mentioned compounds allows a quick interpretation of chromatograms obtained through a product analysis of γ-irradiated aqueous solutions of organic sulfur compounds. Dithia compounds of the type CH 3 -S-(CH 2 )sub(n)-S-Ch 3 (1 1. 2,4-Dithiapentane (n = 1) however will yield primarily monothio-S-methyl formate as a stable end product. The formation of oxygenic reaction products proceeds via sulfur-centred radical kations. Spin trapping experiments with nitroxyl radicals show that it is possible to trap radiation-chemically produced radicals of sulfurous substrates, but the thus obtained adducts with half-life periods of 4-5 min. cannot be identified by means of NMR, IR or mass spectroscopy. (orig.) [de

Reaction between vanadium trichloride oxide and hydrogen sulfide

International Nuclear Information System (INIS)

Yajima, Akimasa; Matsuzaki, Ryoko; Saeki, Yuzo

1978-01-01

The details of the reaction between vanadium trichloride oxide and hydrogen sulfide were examined at 20 and 60 0 C. The main products by the reaction were vanadium dichloride oxide, sulfur, and hydrogen chloride. In addition to these products, small amounts of vanadium trichloride, vanadium tetrachloride, disulfur dichloride, and sulfur dioxide were formed. The formations of the above-mentioned reaction products can be explained as follows: The first stage is the reaction between vanadium trichloride oxide and hydrogen sulfide, 2VOCl 3 (l) + H 2 S(g)→2VOCl 2 (s) + S(s) + 2HCl(g). Then the resulting sulfur reacts with the unreacted vanadium trichloride oxide, 2VOCl 3 (l) + 2S(s)→2VOCl 2 (s) + S 2 Cl 2 (l). The resulting disulfur dichloride subsequently reacts with the unreacted vanadium trichloride oxide, 2VOCl 3 (l) + S 2 Cl 2 (l)→2VCl 4 (l) + S(s) + SO 2 (g). The resulting vanadium tetrachloride reacts with the sulfur formed during the reaction, 2VCl 4 (l) + 2S(s)→2VCl 3 (s) + S 2 Cl 2 (l), and also reacts with hydrogen sulfide, 2VCl 4 (l) + H 2 S(g)→2VCl 3 (s) + S(s) + 2HCl(g). (auth.)

Iron-sulfur clusters as biological sensors: the chemistry of reactions with molecular oxygen and nitric oxide.

Science.gov (United States)

Crack, Jason C; Green, Jeffrey; Thomson, Andrew J; Le Brun, Nick E

2014-10-21

recognized. This remarkable feature suggested that the original [4Fe-4S] cluster can be restored using persulfide as the source of sulfide ion. We have demonstrated that only iron and a source of electrons are required to promote efficient conversion back from the [2Fe-2S] to the [4Fe-4S] form. We propose this as a novel in vivo repair mechanism that does not require the intervention of an iron-sulfur cluster biogenesis pathway. A number of iron-sulfur regulators have evolved to function as sensors of NO. Although it has long been known that the iron-sulfur clusters of many phylogenetically unrelated proteins are vulnerable to attack by NO, our recent studies of Wbl proteins and FNR have provided new insights into the mechanism of cluster nitrosylation, which overturn the commonly accepted view that the product is solely a mononuclear iron dinitrosyl complex (known as a DNIC). The major reaction is a rapid, multiphase process involving stepwise addition of up to eight NO molecules per [4Fe-4S] cluster. The major iron nitrosyl product is EPR silent and has optical characteristics similar to Roussin's red ester, [Fe2(NO)4(RS)2] (RRE), although a species similar to Roussin's black salt, [Fe4(NO)7(S)3](-) (RBS) cannot be ruled out. A major future challenge will be to clarify the nature of these species.

Sulfur isotope fractionation during oxidation of sulfur dioxide: gas-phase oxidation by OH radicals and aqueous oxidation by H2O2, O3 and iron catalysis

Directory of Open Access Journals (Sweden)

J. N. Crowley

2012-01-01

Full Text Available The oxidation of SO2 to sulfate is a key reaction in determining the role of sulfate in the environment through its effect on aerosol size distribution and composition. Sulfur isotope analysis has been used to investigate sources and chemical processes of sulfur dioxide and sulfate in the atmosphere, however interpretation of measured sulfur isotope ratios is challenging due to a lack of reliable information on the isotopic fractionation involved in major transformation pathways. This paper presents laboratory measurements of the fractionation factors for the major atmospheric oxidation reactions for SO2: Gas-phase oxidation by OH radicals, and aqueous oxidation by H2O2, O3 and a radical chain reaction initiated by iron. The measured fractionation factor for 34S/32S during the gas-phase reaction is αOH = (1.0089±0.0007−((4±5×10−5 T(°C. The measured fractionation factor for 34S/32S during aqueous oxidation by H2O2 or O3 is αaq = (1.0167±0.0019−((8.7±3.5 ×10−5T(°C. The observed fractionation during oxidation by H2O2 and O3 appeared to be controlled primarily by protonation and acid-base equilibria of S(IV in solution, which is the reason that there is no significant difference between the fractionation produced by the two oxidants within the experimental error. The isotopic fractionation factor from a radical chain reaction in solution catalysed by iron is αFe = (0.9894±0.0043 at 19 °C for 34S/32S. Fractionation was mass-dependent with regards to 33S/32S for all the reactions investigated. The radical chain reaction mechanism was the only measured reaction that had a faster rate for the light isotopes. The results presented in this study will be particularly useful to determine the importance of the transition metal-catalysed oxidation pathway compared to other oxidation pathways, but other main oxidation pathways can not be distinguished based on stable sulfur isotope measurements alone.

Desulfurization of organic sulfur from a subbituminous coal by electron-transfer process with K{sub 4}(Fe(CN){sub 6})

Energy Technology Data Exchange (ETDEWEB)

Dipu Borah [Pragjyotika J College, Titabar (India). Department of Chemistry

2006-02-01

The desulfurization reaction involving direct electron transfer from potassium ferrocyanide, K{sub 4}(Fe(CN){sub 6}), successfully removed organic sulfur from a subbituminous coal. The temperature variation of desulfurization revealed that increase of temperature enhanced the level of sulfur removal. Moreover, the desulfurization reaction was found to be dependent on the concentration of K{sub 4}(Fe(CN){sub 6}). Gradual increase in the concentration of K{sub 4}(Fe(CN){sub 6}) raised the magnitude of desulfurization, but at higher concentration the variation was not significant. The removal of organic sulfur from unoxidized coal slightly increased with reduced particle size. Desulfurization from oxidized coals (prepared by aerial oxidation) revealed a higher level of sulfur removal in comparison to unoxidized coal. Highest desulfurization of 36.4 wt % was obtained at 90{sup o}C and 0.1 M concentration of K{sub 4}(Fe(CN){sub 6}) in the 100-mesh size oxidized coal prepared at 200{sup o}C. Model sulfur compound study revealed that aliphatic types of sulfur compounds are primarily responsible for desulfurization. Because of higher stability, thiophene and condensed thiophene-type of compounds perhaps remained unaffected by the electron-transfer agent. Infrared study revealed the formation of oxidized sulfur compounds (sulfoxide, sulfone, sulfonic acid, etc.) in the oxidized coals. The desulfurization reaction in different systems is well-represented by the pseudo-first-order kinetic model. Application of the transition state theory indicated that the desulfurization reaction proceeds with the absorption of heat (endothermic reaction) and is nonspontaneous in nature. 53 refs., 6 figs., 3 tabs.

Process for recovery of sulfur from acid gases

Science.gov (United States)

Towler, Gavin P.; Lynn, Scott

1995-01-01

Elemental sulfur is recovered from the H.sub.2 S present in gases derived from fossil fuels by heating the H.sub.2 S with CO.sub.2 in a high-temperature reactor in the presence of a catalyst selected as one which enhances the thermal dissociation of H.sub.2 S to H.sub.2 and S.sub.2. The equilibrium of the thermal decomposition of H.sub.2 S is shifted by the equilibration of the water-gas-shift reaction so as to favor elemental sulfur formation. The primary products of the overall reaction are S.sub.2, CO, H.sub.2 and H.sub.2 O. Small amounts of COS, SO.sub.2 and CS.sub.2 may also form. Rapid quenching of the reaction mixture results in a substantial increase in the efficiency of the conversion of H.sub.2 S to elemental sulfur. Plant economy is further advanced by treating the product gases to remove byproduct carbonyl sulfide by hydrolysis, which converts the COS back to CO.sub.2 and H.sub.2 S. Unreacted CO.sub.2 and H.sub.2 S are removed from the product gas and recycled to the reactor, leaving a gas consisting chiefly of H.sub.2 and CO, which has value either as a fuel or as a chemical feedstock and recovers the hydrogen value from the H.sub.2 S.

Graphene-sulfur nanocomposites for rechargeable lithium-sulfur battery electrodes

Science.gov (United States)

Liu, Jun; Lemmon, John P; Yang, Zhenguo; Cao, Yuiliang; Li, Xiaolin

2014-06-17

Rechargeable lithium-sulfur batteries having a cathode that includes a graphene-sulfur nanocomposite can exhibit improved characteristics. The graphene-sulfur nanocomposite can be characterized by graphene sheets with particles of sulfur adsorbed to the graphene sheets. The sulfur particles have an average diameter less than 50 nm..

Dissimilatory oxidation and reduction of elemental sulfur in thermophilic archaea.

Science.gov (United States)

Kletzin, Arnulf; Urich, Tim; Müller, Fabian; Bandeiras, Tiago M; Gomes, Cláudio M

2004-02-01

The oxidation and reduction of elemental sulfur and reduced inorganic sulfur species are some of the most important energy-yielding reactions for microorganisms living in volcanic hot springs, solfataras, and submarine hydrothermal vents, including both heterotrophic, mixotrophic, and chemolithoautotrophic, carbon dioxide-fixing species. Elemental sulfur is the electron donor in aerobic archaea like Acidianus and Sulfolobus. It is oxidized via sulfite and thiosulfate in a pathway involving both soluble and membrane-bound enzymes. This pathway was recently found to be coupled to the aerobic respiratory chain, eliciting a link between sulfur oxidation and oxygen reduction at the level of the respiratory heme copper oxidase. In contrast, elemental sulfur is the electron acceptor in a short electron transport chain consisting of a membrane-bound hydrogenase and a sulfur reductase in (facultatively) anaerobic chemolithotrophic archaea Acidianus and Pyrodictium species. It is also the electron acceptor in organoheterotrophic anaerobic species like Pyrococcus and Thermococcus, however, an electron transport chain has not been described as yet. The current knowledge on the composition and properties of the aerobic and anaerobic pathways of dissimilatory elemental sulfur metabolism in thermophilic archaea is summarized in this contribution.

Sulfur determination in blood from inhabitants of Brazil using neutron activation analysis

International Nuclear Information System (INIS)

Oliveira, Laura C.; Zamboni, Cibele B.

2013-01-01

In this study the NAA technique was applied to analyze sulfur in blood from inhabitants of Brazil for the proposition of an indicative interval. The measurements were performed considering lifestyle factors (non-smokers, non-drinkers and no history of toxicological exposure) of Brazilian inhabitants. The influence of gender was also investigated considering several age ranges (18-29, 30-39, 40-49, >50 years). These data are useful in clinical investigations, to identify or prevent diseases caused by inadequate sulfur ingestion and for nutritional evaluation of Brazilian population.

Sulfur determination in blood from inhabitants of Brazil using neutron activation analysis

Energy Technology Data Exchange (ETDEWEB)

Oliveira, Laura C.; Zamboni, Cibele B. [Instituto de Pesquisas Energeticas e Nucleares (IPEN-CNEN/SP) Av. Professor Lineu Prestes 2242 05508-000 Sao Paulo, SP (Brazil)

2013-05-06

In this study the NAA technique was applied to analyze sulfur in blood from inhabitants of Brazil for the proposition of an indicative interval. The measurements were performed considering lifestyle factors (non-smokers, non-drinkers and no history of toxicological exposure) of Brazilian inhabitants. The influence of gender was also investigated considering several age ranges (18-29, 30-39, 40-49, >50 years). These data are useful in clinical investigations, to identify or prevent diseases caused by inadequate sulfur ingestion and for nutritional evaluation of Brazilian population.

Comparative sensitivity of photosynthesis and translocation to sulfur dioxide damage in Phaseolus vulgaris L

International Nuclear Information System (INIS)

Noyes, R.D.

1978-01-01

The inhibiting effect of sulfur dioxide on photosynthesis in a mature bean leaf and, simultaneously, on the rate of carbohydrate translocation from this same leaf has been examined. The results show a reduction of 0, 13, and 73% in net photosynthesis and 39, 44, and 69% in translocation, at concentrations of 0.1, 1, and 3 ppm sulfur dioxide, respectively. The inhibition of translocation at 0.1 ppm sulfur dioxide without any accompanying inhibition of net photosynthesis indicates that translocation is considerably more sensitive to sulfur dioxide damage. The mechanism of translocation inhibition at 1 ppm sulfur dioxide or less is shown to be independent of photosynthetic inhibition. Whereas, it is suggested that at higher concentrations significant inhibition of photosynthesis causes an additive reduction of translocation due to reduced levels of transport sugars. Autoradiograms of 14 C-labeled source leaves indicate that one possible mechanism of sulfur dioxide damage to translocation is the inhibition of sieve-tube loading. Inhibition of phloem translocation at common ambient levels (0.1 ppm) of sulfur dioxide is important to the overall growth and yield of major agricultural crops sensitive to sulfur dioxide

A revolution in electrodes: recent progress in rechargeable lithium-sulfur batteries.

Science.gov (United States)

Fang, Xin; Peng, Huisheng

2015-04-01

As a promising candidate for future batteries, the lithium-sulfur battery is gaining increasing interest due to its high capacity and energy density. However, over the years, lithium-sulfur batteries have been plagued by fading capacities and the low Coulombic efficiency derived from its unique electrochemical behavior, which involves solid-liquid transition reactions. Moreover, lithium-sulfur batteries employ metallic lithium as the anode, which engenders safety vulnerability of the battery. The electrodes play a pivotal role in the performance of lithium-sulfur batteries. A leap forward in progress of lithium-sulfur batteries is always accompanied by a revolution in the electrode technology. In this review, recent progress in rechargeable lithium-sulfur batteries is summarized in accordance with the evolution of the electrodes, including the diversified cathode design and burgeoning metallic-lithium-free anodes. Although the way toward application has still many challenges associated, recent progress in lithium-sulfur battery technology still paints an encouraging picture of a revolution in rechargeable batteries. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

COMPONENT DEVELOPMENT NEEDS FOR THE HYBRID SULFUR ELECTROLYZER

Energy Technology Data Exchange (ETDEWEB)

Hobbs, D; Hector Colon-Mercado, H; Mark Elvington, M

2008-05-30

, the kinetic activity decreases. We recommend further testing to determine if these binary alloys will provide the increased reaction kinetic needed to meet the targets. We also plan to test the performance of these catalyst materials for both proton and sulfur dioxide reduction. The latter may provide another parameter by which we can control the reduction of sulfur dioxide upon transport to the cathode catalyst surface. A small scale electrolyzer (2 cm{sup 2}) has been fabricated and successfully installed as an additional tool to evaluate the effect of different operating conditions on electrolyzer and MEA performance. Currently this electrolyzer is limited to testing at temperatures up to 80 C and at atmospheric pressure. Selected electrochemical performance data from the single cell sulfur dioxide depolarized electrolyzer were analyzed with the aid of an empirical equation which takes into account the overpotential of each of the components. By using the empirical equation, the performance data was broken down into its components and a comparison of the potential losses was made. The results indicated that for the testing conditions of 80 C and 30 wt% sulfuric acid, the major overpotential contribution ({approx}70 % of all losses) arise from the slow reaction rate of oxidation of sulfur dioxide. The results indicate that in order to meet the target of hydrogen production at 0.5 A/cm{sup 2} at 0.6 V and 50 wt% sulfuric acid, identification of a better catalyst for sulfur dioxide oxidation will provide the largest gain in electrolyzer performance.

Operating experience with unit for sulfuric acid alkylation of isobutane by butylenes

Energy Technology Data Exchange (ETDEWEB)

Tagavov, I.T.; Sumanov, V.T.; Khadzhiev, S.N.

1988-09-01

The operation of units for the sulfuric acid alkylation of isobutanes by butylenes have been performed. The reaction was carried out in a KSG-3 horizontal sulfuric acid contractor. A butane-butylene fraction from catalytic cracking and an isobutane fraction from the central gas fractionating unit were used as a feedstock. The studies have shown that the unit will give a high-quality product under various conditions of operation. The specific consumption of sulfuric acid in processing different types of feed remains within acceptable limits.

Mass defect of 37Cl(t, p)39Cl: Coulomb displacement energy of the T=5/2, Jsup(π)=3+/2 states in 39Cl-39Ar

International Nuclear Information System (INIS)

Antony, M.S.; Britz, J.; Bueb, J.B.; Pape, A.

1984-01-01

From the Q-value (5701.9+-2.5)keV of the reaction 37 Cl(t, p) 39 Cl, the ground-state mass defect of 39 Cl is found to be (-29802.8+-2.5)keV, an improvement upon the existing value of (-29803+-18)keV. The Coulomb displacement energy of the mirror nuclei 39 Cl- 39 Ar for T=5/2, Jsup(π)=3 + /2 is found to be (6422.1+-10.6)keV. The r 0 parameter of the charge radius is approximately 1.32 fm for A=39

Lower detectable limit of sulfur by fast neutron activation analysis

Energy Technology Data Exchange (ETDEWEB)

Shani, G; Cohen, D [Ben-Gurion Univ. of the Negev, Beersheba (Israel). Dept. of Nuclear Engineering

1976-07-01

For the purpose of air pollution research, the possibility of fast neutron activation analysis of sulfur was investigated. The only reaction that can be used for this purpose is S/sup 34/(n, p)P/sup 34/. A rabbit system was installed, synchronized with a 150 kV D-T neutron generator and an electronic analysing system. The whole system was operated so that the sample was irradiated for 10 sec and the 2.13 MeV ..gamma..-ray was counted for 10 sec. 5 samples were prepared containing sulfur from 0.5 to 0.1 g. Each measurement lasted 30 min and the activity was plotted as a function of sulfur weight. The relative error is increased very much when the amount of sulfur is below 0.1 g. This is what sets the lower detectable limit. Collection of more than 0.1 g of sulfur even during a long collection time means a very high SO/sub 2/ concentration in the air.

Electrolytic nature of aqueous sulfuric acid. 2. Acidity.

Science.gov (United States)

Fraenkel, Dan

2012-09-27

In part 1 of this study, I reported that the Debye-Hückel limiting law and the smaller-ion shell (SiS) model of strong electrolyte solutions fit nicely with the experimental mean ionic activity coefficient (γ(±)) of aqueous sulfuric acid as a function of concentration and of temperature when the acid is assumed to be a strong 1-3 electrolyte. Here, I report that the SiS-derived activity coefficient of H(+), γ(H(+)), of the 1-3 acid is comparable to that of aqueous HCl. This agrees with titration curves showing, as well-known, that sulfuric acid in water is parallel in strength to aqueous HCl. The calculated pH is in good accord with the Hammett acidity function, H(0), of aqueous sulfuric acid at low concentration, and differences between the two functions at high concentration are discussed and explained. This pH-H(0) relation is consistent with the literature showing that the H(0) of sulfuric acid (in the 1-9 M range) is similar to those of HCl and the other strong mineral monoprotic acids. The titration of aqueous sulfuric acid with NaOH does not agree with the known second dissociation constant of 0.010 23; rather, the constant is found to be ~0.32 and the acid behaves upon neutralization as a strong diprotic acid practically dissociating in one step. A plausible reaction pathway is offered to explain how the acid may transform, upon base neutralization, from a dissociated H(4)SO(5) (as 3H(+) and HSO(5)(3-)) to a dissociated H(2)SO(4) even though the equilibrium constant of the reaction H(+) + HSO(5)(3-) ↔ SO(4)(2-) + H(2)O, at 25 °C, is 10(-37) (part 1).

Acidophilic sulfur disproportionation

Science.gov (United States)

Hardisty, Dalton S.; Olyphant, Greg A.; Bell, Jonathan B.; Johnson, Adam P.; Pratt, Lisa M.

2013-07-01

Bacterial disproportionation of elemental sulfur (S0) is a well-studied metabolism and is not previously reported to occur at pH values less than 4.5. In this study, a sediment core from an abandoned-coal-mine-waste deposit in Southwest Indiana revealed sulfur isotope fractionations between S0 and pyrite (Δ34Ses-py) of up to -35‰, inferred to indicate intense recycling of S0 via bacterial disproportionation and sulfide oxidation. Additionally, the chemistry of seasonally collected pore-water profiles were found to vary, with pore-water pH ranging from 2.2 to 3.8 and observed seasonal redox shifts expressed as abrupt transitions from Fe(III) to Fe(II) dominated conditions, often controlled by fluctuating water table depths. S0 is a common product during the oxidation of pyrite, a process known to generate acidic waters during weathering and production of acid mine drainage. The H2S product of S0 disproportionation, fractionated by up to -8.6‰, is rapidly oxidized to S0 near redox gradients via reaction with Fe(III) allowing for the accumulation of isotopically light S0 that can then become subject to further sulfur disproportionation. A mass-balance model for S0 incorporating pyrite oxidation, S0 disproportionation, and S0 oxidation readily explains the range of observed Δ34Ses-py and emphasizes the necessity of seasonally varying pyrite weathering and metabolic rates, as indicated by the pore water chemistry. The findings of this research suggest that S0 disproportionation is potentially a common microbial process at a pH < 4.5 and can create large sulfur isotope fractionations, even in the absence of sulfate reduction.

Interfacial Mechanism in Lithium-Sulfur Batteries: How Salts Mediate the Structure Evolution and Dynamics.

Science.gov (United States)

Lang, Shuang-Yan; Xiao, Rui-Juan; Gu, Lin; Guo, Yu-Guo; Wen, Rui; Wan, Li-Jun

2018-06-08

Lithium-sulfur batteries possess favorable potential for energy-storage applications due to their high specific capacity and the low cost of sulfur. Intensive understanding of the interfacial mechanism, especially the polysulfide formation and transformation under complex electrochemical environment, is crucial for the build-up of advanced batteries. Here we report the direct visualization of interfacial evolution and dynamic transformation of the sulfides mediated by the lithium salts via real-time atomic force microscopy monitoring inside a working battery. The observations indicate that the lithium salts influence the structures and processes of sulfide deposition/decomposition during discharge/charge. Moreover, the distinct ion interaction and diffusion in electrolytes manipulate the interfacial reactions determining the kinetics of the sulfide transformation. Our findings provide deep insights into surface dynamics of lithium-sulfur reactions revealing the salt-mediated mechanisms at nanoscale, which contribute to the profound understanding of the interfacial processes for the optimized design of lithium-sulfur batteries.

An Experimental Study of Low-Temperature Sulfurization of Carbohydrates Using Various Sulfides Reveals Insights into Structural Characteristics and Sulfur Isotope Compositions of Macromolecular Organic Matter in the Environment

Science.gov (United States)

OBeirne, M. D.; Werne, J. P.; Van Dongen, B.; Gilhooly, W., III

2017-12-01

Sulfurization of carbohydrates has been suggested as an important mechanism for the preservation of organic matter in anoxic/euxinic depositional environments. In this study, glucose was sulfurized under laboratory conditions at room temperature (24°C) using three commercially available sulfides - ammonium sulfide ([NH4]2S), sodium sulfide (Na2S), and sodium hydrosulfide (NaHS), each mixed with elemental sulfur to produce polysulfide solutions. The reaction products were analyzed using Fourier transform infrared spectroscopy (FTIR), which revealed structural differences among the products formed via the three sulfide reactants. Additionally, analysis of the bulk sulfur isotope compositions of reactants and products was used to determine the fractionation(s) associated with abiotic sulfur incorporation into organic matter. Samples from both modern (Mahoney Lake, British Colombia, Canada) and ancient (Jurassic aged Blackstone Band from the Kimmeridge Clay Formation, Dorset, United Kingdom) euxinic systems were also analyzed for comparison to laboratory samples. Results from this study provide experimental evidence for the structural and sulfur isotopic relationships of sulfurized organic matter in the geosphere.

Ultrasound-assisted oxidative process for sulfur removal from petroleum product feedstock.

Science.gov (United States)

Mello, Paola de A; Duarte, Fábio A; Nunes, Matheus A G; Alencar, Mauricio S; Moreira, Elizabeth M; Korn, Mauro; Dressler, Valderi L; Flores, Erico M M

2009-08-01

A procedure using ultrasonic irradiation is proposed for sulfur removal of a petroleum product feedstock. The procedure involves the combination of a peroxyacid and ultrasound-assisted treatment in order to comply with the required sulfur content recommended by the current regulations for fuels. The ultrasound-assisted oxidative desulfurization (UAOD) process was applied to a petroleum product feedstock using dibenzothiophene as a model sulfur compound. The influence of ultrasonic irradiation time, oxidizing reagents amount, kind of solvent for the extraction step and kind of organic acid were investigated. The use of ultrasonic irradiation allowed higher efficiency for sulfur removal in comparison to experiments performed without its application, under the same reactional conditions. Using the optimized conditions for UAOD, the sulfur removal was about 95% after 9min of ultrasonic irradiation (20kHz, 750W, run at 40%), using hydrogen peroxide and acetic acid, followed by extraction with methanol.

Effect of Sulfur in Steel on Transient Evolution of Inclusions During Calcium Treatment

Science.gov (United States)

Liu, Yang; Zhang, Lifeng; Zhang, Ying; Duan, Haojian; Ren, Ying; Yang, Wen

2018-04-01

In the current study, the effect of S content in the molten steel on inclusions during calcium treatment was studied using an induction furnace. The calcium in steel decreased from 48 to 2 ppm, and the sulfur in steel changed a little with time. When sulfur content in steel was as low as 25 ppm during calcium treatment, inclusions shifted from CaO-Al2O3-CaS to Al2O3-CaO with about 35 pct CaO. When the sulfur increased over 90 ppm, more CaS-CaO formed just after the addition of calcium, and then the CaS content decreased from over 45 pct to lower than 15 pct and inclusions were mostly Al2O3-CaO-CaS and Al2O3-CaO with a high Al2O3 content. Thermodynamic calculation predicted the variation of the composition of inclusions, indicating good agreement with the measurement, while a certain deviation existed, especially for heats with 90 and 180 ppm sulfur. A reaction model was proposed for the formation of CaO and CaS, which considered the reaction between calcium vapor bubbles in the zone and the dissolved oxygen and sulfur in the molten steel, as described by a Langmuir-type adsorption isotherm with a reaction occurring on the remaining vacant sites. The variation of transient CaS inclusions was discussed based on the thermodynamic calculation and the morphology evolution of typical inclusions containing CaS.

Directly Formed Alucone on Lithium Metal for High-Performance Li Batteries and Li-S Batteries with High Sulfur Mass Loading.

Science.gov (United States)

Chen, Lin; Huang, Zhennan; Shahbazian-Yassar, Reza; Libera, Joseph A; Klavetter, Kyle C; Zavadil, Kevin R; Elam, Jeffrey W

2018-02-28

Lithium metal is considered the "holy grail" of next-generation battery anodes. However, severe parasitic reactions at the lithium-electrolyte interface deplete the liquid electrolyte and the uncontrolled formation of high surface area and dendritic lithium during cycling causes rapid capacity fading and battery failure. Engineering a dendrite-free lithium metal anode is therefore critical for the development of long-life batteries using lithium anodes. In this study, we deposit a conformal, organic/inorganic hybrid coating, for the first time, directly on lithium metal using molecular layer deposition (MLD) to alleviate these problems. This hybrid organic/inorganic film with high cross-linking structure can stabilize lithium against dendrite growth and minimize side reactions, as indicated by scanning electron microscopy. We discovered that the alucone coating yielded several times longer cycle life at high current rates compared to the uncoated lithium and achieved a steady Coulombic efficiency of 99.5%, demonstrating that the highly cross-linking structured material with great mechanical properties and good flexibility can effectively suppress dendrite formation. The protected Li was further evaluated in lithium-sulfur (Li-S) batteries with a high sulfur mass loading of ∼5 mg/cm 2 . After 140 cycles at a high current rate of ∼1 mA/cm 2 , alucone-coated Li-S batteries delivered a capacity of 657.7 mAh/g, 39.5% better than that of a bare lithium-sulfur battery. These findings suggest that flexible coating with high cross-linking structure by MLD is effective to enable lithium protection and offers a very promising avenue for improved performance in the real applications of Li-S batteries.

Measurement of sulfur dioxide oxidation rates in wintertime orographic clouds

International Nuclear Information System (INIS)

Snider, J.R.

1990-01-01

SO2-reaction studies in the clouds are examined and summarized to experimentally confirm model predictions and previous field studies regarding dominant SO2-reaction pathways. Controlled amounts of SO2 were released into nonprecipitating orographic clouds, and sulfate yields are compared to oxidant depletions. The sulfate yields were taken from cloud-water samples and liquid-water-concentration measurements, and oxidant-depletion data were generated from continuous gas-phase measurements. Comparisons of Y sub SO4 and D sub H2O2 suggest that H2O2 is the dominant oxidant, and the in-cloud reaction between H2O2 and the bisulfite ion can be expressed by a simple rate that agrees with predictions and laboratory results. The rate measurements are found to be inconsistent with the rate law proposed by Hegg and Hobbs (1982) and with some observational data. The present conclusions are of interest to evaluating the effects of sulfur dioxide emissions on sulfuric acid deposition. 30 refs

Results of Study of Sulfur Oxide Reduction During Combustion of Coal-Water Slurry Fuel Through use of Sulfur Capturing Agents

Directory of Open Access Journals (Sweden)

Murko Vasiliy I.

2016-01-01

Full Text Available It is shown that an effective way of burning high sulfur coal is to burn coal-water slurry fuel (CWF prepared on its basis containing a sulfur capture agent (SCA entered in the slurry at the stage of preparation. The technique of thermodynamic analysis of chemical reactions during CWF burning has been developed including burning in the presence of SCA. Using the developed calculation program, the optimal temperature conditions have been determined as required for the effective reduction of sulfur oxides in flue gases when using different types of SCA. According to the results of calculating the composition of CWF combustion products when entering various substances in the burner space as SCA it has been determined that magnesite, calcite, and dolomite are the most effective natural minerals. The analysis of calculated and experimental data proves the efficiency of SCA addition as well as validity of the obtained results.

Kinetic study of UV-irradiated amorphous sulfur by EPR spectroscopy

International Nuclear Information System (INIS)

El Mkami, H.; Smith, G.M.

2005-01-01

Electron paramagnetic resonance (EPR) spectroscopy is used to investigate UV-irradiation damage in amorphous sulfur by examining post-irradiation kinetics as a function of UV-exposure time. The kinetic study is described by first-order concurrent reactions where the sulfur, as reactant, undergoes two parallel processes leading to the formation of two distinct defects called S 1 * and S 2 *. The temperature dependence of the EPR intensities of the signals, related to these defects, is used in the kinetic study

Biologically produced sulfur

NARCIS (Netherlands)

Kleinjan, W.E.; Keizer, de A.; Janssen, A.J.H.

2003-01-01

Sulfur compound oxidizing bacteria produce sulfur as an intermediate in the oxidation of hydrogen sulfide to sulfate. Sulfur produced by these microorganisms can be stored in sulfur globules, located either inside or outside the cell. Excreted sulfur globules are colloidal particles which are

Aqueous process for recovering sulfur from hydrogen sulfide-bearing gas

Science.gov (United States)

Basu, Arunabha

2015-05-05

A process for recovering sulfur from a hydrogen sulfide-bearing gas utilizes an aqueous reaction medium, a temperature of about 110-150.degree. C., and a high enough pressure to maintain the aqueous reaction medium in a liquid state. The process reduces material and equipment costs and addresses the environmental disadvantages associated with known processes that rely on high boiling point organic solvents.

Sulfurization of Dissolved Organic Matter Increases Hg-Sulfide-Dissolved Organic Matter Bioavailability to a Hg-Methylating Bacterium.

Science.gov (United States)

Graham, Andrew M; Cameron-Burr, Keaton T; Hajic, Hayley A; Lee, Connie; Msekela, Deborah; Gilmour, Cynthia C

2017-08-15

Reactions of dissolved organic matter (DOM) with aqueous sulfide (termed sulfurization) in anoxic environments can substantially increase DOM's reduced sulfur functional group content. Sulfurization may affect DOM-trace metal interactions, including complexation and metal-containing particle precipitation, aggregation, and dissolution. Using a diverse suite of DOM samples, we found that susceptibility to additional sulfur incorporation via reaction with aqueous sulfide increased with increasing DOM aromatic-, carbonyl-, and carboxyl-C content. The role of DOM sulfurization in enhancing Hg bioavailability for microbial methylation was evaluated under conditions typical of Hg methylation environments (μM sulfide concentrations and low Hg-to-DOM molar ratios). Under the conditions of predicted metacinnabar supersaturation, microbial Hg methylation increased with increasing DOM sulfurization, likely reflecting either effective inhibition of metacinnabar growth and aggregation or the formation of Hg(II)-DOM thiol complexes with high bioavailability. Remarkably, Hg methylation efficiencies with the most sulfurized DOM samples were similar (>85% of total Hg methylated) to that observed in the presence of l-cysteine, a ligand facilitating rapid Hg(II) biouptake and methylation. This suggests that complexes of Hg(II) with DOM thiols have similar bioavailability to Hg(II) complexes with low-molecular-weight thiols. Overall, our results are a demonstration of the importance of DOM sulfurization to trace metal and metalloid (especially mercury) fate in the environment. DOM sulfurization likely represents another link between anthropogenic sulfate enrichment and MeHg production in the environment.

Identification of novel sulfur-containing steroids in sediments and petroleum: probable incorporation of sulfur into δ 5,7-sterols during early diagenesis

Science.gov (United States)

Sinninghe Damsté, Jaap S.; Schouten, Stefan; de Leeuw, Jan W.; van Duin, Adri C. T.; Geenevasen, Jan A. J.

1999-01-01

A novel sulfur-containing sterane, 4α,7α-epithio-5β-cholestane, has been identified in a sediment extract from the Miocene Northern Apennines marl (Italy) after its isolation by column chromatography and high pressure liquid chromatography. The compound has been characterised by GC-MS and mild Nickel boride desulfurisation and one and two-dimensional 1H NMR techniques. C 27-C 29 homologs have been detected in sediment extracts of three different formations and in one petroleum sample. These sulfur-containing steroids are probably formed by an intramolecular reaction of inorganic sulfides with early diagenetic products of Δ 5,7-sterols.

Effect of sulfur content in a sulfur-activated carbon composite on the electrochemical properties of a lithium/sulfur battery

Energy Technology Data Exchange (ETDEWEB)

Park, Jin-Woo; Kim, Changhyeon; Ryu, Ho-Suk; Cho, Gyu-Bong; Cho, Kwon-Koo; Kim, Ki-Won [School of Materials Science and Engineering, Gyeongsang National University, Jinju (Korea, Republic of); Ahn, Jou-Hyeon [Department of Chemical & Biological Engineering, Gyeongsang National University, Jinju (Korea, Republic of); Wang, Guoxiu [School of Chemistry and Forensic Science, University of Technology Sydney, Sydney, NSW 2007 (Australia); Ahn, Jae-Pyeung [Advanced Analysis Center, Research Planning & Coordination Division, KIST, Seoul (Korea, Republic of); Ahn, Hyo-Jun, E-mail: ahj@gnu.ac.kr [School of Materials Science and Engineering, Gyeongsang National University, Jinju (Korea, Republic of)

2015-09-15

Highlights: • The content of sulfur in activated carbon was controlled by solution process. • The sulfur electrode with low sulfur content shows the best performance. • The Li/S battery has capacity of 1360 mAh/g at 1 C and 702 mAh/g at 10 C. - Abstract: The content of sulfur in sulfur/activated carbon composite is controlled from 32.37 wt.% to 55.33 wt.% by a one-step solution-based process. When the sulfur content is limited to 41.21 wt.%, it can be loaded into the pores of an activated carbon matrix in a highly dispersed state. On the contrary, when the sulfur content is 55.33 wt.%, crystalline sulfur can be detected on the surface of the activated carbon matrix. The best electrochemical performance can be obtained for a sulfur electrode with the lowest sulfur content. The sulfur/activated carbon composite with 32.37 wt.% sulfur afforded the highest first discharge capacity of 1360 mAh g{sup −1} at 1 C rate and a large reversible capacity of 702 mAh g{sup −1} at 10 C (16.75 A/g)

Characteristics of Sulfuric Acid Condensation on Cylinder Liners of Large Two-Stroke Marine Engines

DEFF Research Database (Denmark)

Cordtz, Rasmus Lage; Mayer, Stefan; Schramm, Jesper

. Formation of corrosive sulfuric acid in the cylinder gas is modeled with a cali-brated engine model that incorporates a detailed sulfur reaction mechanism. Condensation of sulfuric acid follows the analogy between heat and mass transfer. Average bulk gas acid dew points are calculated by applying two......-phase thermochemistry of the binary H2O-H2SO4 system. Max dew points of typically more than 200 °C are modeled close to max pressure and variations in terms of operating conditions are not large. However small increments of the dew point provided by e.g. the residual gas fraction, operating pressure, sulfur content...

The effect of sulfur on the inhibition of PCDD/F formation during co-combustion of coal and solid waste

Energy Technology Data Exchange (ETDEWEB)

Palladas, A. [Laboratory of Environmental and Energy Processes, Thermi-Thessaloniki (Greece). Chemical Process Engineering Research Institute; Samaras, P. [TEI of Western Macedonia, Kozani (Greece). Dept. of Environmental Technology; Sakellaropoulos, G. [Aristotle Univ. of Thessaloniki (Greece). Dept. of Chemical Engineering

2004-09-15

Co-combustion of solid wastes with coal is a promising technique used to reduce landfilled wastes, utilizing waste the energy content. However, solid wastes often contain chlorine and other substances, which upon combustion may result in the production of extremely toxic compounds like polychlorinated dibenzo-p-dioxins and dibenzofurans. Various compounds have been proposed for their inhibition ability of PCDD/F formation, including sulphuric and nitrogen containing substances. Sulfur compounds may form some kind of complexes with metal species, reducing thus their ability for catalysing the PCDD/F formation pathways. Sulfur inhibitory capacity has been attributed to reaction with copper catalytic sites, altering their form and presumably their ability to produce Cl{sub 2} through the Deacon process reaction. Another second postulated role of sulfur is to undergo homogeneous reactions, converting the primary chlorinating agent, Cl{sub 2}, into a form (HCl) less likely to undergo aromatic substitution reactions forming PCDD/F precursors. The objectives of this work were the measurement of PCDD/F emissions during co-combustion of different fuel mixtures, and the study of the effect of sulfur addition to the fuel on PCDD/F formation.

Thermochemical Study on the Sulfurization of Fission Products in Spent Nuclear Fuel

International Nuclear Information System (INIS)

Lee, Jung Won; Yang, M. S.; Park, G. I.; Kim, W. K.; Lee, J. W.

2005-11-01

The thermodynamic behavior of the sulfurization of Nd, and Eu element, which are contained in spent nuclear fuel as fission products was investigated through collection and properties analysis of thermodynamic data in sulfurization of uranium oxides, thermodynamic properties analysis for the oxidation and reduction of fission products, and test and analysis for sulfurization characteristics of Nd and Eu oxide. And also, analysis on thermodynamic data, such as M-O-S phase stability diagram and changes of Gibbs free energy for sulfurization of uranium and Nd 2 O 3 and Eu 2 O 3 were carried out. Nd 2 O 3 and Eu 2 O 3 are sulfurized into Nd 2 O 2 S and Eu 2 O 2 S or NdySx and EuySx at a range of 400 to 450 .deg. C, while uranium oxides, such as UO 2 and U 3 O 8 remain unreacted up to 450 .deg. C Formation of UOS at 500 .deg. C is initiated by sulfurization of uranium oxides. Hence, reaction temperature for the sulfurization of the Nd 2 O 3 and Eu 2 O 3 was selected as a 450 .deg. C

Sulfur-Kβ /sub emission studies on sulfur-bearing heterocycles

International Nuclear Information System (INIS)

Phillips, D.R.; Andermann, G.G.; Fujiwara, F.

1986-01-01

Sulfur-K/β /sub x-ray fluorescence spectroscopy (XFS) has been used to study the electronic structure and bonding in sulfur-bearing heterocycles. XFS not only has the capability of experimentally measuring valence electron energies in molecular species, but can also provide intensity data which can help define the nature of the molecular orbitals defined by the electrons. This report discusses the feasibility of using XFS as an analytical tool for the determination of total and specific sulfur heterocycle content in samples. A variety of compounds were studied. These include thiophene, thiophene derivatives, tetranydrothiophene, several more complex saturated and unsaturated sulfur heterocycles, and heterocycles containing both sulfur and nitrogen. The sulfur-K/β /sub spectra were obtained using a double crystal spectrometer which provided an instrumental resolution of about 0.7 eV

Graphene-wrapped sulfur nanospheres with ultra-high sulfur loading for high energy density lithium–sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Liu, Ya; Guo, Jinxin; Zhang, Jun, E-mail: zhangjun@zjnu.cn; Su, Qingmei; Du, Gaohui, E-mail: gaohuidu@zjnu.edu.cn

2015-01-01

Graphical abstract: - Highlights: • A graphene-wrapped sulfur nanospheres composite with 91 wt% S is prepared. • It shows highly improved electrochemical performance as cathode for Li–S cell. • The PVP coating and conductive graphene minimize polysulfides dissolution. • The flexible coatings with void space accommodate the volume expansion of sulfur. - Abstract: Lithium–sulfur (Li–S) battery with high theoretical energy density is one of the most promising energy storage systems for electric vehicles and intermittent renewable energy. However, due to the poor conductivity of the active material, considerable weight of the electrode is occupied by the conductive additives. Here we report a graphene-wrapped sulfur nanospheres composite (S-nanosphere@G) with sulfur content up to 91 wt% as the high energy density cathode material for Li–S battery. The sulfur nanospheres with diameter of 400–500 nm are synthesized through a solution-based approach with the existence of polyvinylpyrrolidone (PVP). Then the sulfur nanospheres are uniformly wrapped by conductive graphene sheets through the electrostatic interaction between graphene oxide and PVP, followed by reducing of graphene oxide with hydrazine. The design of graphene wrapped sulfur nanoarchitecture provides flexible conductive graphene coating with void space to accommodate the volume expansion of sulfur and to minimize polysulfide dissolution. As a result, the S-nanosphere@G nanocomposite with 91 wt% sulfur shows a reversible initial capacity of 970 mA h g{sup −1} and an average columbic efficiency > 96% over 100 cycles at a rate of 0.2 C. Taking the total mass of electrode into account, the S-nanosphere@G composite is a promising cathode material for high energy density Li–S batteries.

Multiple-heteroatom-containing sulfur compounds in a high sulfur coal

International Nuclear Information System (INIS)

Winans, R.E.; Neill, P.H.

1990-01-01

Flash vacuum pyrolysis of a high sulfur coal has been combined with high resolution mass spectrometry yielding information on aromatic sulfur compounds containing an additional heteroatom. Sulfur emission from coal utilization is a critical problem and in order to devise efficient methods for removing organic sulfur, it is important to know what types of molecules contain sulfur. A high sulfur Illinois No. 6 bituminous coal (Argonne Premium Coal Sample No. 3) was pyrolyzed on a platinum grid using a quartz probe inserted into a modified all glass heated inlet system and the products characterized by high resolution mass spectrometry (HRMS). A significant number of products were observed which contained both sulfur and an additional heteroatom. In some cases two additional heteroatoms were observed. These results are compared to those found in coal extracts and liquefaction products

Insight into the loading temperature of sulfur on sulfur/carbon cathode in lithium-sulfur batteries

International Nuclear Information System (INIS)

Ye, Huan; Yin, Ya-Xia; Guo, Yu-Guo

2015-01-01

Highlights: • A cost-effective chemical activation method to prepare porous carbon nanospheres. • Carbon nanospheres with bimodal microporous structure show high specific area and large micropore volume. • The S/C composite cathodes with in-situformed S−C bond exhibit high sulfur activity with a reversible capacity of 1000 mA h g −1 . • S−C bond enables well confinement on sulfur and polysulfides. - Abstract: Lithium–sulfur batteries are highly desired because of their characteristics such as high energy density. However, the applications of Li-S batteries are limited because they exist dissolution of polysulfides into electrolytes. This study reports the preparation of sulfur cathodes by using bimodal microporous (0.5 nm and 0.8 nm to 2.0 nm) carbon spheres with high specific area (1992 m 2 g −1 ) and large micropore volume (1.2 g cm −1 ), as well as the encapsulation of polysulfides via formation of carbon–sulfur bonds in a sealed vacuum glass tube at high temperature. Given that sulfur and polysulfides are well confined by the S−C bond, the shuttle effect is effectively suppressed. The prepared S/C cathodes with a sulfur loading of up to 75% demonstrate high sulfur activity with reversible capacity of 1000 mA h g −1 at the current density of 0.1 A g −1 and good cycling stability (667 mA h g −1 after 100 cycles).

Sulfur Cycling in an Iron Oxide-Dominated, Dynamic Marine Depositional System: The Argentine Continental Margin

Directory of Open Access Journals (Sweden)

Natascha Riedinger

2017-05-01

Full Text Available The interplay between sediment deposition patterns, organic matter type and the quantity and quality of reactive mineral phases determines the accumulation, speciation, and isotope composition of pore water and solid phase sulfur constituents in marine sediments. Here, we present the sulfur geochemistry of siliciclastic sediments from two sites along the Argentine continental slope—a system characterized by dynamic deposition and reworking, which result in non-steady state conditions. The two investigated sites have different depositional histories but have in common that reactive iron phases are abundant and that organic matter is refractory—conditions that result in low organoclastic sulfate reduction rates (SRR. Deposition of reworked, isotopically light pyrite and sulfurized organic matter appear to be important contributors to the sulfur inventory, with only minor addition of pyrite from organoclastic sulfate reduction above the sulfate-methane transition (SMT. Pore-water sulfide is limited to a narrow zone at the SMT. The core of that zone is dominated by pyrite accumulation. Iron monosulfide and elemental sulfur accumulate above and below this zone. Iron monosulfide precipitation is driven by the reaction of low amounts of hydrogen sulfide with ferrous iron and is in competition with the oxidation of sulfide by iron (oxyhydroxides to form elemental sulfur. The intervals marked by precipitation of intermediate sulfur phases at the margin of the zone with free sulfide are bordered by two distinct peaks in total organic sulfur (TOS. Organic matter sulfurization appears to precede pyrite formation in the iron-dominated margins of the sulfide zone, potentially linked to the presence of polysulfides formed by reaction between dissolved sulfide and elemental sulfur. Thus, SMTs can be hotspots for organic matter sulfurization in sulfide-limited, reactive iron-rich marine sedimentary systems. Furthermore, existence of elemental sulfur and iron

Hydrolysis of Pentosan for Furfural Preparing Using Sulfuric Acid Catalyst to Improve Diesel Engine Fuel Quality

International Nuclear Information System (INIS)

Setyadji, Moch

2007-01-01

The investigation on furfural preparation from peanut shell using sulfuric acid catalyst has been done. Furfural is an organic solvent used in industry especially petroleum industry. The purpose of this investigation is to know the effects of sulfuric acid concentration and solvent feed ratio towards furfural resulted and the reaction kinetics. The experiment was performed in the batch reactor. The result of this investigation showed that the process optimum condition was reached at sulfuric acid concentration of 7% and the solvent feed ratio of 12.5. The result at the optimum condition above was 5.97% of furfural. The relation between percentage of furfural resulted (Y) and sulfuric acid concentration (X) is Y = 0.893 X 1.7023 . e -0.2554X with average deviation of 5.880 %. The relation between percentage of furfural resulted (Y) and solvent feed ratio (X) is Y = -53.0411 + 9.4137 X - 0.3780 X 2 with average deviation 5.154 %. The relation between reaction rate constant (Y) and sulfuric acid concentration (X) is Y = 3.1916 . 10 -3 + 8.2432 . 10 -3 X - 5.2324 . 10 -4 X 2 with average deviation 8.024 %. (author)

Acclimation of green algae to sulfur deficiency: underlying mechanisms and application for hydrogen production.

Science.gov (United States)

Antal, Taras K; Krendeleva, Tatyana E; Rubin, Andrew B

2011-01-01

Hydrogen is definitely one of the most acceptable fuels in the future. Some photosynthetic microorganisms, such as green algae and cyanobacteria, can produce hydrogen gas from water by using solar energy. In green algae, hydrogen evolution is coupled to the photosynthetic electron transport in thylakoid membranes via reaction catalyzed by the specific enzyme, (FeFe)-hydrogenase. However, this enzyme is highly sensitive to oxygen and can be quickly inhibited when water splitting is active. A problem of incompatibility between the water splitting and hydrogenase reaction can be overcome by depletion of algal cells of sulfur which is essential element for life. In this review the mechanisms underlying sustained hydrogen photoproduction in sulfur deprived C. reinhardtii and the recent achievements in studying of this process are discussed. The attention is focused on the biophysical and physiological aspects of photosynthetic response to sulfur deficiency in green algae.

Improved method for minimizing sulfur loss in analysis of particulate organic sulfur.

Science.gov (United States)

Park, Ki-Tae; Lee, Kitack; Shin, Kyoungsoon; Jeong, Hae Jin; Kim, Kwang Young

2014-02-04

The global sulfur cycle depends primarily on the metabolism of marine microorganisms, which release sulfur gas into the atmosphere and thus affect the redistribution of sulfur globally as well as the earth's climate system. To better quantify sulfur release from the ocean, analysis of the production and distribution of organic sulfur in the ocean is necessary. This report describes a wet-based method for accurate analysis of particulate organic sulfur (POS) in the marine environment. The proposed method overcomes the considerable loss of sulfur (up to 80%) that occurs during analysis using conventional methods involving drying. Use of the wet-based POS extraction procedure in conjunction with a sensitive sulfur analyzer enabled accurate measurements of cellular POS. Data obtained using this method will enable accurate assessment of how rapidly sulfur can transfer among pools. Such information will improve understanding of the role of POS in the oceanic sulfur cycle.

Investigations of solvents and various sulfur sources influence on the shape-controlled synthesis of CuInS2 nanocrystals

International Nuclear Information System (INIS)

Kruszynska, Marta; Borchert, Holger; Parisi, Jürgen; Kolny-Olesiak, Joanna

2011-01-01

CuInS 2 (CIS) nanocrystals were successfully synthesized through a hot-injection technique employing a reaction of copper (I) acetate and indium (III) acetate with tert-dodecanethiol as a source of sulfur, and trioctylphosphine oxide and 1-dodecanethiol were used as ligands. The reaction medium was a mixture of two solvents: oleylamine and 1-octadecene. Varying the ratio between both solvents leads to the formation of wurtzite CuInS 2 particles with shapes ranging from triangular to rod-shaped with length up to 50 nm. Oleylamine turned out to influence the reaction condition in two opposite ways: by leading to monomer depletion before the injection of the sulfur precursor, and at the same time increasing the activity of the monomers remaining in solution. By changing the sulfur source from tert-dodecanethiol to sulfur dissolved in oleylamine, triangular particles with zinc blend structure and a smaller size (∼5 nm) were synthesized. The final materials were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX), and absorption spectroscopy (UV–Vis).

Transnitrosation of alicyclic N-nitrosamines containing a sulfur atom.

Science.gov (United States)

Inami, Keiko; Kondo, Sonoe; Ono, Yuta; Saso, Chiharu; Mochizuki, Masataka

2013-12-15

Aromatic and aliphatic nitrosamines are known to transfer a nitrosonium ion to another amine. The transnitrosation of alicyclic N-nitroso compounds generates S-nitrosothiols, which are potential nitric oxide donors in vivo. In this study, certain alicyclic N-nitroso compounds based on non-mutagenic N-nitrosoproline or N-nitrosothioproline were synthesised, and the formation of S-nitrosoglutathione (GSNO) was quantified under acidic conditions. We then investigated the effect of a sulfur atom as the substituent and as a ring component on the GSNO formation. In the presence of thiourea under acidic conditions, GSNO was formed from N-nitrosoproline and glutathione, and an N-nitroso compound containing a sulfur atom and glutathione produced GSNO without thiourea. The quantity of GSNO derived from the reaction of the N-nitrosamines containing a sulfur atom and glutathione was higher than that from the N-nitrosoproline and glutathione plus thiourea. Among the analogues that contained a sulfur atom either in the ring or as a substituent, the thiazolidines produced a slightly higher quantity of GSNO than the analogue with a thioamide group. A compound containing sulfur atoms both in the ring and as a substituent exhibited the highest activity for GSNO formation among the alicyclic N-nitrosamines tested. The results indicate that the intramolecular sulfur atom plays an important role in the transnitrosation via alicyclic N-nitroso compounds to form GSNO. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

Facile preparation of three-dimensional Co1-xS/sulfur and nitrogen-codoped graphene/carbon foam for highly efficient oxygen reduction reaction

Science.gov (United States)

Liang, Hui; Li, Chenwei; Chen, Tao; Cui, Liang; Han, Jingrui; Peng, Zhi; Liu, Jingquan

2018-02-01

Because of the urgent need for renewable resources, oxygen reduction reaction (ORR) has been widely studied. Finding efficient and low cost non-precious metal catalyst is increasingly critical. In this study, melamine foam is used as template to obtain porous sulfur and nitrogen-codoped graphene/carbon foam with uniformly distributed cobalt sulfide nanoparticles (Co1-xS/SNG/CF) which is prepared by a simple infiltration-drying-sulfuration method. It is noteworthy that melamine foam not only works as a three-dimensional support skeleton, but also provides a nitrogen source without any environmental pollution. Such Co1-xS/SNG/CF catalyst shows excellent oxygen reduction catalytic performance with an onset potential of only 0.99 V, which is the same as that of Pt/C catalyst (Eonset = 0.99 V). Furthermore, the stability and methanol tolerance of Co1-xS/SNG/CF are more outstanding than those of Pt/C catalyst. Our work manifests a facile method to prepare S and N-codoped 3D graphene network decorated with Co1-xS nanoparticles, which may be utilized as potential alternative to the expensive Pt/C catalysts toward ORR.

Improvement of sulfur resistance of Pd/Ce-Zr-Al-O catalysts for CO oxidation

Science.gov (United States)

Shin, Haebin; Baek, Minsung; Ro, Youngsoo; Song, Changyeol; Lee, Kwan-Young; Song, In Kyu

2018-01-01

Two kinds of mesoporous ceria-zirconia-alumina supports were prepared by a single-step epoxide-driven sol-gel method (SGCZA) and by a co-precipitation method (PCZA). Palladium catalysts supported on these materials were then prepared by a wet impregnation method (Pd/SGCZA and Pd/PCZA). The prepared catalysts were applied to the CO oxidation reaction before and after sulfur aging. XRD and N2 adsorption-desorption analyses revealed that these two catalysts retained different physicochemical properties. Pd/SGCZA had higher surface area and larger pore volume than Pd/PCZA before and after sulfur aging. TPR (Temperature-programmed reduction), CO chemisorption, FT-IR, and XPS analyses showed that the catalysts were differently influenced by sulfur species. Pd/SGCZA formed less sulfate and retained higher palladium dispersion than Pd/PCZA after sulfur aging. In the CO oxidation, Pd/PCZA showed better activity than Pd/SGCZA before sulfur aging. However, Pd/SGCZA showed higher CO conversion than Pd/PCZA after sulfur aging. We concluded that Pd/SGCZA was less poisoned by sulfur species than Pd/PCZA.

Desulfurization of organic sulfur from lignite by an electron transfer process

Energy Technology Data Exchange (ETDEWEB)

Demirbas, A. [Selcuk University, Konya (Turkey). Dept. for Chemical Engineering

2006-10-15

This study is an attempt to desulfurize organic sulfur from lignite samples with ferrocyanide ion as the electron transferring agent. Effect of temperature, particle size and concentration of ferrocyanide ion on desulfurization from the lignite samples has been investigated. The desulfurization process has been found to be continuous and gradually increases with increase of temperature from 298 to 368 K. The particle size has no significant impact on sulfur removal from the lignite samples. Particle size has no profound impact on the amount of sulfur removal. The desulfurization reaction has been found to be dependent on the concentration of potassium ferrocyanide. Gradual increase in the concentration of potassium ferrocyanide raised the magnitude of desulfurization, but at a higher concentration, the variation is not significant.

Sulfur based electrode materials for secondary batteries

Science.gov (United States)

Hao, Yong

Developing next generation secondary batteries has attracted much attention in recent years due to the increasing demand of high energy and high power density energy storage for portable electronics, electric vehicles and renewable sources of energy. This dissertation investigates sulfur based advanced electrode materials in Lithium/Sodium batteries. The electrochemical performances of the electrode materials have been enhanced due to their unique nano structures as well as the formation of novel composites. First, a nitrogen-doped graphene nanosheets/sulfur (NGNSs/S) composite was synthesized via a facile chemical reaction deposition. In this composite, NGNSs were employed as a conductive host to entrap S/polysulfides in the cathode part. The NGNSs/S composite delivered an initial discharge capacity of 856.7 mAh g-1 and a reversible capacity of 319.3 mAh g-1 at 0.1C with good recoverable rate capability. Second, NGNS/S nanocomposites, synthesized using chemical reaction-deposition method and low temperature heat treatment, were further studied as active cathode materials for room temperature Na-S batteries. Both high loading composite with 86% gamma-S8 and low loading composite with 25% gamma-S8 have been electrochemically evaluated and compared with both NGNS and S control electrodes. It was found that low loading NGNS/S composite exhibited better electrochemical performance with specific capacity of 110 and 48 mAh g-1 at 0.1C at the 1st and 300th cycle, respectively. The Coulombic efficiency of 100% was obtained at the 300th cycle. Third, high purity rock-salt (RS), zinc-blende (ZB) and wurtzite (WZ) MnS nanocrystals with different morphologies were successfully synthesized via a facile solvothermal method. RS-, ZB- and WZ-MnS electrodes showed the capacities of 232.5 mAh g-1, 287.9 mAh g-1 and 79.8 mAh g-1 at the 600th cycle, respectively. ZB-MnS displayed the best performance in terms of specific capacity and cyclability. Interestingly, MnS electrodes

Selenocysteine in thiol/disulfide-like exchange reactions.

Science.gov (United States)

Hondal, Robert J; Marino, Stefano M; Gladyshev, Vadim N

2013-05-01

Among trace elements used as cofactors in enzymes, selenium is unique in that it is incorporated into proteins co-translationally in the form of an amino acid, selenocysteine (Sec). Sec differs from cysteine (Cys) by only one atom (selenium versus sulfur), yet this switch dramatically influences important aspects of enzyme reactivity. The main focus of this review is an updated and critical discussion on how Sec might be used to accelerate thiol/disulfide-like exchange reactions in natural selenoenzymes, compared with their Cys-containing homologs. We discuss in detail three major aspects associated with thiol/disulfide exchange reactions: (i) nucleophilicity of the attacking thiolate (or selenolate); (ii) electrophilicity of the center sulfur (or selenium) atom; and (iii) stability of the leaving group (sulfur or selenium). In all these cases, we analyze the benefits that selenium might provide in these types of reactions. It is the biological thiol oxidoreductase-like function that benefits from the use of Sec, since Sec functions to chemically accelerate the rate of these reactions. We review various hypotheses that could help explain why Sec is used in enzymes, particularly with regard to competitive chemical advantages provided by the presence of the selenium atom in enzymes. Ultimately, these chemical advantages must be connected to biological functions of Sec.

Dominance of sulfur-fueled iron oxide reduction in low-sulfate freshwater sediments.

Science.gov (United States)

Hansel, Colleen M; Lentini, Chris J; Tang, Yuanzhi; Johnston, David T; Wankel, Scott D; Jardine, Philip M

2015-11-01

A central tenant in microbial biogeochemistry is that microbial metabolisms follow a predictable sequence of terminal electron acceptors based on the energetic yield for the reaction. It is thereby oftentimes assumed that microbial respiration of ferric iron outcompetes sulfate in all but high-sulfate systems, and thus sulfide has little influence on freshwater or terrestrial iron cycling. Observations of sulfate reduction in low-sulfate environments have been attributed to the presumed presence of highly crystalline iron oxides allowing sulfate reduction to be more energetically favored. Here we identified the iron-reducing processes under low-sulfate conditions within columns containing freshwater sediments amended with structurally diverse iron oxides and fermentation products that fuel anaerobic respiration. We show that despite low sulfate concentrations and regardless of iron oxide substrate (ferrihydrite, Al-ferrihydrite, goethite, hematite), sulfidization was a dominant pathway in iron reduction. This process was mediated by (re)cycling of sulfur upon reaction of sulfide and iron oxides to support continued sulfur-based respiration--a cryptic sulfur cycle involving generation and consumption of sulfur intermediates. Although canonical iron respiration was not observed in the sediments amended with the more crystalline iron oxides, iron respiration did become dominant in the presence of ferrihydrite once sulfate was consumed. Thus, despite more favorable energetics, ferrihydrite reduction did not precede sulfate reduction and instead an inverse redox zonation was observed. These findings indicate that sulfur (re)cycling is a dominant force in iron cycling even in low-sulfate systems and in a manner difficult to predict using the classical thermodynamic ladder.

Process for the removal of sulfur oxides and nitrogen oxides from flue gas

International Nuclear Information System (INIS)

Elshout, R.V.

1992-01-01

This patent describes a continuous process for removing sulfur oxide and nitrogen oxide contaminants from the flue gas generated by industrial power plants and boiler systems burning sulfur containing fossil fuels and for converting these contaminants, respectively, into recovered elemental liquid sulfur and nitrogen ammonia and mixtures thereof. It comprises removing at least a portion of the flue gas generated by a power plant or boiler system upstream of the stack thereof; passing the cooled and scrubbed flue gas through an adsorption system; combining a first portion of the reducing gas stream leaving the adsorbers of the adsorption system during regeneration thereof and containing sulfur oxide and nitrogen oxide contaminants with a hydrogen sulfide rich gas stream at a temperature of about 400 degrees F to about 600 degrees F and passing the combined gas streams through a Claus reactor-condenser system over a catalyst in the reactor section thereof which is suitable for promoting the equilibrium reaction between the hydrogen sulfide and the sulfur dioxide of the combined streams to form elemental sulfur

Sulfur-Containing Agrochemicals.

Science.gov (United States)

Devendar, Ponnam; Yang, Guang-Fu

2017-10-09

Modern agricultural chemistry has to support farmers by providing innovative agrochemicals. In this context, the introduction of sulfur atoms into an active ingredient is still an important tool in modulating the properties of new crop-protection compounds. More than 30% of today's agrochemicals contain at least one sulfur atom, mainly in fungicides, herbicides and insecticides. A number of recently developed sulfur-containing agrochemical candidates represent a novel class of chemical compounds with new modes of action, so we intend to highlight the emerging interest in commercially active sulfur-containing compounds. This chapter gives a comprehensive overview of selected leading sulfur-containing pesticidal chemical families namely: sulfonylureas, sulfonamides, sulfur-containing heterocyclics, thioureas, sulfides, sulfones, sulfoxides and sulfoximines. Also, the most suitable large-scale synthetic methods of the recently launched or provisionally approved sulfur-containing agrochemicals from respective chemical families have been highlighted.

Reaction of Hydrogen Sulfide with Oxygen in the Presence ofSulfite

Energy Technology Data Exchange (ETDEWEB)

Weres, Oleh; Tsao, Leon

1983-01-01

Commonly, abatement of hydrogen sulfide emissions from a geothermal powerplant requires that hydrogen sulfide dissolved in the cooling water be eliminated by chemical reaction. Oxidation by atmospheric oxygen is the preferred reaction, but requires a suitable catalyst. Nickel is the most potent and thereby cheapest catalyst for this purpose. One Mg/L nickel in the cooling water would allow 99% removal of hydrogen sulfide to be attained. A major drawback of catalytic air oxidation is that colloidal sulfur is a major reaction product; this causes rapid sludge accumulation and deposition of sulfur scale. The authors studied the kinetics and product distribution of the reaction of hydrogen sulfide with oxygen, catalyzed by nickel. Adding sodium sulfite to the solution completely suppresses formation of colloidal sulfur by converting it to thiosulfate. The oxidation reaction is an autocatalytic, free radical chain reaction. A rate expression for this reaction and a detailed reaction mechanism were developed. Nickel catalyzes the chain initiation step, and polysulfidoradical ions propagate the chains. Several complexes of iron and cobalt were also studied. Iron citrate and iron N-hydroxyEDT are the most effective iron based catalysts. Uncomplexed cobalt is as effective as nickel, but forms a precipitate of cobalt oxysulfide and is too expensive for practical use.

Reaction of hydrogen sulfide with oxygen in the presence of sulfite

Energy Technology Data Exchange (ETDEWEB)

Weres, O.; Tsao, L.

1983-01-14

Commonly, abatement of hydrogen sulfide emission from a geothermal powerplant requires that hydrogen sulfide dissolved in the cooling water be eliminated by chemical reaction. Oxidation by atmospheric oxygen is the preferred reaction, but requires a suitable catalyst. Nickel is the most potent and thereby cheapest catalyst for this purpose. One mg/L nickel in the cooling water would allow 99% removal of hydrogen sulfide to be attained. A major drawback of catalytic air oxidation is that colloidal sulfur is a major reaction product; this causes rapid sludge accumulation and deposition of sulfur scale. We studied the kinetics and product distribution of the reaction of hydrogen sulfide with oxygen, catalyzed by nickel. Adding sodium sulfite to the solution completely suppresses formation of colloidal sulfur by converting it to thiosulfate. The oxidation reaction is an autocatalytic, free radical chain reaction. A rate expression for this reaction and a detailed reaction mechanism were developed. Nickel catalyzes the chain initiation step, and polysulfidoradical ions propagate the chains. Several complexes of iron and cobalt were also studied. Iron citrate and iron N-hydroxyEDTA are the most effective iron based catalysts. Uncomplexed cobalt is as effective as nickel, but forms a precipitate of cobalt oxysulfide and is too expensive for practical use. 33 figures, 9 tables.

Dynamics of biogeochemical sulfur cycling in Mono Lake

Science.gov (United States)

Phillips, A. A.; Fairbanks, D.; Wells, M.; Fullerton, K. M.; Bao, R.; Johnson, H.; Speth, D. R.; Stamps, B. W.; Miller, L.; Sessions, A. L.

2017-12-01

Mono Lake, California is a closed-basin soda lake (pH 9.8) with high sulfate (120mM), and is an ideal natural laboratory for studying microbial sulfur cycling. Mono Lake is typically thermally stratified in summer while mixing completely in winter. However, large snowmelt inputs may induce salinity stratification that persists for up to five years, causing meromixis. During the California drought of 2014-16, the lake has mixed thoroughly each winter, but the abundant 2017 snowmelt may usher in a multi-year stratification. This natural experiment provides an opportunity to investigate the temporal relationship between microbial sulfur cycling and lake biogeochemistry. We analyzed water samples from five depths at two stations in May of 2017, before the onset of meromixis. Water column sulfate isotope values were generally constant with depth, centering at a δ34SVCDT of 17.39 ± 0.06‰. Organic sulfur isotopes were consistently lighter than lake sulfate, with a δ34SVCDT of 15.59 ± 0.56‰. This significant offset between organic and inorganic sulfur contradicts the minimal isotope effect associated with sulfate assimilation. Sediment push core organic values were further depleted, ranging between δ34SVCDT of -8.94‰ and +0.23‰, implying rapid turnover of Mono Lake sulfur pools. Both lipid biomarkers and 16S rRNA gene amplicons identify Picocystis salinarum, a unicellular green alga, as the dominant member of the microbial community. However, bacterial biomarkers and 16S rRNA genes point to microbes capable of sulfur cycling. We found that dsrA increased with depth (R2 = 0.9008, p reducers and sulfide oxidizers after >1 year of stratification. We saw no evidence in May of 2017 of sulfate reducing bacteria across the oxycline. Additionally, no sulfide was detectable in lake bottom waters despite oxygen below 6.25 µM. Preliminary results suggest a dynamic interplay between sulfide oxidation, sulfate reduction, and the onset of lake stratification. Additional

Pyrite sulfur isotopes reveal glacial-interglacial environmental changes

Science.gov (United States)

Pasquier, Virgil; Sansjofre, Pierre; Rabineau, Marina; Revillon, Sidonie; Houghton, Jennifer; Fike, David A.

2017-06-01

The sulfur biogeochemical cycle plays a key role in regulating Earth’s surface redox through diverse abiotic and biological reactions that have distinctive stable isotopic fractionations. As such, variations in the sulfur isotopic composition (δ34S) of sedimentary sulfate and sulfide phases over Earth history can be used to infer substantive changes to the Earth’s surface environment, including the rise of atmospheric oxygen. Such inferences assume that individual δ34S records reflect temporal changes in the global sulfur cycle; this assumption may be well grounded for sulfate-bearing minerals but is less well established for pyrite-based records. Here, we investigate alternative controls on the sedimentary sulfur isotopic composition of marine pyrite by examining a 300-m drill core of Mediterranean sediments deposited over the past 500,000 y and spanning the last five glacial-interglacial periods. Because this interval is far shorter than the residence time of marine sulfate, any change in the sulfur isotopic record preserved in pyrite (δ34Spyr) necessarily corresponds to local environmental changes. The stratigraphic variations (>76‰) in the isotopic data reported here are among the largest ever observed in pyrite, and are in phase with glacial-interglacial sea level and temperature changes. In this case, the dominant control appears to be glacial-interglacial variations in sedimentation rates. These results suggest that there exist important but previously overlooked depositional controls on sedimentary sulfur isotope records, especially associated with intervals of substantial sea level change. This work provides an important perspective on the origin of variability in such records and suggests meaningful paleoenvironmental information can be derived from pyrite δ34S records.

Modeling the Distribution of Sulfur Compounds in a Large Two Stroke Diesel Engine

DEFF Research Database (Denmark)

Cordtz, Rasmus Lage; Schramm, Jesper; Andreasen, Anders

2013-01-01

In many years large low speed marine diesel engines have consumed heavy fuel oils with sulfur contents in the order of 2.5 - 4.5wt%. Present legislations require that the fuel sulfur is reduced and in near future the limit will be 0.5wt% globally. During combustion most of the sulfur is oxidized...... conditions and sulfur feed. This work presents a computational model of a large low speed two-stroke diesel engine where a 0D multi-zone approach including a detailed reaction mechanism is employed in order to investigate in cylinder formation of gaseous SO3 where fuel injection rates are determined using...... experimental pressure traces. Similarly to NO the SO3 is very sensitive to the rate that fresh air mixes with hot combustion products. Therefore a simple mixing rate is proposed and calibrated in order to meet experimental results of NO. Generally 3 - 5 % of the injected sulfur is oxidized to SO3...

Thermal stress analysis of sulfur deactivated solid oxide fuel cells

Science.gov (United States)

Zeng, Shumao; Parbey, Joseph; Yu, Guangsen; Xu, Min; Li, Tingshuai; Andersson, Martin

2018-03-01

Hydrogen sulfide in fuels can deactivate catalyst for solid oxide fuel cells, which has become one of the most critical challenges to stability. The reactions between sulfur and catalyst will cause phase changes, leading to increase in cell polarization and mechanical mismatch. A three-dimensional computational fluid dynamics (CFD) approach based on the finite element method (FEM) is thus used to investigate the polarization, temperature and thermal stress in a sulfur deactivated SOFC by coupling equations for gas-phase species, heat, momentum, ion and electron transport. The results indicate that sulfur in fuels can strongly affect the cell polarization and thermal stresses, which shows a sharp decrease in the vicinity of electrolyte when 10% nickel in the functional layer is poisoned, but they remain almost unchanged even when the poisoned Ni content was increased to 90%. This investigation is helpful to deeply understand the sulfur poisoning effects and also benefit the material design and optimization of electrode structure to enhance cell performance and lifetimes in various hydrocarbon fuels containing impurities.

Non-spectral interferences due to the presence of sulfuric acid in inductively coupled plasma mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

García-Poyo, M. Carmen; Grindlay, Guillermo; Gras, Luis [Department of Analytical Chemistry, Nutrition and Food Sciences, University of Alicante, P.O. Box 99, 03080 – Alicante (Spain); Loos-Vollebregt, Margaretha T.C. de, E-mail: margaretha.deloos@ugent.be [Delft University of Technology, Faculty of Applied Sciences, Analytical Biotechnology, Julianalaan 67, 2628 BC Delft (Netherlands); Ghent University, Department of Analytical Chemistry, Krijgslaan 281 - S12, 9000 Ghent (Belgium); Mora, Juan, E-mail: juan.mora@ua.es [Department of Analytical Chemistry, Nutrition and Food Sciences, University of Alicante, P.O. Box 99, 03080 – Alicante (Spain)

2015-03-01

Results of a systematic study concerning non-spectral interferences from sulfuric acid containing matrices on a large number of elements in inductively coupled plasma–mass spectrometry (ICP-MS) are presented in this work. The signals obtained with sulfuric acid solutions of different concentrations (up to 5% w w{sup −1}) have been compared with the corresponding signals for a 1% w w{sup −1−} nitric acid solution at different experimental conditions (i.e., sample uptake rates, nebulizer gas flows and r.f. powers). The signals observed for {sup 128}Te{sup +}, {sup 78}Se{sup +} and {sup 75}As{sup +} were significantly higher when using sulfuric acid matrices (up to 2.2-fold for {sup 128}Te{sup +} and {sup 78}Se{sup +} and 1.8-fold for {sup 75}As{sup +} in the presence of 5 w w{sup -1} sulfuric acid) for the whole range of experimental conditions tested. This is in agreement with previously reported observations. The signal for {sup 31}P{sup +} is also higher (1.1-fold) in the presence of sulfuric acid. The signal enhancements for {sup 128}Te{sup +}, {sup 78}Se{sup +}, {sup 75}As{sup +} and {sup 31}P{sup +} are explained in relation to an increase in the analyte ion population as a result of charge transfer reactions involving S{sup +} species in the plasma. Theoretical data suggest that Os, Sb, Pt, Ir, Zn and Hg could also be involved in sulfur-based charge transfer reactions, but no experimental evidence has been found. The presence of sulfuric acid gives rise to lower ion signals (about 10–20% lower) for the other nuclides tested, thus indicating the negative matrix effect caused by changes in the amount of analyte loading of the plasma. The elemental composition of a certified low-density polyethylene sample (ERM-EC681K) was determined by ICP-MS after two different sample digestion procedures, one of them including sulfuric acid. Element concentrations were in agreement with the certified values, irrespective of the acids used for the digestion. These

Spectroscopic characteristics of carbon dots (C-dots) derived from carbon fibers and conversion to sulfur-bridged C-dots nanosheets.

Science.gov (United States)

Vinci, John C; Ferrer, Ivonne M; Guterry, Nathan W; Colón, Verónica M; Destino, Joel F; Bright, Frank V; Colón, Luis A

2015-09-01

We synthesized sub-10 nm carbon nanoparticles (CNPs) consistent with photoluminescent carbon dots (C-dots) from carbon fiber starting material. The production of different C-dots fractions was monitored over seven days. During the course of the reaction, one fraction of C-dots species with relatively high photoluminescence was short-lived, emerging during the first hour of reaction but disappearing after one day of reaction. Isolation of this species during the first hour of the reaction was crucial to obtaining higher-luminescent C-dots species. When the reaction proceeded for one week, the appearance of larger nanostructures was observed over time, with lateral dimensions approaching 200 nm. The experimental evidence suggests that these larger species are formed from small C-dot nanoparticles bridged together by sulfur-based moieties between the C-dot edge groups, as if the C-dots polymerized by cross-linking the edge groups through sulfur bridges. Their size can be tailored by controlling the reaction time. Our results highlight the variety of CNP products, from sub-10 nm C-dots to ~200 nm sulfur-containing carbon nanostructures, that can be produced over time during the oxidation reaction of the graphenic starting material. Our work provides a clear understanding of when to stop the oxidation reaction during the top-down production of C-dots to obtain highly photoluminescent species or a target average particle size.

Oxidation of refractory sulfur compounds over Ti-containing mesoporous molecular sieves prepared by using a fluorosilicon compound.

Science.gov (United States)

Jeong, Kwang-Eun; Cho, Chin-Soo; Chae, Ho-Jeong; Kim, Chul-Ung; Jeong, Soon-Yong

2010-05-01

Titanium containing mesoporous molecular sieve (Ti-MMS) catalysts were studied for the oxidative desulfurization of refractory sulfur compounds. Ti-MMS catalysts were synthesized from fluorosilicon compounds and Ti with the hydrolysis reaction of H2SiF6 in an ammonia-surfactant mixed solution. The solid products were characterized by XRD, XRF, nitrogen adsorption, and diffuse reflectance UV-vis spectroscopy. Effects of Ti loading and oxidant/sulfur mole ratio, and sulfur species on ODS activity were investigated.

Beta decay of /sup 39/Cl

International Nuclear Information System (INIS)

Wang, G.; Warburton, E.K.; Alburger, D.E.

1987-01-01

The β decay of /sup 39/Cl, produced in the /sup 37/Cl(t,p)/sup 39/Cl reaction at E/sub t/ = 3.1 MeV, has been investigated with a Ge-NaI(Tl) Compton-suppression γ-ray spectrometer. Nineteen γ-ray transitions were observed, including 10 previously known. Precision energy measurements were carried out on six of the strongest lines. In the proposed decay scheme a weak new β-ray branch is established to the 2950-keV level of /sup 39/Ar, and the populations of /sup 39/Ar levels at 2093 and 2433 keV are accounted for by γ-ray decays from higher excited states. Spin-parity assignments are given

Determination of differential cross-sections for the natK(p, p0) and 39K(p, α0) reactions in the backscattering geometry

International Nuclear Information System (INIS)

Kokkoris, M.; Tsaris, A.; Misaelides, P.; Sokaras, D.; Lagoyannis, A.; Harissopulos, S.; Vlastou, R.; Papadopoulos, C.T.

2010-01-01

In the present work, new, differential cross-section values are presented for the nat K(p, p 0 ) reaction in the energy range E lab = 3000-5000 keV (with an energy step of 25 keV) and for detector angles between 140 o and 170 o (with an angular step of 10 o ). A qualitative discussion of the observed cross-section variations through the influence of strong, closely spaced resonances in the p + 39 K system is also presented. Information has also been extracted concerning the 39 K(p,α 0 ) reaction for E lab = 4000-5000 keV in the same angular range. As a result, more than ∼500 data points will soon be available to the scientific community through IBANDL (Ion Beam Analysis Nuclear Data Library - (http://www-nds.iaea.org/ibandl/)) and could thus be incorporated in widely used IBA algorithms (e.g. SIMNRA, WINDF, etc.) for potassium depth profiling at relatively high proton beam energies.

Synthesis and Odor Evaluation of Five New Sulfur-Containing Ester Flavor Compounds from 4-Ethyloctanoic Acid

Directory of Open Access Journals (Sweden)

Baoguo Sun

2010-07-01

Full Text Available Five sulfur-containing flavor compounds were synthesized for the first time by the reaction of 4-ethyloctanoyl chloride with sulfur-containing alcohols or mercaptans. The synthesized compounds are 3-(methylthiopropyl 4-ethyloctanoate, 2-methyl-3-tetrahydro-furanthiol 4-ethyloctanoate, 4-methyl-5-thiazoleethanol 4-ethyloctanoate, 2-furan-methanethiol 4-ethyloctanoate and 2-methyl-3-furanthiol 4-ethyloctanoate. These five synthetic sulfur-containing ester flavor compounds all have meaty odor and might be used in foods if approved for this purpose in the future.

Synthesis and odor evaluation of five new sulfur-containing ester flavor compounds from 4-ethyloctanoic acid.

Science.gov (United States)

Liu, Yuping; Chen, Haitao; Yin, Decai; Sun, Baoguo

2010-07-29

Five sulfur-containing flavor compounds were synthesized for the first time by the reaction of 4-ethyloctanoyl chloride with sulfur-containing alcohols or mercaptans. The synthesized compounds are 3-(methylthio)propyl 4-ethyloctanoate, 2-methyl-3-tetrahydro-furanthiol 4-ethyloctanoate, 4-methyl-5-thiazoleethanol 4-ethyloctanoate, 2-furan-methanethiol 4-ethyloctanoate and 2-methyl-3-furanthiol 4-ethyloctanoate. These five synthetic sulfur-containing ester flavor compounds all have meaty odor and might be used in foods if approved for this purpose in the future.

Catalyst for the reduction of sulfur dioxide to elemental sulfur

Science.gov (United States)

Jin, Y.; Yu, Q.; Chang, S.G.

1996-02-27

The inventive catalysts allow for the reduction of sulfur dioxide to elemental sulfur in smokestack scrubber environments. The catalysts have a very high sulfur yield of over 90% and space velocity of 10,000 h{sup {minus}1}. They also have the capacity to convert waste gases generated during the initial conversion into elemental sulfur. The catalysts have inexpensive components, and are inexpensive to produce. The net impact of the invention is to make this technology practically available to industrial applications. 21 figs.

Characterization of a novel HLA-B*39:01:01-related allele, HLA-B*39:130, by cloning and phasing.

Science.gov (United States)

Li, L X; Tian, W; Zhu, F M; Wang, W Y; Cai, J H

2017-12-01

A novel HLA-B*39:01:01-related variant, HLA-B*39:130, has been identified in a normal individual of Han ethnicity in Hunan province, southern China. Following Sanger polymerase chain reaction-sequence-based typing (PCR-SBT), this new allele was further confirmed by cloning, phasing and sequencing. Aligned with HLA-B*39:01:01, HLA-B*39:130 has a nonsynonymous thymine substitution at nucleotide position 94 in exon 4, resulting in amino acid change from threonine to isoleucine at codon 214 (ACA→ATA) of the mature HLA-BmRNA molecule. © 2017 John Wiley & Sons Ltd.

Identifying the change in atmospheric sulfur sources in China using isotopic ratios in mosses

Science.gov (United States)

Xiao, Hua-Yun; Tang, Cong-Guo; Xiao, Hong-Wei; Liu, Xue-Yan; Liu, Cong-Qiang

2009-08-01

A considerable number of studies on rainwater sulfur isotopic ratios (δ34Srain) have been conducted to trace sulfur sources at a large number of sites in the past. If longitudinal studies on the isotope composition of precipitation sulfate were conducted, it is possible to relate that to changes in sulfur emissions. But direct measurement needs considerable labor and time. So, in this study, sulfur isotopic ratios in rainwater and mosses were analyzed at Guiyang and Nanchang to evaluate the possibility of using mosses as a substitute for rainwater. We found that present moss sulfur isotopic ratios were comparable to those of present rainwater. Additionally, we investigated the changes of atmospheric sulfur sources and sulfur concentrations using an isotopic graphic analysis at five industrial cities, two forested areas, and two remote areas in China. Mosses in industrial cities show a wide range of δ34S values, with the highest occurring at Chongqing (+3.9‰) and the lowest at Guiyang (-3.1‰). But as compared to those in forested and remote areas, δ34S values of mosses in all the five industrial cities are lower. On the basis of isotopic comparisons between past rainwater (reported in the literature) and present mosses, in the plot of δ34Smoss versus δ34Srain, six zones indicating different atmospheric sulfur change are separated by the 1:1 line and δ34S values of potential sulfur sources. Our results indicate that atmospheric sulfur pollution in most of the industrial cities decreased, while at the two forested areas, no significant changes were observed, and a new anxiousness coming from new energy sources (e.g., oil) appeared in some cities. Studies on the change of ambient SO2 concentrations support these results.

Biogeochemistry of sulfur and iron in Thioploca-colonized surface sediments in the upwelling area off central Chile

DEFF Research Database (Denmark)

Zopfi, Jakob; Michael E., Böttcher; Jørgensen, Bo Barker

2008-01-01

suggest further that pyritization at depth includes light sulfide, potentially originating from bacterial sulfur disproportionation. The δ34S-values of pyrite down to -38‰ vs. V-CDT are among the lightest found in organic-rich marine sediments. Seasonal variations in the sulfur isotope composition...... of dissolved sulfate indicated a dynamic non-steady-state sulfur cycle in the surface sediments. The 18O content of porewater sulfate increased with depth at all sites compared to the bottom water composition due to intracellular isotope exchange reactions during microbial sulfur transformations....

Scintigraphic scoring system for grading severity of gastro-esophageal reflux on 99mTc sulfur colloid gastro-esophageal reflux scintigraphy: A prospective study of 39 cases with pre and post treatment assessment.

Science.gov (United States)

Puranik, Ameya D; Nair, Gopinathan; Aggarwal, Rajiv; Bandyopadhyay, Abhijit; Shinto, Ajit; Zade, Anand

2013-04-01

The study aimed at developing a scoring system for scintigraphic grading of gastro-esophageal reflux (GER), on gastro-esophageal reflux scintigraphy (GERS) and comparison of clinical and scintigraphic scores, pre- and post-treatment. A total of 39 cases with clinically symptomatic GER underwent 99mTc sulfur colloid GERS; scores were assigned based on the clinical and scintigraphic parameters. Post domperidone GERS was performed after completion of treatment. Follow up GERS was performed and clinical and scintigraphic parameters were compared with baseline parameters. Paired t-test on pre and post domperidone treatment clinical scores showed that the decline in post-treatment scores was highly significant, with P value reflux and also for following children post-treatment.

Sulfur-binding in recent environments: II. Speciation of sulfur and iron and implications for the occurrence of organo-sulfur compounds

Science.gov (United States)

Hartgers, Walter A.; Lòpez, Jordi F.; Sinninghe Damsté, Jaap S.; Reiss, Christine; Maxwell, James R.; Grimalt, Joan O.

1997-11-01

Speciation of iron and sulfur species was determined for two recent sediments (La Trinitat and Lake Cisó) which were deposited in environments with a high biological productivity and sulfate-reducing activity. In sediments from calcite ponds of La Trinitat an excess of reactive iron species (iron monosulfides, iron hydroxides) results in a depletion of reactive sulfur which is accompanied by a virtual absence of organo-sulfur compounds, both in low (LMW) and high molecular-weight (HMW) fractions. Small amounts of phytanyl and highly branched isoprenoid (HBI) thiophenes in the extract demonstrate that these molecules exhibit a higher reactivity towards reduced sulfur species as compared to detrital iron. Euxinic sediments from Lake Cisó are characterised by an excess of reduced sulfur species which can rapidly trap reactive iron. High concentrations of H 2S results in the formation of organo-sulfur compounds which were encountered in both LMW and HMW fractions. The major part of the organic sulfur is bound to the carbohydrate portion of woody tissues, whose presence was revealed by a specific alkylthiophene distribution in the flash pyrolysate and by Li/EtNH 2 desulfurisation of the kerogen which resulted in the solubilisation of the sulfur-enriched hemicellulose fraction. Relatively high amounts of sulfurised C 25 HBI compounds in the sediment extract of Lake Cisó reflect the incorporation of sulfur into algal derived organic matter upon early diagenesis. The combined approach of the speciation of iron and sulfur species and the molecular analysis of sedimentary fractions demonstrates that abiotic sulfur binding to organic matter occurs at the earliest stages of diagenesis under specific depositional conditions (anoxic, stratified water column) in which an excess of reduced sulfur species relative to the amount of reactive iron is a controlling factor.

Lithium sulfur batteries and electrolytes and sulfur cathodes thereof

Science.gov (United States)

Visco, Steven J.; Goncharenko, Nikolay; Nimon, Vitaliy; Petrov, Alexei; Nimon, Yevgeniy S.; De Jonghe, Lutgard C.; Katz, Bruce D.; Loginova, Valentina

2017-05-23

Lithium sulfur battery cells that use water as an electrolyte solvent provide significant cost reductions. Electrolytes for the battery cells may include water solvent for maintaining electroactive sulfur species in solution during cell discharge and a sufficient amount of a cycle life-enhancing compound that facilitates charging at the cathode. The combination of these two components enhances one or more of the following cell attributes: energy density, power density and cycle life. For instance, in applications where cost per Watt-Hour (Wh) is paramount, such as grid storage and traction applications, the use of an aqueous electrolyte in combination with inexpensive sulfur as the cathode active material can be a key enabler for the utility and automotive industries, for example, providing a cost effective and compact solution for load leveling, electric vehicles and renewable energy storage. Sulfur cathodes, and methods of fabricating lithium sulfur cells, in particular for loading lithium sulfide into the cathode structures, provide further advantages.

Transboundary transport of anthropogenic sulfur in PM2.5 at a coastal site in the Sea of Japan as studied by sulfur isotopic ratio measurement

International Nuclear Information System (INIS)

Inomata, Yayoi; Ohizumi, Tsuyoshi; Take, Naoko; Sato, Keiichi; Nishikawa, Masataka

2016-01-01

Sulfur isotopic ratios (δ"3"4S) in size separated aerosol particles (PM2.5 and coarse particles) were measured at Niigata-Maki facing the Sea of Japan. Non-sea salt δ"3"4S (δ"3"4S_n_s_s) in PM2.5 showed seasonal variations with relatively high values in winter (1.0–3.9‰ in spring, 2.8–4.5‰ in summer, 1.3–4.5‰ in autumn, 3.7–5.7‰ in winter). Taking into consideration air mass transport routes, δ"3"4S_n_s_s in the air masses which originated in the Asian continent and were transported over the Sea of Japan to the monitoring sites were higher than those values for air masses which were transported over the Japanese islands after leaving the Asian continent for each season. Considering that the δ"3"4S_n_s_s in sulfuric acid derived from domestic emissions in Japan are lower than those of δ"3"4S_n_s_s in coal, the lower δ"3"4S_n_s_s for the air mass transported over the Japanese islands suggest that sulfuric acid in PM2.5 modified the δ"3"4S_n_s_s due to aerosol mixing with sulfuric acid in Japan. Material balance calculations suggested that the relative contribution of transboundary transport in winter was also higher than for other seasons (40–75% in spring, 51–63% in summer, 45–73% in autumn, and 53–81% in winter). In particular, the contribution to the air masses which were transported directly from the Asian continent was relatively large (75% in spring, 59% in autumn, 78% in winter) in comparison with that for the air masses which were transported over Japan. - Highlights: • δ"3"4Snss in PM2.5 is effective to estimate contribution of anthropogenic sulfur. • δ"3"4Snss have characterized with seasonal variation with high values in winter. • The contribution of transboundary transport is 39-81% at the site facing to the Sea of Japan. • δ"3"4Snss in PM2.5 are modified during transport with mixing of domestic sources. • Map of δ"3"4S distribution originated from coal in Northeast Asia is developed.

Transboundary transport of anthropogenic sulfur in PM2.5 at a coastal site in the Sea of Japan as studied by sulfur isotopic ratio measurement

Energy Technology Data Exchange (ETDEWEB)

Inomata, Yayoi, E-mail: inomata@acap.asia [Asia Center for Air Pollution Research, 1182, Sowa, Niigata, Niigata 950-2144 (Japan); Ohizumi, Tsuyoshi [Asia Center for Air Pollution Research, 1182, Sowa, Niigata, Niigata 950-2144 (Japan); Niigata Prefectural Institute of Public Health and Environmental Sciences, 314-1, Sowa, Niigata, Niigata 950-2144 (Japan); Take, Naoko; Sato, Keiichi [Asia Center for Air Pollution Research, 1182, Sowa, Niigata, Niigata 950-2144 (Japan); Nishikawa, Masataka [National Institute for Environmental Studies, 16-2, Onogawa, Tsukuba, Ibaraki 305-8506 (Japan); Tokyo University of Science, 12-1, Ichigaya Funakawara, Shinjuku, Tokyo 162-0826 (Japan)

2016-05-15

Sulfur isotopic ratios (δ{sup 34}S) in size separated aerosol particles (PM2.5 and coarse particles) were measured at Niigata-Maki facing the Sea of Japan. Non-sea salt δ{sup 34}S (δ{sup 34}S{sub nss}) in PM2.5 showed seasonal variations with relatively high values in winter (1.0–3.9‰ in spring, 2.8–4.5‰ in summer, 1.3–4.5‰ in autumn, 3.7–5.7‰ in winter). Taking into consideration air mass transport routes, δ{sup 34}S{sub nss} in the air masses which originated in the Asian continent and were transported over the Sea of Japan to the monitoring sites were higher than those values for air masses which were transported over the Japanese islands after leaving the Asian continent for each season. Considering that the δ{sup 34}S{sub nss} in sulfuric acid derived from domestic emissions in Japan are lower than those of δ{sup 34}S{sub nss} in coal, the lower δ{sup 34}S{sub nss} for the air mass transported over the Japanese islands suggest that sulfuric acid in PM2.5 modified the δ{sup 34}S{sub nss} due to aerosol mixing with sulfuric acid in Japan. Material balance calculations suggested that the relative contribution of transboundary transport in winter was also higher than for other seasons (40–75% in spring, 51–63% in summer, 45–73% in autumn, and 53–81% in winter). In particular, the contribution to the air masses which were transported directly from the Asian continent was relatively large (75% in spring, 59% in autumn, 78% in winter) in comparison with that for the air masses which were transported over Japan. - Highlights: • δ{sup 34}Snss in PM2.5 is effective to estimate contribution of anthropogenic sulfur. • δ{sup 34}Snss have characterized with seasonal variation with high values in winter. • The contribution of transboundary transport is 39-81% at the site facing to the Sea of Japan. • δ{sup 34}Snss in PM2.5 are modified during transport with mixing of domestic sources. • Map of δ{sup 34}S distribution originated

Understanding the role of lithium polysulfide solubility in limiting lithium-sulfur cell capacity

International Nuclear Information System (INIS)

Shen, Chao; Xie, Jianxin; Zhang, Mei; Andrei, Petru; Hendrickson, Mary; Plichta, Edward J.; Zheng, Jim P.

2017-01-01

Highlights: •At normal rate, LiPS soluble reaction pathway dominates the discharge process. •Reduction of sulfur to Li 2 S 8 is not inhibited by high Li 2 S 8 concentration. •Subsequent LiPS electrochemical reactions are restricted by LiPS solubility. •Specific energy of the Li-S cell was reevaluated considering LiPS solubility. -- Abstract: Although the cathode of lithium-sulfur (Li-S) batteries has a theoretical specific capacity of 1,672 mAh g −1 , its practical capacity is much smaller than this value and depends on the electrolyte/sulfur ratio. The operation of Li-S batteries under lean electrolyte conditions can be challenging, especially in the case when the solubility of lithium polysulfide (LiPS) sets an upper bound for polysulfide dissolution. In this work, specially designed cathode structures and electrolyte configurations were built in order to analyze the effects of LiPS solubility on cell capacity. Two reaction pathways involving the reduction of LiPS in liquid and solid phase are proposed and analyzed. We show that at discharge rates above 0.4 mA cm −2 the reaction in the liquid phase dominates the discharge process. Once the electrolyte becomes saturated, the solid phase LiPS cannot be further reduced and does not contribute to the capacity of the cells. This phenomenon prevents Li-S batteries from achieving their high theoretical specific capacity. Finally, the specific energy of the Li-S cell is reevaluated and discussed considering the limitation imposed by LiPS solubility.

Biogeochemistry of the sulfur oxidizer Thiomicrospira thermophila

Science.gov (United States)

Houghton, J.; Fike, D. A.; Wills, E.; Foustoukos, D.

2013-12-01

Near-seafloor hydrothermal environments such as diffuse flow venting or subsurface mixing are characterized by rapidly changing conditions and steep chemical and thermal gradients. Microorganisms living in these environments can take advantage of these changes by switching among metabolic pathways rather than specializing. We present reaction stoichiometry and rates for T. thermophila grown in a closed system both at ambient and elevated pressure (50 bars) that demonstrate substantial metabolic flexibility, shifting between up to 5 different sulfur cycling reactions over a 24 hour period. Based on the stoichiometry between S2O3 consumed and SO4 produced, three reactions are sulfur oxidation and two are disproportionation, which has not previously been demonstrated for Thiomicrospira strains. Reactants include S2O3, elemental S (both polymeric S chains and S8 rings), HS-, and O2, while products include polymeric elemental S, SO4, HS-, and polysulfides. The presence of μmolal concentrations of HS- has been confirmed during the time series only when stoichiometry predicts disproportionation. Production of HS- in the presence of elemental S results in abiotic conversion to polysulfides, keeping the sulfide concentrations low in solution. The transition from oxidation to disproportionation appears to be triggered by a depletion in dissolved oxygen and the rate of reaction is a second order function of S2O3 and O2 concentrations. Growth was tested at conditions spanning their pH tolerance (5.0 - 8.0) using a citrate buffer (pH 5.0), unbuffered media (initial pH 7.0), and Tris buffer (pH 8.0). The highest rates are observed at pH 8.0 with rates decreasing as a function of pH. The lowest rate occurs at pH 5.0 and exhibits pseudo-first order behavior over a 24 hour period, likely due to a long lag and very slow growth. Repeat injections after the culture is acclimated to the experimental conditions result in very high pseudo-first order rates due to rapid consumption of

Sulfur isotopic analysis of carbonyl sulfide and its application for biogeochemical cycles

Science.gov (United States)

Hattori, Shohei; Kamezaki, Kazuki; Ogawa, Takahiro; Toyoda, Sakae; Katayama, Yoko; Yoshida, Naohiro

2016-04-01

Carbonyl sulfide (OCS or COS) is the most abundant gas containing sulfur in the atmosphere, with an average mixing ratio of 500 p.p.t.v. in the troposphere. OCS is suggested as a sulfur source of the stratospheric sulfate aerosols (SSA) which plays an important role in Earth's radiation budget and ozone depletion. Therefore, OCS budget should be validated for prediction of climate change, but the global OCS budget is imbalance. Recently we developed a promising new analytical method for measuring the stable sulfur isotopic compositions of OCS using nanomole level samples: the direct isotopic analytical technique of on-line gas chromatography-isotope ratio mass spectrometry (GC-IRMS) using fragmentation ions S+ (Hattori et al., 2015). The first measurement of the δ34S value for atmospheric OCS coupled with isotopic fractionation for OCS sink reactions in the stratosphere (Hattori et al., 2011; Schmidt et al., 2012; Hattori et al., 2012) explains the reported δ34S value for background stratospheric sulfate, suggesting that OCS is a potentially important source for background (nonepisodic or nonvolcanic) stratospheric sulfate aerosols. This new method measuring δ34S values of OCS can be used to investigate OCS sources and sinks in the troposphere to better understand its cycle. It is known that some microorganisms in soil can degrade OCS, but the mechanism and the contribution to the OCS in the air are still uncertain. In order to determine sulfur isotopic enrichment factor of OCS during degradation via microorganisms, incubation experiments were conducted using strains belonging to the genera Mycobacterium, Williamsia and Cupriavidus, isolated from natural soil environments (Kato et al., 2008). As a result, sulfur isotope ratios of OCS were increased during degradation of OCS, indicating that reaction for OC32S is faster than that for OC33S and OC34S. OCS degradation via microorganisms is not mass-independent fractionation (MIF) process, suggesting that this

Investigation and Modelling of Diesel Hydrotreating Reactions

DEFF Research Database (Denmark)

Boesen, Rasmus Risum

on a commercial CoMo catalyst, and a simple kinetic model is presented. Hydrogenation of fused aromatic rings are known to be fast, and it is possible, that the reaction rates are limited by either internal or external mass transfer. An experiment conducted at industrial temperatures and pressure, using...... naphthalene as a model compound, have shown, that intra-particle diffusion resistance are likely to limit the reaction rate. In order to produce ULSD it is necessary to remove sulfur from some of the most refrac- tive sulfur compounds, such as sterically hindered dibenzothiophenes. Basic nitrogen com- pounds...... are known to inhibit certain hydrotreating reactions. Experimental results are pre- sented, showing the effect of 3 different nitrogen compounds, acridine, 1,4-dimethylcarabazole and 3-methylindole, on the hydrodesulfurization of a real feed and of a model compound, 4,6-dimethyldibenzothiophene. It is shown...

Sulfur bonding in MoS2 and Co-Mo-S structures

DEFF Research Database (Denmark)

Byskov, Line Sjolte; Hammer, Bjørk; Nørskov, Jens Kehlet

1997-01-01

The structure and bonding in small MoS2 structures with and without Co is studied theoretically using self-consistent density functional theory with a non-local exchange-correlation energy. The structures model the catalysts used extensively in hydrotreating. We study in detail the structure...... study the energy required to form sulfur vacancies, which are believed to be the active sites for many hydrotreating reactions. The presence of Co atoms at the edges is shown to lead to a significant lowering of the metal-sulfur binding energy. This imposes an increase in the concentration of active...

Catalase as a sulfide-sulfur oxido-reductase: An ancient (and modern?) regulator of reactive sulfur species (RSS).

Science.gov (United States)

Olson, Kenneth R; Gao, Yan; DeLeon, Eric R; Arif, Maaz; Arif, Faihaan; Arora, Nitin; Straub, Karl D

2017-08-01

Catalase is well-known as an antioxidant dismutating H 2 O 2 to O 2 and H 2 O. However, catalases evolved when metabolism was largely sulfur-based, long before O 2 and reactive oxygen species (ROS) became abundant, suggesting catalase metabolizes reactive sulfide species (RSS). Here we examine catalase metabolism of H 2 S n , the sulfur analog of H 2 O 2 , hydrogen sulfide (H 2 S) and other sulfur-bearing molecules using H 2 S-specific amperometric electrodes and fluorophores to measure polysulfides (H 2 S n ; SSP4) and ROS (dichlorofluorescein, DCF). Catalase eliminated H 2 S n , but did not anaerobically generate H 2 S, the expected product of dismutation. Instead, catalase concentration- and oxygen-dependently metabolized H 2 S and in so doing acted as a sulfide oxidase with a P 50 of 20mmHg. H 2 O 2 had little effect on catalase-mediated H 2 S metabolism but in the presence of the catalase inhibitor, sodium azide (Az), H 2 O 2 rapidly and efficiently expedited H 2 S metabolism in both normoxia and hypoxia suggesting H 2 O 2 is an effective electron acceptor in this reaction. Unexpectedly, catalase concentration-dependently generated H 2 S from dithiothreitol (DTT) in both normoxia and hypoxia, concomitantly oxidizing H 2 S in the presence of O 2 . H 2 S production from DTT was inhibited by carbon monoxide and augmented by NADPH suggesting that catalase heme-iron is the catalytic site and that NADPH provides reducing equivalents. Catalase also generated H 2 S from garlic oil, diallyltrisulfide, thioredoxin and sulfur dioxide, but not from sulfite, metabisulfite, carbonyl sulfide, cysteine, cystine, glutathione or oxidized glutathione. Oxidase activity was also present in catalase from Aspergillus niger. These results show that catalase can act as either a sulfide oxidase or sulfur reductase and they suggest that these activities likely played a prominent role in sulfur metabolism during evolution and may continue do so in modern cells as well. This also appears

Novel bacterial sulfur oxygenase reductases from bioreactors treating gold-bearing concentrates

DEFF Research Database (Denmark)

Chen, Z-W; Liu, Y-Y; Wu, J-F

2007-01-01

The microbial community and sulfur oxygenase reductases of metagenomic DNA from bioreactors treating gold-bearing concentrates were studied by 16S rRNA library, real-time polymerase chain reaction (RT-PCR), conventional cultivation, and molecular cloning. Results indicated that major bacterial......) of bacteria and archaea were 4.59 x 10(9) and 6.68 x 10(5), respectively. Bacterial strains representing Acidithiobacillus, Leptospirillum, and Sulfobacillus were isolated from the bioreactors. To study sulfur oxidation in the reactors, pairs of new PCR primers were designed for the detection of sulfur...... oxygenase reductase (SOR) genes. Three sor-like genes, namely, sor (Fx), sor (SA), and sor (SB) were identified from metagenomic DNAs of the bioreactors. The sor (Fx) is an inactivated SOR gene and is identical to the pseudo-SOR gene of Ferroplasma acidarmanus. The sor (SA) and sor (SB) showed...

Effect of Nickel Coated Multi-Walled Carbon Nanotubes on Electrochemical Performance of Lithium-Sulfur Rechargeable Batteries.

Science.gov (United States)

Wu, Xiao; Yao, Shanshan; Hou, Jinli; Jing, Maoxiang; Qian, Xinye; Shen, Xiangqian; Xiang, Jun; Xi, Xiaoming

2017-04-01

Conventional lithium-sulfur batteries suffer from severe capacity fade, which is induced by low electron conductivity and high dissolution of intermediated polysulfides. Recent studies have shown the metal (Pt, Au, Ni) as electrocatalyst of lithium polysulfides and improved the performance for lithium sulfur batteries. In this work, we present the nickel coated multi-walled carbon nanotubes (Ni-MWNTs) as additive materials for elemental sulfur positive electrodes for lithium-sulfur rechargeable batteries. Compared with MWNTs, the obtained Ni-MWNTs/sulfur composite cathode demonstrate a reversible specific capacity approaching 545 mAh after 200 cycles at a rate of 0.5C as well as improved cycling stability and excellent rate capacity. The improved electrochemical performance can be attributed to the fact the MWNTs shows a vital role on polysulfides adsorption and nickel has a catalytic effect on the redox reactions during charge–discharge process. Meanwhile, the Ni-MWNTs is a good electric conductor for sulfur cathode.

Wolframite Conversion in Treating a Mixed Wolframite-Scheelite Concentrate by Sulfuric Acid

Science.gov (United States)

Shen, Leiting; Li, Xiaobin; Zhou, Qiusheng; Peng, Zhihong; Liu, Guihua; Qi, Tiangui; Taskinen, Pekka

2018-02-01

Complete wolframite conversion in sulfuric acid is significant for expanding the applicability of the sulfuric acid method for producing ammonium paratungstate. In this paper, the conversion of wolframite in treating a mixed wolframite-scheelite concentrate by sulfuric acid was studied systematically. The results show that the conversion of wolframite in sulfuric acid is more difficult than that of scheelite, requiring rigorous reaction conditions. A solid H2WO4 layer forms on the surfaces of the wolframite particles and becomes denser with increasing H2SO4 concentration, thus hindering the conversion. Furthermore, the difficulty in wolframite conversion can be mainly attributed to the accumulation of Fe2+ (and/or Mn2+) in the H2SO4 solution, which can be solved by reducing Fe2+ (and/or Mn2+) concentration through oxidization and/or a two-stage process. Additionally, the solid converted product of the mixed wolframite-scheelite concentrate has an excellent leachability of tungsten in an aqueous ammonium carbonate solution at ambient temperature, with approximately 99% WO3 recovery. This work presents a route for manufacturing ammonium paratungstate by treating the mixed concentrate in sulfuric acid followed by leaching in ammonium carbonate solution.

The life sulfuric: microbial ecology of sulfur cycling in marine sediments.

Science.gov (United States)

Wasmund, Kenneth; Mußmann, Marc; Loy, Alexander

2017-08-01

Almost the entire seafloor is covered with sediments that can be more than 10 000 m thick and represent a vast microbial ecosystem that is a major component of Earth's element and energy cycles. Notably, a significant proportion of microbial life in marine sediments can exploit energy conserved during transformations of sulfur compounds among different redox states. Sulfur cycling, which is primarily driven by sulfate reduction, is tightly interwoven with other important element cycles (carbon, nitrogen, iron, manganese) and therefore has profound implications for both cellular- and ecosystem-level processes. Sulfur-transforming microorganisms have evolved diverse genetic, metabolic, and in some cases, peculiar phenotypic features to fill an array of ecological niches in marine sediments. Here, we review recent and selected findings on the microbial guilds that are involved in the transformation of different sulfur compounds in marine sediments and emphasise how these are interlinked and have a major influence on ecology and biogeochemistry in the seafloor. Extraordinary discoveries have increased our knowledge on microbial sulfur cycling, mainly in sulfate-rich surface sediments, yet many questions remain regarding how sulfur redox processes may sustain the deep-subsurface biosphere and the impact of organic sulfur compounds on the marine sulfur cycle. © 2017 The Authors. Environmental Microbiology published by Society for Applied Microbiology and John Wiley & Sons Ltd.

Sulfur Removal by Adding Iron During the Digestion Process of High-sulfur Bauxite

Science.gov (United States)

Zhanwei, Liu; Hengwei, Yan; Wenhui, Ma; Keqiang, Xie; Dunyong, Li; Licong, Zheng; Pengfei, Li

2018-04-01

This paper proposes a novel approach to sulfur removal by adding iron during the digestion process. Iron can react with high-valence sulfur (S2O3 2-, SO3 2-, SO4 2-) to generate S2- at digestion temperature, and then S2- enter red mud in the form of Na3FeS3 to be removed. As iron dosage increases, high-valence sulfur concentration decreases, but the concentration of S2- increases; sulfur digestion rate decreases while sulfur content in red mud markedly increases; the alumina digestion rate, conversely, remains fairly stable. So sulfur can be removed completely by adding iron in digestion process, which provide a theoretical basis for the effective removal of sulfur in alumina production process.

High School Forum: "Invitations to Enquiry": The Calcite/Acid Reaction.

Science.gov (United States)

Herron, J. Dudley, Ed.; Driscoll, D. R.

1979-01-01

Describes a high school chemistry experiment which involves the reaction between calcite and hydrochloric and sulfuric acids. This reaction can be carried out as a projected demonstration and on an individual basis. (HM)

Sulfur removal from low-sulfur gasoline and diesel fuel by metal-organic frameworks

Energy Technology Data Exchange (ETDEWEB)

Hagen, G.; Haemmerle, M.; Moos, R. [Functional Materials, University of Bayreuth, Bayreuth (Germany); Malkowsky, I.M.; Kiener, C. [BASF SE, Ludwigshafen (Germany); Achmann, S.

2010-02-15

Several materials in the class of metal-organic frameworks (MOF) were investigated to determine their sorption characteristics for sulfur compounds from fuels. The materials were tested using different model oils and common fuels such as low-sulfur gasoline or diesel fuel at room temperature and ambient pressure. Thiophene and tetrahydrothiophene (THT) were chosen as model substances. Total-sulfur concentrations in the model oils ranged from 30 mg/kg (S from thiophene) to 9 mg/kg (S from tetrahydrothiophene) as determined by elementary analysis. Initial sulfur contents of 8 mg/kg and 10 mg/kg were identified for low-sulfur gasoline and for diesel fuel, respectively, by analysis of the common liquid fuels. Most of the MOF materials examined were not suitable for use as sulfur adsorbers. However, a high efficiency for sulfur removal from fuels and model oils was noticed for a special copper-containing MOF (copper benzene-1,3,5-tricarboxylate, Cu-BTC-MOF). By use of this material, 78 wt % of the sulfur content was removed from thiophene containing model oils and an even higher decrease of up to 86 wt % was obtained for THT-based model oils. Moreover, the sulfur content of low-sulfur gasoline was reduced to 6.5 mg/kg, which represented a decrease of more than 22 %. The sulfur level in diesel fuel was reduced by an extent of 13 wt %. Time-resolved measurements demonstrated that the sulfur-sorption mainly occurs in the first 60 min after contact with the adsorbent, so that the total time span of the desulfurization process can be limited to 1 h. Therefore, this material seems to be highly suitable for sulfur reduction in commercial fuels in order to meet regulatory requirements and demands for automotive exhaust catalysis-systems or exhaust gas sensors. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

Application of various types of alumina and nano--alumina sulfuric acid in the synthesis of α-aminonitriles derivatives: comparative study

Directory of Open Access Journals (Sweden)

A. Teimouri

2014-09-01

Full Text Available An efficient and green protocol for the synthesis of α-aminonitrile derivatives by one-pot reaction of different aldehydes with amines and trimethylsilyl cyanide has been developed using natural alumina, alumina sulfuric acid (ASA, nano-g-alumina, nano-g-alumina sulfuric acid (nano-g-ASA under microwave irradiation and solvent-free conditions. The advantages of methods are short reaction times, high yields, milder conditions and easy work up. The catalysts can be recovered for the subsequent reactions and reused without any appreciable loss of efficiency. DOI: http://dx.doi.org/10.4314/bcse.v28i3.13

Hydrogen production by Chlamydomonas reinhardtii under light driven sulfur deprived condition

Energy Technology Data Exchange (ETDEWEB)

Vijayaraghavan, Krishnan; Karthik, Rajendran [Biotechnology Research Division, Department of Biotechnology, Prathyusha Institute of Technology and Management, Aranvoyalkuppam, Thiruvallur District 602025, Tamil Nadu (India); Kamala Nalini, S.P. [Department of Biotechnology, Vel Group of Educational Institutions, Avadi, Alamadhi Road, Chennai 600062, Tamil Nadu (India)

2009-10-15

This article explores the possibility of demonstrating sustainable photohydrogen production using Chlamydomonas reinhardtii when grown in sulfur deprived photoautotrophic condition. The hydrogen evolving capability of the algal species was monitored based on alternating light and dark period. Investigation was carried out during the day time in order to exploit the solar energy for meeting the demand of the light period. The results showed that when the reactor was operated at varying photoperiod namely 2, 3 and 4 h of alternating light and dark period, the gas generation was found to be 32 {+-} 4, 63 {+-} 7 and 52 {+-} 5 mL/h, while the corresponding hydrogen content was 47, 86 and 87% respectively. Functional components of hydrogen generation reaction centers were also analyzed, which showed that the PS(I) reaction centers were involved in hydrogen production pathway, as the light absorption by PS(I) was prerequisite for hydrogen generation under sulfur deprived photoautotrophic condition. The findings showed a higher gas yield and hydrogen content under dark period, whereas under light period the gas content was below detectable level for hydrogen due to the reversible hydrogenase reaction. (author)

Determining total sulfur content in coal by MSC radiometric sulfur meter

Energy Technology Data Exchange (ETDEWEB)

Czerw, B; Sikora, T; Golebiowski, W

1976-01-01

The MSC radiometric sulfur meter is used to determine total sulfur content in brown and black coals. Sulfur content is determined by measuring intensity of radiation beam which has travelled through a coal sample with the optimum constant surface mass. Construction of the MSC, consisting of a measuring head and the electronic measuring system, is shown in a scheme. AM-241 (with activity of 50 mCi) is the source of radiation. Energy of 25.3 keV (tin disc) is selected as the optimum. The SSU-70 probe with NaJ/Tl crystal is the radiation detector. The black coal sample weighs 10 g and the brown coal sample weighs 18 g. Duration of sulfur determination is 10 min. Error of sulfur determination ranges from plus or minus 0.2% to 0.3%. The results of operational tests of MSC radiometric sulfur meters in black and brown coal mines are discussed. Accuracy of measurement is shown in 5 tables. (8 refs.)

Identifying parameter windows for sulfur removal by direct limestone injection in the rich zone of staged heat engine combustors

International Nuclear Information System (INIS)

Colaluca, M.A.

1990-01-01

Recent experimental evidence suggests the possibility of sulfur cleanup by direct injection at gas temperatures that do not thermodynamically favor the absorption of sulfur by the limestone. The purpose of this paper is to analytically investigate possible mechanistic explanations of this observed sulfur capture with the goal of evaluating the potential for limestone injection sulfur capture in direct coal fired gas turbine and diesel engine (heat engines) combustion applications. The method was to use current available data on the physical properties of limestone, and the rates of the pertinent reactions, and to develop mathematical models of the processes experienced by the sorbent particles. The models were then used to predict extent of capture at the high-pressure, high-temperature, short residence time conditions of interest. The goal was to first investigate capture in a single-pulse reactor (combustion bomb) and then to extrapolate these results to advanced coal-fired heat engine combustion environments. Model predictions were in good agreement with observed sulfur capture in cold wall combustion bomb studies and suggest that efficient sulfur capture (in excess of 80 percent calcium utilization) may b e possible when limestone sorbents are injected into high-temperature combustion products, even when the gas temperatures exceed the thermodynamically favored temperature window by several hundred kelvins. This behavior is possible because particle temperatures are moderated and held at levels that favor sulfur capture due to the strongly endothermic calcination reaction

Decoding mass-independent fractionation of sulfur isotopes in modern atmosphere using cosmogenic 35S: A five-isotope approach and possible implications for Archean sulfur isotope records

Science.gov (United States)

Lin, M.; Thiemens, M. H.; Shen, Y.; Zhang, X.; Huang, X.; Chen, K.; Zhang, Z.; Tao, J.

2017-12-01

The signature of sulfur isotopic mass-independent fractionation (S-MIF) observed in Archean sediments have been interpreted as a proxy of the origins and evolution of atmospheric oxygen and early life on Earth [1]. Photochemistry of SOx in the short (negative Δ36S. After eliminating combustion impacts, the obtained Δ36S/Δ33S slope of -4.0 in the modern atmosphere is close to the Δ36S/Δ33S slope (-3.6) in some records from Paleoarchean [4], an era probably with active volcanism [5]. The significant role of volcanic OCS in the Archean atmosphere has been called for in terms of its ability to provide a continual SO2 high altitude source for photolysis [2]. The strong but previously underappreciated stratospheric signature of S-MIF in tropospheric sulfates suggests that a more careful investigation of wavelength-dependent sulfur isotopic fractionation at different altitudes are required. The combustion-induced negative Δ36S may be linked to recombination reactions of elemental sulfur [6], and relevant experiments are being conducted to test the isotope effect. Although combustion is unlikely in Archean, recombination reactions may occur in other previously unappreciated processes such as volcanism and may contribute in part to the heavily depleted 36S in some Paleoarchean records [5,7]. The roles of both photochemical and non-photochemical reactions in the variability of Archean S-MIF records require further analysis in the future. Refs: [1] Farquhar et al., Science 2000; [2] Shaheen et al., PNAS 2014; [3] Lin et al., PNAS 2016; [4] Wacey et al., Precambrian Res 2015; [5] Muller et al., PNAS 2016; [6] Babikov, PNAS 2017; [7] Shen et al., EPSL, 2009.

Oxidation of SO2 by stabilized Criegee intermediate (sCI radicals as a crucial source for atmospheric sulfuric acid concentrations

Directory of Open Access Journals (Sweden)

M. Boy

2013-04-01

Full Text Available The effect of increased reaction rates of stabilized Criegee intermediates (sCIs with SO2 to produce sulfuric acid is investigated using data from two different locations, SMEAR II, Hyytiälä, Finland, and Hohenpeissenberg, Germany. Results from MALTE, a zero-dimensional model, show that using previous values for the rate coefficients of sCI + SO2, the model underestimates gas phase H2SO4 by up to a factor of two when compared to measurements. Using the rate coefficients recently calculated by Mauldin et al. (2012 increases sulfuric acid by 30–40%. Increasing the rate coefficient for formaldehyde oxide (CH2OO with SO2 according to the values recommended by Welz et al. (2012 increases the H2SO4 yield by 3–6%. Taken together, these increases lead to the conclusion that, depending on their concentrations, the reaction of stabilized Criegee intermediates with SO2 could contribute as much as 33–46% to atmospheric sulfuric acid gas phase concentrations at ground level. Using the SMEAR II data, results from SOSA, a one-dimensional model, show that the contribution from sCI reactions to sulfuric acid production is most important in the canopy, where the concentrations of organic compounds are the highest, but can have significant effects on sulfuric acid concentrations up to 100 m. The recent findings that the reaction of sCI + SO2 is much faster than previously thought together with these results show that the inclusion of this new oxidation mechanism could be crucial in regional as well as global models.

Comparison of sulfuric and hydrochloric acids as catalysts in hydrolysis of Kappaphycus alvarezii (cottonii).

Science.gov (United States)

Meinita, Maria Dyah Nur; Hong, Yong-Ki; Jeong, Gwi-Taek

2012-01-01

In this study, hydrolysis of marine algal biomass Kappaphhycus alvarezii using two different acid catalysts was examined with the goal of identifying optimal reaction conditions for the formation of sugars and by-products. K. alvarezii were hydrolyzed by autoclave using sulfuric acid or hydrochloric acid as catalyst with different acid concentrations (0.1-1.0 M), substrate concentrations (1.0-13.5%), hydrolysis time (10-90 min) and hydrolysis temperatures (100-130 (°)C). A difference in galactose, glucose, reducing sugar and total sugar content was observed under the different hydrolysis conditions. Different by-product compounds such as 5-hydroxymethylfurfural and levulinic acid were also observed under the different reaction conditions. The optimal conditions for hydrolysis were achieved at a sulfuric acid concentration, temperature and reaction time of 0.2 M, 130 °C and 15 min, respectively. These results may provide useful information for the development of more efficient systems for biofuel production from marine biomass.

Effects of sulfur on lead partitioning during sludge incineration based on experiments and thermodynamic calculations

Energy Technology Data Exchange (ETDEWEB)

Liu, Jing-yong, E-mail: www053991@126.com [School of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou 510006 (China); Huang, Shu-jie; Sun, Shui-yu; Ning, Xun-an; He, Rui-zhe [School of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou 510006 (China); Li, Xiao-ming [Guangdong Testing Institute of Product Quality Supervision, Guangzhou 510330 (China); Chen, Tao [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Luo, Guang-qian [State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074 (China); Xie, Wu-ming; Wang, Yu-jie; Zhuo, Zhong-xu; Fu, Jie-wen [School of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou 510006 (China)

2015-04-15

Highlights: • A thermodynamic equilibrium calculation was carried out. • Effects of three types of sulfurs on Pb distribution were investigated. • The mechanism for three types of sulfurs acting on Pb partitioning were proposed. • Lead partitioning and species in bottom ash and fly ash were identified. - Abstract: Experiments in a tubular furnace reactor and thermodynamic equilibrium calculations were conducted to investigate the impact of sulfur compounds on the migration of lead (Pb) during sludge incineration. Representative samples of typical sludge with and without the addition of sulfur compounds were combusted at 850 °C, and the partitioning of Pb in the solid phase (bottom ash) and gas phase (fly ash and flue gas) was quantified. The results indicate that three types of sulfur compounds (S, Na{sub 2}S and Na{sub 2}SO{sub 4}) added to the sludge could facilitate the volatilization of Pb in the gas phase (fly ash and flue gas) into metal sulfates displacing its sulfides and some of its oxides. The effect of promoting Pb volatilization by adding Na{sub 2}SO{sub 4} and Na{sub 2}S was superior to that of the addition of S. In bottom ash, different metallic sulfides were found in the forms of lead sulfide, aluminosilicate minerals, and polymetallic-sulfides, which were minimally volatilized. The chemical equilibrium calculations indicated that sulfur stabilizes Pb in the form of PbSO{sub 4}(s) at low temperatures (<1000 K). The equilibrium calculation prediction also suggested that SiO{sub 2}, CaO, TiO{sub 2}, and Al{sub 2}O{sub 3} containing materials function as condensed phase solids in the temperature range of 800–1100 K as sorbents to stabilize Pb. However, in the presence of sulfur or chlorine or the co-existence of sulfur and chlorine, these sorbents were inactive. The effect of sulfur on Pb partitioning in the sludge incineration process mainly depended on the gas phase reaction, the surface reaction, the volatilization of products, and the

Sulfur-Bearing Phases Detected by Evolved Gas Analysis of the Rocknest Aeolian Deposit, Gale Crater, Mars

Science.gov (United States)

Mcadam, Amy Catherine; Franz, Heather Bryant

2014-01-01

The Sample Analysis at Mars (SAM) instrument suite detected SO2, H2S, OCS, and CS2 from approx.450 to 800 C during evolved gas analysis (EGA) of materials from the Rocknest aeolian deposit in Gale Crater, Mars. This was the first detection of evolved sulfur species from a Martian surface sample during in situ EGA. SO2(approx. 3-22 micro-mol) is consistent with the thermal decomposition of Fe sulfates or Ca sulfites, or evolution/desorption from sulfur-bearing amorphous phases. Reactions between reduced sulfur phases such as sulfides and evolved O2 or H2O in the SAM oven are another candidate SO2 source. H2S (approx.41-109 nmol) is consistent with interactions of H2O, H2 and/or HCl with reduced sulfur phases and/or SO2 in the SAM oven. OCS (approx.1-5 nmol) and CS2(approx.0.2-1 nmol) are likely derived from reactions between carbon-bearing compounds and reduced sulfur. Sulfates and sulfites indicate some aqueous interactions, although not necessarily at the Rocknest site; Fe sulfates imply interaction with acid solutions whereas Ca sulfites can form from acidic to near-neutral solutions. Sulfides in the Rocknest materials suggest input from materials originally deposited in a reducing environment or from detrital sulfides from an igneous source. The presence of sulfides also suggests that the materials have not been extensively altered by oxidative aqueous weathering. The possibility of both reduced and oxidized sulfur compounds in the deposit indicates a nonequilibrium assemblage. Understanding the sulfur mineralogy in Rocknest materials, which exhibit chemical similarities to basaltic fines analyzed elsewhere on Mars, can provide insight in to the origin and alteration history of Martian surface materials.

Ruthenium chalcogenonitrosyl and bridged nitrido complexes containing chelating sulfur and oxygen ligands.

Science.gov (United States)

Ng, Ho-Yuen; Cheung, Wai-Man; Kwan Huang, Enrique; Wong, Kang-Long; Sung, Herman H-Y; Williams, Ian D; Leung, Wa-Hung

2015-11-14

Ruthenium thio- and seleno-nitrosyl complexes containing chelating sulfur and oxygen ligands have been synthesised and their de-chalcogenation reactions have been studied. The reaction of mer-[Ru(N)Cl3(AsPh3)2] with elemental sulfur and selenium in tetrahydrofuran at reflux afforded the chalcogenonitrosyl complexes mer-[Ru(NX)Cl3(AsPh3)2] [X = S (1), Se (2)]. Treatment of 1 with KN(R2PS)2 afforded trans-[Ru(NS)Cl{N(R2PS)2}2] [R = Ph (3), Pr(i) (4), Bu(t) (5)]. Alternatively, the thionitrosyl complex 5 was obtained from [Bu(n)4N][Ru(N)Cl4] and KN(Bu(t)2PS)2, presumably via sulfur atom transfer from [N(Bu(t)2PS)2](-) to the nitride. Reactions of 1 and 2 with NaLOEt (LOEt(-) = [Co(η(5)-C5H5){P(O)(LOEt)2}3](-)) gave [Ru(NX)LOEtCl2] (X = S (8), Se (9)). Treatment of [Bu(n)4N][Ru(N)Cl4] with KN(R2PS)2 produced Ru(IV)-Ru(IV)μ-nitrido complexes [Ru2(μ-N){N(R2PS)2}4Cl] [R = Ph (6), Pr(i) (7)]. Reactions of 3 and 9 with PPh3 afforded 6 and [Ru(NPPh3)LOEtCl2], respectively. The desulfurisation of 5 with [Ni(cod)2] (cod = 1,5-cyclooctadiene) gave the mixed valance Ru(III)-Ru(IV)μ-nitrido complex [Ru2(μ-N){N(Bu(t)2PS)2}4] (10) that was oxidised by [Cp2Fe](PF6) to give the Ru(IV)-Ru(IV) complex [Ru2(μ-N){N(Bu(t)2PS)2}4](PF6) ([10]PF6). The crystal structures of 1, 2, 3, 7, 9 and 10 have been determined.

Genomic Insights into the Sulfur Metabolism of Phototrophic Green Sulfur Bacteria

DEFF Research Database (Denmark)

Frigaard, Niels-Ulrik; Bryant, Donald A.

2008-01-01

Green sulfur bacteria (GSB) utilize various combinations of sulfide, elemental sulfur, thiosulfate, ferrous iron, and hydrogen for anaerobic photoautotrophic growth. Genome sequence data is currently available for 12 strains of GSB. We present here a genome-based survey of the distribution...... and phylogenies of genes involved in oxidation of sulfur compounds in these strains. Sulfide:quinone reductase, encoded by sqr, is the only known sulfur-oxidizing enzyme found in all strains. All sulfide-utilizing strains contain the dissimilatory sulfite reductase dsrABCEFHLNMKJOPT genes, which appear...... to be involved in elemental sulfur utilization. All thiosulfate-utilizing strains have an identical sox gene cluster (soxJXYZAKBW). The soxCD genes found in certain other thiosulfate-utilizing organisms like Paracoccus pantotrophus are absent from GSB. Genes encoding flavocytochrome c (fccAB), adenosine-5...

Capital cost: high and low sulfur coal plants-1200 MWe. [High sulfur coal

Energy Technology Data Exchange (ETDEWEB)

1977-01-01

This Commercial Electric Power Cost Study for 1200 MWe (Nominal) high and low sulfur coal plants consists of three volumes. The high sulfur coal plant is described in Volumes I and II, while Volume III describes the low sulfur coal plant. The design basis and cost estimate for the 1232 MWe high sulfur coal plant is presented in Volume I, and the drawings, equipment list and site description are contained in Volume II. The reference design includes a lime flue gas desulfurization system. A regenerative sulfur dioxide removal system using magnesium oxide is also presented as an alternate in Section 7 Volume II. The design basis, drawings and summary cost estimate for a 1243 MWe low sulfur coal plant are presented in Volume III. This information was developed by redesigning the high sulfur coal plant for burning low sulfur sub-bituminous coal. These coal plants utilize a mechanical draft (wet) cooling tower system for condenser heat removal. Costs of alternate cooling systems are provided in Report No. 7 in this series of studies of costs of commercial electrical power plants.

Synergistic capture mechanisms for alkali and sulfur species from combustion. Final report

Energy Technology Data Exchange (ETDEWEB)

Peterson, T.W.; Shadman, F.; Wendt, J.O.L.; Mwabe, P.O.

1994-02-01

Experimental work was carried out on a 17 kW, 600 cm long, gas laboratory combustor, to investigate the post flame reactive capture of alkali species by kaolinite. Emphasis was on alkali/sorbent interactions occurring in flue gas at temperatures above the alkali dewpoint and on the formation of water insoluble reaction products. Time-temperature studies were carried out by injecting kaolinite at different axial points along the combustor. The effect of chlorine and sulfur on alkali capture was investigated by doping the flame with SO{sub 2} and Cl{sub 2} gases to simulate coal flame environments. Particle time and temperature history was kept as close as possible to that which would ordinarily be found in a practical boiler. Experiments designed to extract apparent initial reaction rates were carried using a narrow range, 1-2 {mu}m modal size sorbent, while, a coarse, multi size sorbent was used to investigate the governing transport mechanisms. The capture reaction has been proposed to be between alkali hydroxide and activated kaolinite, and remains so in the presence of sulfur and chlorine. The presence of sulfur reduces sodium capture by under 10% at 1300{degree}C. Larger reductions at lower temperatures are attributed to the elevated dewpoint of sodium ({approximately}850{degree}C) with subsequent reduction in sorbent residence time in the alkali gas phase domain. Chlorine reduces sodium capture by 30% across the temperature range covered by the present experiments. This result has been linked to thermodynamic equilibria between sodium hydroxide, sodium chloride and water.

ADVANCED SULFUR CONTROL CONCEPTS

Energy Technology Data Exchange (ETDEWEB)

Apostolos A. Nikolopoulos; Santosh K. Gangwal; William J. McMichael; Jeffrey W. Portzer

2003-01-01

Conventional sulfur removal in integrated gasification combined cycle (IGCC) power plants involves numerous steps: COS (carbonyl sulfide) hydrolysis, amine scrubbing/regeneration, Claus process, and tail-gas treatment. Advanced sulfur removal in IGCC systems involves typically the use of zinc oxide-based sorbents. The sulfides sorbent is regenerated using dilute air to produce a dilute SO{sub 2} (sulfur dioxide) tail gas. Under previous contracts the highly effective first generation Direct Sulfur Recovery Process (DSRP) for catalytic reduction of this SO{sub 2} tail gas to elemental sulfur was developed. This process is currently undergoing field-testing. In this project, advanced concepts were evaluated to reduce the number of unit operations in sulfur removal and recovery. Substantial effort was directed towards developing sorbents that could be directly regenerated to elemental sulfur in an Advanced Hot Gas Process (AHGP). Development of this process has been described in detail in Appendices A-F. RTI began the development of the Single-step Sulfur Recovery Process (SSRP) to eliminate the use of sorbents and multiple reactors in sulfur removal and recovery. This process showed promising preliminary results and thus further process development of AHGP was abandoned in favor of SSRP. The SSRP is a direct Claus process that consists of injecting SO{sub 2} directly into the quenched coal gas from a coal gasifier, and reacting the H{sub 2}S-SO{sub 2} mixture over a selective catalyst to both remove and recover sulfur in a single step. The process is conducted at gasifier pressure and 125 to 160 C. The proposed commercial embodiment of the SSRP involves a liquid phase of molten sulfur with dispersed catalyst in a slurry bubble-column reactor (SBCR).

The significance of elemental sulfur dissolution in liquid electrolyte lithium sulfur batteries

NARCIS (Netherlands)

Harks, Peter Paul R.M.L.; Robledo, Carla B.; Verhallen, Tomas W.; Notten, Peter H.L.; Mulder, Fokko M.

2017-01-01

It is shown that the dissolution of elemental sulfur into, and its diffusion through, the electrolyte allows cycling of lithium–sulfur batteries in which the sulfur is initially far removed and electrically insulated from the current collector. These findings help to understand why liquid

Sulfur tolerant zeolite supported platinum catalysts for aromatics hydrogenation

Energy Technology Data Exchange (ETDEWEB)

Bergem, Haakon

1997-12-31

The increased demand for transportation fuels at the expence of heavier fuel oil has forced the refinery industry to expand their conversion capacity with hydrotreating as one of the key processes. A shift towards more diesel powered vehicles along with tightening fuel regulations demanding cleaner fuels has lead to increasing interest in catalytic processes for the manufacturing of such environmentally acceptable fuels. This provides the motivation for this thesis. Its main objective was to study possible catalysts active for desulfurization, hydrogenation, and ring-opening of aromatics all in the presence of sulfur. A close examination of the physical properties and kinetical behaviour of the chosen catalysts has been performed. A high pressure reactor setup was designed and built for activity measurements. Zeolite supported platinum catalysts were prepared and both the metal and acid functions were characterized utilizing various experimental techniques. Hydrogenation of toluene was used as a model reaction and the effect of sulfur adsorption on the activity and kinetic behaviour of the catalysts was investigated. The catalyst samples showed hydrogenation activities comparable to a commercial Pt/Al2O3 catalyst. There were no clear differences in the effect of the various sulfur compounds studied. Platinum supported on zeolite Y gave considerably more sulfur tolerant catalysts compared to Al2O3 as support. 155 refs., 58 figs., 36 tabs.

Stabilization of sulfuric acid dimers by ammonia, methylamine, dimethylamine, and trimethylamine

Science.gov (United States)

Jen, Coty N.; McMurry, Peter H.; Hanson, David R.

2014-06-01

This study experimentally explores how ammonia (NH3), methylamine (MA), dimethylamine (DMA), and trimethylamine (TMA) affect the chemical formation mechanisms of electrically neutral clusters that contain two sulfuric acid molecules (dimers). Dimers may also contain undetectable compounds, such as water or bases, that evaporate upon ionization and sampling. Measurements were conducted using a glass flow reactor which contained a steady flow of humidified nitrogen with sulfuric acid concentrations of 107 to 109 cm-3. A known molar flow rate of a basic gas was injected into the flow reactor. The University of Minnesota Cluster Chemical Ionization Mass Spectrometer was used to measure the resulting sulfuric acid vapor and cluster concentrations. It was found that, for a given concentration of sulfuric acid vapor, the dimer concentration increases with increasing concentration of the basic gas, eventually reaching a plateau. The base concentrations at which the dimer concentrations saturate suggest NH3 heuristic models for cluster formation by acid-base reactions are developed to interpret the data. The models provide ranges of evaporation rate constants that are consistent with observations and leads to an analytic expression for nucleation rates that is consistent with atmospheric observations.

Ice nucleation in sulfuric acid/organic aerosols: implications for cirrus cloud formation

Directory of Open Access Journals (Sweden)

M. R. Beaver

2006-01-01

Full Text Available Using an aerosol flow tube apparatus, we have studied the effects of aliphatic aldehydes (C3 to C10 and ketones (C3 and C9 on ice nucleation in sulfuric acid aerosols. Mixed aerosols were prepared by combining an organic vapor flow with a flow of sulfuric acid aerosols over a small mixing time (~60 s at room temperature. No acid-catalyzed reactions were observed under these conditions, and physical uptake was responsible for the organic content of the sulfuric acid aerosols. In these experiments, aerosol organic content, determined by a Mie scattering analysis, was found to vary with the partial pressure of organic, the flow tube temperature, and the identity of the organic compound. The physical properties of the organic compounds (primarily the solubility and melting point were found to play a dominant role in determining the inferred mode of nucleation (homogenous or heterogeneous and the specific freezing temperatures observed. Overall, very soluble, low-melting organics, such as acetone and propanal, caused a decrease in aerosol ice nucleation temperatures when compared with aqueous sulfuric acid aerosol. In contrast, sulfuric acid particles exposed to organic compounds of eight carbons and greater, of much lower solubility and higher melting temperatures, nucleate ice at temperatures above aqueous sulfuric acid aerosols. Organic compounds of intermediate carbon chain length, C4-C7, (of intermediate solubility and melting temperatures nucleated ice at the same temperature as aqueous sulfuric acid aerosols. Interpretations and implications of these results for cirrus cloud formation are discussed.

Effect of sulfur or hydrogen sulfide on initial stage of coal liquefaction in tetralin; Sekitan ekika shoki katei ni okeru io to ryuka suiso no hatasu yakuwari

Energy Technology Data Exchange (ETDEWEB)

Nakada, M. [Government Industrial Research Institute, Kyushu, Saga (Japan)

1996-10-28

It is well known that the solubilization of coal can be accelerated by adding sulfur or hydrogen sulfide during direct liquefaction of difficult coals. From the studies of authors on the coal liquefaction under the conditions at rather low temperatures between 300 and 400{degree}C, liquefaction products with high quality can be obtained by suppressing the aromatization of naphthene rings, but it was a problem that the reaction rate is slow. For improving this point, results obtained by changing solvents have been reported. In this study, to accelerate the liquefaction reaction, Illinois No.6 coal was liquefied in tetralin at temperature range from 300 to 400{degree}C by adding a given amount of sulfur or hydrogen sulfide at the initial stage of liquefaction. The addition of sulfur or hydrogen sulfide provided an acceleration effect of liquefaction reaction at temperature range between 300 and 400{degree}C. The addition of sulfur or hydrogen sulfide at 400{degree}C increased the oil products. At 370 and 400{degree}C, the liquid yield by adding sulfur was slightly higher than that by adding hydrogen sulfide, unexpectedly. The effects of sulfur and hydrogen sulfide were reversed when increasing the hydrogen pressure. 5 figs., 1 tab.

Synthesis of sulfur-containing lubricant additives on the basis of fatty acid ethyl esters

Directory of Open Access Journals (Sweden)

Iurii S. Bodachivskyi

2016-12-01

Full Text Available The study reveals an energy-, resource- and eco-friendly method for preparation of sulfur-containing lubricant additives via interaction of fatty acid ethyl esters of rapeseed oil with elemental sulfur. The structure of synthesized compounds under various reactants ratio (5–50 wt.% of sulfur, duration (30–240 min and temperature of the process (160–215°С was investigated using various analytical techniques. According to the established data, aside from addition to double bonds, the side reaction of hydrogen substitution at α-methylene groups near these bonds occurs and induces the formation of conjugated systems and chromophoric sulfur-rich derivatives. Also, we found that increase of process duration evokes growth of polysulfane chains, in contrast to the raise of temperature, which leads to the formation of sulfur-containing heterocycles and hydrogen sulfide, as a result of elimination. Influence of accelerators on sulfurization of fatty acid ethyl esters was also examined. The most effective among them are mixtures of zinc dibutyldithiocarbamate with zinc oxide or stearic acid, which soften synthesis conditions and doubly decrease duration of the high-temperature stage. In addition, sulfur-containing compositions of ethyl esters and α-olefins, vulcanized esters by benzoyl peroxide, nonylphenols and zinc dinonylphenyldithiophosphate were designed. The study identified that lithium lubricant with sulfurized vulcanized esters provides improved tribological properties, in comparison with base lubricant or lubricant with the non-modified product.

Self-assembled peptides for coating of active sulfur nanoparticles in lithium–sulfur battery

International Nuclear Information System (INIS)

Jewel, Yead; Yoo, Kisoo; Liu, Jin; Dutta, Prashanta

2016-01-01

Development of lithium–sulfur (Li–S) battery is hindered by poor cyclability due to the loss of sulfur, although Li–S battery can provide high energy density. Coating of sulfur nanoparticles can help maintain active sulfur in the cathode of Li–S battery, and hence increase the cyclability. Among myriad of coating materials, synthetic peptides are very attractive because of their spontaneous self-assembly as well as electrical conductive characteristics. In this study, we explored the use of various synthetic peptides as a coating material for sulfur nanoparticles. Atomistic simulations were carried out to identify optimal peptide structure and density for coating sulfur nanoparticles. Three different peptide models, poly-proline, poly(leucine–lysine) and poly-histidine, are selected for this study based on their peptide–peptide and peptide-sulfur interactions. Simulation results show that both poly-proline and poly(leucine–lysine) can form self-assembled coating on sulfur nanoparticles (2–20 nm) in pyrrolidinone, a commonly used solvent for cathode slurry. We also studied the structural integrity of these synthetic peptides in organic [dioxolane (DOL) and dimethoxyethane (DME)] electrolyte used in Li–S battery. Both peptides show stable structures in organic electrolyte (DOL/DME) used in Li–S battery. Furthermore, the dissolution of sulfur molecules in organic electrolyte is investigated in the absence and presence of these peptide coatings. It was found that only poly(leucine–lysine)-based peptide can most effectively suppress the sulfur loss in electrolyte, suggesting its potential applications in Li–S battery as a coating material.Graphical abstract

Electrochemical evaluation of sulfur poisoning in a methane-fuelled solid oxide fuel cell: Effect of current density and sulfur concentration

DEFF Research Database (Denmark)

Hagen, Anke; Johnson, Gregory B.; Hjalmarsson, Per

2014-01-01

, the effect of sulfur was less pronounced on mass transfer/fuel reforming processes but quite significant on the charge transfer/TPB processes. Overall, sulfur related performance loss was more severe at the highest current density (1 A cm−2), due to the deactivation of catalytic fuel reforming reactions......A Ni/ScYSZ based SOFC was tested at 1, 0.5, 0.25, and 0 (OCV) A cm−2 in methane fuel containing 0–100 ppm H2S. Analysis of cell voltage loss during short-term H2S poisoning showed that SOFC performance loss was generally larger at higher current loads. Separating the effect of H2S on catalytic...... reforming and electrochemical activity by evaluating the relevant area specific resistances and charge transfer processes based on impedance spectroscopy revealed that the poisoning of electrochemical activity was not dependent on current density. Two major anode processes were significantly affected...

Vector analyzing power and cross section for the reactions 40Ar(d(pol),p)41Ar and 40Ar(d(pol),t)39Ar

International Nuclear Information System (INIS)

Sen, S.; Darden, S.E.; Yoh, W.A.; Berners, E.D.

1975-01-01

Angular distributions of vector analyzing power and cross section for the reactions 40 Ar(d,p) 41 Ar and 40 Ar(d,t) 39 Ar have been measured at an incident deuteron energy of 14.83 MeV. The bound-state data in the (d,p) reaction and the (d,t) data are compared to DWBA calculations. The data for the neutron-unbound states are analyzed in the framework of the DWBA using (i) a form factor for weakly bound neutron and (ii) a resonance form factor, following the approach of Vincent and Fortune. The j-dependence of the (d,p) vector analyzing power permits definite spin-parity assignments to be made for 19 neutron-bound and 4 neutron unbound states in 41 Ar with excitation energy up to 6.57 MeV. Tentative Jsup(π) assignments have been made for 3 states. The l-value for the 5.62 MeV states has been determined. Data for the observed unbound states are found to be equally well reproduced by the type (i) calculations as by the type (ii) calculations. The (d,t) vector cnalyzing power data show definite J-dependence although not as strongly as in the (d,p) reaction. For relatively weakly excited states a pre-knowledge of the l-value of the transition is desirable for an unambiguous spin assignment. In general, the J-dependence in the (d,t) vector analyzing power can be utilized for definitive Jsup(π) assignments. On this basis, Jsub(π) values have been assigned for seven states in 39 Ar with excitation energies up to 4.47MeV excitation. Possible spin values for three other states are suggested. Spectroscopic factors fo the states in 41 Ar and 39 Ar have been extracted and are in fair agreement with those obtained by other workers. (Auth.)

Sulfur-carbon nanocomposites and their application as cathode materials in lithium-sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Liang, Chengdu; Dudney, Nancy J.; Howe, Jane Y.

2017-08-01

The invention is directed in a first aspect to a sulfur-carbon composite material comprising: (i) a bimodal porous carbon component containing therein a first mode of pores which are mesopores, and a second mode of pores which are micropores; and (ii) elemental sulfur contained in at least a portion of said micropores. The invention is also directed to the aforesaid sulfur-carbon composite as a layer on a current collector material; a lithium ion battery containing the sulfur-carbon composite in a cathode therein; as well as a method for preparing the sulfur-composite material.

Effect of different sulfur levels from various sources on brassica napus growth and soil sulfur fractions

International Nuclear Information System (INIS)

Khalid, R.; Khan, K.S.; Islam, M.; Yousaf, M.; Shabbir, G.

2012-01-01

A two year field study was conducted at two different locations in northern rain fed Punjab, Pakistan to assess the effect of different rates of sulfur application from various sources on soil sulfur fractions and growth of Brassica napus. The treatments included three sulfur sources i. e., single super phosphate, ammonium sulfate and gypsum each applied at five different rates (0, 10, 20, 30 and 40 kg S ha/sup -1/ ). Sulfur application had a significant positive effect on the growth and yield parameters of Brassica napus. Among the sulfur sources ammonium sulfate resulted in maximum increase in plant growth and yield parameters, followed by single super phosphate. Sulfur content and uptake by crop plants was significantly higher with ammonium sulfate application as compared to other two sulfur sources. Sulfur application also exerted a significant positive effect on different S fractions in the soils. On an average, 18.0% of the applied sulfur got incorporated into CaCl/sub 2/ extractable sulfur fraction, while 15.6% and 35.5% entered into adsorbed and organic sulfur fractions in the soils, respectively. The value cost ratio increased significantly by sulfur application up to 30 kg ha/sup -1/. Among sulfur sources, ammonium sulfate performed best giving the highest net return. (author)

Sulfur nanocrystals anchored graphene composite with highly improved electrochemical performance for lithium-sulfur batteries

Science.gov (United States)

Zhang, Jun; Dong, Zimin; Wang, Xiuli; Zhao, Xuyang; Tu, Jiangping; Su, Qingmei; Du, Gaohui

2014-12-01

Two kinds of graphene-sulfur composites with 50 wt% of sulfur are prepared using hydrothermal method and thermal mixing, respectively. Transmission Electron Microscopy (TEM) and Energy Dispersive X-ray Spectra mapping show that sulfur nanocrystals with size of ∼5 nm dispersed on graphene sheets homogeneously for the sample prepared by hydrothermal method (NanoS@G). While for the thermal mixed graphene-sulfur composite (S-G mixture), sulfur shows larger and uneven size (50-200 nm). X-ray Photoelectron Spectra (XPS) reveals the strong chemical bonding between the sulfur nanocrystals and graphene. Comparing with the S-G mixture, the NanoS@G composite shows highly improved electrochemical performance as cathode for lithium-sulfur (Li-S) battery. The NanoS@G composite delivers an initial capacity of 1400 mAh g-1 with the sulfur utilization of 83.7% at a current density of 335 mA g-1. The capacity keeps above 720 mAh g-1 over 100 cycles. The strong adherence of the sulfur nanocrystals on graphene immobilizes sulfur and polysulfides species and suppressed the "shuttle effect", resulting higher coulombic efficiency and better capacity retention. Electrochemical impedance also suggests that the strong bonding enabled rapid electronic/ionic transport and improved electrochemical kinetics, therefore good rate capability is obtained. These results demonstrate that the NanoS@G composite is a very promising candidate for high-performance Li-S batteries.

Enzymatic Synthesis and Structural Characterization of Theanderose through Transfructosylation Reaction Catalyzed by Levansucrase from Bacillus subtilis CECT 39.

Science.gov (United States)

Ruiz-Aceituno, Laura; Sanz, Maria Luz; de Las Rivas, Blanca; Muñoz, Rosario; Kolida, Sofia; Jimeno, Maria Luisa; Moreno, F Javier

2017-12-06

This work addresses the high-yield and fast enzymatic production of theanderose, a naturally occurring carbohydrate, also known as isomaltosucrose, whose chemical structure determined by NMR is α-d-glucopyranosyl-(1 → 6)-α-d-glucopyranosyl-(1 → 2)-β-d-fructofuranose. The ability of isomaltose to act as an acceptor in the Bacillus subtilis CECT 39 levansucrase-catalyzed transfructosylation reaction to efficiently produce theanderose in the presence of sucrose as a donor is described by using four different sucrose:isomaltose concentration ratios. The maximum theanderose concentration ranged from 122.4 to 130.4 g L -1 , was obtained after only 1 h and at a moderate temperature (37 °C), leading to high productivity (109.7-130.4 g L -1 h -1 ) and yield (up to 37.3%) values. The enzymatic synthesis was highly regiospecific, since no other detectable acceptor reaction products were formed. The development of efficient and cost-effective procedures for the biosynthesis of unexplored but appealing oligosaccharides as potential sweeteners, such as theanderose, could help to expand its potential applications which are currently limited by their low availability.

Removal of sulfur compounds from diesel using ArF laser and oxygen.

Science.gov (United States)

Gondal, M A; Siddiqui, M N; Al-Hooshani, K

2013-01-01

A laser-based technique for deep desulfurization of diesel and other hydrocarbon fuels by removal of dimethyldibenzothiophene (DMDBT), a persistent sulfur contaminant in fuel oils has been developed. We report a selective laser excitation of DMDBT in diesel and model compounds such as n-hexane in a reaction chamber under oxygen environment where oxidative reactions can take place. ArF laser emitting at 193 nm was employed for excitation of oxygen and DMDBT, while for process optimization, the laser energy was varied from 50 to 200 mJ/cm(2). The laser-irradiated DMDBT solution under continuous oxygen flow was analyzed by UV absorption spectrometer to determine the photochemical oxidative degradation of DMDBT. In just 5 min of laser irradiation time, almost 95% DMDBT was depleted in a diesel containing 200 ppm of DMDBT. This article provides a new method for the removal of sulfur compounds from diesel by laser based photochemical process.

Extraordinary Difference in Reactivity of Ozone (OOO) and Sulfur Dioxide (OSO): A Theoretical Study.

Science.gov (United States)

Lan, Yu; Wheeler, Steven E; Houk, K N

2011-07-12

Ozone and sulfur dioxide are valence isoelectronic yet show very different reactivity. While ozone is one of the most reactive 1,3-dipoles, SO2 does not react in this way at all. The activation energies of dipolar cycloadditions of sulfur dioxide with either ethylene or acetylene are predicted here by B3LYP, M06-2X, CBS-QB3, and CCSD(T) to be much higher than reactions of ozone. The dipolar cycloaddition of ozone is very exothermic, while that of than sulfur dioxide is endothermic. The prohibitive barriers in the case of SO2 arise from large distortion energies as well as unfavorable interaction energies in the transition states. This arises in part from the HOMO-LUMO gap of sulfur dioxide, which is larger than that of ozone. Valence bond calculations also show that while ozone has a high degree of diradical character, SO2 does not, and is better characterized as a dritterion.

Direct observation of lithium polysulfides in lithium-sulfur batteries using operando X-ray diffraction

Science.gov (United States)

Conder, Joanna; Bouchet, Renaud; Trabesinger, Sigita; Marino, Cyril; Gubler, Lorenz; Villevieille, Claire

2017-06-01

In the on going quest towards lithium-battery chemistries beyond the lithium-ion technology, the lithium-sulfur system is emerging as one of the most promising candidates. The major outstanding challenge on the route to commercialization is controlling the so-called polysulfide shuttle, which is responsible for the poor cycling efficiency of the current generation of lithium-sulfur batteries. However, the mechanistic understanding of the reactions underlying the polysulfide shuttle is still incomplete. Here we report the direct observation of lithium polysulfides in a lithium-sulfur cell during operation by means of operando X-ray diffraction. We identify signatures of polysulfides adsorbed on the surface of a glass-fibre separator and monitor their evolution during cycling. Furthermore, we demonstrate that the adsorption of the polysulfides onto SiO2 can be harnessed for buffering the polysulfide redox shuttle. The use of fumed silica as an electrolyte additive therefore significantly improves the specific charge and Coulombic efficiency of lithium-sulfur batteries.

CR-39 plastic nuclear track detector and its application in nuclear science

International Nuclear Information System (INIS)

Zhai Pengji; Tang Xiaowei; Wang Long; Liang Tianjiao

2000-01-01

The transparent and stable plastic material CR-39 can be used as a nuclear track detector which is highly sensitive to charged particles. It can record tracks induced by protons , alphas, fission fragments and other charged particles. Among various available solid state nuclear track detectors CR-39 has the lowest deposited energy density detection-threshold. The response of CR-39 to charged particles and the response curve of υ T of different charged particles to REL are given. The CR-39 detector is widely used in studies of nuclear reactions, angular distributions and reaction cross-sections caused by neutrons and charged particles. Neutron spectra, over a wide energy range, can be measured by the combination of CR-39 and a transformation screen. The successful applications of CR-39 in alpha particle dosimetry, environmental science (especially in the measurement of radon) and in biomedicine, such as the analysis of alpha radioactivity in sections of organic tissues, are described

Synthesis and reactivity of novel sulfur pentafluorides-Effect of the SF5 group on reactivity of nitrobenzenes in nucleophilic substitution

Czech Academy of Sciences Publication Activity Database

Beier, Petr

2017-01-01

Roč. 192, č. 2 (2017), s. 212-215 ISSN 1042-6507. [International Symposium on the Organic Chemistry of Sulfur (ISOCS) /27./. Jena, 26.07.2016-29.07.2016] Institutional support: RVO:61388963 Keywords : nucleophilic substitution * sulfur * fluorine * reaction rate Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 0.809, year: 2016

Formation of metacinnabar by milling of liquid mercury and elemental sulfur for long term mercury storage

International Nuclear Information System (INIS)

Lopez, F.A.; Lopez-Delgado, A.; Padilla, I.; Tayibi, H.; Alguacil, F.J.

2010-01-01

In this paper we present the results of the formation of black HgS (metacinnabar) from liquid mercury and elemental sulfur using the mechanical energy provided by a ball mill in different conditions. Metacinnabar formation was observed even after short milling times (15 min) and unreacted liquid mercury was no longer detected after 60 min of milling. The reaction mechanism was monitored with a scanning electron microscope. The impact and friction forces of milling on the Hg and S mixture resulted in the formation of metacinnabar by reducing the size of mercury drops, giving rise to microspheres, and lowering the surface tension to allow sulfur grains to become adhered at the reaction interface. After 60 min of milling, the metacinnabar formation reaction was observed to be more than 99.99% complete, yielding a Toxicity Characteristic Leaching Procedure value of 3.1 μg/L Hg. The reaction product thus complies with the limits of the most stringent Universal Treatment Standard requirements, which allow a maximum TCLP concentration of 25 μg/L.

Tetrathionate and Elemental Sulfur Shape the Isotope Composition of Sulfate in Acid Mine Drainage

Directory of Open Access Journals (Sweden)

Nurgul Balci

2017-08-01

Full Text Available Sulfur compounds in intermediate valence states, for example elemental sulfur, thiosulfate, and tetrathionate, are important players in the biogeochemical sulfur cycle. However, key understanding about the pathways of oxidation involving mixed-valance state sulfur species is still missing. Here we report the sulfur and oxygen isotope fractionation effects during the oxidation of tetrathionate (S4O62− and elemental sulfur (S° to sulfate in bacterial cultures in acidic conditions. Oxidation of tetrathionate by Acidithiobacillus thiooxidans produced thiosulfate, elemental sulfur and sulfate. Up to 34% of the tetrathionate consumed by the bacteria could not be accounted for in sulfate or other intermediate-valence state sulfur species over the experiments. The oxidation of tetrathionate yielded sulfate that was initially enriched in 34S (ε34SSO4−S4O6 by +7.9‰, followed by a decrease to +1.4‰ over the experiment duration, with an average ε34SSO4−S4O6 of +3.5 ± 0.2‰ after a month of incubation. We attribute this significant sulfur isotope fractionation to enzymatic disproportionation reactions occurring during tetrathionate decomposition, and to the incomplete transformation of tetrathionate into sulfate. The oxygen isotope composition of sulfate (δ18OSO4 from the tetrathionate oxidation experiments indicate that 62% of the oxygen in the formed sulfate was derived from water. The remaining 38% of the oxygen was either inherited from the supplied tetrathionate, or supplied from dissolved atmospheric oxygen (O2. During the oxidation of elemental sulfur, the product sulfate became depleted in 34S between −1.8 and 0‰ relative to the elemental sulfur with an average for ε34SSO4−S0 of −0.9 ± 0.2‰ and all the oxygen atoms in the sulfate derived from water with an average normal oxygen isotope fractionation (ε18OSO4−H2O of −4.4‰. The differences observed in δ18OSO4 and the sulfur isotope composition of sulfate (δ34SSO4

Steep spatial gradients of volcanic and marine sulfur in Hawaiian rainfall and ecosystems

Energy Technology Data Exchange (ETDEWEB)

Bern, Carleton R., E-mail: cbern@usgs.gov [U.S. Geological Survey, Denver Federal Center, Denver, CO 80225 (United States); Department of Geography University of California, Santa Barbara, CA 93106-4060 (United States); Chadwick, Oliver A. [Department of Geography University of California, Santa Barbara, CA 93106-4060 (United States); Kendall, Carol [U.S. Geological Survey, Menlo Park, CA (United States); Pribil, Michael J. [U.S. Geological Survey, Denver Federal Center, Denver, CO 80225 (United States)

2015-05-01

Sulfur, a nutrient required by terrestrial ecosystems, is likely to be regulated by atmospheric processes in well-drained, upland settings because of its low concentration in most bedrock and generally poor retention by inorganic reactions within soils. Environmental controls on sulfur sources in unpolluted ecosystems have seldom been investigated in detail, even though the possibility of sulfur limiting primary production is much greater where atmospheric deposition of anthropogenic sulfur is low. Here we measure sulfur isotopic compositions of soils, vegetation and bulk atmospheric deposition from the Hawaiian Islands for the purpose of tracing sources of ecosystem sulfur. Hawaiian lava has a mantle-derived sulfur isotopic composition (δ{sup 34}S VCDT) of − 0.8‰. Bulk deposition on the island of Maui had a δ{sup 34}S VCDT that varied temporally, spanned a range from + 8.2 to + 19.7‰, and reflected isotopic mixing from three sources: sea-salt (+ 21.1‰), marine biogenic emissions (+ 15.6‰), and volcanic emissions from active vents on Kilauea Volcano (+ 0.8‰). A straightforward, weathering-driven transition in ecosystem sulfur sources could be interpreted in the shift from relatively low (0.0 to + 2.7‰) to relatively high (+ 17.8 to + 19.3‰) soil δ{sup 34}S values along a 0.3 to 4100 ka soil age-gradient, and similar patterns in associated vegetation. However, sub-kilometer scale spatial variation in soil sulfur isotopic composition was found along soil transects assumed by age and mass balance to be dominated by atmospheric sulfur inputs. Soil sulfur isotopic compositions ranged from + 8.1 to + 20.3‰ and generally decreased with increasing elevation (0–2000 m), distance from the coast (0–12 km), and annual rainfall (180–5000 mm). Such trends reflect the spatial variation in marine versus volcanic inputs from atmospheric deposition. Broadly, these results illustrate how the sources and magnitude of atmospheric deposition can exert controls

Steep spatial gradients of volcanic and marine sulfur in Hawaiian rainfall and ecosystems

International Nuclear Information System (INIS)

Bern, Carleton R.; Chadwick, Oliver A.; Kendall, Carol; Pribil, Michael J.

2015-01-01

Sulfur, a nutrient required by terrestrial ecosystems, is likely to be regulated by atmospheric processes in well-drained, upland settings because of its low concentration in most bedrock and generally poor retention by inorganic reactions within soils. Environmental controls on sulfur sources in unpolluted ecosystems have seldom been investigated in detail, even though the possibility of sulfur limiting primary production is much greater where atmospheric deposition of anthropogenic sulfur is low. Here we measure sulfur isotopic compositions of soils, vegetation and bulk atmospheric deposition from the Hawaiian Islands for the purpose of tracing sources of ecosystem sulfur. Hawaiian lava has a mantle-derived sulfur isotopic composition (δ 34 S VCDT) of − 0.8‰. Bulk deposition on the island of Maui had a δ 34 S VCDT that varied temporally, spanned a range from + 8.2 to + 19.7‰, and reflected isotopic mixing from three sources: sea-salt (+ 21.1‰), marine biogenic emissions (+ 15.6‰), and volcanic emissions from active vents on Kilauea Volcano (+ 0.8‰). A straightforward, weathering-driven transition in ecosystem sulfur sources could be interpreted in the shift from relatively low (0.0 to + 2.7‰) to relatively high (+ 17.8 to + 19.3‰) soil δ 34 S values along a 0.3 to 4100 ka soil age-gradient, and similar patterns in associated vegetation. However, sub-kilometer scale spatial variation in soil sulfur isotopic composition was found along soil transects assumed by age and mass balance to be dominated by atmospheric sulfur inputs. Soil sulfur isotopic compositions ranged from + 8.1 to + 20.3‰ and generally decreased with increasing elevation (0–2000 m), distance from the coast (0–12 km), and annual rainfall (180–5000 mm). Such trends reflect the spatial variation in marine versus volcanic inputs from atmospheric deposition. Broadly, these results illustrate how the sources and magnitude of atmospheric deposition can exert controls over

Conductive framework of inverse opal structure for sulfur cathode in lithium-sulfur batteries.

Science.gov (United States)

Jin, Lu; Huang, Xiaopeng; Zeng, Guobo; Wu, Hua; Morbidelli, Massimo

2016-09-07

As a promising cathode inheritor for lithium-ion batteries, the sulfur cathode exhibits very high theoretical volumetric capacity and energy density. In its practical applications, one has to solve the insulating properties of sulfur and the shuttle effect that deteriorates cycling stability. The state-of-the-art approaches are to confine sulfur in a conductive matrix. In this work, we utilize monodisperse polystyrene nanoparticles as sacrificial templates to build polypyrrole (PPy) framework of an inverse opal structure to accommodate (encapsulate) sulfur through a combined in situ polymerization and melting infiltration approach. In the design, the interconnected conductive PPy provides open channels for sulfur infiltration, improves electrical and ionic conductivity of the embedded sulfur, and reduces polysulfide dissolution in the electrolyte through physical and chemical adsorption. The flexibility of PPy and partial filling of the inverse opal structure endure possible expansion and deformation during long-term cycling. It is found that the long cycling stability of the cells using the prepared material as the cathode can be substantially improved. The result demonstrates the possibility of constructing a pure conductive polymer framework to accommodate insulate sulfur in ion battery applications.

Selective oxidation of refractory sulfur compounds for the production of low sulfur transportation fuel

Energy Technology Data Exchange (ETDEWEB)

Jeong, Kwang-Eun; Kim, Tae-Wan; Kim, Joo-Wan; Chae, Ho-Jeong; Kim, Chul-Ung; Jeong, Soon-Yong [Korea Research Institute of Chemical Technology, Daejeon (Korea, Republic of); Park, Young-Kwon [University of Seoul, Seoul (Korea, Republic of)

2013-03-15

The current technologies for achieving low sulfur in diesel fuel are based on hydrotreating, which requires high temperature, high pressure and excessive supply of hydrogen. Oxidative desulfurization (ODS) is considered one of the promising new methods for super deep desulfurization, which could be carried out under very mild conditions (atmospheric pressure, <100 .deg.. C) without consumption of hydrogen. In this paper, development status of ODS process by major licensors are described as well as general concepts of ODS reaction. In addition, the ODS process has been categorized into single phasic and biphasic system according to the oxidants involved. Recent trends in both systems are reviewed in detail and future work is also proposed.

Selective oxidation of refractory sulfur compounds for the production of low sulfur transportation fuel

International Nuclear Information System (INIS)

Jeong, Kwang-Eun; Kim, Tae-Wan; Kim, Joo-Wan; Chae, Ho-Jeong; Kim, Chul-Ung; Jeong, Soon-Yong; Park, Young-Kwon

2013-01-01

The current technologies for achieving low sulfur in diesel fuel are based on hydrotreating, which requires high temperature, high pressure and excessive supply of hydrogen. Oxidative desulfurization (ODS) is considered one of the promising new methods for super deep desulfurization, which could be carried out under very mild conditions (atmospheric pressure, <100 .deg.. C) without consumption of hydrogen. In this paper, development status of ODS process by major licensors are described as well as general concepts of ODS reaction. In addition, the ODS process has been categorized into single phasic and biphasic system according to the oxidants involved. Recent trends in both systems are reviewed in detail and future work is also proposed

ADVANCED SULFUR CONTROL CONCEPTS FOR HOT-GAS DESULFURIZATION TECHNOLOGY

Energy Technology Data Exchange (ETDEWEB)

A. LOPEZ ORTIZ; D.P. HARRISON; F.R. GROVES; J.D. WHITE; S. ZHANG; W.-N. HUANG; Y. ZENG

1998-10-31

This research project examined the feasibility of a second generation high-temperature coal gas desulfurization process in which elemental sulfur is produced directly during the sorbent regeneration phase. Two concepts were evaluated experimentally. In the first, FeS was regenerated in a H2O-O2 mixture. Large fractions of the sulfur were liberated in elemental form when the H2O-O2 ratio was large. However, the mole percent of elemental sulfur in the product was always quite small (<<1%) and a process based on this concept was judged to be impractical because of the low temperature and high energy requirements associated with condensing the sulfur. The second concept involved desulfurization using CeO2 and regeneration of the sulfided sorbent, Ce2O2S, using SO2 to produce elemental sulfur directly. No significant side reactions were observed and the reaction was found to be quite rapid over the temperature range of 500°C to 700°C. Elemental sulfur concentrations (as S2) as large as 20 mol% were produced. Limitations associated with the cerium sorbent process are concentrated in the desulfurization phase. High temperature and highly reducing coal gas such as produced in the Shell gasification process are required if high sulfur removal efficiencies are to be achieved. For example, the equilibrium H2S concentration at 800°C from a Shell gas in contact with CeO2 is about 300 ppmv, well above the allowable IGCC specification. In this case, a two-stage desulfurization process using CeO2 for bulk H2S removal following by a zinc sorbent polishing step would be required. Under appropriate conditions, however, CeO2 can be reduced to non-stoichiometric CeOn (n<2) which has significantly greater affinity for H2S. Pre-breakthrough H2S concentrations in the range of 1 ppmv to 5 ppmv were measured in sulfidation tests using CeOn at 700°C in highly reducing gases, as measured by equilibrium O2 concentration, comparable to the Shell gas. Good sorbent durability was indicated in

Advanced sulfur control concepts for hot-gas desulfurization technology

International Nuclear Information System (INIS)

Lopez Ortiz, A.; Harrison, D.P.; Groves, F.R.; White, J.D.; Zhang, S.; Huang, W.N.; Zeng, Y.

1998-01-01

This research project examined the feasibility of a second generation high-temperature coal gas desulfurization process in which elemental sulfur is produced directly during the sorbent regeneration phase. Two concepts were evaluated experimentally. In the first, FeS was regenerated in a H2O-O2 mixture. Large fractions of the sulfur were liberated in elemental form when the H2O-O2 ratio was large. However, the mole percent of elemental sulfur in the product was always quite small (<<1%) and a process based on this concept was judged to be impractical because of the low temperature and high energy requirements associated with condensing the sulfur. The second concept involved desulfurization using CeO2 and regeneration of the sulfided sorbent, Ce2O2S, using SO2 to produce elemental sulfur directly. No significant side reactions were observed and the reaction was found to be quite rapid over the temperature range of 500C to 700C. Elemental sulfur concentrations (as S2) as large as 20 mol% were produced. Limitations associated with the cerium sorbent process are concentrated in the desulfurization phase. High temperature and highly reducing coal gas such as produced in the Shell gasification process are required if high sulfur removal efficiencies are to be achieved. For example, the equilibrium H2S concentration at 800C from a Shell gas in contact with CeO2 is about 300 ppmv, well above the allowable IGCC specification. In this case, a two-stage desulfurization process using CeO2 for bulk H2S removal following by a zinc sorbent polishing step would be required. Under appropriate conditions, however, CeO2 can be reduced to non-stoichiometric CeOn (n<2) which has significantly greater affinity for H2S. Pre-breakthrough H2S concentrations in the range of 1 ppmv to 5 ppmv were measured in sulfidation tests using CeOn at 700C in highly reducing gases, as measured by equilibrium O2 concentration, comparable to the Shell gas. Good sorbent durability was indicated in a

Development of once-through hybrid sulfur process for nuclear hydrogen production

International Nuclear Information System (INIS)

Jung, Yong Hun

2010-02-01

Humanity has been facing major energy challenges such as the severe climate change, threat of energy security and global energy shortage especially for the developing world. Particularly, growing awareness of the global warming has led to efforts to develop the sustainable energy technologies for the harmony of the economy, social welfare and environment. Water-splitting nuclear hydrogen production is expected to help to resolve those challenges, when high energy efficiency and low cost for hydrogen production become possible. Once-through Hybrid Sulfur process (Ot-HyS), proposed in this work, produces hydrogen using the same SO 2 Depolarized water Electrolysis (SDE) process found in the original Hybrid Sulfur cycle (HyS) proposed by Westinghouse, which has the sulfuric acid decomposition (SAD) process using high temperature heat source in order to recover sulfur dioxide for the SDE process. But Ot-HyS eliminated this technical hurdle by replacing it with well-established sulfur combustion process to feed sulfur dioxide to the SDE process. Because Ot-HyS has less technical challenges, Ot-HyS is expected to advance the realization of the large-scale nuclear hydrogen production by feeding an initial nuclear hydrogen stock. Most of the elemental sulfur, at present, is supplied by desulfurization process for environmental reasons during the processing of natural gas and petroleum refining and expected to increase significantly. This recovered sulfur will be burned with oxygen in the sulfur combustion process so that produced sulfur dioxide could be supplied to the SDE process to produce hydrogen. Because the sulfur combustion is a highly exothermic reaction releasing 297 kJ/mol of combustion heat resulting in a large temperature rise, efficiency of the Ot-HyS is expected to be high by recovering this great amount of high grade excess heat with nuclear energy. Sulfuric acid, which is a byproduct of the SDE process, could be sent to the neighboring consumers with or even

Sulfur poisoning in cattle

Energy Technology Data Exchange (ETDEWEB)

Julian, R J; Harrison, K B

1975-01-01

A case of sulfur poisoning is described in which 12 of 20 cattle died following the feeding of sulfur. Respiratory distress and abdominal pain were the prominent signs. Examination of one animal revealed vasculitis and necrosis of the rumen and abomasal wall. The possible toxic effects of sulfur are discussed.

Development of techniques of production of sulfur-35 and its inorganic compounds

International Nuclear Information System (INIS)

Shikata, Eiji

1981-12-01

Techniques to produce routinely Curies of carrier-free sulfur-35 from neutron irradiated potassium chloride were developed. Firstly the ratio of sulfur-35 to phosphorus-32 produced respectively by the reactions 35 Cl(n,p) 35 S and 35 Cl(n,α) 32 P was determined. For the post-irradiation process, two processes of anion exchange and cation exchange were studied. The former process was based on the selective elution of carrier-free sulfate after precipitation of the bulk of potassium chloride by ethanol and the latter process on the selective adsorption of carrier-free phosphate on Fe +3 -cation exchange resin. A gloved box with various appendant equipments was constructed for routine production and a glass apparatus was installed in it. Sulfur-35 from 1 Ci to 5 Ci has been produced by the cation exchange process several times every year during past few years, and products of high quality have been obtained with yields higher than 90% without any troubles. In the studies on the synthesis of sulfur-35 labeled inorganic compounds, sulfate[ 35 S] was reduced with tin(II)-phosphoric acid to hydrogen sulfide[ 35 S], which was oxidized to elementary sulfur[ 35 S]. Sulfate[ 35 S] of sodium or copper(II) was precipitated from an aqueous solution of sodium or copper(II) chloride containing carrier-free sulfate [ 35 S] by adding carrier of either one of the sulfates and ethanol. Copper(II) sulfate[ 35 S] was pyrolyzed to evolve sulfur[ 35 S] dioxide, which was fixed in a sodium hydroxide solution as sodium sulfite[ 35 S]. This was allowed to react with colloidal sulfur in a boiling solution in the presence of 2-octanol to form thiosulfate[ 35 S] efficiently. By treating target potassium chloride before and after irradiation in an oxygen-free atmosphere, approximately 60% of sulfur-35 was recovered as thiosulfate. Reduction with nascent hydrogen and decomposition with acid of the thiosulfate were studied to prepare elementary sulfur [ 35 S]. (author)

Photoactive thin film semiconducting iron pyrite prepared by sulfurization of iron oxides

Energy Technology Data Exchange (ETDEWEB)

Smestad, G.; Ennaoui, A.; Fiechter, S.; Tributsch, H.; Hofmann, W.K.; Birkholz, M. (Hahn-Meitner-Institut Berlin GmbH (Germany, F.R.). Abt. Solare Energetik Hahn-Meitner-Institut Berlin GmbH (Germany, F.R.). Abt. Materialforschung); Kautek, W. (Bundesanstalt fuer Materialforschung und -pruefung, Berlin (Germany, F.R.))

1990-03-01

Photoactive iron pyrite (FeS{sub 2}) thin film layers have been synthesized by a simple method involving the reaction of Fe{sub 3}O{sub 4} or Fe{sub 2}O{sub 3} with elemental sulfur. The films were formed on a variety of different substrate materials by converting or sulfurizing iron oxide layers. The subsequent sulfur treatment of the oxide layers consisted of exposure of the films to gaseous sulfur in open or closed ampules at 350degC for 0.5-2 h. The morphology, composition and photoactivity of the films produced were checked using X-ray diffraction, X-ray photoelectron spectroscopy (ESCA), optical absorption, steady state and transient photoconductivity. The best films showed good crystallinity and purity with concurrent photoconductivity and photoelectrochemical response. The ability of this technique to produce photoactive material can be explained by interpretation of the Gibbs ternary phase diagram for the Fe-O-S system, and may be related to the production of photoactive pyrite in nature. A discussion is made as to the future improvement of the solar cell response by proper optimization of geometric and configurational properties. (orig.).

Sulfur emission from Victorian brown coal under pyrolysis, oxy-fuel combustion and gasification conditions.

Science.gov (United States)

Chen, Luguang; Bhattacharya, Sankar

2013-02-05

Sulfur emission from a Victorian brown coal was quantitatively determined through controlled experiments in a continuously fed drop-tube furnace under three different atmospheres: pyrolysis, oxy-fuel combustion, and carbon dioxide gasification conditions. The species measured were H(2)S, SO(2), COS, CS(2), and more importantly SO(3). The temperature (873-1273 K) and gas environment effects on the sulfur species emission were investigated. The effect of residence time on the emission of those species was also assessed under oxy-fuel condition. The emission of the sulfur species depended on the reaction environment. H(2)S, SO(2), and CS(2) are the major species during pyrolysis, oxy-fuel, and gasification. Up to 10% of coal sulfur was found to be converted to SO(3) under oxy-fuel combustion, whereas SO(3) was undetectable during pyrolysis and gasification. The trend of the experimental results was qualitatively matched by thermodynamic predictions. The residence time had little effect on the release of those species. The release of sulfur oxides, in particular both SO(2) and SO(3), is considerably high during oxy-fuel combustion even though the sulfur content in Morwell coal is only 0.80%. Therefore, for Morwell coal utilization during oxy-fuel combustion, additional sulfur removal, or polishing systems will be required in order to avoid corrosion in the boiler and in the CO(2) separation units of the CO(2) capture systems.

Sulfur Earth

Science.gov (United States)

de Jong, B. H.

2007-12-01

Variations in surface tension affect the buoyancy of objects floating in a liquid. Thus an object floating in water will sink deeper in the presence of dishwater fluid. This is a very minor but measurable effect. It causes for instance ducks to drown in aqueous solutions with added surfactant. The surface tension of liquid iron is very strongly affected by the presence of sulfur which acts as a surfactant in this system varying between 1.9 and 0.4 N/m at 10 mass percent Sulfur (Lee & Morita (2002), This last value is inferred to be the maximum value for Sulfur inferred to be present in the liquid outer core. Venting of Sulfur from the liquid core manifests itself on the Earth surface by the 105 to 106 ton of sulfur vented into the atmosphere annually (Wedepohl, 1984). Inspection of surface Sulfur emission indicates that venting is non-homogeneously distributed over the Earth's surface. The implication of such large variation in surface tension in the liquid outer core are that at locally low Sulfur concentration, the liquid outer core does not wet the predominantly MgSiO3 matrix with which it is in contact. However at a local high in Sulfur, the liquid outer core wets this matrix which in the fluid state has a surface tension of 0.4 N/m (Bansal & Doremus, 1986), couples with it, and causes it to sink. This differential and diapiric movement is transmitted through the essentially brittle mantle (1024 Pa.s, Lambeck & Johnson, 1998; the maximum value for ice being about 1030 Pa.s at 0 K, in all likely hood representing an upper bound of viscosity for all materials) and manifests itself on the surface by the roughly 20 km differentiation, about 0.1 % of the total mantle thickness, between topographical heights and lows with concomitant lateral movement in the crust and upper mantle resulting in thin skin tectonics. The brittle nature of the medium though which this movement is transmitted suggests that the extremes in topography of the D" layer are similar in range to

SYNTHESIS OF SULFUR-BASED WATER TREATMENT AGENT FROM SULFUR DIOXIDE WASTE STREAMS

Energy Technology Data Exchange (ETDEWEB)

Robert C. Brown; Maohong Fan; Adrienne Cooper

2002-10-01

Absorption of sulfur dioxide from a simulated flue gas was investigated for the production of polymeric ferric sulfate (PFS), a highly effective coagulant useful in treatment of drinking water and wastewater. The reaction for PFS synthesis took place near atmospheric pressure and at temperatures of 30-80 C. SO{sub 2} removal efficiencies greater than 90% were achieved, with ferrous iron concentrations in the product less than 0.1%. A factorial analysis of the effect of temperature, oxidant dosage, SO{sub 2} concentration, and gas flow rate on SO{sub 2} removal efficiency was carried out, and statistical analyses are conducted. The solid PFS was also characterized with different methods. Characterization results have shown that PFS possesses both crystalline and non-crystalline structure. The kinetics of reactions among FeSO{sub 4} {center_dot} 7H{sub 2}O, NaHSO{sub 3} and NaClO{sub 3} was investigated. The PFS product was used in pilot-scale tests at a municipal water treatment facility and gave good results in removal of turbidity and superior results in removal of disinfection byproduct precursors (TOC, DOC, UV-254) when compared with equal doses of ferric chloride.

The extraction of zirconium (IV) from sulfuric acid solutions with high-molecular weight quaternary ammonium compound

International Nuclear Information System (INIS)

Sato, Taichi; Watanabe, Hiroshi

1982-01-01

The extraction of zirconium sulfate in aqueous sulfuric acid solutions with trioctylmethylammonium chloride (Aliquat-336; R 3 R'NCl) in organic solvents has been investigated under different conditions. In addition, the organic phases extracted sulfuric acid and zirconium sulfate were examined by IR and NMR spectroscopies. It has been found that Aliquat-336 extracts zirconium (IV) from sulfuric acid solutions according to the following ion-exchange reactions. i) The extraction of sulfuric acid is at first carried out through the equilibria, SO 4 2 - (aq) + 2R 3 R'NCl(org) reversible (R 3 R'N) 2 SO 4 (org) + 2Cl - (aq), (R 3 R'N) 2 SO 4 (org) + H + (aq) + HSO 4- (aq) reversible 2R 3 R'NHSO 4 (org). ii) The extraction of zirconium is expressed as the equilibrium reaction, Zr(SO 4 ) 3 2 - (aq) + 2xR 3 R'NHSO 4 (org) + (1-x)(R 3 R'N) 2 SO 4 (org) reversible (R 3 R'N) 2 [Zr(SO 4 ) 3 ](org) + xH 2 SO 4 (aq) + SO 4 2 - (aq), x = [R 3 R'NHSO 4 ]/(2[(R 3 R'N) 2 SO 4 ] + [R 3 R'NHSO 4 ]). Moreover, the hydrolyzed species (R 3 R'N)[ZrO(OH)(SO 4 )] is formed when zirconium is further extracted in an organic phase. (author)

Sulfur-doped graphene via thermal exfoliation of graphite oxide in H2S, SO2, or CS2 gas.

Science.gov (United States)

Poh, Hwee Ling; Šimek, Petr; Sofer, Zdeněk; Pumera, Martin

2013-06-25

Doping of graphene with heteroatoms is an effective way to tailor its properties. Here we describe a simple and scalable method of doping graphene lattice with sulfur atoms during the thermal exfoliation process of graphite oxides. The graphite oxides were first prepared by Staudenmaier, Hofmann, and Hummers methods followed by treatments in hydrogen sulfide, sulfur dioxide, or carbon disulfide. The doped materials were characterized by scanning electron microscopy, high-resolution X-ray photoelectron spectroscopy, combustible elemental analysis, and Raman spectroscopy. The ζ-potential and conductivity of sulfur-doped graphenes were also investigated in this paper. It was found that the level of doping is more dramatically influenced by the type of graphite oxide used rather than the type of sulfur-containing gas used during exfoliation. Resulting sulfur-doped graphenes act as metal-free electrocatalysts for an oxygen reduction reaction.

Status of the INERI sulfur-iodine integrated-loop experiment

International Nuclear Information System (INIS)

Pickard, P.; Carles, Ph.; Buckingham, R.; Russ, B.; Besenbruch, G.

2007-01-01

The Sulfur-Iodine (S-I) thermochemical water-splitting cycle has been studied as a potential source of hydrogen on a large scale. Coupled to a nuclear reactor, an S-I hydrogen plant could efficiently produce hydrogen without greenhouse gas emissions. In the S-I cycle, iodine and sulfur dioxide are combined with water to create two immiscible acid phases - a light sulfuric acid phase, and a heavy hydriodic acid phase. The sulfuric acid phase is decomposed at temperatures near 850 C degrees, and the resulting sulfur dioxide is recycled back into the process. The hydriodic acid in the lower phase is separated from excess water and iodine, and is then decomposed into the product hydrogen and iodine. The water and iodine from these steps are also recycled. In an International Nuclear Energy Research Initiative (INERI) project supported by the US DOE Office of Nuclear Energy, Sandia National Labs (SNL) has teamed with Cea in France, and industrial partner General Atomics (GA) to construct and operate a closed-loop device for demonstration of hydrogen production by the S-I process. Previous work in Japan has demonstrated continuous closed-loop operation of the S-I cycle for up to one week using glass components at atmospheric pressure. This work will aim for operation under process conditions expected at the pilot plant-level and beyond pressures up to 20 bar using engineering materials of construction. Staff at Cea is responsible for the acid-generation step, known as the Bunsen reaction. SNL is handling the sulfuric acid decomposition step, and GA is providing equipment for decomposing hydriodic acid into the product hydrogen. All parties are assembling equipment at the GA site in San Diego, California. Operation of the closed-loop device is expected to commence in the second half of calendar year 2007. This paper will summarize project goals, work done to date, current status, and scheduled future work on the INERI S-I Integrated-Loop Experiment. (authors)

Selective adsorption of refractory sulfur species on active carbons and carbon based CoMo catalyst.

Science.gov (United States)

Farag, Hamdy

2007-03-01

Adsorption technique could be a reliable alternative in removing to a certain remarkable extent the sulfur species from the feedstock of petroleum oil. The performance of various carbons on adsorption of model sulfur compounds in a simulated feed solution and the sulfur containing compounds in the real gas oil was evaluated. The adsorption experiments have been carried out in a batch scale at ambient temperature and under the atmospheric pressure. In general, the most refractory sulfur compounds in the hydrotreatment reactions were selectively removed and adsorbed. It was found that the adsorbents affinities to dibenzothiophene and 4,6-dimethyldibenzothiophene were much more favored and pronounced than the aromatic matrices like fluorene, 1-methylnaphthalene and 9-methylanthracene. Among the sulfur species, 4,6-dimethyldibenzothiophene was the highest to be removed in terms of both selectivity and capacity over all the present adsorbents. The studied adsorbents showed significant capacities for the polyaromatic thiophenes. The electronic characteristics seem to play a certain role in such behavior. Regeneration of the used adsorbent was successfully attained either by washing it with toluene or by the release of the adsorbates through heat treatment. A suggested adsorptive removal process of sulfur compounds from petroleum distillate over carbon supported CoMo catalyst was discussed.

Sulfur problems in Swedish agriculture

Energy Technology Data Exchange (ETDEWEB)

Johansson, O

1959-01-01

The present paper deals with some aspects of the sulfur situation in Swedish agriculture with special emphasis on the importance of and relationships among various sources of sulfur supply. An inventory of the sulfur content of Swedish soils and hay crops includes 649 soil samples and a corresponding number of hay samples from 59 locations. In a special investigation the samples were found to be representative of normal Swedish farm land. It is concluded that the amount of sulfur compounds in the air is the primary factor which determines the amount of sulfur added to the soil from the atmosphere. Compared with values obtained in other countries, the amount of sulfur added by the precipitation in Sweden is very low. The distribution in air and precipitation of sulfur from an industrial source was studied in a special investigation. An initial reason for the present study was the damage to vegetation caused by smoke from an industrial source. It was concluded that the average conditions in the vicinity of the industrial source with respect to smoke constituents in the air and precipitation were unfavorable only to the plants directly within a very narrow region. Relationships among the sulfur contents of air, of precipitation, of soils and of plants have been subject to special investigations. In the final general discussion and conclusions it is pointed out that the results from these investigations indicate evident differences in the sulfur status of Swedish soils. The present trend toward the use of more highly concentrated fertilizers poor in sulfur may be expected to cause a considerable change in the sulfur situation in Swedish agriculture. 167 references, 40 figures, 44 tables.

The Influence of Fuel Sulfur on the Operation of Large Two-Stroke Marine Diesel Engines

DEFF Research Database (Denmark)

Cordtz, Rasmus Faurskov

The present work focusses on SO3/H2SO4 formation and sulfuric acid (H2SO4) condensation in a large low speed 2-stroke marine diesel engine. SO3 formation is treated theoretically from a formulated multizone engine model described in this work that includes a detailed and validated sulfur reaction...... mechanism. Model results show that for a large marine engine generally about 3 % - 6 % of the fuel sulfur converts to SO3 while the remainder leaves the engine as SO2 from which the SO3 is formed during the expansion stroke. SO3 formation scales with the cylinder pressure and inversely with the engine speed...... as also demonstrated by a number of SO3 experiments described in this work. The experiments are carried out with a heavy duty medium speed 4 stroke diesel engine operating on heavy fuel oil including ≈ 2 wt. % sulfur. SO3 was measured successfully in the exhaust gas with the PENTOL SO3 analyzer...

Biogenic sulfur compounds and the global sulfur cycle

International Nuclear Information System (INIS)

Aneja, V.P.; Aneja, A.P.; Adams, D.F.

1982-01-01

Field measurements of biogenic sulfur compounds shows a great variation in concentrations and emission rates for H 2 S, DMS, CS 2 and COS. Measurements by the chamber method and estimates from micrometeorological sampling are employed to determine the earth-atmosphere flux of these gases. Much of the variation can be attributed to differences of climate and surface conditions, with marshes being a large source of biogenic sulfur (mean contribution 4 x 10 to the 6th ton/year maximum contribution 142 x 10 to the 6th ton/year). Considering that the estimated biogenic contribution needed to balance the global sulfur cycle ranges from 40- 230 x 10 to the 6th tons/year, the mean values are not sufficient to balance this cycle. Further experimental investigations are suggested in order to characterize the biogenic processes adequately

Effects of sulfur on lead partitioning during sludge incineration based on experiments and thermodynamic calculations.

Science.gov (United States)

Liu, Jing-yong; Huang, Shu-jie; Sun, Shui-yu; Ning, Xun-an; He, Rui-zhe; Li, Xiao-ming; Chen, Tao; Luo, Guang-qian; Xie, Wu-ming; Wang, Yu-Jie; Zhuo, Zhong-xu; Fu, Jie-wen

2015-04-01

Experiments in a tubular furnace reactor and thermodynamic equilibrium calculations were conducted to investigate the impact of sulfur compounds on the migration of lead (Pb) during sludge incineration. Representative samples of typical sludge with and without the addition of sulfur compounds were combusted at 850 °C, and the partitioning of Pb in the solid phase (bottom ash) and gas phase (fly ash and flue gas) was quantified. The results indicate that three types of sulfur compounds (S, Na2S and Na2SO4) added to the sludge could facilitate the volatilization of Pb in the gas phase (fly ash and flue gas) into metal sulfates displacing its sulfides and some of its oxides. The effect of promoting Pb volatilization by adding Na2SO4 and Na2S was superior to that of the addition of S. In bottom ash, different metallic sulfides were found in the forms of lead sulfide, aluminosilicate minerals, and polymetallic-sulfides, which were minimally volatilized. The chemical equilibrium calculations indicated that sulfur stabilizes Pb in the form of PbSO4(s) at low temperatures (incineration process mainly depended on the gas phase reaction, the surface reaction, the volatilization of products, and the concentration of Si, Ca and Al-containing compounds in the sludge. These findings provide useful information for understanding the partitioning behavior of Pb, facilitating the development of strategies to control the volatilization of Pb during sludge incineration. Copyright © 2014 Elsevier Ltd. All rights reserved.

A convenient method for the quantitative determination of elemental sulfur in coal by HPLC analysis of perchloroethylene extracts

Science.gov (United States)

Buchanan, D.H.; Coombs, K.J.; Murphy, P.M.; Chaven, C.

1993-01-01

A convenient method for the quantitative determination of elemental sulfur in coal is described. Elemental sulfur is extracted from the coal with hot perchloroethylene (PCE) (tetrachloroethene, C2Cl4) and quantitatively determined by HPLC analysis on a C18 reverse-phase column using UV detection. Calibration solutions were prepared from sublimed sulfur. Results of quantitative HPLC analyses agreed with those of a chemical/spectroscopic analysis. The HPLC method was found to be linear over the concentration range of 6 ?? 10-4 to 2 ?? 10-2 g/L. The lower detection limit was 4 ?? 10-4 g/L, which for a coal sample of 20 g is equivalent to 0.0006% by weight of coal. Since elemental sulfur is known to react slowly with hydrocarbons at the temperature of boiling PCE, standard solutions of sulfur in PCE were heated with coals from the Argonne Premium Coal Sample program. Pseudo-first-order uptake of sulfur by the coals was observed over several weeks of heating. For the Illinois No. 6 premium coal, the rate constant for sulfur uptake was 9.7 ?? 10-7 s-1, too small for retrograde reactions between solubilized sulfur and coal to cause a significant loss in elemental sulfur isolated during the analytical extraction. No elemental sulfur was produced when the following pure compounds were heated to reflux in PCE for up to 1 week: benzyl sulfide, octyl sulfide, thiane, thiophene, benzothiophene, dibenzothiophene, sulfuric acid, or ferrous sulfate. A sluury of mineral pyrite in PCE contained elemental sulfur which increased in concentration with heating time. ?? 1993 American Chemical Society.

Modelling of the Kinetics of Sulfure Compounds in Desulfurisation Processes Based on Industry Data of Plant

OpenAIRE

Krivtsova, Nadezhda Igorevna; Tataurshikov, A.; Kotkova, Elena

2016-01-01

Modelling of sulfur compounds kinetics was performed, including kinetics of benzothiophene and dibenzothiophene homologues. Modelling is based on experimental data obtained from monitoring of industrial hydrotreating set. Obtained results include kinetic parameters of reactions.

Significant role of organic sulfur in supporting sedimentary sulfate reduction in low-sulfate environments

Science.gov (United States)

Fakhraee, Mojtaba; Li, Jiying; Katsev, Sergei

2017-09-01

Dissimilatory sulfate reduction (DSR) is a major carbon mineralization pathway in aquatic sediments, soils, and groundwater, which regulates the production of hydrogen sulfide and the mobilization rates of biologically important elements such as phosphorus and mercury. It has been widely assumed that water-column sulfate is the main sulfur source to fuel this reaction in sediments. While this assumption may be justified in high-sulfate environments such as modern seawater, we argue that in low-sulfate environments mineralization of organic sulfur compounds can be an important source of sulfate. Using a reaction-transport model, we investigate the production of sulfate from sulfur-containing organic matter for a range of environments. The results show that in low sulfate environments (50%) of sulfate reduction. In well-oxygenated systems, porewater sulfate profiles often exhibit sub-interface peaks so that sulfate fluxes are directed out of the sediment. Our measurements in Lake Superior, the world's largest lake, corroborate this conclusion: offshore sediments act as sources rather than sinks of sulfate for the water column, and sediment DSR is supported entirely by the in-sediment production of sulfate. Sulfate reduction rates are correlated to the depth of oxygen penetration and strongly regulated by the supply of reactive organic matter; rate co-regulation by sulfate availability becomes appreciable below 500 μM level. The results indicate the need to consider the mineralization of organic sulfur in the biogeochemical cycling in low-sulfate environments, including several of the world's largest freshwater bodies, deep subsurface, and possibly the sulfate-poor oceans of the Early Earth.

Solvent-Free Biginelli Condensation using Tungstate Sulfuric Acid: a Powerful and Reusable Catalyst for Selective Synthesis

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Rezvan Rezaee Nasab

2014-07-01

Full Text Available Tungstate sulfuric acid (TSA has been prepared and used as a recyclable catalyst for the Biginelli syn-thesis of some biologically active quinazolinones/thiones under solvent-free conditions. This method has advantages such as the avoidance of organic solvents, high yield of pure products, short reaction times, and operational simplicity.  © 2014 BCREC UNDIP. All rightsReceived: 28th April 2014; Revised: 15th May 2014; Accepted: 26th May 2014[ How to Cite: Nasab, R.R., Karami, B., Khodabakhshi, S. (2014. Selective Solvent‐free Biginelli Condensation using Tungstate Sulfuric Acid as Powerful and Reusable Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 9 (2: 142-154. (doi:10.9767/bcrec.9.2.6794.148-154][ Permalink/DOI: http://dx.doi.org/10.9767/bcrec.9.2.6794.148-154

Sulfur dimers adsorbed on Au(111) as building blocks for sulfur octomers formation: A density functional study

International Nuclear Information System (INIS)

Hernandez-Tamargo, Carlos E.; Montero-Alejo, Ana Lilian; Pujals, Daniel Codorniu; Mikosch, Hans; Hernández, Mayra P.

2014-01-01

Experimental scanning tunneling microscopy (STM) studies have shown for more than two decades rectangular formations when sulfur atoms are deposited on Au(111) surfaces. The precursors have ranged from simple molecules or ions, such as SO 2 gas or sulfide anions, to more complex organosulfur compounds. We investigated, within the framework of the Density Functional Theory, the structure of these rectangular patterns assuming them entirely composed of sulfur atoms as the experimental evidence suggests. The sulfur coverage at which the simulations were carried out (0.67 ML or higher) provoked that the sulfur-sulfur association had to be taken into account for achieving a good agreement between the sets of simulated and experimental STM images. A combination of four sulfur dimers per rectangular formation properly explained the trends obtained by the experimental STM analysis which were related with the rectangles' size and shape fluctuations together with sulfur-sulfur distances within these rectangles. Finally, a projected density of states analysis showed that the dimers were capable of altering the Au(5d) electronic states at the same level as atomic sulfur adsorbed at low coverage. Besides, sulfur dimers states were perfectly distinguished, whose presence near and above the Fermi level can explain both: sulfur-sulfur bond elongation and dimers stability when they stayed adsorbed on the surface at high coverage

Sulfur dimers adsorbed on Au(111) as building blocks for sulfur octomers formation: A density functional study

Energy Technology Data Exchange (ETDEWEB)

Hernandez-Tamargo, Carlos E.; Montero-Alejo, Ana Lilian [Laboratory of Computational and Theoretical Chemistry (LQCT), Faculty of Chemistry, Havana University, Havana 10400 (Cuba); Pujals, Daniel Codorniu [Higher Institute of Technologies and Applied Sciences (InSTEC), Havana 10400 (Cuba); Mikosch, Hans [Institute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9/E164-EC, 1060 Vienna (Austria); Hernández, Mayra P., E-mail: mayrap@imre.oc.uh.cu [Instituto de Ciencias y Tecnologías de Materiales (IMRE), Havana 10400 (Cuba)

2014-07-28

Experimental scanning tunneling microscopy (STM) studies have shown for more than two decades rectangular formations when sulfur atoms are deposited on Au(111) surfaces. The precursors have ranged from simple molecules or ions, such as SO{sub 2} gas or sulfide anions, to more complex organosulfur compounds. We investigated, within the framework of the Density Functional Theory, the structure of these rectangular patterns assuming them entirely composed of sulfur atoms as the experimental evidence suggests. The sulfur coverage at which the simulations were carried out (0.67 ML or higher) provoked that the sulfur-sulfur association had to be taken into account for achieving a good agreement between the sets of simulated and experimental STM images. A combination of four sulfur dimers per rectangular formation properly explained the trends obtained by the experimental STM analysis which were related with the rectangles' size and shape fluctuations together with sulfur-sulfur distances within these rectangles. Finally, a projected density of states analysis showed that the dimers were capable of altering the Au(5d) electronic states at the same level as atomic sulfur adsorbed at low coverage. Besides, sulfur dimers states were perfectly distinguished, whose presence near and above the Fermi level can explain both: sulfur-sulfur bond elongation and dimers stability when they stayed adsorbed on the surface at high coverage.

Changes in the physicochemical characteristics, including flavour components and Maillard reaction products, of non-centrifugal cane brown sugar during storage.

Science.gov (United States)

Asikin, Yonathan; Kamiya, Asahiro; Mizu, Masami; Takara, Kensaku; Tamaki, Hajime; Wada, Koji

2014-04-15

Changes in the quality attributes of non-centrifugal cane brown sugar represented by physicochemical characteristics as well as flavour components and Maillard reaction products (MRPs) were monitored every 3 months over 1 year of storage. Stored cane brown sugar became darker, and its moisture content and water activity (a(w)) increased during storage. Fructose and glucose levels decreased as non-enzymatic browning via the Maillard reaction occurred in the stored sample, and a similar trend was also discovered in aconitic and acetic acids. Stored cane brown sugar lost its acidic and sulfuric odours (58.70-39.35% and 1.85-0.08%, respectively); subsequently, the nutty and roasted aroma increased from 26.52% to 38.59% due to the volatile MRPs. The browning rate of stored cane brown sugar was positively associated with the development of volatile MRPs (Pearson's coefficient = 0.860), whereas the amount of 3-deoxyglucosone, an intermediate product of the Maillard reaction, had a lower association with the brown colour due to its relatively slow degradation rate. Copyright © 2013 Elsevier Ltd. All rights reserved.

Effects of mix ratio, moisture content and aeration rate on sulfur odor emissions during pig manure composting.

Science.gov (United States)

Zang, Bing; Li, Shuyan; Michel, Frederick; Li, Guoxue; Luo, Yuan; Zhang, Difang; Li, Yangyang

2016-10-01

Sulfur compounds in swine manure can cause odor emissions during composting if conditions are not conducive to their rapid oxidation and degradation. In this study, the effects of controllable composting process variables on sulfur odor emissions were investigated. These included pig manure to corn stalk mix ratio (0.7:1, 1.5:1 and 2.2:1dw basis), initial moisture content (60%, 65%, 70% and 75%) and aeration rate (1.0, 2.0, 3.0 and 4.0m(3)m(-3)h(-1)). The compounds measured were carbonyl sulfide, carbon disulfide, hydrogen sulfide, methyl mercaptan, ethyl mercaptan, diethyl sulfide, dimethyl sulfide (Me2S) and dimethyl disulfide (Me2SS). The results showed that total sulfur losses ranged from 3.9% to 18.3% after 26days of composting. Me2S and Me2SS were the primary (>59.61%) sulfur compounds released during this period. After turning, emission rates of both Me2S and Me2SS increased. Emissions of the other six sulfur compounds were low and inconsistent during composting. Within the compost, feedstock mix ratio significantly influenced the concentration of Me2SS, while aeration rate significantly affected Me2S concentration (pMoisture content did not have a significant effect on the concentrations of either of these two compounds. Concentrations of sulfur odor compounds were the lowest at the highest aeration rate. Therefore, high aeration rates during the thermophilic phase, especially after turning, are recommended to minimize sulfur odors produced during swine manure composting. Copyright © 2016 Elsevier Ltd. All rights reserved.

Genomic and Evolutionary Perspectives on Sulfur Metabolism in Green Sulfur Bacteria

DEFF Research Database (Denmark)

Frigaard, Niels-Ulrik; Bryant, Donald A.

2008-01-01

Green sulfur bacteria (GSB) are anaerobic photoautotrophs that oxidize sulfide, elemental sulfur, thiosulfate, ferrous iron, and hydrogen for growth. We present here an analysis of the distribution and evolution of enzymes involved in oxidation of sulfur compounds in GSB based on genome sequence......, in combination with phylogenetic analyses, suggests that the Dsr system in GSB could be a recent acquisition, which was obtained by lateral gene transfer in part from sulfideoxidizing bacteria and in part from sulfate-reducing bacteria. All thiosulfate-utilizing GSB strains have an identical sox gene cluster...

Acidithiobacillus caldus sulfur oxidation model based on transcriptome analysis between the wild type and sulfur oxygenase reductase defective mutant.

Directory of Open Access Journals (Sweden)

Linxu Chen

Full Text Available Acidithiobacillus caldus (A. caldus is widely used in bio-leaching. It gains energy and electrons from oxidation of elemental sulfur and reduced inorganic sulfur compounds (RISCs for carbon dioxide fixation and growth. Genomic analyses suggest that its sulfur oxidation system involves a truncated sulfur oxidation (Sox system (omitting SoxCD, non-Sox sulfur oxidation system similar to the sulfur oxidation in A. ferrooxidans, and sulfur oxygenase reductase (SOR. The complexity of the sulfur oxidation system of A. caldus generates a big obstacle on the research of its sulfur oxidation mechanism. However, the development of genetic manipulation method for A. caldus in recent years provides powerful tools for constructing genetic mutants to study the sulfur oxidation system.An A. caldus mutant lacking the sulfur oxygenase reductase gene (sor was created and its growth abilities were measured in media using elemental sulfur (S(0 and tetrathionate (K(2S(4O(6 as the substrates, respectively. Then, comparative transcriptome analysis (microarrays and real-time quantitative PCR of the wild type and the Δsor mutant in S(0 and K(2S(4O(6 media were employed to detect the differentially expressed genes involved in sulfur oxidation. SOR was concluded to oxidize the cytoplasmic elemental sulfur, but could not couple the sulfur oxidation with the electron transfer chain or substrate-level phosphorylation. Other elemental sulfur oxidation pathways including sulfur diooxygenase (SDO and heterodisulfide reductase (HDR, the truncated Sox pathway, and the S(4I pathway for hydrolysis of tetrathionate and oxidation of thiosulfate in A. caldus are proposed according to expression patterns of sulfur oxidation genes and growth abilities of the wild type and the mutant in different substrates media.An integrated sulfur oxidation model with various sulfur oxidation pathways of A. caldus is proposed and the features of this model are summarized.

Oxidation-sulfidation behavior of Ni aluminide in oxygen-sulfur mixed-gas atmospheres

International Nuclear Information System (INIS)

Natesan, K.

1988-01-01

Oxidation-sulfidation studies were conducted with sheet samples of nickel aluminide, containing 23.5 at. % Al, 0.5 at. % Hf, and 0.2 at. % B, in an annealed condition and after preoxidation treatments. Continuous weight-change measurements were made by a thermogravimetric technique in exposure atmospheres of air, a low-pO/sub 2/ gas mixture, and low-pO/sub 2/ gas mixtures with several levels of sulfur. The air-exposed specimens developed predominantly nickel oxide; the specimen exposed to a low-pO/sub 2/ environment developed an aluminum oxide scale. As the sulfur content of the gas mixture increased, the alumina scale exhibited spallation and the alloy tended to form nickel sulfide as the reaction phase. The results indicated that the sulfidation reaction of nickel aluminide specimens (both bare and preoxidized) was determined by the rate of transport of nickel from the substrate through the scale to the gas/alumina scale interface, the mechanical integrity of the oxide scale, and the H/sub 2/S concentration in the exposure environment

Sulfur retention by ash during coal combustion. Part I. A model of char particle combustion

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BORISLAV GRUBOR

2003-02-01

Full Text Available A model for the combustion of porous char particles as a basis for modeling the process of sulfur retention by ash during coal combustion is developed in this paper. The model belongs to the microscopic intrinsic models and describes the dynamic behavior of a porous char particle during comustion, taking into account temporal and spatial changes of all important physical properties of the char particle and various combustion parameters. The parametric analysis of the enhanced model shows that the model represents a good basis for the development of a model for the process of sulfur retention by ash during coal combustion. The model enables the prediction of the values of all parameters necessary for the introduction of reactions between sulfur compounds and mineral components in ash, primarily calcium oxide.

Chemical Immobilization Effect on Lithium Polysulfides for Lithium-Sulfur Batteries.

Science.gov (United States)

Li, Caixia; Xi, Zhucong; Guo, Dexiang; Chen, Xiangju; Yin, Longwei

2018-01-01

Despite great progress in lithium-sulfur batteries (LSBs), great obstacles still exist to achieve high loading content of sulfur and avoid the loss of active materials due to the dissolution of the intermediate polysulfide products in the electrolyte. Relationships between the intrinsic properties of nanostructured hosts and electrochemical performance of LSBs, especially, the chemical interaction effects on immobilizing polysulfides for LSB cathodes, are discussed in this Review. Moreover, the principle of rational microstructure design for LSB cathode materials with strong chemical interaction adsorbent effects on polysulfides, such as metallic compounds, metal particles, organic polymers, and heteroatom-doped carbon, is mainly described. According to the chemical immobilizing mechanism of polysulfide on LSB cathodes, three kinds of chemical immobilizing effects, including the strong chemical affinity between polar host and polar polysulfides, the chemical bonding effect between sulfur and the special function groups/atoms, and the catalytic effect on electrochemical reaction kinetics, are thoroughly reviewed. To improve the electrochemical performance and long cycling life-cycle stability of LSBs, possible solutions and strategies with respect to the rational design of the microstructure of LSB cathodes are comprehensively analyzed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Composition and oxidation state of sulfur in atmospheric particulate matter

Directory of Open Access Journals (Sweden)

A. F. Longo

2016-10-01

Full Text Available The chemical and physical speciation of atmospheric sulfur was investigated in ambient aerosol samples using a combination of sulfur near-edge x-ray fluorescence spectroscopy (S-NEXFS and X-ray fluorescence (XRF microscopy. These techniques were used to determine the composition and oxidation state of sulfur in common primary emission sources and ambient particulate matter collected from the greater Atlanta area. Ambient particulate matter samples contained two oxidation states: S0 and S+VI. Ninety-five percent of the individual aerosol particles (> 1 µm analyzed contain S0. Linear combination fitting revealed that S+VI in ambient aerosol was dominated by ammonium sulfate as well as metal sulfates. The finding of metal sulfates provides further evidence for acidic reactions that solubilize metals, such as iron, during atmospheric transport. Emission sources, including biomass burning, coal fly ash, gasoline, diesel, volcanic ash, and aerosolized Atlanta soil, and the commercially available bacterium Bacillus subtilis, contained only S+VI. A commercially available Azotobacter vinelandii sample contained approximately equal proportions of S0 and S+VI. S0 in individual aerosol particles most likely originates from primary emission sources, such as aerosolized bacteria or incomplete combustion.

SYNTHESIS OF SULFUR-BASED WATER TREATMENT AGENT FROM SULFUR DIOXIDE WASTE STREAMS

Energy Technology Data Exchange (ETDEWEB)

Robert C. Brown; Maohong Fan; Adrienne Cooper

2004-11-01

Absorption of sulfur dioxide from a simulated flue gas was investigated for the production of polymeric ferric sulfate (PFS), a highly effective coagulant useful in treatment of drinking water and wastewater. The reaction for PFS synthesis took place near atmospheric pressure and at temperatures of 30-80 C. SO{sub 2} removal efficiencies greater than 90% were achieved, with ferrous iron concentrations in the product less than 0.1%. A factorial analysis of the effect of temperature, oxidant dosage, SO{sub 2} concentration, and gas flow rate on SO{sub 2} removal efficiency was carried out, and statistical analyses are conducted. The solid PFS was also characterized with different methods. Characterization results have shown that PFS possesses both crystalline and non-crystalline structure. The kinetics of reactions among FeSO{sub 4} {center_dot} 7H{sub 2}O, NaHSO{sub 3} and NaClO{sub 3} was investigated. Characterizations of dry PFS synthesized from SO{sub 2} show the PFS possesses amorphous structure, which is desired for it to be a good coagulant in water and wastewater treatment. A series of lab-scale experiments were conducted to evaluate the performance of PFS synthesized from waste sulfur dioxide, ferrous sulfate and sodium chlorate. The performance assessments were based on the comparison of PFS and other conventional and new coagulants for the removal of turbidity and arsenic under different laboratory coagulant conditions. Pilot plant studies were conducted at Des Moines Water Works in Iowa and at the City of Savannah Industrial and Domestic (I&D) Water Treatment Plant in Port Wentworth, Georgia. PFS performances were compared with those of conventional coagulants. The tests in both water treatment plants have shown that PFS is, in general, comparable or better than other coagulants in removal of turbidity and organic substances. The corrosion behavior of polymeric ferric sulfate (PFS) prepared from SO{sub 2} and ferric chloride (FC) were compared. Results

Potential of metal nanoparticles in organic reactions

International Nuclear Information System (INIS)

Ranu, B C; Chattopadhyay, K; Saha, A; Adak, L; Jana, R; Bhadra, S; Dey, R; Saha, D

2008-01-01

Palladium(0) nanoparticle has been used as efficient catalyst for (a) the stereoselective synthesis of (E)- and (Z)-2-alkene-4-ynoates and -nitriles by a simple reaction of vic-diiodo-(E)-alkenes with acrylic esters and nitriles and (b) for the allylation of active methylene compounds by allylacetate and its derivatives. Copper(0) nanoparticle catalyzes aryl-sulfur bond formation very efficiently. All these reactions are ligand-free

Hydrogen sulfide in plants: from dissipation of excess sulfur to signaling molecule.

Science.gov (United States)

Calderwood, Alexander; Kopriva, Stanislav

2014-09-15

Sulfur is essential in all organisms for the synthesis of amino acids cysteine and methionine and as an active component of numerous co-factors and prosthetic groups. However, only plants, algae, fungi, and some prokaryotes are capable of using the abundant inorganic source of sulfur, sulfate. Plants take sulfate up, reduce it, and assimilate into organic compounds with cysteine being the first product of the pathway and a donor of reduced sulfur for synthesis of other S-containing compounds. Cysteine is formed in a reaction between sulfide, derived from reduction of sulfite and an activated amino acid acceptor, O-acetylserine. Sulfide is thus an important intermediate in sulfur metabolism, but numerous other functions in plants has been revealed. Hydrogen sulfide can serve as an alternative source of sulfur for plants, which may be significant in anaerobic conditions of waterlogged soils. On the other hand, emissions of hydrogen sulfide have been detected from many plant species. Since the amount of H2S discharged correlated with sulfate supply to the plants, the emissions were considered a mechanism for dissipation of excess sulfur. Significant hydrogen sulfide emissions were also observed in plants infected with pathogens, particularly with fungi. H2S thus seems to be part of the widely discussed sulfur-induced-resistance/sulfur-enhanced-defense. Recently, however, more evidence has emerged for a role for H2S in regulation and signaling. Sulfide stabilizes the cysteine synthase complex, increasing so the synthesis of its acceptor O-acetylserine. H2S has been implicating in regulation of plant stress response, particularly draught stress. There are more and more examples of processes regulated by H2S in plants being discovered, and hydrogen sulfide is emerging as an important signaling molecule, similar to its role in the animal and human world. How similar the functions, and homeostasis of H2S are in these diverse organisms, however, remains to be elucidated

Biomimetic Ant-Nest Electrode Structures for High Sulfur Ratio Lithium-Sulfur Batteries.

Science.gov (United States)

Ai, Guo; Dai, Yiling; Mao, Wenfeng; Zhao, Hui; Fu, Yanbao; Song, Xiangyun; En, Yunfei; Battaglia, Vincent S; Srinivasan, Venkat; Liu, Gao

2016-09-14

The lithium-sulfur (Li-S) rechargeable battery has the benefit of high gravimetric energy density and low cost. Significant research currently focuses on increasing the sulfur loading and sulfur/inactive-materials ratio, to improve life and capacity. Inspired by nature's ant-nest structure, this research results in a novel Li-S electrode that is designed to meet both goals. With only three simple manufacturing-friendly steps, which include slurry ball-milling, doctor-blade-based laminate casting, and the use of the sacrificial method with water to dissolve away table salt, the ant-nest design has been successfully recreated in an Li-S electrode. The efficient capabilities of the ant-nest structure are adopted to facilitate fast ion transportation, sustain polysulfide dissolution, and assist efficient precipitation. High cycling stability in the Li-S batteries, for practical applications, has been achieved with up to 3 mg·cm(-2) sulfur loading. Li-S electrodes with up to a 85% sulfur ratio have also been achieved for the efficient design of this novel ant-nest structure.

Prehydrolysis of aspen wood with water and with dilute aqueous sulfuric acid

Science.gov (United States)

Edward L. Springer; John F. Harris

1982-01-01

Water prehydrolysis of aspen wood was compared with 0.40% sulfuric acid prehydrolysis at a reaction temperature of 170°C. Acid prehydrolysis gave much higher yields of total anhydroxylose units in the prehydrolyzate and removed significantly less anhydroglucose from the wood than did the water treatment. At maximum yields of total anhydroxylose units in the...

Modelling of the Kinetics of Sulfure Compounds in Desulfurisation Processes Based on Industry Data of Plant

Directory of Open Access Journals (Sweden)

Krivtcova Nadezhda

2016-01-01

Full Text Available Modelling of sulfur compounds kinetics was performed, including kinetics of benzothiophene and dibenzothiophene homologues. Modelling is based on experimental data obtained from monitoring of industrial hydrotreating set. Obtained results include kinetic parameters of reactions.

Capacity Fade Analysis of Sulfur Cathodes in Lithium–Sulfur Batteries

Science.gov (United States)

Yan, Jianhua; Liu, Xingbo

2016-01-01

Rechargeable lithium–sulfur (Li–S) batteries are receiving ever‐increasing attention due to their high theoretical energy density and inexpensive raw sulfur materials. However, their rapid capacity fade has been one of the key barriers for their further improvement. It is well accepted that the major degradation mechanisms of S‐cathodes include low electrical conductivity of S and sulfides, precipitation of nonconductive Li2S2 and Li2S, and poly‐shuttle effects. To determine these degradation factors, a comprehensive study of sulfur cathodes with different amounts of electrolytes is presented here. A survey of the fundamentals of Li–S chemistry with respect to capacity fade is first conducted; then, the parameters obtained through electrochemical performance and characterization are used to determine the key causes of capacity fade in Li–S batteries. It is confirmed that the formation and accumulation of nonconductive Li2S2/Li2S films on sulfur cathode surfaces are the major parameters contributing to the rapid capacity fade of Li–S batteries. PMID:27981001

Standard values of fugacity for sulfur which are self-consistent with the low-pressure phase diagram

Energy Technology Data Exchange (ETDEWEB)

Marriott, Robert A., E-mail: rob.marriott@ucalgary.ca [Alberta Sulphur Research Ltd., University of Calgary, Alberta (Canada); Wan, Herman H. [Alberta Sulphur Research Ltd., University of Calgary, Alberta (Canada)

2011-08-15

following conditions for the low-pressure sulfur phase diagram: T{sup {alpha}-{beta}-g} = 368.39 K, p{sup {alpha}-{beta}-g} = 0.4868 Pa, T{sup {beta}-l-g} = 388.326 K, p{sup {beta}-l-g} = 2.4437 Pa, T{sub fus}{sup {beta}-l}(101.325kPa)=388.348K, T{sup {alpha}-{beta}-l} = 419.06 K, and p{sup {alpha}-{beta}-l} = 124,360 kPa.

Sulfur contents and sulfur-isotope compositions of thiotrophic symbioses in bivalve molluscs and vestimentiferan worms

Science.gov (United States)

Vetter, R.D.; Fry, B.

1998-01-01

Total sulfur (S(TOT)), elemental sulfur (S??) and sulfur-isotope compositions (??34S) of marine animals were analyzed to determine whether these chemical characteristics could help distinguish animals with a sulfur-based, thiotrophic nutrition from animals whose nutrition is based on methanotrophy or on more normal consumption of phytoplankton-derived organic matter. The presence of S??was almost entirely confined to the symbiont-containing tissues of thiotrophs, but was sometimes undetectable in thiotrophic species where sulfide availability was probably low. When S??contents were subtracted, the remaining tissue-sulfur concentrations were similar for all nutritional groups. ??34S values were typically lower for thiotrophs than for other groups, although there was overlap in methanotroph and thiotroph values at some sites. Field evidence supported the existence of small to moderate (1 to 10???)34S fractionations in the uptake of sulfides and metabolism of thiosulfate. In general, a total sulfur content of >3% dry weight, the presence of elemental sulfur, and ??34S values less than + 5??? can be used to infer a thiotrophic mode of nutrition.

Liquid-Liquid extraction of sulfuric acid using tri-n-dodecylamine/kerosene

International Nuclear Information System (INIS)

Stas, J.

2009-01-01

The extraction of sulfuric acid has been investigated by trin- dodecylamine (over line TDA) in kerosene in the presence of octanol- 1 as modifier. The effect of octanol-1 has been studied on the equilibrium constant of (TDAH) 2 SO 4 and TDAHHSO 4 formation in the concentration range from 5 to 25% v/v and within the temperature range from 25 to 50 centigrade degree. The equilibrium constants (K 1 and K 2 , at 25 centigrade degree), the enthalpy (ΔH 0 1 , ΔH 0 2 ) and the entropy (ΔS 0 1 , ΔS 0 2 ) changes were calculated for two extraction reactions of sulfuric acid by tri-n-dodecylamine containing 10% octanol-1 and they were found to be 10 9 .642 l 4 /mol 4 , 10 - 0.899 l/mol, -99.11, -22.17 kJ/mol, -0.149, -0.063 kJ/mol.K, respectively. The two reactions are: 2/overline TDA +2 H + +SO 4 2 -/rightleftarrows K 1 /overline (TDAH) 2 SO 4 and /overline (TDHA) 2 SO 4 H + +HSO 4 - /rightleftarrows K 2 2/overline TDAHHSO 4 . (author)

Layered sulfur/PEDOT:PSS nano composite electrodes for lithium sulfur cell applications

Science.gov (United States)

Anilkumar, K. M.; Jinisha, B.; Manoj, M.; Pradeep, V. S.; Jayalekshmi, S.

2018-06-01

Lithium-Sulfur (Li-S) cells are emerging as the next generation energy storage devices owing to their impressive electrochemical properties with high theoretical specific capacity of 1675 mAh/g. Lack of electronic conductivity of sulfur, its volume expansion during high lithium intake and the shuttling effect due to the formation of soluble polysulfides are the main limitations, delaying the commercialization of this technology. To address these challenges, in the present work, the conducting polymer PEDOT:PSS is used as the covering matrix over the sulfur particles to improve their Li storage properties. The sulfur/PEDOT:PSS nanocomposite is synthesised using the hydrothermal process and its formation with the polymer coating over sulfur nanoparticles is established from the XRD, Raman spectroscopy, FE-SEM and TEM studies. The electrochemical studies show that the cells assembled using the sulfur/PEDOT:PSS nanocomposite as the cathode, with the components taken in the weight ratio of 9:1, offer a reversible capacity of 1191 mAh g-1 at 0.1C rate. These cells display stable electrochemical capacities over 200 cycles at gradually increasing current rates. The polymer layer facilitates electronic conduction and suppresses the polysulfide formation and the volume expansion of sulfur. A reversible capacity of 664 mAh g-1 is observed after 200 cycles at 1C rate with the capacity retention of 75 % of the initial stable capacity. The highlight of the present work is the possibility to achieve high discharge capacities at high C rates and the retention of a good percentage of the initial capacity over 200 cycles, for these Li-S cells.

Demand outlook for sulfur and high-sulfur petroleum coke

Energy Technology Data Exchange (ETDEWEB)

Koshkarov, V.Ya.; Danil' yan, P.G.; Feotov, V.E.; Gimaev, R.N.; Koshkarova, M.E.; Sadykova, S.R.; Vodovichenko, N.S.

1980-01-01

The feasibility of using sulfur and high-sulfur petroleum coke fines in pyrometallurgical processes and also in the chemical and coal-tar chemical industry is examined. Results of industrial tests on briquetting fines of petroleum coke with a petroleum binder are presented. The feasibility of using the obtained briquets in shaft furnace smelting of oxidized nickel ores, production of anode stock, and also in the chemical industry are demonstrated.

In-test and post-test analyses of sodium-sulfur cells

Energy Technology Data Exchange (ETDEWEB)

Wada, Motoi; Kawamoto, Hiroyuki; Hatoh, Hisamitsu

1986-01-15

Cell life of sodium-sulfur cells is often determined by the degradation of the solid electrolyte. Solid electrolyte degradation will cause an increase of electrolyte resistivity, decrease of faradic efficiency, or even an electrolyte rupture which leads to a cell temperature rise due to direct reaction of reactants. Electrolyte degradation in actual sodium-sulfur cells is believed to be caused by the passage of sodium ion current across the solid electrolyte. The degree of degradation has been reported to be a function of amount of charge passed through the electrolyte, and the breakdown of the solid electrolyte was observed to occur above some threshold. For this reason, the concentration of sodium ion current density is to be avoided to prevent solid electrolyte from premature degradation and rupture, and the electrode structure for a sodium-sulfur cell should be determined with enough care to homogenize the current density distribution on the electrolyte. The longitudinal current density distribution of a sodium-sulfur cell was measured by attaching probing terminals on the electrode container. It was found that the current density distribution of a vertically supported cell was inhomogeneous due to the effect of gravity. This setup can be used as a way to locate the place where the first electrolyte cracking occurs. It was also found that the electrolyte cracking accompanies a fluctuation of cycling cell voltage that starts to appear several cycles before the noticeable break down of the electrolyte.

Nucleophilic ring opening reactions of aziridines.

Science.gov (United States)

Akhtar, Rabia; Naqvi, Syed Ali Raza; Zahoor, Ameer Fawad; Saleem, Sameera

2018-05-04

Aziridine ring opening reactions have gained tremendous importance in the synthesis of nitrogen containing biologically active molecules. During recent years, a great effort has been put forward by scientists toward unique bond construction methodologies via ring opening of aziridines. In this regard, a wide range of chiral metal- and organo-catalyzed desymmetrization reactions of aziridines have been reported with carbon, sulfur, oxygen, nitrogen, halogen, and other nucleophiles. In this review, an outline of methodologies adopted by a number of scientists during 2013-2017 for aziridine ring opening reactions as well as their synthetic applications is described.

Confine sulfur in mesoporous metal–organic framework @ reduced graphene oxide for lithium sulfur battery

International Nuclear Information System (INIS)

Bao, Weizhai; Zhang, Zhian; Qu, Yaohui; Zhou, Chengkun; Wang, Xiwen; Li, Jie

2014-01-01

Highlights: • Metal organic framework @ reduced graphene oxide was applied for sulfur cathode. • MIL-101(Cr)@rGO/S composites are synthesized by a facile two-step liquid method. • Cycling stability of MIL-101(Cr)@rGO/S sulfur cathode was improved. -- Abstract: Mesoporous metal organic framework @ reduced graphene oxide (MIL-101(Cr)@rGO) materials have been used as a host material to prepare the multi-composite sulfur cathode through a facile and effective two-step liquid phase method successfully, which is different from the simple MIL-101(Cr)/S mixed preparation method. The successful reduced graphene oxide coating in the MIL-101(Cr)@rGO improve the electronic conductivity of meso-MOFs effectively. The discharge capacity and capacity retention rate of MIL-101(Cr)@rGO/S composite sulfur cathode are as high as 650 mAh g −1 and 66.6% at the 50th cycle at the current density of 335 mA g −1 . While the discharge capacity and capacity retention rate of MIL-101(Cr)/S mixed sulfur cathode is 458 mAh g −1 and 37.3%. Test results indicate that the MIL-101(Cr)@rGO is a promising host material for the sulfur cathode in the lithium–sulfur battery applications

Stability of sulfur slopes on Io

Science.gov (United States)

Clow, G. D.; Carr, M. H.

1980-01-01

The mechanical properties of elemental sulfur are such that the upper crust of Io cannot be primarily sulfur. For heat flows in the range 100-1000 ergs/sq cm sec sulfur becomes ductile within several hundred meters of the surface and would prevent the formation of calderas with depths greater than this. However, the one caldera for which precise depth data are available is 2 km deep, and this value may be typical. A study of the mechanical equilibrium of simple slopes shows that the depth to the zone of rapid ductile flow strongly controls the maximum heights for sulfur slopes. Sulfur scarps with heights greater than 1 km will fail for all heat flows greater than 180 ergs/sq cm sec and slope angles greater than 22.5 deg. The observed relief on Io is inconsistent with that anticipated for a predominantly sulfur crust. However, a silicate crust with several percent sulfur included satisfies both the mechanical constraints and the observed presence of sulfur on Io.

40 CFR 52.1881 - Control strategy: Sulfur oxides (sulfur dioxide).

Science.gov (United States)

2010-07-01

....0 pounds of sulfur dioxide per million BTU actual heat input for the coal-fired boiler and 0.4... BTU actual heat input for coal-fired boiler C exiting through stack 5. (3) 2.24 pounds of sulfur dioxide per million BTU acutal heat input for coal-fired boiler D exiting through stack 6. (E) In lieu of...

Solvent extraction of elemental sulfur from coal and a determination of its source using stable sulfur isotopes

Science.gov (United States)

Hackley, Keith C.; Buchanan, D.H.; Coombs, K.; Chaven, C.; Kruse, C.W.

1990-01-01

Hot tetrachloroethene (perchloroethylene, PCE) extracts significant amounts of elemental sulfur (So) from weathered coals but not from pristine coals. The objective of this study was to determine whether So extracted by PCE is an oxidation product of pyrite or whether it originates in some way from unstable, organically-bound sulfur. The isotopic composition of the PCE-extracted So was compared to the isotopic compositions of the pyritic and the organic sulfur in a coal. The So was shown to have an isotopic signature similar to the pyritic sulfur. Additionally, the isotopic differences observed between the pyritic, So and sulfatic sulfur were consistent with bacterial mediated oxidation of sulfide sulfur (pyrite) as the source of both the sulfatic and elemental sulfur. ?? 1990.

Kinetics of degradation of sulfur mustard and sarin simulants on HKUST-1 metal organic framework.

Science.gov (United States)

Roy, Anuradha; Srivastava, Avanish K; Singh, Beer; Shah, Dilip; Mahato, Timir Haran; Srivastava, Anchal

2012-10-28

The applicability of HKUST-1 for the degradation of sulfur mustard and sarin simulants was studied with and without coadsorbed water. Degradation was found to be via hydrolysis and dependent on the nucleophilic substitution reaction, vapour pressure and molecular diameter of the toxicants.

Process for removing sulfur from sulfur-containing gases: high calcium fly-ash

Science.gov (United States)

Rochelle, Gary T.; Chang, John C. S.

1991-01-01

The present disclosure relates to improved processes for treating hot sulfur-containing flue gas to remove sulfur therefrom. Processes in accordance with the present invention include preparing an aqueous slurry composed of a calcium alkali source and a source of reactive silica and/or alumina, heating the slurry to above-ambient temperatures for a period of time in order to facilitate the formation of sulfur-absorbing calcium silicates or aluminates, and treating the gas with the heat-treated slurry components. Examples disclosed herein demonstrate the utility of these processes in achieving improved sulfur-absorbing capabilities. Additionally, disclosure is provided which illustrates preferred configurations for employing the present processes both as a dry sorbent injection and for use in conjunction with a spray dryer and/or bagfilter. Retrofit application to existing systems is also addressed.

Toward a unifying model for the late Neoproterozoic sulfur cycle

Science.gov (United States)

Johnston, D. T.; Gill, B. C.; Ries, J. B.; OBrien, T.; Macdonald, F. A.

2011-12-01

The latest Proterozoic has always fascinated Earth historians. Between the long identified enigmas surrounding the sudden appearance of animals and the more recent infatuation with large-sale geochemical anomalies (i.e. the Shuram - Wonaka event), the closing 90 million years of the Proterozoic - the Ediacaran - houses a number of important and unanswered questions. Detailed redox geochemistry and stable isotope reconstructions of stratigraphic units covering this time interval have begun to unravel some of it's mysteries, however much remains to be explained. The sulfur cycle, with it's intimate links to both the marine carbon cycle (through remineralization reactions) and overall oxidant budgets (via seawater sulfate), sits poised to provide a sharp tool to track environmental change. Previous work has recognized this potential, and serves as a point of entrance for our current work. However what is lacking - and the goal of this study - is to place quantitative constraints the geochemical evolution of marine basins through this interval. Here we will present multiple sulfur isotope data from pyrite and sulfates through Ediacaran stratigraphy from the Yukon, Russia and Namibia. To maximize the utility of sulfur isotope studies, we have focused on Ediacaran stratigraphic sections from multiple continents that record both the Shuram anomaly and contain rich fossil records. These sections provide, when interpreted together, a fresh opportunity to revisit the geochemical setting that gave rise to animals. Importantly, the inclusion of multiple sulfur isotope data allows us to place further constraints on the mechanisms underpinning isotopic variability. For instance, when coupled with new experimental data, tighter constraints are provided on how fractionation scales with sulfate concentrations. This may allow for decoupling changes in biological fractionations from modifications to the global sulfur cycle (i.e. changes in seawater sulfate concentrations or the vigor

Influence of sulfur oxyanions on reductive dehalogenation activities in Desulfomonile tiedjei.

OpenAIRE

Townsend, G T; Suflita, J M

1997-01-01

The inhibition of aryl reductive dehalogenation reactions by sulfur oxyanions has been demonstrated in environmental samples, dehalogenating enrichments, and the sulfate-reducing bacterium Desulfomonile tiedjei; however, this phenomenon is not well understood. We examined the effects of sulfate, sulfite, and thiosulfate on reductive dehalogenation in the model microorganism D. tiedjei and found separate mechanisms of inhibition due to these oxyanions under growth versus nongrowth conditions. ...

Tuning the oxidative power of free iron-sulfur clusters.

Science.gov (United States)

Lang, Sandra M; Zhou, Shaodong; Schwarz, Helmut

2017-03-15

The gas-phase reactions between a series of di-iron sulfur clusters Fe 2 S x + (x = 1-3) and the small alkenes C 2 H 4 , C 3 H 6 , and C 4 H 8 have been investigated by means of Fourier-transform ion-cyclotron resonance mass spectrometry. For all studied alkenes, the reaction efficiency is found to increase in the order Fe 2 S + desulfurization of the cluster and formation of H 2 S. This indicates an increased propensity to induce oxidation reactions, i.e. oxidative power, of Fe 2 S 3 + that is attributed to an increased formal oxidation state of the iron atoms. Furthermore, the ability of Fe 2 S 3 + to activate and dissociate the C-H bonds of the alkenes is observed to increase with increasing size of the alkene and thus correlates with the alkene ionization energy.

Solvent extraction of elemental sulfur from coal and a determination of its source using stable sulfur isotopes

Energy Technology Data Exchange (ETDEWEB)

Hackley, K.C.; Buchanan, D.H.; Coombs, K.; Chaven, C.; Kruse, C.W. (Eastern Illinois University, Charleston, IL (USA). Chemistry Dept.)

1990-01-01

Hot tetrachloroethene (perchloroethylen PCE) extracts significant amounts of elemental sulfur (S{sup o}) from weathered coals but not from pristine coals. The objective of this study was to determine whether S{sup o} extracted by PCE is an oxidation product of pyrite or whether it originates in some way from unstable, organically-bound sulfur. The isotopic composition of the PCE-extracted S{sup o} was compared to the isotopic compositions of the pyritic and the organic sulfur in a coal. The S{sup o} was shown to have an isotopic signature similar to the pyritic sulfur. Additionally, the isotopic differences observed between the pyritic, S{sup o} and sulfatic sulfur were consistent with bacterial mediated oxidation of sulfide sulfur (pyrite) as the source of both the sulfatic and elemental sulfur. 21 refs., 2 tabs.

Preparation and electrochemical performance of sulfur-alumina cathode material for lithium-sulfur batteries

International Nuclear Information System (INIS)

Dong, Kang; Wang, Shengping; Zhang, Hanyu; Wu, Jinping

2013-01-01

Highlights: ► Micron-sized alumina was synthesized as adsorbent for lithium-sulfur batteries. ► Sulfur-alumina material was synthesized via crystallizing nucleation. ► The Al 2 O 3 can provide surface area for the deposition of Li 2 S and Li 2 S 2 . ► The discharge capacity of the battery is improved during the first several cycles. - Abstract: Nano-sized sulfur particles exhibiting good adhesion with conducting acetylene black and alumina composite materials were synthesized by means of an evaporated solvent and a concentrated crystallization method for use as the cathodes of lithium-sulfur batteries. The composites were characterized and examined by X-ray diffraction, environmental scanning electron microscopy and electrochemical methods, such as cyclic voltammetry, electrical impedance spectroscopy and charge–discharge tests. Micron-sized flaky alumina was employed as an adsorbent for the cathode material. The initial discharge capacity of the cathode with the added alumina was 1171 mAh g −1 , and the remaining capacity was 585 mAh g −1 after 50 cycles at 0.25 mA cm −2 . Compared with bare sulfur electrodes, the electrodes containing alumina showed an obviously superior cycle performance, confirming that alumina can contribute to reducing the dissolution of polysulfides into electrolytes during the sulfur charge–discharge process

Sulfur-centered reactive intermediates derived from the oxidation of sulfur compounds of biological interest

Energy Technology Data Exchange (ETDEWEB)

Abedinzadeh, Z. [Lab. de Chimie Physique, UMR, Univ. Rene Descartes, Paris (France)

2001-02-01

Sulphur compounds play a central role in the structure and activity of many vital systems. In the living cell, sulfur constitutes an essential part of the defense against oxidative damage and is transformed into a variety of sulfur free radical species. Many studies of the chemistry of sulfur-centered radicals using pulse radiolysis and photolysis techniques to detect and measure the kinetics of these radicals have been published and reviewed. This paper discusses the present state of research on the formation and reactivity of certain sulfur-centered radicals [RS{sup .}, RSS{sup .}, RS{sup .+}, (RSSR){sup .+}] and their implications for biological systems. (author)

Sulfur-centered reactive intermediates derived from the oxidation of sulfur compounds of biological interest

International Nuclear Information System (INIS)

Abedinzadeh, Z.

2001-01-01

Sulphur compounds play a central role in the structure and activity of many vital systems. In the living cell, sulfur constitutes an essential part of the defense against oxidative damage and is transformed into a variety of sulfur free radical species. Many studies of the chemistry of sulfur-centered radicals using pulse radiolysis and photolysis techniques to detect and measure the kinetics of these radicals have been published and reviewed. This paper discusses the present state of research on the formation and reactivity of certain sulfur-centered radicals [RS . , RSS . , RS .+ , (RSSR) .+ ] and their implications for biological systems. (author)

Danburite decomposition by sulfuric acid

International Nuclear Information System (INIS)

Mirsaidov, U.; Mamatov, E.D.; Ashurov, N.A.

2011-01-01

Present article is devoted to decomposition of danburite of Ak-Arkhar Deposit of Tajikistan by sulfuric acid. The process of decomposition of danburite concentrate by sulfuric acid was studied. The chemical nature of decomposition process of boron containing ore was determined. The influence of temperature on the rate of extraction of boron and iron oxides was defined. The dependence of decomposition of boron and iron oxides on process duration, dosage of H 2 SO 4 , acid concentration and size of danburite particles was determined. The kinetics of danburite decomposition by sulfuric acid was studied as well. The apparent activation energy of the process of danburite decomposition by sulfuric acid was calculated. The flowsheet of danburite processing by sulfuric acid was elaborated.

Sulfur polymer cement concrete

International Nuclear Information System (INIS)

Weber, H.H.; McBee, W.C.

1990-01-01

Sulfur-based composite materials formulated using sulfur polymer cement (SPC) and mineral aggregates are described and compared with conventional portland cement based materials. Materials characteristics presented include mechanical strength, chemical resistance, impact resistance, moisture permeation, and linear shrinkage during placement and curing. Examples of preparation and placement of sulfur polymer cement concrete (SC) are described using commercial scale equipment. SC applications presented are focused into hostile chemical environments where severe portland cement concrete (PCC) failure has occurred

Synthesis of hierarchical porous honeycomb carbon for lithium-sulfur battery cathode with high rate capability and long cycling stability

International Nuclear Information System (INIS)

Qu, Yaohui; Zhang, Zhian; Zhang, Xiahui; Ren, Guodong; Wang, Xiwen; Lai, Yanqing; Liu, Yexiang; Li, Jie

2014-01-01

Highlights: • A novel HPHC was prepared by a simple template process. • The HPHC as matrix to load sulfur for Lithium-Sulfur battery cathodes. • S-HPHC cathode shows high rate capability and long cycling stability. • The sulfur-HPHC composite presents electrochemical stability up to 300 cycles at 1.5 C. - Abstract: Sulfur has a high specific capacity of 1675 mAh g −1 as lithium battery cathode, but its rapid capacity fading due to polysulfides dissolution presents a significant challenge for practical applications. Here we report a novel hierarchical porous honeycomb carbon (HPHC) for lithium-sulfur battery cathode with effective trapping of polysulfides. The HPHC was prepared by a simple template process, and a sulfur-carbon composite based on HPHC was synthesized for lithium-sulfur batteries by a melt-diffusion method. It is found that the elemental sulfur was dispersed inside the three-dimensionally hierarchical pores of HPHC based on the analyses. Electrochemical tests reveal that the sulfur-HPHC composite shows high rate capability and long cycling stability as cathode materials. The sulfur-HPHC composite with sulfur content of 66.3 wt% displays an initial discharge capacity of 923 mAh g −1 and a reversible discharge capacity of 564 mAh g −1 after 100 cycles at 2 C charge-discharge rate. In particular, the sulfur-HPHC composite presents a long term cycling stability up to 300 cycles at 1.5 C. The results illustrate that the electrochemical reaction constrained inside the interconnected macro/meso/micropores of HPHC would be the dominant factor for the excellent high rate capability and long cycling stability of the sulfur cathode, and the three-dimensionally honeycomb carbon network would be a promising carbon matrix structure for lithium-sulfur battery cathode

Sulfur cathode integrated with multileveled carbon nanoflake-nanosphere networks for high-performance lithium-sulfur batteries

International Nuclear Information System (INIS)

Li, S.H.; Wang, X.H.; Xia, X.H.; Wang, Y.D.; Wang, X.L.; Tu, J.P.

2017-01-01

Tailored design/construction of high-quality sulfur/carbon composite cathode is critical for development of advanced lithium-sulfur batteries. We report a powerful strategy for integrated fabrication of sulfur impregnated into three-dimensional (3D) multileveled carbon nanoflake-nanosphere networks (CNNNs) by means of sacrificial ZnO template plus glucose carbonization. The multileveled CNNNs are not only utilized as large-area host/backbone for sulfur forming an integrated S/CNNNs composite electrode, but also serve as multiple carbon blocking barriers (nanoflake infrastructure andnanosphere superstructure) to physically confine polysulfides at the cathode. The designedself-supported S/CNNNs composite cathodes exhibit superior electrochemical performances with high capacities (1395 mAh g −1 at 0.1C, and 769 mAh g −1 at 5.0C after 200 cycles) and noticeable cycling performance (81.6% retention after 200 cycles). Our results build a new bridge between sulfur and carbon networks with multiple blocking effects for polysulfides, and provide references for construction of other high-performance sulfur cathodes.

Sulfonation of polyester fabrics by gaseous sulfur oxide activated by UV irradiation

International Nuclear Information System (INIS)

Kordoghli, Bessem; Khiari, Ramzi; Mhenni, Mohamed Farouk; Sakli, Faouzi; Belgacem, Mohamed Naceur

2012-01-01

Highlights: ► In this paper, an original technique was present to improve the hydrophilic properties of polyester fibres. ► The modification of PET fabric was carried out using gaseous sulfur trioxide activated by UV irradiations. ► We fully characterized the modified and untreated fabrics. - Abstract: This paper describes an original technique aiming to improve the hydrophilic properties of polyester fibres. In this method, the sulfonation of the aromatic rings is carried out using gaseous sulfur trioxide activated by UV irradiations. Thus, exposing the polyester textile fabric to the UVC light (wavelength around 254 nm) under a stream of sulfur trioxide leads to the fixation of -SO 3 H groups. The amounts of the fixed sulfonate groups depended on the reaction conditions. Evidence of grafting deduced from the measurements of hygroscopic properties was carried out by contact angle measurement, moisture regain as well as by measuring the rate of retention. SEM and FT-IR analysis, DSC and DTA/TGA thermograms showed that no significant modifications have occurred in the bulk of the treated PET fabrics.

28 CFR 39.104-39.109 - [Reserved

Science.gov (United States)

2010-07-01

... 28 Judicial Administration 1 2010-07-01 2010-07-01 false [Reserved] 39.104-39.109 Section 39.104-39.109 Judicial Administration DEPARTMENT OF JUSTICE ENFORCEMENT OF NONDISCRIMINATION ON THE BASIS OF HANDICAP IN PROGRAMS OR ACTIVITIES CONDUCTED BY THE DEPARTMENT OF JUSTICE §§ 39.104-39.109 [Reserved] ...

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2010-07-01

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2010-07-01

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2010-07-01

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Formation of CuxS Layers on Polypropylene Sulfurized by Molten Sulfur

Directory of Open Access Journals (Sweden)

Rasa ALABURDAITĖ

2011-11-01

Full Text Available The processes of formation of electrically conductive layers of copper sulfides CuxS by the sorption-diffusion method on polypropylene (PP using molten sulfur as sulfurizing agent was investigated. The amount of sorbed sulfur increased with the increase of the duration of treatment. Copper sulfide layers were formed on the surface of polypropylene after the treatment of sulfurized polymer with Cu(II/I salt solution. The amount of copper sulfide in layer increased with the increase of treatment duration in copper salt solution. XRD spectra of PP films treated for 3 min with molten sulfur and then with Cu(II/I salt solution for the different time showed that the copper sulfide phases, mostly digenite, Cu2-xS and a-chalcocite, Cu2S were formed in the layers. Electromotive force measurement results confirmed the composition of formed CuxS layers on PP. The phase composition of layers also changed after the annealing. The value of electrical resistance of copper sulfide layers on PP varied from 20 W/cm2 to 80 W/cm2 and after annealing at 80 °C - in the interval of 10 W/cm2 - 60 W/cm2.http://dx.doi.org/10.5755/j01.ms.17.4.776

Removal of sulfur from process streams

International Nuclear Information System (INIS)

Brignac, D.G.

1984-01-01

A process wherein water is added to a non-reactive gas stream, preferably a hydrogen or hydrogen-containing gas stream, sufficient to raise the water level thereof to from about 0.2 percent to about 50 percent, based on the total volume of the process gas stream, and the said moist gas stream is contacted, at elevated temperature, with a particulate mass of a sulfur-bearing metal alumina spinel characterized by the formula MAl 2 O 4 , wherein M is chromium, iron, cobalt, nickel, copper, cadmium, mercury, or zinc to desorb sulfur thereon. In the sulfur sorption cycle, due to the simultaneous adsorption of water and sulfur, the useful life of the metal alumina spinel for sulfur adsorption can be extended, and the sorbent made more easily regenerable after contact with a sulfur-bearing gas stream, notably sulfur-bearing wet hydrogen or wet hydrogen-rich gas streams

Oxidation of alginate and pectate biopolymers by cerium(IV) in perchloric and sulfuric acid solutions: A comparative kinetic and mechanistic study.

Science.gov (United States)

Fawzy, Ahmed

2016-03-15

The kinetics of oxidation of alginate (Alg) and pectate (Pec) carbohydrate biopolymers was studied by spectrophotometry in aqueous perchloric and sulfuric acid solutions at fixed ionic strengths and temperature. In both acids, the reactions showed a first order dependence on [Ce(IV)], whereas the orders with respect to biopolymer concentrations are less than unity. In perchloric acid, the reactions exhibited less than unit orders with respect to [H(+)] whereas those proceeded in sulfuric acid showed negative fractional-first order dependences on [H(+)]. The effect of ionic strength and dielectric constant was studied. Probable mechanistic schemes for oxidation reactions were proposed. In both acids, the final oxidation products were characterized as mono-keto derivatives of both biopolymers. The activation parameters with respect to the slow step of the mechanisms were computed and discussed. The rate laws were derived and the reaction constants involved in the different steps of the mechanisms were calculated. Copyright © 2015 Elsevier Ltd. All rights reserved.

High Mass-Loading of Sulfur-Based Cathode Composites and Polysulfides Stabilization for Rechargeable Lithium/Sulfur Batteries

International Nuclear Information System (INIS)

Hara, Toru; Konarov, Aishuak; Mentbayeva, Almagul; Kurmanbayeva, Indira; Bakenov, Zhumabay

2015-01-01

Although sulfur has a high theoretical gravimetric capacity, 1672 mAh/g, its insulating nature requires a large amount of conducting additives: this tends to result in a low mass-loading of active material (sulfur), and thereby, a lower capacity than expected. Therefore, an optimal choice of conducting agents and of the method for sulfur/conducting-agent integration is critically important. In this paper, we report that the areal capacity of 4.9 mAh/cm 2 was achieved at sulfur mass loading of 4.1 mg/cm 2 by casting sulfur/polyacrylonitrile/ketjenblack (S/PAN/KB) cathode composite into carbon fiber paper. This is the highest value among published/reported ones even though it does not contain expensive nanosized carbon materials such as carbon nanotubes, graphene, or graphene derivatives, and competitive enough with the conventional LiCoO 2 -based cathodes (e.g., LiCoO 2 , <20 mg/cm 2 corresponding to <2.8 mAh/cm 2 ). Furthermore, the combination of sulfur/PAN-based composite and PAN-based carbon fiber paper enabled the sulfur-based composite to be used even in carbonate-based electrolyte solution that many lithium/sulfur battery researchers avoid the use of it because of severer irreversible active material loss than in electrolyte solutions without carbonate-based solutions, and even at the highest mass-loading ever reported (the more sulfur is loaded, the more decomposed sulfides deposit at an anode surface).

Developing porous carbon with dihydrogen phosphate groups as sulfur host for high performance lithium sulfur batteries

Science.gov (United States)

Cui, Yanhui; Zhang, Qi; Wu, Junwei; Liang, Xiao; Baker, Andrew P.; Qu, Deyang; Zhang, Hui; Zhang, Huayu; Zhang, Xinhe

2018-02-01

Carbon matrix (CM) derived from biomass is low cost and easily mass produced, showing great potential as sulfur host for lithium sulfur batteries. In this paper we report on a dihydrogen phosphate modified CM (PCM-650) prepared from luffa sponge (luffa acutangula) by phosphoric acid treatment. The phosphoric acid not only increases the surface area of the PCM-650, but also introduces dihydrogen phosphate onto PCM-650 (2.28 at% P). Sulfur impregnated (63.6 wt%) PCM-650/S, in comparison with samples with less dihydrogen phosphate LPCM-650/S, shows a significant performance improvement. XPS analysis is conducted for sulfur at different stages, including sulfur (undischarged), polysulfides (discharge to 2.1 V) and short chain sulfides (discharge to 1.7 V). The results consistently show chemical shifts for S2p in PCM-650, suggesting an enhanced adsorption effect. Furthermore, density functional theory (DFT) calculations is used to clarify the molecular binding: carbon/sulfur (0.86 eV), carbon/Li2S (0.3 eV), CH3-O-PO3H2/sulfur (1.24 eV), and CH3-O-PO3H2/Li2S (1.81 eV). It shows that dihydrogen phosphate group can significantly enhance the binding with sulfur and sulfide, consistent with XPS results. Consequently a CM functionalised with dihydrogen phosphate shows great potential as the sulfur host in a Li-S battery.

Effect of commercial activated carbons in sulfur cathodes on the electrochemical properties of lithium/sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Park, Jin-Woo; Kim, Icpyo [School of Materials Science and Engineering, Gyeongsang National University, 501 Jinju-daero, Jinju, Gyeongnam 52828 (Korea, Republic of); Kim, Ki-Won; Nam, Tae-Hyun; Cho, Kwon-Koo; Ahn, Jou-Hyeon [Department of Materials Engineering and Convergence Technology, Gyeongsang National University, 501 Jinju-daero, Jinju, Gyeongnam 52828 (Korea, Republic of); Ryu, Ho-Suk [Department of Material and Energy Engineering, Gyeongwoon University, 730, Gangdong-ro, Sandong-myeon, Gumi, Gyeongbuk, 39160 (Korea, Republic of); Ahn, Hyo-Jun, E-mail: ahj@gnu.ac.kr [School of Materials Science and Engineering, Gyeongsang National University, 501 Jinju-daero, Jinju, Gyeongnam 52828 (Korea, Republic of); Department of Materials Engineering and Convergence Technology, Gyeongsang National University, 501 Jinju-daero, Jinju, Gyeongnam 52828 (Korea, Republic of)

2016-10-15

Highlights: • The sulfur/activated carbon composite is fabricated using commercial activated carbons. • The sulfur/activated carbon composite with coal shows the best performance. • The Li/S battery has capacities of 1240 mAh g{sup −1} at 1 C and 567 mAh g{sup −1} at 10 C. - Abstract: We prepared sulfur/active carbon composites via a simple solution-based process using the following commercial activated carbon-based materials: coal, coconut shells, and sawdust. Although elemental sulfur was not detected in any of the sulfur/activated carbon composites based on Thermogravimetric analysis, X-ray diffraction, and Raman spectroscopy, Energy-dispersive X-ray spectroscopy results confirmed its presence in the activated carbon. These results indicate that sulfur was successfully impregnated in the activated carbon and that all of the activated carbons acted as sulfur reservoirs. The sulfur/activated carbon composite cathode using coal exhibited the highest discharge capacity and best rate capability. The first discharge capacity at 1 C (1.672 A g{sup −1}) was 1240 mAh g{sup −1}, and a large reversible capacity of 567 mAh g{sup −1} was observed at 10 C (16.72 A g{sup −1}).

Determination of differential cross-sections for the {sup nat}K(p, p{sub 0}) and {sup 39}K(p, {alpha}{sub 0}) reactions in the backscattering geometry

Energy Technology Data Exchange (ETDEWEB)

Kokkoris, M., E-mail: kokkoris@central.ntua.g [Department of Physics, National Technical University of Athens, Zografou Campus, 157 80 Athens (Greece); Tsaris, A. [Department of Physics, National Technical University of Athens, Zografou Campus, 157 80 Athens (Greece); Misaelides, P. [Department of Chemistry, Aristotle University of Thessaloniki, GR-54124 Thessaloniki (Greece); Sokaras, D.; Lagoyannis, A.; Harissopulos, S. [Institute of Nuclear Physics, TANDEM Accelerator, N.C.S.R. ' Demokritos' , Aghia Paraskevi, 153 10 Athens (Greece); Vlastou, R.; Papadopoulos, C.T. [Department of Physics, National Technical University of Athens, Zografou Campus, 157 80 Athens (Greece)

2010-06-15

In the present work, new, differential cross-section values are presented for the {sup nat}K(p, p{sub 0}) reaction in the energy range E{sub lab} = 3000-5000 keV (with an energy step of 25 keV) and for detector angles between 140{sup o} and 170{sup o} (with an angular step of 10{sup o}). A qualitative discussion of the observed cross-section variations through the influence of strong, closely spaced resonances in the p + {sup 39}K system is also presented. Information has also been extracted concerning the {sup 39}K(p,{alpha}{sub 0}) reaction for E{sub lab} = 4000-5000 keV in the same angular range. As a result, more than {approx}500 data points will soon be available to the scientific community through IBANDL (Ion Beam Analysis Nuclear Data Library - (http://www-nds.iaea.org/ibandl/)) and could thus be incorporated in widely used IBA algorithms (e.g. SIMNRA, WINDF, etc.) for potassium depth profiling at relatively high proton beam energies.

Sulfur isotope in nature. Determination of sulfur isotope ratios in coal and petroleum by mass spectrometry

International Nuclear Information System (INIS)

Derda, M.

1999-01-01

Elementary sulfur or in chemical compounds is one of the elements widespread in the earth's crust and biosphere. Its participation in earth's crust amounts to 0.26 % by weight. Measurement of isotope composition of natural samples can deliver many information about origin, creation and transformation ranges of rocks and minerals. Sulfur isotope ratio contained in minerals is variable and for this reason investigation of isotope sulfur composition can deliver useful information about the geochemistry of each component. Therefore in the investigated sample it is necessary to determine not only the content of sulfur but also the isotope composition of each component. Differentiation of contents of sulfur-34 in natural sulfur compounds can reach up to 110 per mile. So large divergences can be explained by a kinetic effect or by bacterial reduction of sulphates. In this report a wide review of the results of investigations of isotope sulfur compositions in coal and petroleum are presented as well as the methods for the preparation of samples for mass spectrometry analysis are proposed. (author)

Advanced Sulfur Cathode Enabled by Highly Crumpled Nitrogen-Doped Graphene Sheets for High-Energy-Density Lithium-Sulfur Batteries.

Science.gov (United States)

Song, Jiangxuan; Yu, Zhaoxin; Gordin, Mikhail L; Wang, Donghai

2016-02-10

Herein, we report a synthesis of highly crumpled nitrogen-doped graphene sheets with ultrahigh pore volume (5.4 cm(3)/g) via a simple thermally induced expansion strategy in absence of any templates. The wrinkled graphene sheets are interwoven rather than stacked, enabling rich nitrogen-containing active sites. Benefiting from the unique pore structure and nitrogen-doping induced strong polysulfide adsorption ability, lithium-sulfur battery cells using these wrinkled graphene sheets as both sulfur host and interlayer achieved a high capacity of ∼1000 mAh/g and exceptional cycling stability even at high sulfur content (≥80 wt %) and sulfur loading (5 mg sulfur/cm(2)). The high specific capacity together with the high sulfur loading push the areal capacity of sulfur cathodes to ∼5 mAh/cm(2), which is outstanding compared to other recently developed sulfur cathodes and ideal for practical applications.

39 CFR 3001.39 - Intermediate decisions.

Science.gov (United States)

2010-07-01

... 39 Postal Service 1 2010-07-01 2010-07-01 false Intermediate decisions. 3001.39 Section 3001.39 Postal Service POSTAL REGULATORY COMMISSION PERSONNEL RULES OF PRACTICE AND PROCEDURE Rules of General Applicability § 3001.39 Intermediate decisions. (a) Initial decision by presiding officer. In any proceedings in...

Mechanistic aspects of ionic reactions in flames

DEFF Research Database (Denmark)

Egsgaard, H.; Carlsen, L.

1993-01-01

Some fundamentals of the ion chemistry of flames are summarized. Mechanistic aspects of ionic reactions in flames have been studied using a VG PlasmaQuad, the ICP-system being substituted by a simple quartz burner. Simple hydrocarbon flames as well as sulfur-containing flames have been investigated...

Preparation and electrochemical performance of sulfur-alumina cathode material for lithium-sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Dong, Kang [Faculty of Material Science and Chemistry, China University of Geosciences, 388 Lumo Road, 430074 Wuhan (China); Wang, Shengping, E-mail: spwang@cug.edu.cn [Faculty of Material Science and Chemistry, China University of Geosciences, 388 Lumo Road, 430074 Wuhan (China); Zhang, Hanyu; Wu, Jinping [Faculty of Material Science and Chemistry, China University of Geosciences, 388 Lumo Road, 430074 Wuhan (China)

2013-06-01

Highlights: ► Micron-sized alumina was synthesized as adsorbent for lithium-sulfur batteries. ► Sulfur-alumina material was synthesized via crystallizing nucleation. ► The Al{sub 2}O{sub 3} can provide surface area for the deposition of Li{sub 2}S and Li{sub 2}S{sub 2}. ► The discharge capacity of the battery is improved during the first several cycles. - Abstract: Nano-sized sulfur particles exhibiting good adhesion with conducting acetylene black and alumina composite materials were synthesized by means of an evaporated solvent and a concentrated crystallization method for use as the cathodes of lithium-sulfur batteries. The composites were characterized and examined by X-ray diffraction, environmental scanning electron microscopy and electrochemical methods, such as cyclic voltammetry, electrical impedance spectroscopy and charge–discharge tests. Micron-sized flaky alumina was employed as an adsorbent for the cathode material. The initial discharge capacity of the cathode with the added alumina was 1171 mAh g{sup −1}, and the remaining capacity was 585 mAh g{sup −1} after 50 cycles at 0.25 mA cm{sup −2}. Compared with bare sulfur electrodes, the electrodes containing alumina showed an obviously superior cycle performance, confirming that alumina can contribute to reducing the dissolution of polysulfides into electrolytes during the sulfur charge–discharge process.

Clues to early diagenetic sulfurization processes from mild chemical cleavage of labile sulfur-rich geomacromolecules

Science.gov (United States)

Adam, P.; Schneckenburger, P.; Schaeffer, P.; Albrecht, P.

2000-10-01

Macromolecular fractions, isolated from the solvent extract of sulfur-rich Recent (Siders Pond, USA; Lake Cadagno, Switzerland; Walvis Bay, Namibia) and immature sediments (Gibellina, Messinian of Sicily; Vena del Gesso, Messinian of Italy), were investigated by chemical degradation using sodium ethanethiolate/methyliodide. This mild reagent which cleaves polysulfide bonds to yield methylsulfides has the advantage over other methods of leaving intact other functionalities (like double bonds) and preserving sulfur atoms at their incorporation site. The method is, therefore, well-suited to the molecular level investigation of sulfur-rich macromolecules from Recent sediments containing highly functionalized polysulfide-bound subunits. In Recent anoxic sulfur-rich sediments, the release of various methylthioethers clearly demonstrates that intermolecular sulfurization of organic matter does occur at the earliest stages of diagenesis. Steroids and phytane derivatives are the major sulfurized lipids, a feature also observed in more mature sulfur-rich sediments. Several phytene derivatives, such as cis and trans 1-methylthiophyt-2-enes, as well as methylthiosteroids, including 5α- and 5β-3-(methylthio)-cholest-2-enes, were identified by comparison with synthesized standards. Steroid methylthioenolethers are released from polysulfide-bound steroid enethiols present in the macromolecular fractions. The latter, which correspond to thioketones, can be considered as intermediates in the reductive sulfurization pathway leading from steroid ketones to polysulfide-bound saturated steroid skeletons and are characterized for the first time in the present study. Thus, it could be shown that the major part of the polysulfide-bound lipids occurring in Recent sediments is apparently the result of sulfurization processes affecting carbonyls (aldehydes and ketones). The unsaturated methylthioethers obtained from Recent sediments were not present in more mature evaporitic samples, which

Sulfur equilibrium desulfurization of sulfur containing products of combustion

International Nuclear Information System (INIS)

Woodroffe, J.A.; Abichandani, J.S.

1990-01-01

This patent describes the method for the combustion of a carbon- and sulfur-containing fuel for substantially reducing emission of gaseous sulfur compounds formed during combustion of the fuel in a combustion zone. The zone having one or more fuel inlets and one or more oxidizer inlets, and having a combustion products outlet spaced therefrom, and having one or more inorganic sorbent inlets downstream of the fuel inlet(s) and oxidizer inlet(s) and upstream of the combustion products outlet

A sulfur host based on titanium monoxide@carbon hollow spheres for advanced lithium-sulfur batteries.

Science.gov (United States)

Li, Zhen; Zhang, Jintao; Guan, Buyuan; Wang, Da; Liu, Li-Min; Lou, Xiong Wen David

2016-10-20

Lithium-sulfur batteries show advantages for next-generation electrical energy storage due to their high energy density and cost effectiveness. Enhancing the conductivity of the sulfur cathode and moderating the dissolution of lithium polysulfides are two key factors for the success of lithium-sulfur batteries. Here we report a sulfur host that overcomes both obstacles at once. With inherent metallic conductivity and strong adsorption capability for lithium-polysulfides, titanium monoxide@carbon hollow nanospheres can not only generate sufficient electrical contact to the insulating sulfur for high capacity, but also effectively confine lithium-polysulfides for prolonged cycle life. Additionally, the designed composite cathode further maximizes the lithium-polysulfide restriction capability by using the polar shells to prevent their outward diffusion, which avoids the need for chemically bonding all lithium-polysulfides on the surfaces of polar particles.

The mechanism of the catalytic oxidation of hydrogen sulfide: II. Kinetics and mechanism of hydrogen sulfide oxidation catalyzed by sulfur

NARCIS (Netherlands)

Steijns, M.; Derks, F.; Verloop, A.; Mars, P.

1976-01-01

The kinetics of the catalytic oxidation of hydrogen sulfide by molecular oxygen have been studied in the temperature range 20–250 °C. The primary reaction product is sulfur which may undergo further oxidation to SO2 at temperatures above 200 °C. From the kinetics of this autocatalytic reaction we

Experimental and theoretical study about sulfur deactivation of Ni/ CeO{sub 2} and Rh/CeO{sub 2} catalysts

Energy Technology Data Exchange (ETDEWEB)

Ocsachoque, Marco A., E-mail: ocmarco@quimica.unlp.edu.ar [Centro de Investigación y Desarrollo en Ciencias Aplicadas “Dr Jorge J. Ronco”, (CONICET, CCT La Plata), Departamento de Química, Facultad de Cs Exactas (UNLP), Calle 48 N° 257, 1900 La Plata (Argentina); Eugenio Russman, Juan I.; Irigoyen, Beatriz [Instituto de Tecnologías del Hidrógeno y Energías Sostenibles (ITHES), Departamento de Ingeniería Química, Facultad de Ingeniería (UBA), Buenos Aires (Argentina); Gazzoli, Delia [Dipartimento di Chimia, Universitá di Roma “La Sapienza”, Roma (Italy); González, María G. [Centro de Investigación y Desarrollo en Ciencias Aplicadas “Dr Jorge J. Ronco”, (CONICET, CCT La Plata), Departamento de Química, Facultad de Cs Exactas (UNLP), Calle 48 N° 257, 1900 La Plata (Argentina)

2016-04-01

Sulfur deactivation of Ni/CeO{sub 2} and Rh/CeO{sub 2} catalysts were examined through an experimental and theoretical study. These catalysts were characterized by N{sub 2} adsorption, X-ray diffraction, temperature programmed reaction, thermogravimetric analysis, Uv–visible spectroscopy and Raman spectroscopy, and tested under the methane dry reforming reaction in the presence of H{sub 2}S. On the other hand, different possible interactions of sulfur with Rh, Ni or surface sites of the CeO{sub 2} support were evaluated by performing energy calculations with the density functional theory (DFT). Overall, the results indicate that tolerance to sulfur of Rh/CeO{sub 2} catalyst is higher than that of Ni/CeO{sub 2} one. In this sense, TPR measurements show that reduction of CeO{sub 2} is promoted by the presence of Rh. This effect, probably caused by hydrogen spillover to CeO{sub 2} support during the reduction of RhO{sub x} species, could be linked to a high oxygen donation capacity of Rh/CeO{sub 2} catalysts. Accordingly, the O{sup 2−} species existing on Rh/CeO{sub 2} catalysts, revealed by Raman spectra of these samples, could favor sulfur oxidation and prevent Rh–S interactions. Likewise, the theoretical calculations show that desorption of S–O species from Rh/CeO{sub 2} system is more favorable than that from Ni/CeO{sub 2} one. Therefore, our experimental and theoretical study about sulfur deactivation of Ni and Rh supported on CeO{sub 2} allow us to postulate that Rh can help to desorb SO{sub x} species formed on the support, retarding sulfur poisoning of the Rh/CeO{sub 2} catalysts. - Highlights: • CeO{sub 2} support can act as a sacrifice trap decreasing sulfur poisoning. • Theoretical calculations indicate an important nickel affinity with sulfur. • Rh would favor desorption of S–O species formed on the support. • The O{sup 2−} species present on the Rh–CeO{sub 2} sample favor sulfur removal.

A composite of hollow carbon nanospheres and sulfur-rich polymers for lithium-sulfur batteries

Science.gov (United States)

Zeng, Shao-Zhong; Yao, Yuechao; Zeng, Xierong; He, Qianjun; Zheng, Xianfeng; Chen, Shuangshuang; Tu, Wenxuan; Zou, Jizhao

2017-07-01

Lithium-sulfur batteries are the most promising candidates for future high-energy applications because of the unparalleled capacity of sulfur (1675 mAh g-1). However, lithium-sulfur batteries have limited cycle life and rate capability due to the dissolution of polysulfides and the extremely low electronic conductivity of sulfur. To solve these issues, various porous carbons including hollow carbon nanospheres (HCNs) have been used for improving the conductivity. However, these methods still suffer from polysulfides dissolution/loss owing to their weak physical adsorption to polysulfides. Herein, we introduced a covalent grafting route to composite the HCNs and the vulcanized trithiocyanuric acid (TTCA). The composite exhibits a high loading of the vulcanized TTCA by the HCNs with high surface area and large pore volume, and covalent bonds to sulfur, effectively depressing the dissolution of polysulfides. The first discharge capacity of the composite reaches 1430 mAh g-1 at 0.1 C and 1227 mAh g-1 at 0.2 C.

Assessment of the risk of pollution by sulfur compounds and heavy metals in soils located in the proximity of a disused for 20 years sulfur mine (SE Poland).

Science.gov (United States)

Sołek-Podwika, Katarzyna; Ciarkowska, Krystyna; Kaleta, Dorota

2016-09-15

The study assessed the long-term effects of anthropogenic pressure of the sulfur industry on turf-covered soils located in the vicinity of the sulfur mine Grzybów. The study assumes that 20 years which elapsed since the end of the exploitation of sulfur is a period sufficiently long for the content of sulfur compounds in soils not to exceed the permissible level and that soil of the region can be classified as not contaminated. A part of the study involved identification of changes in the contents Stot. and SSO4(2-) in soils collected in the 1970s and early twenty-first century. It was also traced the relationship between the content of sulfur compounds and selected soil properties and estimated risk of soil environment pollution by heavy metals. Mean contents of trace elements studied amounted to 10.2-10.8 mg kg(-1) for Pb, 14.3-39.4 mg kg(-1) for Zn, 0.2-0.4 mg kg(-1) for Cd, 3.8-32.2 mg kg(-1) for Cr, 2.7-15.1 mg kg(-1) for Cu and 2.9-18.7 mg kg(-1) for Ni. Based on the results of SSO4(2-) content in soils collected at a distance of 1 km from the mine, it was found out that despite the passage of years, the amount of this type of sulfur still is increased and exceeds 0.14 g kg(-1). As the distance from the mine grew lower (from 0.017 to 0.03 g kg(-1)) average content of the sulfur form was observed. In the studied soil material we found generally positive, strong correlation between the Stot. and SSO4(2-) content and analyzed trace elements. The degree of contamination of examined soils with heavy metals was estimated on the basis of the integrated pollution index, which pointed to a moderate and low level of antropogenization of this area. In addition, the relationship between the determined characteristics of soils (Corg. contents, the fraction heavy metals confirms that the trace elements present in soils do not occur in mobile forms in the soil solution. Copyright © 2016 Elsevier Ltd. All rights reserved.

Aircraft exhaust sulfur emissions

Energy Technology Data Exchange (ETDEWEB)

Brown, R C; Anderson, M R; Miake-Lye, R C; Kolb, C E [Aerodyne Research, Inc., Billerica, MA (United States). Center for Chemical and Environmental Physics; Sorokin, A A; Buriko, Y I [Scientific Research Center ` Ecolen` , Moscow (Russian Federation)

1998-12-31

The extent to which fuel sulfur is converted to SO{sub 3} during combustion and the subsequent turbine flow in supersonic and subsonic aircraft engines is estimated numerically. The analysis is based on: a flamelet model with non-equilibrium sulfur chemistry for the combustor, and a one-dimensional, two-stream model with finite rate chemical kinetics for the turbine. The results indicate that between 2% and 10% of the fuel sulfur is emitted as SO{sub 3}. It is also shown that, for a high fuel sulfur mass loading, conversion in the turbine is limited by the level of atomic oxygen at the combustor exit, leading to higher SO{sub 2} oxidation efficiency at lower fuel sulfur loadings. While SO{sub 2} and SO{sub 3} are the primary oxidation products, the model results further indicate H{sub 2}SO{sub 4} levels on the order of 0.1 ppm for supersonic expansions through a divergent nozzle. This source of fully oxidized S(6) (SO{sub 3} + H{sub 2}SO{sub 4}) exceeds previously calculated S(6) levels due to oxidation of SO{sub 2} by OH in the exhaust plume outside the engine nozzle. (author) 26 refs.

Aircraft exhaust sulfur emissions

Energy Technology Data Exchange (ETDEWEB)

Brown, R.C.; Anderson, M.R.; Miake-Lye, R.C.; Kolb, C.E. [Aerodyne Research, Inc., Billerica, MA (United States). Center for Chemical and Environmental Physics; Sorokin, A.A.; Buriko, Y.I. [Scientific Research Center `Ecolen`, Moscow (Russian Federation)

1997-12-31

The extent to which fuel sulfur is converted to SO{sub 3} during combustion and the subsequent turbine flow in supersonic and subsonic aircraft engines is estimated numerically. The analysis is based on: a flamelet model with non-equilibrium sulfur chemistry for the combustor, and a one-dimensional, two-stream model with finite rate chemical kinetics for the turbine. The results indicate that between 2% and 10% of the fuel sulfur is emitted as SO{sub 3}. It is also shown that, for a high fuel sulfur mass loading, conversion in the turbine is limited by the level of atomic oxygen at the combustor exit, leading to higher SO{sub 2} oxidation efficiency at lower fuel sulfur loadings. While SO{sub 2} and SO{sub 3} are the primary oxidation products, the model results further indicate H{sub 2}SO{sub 4} levels on the order of 0.1 ppm for supersonic expansions through a divergent nozzle. This source of fully oxidized S(6) (SO{sub 3} + H{sub 2}SO{sub 4}) exceeds previously calculated S(6) levels due to oxidation of SO{sub 2} by OH in the exhaust plume outside the engine nozzle. (author) 26 refs.

Comparison of Xe single bubble sonoluminescence in water and sulfuric acid

International Nuclear Information System (INIS)

An Yu

2008-01-01

Using the equations of fluid mechanics with proper boundary conditions and taking account of the gas properties, we can numerically simulate the process of single bubble sonoluminescence, in which electron–neutral atom bremsstrahlung, electron—ion bremsstrahlung and recombination radiation, and the radiative attachment of electrons to atoms and molecules contribute to the light emission. The calculation can quantitatively or qualitatively interpret the experimental results. We find that the accumulated heat energy inside the compressed gas bubble is mostly consumed by the chemical reaction, therefore, the maximum degree of ionization inside Xe bubble in water is much lower than that in sulfuric acid, of which the vapour pressure is very low. In addition, in sulfuric acid much larger p a and R 0 are allowed which makes the bubbles in it much brighter than that in water. (classical areas of phenomenology)

Organic anodes and sulfur/selenium cathodes for advanced Li and Na batteries

Science.gov (United States)

Luo, Chao

To address energy crisis and environmental pollution induced by fossil fuels, there is an urgent demand to develop sustainable, renewable, environmental benign, low cost and high capacity energy storage devices to power electric vehicles and enhance clean energy approaches such as solar energy, wind energy and hydroenergy. However, the commercial Li-ion batteries cannot satisfy the critical requirements for next generation rechargeable batteries. The commercial electrode materials (graphite anode and LiCoO 2 cathode) are unsustainable, unrenewable and environmental harmful. Organic materials derived from biomasses are promising candidates for next generation rechargeable battery anodes due to their sustainability, renewability, environmental benignity and low cost. Driven by the high potential of organic materials for next generation batteries, I initiated a new research direction on exploring advanced organic compounds for Li-ion and Na-ion battery anodes. In my work, I employed croconic acid disodium salt and 2,5-Dihydroxy-1,4-benzoquinone disodium salt as models to investigate the effects of size and carbon coating on electrochemical performance for Li-ion and Na-ion batteries. The results demonstrate that the minimization of organic particle size into nano-scale and wrapping organic materials with graphene oxide can remarkably enhance the rate capability and cycling stability of organic anodes in both Li-ion and Na-ion batteries. To match with organic anodes, high capacity sulfur and selenium cathodes were also investigated. However, sulfur and selenium cathodes suffer from low electrical conductivity and shuttle reaction, which result in capacity fading and poor lifetime. To circumvent the drawbacks of sulfur and selenium, carbon matrixes such as mesoporous carbon, carbonized polyacrylonitrile and carbonized perylene-3, 4, 9, 10-tetracarboxylic dianhydride are employed to encapsulate sulfur, selenium and selenium sulfide. The resulting composites exhibit

Specific ability of sulfur-ligands on removal of 203Hg-labeled organomercury from hemoglobin in comparison with nitrogen-ligands

International Nuclear Information System (INIS)

Hojo, Yasuji; Sugiura, Yukio; Tanaka, Hisashi

1975-01-01

Removal of 203 Hg-labeled organomercurials, bound to sulfhydryl groups of hemoglobin, by various chelating agents was investigated by the use of equilibrium dialysis. Organomercurials employed were chlormerodrin, methylmercury, ethylmercury and phenylmercury compounds. Higher and more specific effects of the sulfur-ligands, such as penicillamine and glutathione, on removal of organomercurial were found as compared with those of the nitrogen-ligands such as EDTA, glycine and polymethylenediamines. Linear correlation was observed between the degree of organomercury elimination from hemoglobin and the stability constant (log K 1 ) of 1:1 organomercury complex in both the sulfur- and nitrogen-ligand systems and at the same value of log K 1 , the elimination-effect of sulfur-ligands was extremely greater than that of the nitrogen-ligands. The relationship between the average percentage of removal and the Taft's polar substituent constant of organic moiety of the metal was also linear among the organomercury compounds other than chlormerodrin. The average removal percentage by sulfur-ligands increased in the order, ethylmercury>methylmercury>phenylmercury, while that of the nitrogen-ligands was not different among the organomercurials investigated. In addition, direct ligand-exchange reaction between hemoglobin-SH and the ligand coordinating-atom (S or N) against organomercurials rather than Ssub(N2) reaction via the ternary complex, hemoglobin-S-RHg-ligand, is postulated. (auth.)

Metal-free reduction of the greenhouse gas sulfur hexafluoride, formation of SF5 containing ion pairs and the application in fluorinations

KAUST Repository

Rueping, Magnus

2017-05-04

A protocol for the fast and selective two-electron reduction of the potent greenhouse gas sulfur hexafluoride (SF6) by organic electron donors at ambient temperature has been developed. The reaction yields solid ion pairs consisting of donor dications and SF5-anions which can be effectively used in fluorination reactions.

Sandwich-like graphene-mesoporous carbon as sulfur host for enhanced lithium-sulfur batteries

Science.gov (United States)

Tian, Ting; Li, Bin; Zhu, Mengqi; Liu, Jianhua; Li, Songmei

2017-10-01

Graphene-mesoporous carbon/sulfur composites (G-MPC/S) were constructed by melt-infiltration of sulfur into graphene-mesoporous carbon which was synthesized by soft template method. The SEM and BET results of the graphene-mesoporous carbon show that the as-prepared sandwich-like G-MPC composites with a unique microporous-mesoporous structure had a high specific surface area of 554.164 m2 · g-1 and an average pore size of about 13 nm. The XRD analysis presents the existence of orthorhombic sulfur in the G-MPC/S composite, which indicates the complete infiltration of sulfur into the pores of the G-MPC. When the graphene-mesoporous carbon/surfur composites (G-MPC/S) with 53.9 wt.% sulfur loading were used as the cathode for lithium-sulfur (Li-S) batteries, it exhibited an outstanding electrochemical performance including excellent initial discharge specific capacity of 1393 mAh · g-1 at 0.1 °C, high cycle stability (731 mAh · g-1 at 200 cycles) and good rate performance (1038 mAh · g-1, 770 mAh · g-1, 518 mAh · g-1 and 377 mAh · g-1 at 0.1 °C, 0.2 °C, 0.5 °C and 1 °C, respectively), which suggested the important role of the G-MPC composite in providing more electrons and ions channels, in addition, the shuttle effect caused by the dissolved polysulfide was also suppressed.

Desulfurization reaction of high sulfur content flue gas treated by electron beam

International Nuclear Information System (INIS)

Hirosawa, Shojiro; Suzuki, Ryoji; Aoki, Shinji; Kojima, Takuji; Hashimoto, Shoji

2002-01-01

Experiments of flue gas treatment by electron beam were carried out, using simulated ligniteburning flue gas containing SO 2 (5500 ppm), NO (390 ppm) and H 2 O (22%). Removal efficiency of SO 2 was more than 90% at a dose of 1-2 kGy. It shows applicability of electron beam for treatment of lignite-burning flue gas. Another removal reaction besides the radiation-induced radical reaction and the thermal reaction occurring without irradiation was suggested by the facts that removal of SO 2 by the radical reaction is only a few hundreds of ppm and the removal amounts by thermal reaction under irradiation is lower than a half of total desulfurization. The mechanism similar to thermal reaction was proposed, assuming simultaneous uptake reaction of SO 2 and NH 3 on the surface of liquid aerosol. It was suggested that ammonium nitrate having deliquescence relative humidity (DRH) of 60% at 25 deg C plays an important role in producing liquid aerosols. Decrease of DRH of ammonium nitrate with elevating temperature and with formation of double salt of ammonium sulfate results in enhancement of formation of liquid aerosols. (author)

Experimental studies on optimal process of the iodine-sulfur cycle for nuclear hydrogen production

Energy Technology Data Exchange (ETDEWEB)

Yoon, Ho Joon

2010-02-15

For nuclear hydrogen production, we selected Iodine-Sulfur (I-S) cycle as the most promising one by screening process among 115 thermo-chemical water splitting technologies. We developed a thermo-physical model for the hydrogen-iodide (HI) VLE and decomposition behavior in the iodine-sulfur (IS) cycle to improve the conventional I-S cycle suggested by GA. Neumann's modified NRTL model was improved by correcting an unphysical assumption for the non-randomness parameter, and using the two-step equilibrium approach for the HI decomposition modeling. However, the parameters of the model were decided through regression with the 271 sets of existing experimental data: the accuracy of the model should be improved by more experimental data over all operating ranges, especially, in the high temperature and high pressure regions. To obtain the data of those regions, an autoclave for high temperature and high pressure was designed and manufactured. Various materials and surface coating technologies were investigated for preventing corrosion from acids. However, we have currently failed to overcome the corrosion problems with highly corrosive acids at a high temperature and high pressure. We experimentally validated that azeotropic constraint between acid and H{sub 2}O undermined the total efficiency of the I-S cycle. As mentioned above, the conventional I-S cycle suffers from low thermal efficiency and highly corrosive streams. To alleviate these problems, we have proposed the optimal operating conditions for the Bunsen reaction and devised a new KAIST flowsheet that produces highly enriched HI through spontaneous L-L phase separation and simple flash processes under low pressure. A series of phase separation experiments were performed to validate the new flowsheet and extend its feasibility. When the molar ratio of I{sub 2}/H{sub 2}SO{sub 4} in the feed increased from 2 to 4, the molar ratio of HI/(HI+H{sub 2}O) in the HI{sub x} phase improved from 0.157 to 0.22, which

Experimental studies on optimal process of the iodine-sulfur cycle for nuclear hydrogen production

International Nuclear Information System (INIS)

Yoon, Ho Joon

2010-02-01

For nuclear hydrogen production, we selected Iodine-Sulfur (I-S) cycle as the most promising one by screening process among 115 thermo-chemical water splitting technologies. We developed a thermo-physical model for the hydrogen-iodide (HI) VLE and decomposition behavior in the iodine-sulfur (IS) cycle to improve the conventional I-S cycle suggested by GA. Neumann's modified NRTL model was improved by correcting an unphysical assumption for the non-randomness parameter, and using the two-step equilibrium approach for the HI decomposition modeling. However, the parameters of the model were decided through regression with the 271 sets of existing experimental data: the accuracy of the model should be improved by more experimental data over all operating ranges, especially, in the high temperature and high pressure regions. To obtain the data of those regions, an autoclave for high temperature and high pressure was designed and manufactured. Various materials and surface coating technologies were investigated for preventing corrosion from acids. However, we have currently failed to overcome the corrosion problems with highly corrosive acids at a high temperature and high pressure. We experimentally validated that azeotropic constraint between acid and H 2 O undermined the total efficiency of the I-S cycle. As mentioned above, the conventional I-S cycle suffers from low thermal efficiency and highly corrosive streams. To alleviate these problems, we have proposed the optimal operating conditions for the Bunsen reaction and devised a new KAIST flowsheet that produces highly enriched HI through spontaneous L-L phase separation and simple flash processes under low pressure. A series of phase separation experiments were performed to validate the new flowsheet and extend its feasibility. When the molar ratio of I 2 /H 2 SO 4 in the feed increased from 2 to 4, the molar ratio of HI/(HI+H 2 O) in the HI x phase improved from 0.157 to 0.22, which is high enough to generate

Study of vanadium(IV) species and corresponding electrochemical performance in concentrated sulfuric acid media

International Nuclear Information System (INIS)

Wu Xuewen; Wang Jinjin; Liu Suqin; Wu Xiongwei; Li Sha

2011-01-01

Highlights: → Two new UV/Vis absorbance peaks are found in V(IV) sulfuric acid solutions. → We give the structural information on the new corresponding V(IV) species. → Reaction route is given with increasing sulfuric acid and V(IV) concentrations. → We find V(IV) species corresponding to the reversible electrochemical reaction. → A mixed-valence intermediate is invoked in the reversible reaction. - Abstract: The vanadium(IV) ion is found to form the [VO(SO 4 )(H 2 O) 4 ].H 2 O complex, as well as the dimer, [VO(H 2 O) 3 ] 2 (μ-SO 4 ) 2 , in concentrated H 2 SO 4 media. Their formation mechanisms were investigated by UV-Visible spectroscopy (UV-Vis), Raman spectroscopy, X-ray diffraction (XRD), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). UV-Vis spectroscopy study showed that [VO(SO 4 )(H 2 O) 4 ].H 2 O concentration in H 2 SO 4 solution was proportional to concentrations of VO 2+ and SO 4 2- . The increased deviation from the near centrosymmetry of the octahedral complexes is due to the replacement of an equatorial water oxygen in [VO(H 2 O) 5 ]SO 4 by a sulfate oxygen in [VO(SO 4 )(H 2 O) 4 ].H 2 O. The dimer shows symmetrical structure, which correlates very well with non-activity in UV-Vis spectroscopic analysis. Structural information on both vanadium(IV) species can be confirmed by Raman and XRD measurements of crystals from the supersaturated solution of VOSO 4 in 1 M, 6 M and 12 M sulfuric acid. A solution of vanadium(IV) (0.05 M) in 12 M H 2 SO 4 , in which the vanadium(IV) species is [VO(H 2 O) 3 ] 2 (μ-SO 4 ) 2 , exhibits a reversible redox behavior near 1.14 V (vs. SCE) on the carbon paper electrode.

Nitrogen and sulfur co-doped porous carbon – is an efficient electrocatalyst as platinum or a hoax for oxygen reduction reaction in acidic environment PEM fuel cell?

International Nuclear Information System (INIS)

Sahoo, Madhumita; Ramaprabhu, S.

2017-01-01

Non-precious, heteroatom doped carbon is reported to replace commercial Pt/C in both alkaline and acidic half-cell rotating disc electrode study; however the real world full cell measurements with the metal-free electrocatalysts overcoming the practical troubles in acidic environment proton exchange membrane fuel cell (PEMFC) are almost negligible to confirm the claim. Nitrogen and sulfur co-doped porous carbon (DPC) was synthesized in a one step, high yield process from single source ionic liquid precursor using eutectic salt as porogens to achieve porosity. Structural characterization confirms 7.03% nitrogen and 1.68% sulfur doping into the high surface area, porous carbon structure. As the cathode oxygen reduction reaction (ORR) catalyst, metal-free DPC and Pt nanoparticles decorated DPC (Pt/DPC) shows stable and high exchange current density by four electron transfer pathway in acidic half–cell liquid environment due to the synergistic effect of nitrogen and sulfur doping and porous nature of DPC. In an actual solid state full cell measurement, Pt/DPC shows higher performance comparable to commercial Pt/C; however DPC failed to reciprocate the half-cell performance due to blockage of active sites in the membrane electrode assembly fabrication process. - Highlights: • Synthesis of N and S co-doped porous carbon (DPC) in simple one-pot technique. • High surface area DPC shows comparable activity for ORR in half-cell acidic PEMFC study. • Real-world performance of DPC gives 20 mW/cm 2 peak power density at 60 °C. • Homogeneous Pt nanoparticles decorated DPC (Pt/DPC) outperforms commercial Pt/C. • Pt/DPC shows maximum power density of 718 mW/cm 2 with lower 0.3 mg/cm 2 total Pt loading.

Parameters Influencing Sulfur Speciation in Environmental Samples Using Sulfur K-Edge X-Ray Absorption Near-Edge Structure

Directory of Open Access Journals (Sweden)

Siwatt Pongpiachan

2012-01-01

Full Text Available This paper aims to enhance the credibility of applying the sulfur K-edge XANES spectroscopy as an innovative “fingerprint” for characterizing environmental samples. The sensitivities of sulfur K-edge XANES spectra of ten sulfur compound standards detected by two different detectors, namely, Lytle detector (LyD and Germanium detector (GeD, were studied and compared. Further investigation on “self-absorption” effect revealed that the maximum sensitivities of sulfur K-edge XANES spectra were achieved when diluting sulfur compound standards with boron nitride (BN at the mixing ratio of 0.1%. The “particle-size” effect on sulfur K-edge XANES spectrum sensitivities was examined by comparing signal-to-noise ratios of total suspended particles (TSP and particulate matter of less than 10 millionths of a meter (PM10 collected at three major cities of Thailand. The analytical results have demonstrated that the signal-to-noise ratios of sulfur K-edge XANES spectra were positively correlated with sulfate content in aerosols and negatively connected with particle sizes. The combination of hierarchical cluster analysis (HCA and principal component analysis (PCA has proved that sulfur K-edge XANES spectrum can be used to characterize German terrestrial soils and Andaman coastal sediments. In addition, this study highlighted the capability of sulfur K-edge XANES spectra as an innovative “fingerprint” to distinguish tsunami backwash deposits (TBD from typical marine sediments (TMS.

Nitrogen and sulfur co-doped graphene/carbon nanotube as metal-free electrocatalyst for oxygen evolution reaction: the enhanced performance by sulfur doping

International Nuclear Information System (INIS)

Zhao, Jujiao; Liu, Yanming; Quan, Xie; Chen, Shuo; Zhao, Huimin; Yu, Hongtao

2016-01-01

Highlights: • Metal-free 3D architecture N,S co-doped GR/CNT is prepared by a one-step method. • N,S co-doped GR/CNT exhibits good activity and stability for OER. • S doping is indicated beneficial for OER performance of metal-free catalysts. • The catalytic kinetics is highly correlated with the content of C-S-C structure. • 3D architecture composed of GR and CNT also contributes to the OER activity. - Abstract: Highly active metal-free electrocatalysts consisting of earth-abundant elements for oxygen evolution reaction (OER) are extremely desired for renewable energy technologies. Here we prepare the nitrogen and sulfur co-doped graphene/carbon nanotube (NS-GR/CNT) with 3D architecture by one-step hydrothermal method, which presents good performance for OER. The as-prepared NS-GR/CNT exhibits more negative onset potential and lower Tafel slope (0.56 V, 103 mV decade"−"1 vs. S.C.E. in 0.1 M KOH) compared to single N doped graphene/carbon nanotube (0.65 V, 285 mV decade"−"1), which indicates S doping can significantly enhance the OER performance. The X-ray photoelectron spectroscopy reveals that the thiophene-like S (C-S-C) is the dominant S species in all the S doped samples. NS-GR/CNT with C-S-C content of 0.26% has the Tafel slope of 151 mV decade"−"1 while the value for NS-GR/CNT with C-S-C content of 1.09% is 103 mV decade"−"1. The decreased Tafel slope demonstrates the catalytic kinetics are highly correlated with the content of C-S-C. Density functional theory calculations suggest that C-S-C may improve the catalytic kinetics by facilitating the adsorption of the OH"− intermediate. Besides, the 3D architecture composed of graphene and CNTs also contributes to the good performance and chronoamperometric measurement demonstrates the good durability of NS-GR/CNTs.

Flow injection gas chromatography with sulfur chemiluminescence detection for the analysis of total sulfur in complex hydrocarbon matrixes.

Science.gov (United States)

Hua, Yujuan; Hawryluk, Myron; Gras, Ronda; Shearer, Randall; Luong, Jim

2018-01-01

A fast and reliable analytical technique for the determination of total sulfur levels in complex hydrocarbon matrices is introduced. The method employed flow injection technique using a gas chromatograph as a sample introduction device and a gas phase dual-plasma sulfur chemiluminescence detector for sulfur quantification. Using the technique described, total sulfur measurement in challenging hydrocarbon matrices can be achieved in less than 10 s with sample-to-sample time ideal for fast analysis or trace sulfur analysis. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A primer on sulfur for the planetary geologist

Science.gov (United States)

Theilig, E.

1982-01-01

Sulfur has been proposed as the dominant composition for the volcanic material on Io. Sulfur is a complex element which forms many intramolecular and intermolecular allotropes exhibiting a variety of physical properties. Cyclo-S8 sulfur is the most abundant and stable molecular form. The important molecular species within liquid sulfur change in concentration with temperature. Concentrations of the allotropes control the physical properties of the melt. Discontinuities in density, viscosity, and thermal properties reflect the polymerization process within liquid sulfur. Variations in the melting point are related to autodissociation of the liquid. Many solids forms of sulfur have been identified but only orthorhombic alpha and monoclinic beta sulfur, both composed of cyclo-S8 sulfur, are stable under terrestrial conditions. Physical properties of solid sulfur are dependent on the allotrope and, in some cases, the thermal history. Three natural terrestrial sulfur flows are described: (1) Siretoko-Iosan, Japan; (2) Volcan Azufre, Galapagos Islands; and (3) Mauna Loa, Hawaii. All of the flows are associated with fumarolic areas and are considered to have formed by the melting and mobilization of sulfur deposits. Surface textures of the flows indicate a behavior of molten sulfur similar to that of silicate lava. Channels, rivulets, and lobate edges were described for the flows. The solidification of man-made sulfur flows formed as part of the Frasch mining process by which sulfur is removed from the subsurface in a liquid state is described.

Mercury adsorption properties of sulfur-impregnated adsorbents

Science.gov (United States)

Hsi, N.-C.; Rood, M.J.; Rostam-Abadi, M.; Chen, S.; Chang, R.

2002-01-01

Carbonaceous and noncarbonaceous adsorbents were impregnated with elemental sulfur to evaluate the chemical and physical properties of the adsorbents and their equilibrium mercury adsorption capacities. Simulated coal combustion flue gas conditions were used to determine the equilibrium adsorption capacities for Hg0 and HgCl2 gases to better understand how to remove mercury from gas streams generated by coal-fired utility power plants. Sulfur was deposited onto the adsorbents by monolayer surface deposition or volume pore filling. Sulfur impregnation increased the total sulfur content and decreased the total and micropore surface areas and pore volumes for all of the adsorbents tested. Adsorbents with sufficient amounts of active adsorption sites and sufficient microporous structure had mercury adsorption capacities up to 4,509 ??g Hg/g adsorbent. Elemental sulfur, organic sulfur, and sulfate were formed on the adsorbents during sulfur impregnation. Correlations were established with R2>0.92 between the equilibrium Hg0/HgCl2 adsorption capacities and the mass concentrations of elemental and organic sulfur. This result indicates that elemental and organic sulfur are important active adsorption sites for Hg0 and HgCl2.

10 CFR 39.39 - Records of material use.

Science.gov (United States)

2010-01-01

... 10 Energy 1 2010-01-01 2010-01-01 false Records of material use. 39.39 Section 39.39 Energy NUCLEAR REGULATORY COMMISSION LICENSES AND RADIATION SAFETY REQUIREMENTS FOR WELL LOGGING Equipment § 39.39 Records of material use. (a) Each licensee shall maintain records for each use of licensed...

Mixing-assisted oxidative desulfurization of model sulfur compounds using polyoxometalate/H2O2 catalytic system

Directory of Open Access Journals (Sweden)

Angelo Earvin Sy Choi

2016-07-01

Full Text Available Desulfurization of fossil fuel derived oil is needed in order to comply with environmental regulations. Dibenzothiophene and benzothiophene are among the predominant sulfur compound present in raw diesel oil. In this study, mixing-assisted oxidative desulfurization of dibenzothiophene and benzothiophene were carried out using polyoxometalate/H2O2 systems and a phase transfer agent. The effects of reaction time (2–30 min and temperature (30–70 °C were examined in the oxidation of model sulfur compounds mixed in toluene. A pseudo first-order reaction kinetic model and the Arrhenius equation were utilized in order to evaluate the kinetic rate constant and activation energy of each catalyst tested in the desulfurization process. Results showed the order of catalytic activity and activation energy of the different polyoxometalate catalysts to be H3PW12O40 > H3PM12O40 > H4SiW12O40 for both dibenzothiophene and benzothiophene.

Sulfonation of polyester fabrics by gaseous sulfur oxide activated by UV irradiation

Energy Technology Data Exchange (ETDEWEB)

Kordoghli, Bessem [Laboratory of Applied Chemical and Environment (UR-CAE) - University of Monastir (Tunisia); Textile Research Laboratory (LRT) - ISET Kasr Hellal, University of Monastir (Tunisia); Khiari, Ramzi, E-mail: khiari_ramzi2000@yahoo.fr [Laboratory of Applied Chemical and Environment (UR-CAE) - University of Monastir (Tunisia); LGP2 - Laboratory of Pulp and Paper Science, 461, Rue de la Papeterie - BP 65, 38402 Saint Martin d' Heres Cedex (France); Mhenni, Mohamed Farouk [Laboratory of Applied Chemical and Environment (UR-CAE) - University of Monastir (Tunisia); Sakli, Faouzi [Textile Research Laboratory (LRT) - ISET Kasr Hellal, University of Monastir (Tunisia); Belgacem, Mohamed Naceur [LGP2 - Laboratory of Pulp and Paper Science, 461, Rue de la Papeterie - BP 65, 38402 Saint Martin d' Heres Cedex (France)

2012-10-01

Highlights: Black-Right-Pointing-Pointer In this paper, an original technique was present to improve the hydrophilic properties of polyester fibres. Black-Right-Pointing-Pointer The modification of PET fabric was carried out using gaseous sulfur trioxide activated by UV irradiations. Black-Right-Pointing-Pointer We fully characterized the modified and untreated fabrics. - Abstract: This paper describes an original technique aiming to improve the hydrophilic properties of polyester fibres. In this method, the sulfonation of the aromatic rings is carried out using gaseous sulfur trioxide activated by UV irradiations. Thus, exposing the polyester textile fabric to the UVC light (wavelength around 254 nm) under a stream of sulfur trioxide leads to the fixation of -SO{sub 3}H groups. The amounts of the fixed sulfonate groups depended on the reaction conditions. Evidence of grafting deduced from the measurements of hygroscopic properties was carried out by contact angle measurement, moisture regain as well as by measuring the rate of retention. SEM and FT-IR analysis, DSC and DTA/TGA thermograms showed that no significant modifications have occurred in the bulk of the treated PET fabrics.

Climate and air quality trade-offs in altering ship fuel sulfur content

Science.gov (United States)

Partanen, A.-I.; Laakso, A.; Schmidt, A.; Kokkola, H.; Kuokkanen, T.; Pietikäinen, J.-P.; Kerminen, V.-M.; Lehtinen, K. E. J.; Laakso, L.; Korhonen, H.

2013-08-01

Aerosol particles from shipping emissions both cool the climate and cause adverse health effects. The cooling effect is, however, declining because of shipping emission controls aiming to improve air quality. We used an aerosol-climate model ECHAM-HAMMOZ to test whether by altering ship fuel sulfur content, the present-day aerosol-induced cooling effect from shipping could be preserved while at the same time reducing premature mortality rates related to shipping emissions. We compared the climate and health effects of a present-day shipping emission scenario with (1) a simulation with strict emission controls in the coastal waters (ship fuel sulfur content of 0.1%) and twofold ship fuel sulfur content compared to current global average of 2.7% elsewhere; and (2) a scenario with global strict shipping emission controls (ship fuel sulfur content of 0.1% in coastal waters and 0.5% elsewhere) roughly corresponding to international agreements to be enforced by the year 2020. Scenario 1 had a slightly stronger aerosol-induced radiative flux perturbation (RFP) from shipping than the present-day scenario (-0.43 W m-2 vs. -0.39 W m-2) while reducing premature mortality from shipping by 69% (globally 34 900 deaths avoided per year). Scenario 2 decreased the RFP to -0.06 W m-2 and annual deaths by 96% (globally 48 200 deaths avoided per year) compared to present-day. A small difference in radiative effect (global mean of 0.04 W m-2) in the coastal regions between Scenario 1 and the present-day scenario imply that shipping emission regulation in the existing emission control areas should not be removed in hope of climate cooling. Our results show that the cooling effect of present-day emissions could be retained with simultaneous notable improvements in air quality, even though the shipping emissions from the open ocean clearly have a significant effect on continental air quality. However, increasing ship fuel sulfur content in the open ocean would violate existing

46 CFR 151.50-21 - Sulfuric acid.

Science.gov (United States)

2010-10-01

... 46 Shipping 5 2010-10-01 2010-10-01 false Sulfuric acid. 151.50-21 Section 151.50-21 Shipping... BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-21 Sulfuric acid. (a) How sulfuric acid may be carried. (1) Sulfuric acid of concentration of 77.5 percent (1.7019 specific gravity) (59.8...

Effect of sulfur loading on the desulfation chemistry of a commercial lean NOx trap catalyst

Energy Technology Data Exchange (ETDEWEB)

Kim, Do Heui; Yezerets, Aleksey; Li, Junhui; Currier, Neal; Chen, Haiying; Hess, Howard ..; Engelhard, Mark H.; Muntean, George G.; Peden, Charles HF

2012-12-15

We investigate the effects of initial sulfur loadings on the desulfation chemistry and the subsequent final activity of a commercial LNT catalyst. Identical total amounts of SO2 are applied to the samples, albeit with the frequency of desulfation varied. The results indicate that performance is better with less frequent desulfations. The greater the amount of sulfur deposited before desulfation, the more amount of SO2 evolution before H2S is observed during desulfation, which can be explained by two sequential reactions; initial conversion of sulfate to SO2, followed by the reduction of SO2 to H2S. After completing all sulfation/desulfation steps, the sample with only a single desulfation results in a fairly uniform sulfur distribution along the z-axis inside of the monolith. We expect that the results obtained in this study will provide useful information for optimizing regeneration strategies in vehicles that utilize the LNT technology.

Towards Stable Lithium-Sulfur Batteries with a Low Self-Discharge Rate: Ion Diffusion Modulation and Anode Protection.

Science.gov (United States)

Xu, Wen-Tao; Peng, Hong-Jie; Huang, Jia-Qi; Zhao, Chen-Zi; Cheng, Xin-Bing; Zhang, Qiang

2015-09-07

The self-discharge of a lithium-sulfur cell decreases the shelf-life of the battery and is one of the bottlenecks that hinders its practical applications. New insights into both the internal chemical reactions in a lithium-sulfur system and effective routes to retard self-discharge for highly stable batteries are crucial for the design of lithium-sulfur cells. Herein, a lithium-sulfur cell with a carbon nanotube/sulfur cathode and lithium-metal anode in lithium bis(trifluoromethanesulfonyl)imide/1,3-dioxolane/dimethyl ether electrolyte was selected as the model system to investigate the self-discharge behavior. Both lithium anode passivation and polysulfide anion diffusion suppression strategies are applied to reduce self-discharge of the lithium-sulfur cell. When the lithium-metal anode is protected by a high density passivation layer induced by LiNO3 , a very low shuttle constant of 0.017 h(-1) is achieved. The diffusion of the polysulfides is retarded by an ion-selective separator, and the shuttle constants decreased. The cell with LiNO3 additive maintained a discharge capacity of 97 % (961 mAh g(-1) ) of the initial capacity after 120 days at open circuit, which was around three times higher than the routine cell (32 % of initial capacity, corresponding to 320 mAh g(-1) ). It is expected that lithium-sulfur batteries with ultralow self-discharge rates may be fabricated through a combination of anode passivation and polysulfide shuttle control, as well as optimization of the lithium-sulfur cell configuration. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Proton an alpha detections by track recording technique in CR-39

International Nuclear Information System (INIS)

Oliveira, W.A. de; Franco, M.A.R.; Herdade, S.B.; Khouri, M.C.F.; Goncalez, O.L.

1986-07-01

The plastic CR-39 is utilized as proton track detector in the study of the reaction 27 A (e, p) and 59 Co (e, p), near threshold. Preliminary results are presented for the energy calibration (mean track diameter as a function of proton energy) of CR-39 with mono-energetic protons of a Van de Graaff accelerator, in the energy range 1-3 MeV. (author) [pt

46 CFR 153.1046 - Sulfuric acid.

Science.gov (United States)

2010-10-01

... 46 Shipping 5 2010-10-01 2010-10-01 false Sulfuric acid. 153.1046 Section 153.1046 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SHIPS CARRYING BULK....1046 Sulfuric acid. No person may liquefy frozen or congealed sulfuric acid other than by external tank...

Biomedical tracers: technetium-99 m complexing sulfur polydentate ligands

International Nuclear Information System (INIS)

Bendennoune, A.

1994-01-01

Cyclic and acyclic tetra sulfur ligands have been synthesized and some of them have been labelled with technetium-99m. These works have two different aims: 1- Development of methods permitting to obtain easily potential technetium complexing sulfur polydentate chelates. 2- Research of positive and neutral complexes of this metal likely to replace thalium-201 in the coronary flow estimation and [TcO-HMPAO] sup 0 complex in the cerebral scintigraphy, respectively. In this work, first, different ways for obtaining dithioetherdithiols and cyclic tetrathioethers containing functional groups have been carried out, then complexation of the core of nitrutechnetium (TcN) sup 2+ at tracers scale, by dithioetherdithiols, using exchange reaction with [sup 9 sup 9 sup m TcNCl sub 4 ] sup - ion complex or sup 99 sup m TcN Cl sub 2 [P(CH sub 2 CH sub 2 CN) sub 3 ] sub 2 has been studied. Finally, biological distribution in swiss mouse of these technetiated complexes has been studied. 135 refs., 30 figs., 13 tabs. (F.M.)

UV-Photochemistry of the Disulfide Bond: Evolution of Early Photoproducts from Picosecond X-ray Absorption Spectroscopy at the Sulfur K-Edge.

Science.gov (United States)

Ochmann, Miguel; Hussain, Abid; von Ahnen, Inga; Cordones, Amy A; Hong, Kiryong; Lee, Jae Hyuk; Ma, Rory; Adamczyk, Katrin; Kim, Tae Kyu; Schoenlein, Robert W; Vendrell, Oriol; Huse, Nils

2018-05-30

We have investigated dimethyl disulfide as the basic moiety for understanding the photochemistry of disulfide bonds, which are central to a broad range of biochemical processes. Picosecond time-resolved X-ray absorption spectroscopy at the sulfur K-edge provides unique element-specific insight into the photochemistry of the disulfide bond initiated by 267 nm femtosecond pulses. We observe a broad but distinct transient induced absorption spectrum which recovers on at least two time scales in the nanosecond range. We employed RASSCF electronic structure calculations to simulate the sulfur-1s transitions of multiple possible chemical species, and identified the methylthiyl and methylperthiyl radicals as the primary reaction products. In addition, we identify disulfur and the CH 2 S thione as the secondary reaction products of the perthiyl radical that are most likely to explain the observed spectral and kinetic signatures of our experiment. Our study underscores the importance of elemental specificity and the potential of time-resolved X-ray spectroscopy to identify short-lived reaction products in complex reaction schemes that underlie the rich photochemistry of disulfide systems.

Sensing sulfur oxides and other sulfur bearing pollutants with solid electrolyte pellets. I. Gas concentration cells

Energy Technology Data Exchange (ETDEWEB)

Chamberland, A M; Gauthier, J M

1977-01-01

A new sensing technique using a solid electrolyte has been demonstrated for sulfur-bearing pollutants. Based on potentiometric measurements across a pellet of potassium sulfate, this sensor allows concentrations of sulfur dioxides, sulfur trioxide, hydrogen sulfide, methyl mercaptan and carbonyl sulfide in air to be measured with accuracy. Its operational concentration range at the present time is 0.1 ppM up to at least 10,000 ppM. The presence of other common pollutants such as carbon dioxide, methane, nitric oxide and nitrogen dioxide does not interfere with the measurement of air samples containing sulfur-bearing pollutants.

Relationship Between Equilibrium Hydrogen Pressure and Exchange Current for the Hydrogen Electrode-Reaction at Mmni(3.9-X)Mn(0.4)A1(X)Co(0.7) Alloy Electrodes

NARCIS (Netherlands)

Senoh, H.; Morimoto, K.; Inoue, H.; Iwakura, C.; Notten, P.H.L.

2000-01-01

We present a theoretical relationship between equilibrium hydrogen pressure and exchange current for the hydrogen electrode reaction which considers the degree of hydrogen coverage at the electrode surface. Electrochemical measurements at MmNi3.9–xMn0.4AlxCo0.7 (0 x 0.8) electrodes were performed to

Development of neutron dosimeter using CR-39 for measurement of ambient dose equivalent

International Nuclear Information System (INIS)

Maki, Daisuke; Shinozaki, Wakako; Ohguchi, Hiroyuki; Yamamoto, Takayoshi; Nakamura, Takayoshi

2010-01-01

A CR-39 has good advantages such as cumulative type dosimeter, small fading effect and gamma-ray insensitive. Therefore, we developed the wide energy-range environmental neutron dosimeter using eight CR-39s for area monitoring in this study. This dosimeter is made of octagonal columnar polyethylene block which height is 60 mm and bottom side is 25 mm. The dosimeter contains two types of CR-39s for fast neutron detection and slow neutron detection. Four CR-39s for fast neutron detection are used for detection of recoil protons produced by H (n, p) reactions. Four CR-39s for slow neutron detection are used with boron nitride converter to detect alpha-rays produced by 10 B (n, α) 7 Li reactions. Ambient dose equivalent is obtained by adding the number of etch-pits observed in four CR-39s for fast neutron detection to the number of etch-pits observed in four CR-39s for slow neutron detection with appropriate constants respectively. Dosimeters were irradiated with some energetic neutrons and evaluated results of ambient dose equivalent were compared with results from neutron transport calculations. Energy response of dosimeter shows good agreement with neutron fluence to ambient dose equivalent conversion coefficients. Directional dependence of dosimeter is at the same level as the rem-counter. (author)

Trace Elements and Minerals in Fumarolic Sulfur: The Case of Ebeko Volcano, Kuriles

Directory of Open Access Journals (Sweden)

E. P. Shevko

2018-01-01

Full Text Available Native sulfur deposits on fumarolic fields at Ebeko volcano (Northern Kuriles, Russia are enriched in chalcophile elements (As-Sb-Se-Te-Hg-Cu and contain rare heavy metal sulfides (Ag2S, HgS, and CuS, native metal alloys (Au2Pd, and some other low-solubility minerals (CaWO4, BaSO4. Sulfur incrustations are impregnated with numerous particles of fresh and altered andesite groundmass and phenocrysts (pyroxene, magnetite as well as secondary minerals, such as opal, alunite, and abundant octahedral pyrite crystals. The comparison of elemental abundances in sulfur and unaltered rocks (andesite demonstrated that rock-forming elements (Ca, K, Fe, Mn, and Ti and other lithophile and chalcophile elements are mainly transported by fumarolic gas as aerosol particles, whereas semimetals (As, Sb, Se, and Te, halogens (Br and I, and Hg are likely transported as volatile species, even at temperatures slightly above 100°C. The presence of rare sulfides (Ag2S, CuS, and HgS together with abundant FeS2 in low-temperature fumarolic environments can be explained by the hydrochloric leaching of rock particles followed by the precipitation of low-solubility sulfides induced by the reaction of acid solutions with H2S at ambient temperatures. The elemental composition of native sulfur can be used to qualitatively estimate elemental abundances in low-temperature fumarolic gases.

21 CFR 582.1095 - Sulfuric acid.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Sulfuric acid. 582.1095 Section 582.1095 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS....1095 Sulfuric acid. (a) Product. Sulfuric acid. (b) Conditions of use. This substance is generally...

Reaction of Sulfuric Acid in Lube Oil: Implications for Large Two-Stroke Diesel Engines

DEFF Research Database (Denmark)

Lejre, Kasper Hartvig; Kiil, Søren; Glarborg, Peter

2017-01-01

Slow-steaming operation and an increased pressure in the combustion chamber have contributed to increased sulfuric acid (H2SO4) condensation on the cylinder liners in large two-stroke marine diesel engines, thus causing increased corrosion wear. To cope with this, lube oils are formulated...... of CaCO3 compared to the condensed H2SO4. The observed corrosion wear in large two-stroke marine diesel engines could consequently be attributed to local molar excess of H2SO4 compared to CaCO3 reverse micelles on the cylinder liners....

Io's theothermal (sulfur) - Lithosphere cycle inferred from sulfur solubility modeling of Pele's magma supply

Science.gov (United States)

Battaglia, Steven M.; Stewart, Michael A.; Kieffer, Susan W.

2014-06-01

Surface deposits of volatile compounds such as water (Earth) or sulfur (Io) on volcanically active bodies suggest that a magmatic distillation process works to concentrate volatiles in surface reservoirs. On Earth, this is the combined hydrologic and tectonic cycle. On Io, sulfurous compounds are transferred from the interior to the surface reservoirs through a combination of a mantle-sourced magmatic system, vertical cycling of the lithosphere, and a sulfur-dominated crustal thermal system that we here call the "theothermal" system. We present a geochemical analysis of this process using previously inferred temperature and oxygen fugacity constraints of Pele's basaltic magma to determine the behavior of sulfur in the ionian magmas. Sulfate to sulfide ratios of Pele's magma are -4.084 ± 0.6 and -6.442 ± 0.7 log10 units, comparable to or lower than those of mid-ocean ridge basalts. This reflects the similarity of Io's oxidation state with Earth's depleted mantle as previously suggested by Zolotov and Fegley (Zolotov, M.Y., Fegley, B. [2000]. Geophys. Res. Lett. 27, 2789-2792). Our calculated limits of sulfur solubility in melts from Pele's patera (˜1100-1140 ppm) are also comparable to terrestrial mid-ocean ridge basalts, reflecting a compositional similarity of mantle sources. We propose that the excess sulfur obvious on Io's surface comes from two sources: (1) an insoluble sulfide liquid phase in the magma and (2) theothermal near-surface recycling.

Quantification of Discrete Oxide and Sulfur Layers on Sulfur-Passivated InAs by XPS

National Research Council Canada - National Science Library

Petrovykh, D. Y; Sullivan, J. M; Whitman, L. J

2005-01-01

.... The S-passivated InAs(001) surface can be modeled as a sulfur-indium-arsenic layer-cake structure, such that characterization requires quantification of both arsenic oxide and sulfur layers that are at most a few monolayers thick...

Sulfur and Oxygen Isotope Fractionation During Bacterial Sulfur Disproportionation Under Anaerobic Haloalkaline Conditions

NARCIS (Netherlands)

Poser, Alexander; Vogt, Carsten; Knöller, Kay; Sorokin, Dimitry Y.; Finster, Kai W.; Richnow, Hans H.

2016-01-01

Sulfur and oxygen isotope fractionation of elemental sulfur disproportionation at anaerobic haloalkaline conditions was evaluated for the first time. Isotope enrichment factors of the strains Desulfurivibrio alkaliphilus and Dethiobacter alkaliphilus growing at pH 9 or 10 were −0.9‰ to −1‰ for

Model Prebiotic Iron-Sulfur Peptides

Science.gov (United States)

Bonfio, C.; Scintilla, S.; Shah, S.; Evans, D. J.; Jin, L.; Szostak, J. W.; Sasselov, D. D.; Sutherland, J. D.; Mansy, S. S.

2017-07-01

Iron-sulfur clusters form easily in aqueous solution in the presence of thiolates and iron ions. Polymerization of short, iron-sulfur binding tripeptide sequences leads to ferredoxin-like ligand spacing and activity.

Thiocarbamate-Directed Tandem Olefination-Intramolecular Sulfuration of Two Ortho C-H Bonds: Application to Synthesis of a COX-2 Inhibitor.

Science.gov (United States)

Li, Wendong; Zhao, Yingwei; Mai, Shaoyu; Song, Qiuling

2018-02-16

A palladium-catalyzed dual ortho C-H bond activation of aryl thiocarbamates is developed. This tandem reaction initiates by thiocarbamate-directed ortho C-H palladation, which leads to favorable olefin insertion rather than reductive elimination. The oxidative Heck reaction followed by another C-H activation and sulfuration affords the dual-functionalized products. This reaction provides a concise route to the S,O,C multisubstituted benzene skeleton which could be successfully applied for the synthesis of a COX-2 inhibitor.

Cell Concepts of Metal-Sulfur Batteries (Metal = Li, Na, K, Mg): Strategies for Using Sulfur in Energy Storage Applications.

Science.gov (United States)

Medenbach, Lukas; Adelhelm, Philipp

2017-09-29

There is great interest in using sulfur as active component in rechargeable batteries thanks to its low cost and high specific charge (1672 mAh/g). The electrochemistry of sulfur, however, is complex and cell concepts are required, which differ from conventional designs. This review summarizes different strategies for utilizing sulfur in rechargeable batteries among membrane concepts, polysulfide concepts, all-solid-state concepts as well as high-temperature systems. Among the more popular lithium-sulfur and sodium-sulfur batteries, we also comment on recent results on potassium-sulfur and magnesium-sulfur batteries. Moreover, specific properties related to the type of light metal are discussed.

Catalytic mechanism of Sep-tRNA:Cys-tRNA synthase: sulfur transfer is mediated by disulfide and persulfide.

Science.gov (United States)

Liu, Yuchen; Dos Santos, Patricia C; Zhu, Xiang; Orlando, Ron; Dean, Dennis R; Söll, Dieter; Yuan, Jing

2012-02-17

Sep-tRNA:Cys-tRNA synthase (SepCysS) catalyzes the sulfhydrylation of tRNA-bound O-phosphoserine (Sep) to form cysteinyl-tRNA(Cys) (Cys-tRNA(Cys)) in methanogens that lack the canonical cysteinyl-tRNA synthetase (CysRS). A crystal structure of the Archaeoglobus fulgidus SepCysS apoenzyme provides information on the binding of the pyridoxal phosphate cofactor as well as on amino acid residues that may be involved in substrate binding. However, the mechanism of sulfur transfer to form cysteine was not known. Using an in vivo Escherichia coli complementation assay, we showed that all three highly conserved Cys residues in SepCysS (Cys(64), Cys(67), and Cys(272) in the Methanocaldococcus jannaschii enzyme) are essential for the sulfhydrylation reaction in vivo. Biochemical and mass spectrometric analysis demonstrated that Cys(64) and Cys(67) form a disulfide linkage and carry a sulfane sulfur in a portion of the enzyme. These results suggest that a persulfide group (containing a sulfane sulfur) is the proximal sulfur donor for cysteine biosynthesis. The presence of Cys(272) increased the amount of sulfane sulfur in SepCysS by 3-fold, suggesting that this Cys residue facilitates the generation of the persulfide group. Based upon these findings, we propose for SepCysS a sulfur relay mechanism that recruits both disulfide and persulfide intermediates.

Improved Cyclability of Liquid Electrolyte Lithium/Sulfur Batteries by Optimizing Electrolyte/Sulfur Ratio

Directory of Open Access Journals (Sweden)

Sheng S. Zhang

2012-12-01

Full Text Available A liquid electrolyte lithium/sulfur (Li/S cell is a liquid electrochemical system. In discharge, sulfur is first reduced to highly soluble Li2S8, which dissolves into the organic electrolyte and serves as the liquid cathode. In solution, lithium polysulfide (PS undergoes a series of complicated disproportionations, whose chemical equilibriums vary with the PS concentration and affect the cell’s performance. Since the PS concentration relates to a certain electrolyte/sulfur (E/S ratio, there is an optimized E/S ratio for the cyclability of each Li/S cell system. In this work, we study the optimized E/S ratio by measuring the cycling performance of Li/S cells, and propose an empirical method for determination of the optimized E/S ratio. By employing an electrolyte of 0.25 m LiSO3CF3-0.25 m LiNO3 dissolved in a 1:1 (wt:wt mixture of dimethyl ether (DME and 1,3-dioxolane (DOL in an optimized E/S ratio, we show that the Li/S cell with a cathode containing 72% sulfur and 2 mg cm−2 sulfur loading is able to retain a specific capacity of 780 mAh g−1 after 100 cycles at 0.5 mA cm−2 between 1.7 V and 2.8 V.

Seawater sulfate reduction and sulfur isotope fractionation in basaltic systems: interaction of seawater with fayalite and magnetite at 200-3500C

International Nuclear Information System (INIS)

Shanks, W.C. III; Bischoff, J.L.; Rosenbauer, R.J.

1981-01-01

Sulfate reduction during seawater reaction with fayalite and with magnetite was rapid at 350 0 C, producing equilibrium assemblages of talc-pyrite-hematite-magnetite at low water/rock ratios and talc-pyrite-hematite-anhydrite at higher water/rock ratios. At 250 0 C, seawater reacting with fayalite produced detectable amounts of dissolved H 2 S. At 200 0 C, dissolved H 2 S was not detected, even after 219 days. Reaction stoichiometry indicates that sulfate reduction requires large amounts of H + , which, in subseafloor hydrothermal systems is provided by Mg metasomatism. Seawater contains sufficient Mg to supply all the H + necessary for quantitative reduction of seawater sulfate. Systematics of sulfur isotopes in the 250 and 350 0 C experiments indicate that isotopic equilibrium is reached and can be modeled as a Rayleigh distillation process. Isotopic composition of hydrothermally produced H 2 S in natural systems is strongly dependent upon the seawater/basalt ratio in the geothermal system, which controls the relative sulfide contributions from the two important sulfur sources, seawater sulfate and sulfide phases in basalt. Anhydrite precipitation during geothermal heating severely limits sulfate ingress into high temperature interaction zones. Quantitative sulfate reduction can thus be accomplished without producing strongly oxidized rocks and resultant sulfide sulfur isotope values represent a mixture of seawater and basaltic sulfur. (author)

Equipment and obtention process of phosphorus-32 starting from sulfur-32

International Nuclear Information System (INIS)

Alanis M, J.

2004-12-01

In the National Institute of Nuclear Research, it is the Radioisotopes Production plant, which covers in the area of the medicine 70% approximately of the national market and it exports to some countries of Latin America (Technetium-99, iodine-131, Sm-153 among other). At the moment the plant has modern facilities and certified with the ISO-9001-2000 standard, this, gives trust to the clients as for the quality of its products. Besides the production of radioisotopes dedicated for the medical area, the work of the plant tends to be more enlarged every time, producing new radioisotopes not only but with medical purposes but also industrial and agricultural ones, such it is the case of the production of Phosphorus-32 ( 32 P) that has applications with medical, industrial and in the agriculture purposes. The investigation studies from the prime matter (sulfur-32), sulfur purification, sulfur irradiation in the nuclear reactor and the obtaining process of 32 P in a prototype, its took us to design and to build the obtaining process from 32 P to more high level, which is presented in this work. To be able to select the obtaining method of 32 P that is presented it was necessary to study the methods that have been developed in the world, later on it was selected the way that is presented. In that way the physical and chemical properties of the sulfur were studied which is used as prime matter, the interest nuclear reaction was also studied to carry out the production of 32 P by means of the realization of mathematical calculations of irradiation of the sulfur in TRIGA Mark lll nuclear reactor. Once the sulfur is irradiated, it is necessary to carry out the radiochemical separation of the 32 P produced from the sulfur, for this, it was necessary to carry out experimental tests of this separation, later on it was developed a prototype where it was carried out this separation and finally it was developed the final equipment of production of 32 P mainly composed of three

Antibotulinal efficacy of sulfur dioxide in meat.

Science.gov (United States)

Tompkin, R B; Christiansen, L N; Shaparis, A B

1980-01-01

The addition of sodium metabisulfite as a source of sulfur dioxide delayed botulinal outgrowth in perishable canned comminuted pork when it was temperature abused at 27 degree C. The degree of inhibition was directly related to the level of sulfur dioxide. Levels greater than 100 microgram of sulfur dioxide per g were necessary to achieve significant inhibition when a target level of 100 botulinal spores per g was used. Sodium nitrite partially reduced the efficacy of the sulfur dioxide. Sulfur dioxide offers a new option for the control of botulinal outgrowth in cured or noncured meat and poultry products. PMID:6996613

21 CFR 184.1095 - Sulfuric acid.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Sulfuric acid. 184.1095 Section 184.1095 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN... Substances Affirmed as GRAS § 184.1095 Sulfuric acid. (a) Sulfuric acid (H2SO4, CAS Reg. No. 7664-93-9), also...

Effects of Sulfurization Temperature on Properties of CZTS Films by Vacuum Evaporation and Sulfurization Method

Directory of Open Access Journals (Sweden)

Jie Zhang

2013-01-01

Full Text Available Copper zinc tin sulfur (CZTS thin films have been extensively studied in recent years for their advantages of low cost, high absorption coefficient (≥104 cm−1, appropriate band gap (~1.5 eV, and nontoxicity. CZTS thin films are promising materials of solar cells like copper indium gallium selenide (CIGS. In this work, CZTS thin films were prepared on glass substrates by vacuum evaporation and sulfurization method. Sn/Cu/ZnS (CZT precursors were deposited by thermal evaporation and then sulfurized in N2 + H2S atmosphere at temperatures of 360–560°C to produce polycrystalline CZTS thin films. It is found that there are some impurity phases in the thin films with the sulfurization temperature less than 500°C, and the crystallite size of CZTS is quite small. With the further increase of the sulfurization temperature, the obtained thin films exhibit preferred (112 orientation with larger crystallite size and higher density. When the sulfurization temperature is 500°C, the band gap energy, resistivity, carrier concentration, and mobility of the CZTS thin films are 1.49 eV, 9.37 Ω · cm, 1.714×1017 cm−3, and 3.89 cm2/(V · s, respectively. Therefore, the prepared CZTS thin films are suitable for absorbers of solar cells.

Sulfur activation in Hiroshima

International Nuclear Information System (INIS)

Kerr, G.D.; Pace, J.V. III.

1987-01-01

In 1979, we attempted to establish the validity of source terms for the Hiroshima and Nagasaki bombs using experimental data on sulfur activation. Close agreement was observed between measured and calculated values for test firings of Nagasaki-type bombs. The calculated values were based on source terms developed by W.E. Preeg at the Los Alamos National Laboratory (LANL). A discrepancy was found, however, when we compared calculated values for the two bombs because a 1956 report by R.R. Wilson stated that sulfur acitvation by fast neutrons in Hiroshima was approximately three times greater than in Nagasaki. Our calculations based on Preeg's source-term data predicted about equal sulfur activation in the two cities

Determination of sulfur content in fuels

International Nuclear Information System (INIS)

Daucik, P.; Zidek, Z.; Kalab, P.

1998-01-01

The sulfur content in fuels, Diesel fuels, and in the solutions of dibutylsulfide in a white oil was determined by various methods. The results obtained by elemental analysis have shown that the method is not advisable for the determination of sulfur in fuels. A good agreement was found by comparing the results in the determination of the sulfur by Grote-Krekeler's and Hermann-Moritz's methods and by the energy-dispersive X-ray fluorescence analysis. The last method is the modern, comfortable, and timesaving method enabling the fast and precise determination of sulfur contents in the various types of samples. (authors)

Synthesis of three-dimensionally interconnected sulfur-rich polymers for cathode materials of high-rate lithium-sulfur batteries

Science.gov (United States)

Kim, Hoon; Lee, Joungphil; Ahn, Hyungmin; Kim, Onnuri; Park, Moon Jeong

2015-06-01

Elemental sulfur is one of the most attractive cathode active materials in lithium batteries because of its high theoretical specific capacity. Despite the positive aspect, lithium-sulfur batteries have suffered from severe capacity fading and limited rate capability. Here we report facile large-scale synthesis of a class of organosulfur compounds that could open a new chapter in designing cathode materials to advance lithium-sulfur battery technologies. Porous trithiocyanuric acid crystals are synthesized for use as a soft template, where the ring-opening polymerization of elemental sulfur takes place along the thiol surfaces to create three-dimensionally interconnected sulfur-rich phases. Our lithium-sulfur cells display discharge capacity of 945 mAh g-1 after 100 cycles at 0.2 C with high-capacity retention of 92%, as well as lifetimes of 450 cycles. Particularly, the organized amine groups in the crystals increase Li+-ion transfer rate, affording a rate performance of 1210, mAh g-1 at 0.1 C and 730 mAh g-1 at 5 C.

Synthesis of three-dimensionally interconnected sulfur-rich polymers for cathode materials of high-rate lithium–sulfur batteries

Science.gov (United States)

Kim, Hoon; Lee, Joungphil; Ahn, Hyungmin; Kim, Onnuri; Park, Moon Jeong

2015-01-01

Elemental sulfur is one of the most attractive cathode active materials in lithium batteries because of its high theoretical specific capacity. Despite the positive aspect, lithium–sulfur batteries have suffered from severe capacity fading and limited rate capability. Here we report facile large-scale synthesis of a class of organosulfur compounds that could open a new chapter in designing cathode materials to advance lithium–sulfur battery technologies. Porous trithiocyanuric acid crystals are synthesized for use as a soft template, where the ring-opening polymerization of elemental sulfur takes place along the thiol surfaces to create three-dimensionally interconnected sulfur-rich phases. Our lithium–sulfur cells display discharge capacity of 945 mAh g−1 after 100 cycles at 0.2 C with high-capacity retention of 92%, as well as lifetimes of 450 cycles. Particularly, the organized amine groups in the crystals increase Li+-ion transfer rate, affording a rate performance of 1210, mAh g−1 at 0.1 C and 730 mAh g−1 at 5 C. PMID:26065407

An experimental study: Role of different ambient on sulfurization of MoO{sub 3} into MoS{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Kumar, Prabhat, E-mail: prabhat89k@gmail.com; Singh, Megha; Sharma, Rabindar K.; Reddy, G.B.

2016-06-25

Molybdenum disulfide (MoS{sub 2}) nanostructured thin films (NTFs) were synthesised by sulfurizing MoO{sub 3} NTFs using three different non-conventional methods (named methods 1–3). Method 1 uses sulfur vapors, second employs H{sub 2}S/Ar gas and third adopts plasma of H{sub 2}S/Ar gas. HRTEM revealed formation of core–shell nanostructures with maximum shell thickness obtained in method 3. The samples showed uniform nanoflakes (NFs) throughout substrate, revealed by SEM, same as their precursor MoO{sub 3.} XRD and Raman analysis disclosed crystalline MoS{sub 2} and degree of crystallinity was greatest in case of sulfurization in plasma ambient. Quantitative analysis of sulfurized films carried out by XPS shows presence of MoS{sub 2} in all three methods with percentage found to be 18%, 87% and ∼100% respectively. The effect of sulfurizing ambient on its efficiency to convert MoO{sub 3} into MoS{sub 2} has been studied and it was found out that plasma ambient has resulted in high quality of MoS{sub 2} NTFs based on parameters as crystallinity, purity, uniformity and stoichiometry control. - Highlights: • Comparison of three non-conventional methods of sulfurization. • Parameters used for comparison are crystallinity, purity, sulfurized thickness, uniformity and stoichiometry. • H{sub 2}S/Ar plasma based method came out to be best among other techniques. • A soft template reactions for sulfurization of MoO{sub 3} nanoflake is proposed.

An oxidative desulfurization method using ultrasound/Fenton's reagent for obtaining low and/or ultra-low sulfur diesel fuel

Energy Technology Data Exchange (ETDEWEB)

Dai, Yongchuan; Qi, Yutai [Department of Applied Chemistry, School of Science, Harbin Institute of Technology, Harbin 115001 (China); Zhao, Dezhi [Department of Petroleum Chemical Engineering, Liaoning Shihua University, Fushun 113001 (China); Zhang, Huicheng [Fushun Research Institute of Petroleum and Petrochemicals of SINOPEC Corp., Fushun 113001 (China)

2008-10-15

The total development trend in the world is towards continuously lower of sulfur content as a quality standard of diesel fuels. Integrating of an oxidative desulfurization unit with a conventional hydrotreating unit can bring benefits to producing low and/or ultra-low sulfur diesel fuels. Using the hydrotreated Middle East diesel fuel as a feedstock, four processes of the oxidative desulfurization have been studied: a hydrogen peroxide-acetic acid system and a Fenton's reagent system both without/with ultrasound. Results showed that the oxidative desulfurization reaction mechanics fitted apparent first-order kinetics. The addition of Fenton's reagent could enhance the oxidative desulfurization efficiency for diesel fuels and sono-oxidation treatment in combination with Fenton's reagent shows a good synergistic effect. Under our best operating condition for the oxidative desulfurization: temperature 313 K, ultrasonic power 200 W, ultrasonic frequency 28 kHz, Fe{sup 2+}/H{sub 2}O{sub 2} 0.05 mol/mol, pH 2.10 in aqueous phase and reaction time 15 min, the sulfur content in the diesel fuels was decreased from 568.75 {mu}g/g to 9.50 {mu}g/g. (author)

Performance of a pilot-scale packed bed reactor for perchlorate reduction using a sulfur oxidizing bacterial consortium.

Science.gov (United States)

Boles, Amber R; Conneely, Teresa; McKeever, Robert; Nixon, Paul; Nüsslein, Klaus R; Ergas, Sarina J

2012-03-01

A novel sulfur-utilizing perchlorate reducing bacterial consortium successfully treated perchlorate (ClO₄⁻) in prior batch and bench-scale packed bed reactor (PBR) studies. This study examined the scale up of this process for treatment of water from a ClO ₄⁻ and RDX contaminated aquifer in Cape Cod Massachusetts. A pilot-scale upflow PBR (∼250-L) was constructed with elemental sulfur and crushed oyster shell packing media. The reactor was inoculated with sulfur oxidizing ClO₄⁻ reducing cultures enriched from a wastewater seed. Sodium sulfite provided a good method of dissolved oxygen removal in batch cultures, but was found to promote the growth of bacteria that carry out sulfur disproportionation and sulfate reduction, which inhibited ClO₄⁻ reduction in the pilot system. After terminating sulfite addition, the PBR successfully removed 96% of the influent ClO₄⁻ in the groundwater at an empty bed contact time (EBCT) of 12 h (effluent ClO₄⁻ of 4.2 µg L(-1)). Simultaneous ClO₄⁻ and NO₃⁻ reduction was observed in the lower half of the reactor before reactions shifted to sulfur disproportionation and sulfate reduction. Analyses of water quality profiles were supported by molecular analysis, which showed distinct groupings of ClO₄⁻ and NO₃⁻ degrading organisms at the inlet of the PBR, while sulfur disproportionation was the primary biological process occurring in the top potion of the reactor. Copyright © 2011 Wiley Periodicals, Inc.

Study on in-situ electrochemical impedance spectroscopy measurement of anodic reaction in SO_2 depolarized electrolysis process

International Nuclear Information System (INIS)

Xue Lulu; Zhang Ping; Chen Songzhe; Wang Laijun

2014-01-01

SO_2 depolarized electrolysis (SDE) is the pivotal reaction in hybrid sulfur process, one of the most promising approaches for mass hydrogen production without CO_2 emission. The net result of hybrid sulfur process is to split water into hydrogen and oxygen at a relatively low voltage, which will dramatically decrease the energy consumption for the production of hydrogen. The potential loss of SDE process could be separated into four components, i.e. reversible cell potential, anode overpotential, cathode overpotential and ohmic loss. So far, it has been identified that the total cell potential for the SO_2 depolarized electrolyzer is dominantly controlled by sulfuric acid concentration of the anolyte and electrolysis temperature of the electrolysis process. In this work, an in-situ Electrochemical Impedance Spectroscopy (EIS) measurement of the anodic SDE reaction was conducted. Results show that anodic overpotential is mainly resulted from the SO_2 oxidation reaction other than ohmic resistance or mass transfer limitation. This study extends the understanding to SDE process and gives suggestions for the further improvement of the SDE performance. (author)

Effects of sulfur dioxide on vegetation

Energy Technology Data Exchange (ETDEWEB)

Whitby, G S

1939-11-11

A discussion is presented on the effects of sulfur dioxide on vegetation as observed at Trail, British Columbia. The investigation was carried out over a period of eight years, 1929 to 1937. The concentration of sulfur dioxide at the United States border was carefully determined throughout the crop season at a point 16 miles from the source of sulfur dioxide. Maximum and average concentrations in part per million are given. The sulfur content of vegetation was determined and was found to diminish as the distance from the smelter increased. It was determined that the sulfur content may rise to four times the normal amount without injurious effect. This is particularly so with prolonged low concentration. The effect on the soil was determined by measuring soluble sulfate, pH and exchangeable bases. The soil near the plant was affected, but this fell off rapidly with increase in distance so that eight miles from the smelter the soil was substantially normal. No effect on water supplies was found. An appreciable retardation in growth, as determined by annular rings, was noted for trees exposed to the sulfur dioxide. This effect was lost following installation of sulfur dioxide control at Trail. Conifers were found more susceptible during periods of active growth than when dormant. Also, transplanted conifers were more severly affected than native trees. Seedlings were less resistant that older trees.

Influence of sulfurous oxide on plants

Energy Technology Data Exchange (ETDEWEB)

Schroeder, J

1872-01-01

It has been determined that of the trees living in an atmosphere containing sulfurous oxide, the conifers suffer more injuries than ordinary foliaged trees. Experiments were conducted to find the causes of injuries and their relation in these two kinds of plants. Pine and alder were chosen as test plants. It was found that 1000 square centimeters of pine leaves had absorbed 1.6 c.c. of sulfurous oxide and the same surface area of alder leaves had accumulated 7.9 c.c. of sulfurous oxide. Experiments were also conducted to determine the effects of sulfurous oxide on transpiration in plants. Two similar twigs of a sycamore were arranged so that the water transpired could be weighed. Results indicate that the ratio between the total amount of water transpired by the leaves not acted on by the sulfurous oxide and those under its influence was 3.8:1. The author concludes that the amount of sulfurous oxide absorbed by pine leaves is smaller than that absorbed by trees with ordinary foliage for equal surfaces. Since its effect on transpiration is less in the case of pine, the cause of the greater injury to pine trees in nature must be due to the accumulation of sulfur. In trees annual leaves the damage to one year's foliage would have only an indirect influence on that of the following year.

Reaction of Acetaldehyde with Wine Flavonoids in the Presence of Sulfur Dioxide.

Science.gov (United States)

Sheridan, Marlena K; Elias, Ryan J

2016-11-16

Acetaldehyde is responsible for many of the beneficial changes that occur in red wine as a result of oxidation. Ethylidene bridges are formed between flavonoids upon their reaction with acetaldehyde, which can contribute to improvements in color stability and SO 2 -resistant pigments. In the present study, the reactions between acetaldehyde and various flavonoids (catechin, tannins from grape seed extract, and malvidin-3-glucoside) were examined in a model wine system. Lower pH conditions were seen to significantly increase the rate of reaction with acetaldehyde, whereas dissolved oxygen did not affect the rate. In systems containing SO 2 , the rate of reaction of acetaldehyde with catechin was slowed but was not prevented until SO 2 was in great excess. Significant improvements in color stability were also observed after treatment with acetaldehyde, despite the presence of equimolar SO 2 . These results demonstrate that acetaldehyde is reactive in its sulfonate form, which is contrary to widely held assumptions. In addition, the products of the reaction of flavonoids with acetaldehyde were characterized using MALDI-TOF MS in this study. Ethyl-bridged catechin nonamers were observed, as well as anthocyanin and pyranoanthocyanin derivatives of catechin and tannin oligomers. The results of this work illustrate the significance of acetaldehyde reactions in forming stable pigments in wine and the reactivity of acetaldehyde from its sulfonate form.

Sulfur metabolism in the extreme acidophile Acidithiobacillus caldus

Directory of Open Access Journals (Sweden)

Stefanie eMangold

2011-02-01

Full Text Available Given the challenges to life at low pH, an analysis of inorganic sulfur compound oxidation was initiated in the chemolithoautotrophic extremophile Acidithiobacillus caldus. A. caldus is able to metabolize elemental sulfur and a broad range of inorganic sulfur compounds. It has been implicated in the production of environmentally damaging acidic solutions as well as participating in industrial bioleaching operations where it forms part of microbial consortia used for the recovery of metal ions. Based upon the recently published A. caldus type strain genome sequence, a bioinformatic reconstruction of elemental sulfur and inorganic sulfur compound metabolism predicted genes included: sulfide quinone reductase (sqr, tetrathionate hydrolase (tth, two sox gene clusters potentially involved in thiosulfate oxidation (soxABXYZ, sulfur oxygenase reductase (sor, and various electron transport components. RNA transcript profiles by semi-quantitative reverse transcription PCR suggested up-regulation of sox genes in the presence of tetrathionate. Extensive gel based proteomic comparisons of total soluble and membrane enriched protein fractions during growth on elemental sulfur and tetrathionate identified differential protein levels from the two Sox clusters as well as several chaperone and stress proteins up-regulated in the presence of elemental sulfur. Proteomics results also suggested the involvement of heterodisulfide reductase (HdrABC in A. caldus inorganic sulfur compound metabolism. A putative new function of Hdr in acidophiles is discussed. Additional proteomic analysis evaluated protein expression differences between cells grown attached to solid, elemental sulfur versus planktonic cells. This study has provided insights into sulfur metabolism of this acidophilic chemolithotroph and gene expression during attachment to solid elemental sulfur.

Performance Factors and Sulfur Tolerance of Metal Supported Solid Oxide Fuel Cells with Nanostructured Ni:GDC Infiltrated Anodes

DEFF Research Database (Denmark)

Nielsen, Jimmi; Sudireddy, Bhaskar Reddy; Hagen, Anke

2016-01-01

galvanostatic operation at a current load of 0.25 Acm−2. The results were compared with literature on the sulfur tolerance of conventional SOFC Ni/YSZ cermet anode. The comparison in terms of absolute cell resistance increase and relative anode polarization resistance increase indicates, that the nanostructured...... Ni:GDC MS-SOFC based anode is significantly more sulfur tolerant than the conventional Ni/YSZ cermet anode. Furthermore, it was shown that the believed extension of the electrochemical three-phase-boundary reaction zone in the presence of GDC must be very limited and cannot account for the higher...

Graphene-wrapped sulfur/metal organic framework-derived microporous carbon composite for lithium sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Chen, Renjie, E-mail: kx210@cam.ac.uk, E-mail: chenrj@bit.edu.cn; Zhao, Teng [Beijing Key Laboratory of Environmental Science and Engineering, School of Chemical Engineering and Environment, Beijing Institute of Technology, Beijing 100081 (China); Department of Materials Science and Metallurgy, University of Cambridge, Cambridge CB3 0FS (United Kingdom); Tian, Tian; Fairen-Jimenez, David [Department of Chemical Engineering and Biotechnology, University of Cambridge, Pembroke Street, Cambridge CB2 3RA (United Kingdom); Cao, Shuai; Coxon, Paul R.; Xi, Kai, E-mail: kx210@cam.ac.uk, E-mail: chenrj@bit.edu.cn; Vasant Kumar, R.; Cheetham, Anthony K. [Department of Materials Science and Metallurgy, University of Cambridge, Cambridge CB3 0FS (United Kingdom)

2014-12-01

A three-dimensional hierarchical sandwich-type graphene sheet-sulfur/carbon (GS-S/C{sub ZIF8-D}) composite for use in a cathode for a lithium sulfur (Li-S) battery has been prepared by an ultrasonic method. The microporous carbon host was prepared by a one-step pyrolysis of Zeolitic Imidazolate Framework-8 (ZIF-8), a typical zinc-containing metal organic framework (MOF), which offers a tunable porous structure into which electro-active sulfur can be diffused. The thin graphene sheet, wrapped around the sulfur/zeolitic imidazolate framework-8 derived carbon (S/C{sub ZIF8-D}) composite, has excellent electrical conductivity and mechanical flexibility, thus facilitating rapid electron transport and accommodating the changes in volume of the sulfur electrode. Compared with the S/C{sub ZIF8-D} sample, Li-S batteries with the GS-S/C{sub ZIF8-D} composite cathode showed enhanced capacity, improved electrochemical stability, and relatively high columbic efficiency by taking advantage of the synergistic effects of the microporous carbon from ZIF-8 and a highly interconnected graphene network. Our results demonstrate that a porous MOF-derived scaffold with a wrapped graphene conductive network structure is a potentially efficient design for a battery electrode that can meet the challenge arising from low conductivity and volume change.

Graphene-wrapped sulfur/metal organic framework-derived microporous carbon composite for lithium sulfur batteries

Directory of Open Access Journals (Sweden)

Renjie Chen

2014-12-01

Full Text Available A three-dimensional hierarchical sandwich-type graphene sheet-sulfur/carbon (GS-S/CZIF8-D composite for use in a cathode for a lithium sulfur (Li-S battery has been prepared by an ultrasonic method. The microporous carbon host was prepared by a one-step pyrolysis of Zeolitic Imidazolate Framework-8 (ZIF-8, a typical zinc-containing metal organic framework (MOF, which offers a tunable porous structure into which electro-active sulfur can be diffused. The thin graphene sheet, wrapped around the sulfur/zeolitic imidazolate framework-8 derived carbon (S/CZIF8-D composite, has excellent electrical conductivity and mechanical flexibility, thus facilitating rapid electron transport and accommodating the changes in volume of the sulfur electrode. Compared with the S/CZIF8-D sample, Li-S batteries with the GS-S/CZIF8-D composite cathode showed enhanced capacity, improved electrochemical stability, and relatively high columbic efficiency by taking advantage of the synergistic effects of the microporous carbon from ZIF-8 and a highly interconnected graphene network. Our results demonstrate that a porous MOF-derived scaffold with a wrapped graphene conductive network structure is a potentially efficient design for a battery electrode that can meet the challenge arising from low conductivity and volume change.

Isolation of Sulfur Reducing and Oxidizing Bacteria Found in Contaminated Drywall

Directory of Open Access Journals (Sweden)

Frederick T. Guilford

2010-02-01

Full Text Available Drywall from China has been reported to release sulfur producing products which are corrosive to metals, result in noxious odors, and represent a significant health risk. It has been reported that these emissions produce medical symptoms such as respiratory or asthma type problems, sinusitis, gastrointestinal disorders, and vision problems in home owners and their household pets. We report here a method of identifying a causative agent for these emissions by sampling affected gypsum wallboard and subjecting those samples to Real Time Polymerase Chain Reaction [RT-PCR] studies. Specific DNA probes and primers have been designed and patented that detect a specific iron and sulfur reducing bacterium (i.e., Thiobacillus ferrooxidans. One hundred percent of affected drywall samples obtained from homes located in the southeastern United States tested positive for the presence of T. ferrooxidans. All negative controls consisting of unaffected wallboard and internal controls, Geotrichum sp., tested negative within our limits of detection.

Standardization of 40Ar-39Ar dating facility at KDMIPE, ONGC, Dehradun

International Nuclear Information System (INIS)

Rathore, S.S.; Singh, M.P.; Vijan, A.R.; Bansal, M.; Prabhu, B.N.; Misra, K.N.

2003-01-01

In the pursuit of acquiring state of the art technology, efforts were being made for last more than two years to establish 40 Ar- 39 Ar dating facility at KDMIPE. The 40 Ar- 39 Ar dating technique is an analytical conversion of the conventional K-Ar dating method. In this method, the sample to be dated is first irradiated in a nuclear reactor to transform a portion of 39 K to 39 Ar by the fast neutron reaction i.e. 39 K(n, p) 39 Ar. After irradiation, the sample is placed in an ultra-high vacuum system and the argon extracted from it by fusion is purified and analyzed isotopically in a mass spectrometer. The relative abundances of 40 Ar, 39 Ar, 37 Ar and 36 Ar are measured. The 40 Ar/ 39 Ar K is determined, where 40 Ar is the radiogenic argon, and 39 Ar K is the 39 Ar produced from 39 K during the irradiation. The 40 Ar/ 39 Ar K ratio is proportional to the 40 Ar/ 40 K ratio in the sample and, therefore, is proportional to age

The Role of Sulfur in the Synthesis of Novel Carbon Morphologies: From Covalent Y-junctions to Sea Urchin?like Structures

Energy Technology Data Exchange (ETDEWEB)

Sumpter, Bobby G [ORNL; Romo Herrera, Jose M [ORNL; Cruz Silva, Eduardo [ORNL; Meunier, Vincent [ORNL; Terrones Maldonado, Humberto [ORNL; Smith, David J [Arizona State University; Cullen, David A [Arizona State University; Terrones Maldonado, Mauricio [ORNL

2009-01-01

In this paper we show how sulfur-assisted CVD synthesis of carbon nanostructures is very sensitive to local conditions (such as the local amount of S or the feeding rate) during chemical reaction. Sulfur not only acts on the catalyst but also on its diffusion and incorporation into the resulting carbon nanostructure. A detailed synthesis study with extensive analytical and microscopy evidence for a wide range of morphologies reveals the presence of sulfur in the metallic catalyst and even in the carbon body of nanostructures obtained under the same CVD conditions. These drastic changes can be correlated to carrier gas flux, sulfur content, temperature and catalyst composition. Five different types of covalent Y-junctions ranging from Y-junctions with arms of micrometers in diameter, Y-junctions of cone-stacked carbon cylinders to concentric cylinders multi-walled CNTs Y-junctions can be obtained. In addition, unique sea urchin shaped nanostructures are observed under specific synthesis conditions.

Honeycomb-like Nitrogen and Sulfur Dual-Doped Hierarchical Porous Biomass-Derived Carbon for Lithium-Sulfur Batteries.

Science.gov (United States)

Chen, Manfang; Jiang, Shouxin; Huang, Cheng; Wang, Xianyou; Cai, Siyu; Xiang, Kaixiong; Zhang, Yapeng; Xue, Jiaxi

2017-04-22

Honeycomb-like nitrogen and sulfur dual-doped hierarchical porous biomass-derived carbon/sulfur composites (NSHPC/S) are successfully fabricated for high energy density lithium-sulfur batteries. The effects of nitrogen, sulfur dual-doping on the structures and properties of the NSHPC/S composites are investigated in detail by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and charge/discharge tests. The results show that N, S dual-doping not only introduces strong chemical adsorption and provides more active sites but also significantly enhances the electronic conductivity and hydrophilic properties of hierarchical porous biomass-derived carbon, thereby significantly enhancing the utilization of sulfur and immobilizing the notorious polysulfide shuttle effect. Especially, the as-synthesized NSHPC-7/S exhibits high initial discharge capacity of 1204 mA h g -1 at 1.0 C and large reversible capacity of 952 mA h g -1 after 300 cycles at 0.5 C with an ultralow capacity fading rate of 0.08 % per cycle even at high sulfur content (85 wt %) and high active material areal mass loading (2.8 mg cm -2 ) for the application of high energy density Li-S batteries. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effective synthesis of Insoluble sulfur using electron beam

Energy Technology Data Exchange (ETDEWEB)

Kim, Daejin; Yu, Kookhyun [Dongguk Univ., Seoul (Korea, Republic of)

2013-07-01

Vulcanization is process that formed crosslinking by Insoluble sulfur between linear structure of rubber polymer. Recently, Synthesis of Insoluble sulfur is used Thermal polymerization using about 250 {approx} 300 .deg. C and extraction process is used carbon disulfide(CS2) for separation between soluble sulfur and insoluble sulfur. But this process isn't environmental, economical and safety. This research was focus on developing of insoluble sulfur synthesis process using electron beam. This new process is using under the 140 .deg. C. Because of that, explosion risk is decrease, environmental and economical factor is increased. The sulfur can be melt by increase temperature or made solution using carbon disulfide. And electron beam is irradiated melting sulfur or sulfur solution. After irradiation, The high purity insoluble sulfur can be obtained by separation with carbon disulfide.

Removal of sulfur and nitrogen containing pollutants from discharge gases

Energy Technology Data Exchange (ETDEWEB)

Joubert, James I. (Pittsburgh, PA)

1986-01-01

Oxides of sulfur and of nitrogen are removed from waste gases by reaction with an unsupported copper oxide powder to form copper sulfate. The resulting copper sulfate is dissolved in water to effect separation from insoluble mineral ash and dried to form solid copper sulfate pentahydrate. This solid sulfate is thermally decomposed to finely divided copper oxide powder with high specific surface area. The copper oxide powder is recycled into contact with the waste gases requiring cleanup. A reducing gas can be introduced to convert the oxide of nitrogen pollutants to nitrogen.

Removal of sulfur and nitrogen containing pollutants from discharge gases

Energy Technology Data Exchange (ETDEWEB)

Joubert, J.I.

1985-02-08

Oxides of sulfur and of nitrogen are removed from waste gases by reaction with an unsupported copper oxide powder to form copper sulfate. The resulting copper sulfate is dissolved in water to effect separation from insoluble mineral ash and dried to form solid copper sulfate pentahydrate. This solid sulfate is thermally decomposed to finely divided copper oxide powder with high specific surface area. The copper oxide powder is recycled into contact with the waste gases requiring cleanup. A reducing gas can be introduced to convert the oxide of nitrogen pollutants to nitrogen.

Thermally-Induced Chemistry and the Jovian Icy Satellites: A Laboratory Study of the Formation of Sulfur Oxyanions

Science.gov (United States)

Loeffler, Mark J.; Hudson, Reggie L.

2011-01-01

Laboratory experiments have demonstrated that magnetospheric radiation in the Jovian system drives reaction chemistry in ices at temperatures relevant to Europa and other icy satellites. Here we present new results on thermally-induced reactions at 50-100 K in solid H2O-SO2 mixtures, reactions that take place without the need for a high-radiation environment. We find that H2O and SO2 react to produce sulfur Oxyanions, such as bisulfite, that as much as 30% of the SO2 can be consumed through this reaction, and that the products remain in the ice when the temperature is lowered, indicating that these reactions are irreversible. Our results suggest that thermally-induced reactions can alter the chemistry at temperatures relevant to the icy satellites in the Jovian system.

Efficient Electrolytes for Lithium–Sulfur Batteries

International Nuclear Information System (INIS)

Angulakshmi, Natarajan; Stephan, Arul Manuel

2015-01-01

This review article mainly encompasses on the state-of-the-art electrolytes for lithium–sulfur batteries. Different strategies have been employed to address the issues of lithium–sulfur batteries across the world. One among them is identification of electrolytes and optimization of their properties for the applications in lithium–sulfur batteries. The electrolytes for lithium–sulfur batteries are broadly classified as (i) non-aqueous liquid electrolytes, (ii) ionic liquids, (iii) solid polymer, and (iv) glass-ceramic electrolytes. This article presents the properties, advantages, and limitations of each type of electrolytes. Also, the importance of electrolyte additives on the electrochemical performance of Li–S cells is discussed.

Efficient Electrolytes for Lithium-Sulfur Batteries

Directory of Open Access Journals (Sweden)

Natarajan eAngulakshmi

2015-05-01

Full Text Available This review article mainly encompasses on the state-of-the-art electrolytes for lithium–sulfur batteries. Different strategies have been employed to address the issues of lithium-sulfur batteries across the world. One among them is identification of electrolytes and optimization of their properties for the applications in lithium-sulfur batteries. The electrolytes for lithium-sulfur batteries are broadly classified as (i non-aqueous liquid electrolytes, (ii ionic liquids, (iii solid polymer and (iv glass-ceramic electrolytes. This article presents the properties, advantages and limitations of each type of electrolytes. Also the importance of electrolyte additives on the electrochemical performance of Li-S cells is discussed.

Efficient Electrolytes for Lithium–Sulfur Batteries

Energy Technology Data Exchange (ETDEWEB)

Angulakshmi, Natarajan [Department of Materials Science and Engineering, Politecnico di Torino, Turin (Italy); Stephan, Arul Manuel, E-mail: arulmanuel@gmail.com [Central Electrochemical Research Institute (CSIR-CECRI), Karaikudi (India)

2015-05-21

This review article mainly encompasses on the state-of-the-art electrolytes for lithium–sulfur batteries. Different strategies have been employed to address the issues of lithium–sulfur batteries across the world. One among them is identification of electrolytes and optimization of their properties for the applications in lithium–sulfur batteries. The electrolytes for lithium–sulfur batteries are broadly classified as (i) non-aqueous liquid electrolytes, (ii) ionic liquids, (iii) solid polymer, and (iv) glass-ceramic electrolytes. This article presents the properties, advantages, and limitations of each type of electrolytes. Also, the importance of electrolyte additives on the electrochemical performance of Li–S cells is discussed.

One-step hydrothermal synthesis of three-dimensional porous graphene aerogels/sulfur nanocrystals for lithium–sulfur batteries

International Nuclear Information System (INIS)

Jiang, Yong; Lu, Mengna; Ling, Xuetao; Jiao, Zheng; Chen, Lingli; Chen, Lu; Hu, Pengfei; Zhao, Bing

2015-01-01

Highlights: • 3D porous GA/S nanocrystals are prepared by a one-step hydrothermal method. • The structure is affected by hydrothermal temperature and liquid sulfur’s viscosity. • The hybrid delivers a capacity of 716.2 mA h g −1 after 50 cycles at 100 mA g −1 . • The nanosized S, strong adsorbability and intimate contact of GNS are main factors. - Abstract: Lithium–sulfur (Li–S) batteries are receiving significant attention as a new energy source because of its high theoretical capacity and specific energy. However, the low sulfur loading and large particles (usually in submicron dimension) in the cathode greatly offset its advantage in high energy density and lead to the instability of the cathode and rapid capacity decay. Herein, we introduce a one-step hydrothermal synthesis of three-dimensional porous graphene aerogels/sulfur nanocrystals to suppress the rapid fading of sulfur electrode. It is found that the hydrothermal temperature and viscosity of liquid sulfur have significant effects on particle size and loading mass of sulfur nanocrystals, graphitization degree of graphene and chemical bonding between sulfur and oxygen-containing groups of graphene. The hybrid could deliver a specific capacity of 716.2 mA h g −1 after 50 cycles at a current density of 100 mA g −1 and reversible capacity of 517.9 mA h g −1 at 1 A g −1 . The performance we demonstrate herein suggests that Li–S battery may provide an opportunity for development of rechargeable battery systems

Chiral Nickel(II) Complex Catalyzed Enantioselective Doyle-Kirmse Reaction of α-Diazo Pyrazoleamides.

Science.gov (United States)

Lin, Xiaobin; Tang, Yu; Yang, Wei; Tan, Fei; Lin, Lili; Liu, Xiaohua; Feng, Xiaoming

2018-03-07

Although high enantioselectivity of [2,3]-sigmatropic rearrangement of sulfonium ylides (Doyle-Kirmse reaction) has proven surprisingly elusive using classic chiral Rh(II) and Cu(I) catalysts, in principle it is due to the difficulty in fine discrimination of the heterotopic lone pairs of sulfur and chirality inversion at sulfur of sulfonium ylides. Here, we show that the synergistic merger of new α-diazo pyrazoleamides and a chiral N, N'-dioxide-nickel(II) complex catalyst enables a highly enantioselective Doyle-Kirmse reaction. The pyrazoleamide substituent serves as both an activating and a directing group for the ready formation of a metal-carbene- and Lewis-acid-bonded ylide intermediate in the assistance of a dual-tasking nickel(II) complex. An alternative chiral Lewis-acid-bonded ylide pathway greatly improves the product enantiopurity even for the reaction of a symmetric diallylsulfane. The majority of transformations over a series of aryl- or vinyl-substituted α-diazo pyrazoleamindes and sulfides proceed rapidly (within 5-20 min in most cases) with excellent results (up to 99% yield and 96% ee), providing a breakthrough in enantioselective Doyle-Kirmse reaction.

Early steroid sulfurization in surface sediments of a permanently stratified lake (Ace Lake, Antarctica)

Science.gov (United States)

Kok, Marika D.; Rijpstra, W. Irene C.; Robertson, Lisette; Volkman, John K.; Sinninghe Damstéé, Jaap S.

2000-04-01

Surface sediments (0-25 cm) from Ace Lake (eastern Antarctica), a saline euxinic lake, were analyzed to study the early incorporation of reduced inorganic sulfur species into organic matter. The apolar fractions were shown to consist predominantly of dimeric (poly)sulfide linked C 27-C 29 steroids. These steroid moieties were identified by GC-MS analysis of the apolar fractions after cleavage of polysulfide linkages using MeLi and MeI and after desulfurisation. The polar fractions contained the oligomeric analogues. The S-bound steroids are most likely formed by sulfur incorporation into steroidal ketones formed from Δ 5 sterols by biohydrogenation by anaerobic bacteria. The concentrations of these sulfurised steroids increased with depth in the sediment. The sulfurisation reaction is completed in 1000-3000 years. Despite a wide range of functionalised lipids present in these sediments that are potentially available for sulfurisation, there is a very strong preference for the incorporation of sulfur into steroidal compounds. A predominance of sulfurised C 27 steroids contrasted with the distribution of free sterols, which showed a strong predominance of C 29 sterols. This indicates that the incorporation of sulfur is biased towards C 27 sterols. The results demonstrate that intermolecular sulfurisation of organic matter can occur in surface sediments at low temperatures and in the absence of light.

Micro-Spherical Sulfur/Graphene Oxide Composite via Spray Drying for High Performance Lithium Sulfur Batteries

Science.gov (United States)

Tian, Yuan; Sun, Zhenghao; Zhang, Yongguang; Yin, Fuxing

2018-01-01

An efficient, industry-accepted spray drying method was used to synthesize micro-spherical sulfur/graphene oxide (S/GO) composites as cathode materials within lithium sulfur batteries. The as-designed wrapping of the sulfur-nanoparticles, with wrinkled GO composites, was characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The unique morphological design of this material enabled superior discharge capacity and cycling performance, demonstrating a high initial discharge capacity of 1400 mAh g−1 at 0.1 C. The discharge capacity remained at 828 mAh g−1 after 150 cycles. The superior electrochemical performance indicates that the S/GO composite improves electrical conductivity and alleviates the shuttle effect. This study represents the first time such a facile spray drying method has been adopted for lithium sulfur batteries and used in the fabrication of S/GO composites. PMID:29346303

Anodic Dissolution of Spheroidal Graphite Cast Iron with Different Pearlite Areas in Sulfuric Acid Solutions

Directory of Open Access Journals (Sweden)

Yoshikazu Miyata

2013-01-01

Full Text Available The rate equation of anodic dissolution reaction of spheroidal graphite cast iron in sulfuric acid solutions at 298 K has been studied. The cast irons have different areas of pearlite. The anodic Tafel slope of 0.043 V decade−1 and the reaction order with respect to the hydroxyl ion activity of 1 are obtained by the linear potential sweep technique. The anodic current density does not depend on the area of pearlite. There is no difference in the anodic dissolution reaction mechanisms between pure iron and spheroidal graphite cast iron. The anodic current density of the cast iron is higher than that of the pure iron.

Organosulfate Formation through the Heterogeneous Reaction of Sulfur Dioxide with Unsaturated Compounds

Science.gov (United States)

George, C.; Passananti, M.; Kong, L.; Shang, J.; Perrier, S.; Jianmin, C.; Donaldson, D. J.

2016-12-01

The atmospheric formation of organosulfur derivatives through reaction with SO2 is generally mediated by oxidants such as O3, OH; recently we have proposed a direct reaction between SO2 and unsaturated compounds as another possible pathway for organosulfate formation in the troposphere. For the first time it was shown recently that a heterogeneous reaction between SO2 and oleic acid (OA; an unsaturated fatty acid) takes place and leads efficiently to the formation of organosulfur products. Here, we demonstrate that this reaction proceeds on various unsaturated compounds, and may therefore have a general environmental impact. We used different experimental strategies i.e., a coated flow tube (CFT), an aerosol flow tube (AFT) and a DRIFT (diffuse reflectance infrared Fourier transform) cell. The reaction products were analyzed by means of liquid chromatography coupled to a high resolution mass spectrometer (LC-HR-MS). We report indeed that SO2 reacts with large variety of C=C unsaturations and that even in the presence of ozone, SO2 reacts with OA leading to organosulfur products. A strong enhancement in product formation is observed under actinic illumination, increases the atmospheric significance of this chemical pathway. This is probably due to the chromophoric nature of the SO2 adduct with C=C bonds, and means that the contribution of this direct addition of SO2 could be in excess of 5%. The detection in atmospheric aerosols of organosulfur compounds with the same chemical formulae as the products identified here seems to confirm the importance of this reaction in the atmosphere.

Preparation of Cu{sub 2}ZnSnS{sub 4} thin films by sulfurizing stacked precursor thin films via successive ionic layer adsorption and reaction method

Energy Technology Data Exchange (ETDEWEB)

Su Zhenghua; Yan Chang; Sun Kaiwen; Han Zili [School of Metallurgical Science and Engineering, Central South University, Changsha 410083 (China); Liu Fangyang, E-mail: liufangyang@csu.edu.cn [School of Metallurgical Science and Engineering, Central South University, Changsha 410083 (China); Liu Jin [School of Metallurgical Science and Engineering, Central South University, Changsha 410083 (China); Lai Yanqing, E-mail: laiyanqingcsu@163.com [School of Metallurgical Science and Engineering, Central South University, Changsha 410083 (China); Li Jie; Liu Yexiang [School of Metallurgical Science and Engineering, Central South University, Changsha 410083 (China)

2012-07-15

Earth-abundant Cu{sub 2}ZnSnS{sub 4} is a promising alternative photovoltaic material which has been examined as absorber layer of thin film solar cells. In this study, Cu{sub 2}ZnSnS{sub 4} (CZTS) thin films have been successfully fabricated by sulfurizing stacked precursor thin films via successive ionic layer adsorption and reaction (SILAR) method. The prepared CZTS thin films have been characterized by X-ray diffraction, energy dispersive spectrometer, Raman spectroscopy, UV-vis spectroscopy, Hall effect measurements and photoelectrochemical tests. Results reveal that the thin films have kesterite structured Cu{sub 2}ZnSnS{sub 4} and the p-type conductivity with a carrier concentration in the order of 10{sup 18} cm{sup -3} and an optical band gap of 1.5 eV, which are suitable for applications in thin film solar cells.

In-beam γ-ray spectroscopy of the neutron rich 39Si

International Nuclear Information System (INIS)

Sohler, D.; Dombradi, Zs.; Achouri, N.L.; Angelique, J.C.; Bastin, B.; Azaiez, F.; Baiborodin, D.; Borcea, R.

2009-01-01

Complete text of publication follows. In order to clarify the role of proton excitations across the Z = 14 subshell closure in neutron-rich Si isotopes, we investigated the structure of the 14 39 Si 25 isotope, having three neutron-hole configurations with respect to an N = 28 core. The excited states of 39 Si were studied by in-beam γ-ray spectroscopy trough fragmentation of radioactive beams. The experiment was performed at the GANIL facility in France. The radioactive beams were produced by the fragmentation of the stable 48 Ca beam of 60 MeV/u energy and 4μA intensity on a 12 C target in the SISSI device. The cocktail beam produced was impinged onto a 9 Be target. The nuclei produced in the secondary fragmentation reaction were selected and unambiguously identified by the SPEG spectrometer. In the performed experiment the 39 Si nuclei were obtained via 1p, 1p1n, 2p1n and 2p2n knockout reactions from the 40,41 P and 42,43 S secondary beams. To measure the γ rays emitted from the excited states, the secondary target was surrounded by the 4π 'Chateau de Crystal' array consisting of 74 BaF 2 scintillators. The γ-ray spectra were generated by gating event-by-event on the incoming secondary beam particles and the ejectiles after the secondary target. For the γ rays emitted by the fast moving fragments accurate Doppler correction was performed. From the obtained γ spectra of 39 Si displayed in Figure 1, two strong γ transitions at 163 and 397 keV as well as weaker ones at 303, 657, 906, 1143 and 1551 keV have been identified. γγ coincidences were obtained in 39 Si after having added all data from the various reaction channels giving rise to 39 Si. Analysing these data the 163 keV transition was found to be in coincidence with the 657, 1143 and 1551 keV ones, but not with the 397 keV transition. The two lines of the 303+397 keV doublet are in mutual coincidence, and one or both of them are found in coincidence with the 906 keV transition.

Porous-Shell Vanadium Nitride Nanobubbles with Ultrahigh Areal Sulfur Loading for High-Capacity and Long-Life Lithium-Sulfur Batteries.

Science.gov (United States)

Ma, Lianbo; Yuan, Hao; Zhang, Wenjun; Zhu, Guoyin; Wang, Yanrong; Hu, Yi; Zhao, Peiyang; Chen, Renpeng; Chen, Tao; Liu, Jie; Hu, Zheng; Jin, Zhong

2017-12-13

Lithium-sulfur (Li-S) batteries hold great promise for the applications of high energy density storage. However, the performances of Li-S batteries are restricted by the low electrical conductivity of sulfur and shuttle effect of intermediate polysulfides. Moreover, the areal loading weights of sulfur in previous studies are usually low (around 1-3 mg cm -2 ) and thus cannot fulfill the requirement for practical deployment. Herein, we report that porous-shell vanadium nitride nanobubbles (VN-NBs) can serve as an efficient sulfur host in Li-S batteries, exhibiting remarkable electrochemical performances even with ultrahigh areal sulfur loading weights (5.4-6.8 mg cm -2 ). The large inner space of VN-NBs can afford a high sulfur content and accommodate the volume expansion, and the high electrical conductivity of VN-NBs ensures the effective utilization and fast redox kinetics of polysulfides. Moreover, VN-NBs present strong chemical affinity/adsorption with polysulfides and thus can efficiently suppress the shuttle effect via both capillary confinement and chemical binding, and promote the fast conversion of polysulfides. Benefiting from the above merits, the Li-S batteries based on sulfur-filled VN-NBs cathodes with 5.4 mg cm -2 sulfur exhibit impressively high areal/specific capacity (5.81 mAh cm -2 ), superior rate capability (632 mAh g -1 at 5.0 C), and long cycling stability.

Molecular characterization of anaerobic sulfur-oxidizing microbial communities in up-flow anaerobic sludge blanket reactor treating municipal sewage.

Science.gov (United States)

Aida, Azrina A; Hatamoto, Masashi; Yamamoto, Masamitsu; Ono, Shinya; Nakamura, Akinobu; Takahashi, Masanobu; Yamaguchi, Takashi

2014-11-01

A novel wastewater treatment system consisting of an up-flow anaerobic sludge blanket (UASB) reactor and a down-flow hanging sponge (DHS) reactor with sulfur-redox reaction was developed for treatment of municipal sewage under low-temperature conditions. In the UASB reactor, a novel phenomenon of anaerobic sulfur oxidation occurred in the absence of oxygen, nitrite and nitrate as electron acceptors. The microorganisms involved in anaerobic sulfur oxidation have not been elucidated. Therefore, in this study, we studied the microbial communities existing in the UASB reactor that probably enhanced anaerobic sulfur oxidation. Sludge samples collected from the UASB reactor before and after sulfur oxidation were used for cloning and terminal restriction fragment length polymorphism (T-RFLP) analysis of the 16S rRNA genes of the bacterial and archaeal domains. The microbial community structures of bacteria and archaea indicated that the genus Smithella and uncultured bacteria within the phylum Caldiserica were the dominant bacteria groups. Methanosaeta spp. was the dominant group of the domain archaea. The T-RFLP analysis, which was consistent with the cloning results, also yielded characteristic fingerprints for bacterial communities, whereas the archaeal community structure yielded stable microbial community. From these results, it can be presumed that these major bacteria groups, genus Smithella and uncultured bacteria within the phylum Caldiserica, probably play an important role in sulfur oxidation in UASB reactors. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

One-step hydrothermal synthesis of three-dimensional porous graphene aerogels/sulfur nanocrystals for lithium–sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Jiang, Yong; Lu, Mengna; Ling, Xuetao; Jiao, Zheng; Chen, Lingli; Chen, Lu [School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444 (China); Hu, Pengfei [Instrumental Analysis and Research Center, Shanghai University, Shanghai 200444 (China); Zhao, Bing, E-mail: bzhao@shu.edu.cn [School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444 (China)

2015-10-05

Highlights: • 3D porous GA/S nanocrystals are prepared by a one-step hydrothermal method. • The structure is affected by hydrothermal temperature and liquid sulfur’s viscosity. • The hybrid delivers a capacity of 716.2 mA h g{sup −1} after 50 cycles at 100 mA g{sup −1}. • The nanosized S, strong adsorbability and intimate contact of GNS are main factors. - Abstract: Lithium–sulfur (Li–S) batteries are receiving significant attention as a new energy source because of its high theoretical capacity and specific energy. However, the low sulfur loading and large particles (usually in submicron dimension) in the cathode greatly offset its advantage in high energy density and lead to the instability of the cathode and rapid capacity decay. Herein, we introduce a one-step hydrothermal synthesis of three-dimensional porous graphene aerogels/sulfur nanocrystals to suppress the rapid fading of sulfur electrode. It is found that the hydrothermal temperature and viscosity of liquid sulfur have significant effects on particle size and loading mass of sulfur nanocrystals, graphitization degree of graphene and chemical bonding between sulfur and oxygen-containing groups of graphene. The hybrid could deliver a specific capacity of 716.2 mA h g{sup −1} after 50 cycles at a current density of 100 mA g{sup −1} and reversible capacity of 517.9 mA h g{sup −1} at 1 A g{sup −1}. The performance we demonstrate herein suggests that Li–S battery may provide an opportunity for development of rechargeable battery systems.

Method for Derivatization and Detection of Chemical Weapons Convention Related Sulfur Chlorides via Electrophilic Addition with 3-Hexyne.

Science.gov (United States)

Goud, D Raghavender; Pardasani, Deepak; Purohit, Ajay Kumar; Tak, Vijay; Dubey, Devendra Kumar

2015-07-07

Sulfur monochloride (S2Cl2) and sulfur dichloride (SCl2) are important precursors of the extremely toxic chemical warfare agent sulfur mustard and classified, respectively, into schedule 3.B.12 and 3.B.13 of the Chemical Weapons Convention (CWC). Hence, their detection and identification is of vital importance for verification of CWC. These chemicals are difficult to detect directly using chromatographic techniques as they decompose and do not elute. Until now, the use of gas chromatographic approaches to follow the derivatized sulfur chlorides is not reported in the literature. The electrophilic addition reaction of sulfur monochloride and sulfur dichloride toward 3-hexyne was explored for the development of a novel derivatization protocol, and the products were subjected to gas chromatography-mass spectrometric (GC-MS) analysis. Among various unsaturated reagents like alkenes and alkynes, symmetrical alkyne 3-hexyne was optimized to be the suitable derivatizing agent for these analytes. Acetonitrile was found to be the suitable solvent for the derivatization reaction. The sample preparation protocol for the identification of these analytes from hexane spiked with petrol matrix was also optimized. Liquid-liquid extraction followed by derivatization was employed for the identification of these analytes from petrol matrix. Under the established conditions, the detection and quantification limits are 2.6 μg/mL, 8.6 μg/mL for S2Cl2 and 2.3 μg/mL, 7.7 μg/mL for SCl2, respectively, in selected ion monitoring (SIM) mode. The calibration curve had a linear relationship with y = 0.022x - 0.331 and r(2) = 0.992 for the working range of 10 to 500 μg/mL for S2Cl2 and y = 0.007x - 0.064 and r(2) = 0.991 for the working range of 10 to 100 μg/mL for SCl2, respectively. The intraday RSDs were between 4.80 to 6.41%, 2.73 to 6.44% and interday RSDs were between 2.20 to 7.25% and 2.34 to 5.95% for S2Cl2 and SCl2, respectively.

Benzene destruction in claus process by sulfur dioxide: A reaction kinetics study

KAUST Repository

Sinha, Sourab; Raj, Abhijeet Dhayal; Alshoaibi, Ahmed S.; Alhassan, Saeed M.; Chung, Suk-Ho

2014-01-01

interactions. The mechanism begins with SO2 addition to phenyl radical after overcoming an energy barrier of 6.4 kJ/mol. This addition reaction is highly exothermic, where a reaction energy of 182 kJ/mol is released. The most favorable pathway involves O-S bond

Sulfur impregnated in tunable porous N-doped carbon as sulfur cathode: effect of pore size distribution

International Nuclear Information System (INIS)

Wang, Sha; Zhao, Zhenxia; Xu, Hui; Deng, Yuanfu; Li, Zhong; Chen, Guohua

2015-01-01

Highlights: •Effects of pore size were investigated on electrochemistry for S cathode. •Activation energy of sulfur desorption from the PDA-C was estimated. •Strong interaction was formed between sulfur and porous N-doped carbon. •PDA-C@S showed good cycling performance of 608 mA h g −1 at 2 C over 300 cycles. •PDA-C@S showed good rate stability and high rate capacity. -- Abstract: A novel porous N-doped carbon microsphere (polymer-dopamine derived carbon, PDA-C) with high specific surface area was synthesized as sulfur host for high performance of lithium-sulfur batteries. We used KOH to adjust the pore size and surface area of the PDA-C materials, and then impregnated sulfur into the PDA-C samples by vapor-melting diffusion method. Effects of pore size of the PDA-C samples on the electrochemical performance of the PDA-C@sulfur cathodes were systematically investigated. Raman spectra indicated an enhanced trend of the degree of graphitization of the PDA-C samples with increasing calcination temperature. The surface area of the PDA-C samples increases with amount of the KOH in the pore-creating process. The graphitized porous N-doped carbon provides the high electronic conductive network. Meanwhile, the PDA-C with high surface area and uniform micropores ensures a high interaction toward sulfur as well as the high dispersion of nanoscale sulfur layer on it. The microporous PDA-C@S cathode material exhibits the excellent high rate discharge capability (636 mA h g −1 at 2.0 C) and good low/high-rate cycling stability (893 mA h g −1 (0.5 C) and 608 mA h g −1 (2.0 C) over 100 and 300 cycles). Cyclic voltammogram curves and electrochemical impedance plots show that both the impedance and polarization of the cells increase with decreasing pore size

Sulfur containing nanoporous materials, nanoparticles, methods and applications

Science.gov (United States)

Archer, Lynden A.; Navaneedhakrishnan, Jayaprakash

2018-01-30

Sulfur containing nanoparticles that may be used within cathode electrodes within lithium ion batteries include in a first instance porous carbon shape materials (i.e., either nanoparticle shapes or "bulk" shapes that are subsequently ground to nanoparticle shapes) that are infused with a sulfur material. A synthetic route to these carbon and sulfur containing nanoparticles may use a template nanoparticle to form a hollow carbon shape shell, and subsequent dissolution of the template nanoparticle prior to infusion of the hollow carbon shape shell with a sulfur material. Sulfur infusion into other porous carbon shapes that are not hollow is also contemplated. A second type of sulfur containing nanoparticle includes a metal oxide material core upon which is located a shell layer that includes a vulcanized polymultiene polymer material and ion conducting polymer material. The foregoing sulfur containing nanoparticle materials provide the electrodes and lithium ion batteries with enhanced performance.

Preliminary study on 2-dimensional distributions of 10B reaction rate in a water phantom with boron-doped CR-39 for 7Li(p, n)7Be neutrons by 1.95 MeV protons

International Nuclear Information System (INIS)

Hasegawa, Y.; Tanaka, K.; Tsuruta, T.

2000-01-01

In an Accelerator-based neutron irradiation field using 7 Li(p, n) 7 Be neutrons by 1.95 MeV protons, the distributions of 10 B reaction rates and thermal neutron fluence in a water phantom were measured using Boron-doped CR-39 and Au activation analysis, respectively. Comparing the results of the measurements, we discussed the validity of the evaluation method of 10 B reaction rate using thermal neutron fluence. (author)

In situ tribochemical sulfurization of molybdenum oxide nanotubes.

Science.gov (United States)

Rodríguez Ripoll, Manel; Tomala, Agnieszka; Gabler, Christoph; DraŽić, Goran; Pirker, Luka; Remškar, Maja

2018-02-15

MoS 2 nanoparticles are typically obtained by high temperature sulfurization of organic and inorganic precursors under a S rich atmosphere and have excellent friction reduction properties. We present a novel approach for making the sulfurization unnecessary for MoO 3 nanotubes during the synthesis process for friction and wear reduction applications while simultaneously achieving a superb tribological performance. To this end, we report the first in situ sulfurization of MoO 3 nanotubes during sliding contact in the presence of sulfur-containing lubricant additives. The sulfurization leads to the tribo-chemical formation of a MoS 2 -rich low-friction tribofilm as verified using Raman spectroscopy and can be achieved both during sliding contact and under extreme pressure conditions. Under sliding contact conditions, MoO 3 nanotubes in synergy with sulfurized olefin polysulfide and pre-formed zinc dialkyl dithiophosphate tribofilms achieve an excellent friction performance. Under these conditions, the tribochemical sulfurization of MoO 3 nanotubes leads to a similar coefficient of friction to the one obtained using a model nanolubricant containing MoS 2 nanotubes. Under extreme pressure conditions, the in situ sulfurization of MoO 3 nanotubes using sulfurized olefin polysulfide results in a superb load carrying capacity capable of outperforming MoS 2 nanotubes. The reason is that while MoO 3 nanotubes are able to continuously sulfurize during sliding contact conditions, MoS 2 nanotubes progressively degrade by oxidation thus losing lubricity.

Microbial contributions to coupled arsenic and sulfur cycling in the acid-sulfide hot spring Champagne Pool, New Zealand

Directory of Open Access Journals (Sweden)

Katrin eHug

2014-11-01

Full Text Available Acid-sulfide hot springs are analogs of early Earth geothermal systems where microbial metal(loid resistance likely first evolved. Arsenic is a metalloid enriched in the acid-sulfide hot spring Champagne Pool (Waiotapu, New Zealand. Arsenic speciation in Champagne Pool follows reaction paths not yet fully understood with respect to biotic contributions and coupling to biogeochemical sulfur cycling. Here we present quantitative arsenic speciation from Champagne Pool, finding arsenite dominant in the pool, rim and outflow channel (55-75% total arsenic, and dithio- and trithioarsenates ubiquitously present as 18-25% total arsenic. In the outflow channel, dimethylmonothioarsenate comprised ≤9% total arsenic, while on the outflow terrace thioarsenates were present at 55% total arsenic. We also quantified sulfide, thiosulfate, sulfate and elemental sulfur, finding sulfide and sulfate as major species in the pool and outflow terrace, respectively. Elemental sulfur reached a maximum at the terrace. Phylogenetic analysis of 16S rRNA genes from metagenomic sequencing revealed the dominance of Sulfurihydrogenibium at all sites and an increased archaeal population at the rim and outflow channel. Several phylotypes were found closely related to known sulfur- and sulfide-oxidizers, as well as sulfur- and sulfate-reducers. Bioinformatic analysis revealed genes underpinning sulfur redox transformations, consistent with sulfur speciation data, and illustrating a microbial role in sulfur-dependent transformation of arsenite to thioarsenate. Metagenomic analysis also revealed genes encoding for arsenate reductase at all sites, reflecting the ubiquity of thioarsenate and a need for microbial arsenate resistance despite anoxic conditions. Absence of the arsenite oxidase gene, aio, at all sites suggests prioritization of arsenite detoxification over coupling to energy conservation. Finally, detection of methyl arsenic in the outflow channel, in conjunction with

Sulfur induced selectivity changes for methanol decomposition on Ni(100)

Energy Technology Data Exchange (ETDEWEB)

Johnson, S.; Madix, R.J.

1979-01-01

The effects of structured overlayers as selective poisons were demonstrated by the adsorption of methanol on Ni(100), Ni(100)p(2 x 2)S, Ni(100)c(2 x 2)S at a crystal temperature of 137/sup 0/K and temperature programed reaction in an ultra-high vacuum. On the clean surface, mixed isotopes of dihydrogen and carbon monoxide were formed in desorption-limited processes above 300/sup 0/K. Evidence for the existence of an absorbed (COD) intermediate was obtained. The p(2 x 2)S surface gave similar results. The sulfur decreased the amount of absorbed methanol which reacted and interacted significantly with the (COD) intermediate. On the c(2 x 2)S structure, the primary reaction intermediate was methoxy. Formaldehyde was formed with an activation energy of 26 kcal/g-mole. No desorption-limited carbon monoxide was observed.

Sulfur impact on NO{sub x} storage, oxygen storage, and ammonia breakthrough during cyclic lean/rich operation of a commercial lean NO{sub x} trap

Energy Technology Data Exchange (ETDEWEB)

Choi, Jae-Soon; Partridge, William P.; Daw, C. Stuart [Fuels, Engines, and Emissions Research Center, Oak Ridge National Laboratory, P.O. Box 2008, MS-6472, Oak Ridge, TN 37831-6472 (United States)

2007-11-30

The objective of the present study was to develop an improved understanding of how sulfur affects the spatiotemporal distribution of reactions and temperature inside a monolithic lean NO{sub x} trap (LNT). These spatiotemporal distributions are believed to be major factors in LNT function, and thus, we expect that a better understanding of these phenomena can benefit the design and operation of commercial LNTs. In our study, we experimentally evaluated a commercial LNT monolith installed in a bench-flow reactor with simulated engine exhaust. The reactor feed gas composition was cycled to simulate fast lean/rich LNT operation at 325 C, and spatiotemporal species and temperature profiles were monitored along the LNT axis at different sulfur loadings. Reactor outlet NO{sub x}, NO, N{sub 2}O, and NH{sub 3} were also measured. Sulfur tended to accumulate in a plug-like fashion in the reactor and progressively inhibited NO{sub x} storage capacity along the axis. The NO{sub x} storage/reduction (NSR) reactions occurred over a relatively short portion of the reactor (NSR zone) under the conditions used in this study, and thus, net NO{sub x} conversion was only significantly reduced at high sulfur loading. Oxygen storage capacity (OSC) was poisoned by sulfur also in a progressive manner but to a lesser extent than the NO{sub x} storage capacity. Global selectivity for N{sub 2}O remained low at all sulfur loadings, but NH{sub 3} selectivity increased significantly with sulfur loading. We conjecture that NH{sub 3} breakthrough increased because of decreasing oxidation of NH{sub 3}, slipping from the NSR zone, by downstream stored oxygen. The NSR and oxygen storage/reduction (OSR) generated distinctive exotherms during the rich phase and at the rich/lean transition. Exotherm locations shifted downstream with sulfur accumulation in a manner that was consistent with the progressive poisoning of NSR and OSR sites. (author)

Orientations of Iron-Sulfur Clusters FA and FB in the Homodimeric Type-I Photosynthetic Reaction Center of Heliobacterium modesticaldum.

Science.gov (United States)

Kondo, Toru; Matsuoka, Masahiro; Azai, Chihiro; Itoh, Shigeru; Oh-Oka, Hirozo

2016-05-12

Orientations of the FA and FB iron-sulfur (FeS) clusters in a structure-unknown type-I homodimeric heriobacterial reaction center (hRC) were studied in oriented membranes of the thermophilic anaerobic photosynthetic bacterium Heliobacterium modesticaldum by electron paramagnetic resonance (EPR), and compared with those in heterodimeric photosystem I (PS I). The Rieske-type FeS center in the cytochrome b/c complex showed a well-oriented EPR signal. Illumination at 14 K induced an FB(-) signal with g-axes of gz = 2.066, gy = 1.937, and gx = 1.890, tilted at angles of 60°, 60°, and 45°, respectively, with respect to the membrane normal. Chemical reduction with dithionite produced an additional signal of FA(-), which magnetically interacted with FB(-), with gz = 2.046, gy = 1.942, and gx = 1.911 at 30°, 60°, and 90°, respectively. The angles and redox properties of FA(-) and FB(-) in hRC resemble those of FB(-) and FA(-), respectively, in PS I. Therefore, FA and FB in hRC, named after their g-value similarities, seem to be located like FB and FA, not like FA and FB, respectively, in PS I. The reducing side of hRC could resemble those in PS I, if the names of FA and FB are interchanged with each other.

Peatland Acidobacteria with a dissimilatory sulfur metabolism.

Science.gov (United States)

Hausmann, Bela; Pelikan, Claus; Herbold, Craig W; Köstlbacher, Stephan; Albertsen, Mads; Eichorst, Stephanie A; Glavina Del Rio, Tijana; Huemer, Martin; Nielsen, Per H; Rattei, Thomas; Stingl, Ulrich; Tringe, Susannah G; Trojan, Daniela; Wentrup, Cecilia; Woebken, Dagmar; Pester, Michael; Loy, Alexander

2018-02-23

Sulfur-cycling microorganisms impact organic matter decomposition in wetlands and consequently greenhouse gas emissions from these globally relevant environments. However, their identities and physiological properties are largely unknown. By applying a functional metagenomics approach to an acidic peatland, we recovered draft genomes of seven novel Acidobacteria species with the potential for dissimilatory sulfite (dsrAB, dsrC, dsrD, dsrN, dsrT, dsrMKJOP) or sulfate respiration (sat, aprBA, qmoABC plus dsr genes). Surprisingly, the genomes also encoded DsrL, which so far was only found in sulfur-oxidizing microorganisms. Metatranscriptome analysis demonstrated expression of acidobacterial sulfur-metabolism genes in native peat soil and their upregulation in diverse anoxic microcosms. This indicated an active sulfate respiration pathway, which, however, might also operate in reverse for dissimilatory sulfur oxidation or disproportionation as proposed for the sulfur-oxidizing Desulfurivibrio alkaliphilus. Acidobacteria that only harbored genes for sulfite reduction additionally encoded enzymes that liberate sulfite from organosulfonates, which suggested organic sulfur compounds as complementary energy sources. Further metabolic potentials included polysaccharide hydrolysis and sugar utilization, aerobic respiration, several fermentative capabilities, and hydrogen oxidation. Our findings extend both, the known physiological and genetic properties of Acidobacteria and the known taxonomic diversity of microorganisms with a DsrAB-based sulfur metabolism, and highlight new fundamental niches for facultative anaerobic Acidobacteria in wetlands based on exploitation of inorganic and organic sulfur molecules for energy conservation.

Zeolite synthesis from the pyrrolidine containing system and their catalytic properties in the methanol conversion reaction

Energy Technology Data Exchange (ETDEWEB)

Suzuki, Kunio; Kiyozumi, Yoshimichi; Shin, Shigemitsu; Ogawa, Kiyoshi; Yamazaki, Yasuyoshi; Watanabe, Hideo

1987-12-18

Systhesis of zeolite from a system containing cheaper pyrrolidine as a crystallization regulator than quaternary ammonium ion was carried out and the methanol conversion reaction was studied over the systhesized zeolite to get C/sub 2/ and C/sub 3/ olefins. Hydrous gels were prepared by adding and agitating pyrrolidine, water glass and sulfuric acid to aluminum sulfate solution; and aluminum nitrate, colloidal silica and pyrrolidine to NaOH solution. Five zeolite, that is, ZSM-5, ZSM-35, ZSM-39, ZSM-48 and KZ-1 were synthesized by changing gel components. X-ray powder diffraction, BET specific surface areas, micropore diameters, micropore volumes, oxygen contents by scanning electron photomicrographs and infra-red spectra were examined. The organic base in hydrous gels influenced greatly on the zeolite composition and structure. The ZSM-5 zeolite exhibited the superior performance as to a high selectivity of light olefins over the target of development. (12 figs, 1 tab, 20 refs)

Sulfurized activated carbon for high energy density supercapacitors

Science.gov (United States)

Huang, Yunxia; Candelaria, Stephanie L.; Li, Yanwei; Li, Zhimin; Tian, Jianjun; Zhang, Lili; Cao, Guozhong

2014-04-01

Sulfurized activated carbon (SAC), made by coating the pore surface with thiophenic sulfur functional groups from the pyrolysis of sulfur flakes, were characterized and tested for supercapacitor applications. From X-ray photoelectron spectroscopy (XPS), the sulfur content in the SAC was found to be 2.7 at%. Electrochemical properties from potentiostatic and galvanostatic measurements, and electrochemical impedance spectroscopy (EIS) were used to evaluate the effect of sulfur on porous carbon electrodes. The SAC electrode exhibits better conductivity, and an obvious increase in specific capacitance that is almost 40% higher than plain activated carbons (ACs) electrode at a high current density of 1.4 A g-1. The proposed mechanism for improved conductivity and capacitive performance due to the sulfur functional groups on ACs will be discussed.

Metal-free reduction of the greenhouse gas sulfur hexafluoride, formation of SF5 containing ion pairs and the application in fluorinations

KAUST Repository

Rueping, Magnus; Nikolaienko, Pavlo; Lebedev, Yury; Adams, Alina

2017-01-01

A protocol for the fast and selective two-electron reduction of the potent greenhouse gas sulfur hexafluoride (SF6) by organic electron donors at ambient temperature has been developed. The reaction yields solid ion pairs consisting of donor

Biologically removing sulfur from dilute gas flows

Science.gov (United States)

Ruitenberg, R.; Dijkman, H.; Buisman, C. J. N.

1999-05-01

A biological process has been developed to clean off-gases containing sulfur dioxide from industrial installations. The sulfur dioxide is converted into hydrogen sulfide, which can then be oxidized to elemental sulfur if not used on-site. The process produces no waste products that require disposal and has a low reagent consumption.

Sulfur-induced structural motifs on copper and gold surfaces

Energy Technology Data Exchange (ETDEWEB)

Walen, Holly [Iowa State Univ., Ames, IA (United States)

2016-01-01

The interaction of sulfur with copper and gold surfaces plays a fundamental role in important phenomena that include coarsening of surface nanostructures, and self-assembly of alkanethiols. Here, we identify and analyze unique sulfur-induced structural motifs observed on the low-index surfaces of these two metals. We seek out these structures in an effort to better understand the fundamental interactions between these metals and sulfur that lends to the stability and favorability of metal-sulfur complexes vs. chemisorbed atomic sulfur. The experimental observations presented here—made under identical conditions—together with extensive DFT analyses, allow comparisons and insights into factors that favor the existence of metal-sulfur complexes, vs. chemisorbed atomic sulfur, on metal terraces. We believe this data will be instrumental in better understanding the complex phenomena occurring between the surfaces of coinage metals and sulfur.

Microbial Desulfurization of a Crude Oil Middle-Distillate Fraction: Analysis of the Extent of Sulfur Removal and the Effect of Removal on Remaining Sulfur

Science.gov (United States)

Grossman, M. J.; Lee, M. K.; Prince, R. C.; Garrett, K. K.; George, G. N.; Pickering, I. J.

1999-01-01

Rhodococcus sp. strain ECRD-1 was evaluated for its ability to desulfurize a 232 to 343°C middle-distillate (diesel range) fraction of Oregon basin (OB) crude oil. OB oil was provided as the sole source of sulfur in batch cultures, and the extent of desulfurization and the chemical fate of the residual sulfur in the oil after treatment were determined. Gas chromatography (GC), flame ionization detection, and GC sulfur chemiluminesce detection analysis were used to qualitatively evaluate the effect of Rhodococcus sp. strain ECRD-1 treatment on the hydrocarbon and sulfur content of the oil, respectively. Total sulfur was determined by combustion of samples and measurement of released sulfur dioxide by infrared absorption. Up to 30% of the total sulfur in the middle distillate cut was removed, and compounds across the entire boiling range of the oil were affected. Sulfur K-edge X-ray absorption-edge spectroscopy was used to examine the chemical state of the sulfur remaining in the treated OB oil. Approximately equal amounts of thiophenic and sulfidic sulfur compounds were removed by ECRD-1 treatment, and over 50% of the sulfur remaining after treatment was in an oxidized form. The presence of partially oxidized sulfur compounds indicates that these compounds were en route to desulfurization. Overall, more than two-thirds of the sulfur had been removed or oxidized by the microbial treatment. PMID:9872778

Sulfur isotope study of the Velardeña skarn (Zn-Pb), Durango, Mexico

Science.gov (United States)

Jimenez, A.

2012-04-01

outside the common range of magmatic sulfur; it corresponds to a sphalerite crystal with δ34S of -3.9 ‰. This negative value could be explained by the incorporation of sulfur leached from the sedimentary host rocks. Pyrite and galena in paragenesis were analyzed from one sample (CO-9F); the isotope fractionation equation of Ohmoto and Rye (1979) was applied for geothermometry purposes. This calculation yields a temperature of 346° ±25° C, from fractionation Δpyrite-galena of 2.66 ‰.

Study on the Influence of Sulfur Fumigation on Chemical ...

African Journals Online (AJOL)

Purpose: To study the influence of different sulfur fumigation time and ... after sulfur fumigation though sulfur fumigation time and dosage were at low levels – 2 h ... Conclusion: Sulfur fumigation is not a desirable method for field processing of ...

Coupled sulfur isotopic and chemical mass transfer modeling: Approach and application to dynamic hydrothermal processes

International Nuclear Information System (INIS)

Janecky, D.R.

1988-01-01

A computational modeling code (EQPSreverse arrowS) has been developed to examine sulfur isotopic distribution pathways coupled with calculations of chemical mass transfer pathways. A post processor approach to EQ6 calculations was chosen so that a variety of isotopic pathways could be examined for each reaction pathway. Two types of major bounding conditions were implemented: (1) equilibrium isotopic exchange between sulfate and sulfide species or exchange only accompanying chemical reduction and oxidation events, and (2) existence or lack of isotopic exchange between solution species and precipitated minerals, parallel to the open and closed chemical system formulations of chemical mass transfer modeling codes. All of the chemical data necessary to explicitly calculate isotopic distribution pathways is generated by most mass transfer modeling codes and can be input to the EQPS code. Routines are built in to directly handle EQ6 tabular files. Chemical reaction models of seafloor hydrothermal vent processes and accompanying sulfur isotopic distribution pathways illustrate the capabilities of coupling EQPSreverse arrowS with EQ6 calculations, including the extent of differences that can exist due to the isotopic bounding condition assumptions described above. 11 refs., 2 figs

Investigation of the Li–S Battery Mechanism by Real-Time Monitoring of the Changes of Sulfur and Polysulfide Species during the Discharge and Charge

International Nuclear Information System (INIS)

Zheng, Dong; Liu, Dan; Harris, Joshua B.; Ding, Tianyao; Si, Jingyu

2016-01-01

The mechanism of the sulfur cathode in Li-S batteries has been proposed. It was revealed by the real-time quantitative determination of polysulfide species and elemental sulfur by means of the high performance liquid chromatography in the course of the discharge and recharge of a Li-S battery. A three-step reduction mechanism including two chemical equilibrium reactions was proposed for the sulfur cathode discharge. The typical two-plateau discharge curve for sulfur cathode can be explained. A two-step oxidation mechanism for the Li_2S and Li_2S_2 with a single chemical equilibrium among soluble polysulfide ions was proposed. In conclusion, the chemical equilibrium among S_5"2"-, S_6"2"-, S_7"2"- and S_8"2"- throughout the entire oxidation process resulted for the single flat recharge curve in Li-S batteries.